Hair

and Hair Care Cosmetic Science and

title:
Technology Series ; V. 17
author: Johnson, Dale H.
publisher: CRC Press
isbn10 | asin: 082479365X
print isbn13: 9780824793654
ebook isbn13: 9780585157344
language: English
Hair preparations, Hair--Care and hygiene, Hair
subject
preparations industry--United States.
publication date: 1997
lcc: TT969.H343 1997eb
ddc: 646.7/24
Hair preparations, Hair--Care and hygiene, Hair
subject:
preparations industry--United States.
 Page aa

Hair and Hair Care

 Page ab
COSMETIC SCIENCE AND TECHNOLOGY
Series Editor
ERIC JUNGERM ANN
Jungermann Associates, Inc.
Phoenix, Arizona
1. Cosmetic and Drug Preservation: Principles and Practice, edited by Jon J. Kabara
2. The Cosmetic Industry: Scientific and Regulatory Foundations, edited by Norman F.
Estrin
3. Cosmetic Product Testing: A Modern Psychophysical Approach, Howard R. Moskowitz
4. Cosmetic Analysis: Selective Methods and Techniques, edited by P. Boré
5. Cosmetic Safety: A Primer for Cosmetic Scientists, edited by James H. Whittam
6. Oral Hygiene Products and Practice, Morton Pader
7. Antiperspirants and Deodorants, edited by Karl Laden and Carl B. Felger
8. Clinical Safety and Efficacy Testing of Cosmetics, edited by William C. Waggoner
9. Methods for Cutaneous Investigation, edited by Robert L. Rie0tschel and Thomas S.
Spencer
10. Sunscreens: Development, Evaluation, and Regulatory Aspects, edited by Nicholas J.
Lowe and Nadim A. Shaath
11. Glycerine: A Key Cosmetic Ingredient, edited by Eric Jungermann and Norman O. V.
Sonntag
12. Handbook of Cosmetic Microbiology, Donald S. Orth
13. Rheological Properties of Cosmetics and Toiletries, edited by Dennis Laba
14. Consumer Testing and Evaluation of Personal Care Products, Howard R. Moskowitz
15. Sunscreens: Development, Evaluation, and Regulatory Aspects. Second Edition,
Revised and Expanded, edited by Nicholas J. Lowe, Nadim A. Shaath, and Madhu A.
Pathak
16. Preservative-Free and Self-Preserving Cosmetics and Drugs: Principles and Practice,
edited by Jon J. Kabara and Donald S. Orth
17. Hair and Hair Care, edited by Dale H. Johnson
 ADDITIONAL VOLUMES IN PREPARATION

 Page i

Hair and Hair Care

edited by
Dale H. Johnson
Helene Curtis, Inc.
Rolling Meadows, Illinois

MARCEL DEKKER, INC.

NEW YORK BASEL HONG KONG

 Page ii
Library of Congress Cataloging-in-Publication Data
Hair and hair care/edited by Dale H. Johnson.
p. cm.(Cosmetic science and technology; 17)
Includes index.
ISBN 0-8247-9365-X (alk. paper)
1. Hair preparations. 2. HairCare and hygiene. 3. Hair preparations industryUnited States.
I. Johnson, Dale H. II. Series: Cosmetic science and technology series; v. 17.
TT969.H343 1997
646.7'24dc21
974018
CIP
The publisher offers discounts on this book when ordered in bulk quantities. For more
information, write to Special Sales/Professional Marketing at the address below.
This book is printed on acid-free paper.
Copyright © 1997 by MARCEL DEKKER, INC. All Rights Reserved.
Neither this book nor any part may by reproduced or transmitted in any form or by any
means, electronic or mechanical, including photocopying, microfilming, and recording, or
by any information storage and retrieval system, without permission in writing from the
publisher.
MARCEL DEKKER, INC.
270 Madison Avenue, New York, New York 10016
Current printing (last digit):
10 9 8 7 6 5 4 3 2 1
PRINTED IN THE UNITED STATES OF AMERICA

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About the Series

The Cosmetic Science and Technology series was conceived to permit discussion of a
broad range of current knowledge and theories of cosmetic science and technology. The
series is made up of books written by one or more authors or edited volumes with a
number of contributors. Authorities from industry, academia, and the government are
participating in writing these books.
The aim of this series is to cover the many facets of cosmetic science and technology.
Topics are drawn from a wide spectrum of disciplines ranging from chemistry, physics,
biochemistry, and analytical and consumer evaluations to safety, efficacy, toxicity, and
regulatory questions. Organic, inorganic, physical, and polymer chemistry, emulsion
technology, microbiology, dermatology, and toxicology all play a role in cosmetic science.
There is little commonality in the scientific methods, processes, or formulations required
for the wide variety of cosmetics and toiletries manufactured. Products range from hair
care, oral care, and skin care preparations to lipsticks, nail polishes and extenders,
deodorants, body powders and aerosols to over the counter products, such as
antiperspirants, dandruff treatments, antimicrobial soaps, and acne and sunscreen
products.
Cosmetic and toiletries represent a highly diversified field with many sub-

 Page iv
section of science and art. Indeed, even in these days of high technology, art and intuition
continue to play an important part in the development and evaluation of formulations and
the selection of raw materials. There is a move toward more sophisticated scientific
methodologies in the fields of preservative efficacy testing, claim substantiation, safety
testing, product evaluation, and chemical analyses.
Emphasis in the Cosmetic Science and Technology series is placed on reporting the
current status of cosmetic technology and science in addition to historical reviews. The
series includes books on safety, efficacy testing, oral hygiene, scientific and regulatory
foundations, cosmetic product testing, analytical methods and techniques, antiperspirants
and deodorants, glycerine, rheological properties, cosmetic microbiology, sunscreens,
methods of cutaneous investigation, and consumer testing and evaluation of personal care
products. Several of the books have found an international audience and have been
translated into Japanese. Contributions range from highly sophisticated and scientific
treatises to primers, practical applications, and pragmatic presentations. Authors are
encouraged to present their own concepts as well as established theories. Contributors
have been asked not to shy away from fields that are still in a state of transition, nor to
hesitate to present detailed discussions of their own work. Altogether, we intend to
develop in this series a collection of critical surveys and ideas covering diverse phases of
the cosmetic industry.
Hair and Hair Care is the seventeenth book published in the Cosmetic Science and
Technology series. In its twelve chapters, the book covers the theoretical and practical
aspects of hair care products. Many product categories are covered: various classes of
shampoos, conditioners, rinses, styling aides, and hair dyes. The authors not only treat the
subject as a physical science but also address the importance of aesthetic and sensory
effects that contribute so importantly to the success of products in this field. This book
will be of real value to both product development chemists and marketing managers who
identify new opportunities and place new hair care products into the market place.
I want to thank the editor, Dr. Dale Johnson, and all the contributors for participating in
the writing of this book. Special recognition is also due to Sandra Beberman and the
editorial staff at Marcel Dekker, Inc. In addition, I would like to thank my wife, Eva,
without whose constant support and editorial help I would never have undertaken this
project.
ERIC JUNGERMANN, Ph.D.
SERIES EDITOR

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Preface
The goal of this book on hair and hair care is to provide an authoritative and useful
source of information aimed not only at the cosmetic chemist, but also at all of those
involved in the process of conceiving, developing, marketing, and selling hair care
products. Dermatologists, physicians, pharmacists, beauticians, barbers, hair stylists, and
estheticians also will find much of interest in this volume. Our colleagues in academia
will find a pragmatic approach to the real world of hair carethe problems and
challengesas well as the way solutions are found through the product development
process.
A decade ago, Charles Zviak of L'Oréal, Paris produced an excellent volume entitled The
Science of Hair Care (Marcel Dekker, 1986), which had a more medical orientation. Hair
and Hair Care is intended to complement Zviak's volume in terms of the subject areas
covered and the intended audience. This book provides up-to-date information in those
areas where significant progress has occurred during the past decade.
This volume will increase the reader's understanding of the many aspects of hair care
beyond one's particular area of focus and specialization. It deals with many aspects of the
product development process as currently practiced in the laboratories of some of the
world's leading manufacturers of hair care prod-

 Page vi
ucts. Much of what is discussed applies with only minor variations to the process of
developing personal care products of all types. Similarly, techniques and procedures that
have been developed for other personal care products can often be adapted to hair care
product development.
The products and techniques used to deal with the myriad of concerns people have with
respect to their hairits behavior, condition and appearancehave evolved over time from a
trial-and-error approach through a technological or engineering phase to a complex blend
of art, intuition, and science. In the rush to make everything objective, measurable and
scientific, it is critical that we do not lose touch with the basic artistic nature of the results
nor with the ultimate beneficiary of our craft: the consumer.
The strong growth of the specialized businesses serving the ethnic hair care market
reflects the cultural changes and increasing diversity of the U.S. population. People of
Afro-American and Hispanic background require specialized products with performance
and esthetic characteristics distinct from those of the Caucasian population. A separate
chapter has been devoted to the characteristics of ethnic hair and products designed for its
care.
Ultimately, the consumers of hair care products both define the needs of and enjoy the
benefits of the development scientist's art. Accurate and projectable consumer research is
a key element in the process to ensure that products under development closely match
consumer wants and needs. This work includes information on consumer testing
techniques, with particular emphasis on the special needs of hair care products. This
should prove particularly useful for those involved in marketing and development.
The developers and marketers of consumer products have to operate in a rapidly
changing environment that includes governmental regulations on all levels, consumer
activist pressures, and the competitive atmosphere that has always been with us. An
assessment of regulations aimed at both domestic and international hair care products is
provided to help cosmetic scientists and their support teams avoid potentially costly
pitfalls and continue to focus on their core strategic directions.
In summary, Hair and Hair Care is targeted to the scientific community involved with
development and manufacturer of hair care products, but it will also prove valuable to
marketing and sales specialists and upper management of such firms. In addition,
physiciansespecially dermatologistsas well as pharmacists who deal with any aspect of
hair care will find this volume of value.
I wish to acknowledge the contributions of each of the authors. The sharing of their
knowledge and expertise is their gift to us all. Their time and dedication to getting the
work accomplished made my job very rewarding. I want to give special recognition and
thanks to Dr. Eric Jungermann, father of the

 Page vii
Cosmetic Science and Technology series, and my mentor for close to two decades. The
tireless assistance and encouragement from Sandra Beberman and her editorial staff at
Marcel Dekker, Inc., played an essential role in production of this volume. Above all, I
whish to express my deepest thanks and love to my wife, Winni, without whose support
and encouragement none of this would have happened.
DALE H. JOHNSON

 Page ix

Contents
Ahashare.com
About the Series iii
Preface v
Contributors xi
1. Morphology and Properties of Hair
1
Max Feughelman
2. Physical Properties of Hair
13
Max Feughelman
3. Cleansing of Hair
33
Michael Wong
4. Conditioning of Hair
65
Myra A. Hoshowski
5. Hair Styling/Fixative Products
105
Joseph A. Dallal and Colleen M. Rocafort

 Page x
6. Hair Waving
167
Edward T. Borish
7. Hair Coloring
191
Keith C. Brown
8. Fragrance for Hair Care Products
217
Peter Dichter
9. Ethnic Hair Care Products
235
Ali N. Syed
10. Objective and Instrumental Methods for Evaluation of
Hair Care Product Efficacy and Substantiation of Claims 261
Marion K. Ishii
11. Consumer Research Techniques
303
Ralph Blessing
12. International Regulations for Hair Care Products
331
Richard M. Bednarz and Thomas E. Hamernik
Index 355

 Page xi

Contributors
Richard M. Bednarz, Ph.D. Amway Corporation, Ada, Michigan
Ralph Blessing Helene Curtis, Inc., Chicago, Illinois
Edward T. Borish, B.S., Ph.D. Zotos Corporation, Darien, Connecticut
Keith C. Brown, Ph.D. Clairol, Inc., Stamford, Connecticut
Joseph A. Dallal, L.C., M.Sc. International Specialty Products, Wayne, New Jersey
Peter Dichter Peter Dichter and Associates, New York, New York
Max Feughelman, B.Sc., D. Sc. School of Fiber Science and Technology, University of
New South Wales, Sydney, New South Wales, Australia
Thomas E. Hamernik, B.S. Amway Corporation, Ada, Michigan
Myra A. Hoshowski, B.S. Helene Curtis, Inc., Chicago, Illinois
Marion K. Ishii, M.A.* Helene Curtis, Inc., Chicago, Illinois
Colleen M. Rocafort, B.A., M.A. International Specialty Products, Wayne, New Jersey
Ali N. Syed, B.Sc. Honors, M.Sc., M.B.A. Avlon Industries, Inc., Chicago, Illinois
Michael Wong, Ph.D. Clairol, Inc., Stamford, Connecticut
*Retired

 Page 1

1
Morphology and Properties of Hair
Max Feughelman
School of Fiber Science and Technology, University of New South Wales,
Sydney, New South Wales, Australia
I.
Introduction
Hair fibers form a major component of the outer covering for most mammals. They create
a physical barrier between the animal and its environment, and have evolved as a result of
their necessary exposure to harsh conditions and the need to be stable over long periods
of time to quite severe treatment. All mammalian hairs, together with wools, horns, claws,
nails, and quills, mainly consist of a protein material known as -keratin. As a protein,
alpha keratin is a biological polymer consisting of polypeptide chains formed by the
condensation of amino acids. In the general formula for a polypeptide chain,

the groups R1 and R2 are the side chains of the amino acid residues for -keratin
corresponding to 20 different compositions. The distinguishing feature of all keratins and
the factor basic to the stability of their structure is the presence of a large proportion of
the sulfur-containing diamino acid cystine. With its two amino and two carbonyl groups
cystine can form part of two adjoining polypeptide chains forming via the disulfide bond
of the cystine residue a covalent crosslink between the two chains. Such covalent
crosslinks form part of some

 Page 2
10% of the residues of the keratin structures, confirming a high degree of physical and
chemical stability to the fiber. In particular in the hair setting process, it will be noted that
the disulfide crosslink plays a basic role. Destabilization of the disulfide bond is a key
step in most commercial setting procedures.
X-ray diffraction studies of ordered structures such as crystalline solids reveal the spatial
repeats and the nature of the molecules forming the repeats. This technique has been
applied to the study of hair fibers and indicates a high degree of order (crystallinity)
present in the keratin structure. The in -keratins refers to the typical high-angle x-ray
diffraction pattern obtained from hair fibers. Under low-resolution conditions in a dry
environment two major reflections are obtained, which are diagnostic for -keratins. The
0.516-nm reflection on the meridian corresponds to a repeat in the fiber direction and the
0.94-nm reflection on the equator corresponds to spacing repeat at right angles to the fiber
direction (1). This latter equatorial reflection is usually quoted at 0.98 nm, this value being
based on x-ray tests on fibers carried out at room humidity with no correction for the
presence of water (2,3). The -helix proposed by Pauling to describe the protein
molecules forming the ordered regions of the keratin structure was based on this x-ray
data taken together with other relevant information (4). Other specialized forms of keratin
exist such as feather- and -keratin. Both of these forms produce a distinctly different
high-angle X-ray diffraction pattern, of which only the -keratin as the result of extension
of the -keratin structure will be discussed as being of direct interest in this work.
Hairs are produced completely within the hair follicle. Starting at the bottom part of the
follicle, which is bulbous and contains the germinal matrix where cell division occurs,
and the presumptive cortical cells, which form the bulk of a hair fiber, grow and elongate
immediately above the bulb. Keratinization, the process of stabilization of the elongated
cortical cells, occurs from the top of the bulb and is complete well before the fiber
protrudes beyond the surface of the skin. The process of stabilization of the structure of
the hair fiber involves the formation of disulfide bonds by oxidation of the thiol groups
(SH) present in the material immediately above the bulb and is almost absent in the
keratinized fiber prior to its protrusion out of the follicle. That the molecular structure of
the hair fiber is stabilized in the moist environment of the follicle means that the fiber is
formed in mechanical equilibrium in the wet or near wet state. It follows that in the
consideration of the physical properties of hair fibers in any arbitrary environment we
must recognize that the fiber has shrunk from a water-swollen state at which mechanical
equilibrium existed, and has not swollen from a dry state. As will be seen later in this
discussion, this emphasis of the wet equilibrated state is necessary for our understanding
of the variation of moisture uptake of different hair fibers. Water, by its plasticization of
the biopolymeric structure of keratin, is a major contributor to the variation of the
physical properties of these fibers. An understanding of the interaction of

 Page 3
water in the keratin structure is vital. In basic terms we are examining the physical
properties of the keratin-water system.
The polypeptide chains forming the keratin structure not only are crosslinked at intervals
by covalent bonding formed by the cystine residues, but are held in various states of
order by secondary bonds such as Van der Waals interactions, hydrogen bonds, and
coulombic interactions sometimes referred to as salt links (5). These latter interactions
arise from the presence of negatively charged ionised carboxylic acid groups (COO-) and
positive amino groups ( ) formed on the side chains of acidic and basic residues. The
presence of the latter bonds can be reduced or eliminated by placing the keratin fiber in
an acidic aqueous medium (low pH) in which in the presence of excess hydrogen ions
that is, the charge on the carboxylic acid groups is neutralized. A similar
effect can be obtained in a basic aqueous medium (high pH) with the elimination of the
charge on the amino groups in the presence of excess hydroxyl ions. These
latter interactions together with the other secondary bonds play an important role in the
maintenance of the molecular and near molecular order present in -keratin fibers. This
order controls the freedom of movement and physical cooperation between the molecular
chains forming the keratin, and obviously plays a major role in the mechanical and other
physical properties of fibers. A discussion follows on a more detailed morphology of hair
fibers indicating the relationships between the various components forming such fibers
right down to the molecular level. The discussion is limited to those features of direct
interest in the understanding of the properties of hair fibers. A detailed and wideranging
discussion of morphology is left for others (6,7). There follows a discussion of the
chemistry of the fibrous protein keratin of particular relevance to human hair and in
particular the chemical factors that affect the physical behavior of the hair.
II.
Morphology
Fibrous -keratins such as hairs, furs, and wools have in common the structural features
of an external cuticle layer covering the cortex, the main material component of the fiber,
with a central axial medulla present often in the coarser fibers. The cuticle consists of
layers of scales each about 0.5 m thick in the case of human hair, and nearly 1 m for
wools. The number of scales present in the cross section of a fiber is also dependent on
the type of fiber. In a newly formed human hair, up to 10 scales are present overlapping
in one cross section, whereas in a wool fiber the scales are barely overlapping, resulting
in mainly one scale thickness covering the fiber. The scale structure of the cuticle in the
growing hair fiber in the follicle interlocks with the inner root sheath of the follicle. This
inner root sheath travels outward at the same rate as the hair

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fiber and represents by its interlocking action the major mechanical stabilization of a hair
fiber in the follicle. When a hair fiber is forcibly removed from the follicle, the inner root
sheath is destroyed by this action. The inner root sheath as it moves outward is eliminated
by chemical enzyme action, and the hair fiber is freed from its mechanical hold. The
scales in all hairs form a ratchettlike structure resulting in a directional friction effect,
which plays a vital role in the entanglement of fibers (Fig. 1). Disentanglement of hair by
direct mechanical means such as combing and brushing tends to strip the cuticle structure,
the complete removal of the scale structure being associated with the splitting of the hair
due to the fragmentation of the exposed cortex structure (8). Examination of human hair
by optical microscopy reveals a progressive removal of scale structure from root to tip
with splitting and fracture of the hair at the tip end, where all the scale structure has been
removed. One of the functions of hair conditioners is to reduce the force of friction on
the surface of hair fibers, thus facilitating distentanglement and reducing the possibility of
stripping of the scale structure. The result is a longer life for the protective scale structure,
and for hair potentially a longer period prior to fracture and splitting of the hair tip. The
technique of entanglement of hair used by hairdressers called back-combing raises and
causes removal of scales by combing the hair from tip to scalp. The result of this action
may cause splitting of the hair ends.

Figure 1
Scanning electron micrograph of a human hair fiber cut at an acute angle
to the fiber axis revealing the layers of cuticle (scales), and the separation
of cortical cells. (Courtesy of J.W.S. Snaith, CSIRO, Division of Wool
Technology, Ryde.)

 Page 5

Figure 2
Diagrammatic representation of a hair fiber at various dimensional levels, indicating
the scale and cortex structure down to the -helices present as a component of the
microfibrils of the cortex structure.
In the undamaged hair as it protrudes from the follicle, the outer surface of the fiber is
covered by a very thin membrane (about 3 nm thick)* called the epicuticle. The epicuticle
is visible in the cross section of a fiber by use of transmission electron microscopy. Below
the epicuticle in each scale cell is the exocuticle, a cystine-rich component representing
about two-thirds of the cuticle structure. The a layer of the exocuticle is the extremely
cystine-rich component ( 30% cystine) just below the epicuticle. In each scale beneath
the exocuticle is the endocuticle followed by a thin layer of cell membrane complex (Fig.
2). The endocuticle is mechanically the weakest component of the cuticle, with a low
cystine content. The material forming the cuticle does not display any molecular ordering
as indicated by simple measurement techniques such as optical birefringence (9). As
indicated earlier, the cuticle does have a mechanically protective role for the cortex, which
forms the bulk of the fiber, and is an important barrier to dye sorption by the fiber.
Mechanically its behavior, on the basis of torsional measurements on human hair, does
not appear to differ markedly from the matrix of the cystine-rich phase of the cortex of
low mol-
* 1 nm = 10-9 m.

 Page 6
ecular order and relatively high moisture sorption (10). For further detail of cuticle
morphology the reader is referred to the report by Fraser et al (7).
The cortex of hair fibers is formed from elongated cortical cells (Fig. 2) of a few microns
in cross section packed tightly together and oriented parallel to the fiber direction. When
viewed under an electron microscope the cortical cells are seen to consist of long uniform
filaments oriented parallel to the axis of the hair fiber. These filaments or microfibrils are
about 7.5 nm in diameter set apart about 10 nm center to center. The microfibrils in each
cortical cell are grouped together into units about 0.5 m diameter known as macrofibrils.
The microfibrils in the macrofibrils are separated by a cystine-rich matrix and within each
macrofibril, the microfibrils are spatially related to each other. This relationship in the
case of human hair is often a near hexagonally packed configuration as seen in cross
sections under an electron microscope (see Fig. 3). Mechanical evidence combined with
electron microscopic observation of extended samples of keratin fibers (11,12) suggests
that, within each macrofibril at least,

Figure 3
Electron micrograph of an -keratin fiber (porcupine quill tip) (a) in
cross section and (b) in longitudinal section of the cortex. The lightly
stained components are the microfibrils embedded in the heavily
stained matrix. The microfibrils are hexagonally packed in the cross
section of the cortex and parallel to each other in the fiber axis
direction. In less organized fibers such as hair, the packing only
approaches the near-hexagonal situation toward the center of the
macrofibrils (see text). (Courtesy of G.E. Rogers, University
of Adelaide.)

 Page 7
the microfibrils extend cooperatively, indicating a close interaction with each other.
Basically the macrofibril acts as a single mechanical unit.
The microfibrils contain the organised -helical material responsible for the characteristic
high-angle X-ray pattern of all -keratins (7). The -helices present within the
microfibrils are organized in the form of helical ropes formed by two -helices wrapped
around each other, all the ropes forming the organized structure of the microfibrils (13).
The microfibrils do not appear to differ from one form of -keratin to another, in
contrast with the less ordered matrix material which varies considerably in amount
present for the various -keratin fibers. The relationship of the microfibrils to the
embedding matrix and in particular the presence of the organized -helices within the
microfibrils plays a dominant role in the mechanical and water sorption properties of the
whole fiber. More of this relationship will be brought out in the following discussion of
the physical properties of -keratin fibers.
Medulla is present in either continuous or discontinuous form along the axis of coarser -
keratin fibers. Its role essentially is that of empty space, increasing the thermal insulation
of the fiber with economy of weight and little loss in bending characteristics. The latter
characteristic is of obvious importance for quills, but in the case of human hair is of
minor importance. The presence of medulla has an effect on the optical appearance
particularly in low-pigmented fibers such as wool. The medulla causes an increase in the
scatter of light especially at the blue end of the optical spectrum, making the fibers with a
natural yellowish color to appear white. The role of the medulla in physical properties
such as mechanical properties is no more than that of empty space. Further discussion of
the medulla will be omitted.
Also present in human hairs are granules of melanin, the material that gives various hairs
their characteristic color. Melanin granules are formed in cells called melanocytes at the
base of the hair follicle. These melanin granules are extruded from the cells to form part
of the growing hair fiber as it progress upward from the follicle base. These granules are
round to oval in shape and are of two basic color varietiesbrown-black and yellow-red.
Keratin itself is transparent and almost colorless, and it is the concentration and size of the
melanin granules present in the hair that give us the complete range of hair colors present
in all human hair.
In the mature hair the malanin granules, which are about three times as long as they are
broad, are aligned with their long axis parallel to the fiber axis. There is little evidence of
structure within these granules, and in dark human hair they vary in length from 0.4 to 1.0
m and breadth 0.1 to 0.5 m. Being completely external to the cortical cells, their
mechanical role in the hair fiber is limited to that of a presence of scattered small, hard
granules. The chemical precursor to melanin (black-brown) is the amino acid tyrosine; the
other form of melanin (yellow-red), known as pheomelanin, is derived ultimately from
the

 Page 8
amino acid tryptophan. In the procedure of dyeing of hair it is often necessary to
eliminate the melanin as its presence in the hair can modify the coloring effect of the
dyes. Discussion of this and other factors relating to the presence of melanin is left to
others. In the study of the mechanical properties of keratin fibers the effect of melanin is
avoided by the use of colorless or nearly colorless fibers.
III.
Structural Chemistry
To understand the properties of -keratin fibers and how they behave with various
modifications it is essential to recognize certain chemistry related to structure which is
unique for keratin fibers. As indicated earlier, the disulfide bond of the cystines from the
point of view of -keratins as polymers represents the major stabilizing covalent link
between the polypeptide chains forming the fibrous structure. This covalent link in the
presence of ionized thiol groups (S-) can be involved in the reaction, first suggested for
-keratins by Burley (14), of sulfhydryl-disulfide interchange, which may be represented
by the following equation:

As indicated, this reaction is reversible. However, if for example the disulphide

bondSbScwere under mechanical stress, whereas the reformed bondSaScwere at lower or
no stress, the reaction would be favored in the forward direction. The reaction results in
relaxation of stress in an extended keratin structure, the interchange favoring the
breakdown of bonds under stress and the reformation of new bonds in equilibrium with
the extended system. The number of ionized sulfhydryl groups may be quite limited, in
the native -keratin structure, less than about 1 thiol of the residue of cysteine existing for
every 10 disulfides of cystine. However, one thiol group may progressively be involved
via a zipper reaction in the interchanging in turn of many stressed disulfide bonds, the
thiol group being continuously replaced at each interchange. Further, in the particular case
of the setting of hair in a predetermined configuration, the interchange reaction may be
speeded up by the chemical production of more thiol groups through the reduction of
disulfide bonds present in the keratin structure. This reduction may be obtained by a
number of reagents, in particular thiols such as thioglycollic acid or mercapto ethanol. It
should be noted that the thiol group must be ionized for the sulfydril-disulfide
interchange to occur. The interchange is therefore also favored by neutral and alkaline
conditions, and is prevented from occurring under acid conditions.
Although keratins are complex substances from which many protein fractions have been
extracted, it has been possible by a minimal of chemical dis-

 Page 9
ruption to the keratin fibers in which disulfide bonds are broken in the presence of an
alkali or a suitable dispersing agent such as urea, to extract two major protein fractions
from human hair, and a third fraction in the case of other keratins. In the case of human
hair the two fractions are a low and a high sulfur component, referred to respectively as
S-carboxy methyl kerateine A (SCMKA) and S-carboxy methyl kerateine B (SCMKB), the
names deriving from the method of preparation of the fractions (15). Considerable effort
over the years has been applied to the purefication, separation, and characterization in
terms of amino acid sequence analysis of these two fractions.
A.
Amino Acid Analysis (general)
It has been shown that -helices are only present in the SCMKA low sulfur fraction and
represent about one-half of this fraction. The amino acid analysis shows a greater
presence of cystine by a factor of 3 or 4 in concentration in the SCMKB as against the
SCMKA (see Table 1) and that in the latter component the cystine is concentrated in the
nonhelical components of the molecule (7). The SCMKB high-sulfur fraction was
extracted from the matrix component of the cortex structure of the keratin fiber. The helix
containing low sulfur fraction forms the highly organized microfibrils or filaments with
possibly some of
Table 1 Amino Acid Analyses of High and Low Sulfur Fractions
Compared with the Whole -Keratin Fiber (wool) Expressed as
Residues per 100 Residues (7).
Amino acid
Whole fiberLow sulfur fractionHigh sulfur fraction
residue
Alamine 5.5 6.4 2.9
Arginine 6.6 7.3 6.7
Aspartic Acid 6.5 8.1 4.1
Half-cystine 11.4 6.8 17.9
Glutamic Acid 11.3 14.1 6.4
Glycine 8.8 8.8 5.4
Histidine 0.8 0.7 0.9
Isoleucine 3.4 3.7 3.0
Leucine 7.8 10.3 5.0
Lysine 3.0 4.1 0.7
Methionine 0.5 0.6 0
Phenylalanine 2.9 3.0 2.4
Proline 6.0 4.2 13.6
Serine 9.6 7.3 11.9
Threonine 6.1 4.4 10.4
Tyrosine 4.1 4.3 1.9
Valine 5.9 5.9 6.7

 Page 10
the nonhelical tails of the low sulfur fraction protruding into the matrix to form an
interacting network between the microfibrils (16). This network may be the stabilizing
factor that maintains the distance between the microfibrils in the wet state (17,18).
In the microfibrils the -helices are formed into ropes of two -helices. Amino acid
sequence analysis of the helical components of -keratins has shown the presence of a
repeating sequence pattern of the residues in the helical component (13). These repeating
sequences result in the interaction between pairs of -helices via lipophyllic residues such
as alanine, leucine, isoleucine, and tyrosine, which in the presence of water result in
hydrophobic interactions (19). Neighboring to these hydrophobic interactions, charged
residues are present which form coulombic interactions between the -helices (see Fig.
4). It is suggested that these interactions play an important role in the mutual cooperation
of the helical chains during the rope formation. The possible mechanical effects of these
interactions will be discussed in Chapter II.
As indicated, the bulk of the keratin material consists of polypeptide chains of which the
repeat units (residues) differ only in the side chain R groups, which correspond to 20
different compositions. Certain of these R groups are reactive, and, together with the
chain-end groups, a great range of chemical modifications have been carried out. Only
some reactions of interest to the structure and physical properties of keratin fibers will be
mentioned. The tyrosine residues, for example, by reacting with the heavy atom iodine,
increase the intensity of certain x-ray diffraction reflections, indicating the presence of
regular structural repeats involving the side chain tyrosine (20). Modification by various
chemical reactions of sites of hydration such as the R groups containingCOO- or have
been carried out in studies on the keratin-

Figure 4
Residues of two interacting -helices in a rope showing
one heptad sequence of residues in each helix. Amino acid
residues A and D are hydrophobic, and E and G oppositely
electrically charged.

 Page 11
water system. Changes in the mechanical properties of keratin fibers have been obtained
by reacting the fibers with cross-linking reagents such as formaldehyde and
nitrophenylesters (21).
In the permanent setting procedure, in order to produce a higher concentration of thiols
(SH) in the fiber structure, disulfide bonds are reduced. The most satisfactory reducing
agents with a minimal of protein damage in human hair are the thiols of which
thioglycollic acid under alkaline conditions is the most effective. The reaction proceeds
via two reversible reactions

in which M = hair polypeptide chain. The reader will note that the thiol RS- is ionized;
that is, the pH of the reacting solution has to be on the alkaline side for a sufficient
density of RS- to exist. Extensive reduction can still occur in neutral or slightly acidic
solutions if a sufficiently large excess of thiol is used. However, this is not practical in the
standard permanent cold wave procedure and in practice the solutions of thioglycollic
acid used in ammonia are around pH 9.0 to 9.5. To reform the excessive amount of thiols
produced by the reduction procedure in permanent waving of hair, it is necessary to
oxidize the thiols back to disulfides, thus restabilizing the keratin structure. This oxidizing
procedure, euphemistically referred to as neutralizing in the hair toiletry industry, not only
oxidizes thiols

but also may oxidize disulfide bonds to cysteic acid

and cleave the peptide bonds of the main protein chains. This potential for damage by
oxidation necessitates that care be used in the formulation and application of the
neutralizers in the permanent waving procedure.
Sulfitolysis, that is, the cleavage of a disulfide bond by sulfite to give a thiol and an S
sulfonate anion,

has been applied to keratin fibers, particularly in wool fibers, as a permanent setting
procedure. The formation of the thiol group MS- increases the possibility of sulfhydril
disulfide interchange, a necessary mechanism in the setting of keratin structures.
The chemistry of the molecular components of keratin fibers has been dealt with in
greater depth and detail by others to whom the reader is referred. In this chapter the
author has indicated and discussed briefly the chemistry of

 Page 12
keratin fibers needed to understand the nature of a wider spectrum of events within these
fibers. Some of these events, such as the absorption of water by keratin fibers and the
behavior of fibers during permanent and cohesive setting, will be discussed in the
following chapter.
References
1. Bendit EG, quoted in Keratin in Encyclopedia of Polymer Science and Technology,
Bendit E G, Feughelman M, eds. New York: John Wiley & Sons. 1968, Vol 8, pp 144.
2. Astbury WT, Street A. Phil Trans R Soc Lond 1931; Ser. A230:75.
3. Astbury WT, Woods HJ. Phil Trans R Soc Lond 1933; Ser. A232:333.
4. Pauling L, Corey RB, Branson, HR. Proc Natl Acad Sci USA 1951; 37:205.
5. Speakman JB, Hirst MC. Trans Faraday Soc 1933; 29:143.
6. Mercer EH. Keratins and KeratinisationAn Essay in Molecular Biology. New York:
Pergamon Press, 1961.
7. Fraser RDB, Macrae TP, Rogers GE. Keratins, Their Composition, Structure and
Biosynthesis. Springfield, IL: Charles C. Thomas, 1972.
8. Kelly SE, Robinson VNE. J Soc Cosmetic Chem, 1982; 33:293.
9. Bradbury JH. Adv Protein Chem 1973; 27:111.
10. Wortmann FJ, Feughelman M, Kelly SE. Unpublished data.
11. Haly AR. Textile Res J 1970; 40:965.
12. Feughelman M. Appl Polymer Symp 1971; 18:757.
13. Crewther WG, Dowling LM, Stewart PM, Parry DAD. Int J Biol Macromol 1983;
5:267.
14. Burley RW. Proc Int Wool Textile Res Conf, Australia 1955; D:88.
15. Crewther WG, Fraser RDB, Lennox FG, Lindley H. Adv Protein Chem 1965; 20:191.
16. Bendit EG. Textile Res J 1968; 38:15.
17. Feughelman M. Textile Res J 1979; 49:704.
18. Fraser RDB, Macrae TP. Symp Soc Exp Biol Lond 1980; 34:212.
19. Fraser RDB, Jones LN, Macrae TP, Suzuki E, Tulloch PA. In: International
Symposium on Bio-molecular Structure, Conformation, Function and Evolution.
Srinivasan R, ed. Oxford: Pergamon Press, 1978.
20. Haly AR, Feughelman M. Textile Res J 1960; 30:365.
21. Feughelman M, Watt IC. Textile Res J 1964; 34:643.
Special Chemistry of Keratin Reference
Maclaren, John A., and Milligan, Brian, Wool Science, the Chemical Reactivity of the
Wool Fibre, Australia: Science Press.

 Page 13

2
Physical Properties of Hair
Max Feughelman
School of Fiber Science and Technology, University of New South Wales, Sydney,
Australia
I.
The Keratin-Water System
Water modifies the mechanical, thermal, electrical, and other physical properties of -
keratin fibers to such an extent both qualitatively and quantitatively that it is more
appropriate to consider -keratins with differing water contents as being different
keratin-water materials. Water, which exists as a continuous three-dimensional network
inside the -keratin structure, forms with the polypeptide chains of the keratin an
interpenetrating polymer network. This intimate combination of the two continuous
polymers of keratin chains and water results from the similarity of the cohesive bonding
of each polymer and their ability to interact at their interfaces with a high degree of
compatibility. This compatibility of water with the keratin polymer results in a mixing of
the two phases (keratin and water) so that both phases are reduced to the dimensions of
nanometers. The intimacy of the interaction is such that all the molecules of both phases
are mutually modified and the properties of the phases can only be considered as a
combined polymer. To understand the physical properties of this combined polymer, the
keratin-water system, it is necessary to understand the nature of water and its behavior in
the structure of -keratin fibers.
Water is a highly polar molecule, extremely mobile and penetrating, dimensionally
equivalent to little more than an atom of oxygen. In the keratin structure it can interact
with both negatively and positively charged groups such as the ends of acidic (COO-) and
basic ( ) side groups of the residues of the polypeptide chains. One water molecule can
form up to four hydrogen

 Page 14
bonds (1) with other water molecules or suitable hydrogen bonding groups such as
amideNH, carboxyl , and hydroxylOH. Because of this ability to form so many
interactions, water forms within the keratin structure a continuous three-dimensional
network of interactions between water and water molecules, and water and keratin
structure. Electrical conductivity of the keratin-water system is a proton conduction
mechanism in which hydrogen protons jumping between two equilibrium positions
followed by a rotation of a water molecule provide the charge transport mechanism (see
Fig. 1). The system acts as a proton semiconductor in the same way as has been shown to
exist in ice and in the nylon-water system (2,3). This electrical conductivity refers to that
of the bulk of the keratin fiber. Surface conductivity of a keratin fiber, which operates in
parallel with bulk conductivity, is primarily a property of the state of the surface and
whatever film or deposit exists on that surface.
Of prime importance to our understanding of the physical, especially mechanical,
properties of -keratin fibers is the structural location of the water molecules. Water acts
as a major modifier of the mechanical properties of hair fibers, acting as a plasticizer
reducing the longitudinal stiffness of a fiber by a

Figure 1
Sequence of proton displacement in interacting water
molecules in the presence of an electric field E: (a)
proton jump (b) water molecule rotation. Proton
conductivity results from the sequences (a) and (b)
in the three-dimensional water polymer which
interpenetrates the amorphous protein polymer network
primarily in the matrix of the -keratin fibers.

 Page 15
factor of about 3 from dry to wet. The swelling of hair fibers due to the absorption of
water is confined primarily to the radial direction. From dry to wet hair fibers swell about
16% radially and only a little over 1% longitudinally. Low-angle x-ray measurements have
shown that diametral swelling of the -keratin fiber is paralleled by an equivalent
separation change between the microfibrils of the corticular microfibril-matrix structure
(4). It has been shown from polarized infrared absorption studies of deuterum-hydrogen
exchange in -keratin fibers (5) placed into deuterum oxide (heavy water), that the amide
groups of the organised -helices do not interact with water. After 24 hours in the heavy
water about 30% undeuterated amide groups were found present in the fiber nearly all
from organized -helices. From a theoretical estimate based on the absorption infrared
dichroic measurements these undeuterated groups could be accounted for by an 80%
perfectly aligned -helical material and 20% randomly oriented amide groups. Ordered -
helices form the major components of the microfibrils, which would suggest an exclusion
of water in the crystalline components of the microfibrils. Fraser et al. (16) have estimated
for porcupine quill (a fibrous -keratin) on the basis of x-ray data that in a fully hydrated
quill the volume swelling due to water of the matrix and microfibrils were respectively
53% and 11%. The high volume swelling of the matrix implies that water absorbed is not
primarily into the matrix protein, a highly cross-linked network formed by polypeptide
chains heavily cross-linked by disulfide bonds, but rather that the high sulfur protein
material of the matrix is globular with most of the water external to this globular material.
The nature of the wet matrix has been further elucidated by the results of a number of
workers who have studied the changes of water sorption and mechanical properties of
different -keratin fibers with change in the proteins content of the matrix. The results of
this work can be summarized as follows (7,8): (a) Increase of matrix protein reduces the
water sorption of the matrix. (b) Concomitant with the reduction of water content of the
matrix is an increase in the mechanical stiffness of the matrix.
Conclusions from these results (9), taken together with changes in sorption and
mechanical properties of -keratin fibers before and after uptake of nonreactive dye
molecules (10) have been shown to be explicable in terms of the following general two-
phase structured model for -keratin fibers. The two-phase structure, which is taken to
represent physically the properties of the whole fibers, is that of a composite consisting of
two phases, C and M (see Fig. 2). C consists of rods of water impenetrable material set
parallel to the fiber axis embedded in phase M, a water-swellable material. The rods of
phase C, which have been shown to be about 30% of the whole fiber, correspond to the
crystalline -helical structure of the microfibrils (11). Phase M corresponds to the rest of
the keratin structure, which is the matrix and the noncrystalline parts of the microfibrils
that absorb water.

 Page 16

Figure 2
Diagrammatic representation of
-keratin fiber in terms of the
two phase: C, the
water-impenetrable phase, and
M, the water-weakened
penetrable phase in which C is
embedded (see text).
The two-phase system is formed in the follicle of the hair fiber and so as shown by
mechanical measurements (12,13) is in mechanical equilibrium for the wet state. In the
fully keratinized fiber in the wet state the distance between microfibrils that contain phase
C is limited at about 11 nm for many forms of fibrous -keratin. This limitation must
again have been formed in the follicle and has been suggested to consist of molecular
chains traversing from one microfibril to another (14). With the distance between
microfibrils fixed for the fiber in the wet state an increase of high sulfur protein (or any
other material) into the matrix space between the microfibrils reduces the space available
for water. Simultaneously this would increase the effective mechanical stiffness of the
matrix, a matrix that must be considered to be matrix protein plus water. The above
general two-phase representation of the physical properties of fibrous -keratins will be
extended to properties other than water sorption.
Although the above picture of sorption suggests together with other physical data that the
matrix is the major absorber of water, an inverse sorption pattern has been put forward
based on the chemistry of the microfibril and matrix proteins (15,16). The low sulfur
protein of the microfibril is high in hydrophilic groups such as acidic and basic side-chain
residues, together with a low-crosslink density as indicated by the low cystine content of
this protein (see Table 1). In contrast with this the high sulfur protein of the matrix is low
in hydrophilic groups, high in hydrophobic sidechain residues, and high in cystine

 Page 17
Table 1 The Calculation of a Swelling Factor A/B for the Two Major
Components, Microfibrils and Matrix, of the -Keratin Cortex. The
sum total A of the basic and acid amino acids represents the
hydrophilic groups present responsible for water sorption, and the
factor B the half-cystine content, the swelling-restricting covalent
bonds between the protein chains.
Low sulfur protein, High sulfur protein,
Amino acid
MoL. % MoL %
Arginine 7.3 6.7
Lysine 4.1 0.1
Histidine 0.7 0.9
Aspartic Acid +
8.1 4.1
Asparagine
Glutamic Acid +
14.1 6.4
Glutamine
Sum A 34.3 18.0
Half-Cystine B 6.8 17.9
Swelling Factor A/B 5.0 1.1

content, suggesting a high crosslink density. This difference in crosslink density and
water sorption sites (hydrophilic groups) has raised the suggestion that the microfibrils
should absorb much more water than the matrix. This would be a correct consequence if
the two phases were both amorphous solids and the sorption being considered were into
both phases. However, the water sorption into the matrix is not into the highly cross-
linked globular protein of the matrix, but around the globular high sulfur protein, forming
a three-dimensional water network. The microfibrils contain highly ordered para-
crystalline structures with water sorptions limited by the highly cooperative bonding of
the ordered structure. Some charged groups on the -helical ropes which form a
cooperative interaction system alongside the hydrophobic groups stabilizing these ropes
(see Fig. 4 of Chapter 1) would normally be expected to interact with water. However,
because of the hydrophobic interaction, they are prevented from directly interacting and
playing a major role in sorption of water into the microfibrils. Mechanical data (9)
certainly show no change in the effectiveness of coulombic interactions in mechanically
stabilizing the -helices with change of moisture content of the fiber. It appears that
physical order primarily decides the limitation of water sorption of the matrix and
microfibrils.
II.
Sorption of Water and Other Solvents into -Keratin Fibers
Water entering a dry fiber will initially be absorbed onto hydrophilic sites present on the
surface of the globular protein of the matrix and on the surface of the microfibrils.
Further water sorption will be a build up onto water molecules

 Page 18
already attached to the protein structure, a three-dimensional network of water molecules
hydrogen-bonded together via the four bonds available per water molecule. Nuclear
magnetic resonance (NMR) measurements (17) show that all the water molecules present
in a fiber at all moisture contents are mobile compared to the components of the keratin
protein. These water molecules are continously interchanging with each other so that
NMR cannot distinguish between water molecules attached momentarily to the relatively
rigid keratin structure and water molecules attached only to other water molecules. NMR
measurement does, however, indicate that as the moisture content of a fiber is changed
progressively from dry to wet, the mobility of all water molecules present progressively
increases. However, even at high relative humidities (90%), the mobility of the water
molecules present is far below that of liquid water. Cassie's and others (1820) division of
the water present in the structure of a keratin fiber into free or liquid water, and bound or
localized water, although a useful concept for the understanding of certain events within
the structure, fails to be justified by the direct measurement of mobility of water
molecules using NMR. From a moisture content of 7.7% of dry weight to 26.1%
corresponding to relative humidities (RH) of 25% to 90%, water in -keratin fibers
increased in mobility by a decade. However, at no stage was there any indication of the
presence either of any water fraction as immobilized as the keratin structure or anywhere
as mobile as liquid water.
The keratin-water isotherm is typical of the sorption isotherm of other water-sorbing
polymers such as nylons and celluloses (see Fig. 3). The initial portion of the curve from
0% to about 30% RH has been associated with a large proportion of the water interacting
directly with the keratin structure rather than with other water molecules. This is the
Langmuir sorption component of the curve having been initially obtained by Langmuir on
the basis of a model of molecules in a vapor in equilibrium with a single layer of
molecules attached directly to sites of a solid material structure (21). The latter portion of
the keratin-water isotherm up to 100% RH is considered as the solution region, where
water molecules primarily associate with other water molecules and the saturation water
content at 100% RH is limited by some physical structural factors, which limit the
swelling of the polymer. In the case of keratin fibers this limitation of swelling in the
matrix is produced by the molecular chains that have been proposed to set the
intermicrofibrillar distance for the wet structure formed in the hair follicle. Globular
proteins such as high sulfur proteins in human hair partially preswell the
intermicrofibrillar space (i.e., the matrix) and set a limit to the maximum amount of
further swelling by water of the matrix. The microfibrils also absorb some water, but this
is as noted earlier limited by the paracrystalline nature of the microfibrils and the
hydrophobic bonding stabilising the ropes of -helices which form a large proportion of
the microfibrils.

 Page 19

Figure 3
A typical water absorption isotherm obtained at 35°C for
-keratin fibers (merino wool). The fibers were subjected to
successive increments of humidity from the dry state. Different
symbols represent separate determinations with varying
magnitude of humidity steps. The total sorption curve is
considered as consisting of two components: the Langmuir
sorption with a saturation content of (a), and the solution
component (b). (Courtesy of Watt IC, CSIRO, Division of
Wool Technology, Ryde.)
The above keratin-water isotherm can certainly be simply considered in terms of the
bound and free water model as expressed by Cassie, with the bound water corresponding
to the Langmuir sorption component and the free water to the solution water swelling the
structure as saturation humidity is approached. However, as pointed out earlier, the NMR
data, which examine directly the state of the protons associated with the water molecules
in the keratin structure, do not indicate the presence of two distinct types of water, but
rather molecules of water mobile enough to result in a general averaging of their
interactions even over extremely short time periods (~ 10-8 sec). The water molecules
present in the keratin-water system at low relative humidities correspond to water
molecules, which on average interact mainly with the keratin structure. As the humidity of
the environment of the keratin fiber is increased, the water in the keratin-water system
progressively on average reduced the proportion of interactions with the keratin structure
and increases the interaction with other water molecules. Certainly all the water in the
keratin-water system near dryness behaves more like bound water, and near water satura-

 Page 20
tion of a fiber it is most mobile or free but never nearly as mobile as in liquid water.
Thermal measurements by Haly and Snaith (22) on keratin-water systems at various water
contents were able to show the water molecules interacting with other water molecules
initiating liquid-like behavior at sufficiently high water contents. Thermal transitions
corresponding to freezing for fibers with water contents over about 20% by weight of dry
keratin were obtained. These transitions were well below 0°C and did not reach the 0°C
or a latent heat of the transition approaching the values for ice water even for fibers
saturated with water. Again these data suggest the absence of any purely liquid water but
rather water which near saturation of a fiber becomes progressively liquidlike in the sense
that groups of a few water molecules act sufficiently cooperatively to display certain
aspects of liquidlike behavior.
Consideration of the water sorption of -keratin fibers in the above discussion has been
primarily taken in terms of the microfibrils and matrix of the cortical cells. These cells
represent in -keratin fibers including human hair some 85% or more of the material of
the fiber. In hair the scales of the cuticle do represent the most important other material
present. Because of the lack of any notable degree of order in the cuticle structure (23),
their behavior both for swelling in water and mechanically appears to approximate that of
the matrix (24). No specific component of the sorption for the keratin-water system has
been experimentally associated with the cuticle or any of the other material present in the
fiber. In the study of the bulk physical properties such as reversible mechanical
properties, water sorption, thermal properties, and electrical conductivity, the role of the
microfibril-matrix system of the cortical cells appears to be overwhelmingly dominant.
Only in physical measurements, where the surface structure of the fiber becomes of prime
importance, such as in the measurement of rates of uptake of dyes or the forces of
friction and entanglement between fibers, must the cuticle be considered as a major
controlling factor in the data obtained.
Alcohols such as methanol, ethanol, and propanol are also absorbed by -keratin fibers.
They are all capable of hydrogen bonding and volumetrically are absorbed at saturation
by approximately the same amount as water (25). The rate of diffusion into the fibrous
structure of the alcohols progressively decreases with increase of the molecular size of the
molecules. Further, alcohols, because of their hydrophobic components of hydrocarbon
chains, are able to penetrate the crystalline region of the microfibrils and increase the
separation of the -helices in the helical ropes (26).
Solvents such as formic acid, which is a strong hydrogen bond breaking agent, swell the
-keratin structure much further than water or alcohols by not only disorienting the
crystalline helical structure but also by penetrating and swelling the -helices apart.
Aqueous solutions of lithium bromide (LiBr) of

 Page 21
concentration greater than 6.4 molar completely disorganizes the -helices to random
coils, swelling the fiber by well over 100% by volume. This latter case will be considered
in the section on supercontraction. Many other hydrogen breaking solvents are available
which to varying degrees swell the -keratin structure. Invariably, because of their action,
they are not of practical importance in the hair industry, but have application for wool
textiles.
III.
Mechanical Properties
Speakman (27) produced the initial data which laid the foundation for our understanding
of the mechanical properties of -keratin fibers. He demonstrated that the longitudinal
mechanical properties of these fibers varied with temperature, time, and the relative
humidity of the environment at which they were equilibrated. He showed that the stress-
strain relationship in general could be represented by three distinct regions of extension.
As a fiber is initially extended, the stress-strain curve, up to a few percent strain (see Fig.
4), is referred to as the Hookean region. This is an apparently near linear region of stress-
strain behavior for the fiber with a stiffness at room temperature corresponding to a
Young's modulus of about 2 to 5 GPa depending on the moisture content of the fiber.
This region in fact does not closely approximate a purely Hookean spring in its properties;
a discussion of this feature has been published by Bendit (28), who refers to this region as
the pre-Yield region. However, because of the general familiarity with the name Hookean,
the latter nomenclature remains.
At extensions beyond a few percent strain the stress in the fiber does not change greatly
up to a strain of about 25% to 30% depending on the keratin fiber under test. This is the
Yield region of the stress-strain curve of the fiber. For extensions beyond the Yield region
the fiber becomes stiffer with further strain into the post-Yield region. The three regions
are most distinctly defined for uniform diameter fibers in water, the moduli
corresponding to the slopes of the linear segments of the Hookean, Yield, and post-Yield
regions are in the approximate ratio of 100:1:10. All fibrous forms of -keratin, such as
hairs, wools, quills, and horns, qualitatively have similar longitudinal stress-strain curves
with the three distinct regions of mechanical behavior.
An important observation was first made by Speakman (27) with regard to the
reproducibility of mechanical data for single -keratin fibers. He showed that, provided a
fiber was not extended to strains beyond the Yield region and was held extended only for
limited periods of time (not greater than ~ 1 hour) at room temperature (~ 20°C), the
mechanical properties of the fiber could be recovered by release in water at room
temperature overnight. The same release has been shown (29) to occur in water at 52°C in
about 1 hour. This observation has meant that within limitations any one fiber may be put
through differ-

 Page 22

Figure 4
A typical stress-strain curve of a uniform cross section -keratin fiber showing
the Hookean region (AB), Yield region (BC), and post-Yield region (CD).
ing mechanical tests provided release is carried out between tests. The results of these
different tests may be compared for the one fiber, eliminating in many experiments the
necessity of knowing diameter variation and avoiding a large number of tests with the
associated statistical assessment.
Speakman and Cooper (30) had also observed that no chemical degradation of wool
fibers in water was detectable for temperatures below 55°C. The temperature of 52°C at
which fibers were relaxed for 1 hour to regain their native mechanical properties,
mentioned above, was chosen as a suitable safe high temperature at which fibers could be
held without degradation. Stress-relaxation experiments (31) carried on wool fibers held
extended in water at 0.8% strain (well within the Hookean region) showed that the initial
indication of cystine breakdown via the mechanism of sulfhydryl-disulfide interchange
occurred in the temperature range 50°C to 60°C. This result concurs with Speakman's
prior observation that the degradation within wet wool fibers observed above 55°C cor-

 Page 23
responded to disulfide bond breakdown. In fact, mechanical tests may be carried out on
keratin fibers such as human hair normally up to temperatures of 50°C and within limits
of extension and time these show an ability for the fiber to recover its mechanical
properties after suitable release.
Further experiments (32) carried out on uniform-diameter Lincoln wool fibers for
estimates, after extension, of the recoverability of mechanical properties demonstrate the
sharpness of the onset of irrecoverability of mechanical properties for extension into the
post-Yield region. These results and others (33) demonstrate the initiation of covalent
bond breakdown immediately the fiber is extended into the post-Yield region. The
sharpness with which the phenomenon occurs with extension suggests a highly organized
or crystalline associated origin for the onset of the mechanical stiffness of the fiber as it is
extended into the post-Yield region.
It was Astbury and colleagues (34,35) who first noted the close link between mechanical
extension of -keratin fiber and change in its molecular structure as indicated by its high-
angle x-ray diffraction pattern. They had observed the change in the -keratin x-ray
pattern to the pattern of the extended fiber and concluded that extension of the whole
fiber was a direct reflection of molecular extension. In the -keratin structure of an
unextended fiber, the molecular chains, he proposed, must be folded, and in the -keratin
state of the highly extended fiber, the molecular chains must be in an extended
configuration. The folded -keratin structure has been shown by Pauling to correspond
to a helical structure, the -helix, present in a large proportion of protein structures. The
opposition to extension of an -helix has been shown (36) to be mainly due to the
hydrogen bonds between the helical turns together with coulombic interactions (37). The
range of values of the stiffness of -keratin fibers in the Hookean region under differing
conditions (in the range of 109 to 1010 Pascals) is compatible with values expected for a
hydrogen bonded network, as for example ice with a Young's modulus around 1010
Pascals (38).
The distinct changes in the nature of the mechanical events within -keratin fibers
depend on whether they are being extended in the Hookean, Yield, or post-Yield region.
These mechanical events are best understood in terms of mechanical models, which have
been developed in terms of physical data available about both the dynamic and
equilibrium state of the -keratin structure. The simple two-phase mode has already been
described as a crystalline phase C consisting of water unaffected and impenetrable -
helical rods and an embedding phase M corresponding to the rest of the keratin fiber.
Phase M is water-absorbing and mechanically weakened by water. Phase C, which
represents the ordered -helical ropes of the microfibrils, is about 30% of the whole fiber
structure. Phase M consists of the globular protein of the matrix together with the network
of polypeptide chains not part of the -helical crystalline material and the network of
interacting water molecules. Some of the

 Page 24
network of polypeptide chains may traverse from one microfibril to another, stabilizing
the relative position of the microfibrils.
This two-phase model is limited in its application to small distortions. The stiffness of the
fiber (Young's modulus) in the Hookean region changes from dry (0% water content) to
wet by about 3 to 1. This results from the progressive mechanical weakening of phase M
with phase C, which acts in parallel, being unaffected by the change in water content. For
small distortion of the fiber in torsion, the torsional stiffness of the fiber changes from
dry to wet by a factor of 10 or more (39). This results from the twisting of a fiber when
wet, mainly distorting phase M, phase C being much stiffer. In the lateral direction a
similar large change of mechanical stiffness from dry to wet has been observed, because
again nearly all the distortion in the wet fiber is confined to phase M (40).
For a fiber being extended at a fixed rate, once extension exceeds about 2%, the -helices
of phase C begin to unfold to an extended state with no break-down of covalent
bonding (41). This unfolding is opposed in phase C by the hydrogen bonds, coulombic
interactions, and other minor interactions which stabilize the -helices. In parallel with
this unfolding in phase C, phase M acts as a viscous opposition to the extension. The
unfolding of the -helices into the extended -configuration corresponds
thermodynamically to a phase change accompanying the extension of the fiber. Such a
phase change theoretically should occur at a constant stress level explaining the near
invariance with extension of the stress in the Yield region. The viscosity of phase M
changes markedly with water content. This results in the general stress level in the Yield
region changing by a factor of 4 to 1 for a fiber with a change of water content from dry
to wet.
At the end of the Yield region (25% to 30% extension), about 30% of the -helices in
phase C have unfolded. In the post-Yield region (30% extension), further unfolding of -
helices is accompanied by a rapid increase in opposition to further extension. This
increase of stress with extension in the post-Yield region is independent of the water
content of the fiber, indicating that covalent bonds are involved in this increase. The
stress increase is accompanied by breakdown of disulfide bonds. The mechanical
properties of the fiber with extension become progressively unrecoverable, when the
fiber is released under zero stress in water overnight at room temperature or at 52°C for 1
hour. The onset of unrecoverability occurs quite sharply with the initiation of the
mechanical stiffening in the post-Yield region and has been discussed in terms of the
series-zone model. This model, which was developed on the basis of a number of
physical phenomena, proposes the existence of zones of alternative groups in -helical
ropes. In one series of zones (X zones), -helices unfold with no hindrance, while in the
alternative zones (Y zones), unfolding of -helices results in the opposition and
breakdown of covalent bonds, mainly disulfide bonds. Extension into the Yield region
involves only the -helices of the X zone, and extension into the post-Yield region the
extension of the -

 Page 25
helices of the Y zones. The reader is referred elsewhere for further discussion of this
model (42).
Wortmann and Zahn (43) have further extended the series-zone concept by considering
the detail structure of the microfibrils (referred to alternatively as intermediate filaments).
Based on the known amino acid residue sequence of the -helical ropes forming the
crystalline component of the microfibrils and the cystine bonds present within these
ordered components, they were able to explain the change of the stress with extension
longitudinally of an -keratin fibre from the Yield to post-Yield region. Feughelman (44)
has modified the series-zone concept with the extended two-phase model in which the
increase of the stress in the post-Yield legion is produced by the globular matrix proteins
jamming the microfibrils as the fiber is being extended into the post-Yield region. The
justification of this latter model depends on the observed distinct difference of the
temperature stability of the cystine bonds in the microfibrillar, and matrix protein of the
-keratin structure (45). The extended two-phase model predicts the change in the turn
over from the Yield to post-Yield regions with change in matrix protein content of the -
keratin fibers tested. Further it predicts correctly the change in the longitudinal swelling of
-keratin fibers with change of the relative humidity of the fibers environment.
Most hair fibers in water at room temperature can be extended to 50% to 60% strain
before break occurs. However, with reduction of moisture content, extensibility is
considerably curtailed due to the reduction in the mobility of the molecular structure. This
loss of the ability for molecular flow results in a rapid buildup of stress in a fiber under
extension. This was demonstrated for wool fibers in liquid nitrogen (-196°C). Under these
conditions (46), no molecular flow was possible within the time frame of the extension (~
10 sec), and all fibers broke at 3% with no unfolding of the -helices. This type of break
is referred to as a glassy break in which failure of the structure starts at a point of high
stress and travels rapidly across the fibers' cross section. Similar fractures occur for dry
fibers and fibers extended very rapidly for which times are too short for molecular flow
to occur. At high humidities and slow rates of extension, fracture occurs along structural
boundaries exposing structural features such as macrofibrils and cortical cells at the point
of fracture.
IV.
Supercontraction in Keratin Fibers
Under special conditions of treatment it has been demonstrated (47) that -keratin fibers
could be made to contract up to over 30% in length, a phenomenon named
supercontraction. This effect occurs under a number of similar circumstances involving
the destabilizing of the organised -helical system of the microfibrils of the keratin
cortex. For example, if a fiber is placed at room temperature into an aqueous lithium
bromide solution of molarity of 6.4 or more,

 Page 26
the -helices become random coils, as mentioned earlier; the fiber is swollen and
contracts about 10% to 15% depending on the fiber (48). The contraction arises from
complete loss of stability of the oriented -helices by the breaking up of the hydrogen
bond system by lithium bromide solution. The previously oriented -helices becoming
randomized chains, the whole system of chains, which form the fiber, is a swollen
elastomer cross-linked primarily by the covalent disulfide bonds of the cystine residues.
The length the elastomer attains, which happens to be a contraction, corresponds to its
highest entropy state, since the forces acting on the molecular chains arise only from the
Brownian movement of these chains. In this swollen elastomeric state, mechanical
measurements such as longitudinal stress-strain have been carried out. Theoretically these
data are directly related to the density of cross-linking between the randomized
polypeptide chains of the -keratin fibers. However, the physical theory requires that the
basic units of peptide residues forming the randomized chains to be completely freely
jointed to each other. Correction for this lack of free jointing and other restricting factors
makes the application of the theory of elastomers, as a means of estimation of cross-
linking, of limited use. The theory does give estimates of change of proportion of cross-
linking, but is difficult to apply as an absolute method of assessment of cross-linkage
present in a fiber.
If the lithium bromide solution is washed out with water, the contracted fiber completely
reverts to its original length and the original configuration of -helical crystallites returns.
However, if the fiber contracted in the lithium bromide solution is heated above 50°C to
60°C, at which temperature sulfhydryl-disulfide interchange can occur, then the fiber is
further contracted as far as 40% below its native length (49). Apparently the covalent
bonds cross-linking the chains of the elastomer are able to re-form, permitting the
molecular chains to go to an even higher entropy configuration, which is the highly
supercontracted condition. If in this condition the lithium bromide is washed out of the
fiber, it does not recover its length or native configuration. The whole process of
recoverability is lost with the randomization of the covalent crosslinks, which on washing
out the lithium bromide interfere with the recovery mechanism. The fiber remains after
washing in a contracted state with a partial re-formation of -helices generally no longer
oriented strongly in the fiber direction, as indicated by x-ray diffraction measurements.
Similar supercontraction phenomena can be obtained by other means of breaking up of
the -helices in -keratin fibers (5053). Fibers held in water superheated at around 130°C
will generally supercontract after a few minutes (54). This contraction is again irreversible
because the high temperature has not only destabilized (or melted) the -helices but also
degraded the disulfide bonds, which maintained the crosslinks between the chains and
provide the memory for the fiber of its native state. After contraction at the high
temperature and reverting to room temperature, these fibers remain contracted, and

 Page 27
x-ray diffraction again shows the presence of randomized -keratin crystallites. The
superheating treatment completely destroys the ability of the chains to reform into their
original native configuration of oriented -helical crystallites.
Astbury's original supercontraction technique (35) involved heating the fiber in saturated
steam at 100°C with the fiber considerably extended in length and then released after a
short period of time of the order of 1 minute. In these circumstances the fiber would
normally supercontract. Apparently the procedure of having the fiber extended with the
-helices unfolded resulted at 100°C for sufficient instability in the -helical
configurations for the fiber on release to contract to a randomized state rather than the
native -helical crystallites. This would have been assisted by some disulfide bonds
interchanging at the high temperature interfering with the possibility of the -helices re-
forming. If in the above conditions the fiber were held extended for longer periods of
time than 1 minute prior to release, disulfide bond re-formation in the extended fiber
tends to stabilize the extended state. Beta-crystallites formed from the unfolded -helices
are stabilized by the re-formed crosslinks, and the fiber becomes with time set in the
extended configuration rather than supercontracting on release.
The supercontracted state of a keratin fiber is basically produced by the reversible or
irreversible destabilization of the -helical crystallites of the microfibrils and may be
considered as a step for a fiber in the process of being set in longitudinal extension. For
longitudinal set stable in water it is necessary not only to destabilize -helices but further
to stabilize the structure in the extended configuration.
V.
Set in -Keratin Fibers
When a fiber is being set in a distorted state differing from its native configuration, two
distinct conditions have to be met to maintain this distorted or set state. The distortion of
the native state of a fiber results in forces acting on the fiber tending to return it to its
original configuration. To overcome these forces it is necessary to create bonds in
equilibrium with the distorted state so that on release of the fiber these newly created
bonds come under tension as the fiber tends to return to its original state. Equilibrium and
set are reached when the forces of retraction to the original state are equal and opposite to
the forces created in the newly formed bonds. To further increase the effectiveness of the
newly formed bonds in maintaining the fiber as close as possible to the applied distortion,
it is necessary to reduce the forces of retraction returning the fiber to its native state.
Summarized, these two conditions are: (a) bond breakdown to reduce the forces of
retraction of the fiber in the distorted state, and (b) creation of bonds in equilibrium with
the distorted state.
Figure [5] expresses the events that occur in a fiber in which the distortion applied is a
longitudinal strain (AD) referred to as the setting strain. The

 Page 28

Figure 5
The force-strain behavior of a fiber being set.
The fiber is extended to strain AD at which the
force in the fiber initially at DB drops during
the setting time to DC. On release the strain of
the fiber drops to the set strain AF at which the
force in the fiber FG returning the fiber to its
native length is in equilibrium with the force
FE due to bonds created during the setting
process at equilibrium with the setting strain
AD (see text).
final set (AF) of the fiber, that is the strain of the fiber on release occurs at the value
where equilibrium exists between the force of retraction (GF) and force in the bonds
formed in equilibrium with the setting strain (FE). The value of the set strain (FA) is time-
dependent to the degree that the newly formed bonds responsible for the setting strain are
stable under stress in their opposition to the forces of retraction.
In the case of wet setting of hair and wool fibers, the setting strain is applied to the fiber
in a wet state, which assists in the rapid breakdown of weak interactions (hydrogen
bonds, coulombic interactions, etc.). If the fiber is dried while held strained, new
interactions are formed between components of the keratin structure by the removal of
water and the reduction of swelling. On release dry, the greater part of the fiber strain is
retained; the fiber is set. However, if placed in water, this set is released, and the fiber
returns to its native configuration. This set is referred to as cohesive set, and is dependent
on the breakdown and re-formation of weak cohesive forces within the fiber. In
commercial practice, where set in hair or wool textile material must be stable in the
presence of moisture, it is necessary for the breakdown and re-formation of bonds at the
setting strain to involve some covalent bonds, which will not be affected by the presence
of moisture in the fiber. The disulfide bond formed by the diamino acid cystine present in
-keratins is important in stabilizing the native configuration of the fiber. The breakdown
and re-formation of this bond via

 Page 29
the mechanism of sulfhydryl-disulfide interchange forms the basis of many techniques of
permanent setting of -keratin fibers. Disulfide bonds in neutral or alkaline aqueous
solutions can undergo breakdown and re-formation via sulfhydryl-disulfide interchange
in the presence of ionized thiol groups (55). This results in the removal of disulfide bonds
opposing the setting strain, the interchange favoring the breakdown of strained bonds,
and their re-formation in equilibrium, with the set configuration. In -keratin fibers up to
about 0.5% of the amino acid residues are thiols, and the above mechanism proceeds in
water at temperatures above 50°C to 60°C. If more rapid interchange at lower
temperatures is required to obtain this bond breakdown and re-formation, it is necessary
to form more thiols by reduction of disulfide groups.
In the permanent hair waving procedure, which is carried out at or near room
temperature, 20% to 40% of the disulfide bonds are normally reduced to provide
sufficient thiols. On completion of the setting procedure these thiols are reoxidized to
disulfides to prevent back-exchange by the mechanism of sulfhydryl-disulfide
interchange reverting the bonds in equilibrium with the set strain back to the unset
condition.
In research carried out on the permanent setting of -keratin fibers such as wool and hair,
most of the mechanical measurements have been carried out on setting in extension. Data
on set in bending, however, indicate that set both for various wool fibers and human hair
is more easily attained in bending than for small longitudinal extensions (56). In the case
of human hair this difference of setting behavior was explained by proposing that the
setting lotion used did not completely penetrate radially through the hair fibers (57). This
explanation was not applicable to the case of fine wools and hairs such as cashmere. An
alternative satisfactory explanation is based on the two-phase model in conjunction with
the plasticization of the matrix of fibers by sulfhydril-disulfide interchange during the
setting procedure (56). The chemistry of the normal setting procedure is well understood.
However, where this chemistry occurs in the physical components of the -keratin
structure remains a matter for further investigation.
VI.
Concluding Remarks
Our basic understanding of hair and other -keratin fibers has by the limitation of space
and time resulted in the omission in this discussion so far presented of a number of
relevant topics. What is the role physically of the cell membrane complex, for example?
Some chemical investigations have been carried out and the importance of this membrane
in the mechanical failure of wool fibers in fabrics is well documented. However, its role
mechanically is that of the weakest link in a chain, and its own specific physical
properties await further investigation.

 Page 30
Study of the difference of properties between African, Caucasian, and Mongolian hair has
been initiated but still leaves much to be done. A far greater amount of investigation into
the basic science of -keratin fibers exists for wool fibers. Much of this work, such as
sequence analysis of the residues of the helical and nonhelical components of fibers,
requires parallel data for human hair.
Bibliography
Bendit EG, Feughelman M. Keratin in Encyclopedia of Polymer Science and Technology,
Publisher: John Wiley & Sons, NY, 1968.
Feughelman M. Keratin in Encyclopedia of Polymer Science and Engineering. Publisher:
John Wiley & Son, NY, 1987.
Fraser RDB, McRae TP and Rogers GE, Keratins: Their Composition, Structure and
Biosynthesis. CC Thomas Publishing, Springfield, IL, 1972.
MacLaren JA, Milligan B. Wool Science. Science Press, Marrickville, NSW, Australia,
1981.
References
1. Coulson CA. Research (London) 1957; 10:149.
2. Algie JE, Downes JG, Mackay BH. Textile Res J 1960; 30:432.
3. Conway BE, Bockris JOM. J Chem Phys 1958; 28:354.
4. Fraser RDB, Macrae TP, Millward GR, Parry DAD, Suzuki E, Tullock PA. Appl
Polymer Symp 1971; 18:65.
5. Fraser RDB, Suzuki E. J Molec Biol 1964; 3:829.
6. Fraser RDB, Macrae TP, Rogers GE. Keratins, Their Composition, Structure and
Biosynthesis. Springfield, Il: Charles C Thomas, 1972.
7. Bendit EG, Gillespie JM. Biopolymers 1978; 17:2743.
8. Bendit EG. In: Parry DAD, Creamer LK, eds. Fibrous Proteins, Scientific, Industrial
and Medical Aspects. London: Academic Press; 1980:185.
9. Feughelman M, Danilatos GD, Dubro D. In: Parry DAD, Creamer LK, eds. Fibrous
Proteins, Scientific, Industrial and Medical Aspects. London: Academic Press; 1980:195.
10. Feughelman M, Watt IC. Textile Res J 1964; 34:643.
11. Feughelman M. Textile Res J 1989; 59:739.
12. Menefee E. Textile Res J 1968; 38:1149.
13. Feughelman M, Robinson MS. Textile Res J 1971; 41:469.
14. Feughelman M. Textile Res J 1979; 49:704.
15. Zahn H. Lanziger Ber 1977; 42:19.
16. Zahn H. Schriftenreiche des Deutchen Wollforschungsinstitutes an der RWTH,
Aachen 73:19.
17. West GW, Haly AR, Feughelman M. Textile Res J 1961;31:899.

 Page 31
18. Cassie ABD. Trans Faraday Soc 1945; 41:459.
19. Cooper DME, Askpole DK. J Textile Inst 1956; 50:T223.
20. Morrison JL, Hanlon JF. Proceedings of the 2nd International Congress of Surface
Activity: Solid-Gas Interface. London: Butterworth's; 1957:322.
21. Langmuir J. J Am Chem Soc 1918; 40:1361.
22. Haly AR, Snaith J Biopolymers 1969; 7:459.
23. Bradbury JH. Adv Protein Chem 1973; 27:111.
24. Wortmann FJ, Feughelman M, Kelly SE. Unpublished data.
25. Bradbury JH. Textile Res J 1957; 27:829.
26. Feughelman M, Snaith JW. Biochim Biophys Acta 1964; 79:203.
27. Speakman JB. J Textile Inst 1927; 18:T431.
28. Bendit EG. Proc 6th International Wool Textile Research Conference, Pretoria, 1980;
2:41.
29. Feughelman M. J Textile Inst 1954; 45:T630.
30. Speakman JB, Cooper CA. J Textile Inst 1936; 27:T191.
31. Feughelman M, Robinson MS. Textile Res J 1969; 39:196.
32. Feughelman M. J Textile Inst 1968; 59:T548.
33. Feughelman M. Textile Res J 1964; 34:539.
34. Astbury WT, Street A. Phil Trans Soc Lond 1931; Ser A230:75.
35. Astbury WT, Woods HJ. Phil Trans R Soc Lond 1933; Ser A232:333.
36. Feughelman M, Druhala M. Polymer Lett Ed 1977; 15:311.
37. Feughelman M. In: Carnaby GA, Wool EJ, Story LF, eds. The Application of
Mathematics and Physics in the Wool Industry. New Zealand: Lincoln; 1968:114117.
38. Fletcher NH. The Chemical Physics of Ice. Cambridge: Cambridge University Press,
1970.
39. Speakman JB. Trans Faraday Soc 1929; 25:92.
40. Feughelman M, Druhala M.
41. Bendit EG. Nature 1957; 179:535.
42. Feughelman M. Appl Polymer Symp 1971; 18:757.
43. Wortmann FJ, Zahn H. Textile Res J 1994; 64:737.
44. Feughelman M. Textile Res J 1994; 64:236.
45. Feughelman M. Textile Res J 1963; 33:1013.
46. Feughelman M, Robinson MS. Textile Res J 1967; 37:705.
47. Peters L, Wood HJ. In: Meredith R, ed. Mechanical Properties of Textile Fibres.
Amsterdam: North Holland; 1956:168 ff.
48. Feughelman M. Symposium on Fibrous Proteins, Australia; 1967:397407.
49. Haly AR, Griffith JG. Textile Res J 1958; 28:32.
50. Elod E, Zahn H. Melliand Textilber 1949; 30:17.
51. Zahn H. Kolloid Z 1949; 113:137.
52. Whewell CS, Woods HJ. In: Bird CL, ed. Fibrous Proteins. Bradford: Society of
Dyers and Colourists; 1946:50.

 Page 32
53. Crewther WG. J Soc Dyers Colourists 1959; 75:189.
54. Mitchell TW, Feughelman M. Kolloid Z 1969; 229:124.
55. Burley RW. Proc Int Wool Textile Res Conf, Australia, 1955. 1956:D88.
56. Feughelman M. Proc. 8th Int Wool Textile Res Conf, New Zealand, 1990. 1990; 1:517.
57. Wortmann FJ, Kure N. J. Cosmet Chem 1990; 41:123.

 Page 33

3
Cleansing of Hair
Michael Wong
Clairol, Inc., Stamford, Connecticut
I.
Introduction
Some people wash their hair more often than others, but practically everyone does it on a
regular basis. Cleaning the hair is not only a practice essential for personal hygiene, it is
also a cosmetic ritual that addresses a concern for appearance. Hair soil, from whatever
sources, has major ramifications on how the hair looks. Soiled hair is dull, greasy, and
stringy, and becomes difficult to manage and style. Given these various unappealing
aspects of soiled hair, it is easy to understand the need for frequent cleaning, a need that
has indeed fueled a huge market for hair cleaning products.
In this chapter, we are going to focus on four areas of hair cleaning. We will begin with
the topic of hair sebum: its composition and its effects on hair aesthetics. A brief
description of the mechanism of shampoo actions is to follow. Then, the various aspects
of shampoo performance and shampoo properties will be discussed. Finally, the different
types of shampoos and the essential ingredients for shampoo formulations will be
reviewed.
II.
Hair Soils
Soil is generally viewed as unwanted matter or matter in the wrong place (1). A more
precise definition is perhaps the one given by Lange (2), describing soil as undesirable
matter adhering to object or living body and influencing the appearance, the odor, etc.
The matter that makes up the ordinary hair soil, however, is complex. It is known to be a
heterogeneous mixture of materials of var-

 Page 34
ious origins. The major components of hair soil have been identified. One of these
components consists of materials picked up by the hair as a result of exposure to airborne
contaminants such as hydrocarbons, or dust particles made up mainly of clay, silica, and
iron oxides (3). Hair soil could also contain such materials as hair sprays and hair
dressing products that are deliberately put on the hair. However, the most important
component of hair soil consists of materials of natural origin, such as dandruff scales and,
more importantly, hair lipid. Hair lipid is a mixture of mostly sebum from the sebaceous
glands and a minor amount of fatty substances originating from the epidermal cells. It is
constantly renewed and is relatively more difficult to remove.
Sebum is a viscous oil or a waxy solid depending on the degree of aging after it is
discharged from the hair follicle. The properties of sebum have been studied rather
extensively (413). The main constituents have been pretty much established and they
consist of triglycerides, free fatty acids, wax and cholesterol esters, squalene, and
paraffins. The relative amounts of these materials present in sebum, however, are found
to vary significantly from individual to individual depending on numerous factors such as
diet (14), environmental conditions (15), age (5), sex (16), and whether the sebum is
freshly collected (12). For this reason, some of these investigators have preferred the
concept of an average composition for sebum. One such average sebum composition is
shown in Table 1, as suggested by Gloor et al. (16).
Hair oiliness is a consequence of having too much sebum depositing on the hair shaft.
The degree of hair oiliness is directly related to how fast the sebum is produced (17) and
how much of this secreted sebum is able to find its way to the surface of the hair. The
source of sebum is the very large number of sebaceous glands, which are believed to be
as much as 900 per square centimeter of skin (18). For an average young adult, sebum is
secreted at the typical rate of about 1.5 to 2 mg/cm2 of scalp surface over 24 hours. The
rate of sebum secretion, however, is not constant, but depends on numerous factors. Two
very important factors are age and sex. Several studies (16,19,20) have
Table 1 Average Composition of Hair Sebum
Components of sebum %
Triglycerides 35
Free fatty acids 20
Wax and cholesterol esters 19
Squalene 11
Free cholesterol 9
Paraffins 6
Source: Gloor et al. (16).

 Page 35
clearly established that sebum secretion increases from childhood to adulthood and stays
at this plateau up to the age of 70 for males, but only up to the age of 50 for females. The
age dependency is suspected to relate to the influence of androgen and estrogen as some
studies seem to indicate (21,22). It is interesting that this peak period of hair oiliness
coincides with the age when grooming consideration is paramount. There are also other
factors found to impact the amounts of sebum secretion. These factors include genetics
(23), seasonal variation (2429), exposure to sunlight (3032), and even the length of hair
(10), or the frequency of blow-drying the hair (33). Given such a variation in sebum
secretion, it is perhaps not totally surprising to find a diversity of hair cleansing needs
among consumers.
The migration of sebum to the hair has also been studied. It has long been held that the
mode of transfer was through the wicking actions of the sebum from the follicles
spreading along the hair surface. The observations made by Eberhardt (34), however,
have revealed a somewhat different mechanism. By examining the spreading behavior of
sebum droplets on hair fiber, he came to the conclusion that the arrival of sebum to the
hair was mainly through direct physical contact between a hair fiber from one follicle and
the sebum pool in another follicle. Another study (35), using a hair replica technique to
follow the process of hair regreasing, also demonstrated that physical contact was a major
mode of sebum migration from the scalp to the hair, even though there could be some
minor contributions from capillary actions at the initial stage of regreasing.
III.
Aesthetics of Oily Hair
Excessive build-up of sebum on the hair manifests itself in ways that make the hair
unappealing to the eye and unpleasant to the touch. The rats-tails effect, which is
commonly associated with greasy hair, is a result of hair fibers clumping together, and is
perhaps the easiest to recognize. Interfiber adhesion is a major contributor to the loss of
hair body (36) resulting in the compression of the volume of the hair mass and retarding
the ability of the hair to bounce. It also helps to amplify the actions of diffused light
scattering and reduces the sheen and luster of the hair (37,38). Precisely how the sebum
acts on hair aesthetics, however, is a complex phenomenon dependent on a number of
factors. One of these factors is believed to be related to the viscoelastic properties of the
sebum (39,40). Using oil as hair soil, Dobinson and Peter (39) were able to show that
both the tactile and visual perception of hair greasiness increase with the viscosity of the
oil. Another factor is the specific composition of the sebum. In one study, Bore et al. (41)
found that oily hair and dry hair differ in the contents of unsaturated fatty acids. In
another study, Koch et al. (42,43), based on analysis of hair clippings collected on human
heads, were able to show that the

 Page 36
Table 2 Hair Curliness and Sebum Threshold
Sebuma thresholdb (mg/g
Hair curliness
hair)
Straight hair 0.4
Moderately wavy hair 0.5
Curly African-American
0.8
hair
aArtificial sebum described by Barnett and Powers
(44).
bThreshold refers to the smallest quantity of sebum
that would make the hair look greasy.

perception of hair oiliness tends to increase with the amount of wax esters and
monoglycerides, but decrease with the ratio of saturated to unsaturated fatty acid, and
with the amount of cholesterol esters.
Certain hair characteristics, such as the coarseness of the hair, hair length, and the degree
of hair curliness, are also believed to be important factors. The aesthetics of fine hair, for
example, is generally known to be easily affected by the buildup of sebum. A relatively
small amount of sebum is sufficient to make such hair clump together and look greasy.
Curly hair, on the other hand, is able to accommodate better the impact of similar buildup
of sebum. Our own studies have found that on straight Caucasian brown hair, 0.5 mg of
sebum per gram of hair is sufficient to make the hair look greasy. For the very curly
African-American hair, it takes almost twice as much of sebum for a similar degree of
greasiness to be perceptible (Table 2). The reasons are believed to the superior hair body
effect associated with curly hair, and also the lesser degree of interfiber adhesions.
IV.
Shampoo Detergency and Mechanism of Cleaning Action
Hair cleansing nowadays is synonymous with shampooing, using shampoo products that
are available in a broad selection of product forms, performance, and product attributes.
Most shampoos are preparations of either aqueous solutions, emulsions or dispersions,
containing cleansing agents, fragrances, preservatives, and other additives such as
thickeners and foam builders. Soaps are still used occasionally, but synthetic surfactants
are the prime cleansing agents in modern shampoos. These surfactants, containing both
an oleophilic moiety and a hydrophilic moiety in the same molecule, have some unusual
properties, and are uniquely suited for hair soil removal. They are highly surface-active to
provide effective wetting of the hair surface. In aqueous solution, they tend to form
micellar structures to help the process of solubilization and emulsification.

 Page 37
While the phenomena associated with fabric laundering have been studied and reported
extensively, published information regarding the mechanisms of shampoo detergency is
comparatively meager. There are important differences between these two detersive
systems: the properties of the substrate being washed; the nature of the soils to be
removed; the duration and temperature of the washing process; and the level of
mechanical agitation. There are some similarities to suggest that certain fundamental
processes of detergency are operating to some extent in both systems. It is therefore
instructive to review the three basic processes involved and examine their relevancy to
hair shampooing.
One of these processes believed to be at work for the removal of oily soil is the so called
roll-up mechanism, first suggested by Adams (45). A key element of this model is the
initial wetting of the fiber surface by a surfactant solution to develop sufficient surface
tension at the oil/fiber/water interfaces. The development of such surface tension is to
allow the contact angle of the soil on the fiber to increase from 0° to 90° and finally to
180°, thus causing the soil to roll up gradually and eventually separate from the fiber
surface. A contact angle of 180° would correspond to automatic and complete separation
of the soil from the fiber, but this is rarely achieved. In practice, however, it is only
necessary for the contact angle to become sufficiently large for the soil to roll up and then
be removed by mechanical actions or agitation.
The mechanics of this rolling-up process is dictated by the interplay of the various
interfacial tensions: the fiber-soil interfacial tension ( fs); the fiber/water interfacial
tension ( fw); and the interfacial tension between soil and water ( sw). The net force (F)
acting on the soil at any given moment (Fig. 1) is related to the relative magnitude of these
interfacial tensions by the following equation:
F = fs - fw + sw CosA (1)
where A is the contact angle between the soil and fiber.
For the soil to continue to roll up, the net force F has to remain positive. Otherwise, the
process of rolling up would stop, and separation of soil from the fiber surface would be
incomplete. Consideration of this requirement in equation (1) suggests that rolling up of
soil is most favorable when fs - fw > sw. This is the condition that would guarantee that
F stays positive whether CosA is positive or negative. In other words, this is the condition
that allows F to stay positive over the whole range of contact angle A from 0° to 180°. In
practice, this is a condition that is more likely to be met for fiber surface that is highly
hydrophilic, or for soil that is highly nonpolar (46).
Even though hair fiber is relatively hydrophilic, an argument (17) against this mechanism
is the fact that hair sebum, aged for even a day or two, is typically a viscous waxy
material. The viscosity of such aged sebum might not be

 Page 38

Figure 1
Force diagram at the fiber/water/soil boundary.
able to respond properly to the influence of the surface tension to roll up from the surface
of the hair. For this reason, it is likely that rolling up of sebum would occur only when
the sebum is still fresh and fluidlike, and when the hair surface has become more
hydrophilic (highly bleached hair, for example).
Another mechanism of soil removal is believed to involve an emulsification process
(47,48), in which the surfactants would diffuse into the soil and emulsify it. Studies of the
penetration of surfactants into the soil have led to the suggestion that the result of the soil
emulsification is the formation of a so-called mesomorphic phase (49), which would
break up and separate from the fiber surface, perhaps aided by external mechanical or
hydrodynamic actions. There are arguments against emulsification playing a major role.
One of these arguments is related to the polar nature of sebum. It has been pointed out
(46) that this mechanism is important only if the soil is polar or contains a substantial
amount of polar components, since it requires direct interactions between the soil and the
surfactant molecules. Also, the viscosity of sebum is believed to argue against any
substantial role of emulsification, which requires that the shampoo surfactants diffuse
into the hair sebum. It is unlikely that the relatively short shampooing time, typically 1 to
2 minutes, is long enough for the surfactants to be able to reach into the sebum to achieve
the necessary degree of emulsification.
The third mechanism of detersive actions that has been proposed (50) is based on the
solubilization of the soil. An essential element of this detersive process is the presence of
surfactant micelles in the washing liquor. On contact with the micelles, the soil is
solubilized into the micellar structures and removed from the fiber surface. The more
recent data of Chan et al. (51) and Schaewitz et al. (52) indicate that soil solubilization is
rather complex, consisting of numerous steps involving diffusion and adsorption of the
micelles onto the soil, mixing of the soil surfactant molecules, followed by desorption of
the oil-containing micelles from the fiber surface. With surfactant micelles as the main
vehicle for soil removal, the prime requirement for solubilization to occur

 Page 39
is that the amount of detergent in the wash liquor must be above the critical micelle
concentration (CMC). This requirement seems to be easily fulfilled in most practical
shampooing situations, since most shampoos contain sufficient amounts of surfactants
that even after a significant dilution (when the shampoo is applied to wet hair), the
surfactant concentration would be still well above the CMC.
With regard to the validity of the above mechanism, some published data appear to be
significant. Several studies (12,17,42,5355) have found that shampoos tend to remove
certain components of sebum more readily than others, suggesting the likelihood of
selective solubilization. The data by Wong and Conklin (56) also indicate the possibility
of selective solubilization. In comparing the efficacy of various surfactants to remove
sebum from human hair, they found that below their critical micelle concentrations, the
detersive actions of these surfactants were relatively insignificant, suggesting that some
degree of solubilization is probably involved. However, whether solubilization is acting
alone or in concert with some other processes is not entirely clear. The precise mechanism
of sebum removal in shampooing is still somewhat obscure.
V.
Shampoo Performance And Other Properties
A.
Cleansing Efficacy
A good shampoo should have many attributes, the most important one being to provide
adequate cleansing of the hair. It can be viewed simply as a preparation of surfactants that
will remove surface grease, dirt, and skin debris from the hair shaft (57). Shampoo
detergency has become a central issue that has prompted numerous attempts to quantify it
with objective measurements. The earliest methods (58) were basically borrowed from
work in textile research, using wool as the substrate and wool grease as soil. Later on,
other researchers conducted their evaluations of shampoo detergency directly on hair
clippings collected from human heads before and after a shampoo (53,59,60); in those
studies, the amount of hair soil was extracted from the hair samples and measured to
determine the amount of soil removed by the shampoo. Recently, methodologies have
also been reported (55,56) using hair samples soiled with synthetic sebum. The soiled hair
was then soaked or immersed in a test shampoo solution under a set of controlled
conditions in regard to shampooing time, the mode and degree of mechanical agitation,
and the amount of rinsing.
The results from all these investigations, however, have not been able to arrive at a
consensus as to the precise degree of shampoo detergency. Some studies have
demonstrated that shampoos are capable of removing more than 90% of the sebum in the
hair (9,55,56); others have found a low level (less than 50% of the solvent extractable
materials) of sebum removal by shampoos

 Page 40
(53,59). In fact, shampoos are believed to be particularly ineffective for the so-called
internal sebum, which has been found to be rather substantive (12,43) and cannot be
removed even by successive extraction with boiling water-saturated ether and ethereal
hydrochloric acid. The composition of this internal sebum is found to be similar to that of
the surface sebum, but its origin has yet to be identified. Furthermore, there are
indications that the detersive actions of shampoos are not the same for the various sebum
components (55,56). The in vitro study by Thompson et al. (55), for example, has found
that the paraffin component of sebum is more difficult to remove by shampoo
surfactants. Their data also indicated that there is a buildup of paraffin on the hair after a
number of shampoo cycles, leading these researchers to speculate that such paraffin
residues might be the cause of the shampoo fatigue phenomenon that has been much
talked about but has never been proven.
B.
Aesthetics of Shampooed Hair
In spite of this disparity of results, it is fair to suggest that most shampoos, when used
regularly, are probably sufficiently efficacious to remove the sebum on the hair surface
and are mostly perceived as fulfilling their primary functionto clean the hair (62). The
issue as to how much sebum is removed in shampooing is perhaps less meaningful to a
consumer than how the hair looks after a shampoo (6366), as manifested by such hair
attributes as luster, hair body, and hair drying characteristics.
A good cleaning shampoo is expected to restore hair luster or sheen (67). With the
removal of sebum and other dirt particles, light scattering on hair surface should be
reduced, with a corresponding increase in specular reflection and hair luster. In this
regard, the synthetic surfactants commonly used in shampoo formulations nowadays are
far superior to the early shampoo technology, which was based primarily on fatty acid
soaps, and had a tendency to interact with hard water and leave some delustering residues
on the surface of the hair (68).
Clean hair after a shampoo should have more body. The absence of interfiber adhesions
in clean hair increases the volume of the hair mass, its resiliency, and bounciness, that are
believed to be essential for hair body. The improvement in hair body is also a result of the
fact that clean hair is easier to style and the style lasts longer.
Clean hair should also dry faster. Both the oil and the interfiber adhesions of oily hair
help to entrap some of the water and make it more difficult for the hair to dry.
Elimination of oily materials on the hair surface would allow the water to escape more
readily.
On the other hand, shampoos in general tend to increase the propensity for static charge
generation (67), which could result in a large amount of flyaway, especially in an
environment of low humidity. Also, most good-

 Page 41
cleaning shampoos would increase the frictional coefficient of hair fibers (69), thus
making the hair more difficult to comb through. Moreover, even under normal grooming,
squeaky clean hair may lead to considerable amount of cuticle wear on the hair surface
(7072). Indeed there have been opinions (59,7375) that total removal of hair sebum may
not be desirable, and that a good shampoo should not clean too well to strip the hair of all
its natural sebum. Such reasoning is perhaps due to the concern that total removal of hair
sebum is detrimental to hair care and hair manageability.
C.
Effect of Shampoo on Reoiling of Hair
Hair picks up sebum continuously from the scalp to reoil the hair, and thus the hair
slowly becomes oily again following a shampoo. The reoiling of hair is of concern
especially to people with oily hair, and those who believe that a good shampoo should not
allow the hair to get oily again too quickly. The kinetics of hair reoiling depends primarily
on the rate of sebum secretion from the sebaceous glands, and data showing the effect of
shampoos are inconclusive. While there is evidence that sebum secretion is accelerated by
shampoo detergency and frequency (7680), other studies (81,82) show that shampooing
has no significant effect on sebum secretion.
Hair reoiling also depends on how fast the sebum would accumulate on the hair, and
there are indications that it is related to the nature of the surfactants used to wash the hair
(83,84). The accumulation of sebum on the hair is believed to be the net result of sebum
migration from the follicles to the hair and the sebum loss through routine combing and
brushing (35,85). Given that both processes are highly dependent on the surface
characteristics of the hair, which can be substantially modified by a shampoo, it is
reasonable to speculate that shampooing could have an important impact on the
postshampoo reoiling of hair.
D.
Shampoo Lather
A good lathering during shampooing is a desirable feature, even though there has been
little evidence to support that it has any meaningful contribution to the functional
performance of a shampoo (86). A good lather is invariably described as copious, rich,
and luxurious, and is supposed to be made up of small bubbles that are densely packed,
bubbles that do not collapse easily and are stable to drainage. While most anionic
surfactants are normally able to generate good foam, the quality of such foams tends to
deteriorate in the presence of soil, especially sebum. In most shampoo formulations, a
foam booster and/or a foam stabilizer is found to be a necessary additive to maintain the
quality of lathering in shampooing. Some of the more effective and commonly used foam
boosters are fatty alcohols, alkanolamides, amine oxides, and betaines (8789).

 Page 42
A number of techniques to assess these various foam attributes of a shampoo have been
reported (9094). These techniques were developed to measure either the amounts of foam
generated (in terms of foam volume or foam height), foam viscosity, draining
characteristics, and foam stability. Recently, a semiautomated lather generator was
described (95) claiming to be able to mimic the finger/hair interaction at the scalp.
E.
Other Shampoo Attributes
1.
Shampoo Consistency
Proper consistency is essential, especially for a liquid shampoo, which should be thin
enough to allow the shampoo to pour out easily but sufficiently viscous to hold on the
hand and apply to hair and scalp. A gel or cream shampoo should also have the
appropriate consistency and rheology to ensure easy usage and application.
2.
Ease of Spreading and Rinsing
A shampoo should be able to spread evenly into the hair and rinse well without excessive
effort.
3.
Mildness
The mildness of a shampoo is another, equally important consideration. A low level of
irritation and eye stinging is an essential property of a good shampoo. There are
indications that irritancy could be reduced by blending certain types of surfactants (9699)
or inclusion of polyglucosides in the shampoos (100,101).
4.
Fragrance
This is a key shampoo attribute that has a strong influence on consumers' preference and
acceptance of the product (62,66). Shampoo fragrancing has gone through trends over the
years, but a recent survey (102) seems to indicate that the popular fragrances in major
shampoo brands are still based on the floral varieties. Fragrancing of shampoos will be
discussed in greater detail in another chapter (The Dynamic Role of Fragrancing in Hair
Care Products) of this book.
F.
Evaluation of Shampoos
1.
Laboratory Assessments
The foaming and cleansing characteristics of a shampoo can be routinely evaluated in the
laboratory, using methodologies described in previous sections. The effects of a shampoo
on hair attributes such as combing ease, hair luster, hair body, and hair flyaway can also
be assessed using the instrumental techniques reported in the literature (36,37,103111).
The chapter on Claim Substantiation provides greater information on these subjects.

 Page 43
2.
Half-Head Tests
These tests are normally conducted as an early step to simulate actual use of a shampoo.
In half-head tests, a shampoo prototype is used on one side of the head, while a control
product is used on the other side of the head. Various shampoo attributes are evaluated by
trained hairdressers to identify the key performance characteristics and associate them
with formulation variations being developed.
3.
Panel Tests
The panel tests are more elaborate, typically involving 100 to 300 individuals who use the
shampoo prototype at home over a period of 2 to 3 weeks. A properly designed and
conducted panel test is believed to be able to assess the degree of preference of the
various shampoo attributes of the prototype. Evaluation of data from such panel testing
usually forms the basis for more extensive consumer testing of the shampoo prototype.
The reader is referred to the chapter on Consumer Evaluation for more details.
VI.
Shampoo Forms And Types
Shampoo products are available as transparent or opaque liquids, gels and lotions, as
pastes, creams, or even dry powder and aerosols. Based on specific functional appeals,
shampoos can also be classified into the following major categories:
A.
General-Purpose Cleaning Shampoos
This is by far the largest shampoo category, whose primary function is to leave the hair
squeaky clean. These shampoos are generally in the form of a clear liquid, or lotion, with
the appropriate consistency to be easily poured into the palm and worked into the hair.
They are formulated with the proper types of surfactants in sufficient amounts to produce
a high degree of detersive actions as well as a dense and copious lather. Within this
category are also numerous subcategories, or facings, of shampoos. Thus, there are
shampoos for normal hair, shampoos for oily hair, shampoos for dry hair, shampoos for
damaged hair, etc. While it is unlikely that significant performance difference could be
demonstrated on a blind basis for many of these varieties, the consumer demands and
marketing need are clear and real and a powerful driving force for future technologcal
innovations.
This type of shampoo has become very popular with the availability of synthetic
detergents, which have made it possible for the shampoo to work with hard water as well
as soft water, without leaving behind a slimy residue on the hair. In fact, there have been
a number of notable shampoo franchises that capi-

 Page 44
talized on the theme of clean hair. The long success of Liquid Prell in the 1960s and 1970s
was one example. Another was the introduction of Agree Shampoo (S.C. Johnson),
claiming 99% oil free based on its simple formulation with a bare minimum number of
ingredients. The impact of Clairol's Herbal Essence on the shampoo market was another
example. Its introduction of an herbal fragranced shampoo in the early 1970s was
intended to echo the prevailing movement toward back to nature and the flower power
generation. Its recent launch of a botanical-based new Herbal Essence was yet another
attempt to identify with the environmentally friendly sentiments of the 1990s (112).
The majority of these cleaning shampoos are formulated mainly with 15% to 20% of
anionic surfactants in conjunction with an effective foam stabilizer, such as an
alkanolamide. A rich and stable foam is indispensable and is still perceived and equated
with good cleaning of the hair. Typical formulations for this category of shampoos, as
illustrated by the two examples in Table 3, are available in recent literature (113).
Table 3 Typical Formulations for General-Purpose
Cleaning Shampoos
Ingredients Wt %
Formulation #1
Sodium lauryl sulfate, 40% active 30.0
Ammonium lauryl sulfate, 40% active 15.0
Glycerine 3.0
Lauric diethanolamide 2.0
Lauramine oxide 1.0
Sodium chloride 1.0
Methylcellulose 1.0
Preservative, dyes, and fragrance qs
Citric acid to pH 66.5 qs
Deionized water qs to 100
Formulation #2
Sodium lauryl sulfate, 40% active 30.0
Sodium lauryl sarcosinate, 30% active 10.0
Sodium chloride 5.2
Cocamide MEA 1.0
Quaternium-22 1.0
Preservatives 1.0
Disodium EDTA 0.2
Deionized water qs to 100
Source: Shampoo formulary (113).

 Page 45
B.
Conditioning Shampoos
While a good-cleansing shampoo is effective to remove hair soil, its detersive actions
would sometimes leave the hair feeling harsh, difficult to comb through, and easy to
acquire an excess amount of flyaway. The shampooed hair very often requires an after-
treatment of conditioner or cream rinse to make the hair feel soft and smooth, easier to
comb, and more manageable. The idea of a conditioning shampoo is to be able to achieve
hair cleaning and hair conditioning in one step, making it unnecessary to follow up a
shampoo with another treatment product. The majority of conditioning shampoos are
formulated as an opaque or pearly cream or lotion, to convey the perception of rich
conditioning.
Even though the significant growth of this particular shampoo segment is a recent
phenomenon, the concept of a conditioning shampoo has been around for a while. In
fact, considerable amounts of research and patent activities have been reported over the
years, as reviewed by Alexander (114), Gerstein (115), Tolgyesi et al. (116), and Hunting
(117).
One of the earlier approaches to the formulation of conditioning shampoos was to
incorporate a hair conditioning agent into a shampoo base consisting primarily of
amphoteric surfactants. A number of such agents have been mentioned, including protein
hydrolysates (118) and mineral oil (119). The hair conditioning materials most commonly
used in shampoos, however, have been monomeric quaternary ammonium compounds
(120,121) or quaternized polymers (122124). The uses of these cationic polymers to
formulate conditioning shampoos have been particularly popular, as testified by the early
initial success of Milk Plus Six (by Revlon) and its impact on the market place.
However, conditioning shampoos based on amphoterics alone have some obvious
drawbacks. One of the drawbacks is that they do not foam well. Other problems have
been some purported incidents of overconditioning for certain hair types, and the
possibility of slow buildup of residues on the hair surface. Consideration of these
drawbacks has led to the development of conditioning shampoos utilizing cationic
surfactants or quaternized polymers directly in a shampoo base consisting of anionic
surfactants (125129).
One obvious difficulty of having a system of mixed cationic-anionic substances is that
these two types of materials are normally not compatible, leading to potential
precipitation. If properly balanced, however, even cationic polymers and anionic
surfactants can be mixed to form a complex that could be further solubilized to become
part of a stable emulsion, as claimed by a patent issued to Warner Lambert (125). Certain
types of such complexes are found to be effective hair conditioners, and they can be
precipitated onto the hair surface on dilution with water (130). There are indeed several
studies to understand the mechanism of such cationic-anionic complexations (119,
131135), and efforts

 Page 46
to identify the parameters that would enhance the stability and compatibility of such
cationic-anionic complexes (136139).
In addition to the quaternized compounds, certain silicone materials have also been
claimed to be effective agents for conditioning shampoos (140145). Because of their
molecular structures and flexibility (146), these materials are believed to be very effective
in imparting an excellent dry feel to the hair. The challenge to the use of silicones in
shampoo formulations is to keep the various ingredients properly suspended. In this
regard, the patents issued to Procter & Gamble (143,144) are particularly significant. They
have revealed a technology to formulate and manufacture a conditioning shampoo
composition containing nonvolatile silicones, anionic surfactants, and other additives to
achieve a stable emulsion. The technology is the basis of Pert Plus and similar two-in-one
type shampoos across P&G's product line. Thus, Vidal Sassoon, Ivory, Head and
Shoulders, all have taken this major technological advance and utilized it to provide
improved performance across the board on a large front. In response to this development,
other shampoo manufacturers have also mounted major efforts to match or surpass this
patented technology, resulting in a flurry of product launches (147), as well as research
and patent activities (148153).
Can a shampoo clean and condition hair at the same time? There have been considerable
debates on this question in the past (115,154), and there are going to have similar debates
in the future. One suspects that a properly formulated two-in-one conditioning shampoo
could satisfy some specific needs of a segment of consumers, but it is unlikely that it will
have both the cleansing and conditioning efficacy matching that of a traditional two-
stepped shampoo/cream rinse combination. Some typical conditioning shampoo
formulations, as shown in Table 4 below, can be found in recent literature or patents
(144,155).
C.
Antidandruff Shampoos
These are basically shampoo preparations that contain, in addition to the usual
surfactants, some special ingredients to address the problems of seborrhea. Seborrhea is a
condition manifested by a chronic noninflammatory scaling of the scalp (156). The active
ingredients commonly used for antidandruff are zinc pyrithion, selenium sulfide, sulfur,
coal tar, and salicylic acid. A number of theories have been suggested as the causes for
dandruff (157161), and the modes of antidandruff of these ingredients are believed either
to slow the keratinization process or to impede the amounts of dandruff flakes by
breaking them down to tiny aggregates (162). Since most of these antidandruff
ingredients are relatively insoluble, these shampoo products are mostly formulated as
opaque lotions or creams. All antidandruff agents are under review by the FDA. Also, in
the United States and in many foreign countries, antidandruff shampoos are regulated as
OTC drugs, such that the identity and concentration of the active

 Page 47
Table 4 Typical Formulations for Conditioning
Shampoos
Ingredients Wt %
Formulation #3a
TEA lauryl sulfate, 40% active 18.5
Cocoamphodiacetate (and)
disodium
cocamido MIPA-sulfosuccinate 18.5
Cocamide DEA 4.0
Propylene glycol 2.0
Polyquaternium-10 0.7
Citric acid 0.5
Preservative, fragrance qs
qs to
Deionized water
100
Formulation #4b
Ammonium lauryl sulfate, 40%
16.00
active
Xanthan gum 0.75
Cocamide MEA 2.00
Dimethicone 1.00
Cetearyl alcohol 1.00
Silicone gum 1.00
Fragrance 1.00
Sodium chloride 0.10
Preservatives 0.03
Caustic soda, 50% active 0.01
Ethylene glycol 0.75
Dye solution 0.65
qs to
Water (double reverse osmosis)
100
aShampoos & Conditioner Formulary (155).
bUS Patent 4,788,006 (144).

ingredients are set by law. Antidandruff shampoos make up about 10% of the total
shampoo market, and some typical formulations, as shown in Table 5, can be found in
review articles (113,163).
D.
Baby Shampoos
The main characteristic of this category of shampoo is mildness, with a low level of eye
stinging and scalp irritation. The baby shampoos have about 5% of the total shampoo
market (164) and are specifically targeted to uses for babies and young children.
However, because of their message proclaiming mildness, such shampoos are believed to
be often used by adults (165). Johnson & Johnson was the first to recognize this potential
opportunity and initiated a major

 Page 48
Table 5 Typical Formulations for Antidandruff
Shampoos
Ingredients Wt %
Formulation #5
Sodium lauryl sulfate, 40% active 40.00
Myristamide DEA 5.00
Zinc pyrithione 2.10
Magnesium aluminum silicate 1.20
Tetrasodium pyrophosphate 0.06
Citric acid, to pH 7.0 qs
Preservatives, color, and fragrance qs
qs to
Deionized water
100
Formation #6
Sodium C14-16 olefin sulfonate, 40%
30.0
active
Cocamidopropyl betaine 8.3
Magnesium aluminum silicate 1.0
Selenium sulfide 1.0
Titanium dioxide 0.7
Methylcellulose 0.7
Ammonium chloride 0.7
Preservative, color, and fragrance qs
qs to
Deionized water
100
aSource, Formulation 5: (113).
bSource, Formulation 6: (163).

campaign in the 1980s which talked about their baby shampoo being gentle enough for
everyday use. This campaign in turn triggered a response from Helene Curtis with their
Everynight shampoos, proclaiming to be gentle enough to use every night. The initial
success of these campaigns has in fact encouraged others to market similar products.
Baby shampoos are typically formulated mainly with amphoteric surfactants that have a
characteristically low level of irritancy. One approach, as described in a patent (166), is to
use a mixture of surfactants that claims to have a synergistic effect to lower irritancy and
also to possess a counterirritancy effect. One negative shampoo attribute of amphoteric
surfactants, however, is the relatively poor foam quality. It has been claimed that
additions of certain betaines and foam boosters would help to remedy this deficiency
(167169). Typical formulations for baby shampoos, as shown in the examples in Table 6,
have also been described (113).
E.
Dry Shampoos
These are a special type of hair cleansing products that does not rely on the surfactants as
cleansing agent. They use powder, such as starch, and are formulated as an aerosol. The
powder is sprayed on the hair to absorb the sebum, and

 Page 49
Table 6 Typical Formulations for Baby
Shampoos
Ingredients Wt%
Formulation #7a
Cocoamphocarboxyglycinate, 30%
20.0
active
TEA-N-cocoyl glutamate, 30%
20.0
active
Coco-betaine 5.0
Cocamide DEA 5.0
PEG-120 methyl glucose dioleate 2.7
Preservative, color, and fragrance qs
qs to
Deionized water
100
Formulation #8a
Sodium myreth sulfate, 40% active 11.7
Oleoamphohydroxypropyl sulfonate 9.2
Lauramide DEA 3.0
Dimethicone copolyol 1.0
Isopropyl PPG-2 isodeceth-7-
1.0
carboxylate
Sodium laureth-13-carboxylate 0.5
Propylene glycol and preservatives 1.0
qs to
Deionized water
100
aSource: (113).

then it is brushed off. This type of shampoo finds appeal in situations when someone
wants to clean the hair quickly without having to go through the time-consuming steps of
wetting, lathering, rinsing, and drying the hair, or for the elderly and bedridden patients
who need to be helped to clean their hair (170). A typical dry aerosol shampoo consists of
5% starch, 5% methylene chloride, and propellants (171).
VII.
Shampoo Ingredients
Modern shampoo formulations contain ingredients that deliver specific functional
attributes as well as ingredients that enhance the cosmetic attributes of the product. The
more essential ingredients are:
A.
Cleansing Agents
1.
Anionic Surfactants
Most shampoos today are based on anionic surfactants (172,173) because of their superior
foaming, cleansing, and emulsifying characteristics as well as their reasonable cost. The
classes of anionic surfactants more commonly used are:

 Page 50
a. Alkyl Sulfates. The alkyl sulfates have the following chemical structure:
ROSO3M
where R is an alkyl chain of 12 carbons (lauryl) or 14 carbons (myristyl), and M is a
cation such as sodium, ammonium, or triethanolamine (TEA).
Alkyl sulfates are prepared (174) by sulfation of a fatty alcohol with sulfur trioxide,
sulfuric acid, or chlorosulfonic acid and subsequent neutralization with alkali. The three
alkyl sulfates most often used in shampoos are sodium lauryl sulfate, ammonium lauryl
sulfate, and TEA lauryl sulfate. The choice of each of these surfactants is dictated by
considerations of water solubility and pH stability. Sodium lauryl sulfate, for example, is
not very soluble in cold water, and its use in clear shampoos is somewhat limited because
of its relatively high cloud point. On the other hand, ammonium lauryl sulfate and TEA
lauryl sulfate are more soluble in cold water, but ammonium lauryl sulfate needs to be
formulated at acidic pH, while TEA lauryl sulfate tends to hydrolyze at low pH.
b. Alkyl Ether Sulfates. The chemical structure of an alkyl ether sulfate is:
R(OCH2CH2)nOSO3M
where R is an alkyl chain usually of 12 to 14 carbons, and n is the degree of ethoxylation,
which is usually between 1 and 5.
Alkyl ether sulfates are prepared by sulfation of an ethoxylated ether (174). Compared to
alkyl sulfates, alkyl ether sulfates are milder and less irritating to the eyes, but their
lathering and viscosity characteristics are believed to be not as good. For these reasons,
blending of an alkyl sulfate and an alkyl ether sulfate is sometimes practiced in shampoo
formulations (88). The commonly used alkyl ether sulfates are sodium laureth sulfate and
ammonium laureth sulfate.
c. Alkyl Sulfonates. The alkyl sulfonates most commonly used in shampoos are alpha-
olefin sulfonates (AOS). They are prepared by sulfonating alpha olefins with sulfur
trioxide. Subsequent neutralization produces a mixture of alkene sulfonates and hydroxy
alkane sulfonates. The chemical structures of these two sulfonates are as follows:
(alkene sulfonate)
RCH (OH) CH2CH2SO3M (hydroxy alkane sulfonate)
where R is an alkyl chain with 12 to 14 carbons, and M is a cation such as sodium.
Alpha-olefin sulfonates have excellent flash foaming and are stable over a wide range of
pH (88), but these advantages are somewhat negated by the difficulties of viscosity
control and consistency. In addition to variations

 Page 51
among supplier sources, there could also be variations from batch to batch from any one
source (175). Extra care is indeed required to ensure uniformity of viscosity
characteristics in finished products. This consideration is perhaps one reason why alpha-
olefin sulfonates have not been as widely used as their advantages would suggest. The
frequency of use as a primary cleansing agent in shampoos is believed to be less than
10% (88). Sodium C1416 olefin sulfonate is the most prominent one within this category.
d. Alkylbenzene Sulfonates. These surfactants are prepared by sulfonation of an alkyl
benzene with sulfur trioxide or sulfuric acid (176). The most commonly used
alkylbenzene sulfonate in shampoo is TEA-dodecylbenzene sulfonate. It has high
detersive power and excellent flash foaming characteristics, but it tends to be more
irritating to eyes and skin. Its defatting action on the skin is believed to impair the barrier
characteristics of the stratum corneum. These reasons have probably accounted for the
low usage frequency of less than 5% (88).
e. Alkyl Sulfosuccinate Half-Esters and N-acyl Sarcosinates. These two surfactants are
also commonly used in shampoos but not as primary cleansing agents, because they do
not lather well by themselves. The alkyl sulfosuccinates have been found to be extremely
mild (177), and they are frequently used in conjunction with another anionic surfactant to
achieve a lower degree of eye and skin irritation. The sulfosuccinates are prepared by first
reacting an alkyl alcohol or a hydroxy amide with a maleic anhydride to yield a
monomaleate, which is then reacted with sodium sulfite to form the disodium alkyl
sulfosuccinate (or amido sulfosuccinate if a hydroxy amide is used):

The sarcosinates are used with other anionic surfactants to provide some hair
conditioning effects. They are prepared by reacting a fatty acyl chloride with N-
methylglycine, and are sometimes referred to as interrupted soaps. As in the case of
soaps, the sarcosinates tend to form a precipitate in hard water. Typical reaction sequences
to prepare sarcosinate surfactants are as follows:

The sulfosuccinates and sarcosinates most commonly used in shampoos are disodium
monooleamide MEA sulfosuccinate, disodium monococamido

 Page 52
MIPA sulfosuccinate, disodium monolaurylsulfosuccinate, cocoyl sarcosinate, and
sodium lauryl sarcosinate.
2.
Amphoteric Surfactants
These are compounds that carry two ionic centers on the same molecule. The cationic
sites are typically amino nitrogen or quaternary, while the anionic sites could be sulfates,
carboxylates, or sulfonates (178). Depending on the pH of the medium, these surfactants
are cationic, anionic, or zwitterionic. Compared to anionic surfactants, the amphoteric
surfactants generally do not cleanse or foam as well. One unique property of amphoteric
surfactants however, is the very low irritation potential, which has become the basis of
the formulation of baby shampoos, as first disclosed in a patent by Johnson & Johnson
(166). Moreover, it has also been demonstrated that the presence of certain amphoteric
surfactants could even reduce substantially the irritancy of shampoos (96,179). Verdicchio
and Walt (96), for example, have claimed that certain amphoteric surfactants can be
combined with anionic surfactants to lower the eye irritatancy very significantly, based on
a modified Draize test. Also, Blake-Haskins et al., using an in vitro technique, have found
that the skin irritancy of sodium lauryl sulfate in the presence of cocamidpropyl betaine is
reduced substantially (179).
For all the above reasons, amphoteric surfactants are extensively used in baby shampoos
or shampoos with low irritation. They are also used in conditioning shampoos, since most
amphoteric surfactants are compatible with quaternary compounds. The amphoteric
surfactants most commonly found in shampoos fall into the category of amphoteric
glycinates, amphoteric propionates, amino propionates, imino propionates, or betaines.
The general formulas of these classes of surfactants are as follows:

Amohoteric
R(CO)NHCH2CH2N+H(CH2CH2OH)CH2COO-
glycinates:
Amohoteric
R(CO)NHCH2CH2N+H(CH2CH2OH)CH2CH2COO-
propionates:
Imino
R-N+H(CH2CH2COOH)CH2CH2COO-
propionates:
Amino
R-CH2N+H2CH2CH2COO-
propionates:
Betaine: R-CH2N+(CH3)2CH2COO-
where R is an alkyl chain with 14 to 18 carbons.
The amphoteric surfactants most commonly used in shampoos are cocamidopropyl
betaine, cocamphocarboxyglycinate-propionate, sodium lauri-iminodipropionate, and
sodium lauri-iminodipropionate. The frequency of uses of amphoteric surfactants exceeds
30%.
B.
Foam Boosters
These are materials formulated into a shampoo to improve its lathering characteristics.
Even though many of the surfactants used in shampoos are themselves

 Page 53
good foamers, the foams produced are mostly lacy, and especially so in the presence of
sebum or other oily materials. The functions of a foam booster in shampoos are to
modify the lather from a loose structure to a dense foam with relatively small bubbles,
and also to maintain such foam quality even in the presence of sebum. Two types of
materials are generally used in shampoos as foam boosters:
1.
Fatty Acid Alkanolamides
Fatty acid alkanolamides are nonionic surfactants, prepared by reacting a fatty acid or a
fatty ester with a primary or secondary alkanolamine. The nature of the reaction products,
however, depends on the ratio of the two reactants. One part of fatty acid to one part of
alkanolamine would result in a yield of over 90% of the so-called superamide, which is a
waxy, water-insoluble solid. However, when the ratio of amine to fatty acid is 2 to 1, the
yield of amide is much lower, and this so-called low-active amide, as first described by
Kritchevsky (180), is a liquid and is water-soluble. While this low-active amide is much
easier to work with, it does have a high free-amine content, which is undesirable in
product formulations because of the potential for N-nitrosamine formation, especially if
the amine is in the form of diethanolamine. Both the superamide and the low-active
amide are still being marketed, but the superamide is more widely used in shampoos.
The most frequently used alknaolamids are lauramide diethanolamine, cocamide
diethanolamine, and cocamide monoethanolamine. These three alkanolamids alone are
believed to make up 80% of the foam boosters used for shampoos (88). Their chemical
structures are as follows:

Lauramide CH3(CH2)10CON
diethanolamine: (CH2CH2OH)2
Cocamide
RCON(CH2CH2OH)2
diethanolamine:
Cocamide
RCONH-CH2CH2OH
monoethanolamine:

where R is a coconut acid radical

2.
Betaines and Amine Oxides
These classes of materials are also found to be effective foam boosters for shampoos.
Both are ionic surfactants that tend to display cationic characteristics under the pH at
which shampoos are normally formulated. The important betaine and amine oxides used
in shampoos as foam boosters are cocamidopropyl betaine, cocamidopropyl
hydroxysultaine, lauramine oxide, dihydroxyethyl C1215 alkoxypropylamine oxide, and
cocamidopropylamine oxide (see structures below). The uses of amine oxides have been
somewhat restrained by the concern that some of them (such as lauramine oxide and
stearamine oxide) are potential precursors of N-nitrosamine (181,182).

 Page 54

where R is a coconut acid radical.

C.
Conditioning Agents
These ingredients are used in shampoos, especially in the conditioning shampoos, to
provide conditioning effects (see Conditioning Shampoos) to the hair. A large number of
materials have been claimed to be suitable conditioning agents for shampoos (183). The
more important ones include the following types of materials:
1.
Quaternary Ammonium Compounds
The quaternary ammonium compounds are cationic surfactants with one or more alkyl
chains attached to a quaternized nitrogen. They are widely used in hair conditioners and
rinses because they are very substantive to hair (184,185) and are effective to make the
hair feel soft and smooth, easy to comb, and resistant to static buildup (107,186188).
However, the challenge of using the quaternary ammonium compounds in a typical
shampoo formulation that contains anionic surfactants is to overcome the inherent
incompatibility and loss of efficacy (189).
The potential for increased eye irritation is another consideration. The selection of an
appropriate quaternary compound for a specific shampoo formulation is important. The
quaternary surfactants that are more frequently used in shampoos are quaternium-22
(Ceraphyl 60), PPG-9 diethylmonium chloride

 Page 55
(EMCOL-CC9), and quaternium-26 (Ceraphyl 65), which have the following structures:

where n has an average of 9.

Quaternium-26: RCONH(CH2)3N+CH2CH2OHCl-
where RCO is a fatty acid group.

2.
Quaternized Polymers
These cationic polymers, which have quaternized nitrogen attached to the backbone of the
polymer, are sometimes used as conditioning agents in shampoos. Being cationic, these
polymers are also substantive to hair and are able to impart certain desirable attributes.
(130). One unique aspect of some of these polymers is that they can form complexes with
anionic surfactants (131,190) and can be deposited onto hair on dilution with rinsing
water. Such complexes are found to be effective in making the hair soft and easy to
comb. One drawback of cationic polymers, however, is that they are not effective to
prevent development of static buildup and hair flyaway. The most commonly used
quaternized polymers are polyquaternium-10 (Polymer JR), polyquaternium-7 (Merquat
550), and polyquaternium-11 (Gafquat 734 and Gafquat 755), which can be represented
by the following structures:
Polyquaternium-10:

 Page 56

3.
Silicones
The use of silicone compounds as conditioning agents for shampoos has increased in
recent years (148152,191), especially after the impact of Pert Plus (a two-in-one shampoo
from Procter & Gamble) on the shampoo market. The key to the technical success of Pert
Plus is believed to be a proprietary process (as disclosed in US patent 4,788,006) which
would allow them to formulate a complex suspension of surfactants and silicone gums in
such a way that the silicone would have minimal effect on shampoo lather and cleansing,
but would deposit on hair via dilution of the suspending agent upon rinsing. The silicone
compounds that are most often used in shampoos are dimethicone, dimethicone copolyol,
and silicone gum. Dimethicone belongs to the class of materials known as
polydiemthylsiloxanes. Dimethicone copolyol is a derivative of dimethicone in which
polyether side chains replace some of the methyl groups. Silicone gum is a mixed high-
molecular-weight (from 200,000 to 1,000,000) dimethicone material that is gumlike in
nature. Dimethicone and dimethicone copolyol can be represented by the following
structures:
Dimethicone:

 Page 57
Dimethicone copoyol:

4.
Others
A large number of materials have also been identified to be used as conditioning agents in
shampoos. They include the fatty materials such as fatty alcohols, sterols, fatty acid,
lanolin, and fatty esters, as well as protein derivatives and certain amphoteric surfactants.
D.
Thickening Agents
To achieve a desired viscosity in a shampoo, a thickening agent needs to be incorporated
into the product. The more common thickening agents for shampoos are:
1.
Inorganic and Organic Salts
For anionic shampoos, a number of inorganic and organic salts are effective. The two that
are most frequently used in shampoos are sodium and ammonium chlorides. The
thickening action of these electrolytes is believed to arise from their ability to increase the
swelling and resistance to movement of the surfactant micelles. Ammonium chloride is
said to be a more effective thickener (160,192,193), but it needs to be formulated at a pH
well below 7 to avoid the production of ammonia fumes. Sodium chloride can be used
over a broader range of pH, but the viscosity actions of sodium chloride in shampoo are
more sensitive to variations in temperature and concentration of the salt (192,194,195).
2.
Cellulose and Other Polymers
The cellulose derivatives are water-soluble polymers that are compatible with most
shampoo ingredients. Among the cellulose polymers more frequently used as thickening
agents for shampoos are methylcellulose, hydroxypropyl methylcellulose (Methocel), and
hydroxyethyl cellulose (Natrosol). Other polymers that have also been suggested as good
thickening agents for shampoos include carbomers and a modified version of acrylate
polymer (193,196). Even though two polymers (such as Natrosol and Methocel) will give
similar Brookfield viscosities at a particular shear rate, it is important to recognize that the
overall rheology can markedly differ, leading to significant consumer-perceptible
differences.

 Page 58
E.
Preservatives
Preservatives are required in shampoos to safeguard against microbial actions that could
cause spoilage of the product or, more importantly, pose a health hazard to consumers.
The choice of a proper preservative system in shampoo is becoming more critical with the
increasing uses of nonionic surfactants and other additives, such as proteins, gums and
vitamins, that are believed to support the growth and propagation of microorganismsin
particular the gram-negative family of Pseudomonas (197199). Formaldehyde used to be
popular, but has since been largely replaced because of toxicological concerns. Other
compounds that are found to be effective preservatives and are frequently used in
shampoos (181,200) are methyl and propyl para-hydroxybenzoates alone or in
combination with imidazolidinyl urea, methylisothiazolinone,
methyloldiethylhydantoin(DMDMH), methychloroisothiazolinone, and N-(3-
chloroallyl)hexaminium chloride (Quaternium 15). The selection of a suitable
preservative, however, must be customized for a specific shampoo formulation to achieve
the proper trade-off among efficacy, safety, and compatibility (201205).
F.
Other Additives
Shampoos also contain a few other additives to achieve the most desirable cosmetic
attributes. These additives include color, opacifiers, or pearling agents (206) to enhance
the appearance and fragrance for emotional appeal of the product; sequestering agents to
counteract the effect of hard water; or organic solvents to promote better clarity and
solubilization of the product.
VIII.
Concluding Remarks
It is probably fair to say that the majority of shampoos nowadays are so formulated and
packaged that the essential needs for hair cleansing are generally satisfied. Mostly they
seem to meet the consumer's expectations in terms of usage convenience, aesthetics of the
products, and functional efficacy. It is perhaps this sense of adequacy that has led to a
more or less status quo environment in recent years. Even the enormously successful
two-in-one shampoo category is essentially a more advanced version of the conditioning
shampoos first introduced in the 1970s. Nonetheless, there are still important issues and
problems pertaining to the basics of hair cleansing that could be fertile grounds for
innovative efforts. An area of opportunity, for example, is to address and clarify the
possibility of residue buildup on the hair. Given the affinity of the surfactants for hair
surface, one would speculate that some buildup of residues is possible. The increasing
use of additives such as proteins or silicone gums in shampoo formulations should
further compound the situation. It is generally believed that such residues can impact hair
aesthetics negatively, and in some

 Page 59
cases could even interfere with the coloring or permanent waving of the hair.
Furthermore, the shampoo residues could also interact with hair sebum in a way to make
the sebum more resistant to shampoo removal. In fact, one begins to wonder whether
such interactions are possibly linked to the so-called shampoo fatigue phenomenon that is
so often talked about but never confirmed. Answers to these questions are undoubtedly
very valuable.
The prospect of making the hair stay clean longer is equally intriguing. For some people,
especially those with the condition of seborrhea, the very rapid reoiling of the hair is an
inconvenience. Making the hair stay clean longer is something that would surely be
welcome. There have been some attempts reported to address the issue. One approach is
to treat the underlying cause of seborrhea, using chemical agents to inhibit the activities of
the sebaceous glands. This approach has drawn considerable attentions as illustrated by
the amount of research and patent activities (207215). The main obstacle is to find a
compound that is both efficacious and nontoxic. Moreover, one potential complication to
commercialize such a product is that it could fall into the drug category. But there is
undoubtedly continual research effort in this direction because of the potential for
substantial demand.
Another approach to keep the hair stay clean longer is to focus on the surface properties
of the hair, making the hair more oleophobic and therefore less receptive to sebum
accumulation. It is in fact akin to the antisoiling processes that have been extensively
researched and developed in the textile field (46). The relevance of this technology is
beginning to be recognized, as evidenced by numerous patent disclosures on methods to
retard the appearance of hair greasiness (216219). But so far the absence of any such
commercial products suggests that major obstacles are still to be solved.
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 Page 65

4
Conditioning of Hair
Myra A. Hoshowski
Helene Curtis, Inc., Chicago, Illinois
I.
Introduction
Hair that is conditioned is in a proper and healthy state. Healthy hair looks shiny, feels
soft, is easy to comb and style, and retains body and bounce.
If hair were left alone, it would tend to remain in a conditioned state. The cuticle, or outer
layer of hair would remain intact and a layer of sebum would provide the hair with
protection from mechanical friction. However, a buildup of sebum gives the hair an
undesirable appearance. During the process of cleansing, wet hair is vulnerable to
mechanical abrasion and therefore becomes damaged. Chemical treatments used to
permanently alter hair's color and curl further weaken and damage hair.
It is the job of conditioners to help counteract these negative effects. When conditioning
agents are applied to the hair, frictional force is reduced and combing becomes easier,
thus maintaining the hair in its proper and healthy state. Some conditioning agents may
even penetrate the hair fiber to actually restore damaged hair to a healthy condition.
There is no single perfect conditioning agent, but rather a multitude of conditioning
agents available to the formulating scientist. An endless number of combinations of these
conditioning agents can be used in conditioners. By utilizing the technical information that
is provided about the conditioning agents and examining the examples of formulations,
the formulator can use this chapter as a starting point for developing a balanced
conditioner which meets the needs of his or her target market segments.

 Page 66

II.
How Hair Structure Relates to its Condition
The hair shaft is composed of two major morphological regions, the cortex and the
cuticle. The cortex's function is to provide mechanical properties such as strength to the
hair fiber. The cuticle is the chemically resistant outer layer responsible for protecting the
cortex. Six to 10 layers thick, the cuticle resists physical and chemical degradation by
forces such as friction, pulling, bending, and ultraviolet radiation. Hair's appealing visual
and tactile characteristics are due to the cuticle's arrangement. Cuticle cells arranged in
overlapping scales lie flat, reflecting light and allowing each strand to slide smoothly
against its adjacent neighbors. Even though the cuticle is remarkably resistant, it is not
impervious to attack and will break down from repeated exposure to the environment,
physical manipulation during grooming, and chemical alteration. This greatly simplified
overview of hair structure is provided to show how hair's structure relates to its
condition. Robbins (1) and Chapters 1 and 2 of this volume explain the morphology of
hair in greater detail.
III.
Hair Damage and its Causes
Numerous researchers have studied the way in which physical and chemical processes
damage hair by observing how hair loses its color and luster, becomes more harsh, stiff,
weak, brittle, and flyaway.
A.
Grooming
Gould and Sneath (2) compared the cross sections of proximal, or root portions of the
hair to the distal, or end portions of the hair before and after repeated shampooings. They
found that damage was limited to the cuticle and increased from the proximal to the distal
portion of the hair fiber.
Kelly and Robinson (3) studied the effect of the normal grooming process of
shampooing, towel drying, wet combing, and wet brushing on the cuticle. During the
shampooing stage of the grooming process, hair becomes tangled in knots. Wet hair has a
lower resistance to abrasion than dry hair, while at the same time, the wet hair is subjected
to very strong abrasive forces. Although shampooing and towel drying alone can abrade
the cuticle, wet combing and particularly wet brushing inflicts much greater damage.
Cuticle layers are lost at a rate of 1 to 2.5 cuticles per 50 treatments. On the basis of this
rate, if the grooming procedure is undertaken only twice per week, the entire cuticle is
removed in only 14 to 60 months leading to subsequent splitting of the cortex.
Sandhu et al. (4) developed a sensitive colorimetric method to quantify the amount of
hair protein fragments abraded during combing. Chemically treated hair exhibits greater
protein loss than untreated hair.

 Page 67
Kamath et al. (5) used tensile tests and scanning electron microscopy studies to show how
negroid hair is particularly susceptible to damage during the grooming process because of
its unique configuration. Frequent twists along the fiber axis with random reversals in
direction lead to stress concentrations during the tensile deformation experienced when
combing or brushing the hair.
B.
Climatic Exposure
Tolgyesi (6) describes the effects of cumulative climatic exposure, or weathering on hair
as it ages. Hair grows approximately 6 inches per year until it reaches a genetically
predetermined length of about 3 feet. Since the distal portion of the hair fibers have been
exposed longer than the proximal portion, the damaging effects of weathering are
progressively more noticeable as one proceeds from the proximal portion to the distal
portion of the hair fiber. In the initial stages of weathering, hair becomes discolored,
followed by cuticle loss, fiber splitting, and finally, breakage.
Dubief (7) used xenon lamp solar simulators in the laboratory to mimic hair damage
caused by natural sunlight. Dubief found that damp conditions are necessary to induce the
structural alteration and photobleaching of hair.
C.
Chlorine and Salt Water
Fair and Gupta (8) discuss the chemical interaction of hair with the chlorine that is found
in pool water. Chlorine weakens hair by forming distinctive All-worden sacs or bubbles
of dissolved protein which burst through the cuticle. These sacs tend to catch on combs
and brushes, forming splits and cracks in the cuticle. While salt does not interact
chemically with hair, salt that is left behind on hair after swimming in the sea dries into
hard crystals which cause mechanical abrasion of the cuticle.
D.
Heat Styling
Wolfram (9) has shown that hot rollers which employ moderate heat, typically less than
120°C, do not damage hair even after 50 repeated cycles. Hair breakage may occur,
though, from careless winding and unwinding of the hair from the rollers. Other heat-
styling appliances such as curling irons, crimpers, and straightening irons operate at much
hotter temperatures and can exceed 175°C. These excessive temperatures reduce hair's
tensile strength after repeated use, resulting in a weakened fiber (10).
E.
Chemical Agents
A variety of chemical agents are utilized to alter hair's natural color or texture. Permanent
colors and bleaches use hydrogen peroxide to oxidize hair's natural pigment, called
melanin, and replace it with synthetic dyes resulting in a new

 Page 68
more fashionable color. Corbett (11,12) provides a detailed explanation of the permanent
hair coloring and bleaching processes. Even though hydrogen peroxide weakens hair by
cleaving disulfide bonds, Jachowicz (13) suggests that the most important aspect of the
damaging effect of the coloring process is the deposition of dye particles on the hair's
surface, considerably increasing the frictional force and, consequently, the combing force.
Bleaching is a more aggressive oxidative process which damages hair further, decreasing
the crosslink density and providing additional anionic sites on the hair in the form of
cysteic acid residues.
Permanent waves rearrange hair's natural curl by breaking and reforming the disulfide
linkages into a new, more desirable and usually more curly style, although this process is
also used to relax curl. Wickett (14) has shown that permanent waving has a profound
effect on the mechanical behavior of hair, including swelling, length contraction under no
load, stress relaxation under load, and changes in elastic properties. Permanent waving
reduces hair's tensile strength, leading to breakage during combing or brushing.
The end result of all of these physical and chemical processes may be a weakened hair
fiber with uplifted cuticle scales. Uplifted cuticle and torn cuticle edges increase the
frictional forces between the hair fibers and the comb or brush, resulting in triboelectric
charging of the hair causing a phenomenon known as flyaway (15).
Each of these physical and chemical processes will act synergystically with one another to
inflict ever increasing damage upon the hair fiber. It becomes the job of a conditioner to
provide hair with a protective coating that prevents this damage from occurring by
lowering frictional forces and eliminating static charge. Therapeutic or deep conditioners
may actually deposit materials which become absorbed by the cortex and replace some of
what has been lost.
IV.
Conditioning Agents
A.
Definition of a Conditioning Agent
Nearly all hair care products are formulated to maintain or restore hair to its natural
healthy condition by incorporating one or more conditioning agents. Idson (16) defines
conditioning agents as additives which enhance the appearance, feel, fullness, lubricity,
reflectance, and general manageability of hair. The second edition of the CTFA Cosmetic
Ingredient Handbook (17) lists 755 lubricious or substantive hair conditioning additives
and 438 antistatic agents for creating special effects on hair.
B.
Depositing Conditioning Agents onto Hair
For conditioning agents to deliver these special benefits to hair, they must first deposit on
the hair or be absorbed by the hair. Conditioners may be applied to

 Page 69
the hair and left on or they may be rinsed off. Depositing a conditioning agent on hair
from a rinse-off formula is dependent on its affinity for the aqueous phase of the
formulation versus its binding affinity for the hair.
The conditioning agent's attraction for the formulation matrix is dependent on the charge
of the conditioning agent and the number of polar versus nonpolar groups. A
conditioning agent's ability to bind with hair is influenced by the pH of the formulation,
the conditioning agent's charge and molecular weight, and the isoelectric point of hair
(18).
The isoelectric point of hair is the pH at which a protein does not migrate in an electric
field and it relates to the acid-base properties of hair's surface. Since hair is a protein, it
contains both negatively charged carboxyl groups and positively charged amino groups at
its surface. Below the isoelectric point, hair becomes more positive; above the isoelectric
point, hair becomes more negative, attracting materials with a positive charge. The
isoelectric point of normal cuticle is about pH 3.7 (18).
Cationic substances bear a positive charge at all pH's and become more strongly absorbed
on hair as the pH increases above the isoelectric point. Bleached hair has a lower
isoelectric point; therefore cationics tend to bind more strongly to bleached hair.
The adsorption of cationic surfactants on the cuticle surface neutralizes negative charge
and reduces the coulombic repulsion between adjacent cuticle scales allowing the cuticle
scales to lie flat. The hair fiber then becomes smooth and easy to comb in the dry state
(19).
Not all conditioning agents are cationic, however. Many lubricious materials, such as
silicones, oils, and esters, are nonionic; that is, they have no electrical charge. The binding
of nonionics to hair is dependent on the hydrophobicity or number of nonpolar groups.
Binding occurs via Van der Waals forces and can be quite strong.
C.
Cationic Conditioning Agents
Cationic conditioning agents are classified into two typescationic surfactants, and cationic
polymers. Cationic surfactants are compounds that contain at least one hydrophobic long-
chain radical, usually derived from either fatty acids or petrochemical sources, and a
positively charged nitrogen atom. Linfield (20) discusses the chemistry of cationic
surfactants in detail. In the Surfactant Encyclopedia (21), cationic surfactants are further
subdivided into four major classes: alkyl amines, ethoxylated amines, quaternary salts,
and alkyl imidazolines. Of these four classes, the quaternary salts are the most widely
used because of their cationic nature and the large historical database of information
available on their performance, stability, and safety. Quaternary salts are also the most
cost-effective on a pound-for-pound basis.

 Page 70
1.
Cationic Surfactants
a. Alkyl Amines. Organic tertiary amines are the precursors of quaternary salts. Organic
tertiary amines are derivatives of ammonia where three hydrogens have been replaced by
organic radicals. These radicals may be the same or different, straight-chain or branched-
chain, saturated or olefinic. The structure of the resulting tertiary amine is dependent on
the source of the fatty acid used to create the amine. A variety of natural sources such as
coconut, palm, tallow, soybean oils, etc. yield mixtures of fatty acids as shown in Table 1.
While the tertiary alkyl amines have been used extensively as conditioning agents, more
recently the amido amine structure shown in Figure 1 has gained favor over the tertiary
amine because of its performance advantages. Both amines and amido amines contain a
long alkyl group, but in the case of the amido amine, an amido group is inserted between
the nitrogen and the alkyl group. The presence of an amido group radically influences the
functional differences between amines and amido amines. Concentration of positive
charge on the hydrophobic portion of the molecule imparts strong cationic properties. At
an acidic pH, the amine group becomes protonated and the character changes from water-
insoluble to water-soluble. Friedli (22) discusses the organic chemistry of amido amines
in detail.
A variety of organic salts can be formed by complexing amido amines with hydroxy acids
such as gluconic, glycolic, lactic, and salicylic acids and their derivatives. The complex
salts that are obtained become soluble in water and retain their substantivy to hair. The
amino benzoic acids, such as para amino benzoic, salicylic, and their derivatives have
limited solubility in water and oil. Complexing them with amido amines yields cationic
salts that are easily incorporated into a formulation while being substantive to hair (23).
Table 1 Typical Fatty Acid Compositions of Commonly Used Fats and
Oils
Fatty acid %/source Coconut Palm Tallow Soybean
Caprylic C8 5.4
Capric C10 8.4
Lauric C12 45.4
Myristic C14 18.0 1.0 3.5
Palmitic C16 10.5 43.5 25.0 6.5
Palmitoleic C16:1 0.4 4.0
Stearic C18 2.3 4.5 19.5 4.2
Oleic C18:1 7.5 40.0 41.0 33.6
Linolenic C18:2 0.9 11.0 2.5 52.6
Linolenic C18:3 2.3
Other 1.2 4.5 0.8

 Page 71

Figure 1
Amido amine.
Amido amines are generally used as secondary conditioning agents to provide a special
effect such as complexation, while a primary conditioning agent such as a cationic
surfactant is added to reduce combing force and eliminate static. Formulation example #5
contains stearamidopropyl dimethylamine as the secondary conditioning agent.
b. Ethoxylated Amines. Ethoxylated amines are nitrogen containing surfactants whose
degree of water solubility depends largely on the type and degree of alkoxylation.
Ethoxylated amines are useful as hair conditioning agents in shampoos and clear
conditioning rinses. Smith et al. (24) compared didecylmethylamine oxide (DDMAO),
shown in Figure 2, to stearyldimethylamine oxide (SDMAO), shown in Figure 3, and
found that in a shampoo formulation the DDMAO was effective as a detangling agent at
lower concentrations than SDMAO, but produced less foam. While in conditioning
rinses, DDMAO was more effective in detangling and static control than SDMAO and
stearalkonium chloride. The conditioning rinse formulas were compared at neutral pH,
since DDMAO is not soluble at acidic pH. At acidic pH there may no longer be an
advantage for DDMAO.
c. Quaternary Salts. The various tertiary amines and ethoxylated amines can be alkylated
with metal halide or dimethylsulfate to produce a wide variety of possible quaternary
salts. Representative structures are shown in Figures

Figure 2
Didecylmethylamine
oxide.

Figure 3
Stearyldimethylamine
oxide.

 Page 72

Figure 4
Monoalkyl quaternary salt.
47. The number of alkyl groups, their chain length, and the absence or presence of
ethylene oxide groups determine the physical properties and performance characteristics
of quaternary salts.
Quaternary salts with alkyl chains of 8 to 10 carbons exhibit germicidal and fungicidal
properties. Recognition of this property of quaternary salts by Domagk in 1935 (25) led to
the first important commercial use of quaternary salts.
The shorter-chain monoalkyl quaternary salts are soluble in hydrophilic solvents such as
water, isopropanol, and propylene glycol, while the longerchain monoalkyl quaternary
salts are only dispersible in water. The dialkyl quaternary salts are soluble in isopropyl
alcohol and propylene glycol, and some may be dispersible in water. Ethoxylated
quaternary salts are soluble in hydrophilic solvents.
When Jurczyk, et al. (26) studied the relationship between quaternary structure and
performance characteristics on hair, they found that the chain length and number of fatty
alkyl chains is directly proportional to improved conditioning performance. They
compared the substantivity as well as the detangling, wet combing, dry combing, and
static control properties of a number of quaternary salts. Ethoxylated quaternary salts
were found to be less substantive due to their greater solubility, with lower conditioning
scores. Increasing the number and the length of alkyl chains resulted in increased
substantivity with a resulting increase in conditioning properties.

Figure 5
Dialkyl quaternary salts.

 Page 73

Figure 6
Trialkyl quaternary salt.
Finkelstein and Laden (27) studied the kinetics of the adsorption process and found that
quaternary salts formed micelles on the hair surface. A micelle is a molecular aggregate of
50 to 100 molecules that constitutes a collodial particle, which takes the shape of spheres
with their hydrophilic groups facing outward and their hydrophobic groups facing
inward. Micelle formation can occur only with the relatively longer-chain quaternary salts
and then only when a sufficient concentration, called the critical micelle concentration, is
reached. Increasing the chain length of a cationic surfactant increases the degree of
hydrophobic interactions and thus increases the surface activity. Books by Rosen (28) and
Rubingh and Holland (29) explain the surface chemistry of surfactants in detail.
Besides improving conditioning, the longer alkyl chains also contribute to greater
mildness. The behenyl or C22 quaternary salts offer improved skin and eye irritation
profiles over the stearyl or C18 chain length quaternary salts (30).
There is a limit, however, to how much conditioning is desirable. Quaternary salts that are
highly substantive to hair tend to deposit too heavily and may buildup, particularly on
damaged hair. This can leave hair, especially fine hair, limp and difficult to style. Highly
substantive conditioning agents are usually utilized in deep conditioning treatments used
weekly, rather than in daily-use conditioners. Formulation example #3 is such a deep
conditioner.
A twist on the quaternary salt structure is the diquaternary salt. The diquaternary salt
contains two positively charged nitrogen atoms. Jurcyzk et al.

Figure 7
Ethoxylated quaternary salt.

 Page 74

Figure 8
Di-quaternary salt.
(31) found that the tallowdimonium propyltrimonium dichloride, whose structure is
shown in Figure 8, imparts greater conditioning benefits than its mononitrogen
counterpart. The presence of the two positively charged nitrogen atoms in one molecule
can offer a favorable economy versus performance profile over the mononitrogen
quaternary salts.
A single quaternary salt may provide enough conditioning and antistatic benefits to be
used as the sole conditioning agent in a simple, economical conditioner formulation.
Formulation example #1 is an economical rinse-off conditioning rinse. Usually, though, a
quaternary salt is the primary conditioning agent, and additional secondary conditioning
agents are used to further enhance a conditioning formulation's performance.
d. Alkyl Imidazolines. Alkyl imidazolines (32) are five-membered heterocyclic rings
containing two nitrogens in the 1,3 positions. They are produced by condensation of
long-chain fatty acids with ethylene diamine or its derivatives. The salts of these
imidazolines are widely used as cationic surfactants in non-personal-care applications
such as textile or fabric softeners. To obtain materials acceptable for cosmetic use, the
imidazolines are reacted with an alkylating agent which usually opens the ring resulting in
an amphoteric structure shown in Figure 9. Amphoterics behave as anionics above the
isoelectric point and as cationics below this pH. These mild materials are usually used to
provide conditioning in shampoos and bath products.
2.
Cationic Polymers
The second type of cationic conditioning agent is the cationic polymer. Polymers can be
natural, synthetic, or biosynthetic. A biosynthetic polymer is a nat-

Figure 9
Alkyl imidazolines.

 Page 75
ural polymer which has been modified with one or more synthetic functional groups.
Lochhead (33) provides a detailed listing of polymers including chemical and trade
names, use concentration and function in the formulation, solubility characteristics, and
other pertinent information.
Three types of natural polymers are used for hair conditioningpolysaccharides, proteins,
and nucleic acids. Numerous synthetic polymers are available such as those derived from
vinyl pyrrolidone and silicones. The polymer backbones may impart one or more of the
following attributes to hairslip, sheen, humectancy, and body. The addition of substantive
cationic sites to any of these types of polymers greatly increases the amount of polymer
that deposits on the hair.
a. Polysaccharides. Polysaccharides are made up of a number of repeating
monsaccharide units, or simple sugars, joined together in long linear or branched chains.
Polysaccharides have two major biological functionsas a storage form of fuel, and as
structural elements. The most abundant storage polysaccharides are starch in plants and
glycogen in animals. Cellulose is the most abundant structural polysaccharide in plants,
while chitin is a major component of the exoskeletons of invertebrates.
A number of polysaccharides are used in conditioners for their thickening and slip
properties. Attaching quaternary groups to polysaccharides results in molecules that
combine the properties of thickening and conditioning.
Even though both starch and cellulose are linear polymers of D-glucose, most mammals
cannot use cellulose as food. In starch, the D-glucose units are bound in alpha (1 4)
linkages, while in cellulose, the linkages are beta(1 4). Most mammals, except the
ruminants such as cows, do not have enzymes that are capable of hydrolyzing the beta (1
4) linkages. Only a few starch derivatives are used in hair care preparations, while
cellulose and its many derivatives are commonly used in hair care products.
A number of quaternary structures have been attached to cellulose in order to create a
variety of cationic celluloses. Studied extensively by Goddard (34), Polymer JR, or
polyquaternium-10, is a quaternary ammonium salt of hydroxyethyl cellulose and a
trimethyl ammonium substituted epoxide. Adsorption of the cationic polymer onto hair
occurs rapidly and is greater than the amount expected for simple monolayer adsorption,
thus indicating that the polymer penetrates into the hair, particularly bleached hair.
Goddard found that deposition is dependent on the type of surfactant and the ratio of
polyquaternium-10 to surfactant in the formulation (35). In formulation example #7, an
ester is used in conjunction with polyquaternium-10 to provide conditioning benefits
without static flyaway.
Celquat, or polyquaternium-4, is the copolymer of hydroxyethylcellulose and
diallydimethyl ammonium chloride. Polyquaternium-4 is soluble in water, hydrolytically
stable from pH 3 to 8, and forms glossy films on hair which impart excellent curl
retention even in high humidity (36).

 Page 76
Quatrisoft Polymer LM-200, or polyquaternium-24, is a hydroxyethylcellulose that has
been reacted with a lauryl dimethyl ammonium substituted epoxide. Besides providing
conditioning attributes such as good wet combing, reduced static, and a soft silky feel,
polyquaternium-24 increases stability of oil-in-water emulsions and increases the foam
stability of aerosol mousses (37).
Another group of quaternized cellulose polymers, the Crodocels, combine the cellulose
polymer with a fatty quaternary salt. A unique combination of lubricity and a silky feel on
the hair is a direct result of covalently binding a fatty quaternary group to the cellulose
backbone (38).
Guar hydroxy propyltrimonium chloride is an excellent thickener which disperses easily
in water, is pH-stable over a wide range, and is compatible with surfactants and salts.
Guar gums are available in a variety of viscosities and degrees of quaternization, offering
the cosmetic chemist formulation flexibility (39).
Derived from crustacean shells, chitin and its more soluble deacetylated derivative,
chitosan, are natural cationic materials that have found a number of intriguing
applications, including use as wound healing agents, beverage clarifying agents, and
flocculants in wastewater treatment. Combining chitosan with pyrrolidone carboxylic acid
(PCA) forms a water-soluble substantive humectant whose CTFA name is chitosan PCA.
Chitosan PCA is nonirritating and forms polymeric films on the hair (40).
Chitosan that has been reacted with propylene glycol and quaternized with
epichlorohydrin has the CTFA name of polyquaternium-29. Compatible with all types of
surfactants and stable over the pH range from 2 through 12, polyquaternium-29 exhibits
excellent hair fixative properties at low active levels (41).
b. Proteins. Proteins serve many diverse biological functions acting as catalysts in
enzymes, structural elements in bone collagen and hair keratin, nutrient storehouses in
milk casein and egg ovalbumin, and many more. Proteins are made up of one or more
polypeptide chains which in turn are made up of many alpha-amino acid residues linked
together by a peptide bond. There are 20 different alpha-amino acids commonly found in
proteins (42), listed in Table 2. All of these amino acids, except for proline, contain a free
carboxyl group and a free unsubstituted amino group on the alpha-carbon. The amino
acids differ from one another by their side chain R groups. Many amino acid residues are
Table 2 Alpha Amino Acids
Alanine Glutamine Leucine Serine
Arginine Glutamic acid Lysine Threonine
Asparagine Glycine Methionine Tryptophane
Aspartic Acid Histidine Phenylalanine Tyrosine
Cysteine Isoleucine Proline Valine

 Page 77
arranged in complex specific sequences to form proteins which range in molecular weight
from about 5000 to over 1 million.
Since protein molecules are too large to penetrate normal hair, proteins are partially
hydrolyzed to a peptide mix or completely hydrolyzed and used as the individual amino
acids. Johnsen (43) found that protein fractions with a molecular weight of 1000 or less
were the most substantive to hair.
Since proteins contain both positively and negatively charged R groups, they exhibit
amphoteric behavior. Commercially available proteins have isoelectric points in the pH
range of 4.0 to 6.0, limiting the practical range for true cationic behavior. Also, the
amount of positive charge on the protein is small.
By covalently grafting a quaternary ammonium group onto a protein, the cationic
properties are greatly enhanced. Protein fractions of higher molecular weights become
substantive to hair. Quaternization increases the isoelectric point considerably; thus,
quaternized proteins retain cationic properties over a wider pH range increasing their
versatility in formulations. Jones (44) used radioactive labeling techniques to compare
deposition on hair of a quaternized protein versus its parent protein and found that twice
as much of the quaternized protein deposits on hair.
Attaching a fatty alkyl group to the quaternary nitrogen of a protein hydrolysate that has a
molecular weight of 1000 to 2000 results in materials with a unique combination of
properties. These protein derivatives are stongly cationic, yet compatible with
amphoterics and anionics, soluble at acid pH, mild to skin and eyes, and exhibit biocidal
and foaming properties. Steartrimonium hydrolyzed animal protein is the stearyl
trimethylammonium salt of a collagen hydrolysate, which gives a substantive conditioning
agent, that provides body and gloss to hair. Stern and Johnsen (45) found that
cocotrimonium collagen hydrolysate performed similarly to stearalkonium chloride in
combing properties, but was preferred over stearalkonium chloride for the hair's bodying
effects as measured by curl bounce and fullness.
Recently, proteins derived from vegetable sources have been introduced. Plant-derived
proteins, in particular wheat and soy that have been extensively hydrolyzed to low-
molecular-weight polypeptides or amino acids, are claimed to be comparable to the
animal-derived protein hydrolysates. However, where a more complex, three-dimensional
protein structure is involved, as in the case of collagen, it is not possible to offer plant-
derived proteins with similar structures, properties, and functionality (46).
c. Nucleic Acids. Nucleic acids are macromolecules whose biological functions are storing
and transferring genetic information in the cells. Small amounts of nucleic acids are used
in conditioners to provide more of a marketing story than to provide any conditioning
benefits.
d. Silicones. There are a number of synthetic polymers used to create hair conditioning
agents. One such class is based on alternating atoms of silicon and

 Page 78

Figure 10
Dimethicone.
oxygen with two methyl groups attached to each silicon. These polymers are polydimethyl
siloxanes and are commonly referred to as silicones. The CTFA designation for the
polydimethyl siloxane polymer, whose structure is shown in Figure 10, is dimethicone.
Dimethicone smooths damaged cuticle, allowing it to lie flat, refecting light and appearing
more shiny.
When some of the methyl groups are replaced by amino groups, the resulting
aminofunctional silicone, shown in Figure 11, develops a positive charge below a pH of
7. The presence of amino groups considerably increases dimethicone's affinity for hair as
demonstrated by Wendel and DiSapio (47) using electron spectroscopy for chemical
analysis (ESCA). In formulation example #13, amodimethicone is a durable conditioning
agent; that is, it remains on the hair for several shampooings.
When Starch (48) compared hair tresses before and after silicone treatments using an
Instron combing test, he found that the increased deposition of amino functional silicone
resulted in a significantly lower average combing load. Although amino functional
silicones are strongly substantive to hair, their deposition is self-limiting, avoiding the
problem of buildup on the hair.
Besides amino groups, a quaternary group may also be attached to a dimethicone
backbone. Quaternium-80, shown in Figure 12, can be used in both shampoo and
conditioner formulations. The cationic group adds the properties of solubility and
substantivity to the dimethicone backbone (49).
The shine-enhancing characteristics of a silicone has been combined with the
conditioning properties of a vegetable protein in Crodosone W, or wheat sil-

Figure 11
Aminofunctional silicone.

 Page 79

Figure 12
Quaternium-80.
icone copolymer. The protein portion of the wheat silicone copolymer has a positive
charge which is attracted to the negatively charged damaged sites on the cuticle to form an
ionic-type bond. The silicone portion forms a protective layer on the surface of the hair to
smooth it out and enhance sheen (50,51).
e. Copolymers. Other synthetic cationic polymers are copolymers which consist of two
monomers that each contribute different properties to form a unique conditioning agent.
Gafquat, or polyquaternium-11, shown in Figure 13, is a quaternary ammonium polymer
formed by the reaction of diethyl sulfate and a copolymer of vinyl pyrrolidone and
dimethyl aminoethylmethacrylate (DMAEMA). The vinylpyrrolidone enables
polyquaternium-11 to form clear, nontacky, glossy, continuous films on the hair, while the
DMAEMA is responsible for the cationic properties. Polyquaternium-11 is compatible
with nonionic, anionic, and amphoteric surfactants and is soluble in alcohol. Used to
provide conditioning in styling gels, lotions, and mousses, polyquaternium-11 also
provides excellent curl retention benefits (52).
There are a number of cationic polymers listed under the polyquaternium and quaternium
designations in the sixth edition of the CTFA International Cosmetic Ingredient
Dictionary (53). Manufacturers' names are listed, and each manufacturer can provide
more detailed information about each of their materials.

Figure 13
Polyquaternium-11.

 Page 80
D.
General Comments on Polymeric Conditioning Agents
Although cationic polymer structures and chemistry vary greatly, some general comments
can be made concerning their performance properties on hair. In addition to improving
combability, cationic polymers often provide curl retention properties when curls are
exposed to high humidity conditions. Although cationic polymers do reduce static, Patel
(54) found cationic surfactants to be more efficient antistatic agents within a day after
treatment. However, when time and subsequent shampoos were considered, the cationic
polymers showed longer-lasting static reduction. Patel recommends that a combination of
cationic surfactants and cationic polymers be used in conditioner formulations. In the
section on developing conditioners, formulations that contain both cationic surfactants
and cationic polymers are presented.
E.
Lipid Conditioning Agents
1.
Function
Used to lubricate the hair shaft and to provide reflective properties, the first conditioning
agents were natural fats, oils, and waxes. Members of a class of materials called lipids, the
fats, oils, and waxes have the common property of hydrophobicity due to the presence of
long-chain hydrocarbon groups as a major portion of their structure. Lipids have several
important biological functionsserving as structural components of cell membranes,
performing various functions within the cells, and acting as a protective coating on the
surface of many organisms.
2.
Types of Lipids
Lipids are classified into several chemical classes. Their functional properties, however,
are of more interest to the formulating chemist. Fatty acids form the building blocks of
the most abundant lipids giving them their characteristic oily or greasy feel. Over 100
different kinds of fatty acids have been isolated from the lipids of animals, plants, and
microorganisms (55). Fatty acids contain a long hydrocarbon chain that can be either
saturated or unsaturated and a terminal carboxy group.
Most unsaturated fatty acids are liquids at room temperature, while most saturated fatty
acids are solids. The essential fatty acids, linoleic and gammalinoleic, are necessary
precursors for biosythesis in mammals that must be obtained from plant sources where
fortunately, they are abundant (56).
a. Fats and Fatty Esters. Fats, commonly called triglycerides, are triacylglycerols, esters
of the alcohol glycerol with three same or different fatty acid molecules. Triglycerides
provide sheen and lubricity to hair.
Fatty esters such as isopropyl myristate are often used in place of oils to provide
emolliency. Their feel is less greasy than that of oils. Esters also func-

 Page 81
tion as coupling agents helping to incorporate materials such as sunscreens and silicones
into the oil phase of a conditioner.
b. Waxes. Closely related to the triglycerides in structure are the waxes, which are defined
as esters of higher fatty acids with long-chain alcohols. Occurring naturally along with
these wax esters are diesters, long-chain paraffins, fatty aldehydes, and fatty alcohols. All
of these materials have been traditionally referred to as waxes. Waxes play an important
role in hair conditioner formulations. Besides forming a protective coating on the hair,
waxes provide emulsion thickening and stabilization, thus producing a thick and rich
esthetic sensation.
c. Others. Other types of complex lipids include the phosphoglycerides and
sphingolipids. Widely used in skin care, these lipds have not had much use in hair care
until recently. Braida et al. (57) identified sphinganine within the hydrolysates of virgin
hair. Inside hair, the sphinganine is attached by an amide linkage to long-chain fatty acids
and is called a ceramide. Braida et al. found that a synthetic ceramide improves hair
condition even though it is deposited in small amounts and only in the cuticle layer.
F.
Lipid Substitutes
There are a number of materials which function much the same as lipids and are used as
substitutes for them even though they are not structurally classified as lipids. These
materials include silicones and hydrocarbons.
Cyclic silicones and volatile hydrocarbons can be used to provide transient effects during
the wet combing stage, but evaporate when the hair is dried, leaving no greasy materials
behind, as illustrated in formulation examples #8 and #9.
Okumura et al. (58) found that adding silicone to a conditioner formula reduces the
mechanical friction of dry hair during brushing, thus decreasing hair damage
substantially.
Gant (59) suggests replacing some or all of the mineral oil with silicones in products for
ethnic hair to lubricate the hair shaft to avoid adding a heavy greasy feel.
Nanavati and Hami (60) observed a synergistic effect between polydimethylsiloxanes and
tricetylmonium chloride. The amount of silicone that was deposited on the hair was
nearly doubled when the quat was added to the silicone. A dramatic reduction in wet
combing force was noted.
G.
Low-Molecular-Weight Conditioning Agents
Low-molecular-weight materials may be used as conditioning agents, since they are small
enough to penetrate the hair shaft, thus beautifying the hair from within.
Topically applied, panthenol, or pro-vitamin B5, whose structure is shown in Figure 14,
converts to panthothenic acid on the hair. Pantothenic acid is a

 Page 82

Figure 14
Panthenol.
normal constitutent of healthy hair. Pantothenic acid penetrates into the cortex where it
can help repair some of the damage caused by perming and coloring and possibly slow
down the hair aging process caused by repeated grooming (61). Driscoll (62) uses SEM
photographs to illustrate how a 5% solution of panthenol helped to mend some of the
damaged areas of the hair shaft.
Substantivity on the hair is increased by 31% when panthenol is attached to a fatty
quaternary group. Steardimonium panthenol's functional properties include foaming,
fragrance solubilization, and compatibility with anionic surfactants (63).
Glycerine is a small molecule that can penetrate the hair fiber to restore moisture to
damaged areas. Glycerine has been used to reduce damage from thioglycolates during
permanent waving (64). Glycerine's role as a key cosmetic ingredient is described in
Volume 11 of the Cosmetic Science and Technoloqy Series, edited by Eric Jungermann
and Norman O. V. Sonntag.
V.
Other Materials Found In Conditioners
A large number of other materials may be incorporated into conditioner formulations to
thicken, stabilize, preserve, opacify, increase, or decrease foaming, etc. of these
formulations. Hunting provides a list of ingredients and their properties in the
Encyclopedia of Conditioning Rinse Ingredients (65).
A.
Thickeners
Many of the cationic polymers that are used as conditioning agents may also be used to
provide thickening. However, in formulations such as conditioning shampoos,
conditioning styling aids, or cream rinses based on cationic surfactants, a nonionic
thickener may also be needed. In the Encyclopedia of Polymers and Thickeners for
Cosmetics, Lochhead (66) describes a number of thickeners and gives their typical use
concentrations.
B.
Emulsifiers
Oils, silicones, esters, and all the other hydrophobic conditioning agents need to be
solubilized or emulsified into a water-based product using either cationic

 Page 83
or nonionic emulsifiers. McCutcheon (67) provides a list of hundreds of emulsifiers.
Many books and articles discussing emulsion and solubilization theory and practice are
available, but publications by Lisant (68), Becher (69), Shinoda and Friberg (70), and
Rieger (71) should be particularly helpful in formulating conditioning products.
To simplify the selection of emulsifiers, raw-materials manufacturers have developed
blends called self-emulsifying bases (SEB) (72). Originally developed in the 1940s, SEBs
were formed by an association of a fatty alcohol or a wax and a soap. In current SEBs,
the soap has been replaced with a variety of modern emulsifiers. SEBs are considered to
be true preformulations where the supplier has already selected the lipophile and one or
more emulsifiers to which conditioning agents can be added. SEBs are used by simply
heating all the components of the formula which are not heat-sensitive, gently agitating to
ensure uniform mixing, cooling, and then adding the materials which are heat-sensitive
such as fragrance and volatile silicone. Table 3 shows some of the nonionic SEBs that
may be used in formulating conditioners.
C.
Fragrances
Although fragrance-free conditioners are available in the marketplace, most conditioning
products contain a fragrance. Fragrance is used to mask raw material odors or to evoke a
particular image when the bottle is opened as well as during and after product use.
Fragrances that are used in other personal care products can usually be used in a
conditioner formulation. However, cationics may react with some of the fragrance
components. For instance, 3,7,-dimethyl 2,6-octadienal, a component of natural lemon,
reacts with the free amine in cationics to form colored Schiff's bases which may change
the final product's color and odor characteristics (73).
Table 3 Nonionic Self-Emulsifying Bases
Beeswax and PEG-6
Glyceryl stearate and laureth-23
Cetearyl alcohol and ceteth-20
Cetearyl alcohol and ceteareth-20
Cetearyl alcohol and polysorbate 60 and PEG-150 stearate and
steareth-20
Glyceryl stearate and PEG-75 stearate
Cetearyl alcohol and ceteth-12 and oleth-12
PEG-6-32 stearate and glycol stearate
PEG-6 stearate and ceteth-20
Glyceryl stearate and PEG-6 stearate and ceteth-20
Glyceryl stearate and ceteth-20

 Page 84
D.
Sunscreens
Sunscreens are compounds which absorb ultraviolet radiation in the range between 250
and 320 nm, thus protecting the surface of the substrate such as skin or hair, onto which
the sunscreen is applied.
There are many sunscreens available to protect skin from ultraviolet radiation, but only a
few of these are suitable for use on hair. Nacht (74) describes the ideal sunscreen for hair
as substantive to the cuticle even in the presence of surfactants, without causing hair to
become dull or tacky. Nacht found octyl dimethyl p-aminobenzoic acid (PABA) to be the
most suitable hair sunscreen. When incorporated into commercial shampoos, 1.0% octyl
dimethyl PABA provided the hair with significant protection from sun damage as
measured by the hair tensile strength test. The degree of protection improved when the
shampoos contained conditioning ingredients, indicating that conditioning ingredients
may enhance the sunscreen's substantivity or promote its even distribution on hair.
Formulation example #16 utilizes a sunscreen in a conditioning mousse formulation. In
Volume 10 of the Cosmetic Science and Technology Series edited by Nicholas J. Lowe
and Nadim A. Shaath, the development, evaluation, and regulatory aspects of sunscreens
are covered in detail.
E.
Plant and Herbal Extracts
Over the centuries, plant and herbal extracts have added fragrance, sheen, and softness to
hair. The list of plant and herbal extracts that may be added to conditioners is long and
varied (75), but the three herbs that are most commonly used to condition hair are
rosemary, sage, and chamomile. Infusions of rosemary or sage add sheen to brunette hair,
while chamomile adds highlights and softness to blond hair.
The amount of conditioning benefit obtained from a plant or herbal extract depends on
the level of active components present in the extract. Researchers all over the world are
evaluating the functional properties of a vast number of active constituents found in
plants.
Some extracts contain UV-absorbing compounds. In order to protect themselves from a
harsh environment, plants evolved sophisticated defense mechanisms. For instance, the
UV absorption spectrum of the liquid extract of aloe leaf sap shows excellent UV-B
absorption with a maximum peak at 297 nm (76). Green coffee extract absorbs at a
maximum peak of 270 nm, while wild pansy extract absorbs at a maximum peak of 352
nm. Protection for hair over much of the UV spectrum may be obtained by blending
suitable extracts (77).
Steinberg (78) suggests that when using plant extracts in the laboratory, the formulating
scientist should make sure that the samples are fresh and free of microbial contamination.

 Page 85
As with other conditioner formulations, the efficacy, stability, and safety of conditioner
formulations containing plant extracts should be evaluated thoroughly before
commercialization. In some cases, additional preservatives or antioxidants may be
needed.
F.
Preservatives
Even though many cationics exhibit bacteriocidal properties, a conditioner formulation
will almost always need additional preservatives to maintain product integrity thoughout
its useful life. The Cosmetic Preservatives Encyclopedia (79) lists the preservatives that
are used in personal care products and includes information on compatibility. Paraben
esters are incompatible with cationic surfactants, whereas DMDM hydantoin is an
example of one of the many preservatives that are compatible with cationics. Generally, a
mixture of preservatives is best, and each formulation should be challenge tested (80).
The principles and practice of preservation are covered in Volume 1 of the Cosmetic
Science and Technology Series edited by Jon J. Kabara (80a).
G.
Colors
FD&C colors may be used to add a tint to the conditioner for esthetic reasons, i.e., to
match packaging, or to create an impression. Not all dyes may be compatible with
strongly cationic formulations. Each formulation should be tested with the single colors
and blends of several colors in order to determine the most suitable color system. In most
cases, the level of color should be selected, such that no color remains on the hair after
rinsing. However, in some instances, it is desirable to add color from the conditioner onto
the hair. The amount of color that is deposited on the hair is usually slight and acts to tone
or highlight the hair. For example, D&C Violet#2 has been used to neutralize bleached or
blond hair's red tones (81). In formulation example #17, a cationic conditioning agent and
D&C Violet#2 are combined to neutralize yellow tones while eliminating skin staining.
VI.
Developing a Balanced Conditioner Formulation
When developing a conditioner, the formulating scientist must balance product attributes,
esthetics, safety, and cost parameters.
A.
Project Request
The development process usually begins when a project request is received from the
marketing department. The project request usually includes the following information:

 Page 86
1. A description of the product concept, listing features and benefits
2. The required product performance, whether the conditioner should be an improvement
over a competitive target, or just match its performance
3. Physical properties such as color, appearance, and viscosity, the form the conditioner
will take (leave-on, rinse-off, or spray)
4. Packaging components, whether the container will be glass, plastic, clear, or opaque,
and the type of closure required
5. Type of hair on which the conditioner will be applied, such as normal, oily, damaged,
gray, etc.
6. A list of ingredients which must be incorporated in the conditioner formulation such as
botanical extracts, moisturizers, sunscreens, etc.
B.
Formulation Ideas
The first step a formulating scientist should take when developing a conditioner is to
consult the available information resources. Literature sources such as books, journals,
and patents, supplier's literature and formularies, competitive product labels, and in-house
formulations can provide pertinent background material. Experts or consultants such as
those from the Teltech Technical Knowledge Service can answer questions or furnish
ideas. The patent literature is a rich source of novel conditioner formulations, many of
which are successful commercial products. Eighteen representative patented conditioner
formulations are provided in the following section, illustrating the uniqueness and
diversity of conditioner formulations. Perhaps these formulas will touch off a spark of
imagination and help the formulating scientist develop new, innovative conditioner
formulations.
Formulation 1. Rinse-Off Creme Rinse (82)
In U.S. patent #4,421,740, assigned to S. C. Johnson & Son, Inc. (1983), Burton
discloses a composition and process with excellent performance characteristics using
low levels of active ingredients.

Weight
Ingredient
percent
Stearalkonium chloride,
3.60
25%
Cetyl alcohol 1.10
Hydroxyethylcellulose 0.75
Perfume 0.25
Water 94.30

Mixing instructions
Phase I. Mix the stearalkonium chloride with a portion of the water and heat to 180°F.
Melt the cetyl alcohol above about 150°F and add it to the water/quaternary mixture.
Cool to 85°F to 100°F and homogenize at a pressure of 5000 psi.

 Page 87
Phase II. Disperse the hydroxyethylcellulose in the remaining water and heat to 120°F.
Cool to 75°F and blend the hydroxyethylcellulose dispersion into phase I.
Formulation 2. Leave-On Creme Rinse (83)
People whose scalps secrete too much sebum have oily hair which readily picks up
dust and dirt from the environment. In U.S. patent #4,013,786, assigned to Alberto
Culver (1977), Cella, Fiebig, and Pum disclose a leave-on creme rinse formulation
which contains a perfluorinated compound to reduce the flow of sebum over the hair.

Weight
Ingredient
percent
Water 83.75
Quaternium-18 15.00
Trimethyl soy ammonium
0.10
chloride
Perfluorinated compound* 1.00
Perfume 0.15

Mixing instructions
Add the quaternium-18 to the water. Premix the perfume with the trimethyl soy
ammonium chloride and add to the water/quaternary mixture. Add the perfluorinated
compound and stir until incorporated.
*CF3 - (CF3)x - (CH2)y - Z
Formulation 3. Deep Treatment Conditioner (84)
Damaged hair may be deficient in normal moisture. In U.S. patent #4,220,166,
assigned to Helene Curtis, Inc. (1980), Newell discloses a method for restoring normal
moisture level to severely moisture deficient hair, by applying this deep heat treatment
conditioner containing glycerin at least once a week.

Weight
Ingredient
percent
Sodium PCA 5.0
Glycerin 5.0
Protein 2.5
Cetrimonium chloride, 30% 4.3
Panthenol 0.1
Glyceryl stearate, acid-
1.0
stabilized
Cetearyl alcohol and
1.0
ceteareth-20
Mineral oil 65/75 2.0
Isopropyl myristate 2.0
Cetyl alcohol 3.5
Glycol stearate 2.0
Perfume 0.4
Color solution 0.2
Preservative q.s.
Water 71.0

 Page 88
Mixing instructions
Oil phase. Add the glyceryl stearate, cetearyl alcohol and ceareteth-20, mineral oil,
ispropyl myristate, cetyl alcohol, and glycol stearate to a suitable mixing tank. Heat to
80°C to 85°C or until all ingredients are melted and a uniform mixture is obtained.
Water phase. In a second tank, add the sodium PCA, glycerin, cetrimonium chloride,
and panthenol to the water. Mix and heat to 80°C to 85°C.
Add the water phase to the oil phase with agitation. Begin cooling to 40°C; add the
protein, perfume, preservatives, and color solution. Mix until uniform.
Formulation 4. Clear Conditioner I (85)
Clear conditioner formulations provide an esthetic difference for the consumer. In
U.S. patent #4,610,874, assigned to Neutrogena Corp. (1986), Matravers discloses a
formulation which eliminates undesirable conditioner buildup on the hair.

Ingredient Weight percent

Purified water 84.32
Hydroxyethylcellulose 0.85
Polyquaternium-10 0.80
Coleth-24 and ceteth-24 2.00
PVP (K30) 0.50
Citric acid, 50% 0.03
Methylparaben 0.15
Propylparaben 0.05
Imidazolidinyl urea 0.30
Propylene glycol 5.00
Polyquaternium-11 2.00
Sodium PCA 3.00
Glycerin 1.00

Mixing instructions
 Disperse the hydroxyethylcellulose and polyquaternium-10 in water and heat to 75°C.
While maintaining the temperature, blend in the coleth-24 and ceteth-2 to form a
homogeneous blend. Add the polyquaternium-11, PVP, propylene glycol, sodium
PCA, citric acid, 50% and preservatives. Cool the batch to ambient temperature.
Formulation 5. Clear Conditioner II (86)
In U.S. patent #4,954,335, assigned to Helene Curtis, Inc. (1990), Janchitraponvej
discloses a clear conditioner formulation containing a cationic surfactant, amido
amine, and a volatile silicone. A solubilizing nonionic surfactant, lauryl pyrrolidone, is
used to obtain the clarity.

 Page 89

Weight
Ingredient
percent
Soft water 77.40
Dicetyldimmonium
2.00
chloride, 70%
Cyclomethicone 1.00
Lauryl pyrrolidone 2.00
Stearamidopropyl
0.80
dimethylamine
Lactic acid, 85% 0.30
Hexylene glycol 5.00
Octoxynol-9 1.20
Fragrance 0.40
Hydroxyethylcellulose 0.75
Preservative 0.15
Ethanol 9.00

Mixing instructions
Main batch. Mix together the hexylene glycol, stearamidopropyl dimethylamine, and
lactic acid. Heat to 150°F to 165°F and hold temperature for 30 min. Cool to 100°F.
Premix I. Thoroughly mix together the dicetyldimonium chloride and ethanol and add
to the main batch, blending until clear.
Premix II. Disperse the hydroxyethylcellulose in water and mix until clear. Add to the
main batch.
Premix III. Thoroughly mix together the cyclomethicone and the lauryl pyrrolidone.
Add to the main batch, blending until clear.
Premix IV. Thoroughly mix together the octoxynol-9 and the fragrance. Add to the
main batch, blending until clear. Blend in the preservatives.
 Formulation 6. Pearlescent Conditioner (87)
Additives such as cetyl alcohol or glycol fatty acid ester can be added to conditioners
to achieve a pearlescent appearance. These pearlizing additives add cost and may not
be desired on the hair. In U.S. patent #4,007,261, assigned to the Millmaster Onyx
Corporation (1977), Sorrentino and Like use alkyl dimethylamine oxides as
combination conditioning/pearlizing agents.

Weight
Ingredient
percent
Stearalkonium chloride,
7.50
25%
Cetyl alcohol 0.30
Water (1) 81.45
Potassium chloride 0.75
Water (2) 10.00

 Page 90
Mixing instructions
Mix together the stearalkonium chloride, cetyl alcohol, and water (1). Heat to 60°C to
70°C, with agitation until uniform. Mix together the potassium chloride and water (2),
and gradually add to the batch. Cool to 40°C to 50°C and add any fragrance, color,
preservatives, etc. At the set point of about 28°C to 30°C, slow down the agitation to
prevent localized cooling.
Formulation 7. Conditioner Containing a Cationic Polymer (88)
Cationic polymers may induce a static charge on the hair in the dry state. In U.S. patent
#4,719,104, assigned to Helene Curtis, Inc. (1988), Patel utilizes a static reducing agent
such as caprylic/capric triglyceride to eliminate the static charge.

Weight
Ingredient
percent
Distearyldimonium
0.5
chloride
Caprylic/capric
0.5
triglyceride
Stearyl alcohol 1.0
Steareth-2 1.0
Ceteth-30 0.5
Hydroxyethylcellulose 0.25
Polyquaternium-10 0.10
Preservative 0.05
Potassium chloride 0.05
Soft water 96.05

Mixing instructions
Oil phase I. Place the distearyldimonium chloride, caprylic/capric triglyceride, stearyl
alcohol, steareth-2, and ceteth-30 into a suitable mixing tank and heat to 80°C to 85°C.
Water phase II. Disperse the hydroxyethylcellulose and polyquaternium-10 in the
 water. Add the preservative and potassium chloride. Heat to 77°C to 80°C.
Add the water phase II to the oil phase I with mixing until a homogeneous emulsion is
formed. Cool while maintaining agitation.
Formulation 8. Conditioner Containing Volatile Silicone I (89)
Volatile silicones improve wet combing characteristics of hair, yet evaporate when the
hair is dried, leaving no greasy residue. In U.S. patent #4,387,090, assigned to Procter
& Gamble Company (1983), Bolich incorporates a volatile silicone into a hair
conditioner that is thickened with a hydrophobic thickening agent.

 Page 91

Weight
Ingredient
percent
Cyclomethicone 8.000
Polyvinyl isobutyl ether 0.008
Hydroxypropyl guar gum 1.100
Ethanol 8.000
Dihydrogenated
0.240
tallowdimonium chloride
Perfume 0.500
q.s. to
Distilled water
100%

Mixing instructions
Stock solution. Prepare a stock solution by dissolving 2% polyvinyl isobutyl ether in
98% cyclomethicone and stir with a magnetic stirrer for 24 hours.
Premix. Prepare a premix of dihydrogenated tallowdimonium chloride and
hydroxypropyl guar gum in ethanol. Mix at ambient temperature for 10 min.
Main batch. Add enough of the stock solution to give 0.008% of the polyvinyl
isobutyl ether to the volatile silicone. Add the premix and shear with a high shear
dispersator for 5 min. Add the water and the perfume. Mix for 15 min with a
conventional mixer.
Formulation 9. Conditioner Containing a Volatile Silicone II (90)
In U.S. Patent #4,777,037, assigned to Helene Curtis, Inc. (1988), Wagman and
Johnson combine a quaternary salt and a volatile silicone.

Weight
Ingredient
percent
Dicetyldimonium chloride,
3.3
68%
Cetyl alcohol 3.25
Cyclomethicone 2.0
Stearyl alcohol and
1.0
ceteareth-20
Dimethylaminopropyl
2.0
stearamide
Propylene glycol 0.5
Perfume 0.4
Potassium chloride 0.3
Panthenol 0.1
Citric acid 0.1
Preservative solution (7 ppm
0.2
active)
Deionized water 88.35

Mixing instructions
Add the dicetyldimonium chloride, citric acid, propylene glycol, and
dimethylaminopropyl stearamide to the water with agitation and heat to 145°F. When
the mixture is uniform, add the cetyl alcohol and stearyl alcohol and ceteareth-20 and
heat to 155°F. Continue agitation for 30 min and cool to 115°F. Add

 Page 92
the potassium chloride. When the mixture is uniform, add the panthenol, perfume, and
preservative solution.
Formulation 10. Conditioner With Style Retention Properties I (91)
Conditioned hair may be too soft to hold a set well. It is a difficult task to optimize
both conditioning and style retention properties in the same formulation. In U.S. patent
#4,210,161, assigned to Helene Curtis, Inc. (1980), Wagman combines an anionic
polymer and a cationic surfactant to form a water-insoluble reaction product which
provides style retention from this rinse-off conditioner formulation.

Weight
Ingredient
percent
PVM/MA copolymer 0.29
Olealkonium chloride,
1.40
50%
Water 98.31

Mixing instructions
Blend all the ingredients together and mix until uniform.
Formulation 11. Conditioner With Style Retention Properties II (92)
Anionic polymers add setting and hold properties to hair, but they exhibit poor
substantivity in a rinse-off formulation. Cationic polymers are substantive to hair, but
do not provide the same setting and hold properties as the anionic polymers. In U.S.
patent #4,445,521, assigned to L'Oreal (1984), Grollier, Fiquet, Fourcadier, Dubief, and
Cauwet anchor the anionic polymers to hair with cationic polymers in this rinse-off
conditioner formulation that is applied before shampooing.

Weight
Ingredient
percent
Adipic acid-dimethylamino-
hydroxypropyl diethylenetriamine 1.8
copolymer
Sodium polystyrene sulfonate 1.2
Lauryl alcohol 2.0
Steareth-2 15.0
Water 80.0

When the composition is prepared, the pH should be 9.0.

Formulation 12. Conditioner With Style Retention Properties III (93)
In U.S. patent #4,983,383, assigned to Procter & Gamble Company (1991),
Maksimoski and Murphy disclose a composition containing a style retention resin
dispersed in a nonrigid silicone gum.

 Page 93

Weight
Ingredient
percent
Cyclomethicone 4.41
Cetyl alcohol 1.0
Quaternium-18 0.85
Stearyl alcohol 0.75
Hydroxyethylcellulose 0.50
Stearamidopropyl dimethylamine 0.35
Ceteareth-20 0.25
Glyceryl stearate 0.25
Fragrance 0.25
Dimethicone gum 0.10
silicone resin 0.40
Citric acid 0.13
Dimethicone copolyol 0.10
Octylacrylamide/acrylates,
butylaminoethyl methacrylate, 0.04
copolymer particulate
Preservative 0.033
q.s. to
Water
100%

Mixing instructions
Disperse the hydroxyethylcellulose in the water. When dispersed, heat to 60°C to 90°C.
Add the cetyl alcohol, quaternium-18, stearyl alcohol, stearamidopropyl
dimethylamine, ceteareth-20, and gyceryl stearate, and mix for 10 min. Cool to 50°C
and add the rest of the ingredients. Mill the mixture under high shear for 2 min and
cool to room temperature.
 Formulation 13. Durable Conditioner With Aminofunctional Silicone (94)
A conditioner that lasts through several shampooings may be beneficial to those who
do not wish to apply a conditioner every time they shampoo their hair. In U.S. patent
#4,529,586, assigned to Clairol, Inc. (1985), DeMarco, Varco, Wolfram, and Wong use
a cationic polymer and an aminofunctional silicone in a cationic emulsion to improve
the durability of the conditioning effect to shampooing.

Weight
Ingredient
percent
Amodimethicone (cationic
1.6
emulsion)
Quaternium-40 1.6
Hydroxyethylcellulose 1.5
Citric acid 0.5
Water q.s. to 100%

 Page 94
Mixing Instructions
Disperse the hydroxyethylcellulose in the water. Mix until clear and uniform. Add the
quaternium-40, amodimethicone, and citric acid. Mix until uniform.
Formulation 14. Preshampoo Conditioner (95)
To avoid overconditioning, a conditioner may be applied prior to the shampooing step
so that excess conditioning agent can be removed. In U.S. patent #Re. 30,874, assigned
to Alberto Culver (1982), Dasher, O'Cull, and Schamper use quaternary salts in
combination with polyethylenimines and N-ethanolacetamide to provide conditioning
that is retained after shampooing.

Weight
Ingredient
percent
Cocotrimonium chloride,
4.0
50%
N-ethanolacetamide 15.0
Polyethylenimine 1.25
Oleth-20 2.0
Formic acid, 90% 1.4
Ethoxyethanol 0.37
Methylparaben 0.10
Deionized water q.s. to 100%

Mixing instructions
The order of mixing the ingredients is not critical. Mix ingredients with stirring
applying slight heating to hasten the formation of the solution until clear.
Formulation 15. Lathering Conditioner (96)
Creme rinse conditioners reduce flyaway, but leave a perceivable coating on the hair
which may signal to the consumer that their hair does not feel completely clean. In
U.S. patent #4,333,921, assigned to American Cyanamid Company (1982), Luedicke,
Domzalski, and Zajac disclose a novel lathering conditioner which combines long-
lasting conditioning with a cleaner feeling.
 Weight
Ingredient
percent
Lauramine oxide, 40% 10.00
Stearalkonium chloride,
6.00
25%
Glycerin 5.00
Sorbitan oleate 2.50
Hydroxyethylcellulose 1.00
Fragrance 1.00
Citric acid 0.60
Glycolamido stearate 0.50
Cetrimonium chloride,
0.25
25%
Water q.s. to 100%

 Page 95
Mixing instruction
No mixing instructions were given in the patent. The pH of the composition is 4 to 6.
Formulation 16. Conditioning Mousse Containing Sunscreen (97)
Ultraviolet radiation causes hair to become weakened and discolored. Applying a
sunscreen to the hair can prevent UV damage. In U.S. patent #4,567,038, assigned to
Revlon (1986), Ciandelli and Brand disclose a conditioning mousse with a sunscreen
agent.

Ingredient Weight percent

Hydroxyethylcellulose 0.225
Benzophenone-9 0.001
Hydrolyzed animal
0.010
protein
Steareth-2 0.500
Dimethicone copolyol 0.300
Nonoxynol-10 0.150
Polysorbate-20 0.638
Polyquaternium-11 2.000
Ethanol (SDA 40B) 3.000
Tallowtrimonium chloride 0.500
Polyquaternium-4 0.050
Benzophenone-2 0.001
PVP/VA copolymer 6.750
Water q.s. to 100%

Mixing instructions
Mixture A. Disperse the hydroxyethylcellulose in 5070 parts of the water. Begin heating
to 60°C to 65°C, and add the benzophenone-9, hydrolyzed animal protein, steareth-2,
and dimethicone copolyol. Continue agitation at least 30 min, or until the mixture is
 uniform and free of lumps. Cool the mixture to 40°C to 45°C, and add the nonoxynol-
10, polysorbate-20, and polyquaternium-11. Maintain slow agitation and cool to 30°C
to 35°C.
Mixture B. In a suitable size container, blend together the ethanol, tallowtrimonium
chloride, benzophenone-2, polyquaternium-4, and PVP/VA copolymer, and mix until
all the ingredients are dissolved.
Add Mixture B to Mixture A with slow, continuous agitation.
The composition is filled into cans and pressurized, using conventional techniques.
Formulation 17. Conditioner With a Violet Dye (98)
Gray and white hair yellows naturally with age or with the use of yellow-colored
shampoos, hair sprays, etc. Ext. D&C Violet #2 neutralizes yellow cast

 Page 96
on the hair, but may also stain the skin. In U.S. patent #4,678,475, assigned to Helene
Curtis, Inc. (1987), Hoshowski and Patel utilize a dialkyl quaternary salt with alkyl
chain lengths of 12 to 16 carbons to prevent the Ext. D&C Violet #2 from staining the
skin.

Weight
Ingredient
percent
Soft water 52.48
Hydroxyethylcellulose 0.50
Soft water 42.00
Stearyl alcohol 1.00
Dicetyldimmonium
2.50
chloride
Stearamidopropyl amine 0.50
Isopropyl myristate 1.00
Ext. D&C Violet #2 0.02
Preservative q.s.
Citric or lactic acid q.s.

Mixing instructions
Tank I. Disperse the hydroxyethylcellulose in the first amount of soft water. Mix until
clear and uniform. Heat the mixture to 160°F.
Tank II. Heat the second amount of soft water to 160°F. Add the stearyl alcohol,
dicetyldimmonium chloride, and stearamidopropyl amine. Add the desired amount of
acid. Mix until uniform, and add this mixture to the mixture in tank I.
Cool the batch to 110°F and add the isopropyl myristate, Ext. D&C Violet #2, and
preservative. Continue mixing until cool.
Formulation 18. Conditioning Comb (99)
Not all conditioning agents have to be applied to the hair from a formulation. In U.S.
Patent #3,992,336, assigned to Union Carbide Corp. (1976), Faucher and Meyer
 disclose a novel method of applying a conditioning polymer to the hair.
A water-soluble conditioning polymer at about 20% to 30% by weight and a water-
insoluble molding resin are blended together and molded into a hard comb.
Applying water to the comb results in the leaching out of the soluble conditioning
polymer onto the hair. Either the hair or the comb may be wetted. Combing studies
with this comb showed that the conditioning polymer provides improved wet combing
and reduces flyaway.
C.
Formulating Prototypes
Once the formulating scientist has received the product profile and consulted literature
and other sources, he or she is ready to begin formulating prototypes.

 Page 97
Prototypes are simple formulations with a few key ingredients which are used to quickly
screen a number of raw materials for their performance versus product concept. By
utilizing experimental design techniques rather than varying one ingredient at a time, the
formulating scientist receives more information with fewer experiments in less time.
Interactions between ingredients can be easily determined with the appropriate
experimental design.
Many publications teach experimental design techniques, but those by Snee (100),
Schwartz (101), Cornell (102), and Bayne and Rubin (103) should be immediately useful
to the formulating scientist.
D.
Evaluation of Candidate Formulations
After the prototype conditioner formulations have been developed, the formulating
scientist needs to determine which candidates, if any, best fit the product requirements.
Each prototype's performance on the target hair type, its stability in the desired packaging,
and its safety are all areas that need to be considered. While these issues have been
addressed in detail elsewhere in this book, the following summary relates specifically to
conditioners.
1.
Performance Testing
To evaluate a conditioner formulation's effectiveness, we need to remember that the
purpose of a conditioner is to return hair to its natural and healthy state, even if only
temporarily. Healthy hair combs easily, is shiny, has little or no flyaway, and so on. There
are many methods to evaluate the physical properties of hair before and after application
of a conditioner. The following are just some of the techniques that might be used and are
by no means an exhaustive list.
The Instron combing test, which measures combing force, is usually the first instrumental
test of a conditioner formulation's performance on hair. The lower the gram-force values,
the easier the hair is to comb. The formulator can usually improve the combing ease by
increasing the level of conditioning agents or increasing their chain lengths. This
approach can lead to limp, over-conditioned hair. There is no single instrumental method
to indicate hair limpness, but rather a number of methods that, taken together, will
indicate that the hair has become limp. Each of these methods tells only part of the story
and may not always correlate to actual human experience. The chapter on product
evaluation explains these methods in detail.
Test methods employing humans include testing in a simulated situation in a controlled
environment with trained technicians, and at-home use tests with uncontrolled but real-
life conditions. Simulated use tests are used as screening tools to evaluate a large number
of formulations quickly and relatively inexpensively (104). In a salon type of setting, a
subject's hair is treated with a controlled amount of product and evaluated with data
recorded on a standardized

 Page 98
form. A half-head technique may be used, where one side of the subject's head receives
the experimental formulation, while the other side of the subject's head receives a target
or ideal formulation. The two sides are then compared at the same time, which reduces
subject-to-subject variability.
The development process is a cyclical one where prototypes are developed, tested,
redeveloped, and retested until the desired results are obtained. Once a few promising
candidates remain, a larger-scale market research test is usually conducted to determine
the product's relative performance to competition or to another benchmark product.
In Volume 3 of the Cosmetic Science and Technology series, Moskowitz (105) discusses
the differences between research and development and market research tests. Research
and development tests are used to narrow down prototypes, while market research tests
determine the best product versus competition. A fine line often exists between the two
types of tests. Research and development must communicate effectively with marketing
research to best utilize each type of testing.
2.
Stability Testing
A conditioner formulation should retain its original characteristics such as color, odor,
and appearance over a period of time, called its shelf-life. Normally the shelf-life is from
the time the product is produced, through storage and shipping by the manufacturer, until
the product is used up by the ultimate consumer. A shelf-life of no less than 2 years and
up to about 5 years is usually considered acceptable. Since product development time
lines rarely allow real-time stability testing of this duration, accelerated tests are used to
predict the shelf-life. Rieger (106) recommends that the stability of a new formulation be
compared at the same time under the same conditions to the stability of an old
formulation with a known shelf-life.
The accelerated conditions that should be used for testing will vary depending upon the
intended use of the conditioner formulation. Fishman (107) lists some of the accelerated
stability tests which are commonly used as:
1. Heatusually 40°50°C in a constant temperature oven
2. Coldusually 4° or 5°C in a refrigerator
3. Freezing0°C or below
4. Freeze/thawcold followed by heat in cycles
5. Color fastnessusing natural or artificial light
6. Centrifugefor emulsions and dispersions
Samples should also be kept at room temperature.
3.
Safety Testing
There is no single test or even a set series of tests that must be used to determine the
human safety of conditioners. Rather, the types and numbers of safety

 Page 99
tests needed is dependent on the intended product usage, the safety history of the raw
materials used, any available historical data on similar products, and corporate policy.
Volume 5 of the Cosmetic Science and Technology series, Whittam (108) gives some
general guidelines for safety evaluation. The formulating scientist should establish a
dialogue early in the project with their corporate safety department to determine which, if
any, safety tests may be required.
Biodegradability of personal care products is becoming an increasingly important issue in
the 1990s. Every conditioner formulation that is applied to the hair will ultimately find its
way into the environment. Research studies are ongoing to determine the fate and effects
on ecosystems of a variety of chemicals (109), including those present in hair
conditioners. It is therefore important that the formulating scientist should consider the
impact of his or her product on the environment.
Before selecting conditioner raw materials, the formulating scientist should review
biodegradation data found in the literature (110). While the literature alone cannot
completely predict a formulation's biodegradability, a fair idea may be obtained.
Biodegradability tests should then be used to determine actual degradation under specific
conditions. Biodegradability tests are controlled laboratory studies which measure the rate
and degree that organic chemicals and products are degraded by biological activity. These
tests simulate the environment found in water, waste water, and soil (111).
There are several types of biodegradability tests available. Since many companies wish to
use the results to make environmentally friendly claims, the formulating scientist should
discuss the new product with the corporate environmental department or with an outside
testing laboratory to determine the most appropriate test protocol.
VII.
Conclusions
Conditioners help to maintain hair in a proper and healthy state. There is no single,
perfect conditioning agent, but rather a wide variety of conditioning materials available.
Furthermore, combinations of ingredients must be used to formulate a balanced
conditioner.
One chapter alone cannot provide all of the information available on formulating
conditioners. The purpose of this chapter is to provide guidance to the formulating
scientist in selecting cationic and lubricious conditioning agents, as well as other materials
found in conditioners. A summary of the functional aspects of formulating conditioners,
including stability and safety issues, is meant to serve as a basic checklist, while
experimental design techniques are advocated in optimizing ingredients and their use
levels. Examples from patents and the listings of sources and references are provided to
broaden the formulating scientist's experience and enable him or her to develop
conditioner formulations which meet the needs of the target market.

 Page 100

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75. Leung AY. Encyclopedia of Common Natural Ingredients Used in Food, Drugs, and
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105(3):4963.
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Containing a Certified Violet Dye and a Quaternary Ammonium Compound. U.S. Patent
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Carbide Corp., 1976.
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 Page 105

5
Hair Styling/Fixative Products
Joseph A. Dallal and Colleen M. Rocafort
International Specialty Products, Wayne, New Jersey
I.
Introduction
Hair styling and fixative products cover a wide range of product categories, forms, and
styles as well as information on its use and application. These products can be use on wet
or dry hair. They can be used at almost any point in a hair care regimen: to start a hair
style, to refresh or change a hair style, and to hold (fix) a hair style.
Polymers seem to dominate the functional ingredient roles of holding the hair in place
during the styling process and in the fixing step (both immediate hold and long-term hold,
even under high humidity). All the other ingredients are used to dilute the resin, to create
the physical form of the product to allow for distribution of the resin to the hair, and to
modify the stiffness, feel, flaking, tackiness, combability, removability, solubility, shine,
durability, fragrance, and consumer desirability of the final polymer system. It takes only
a small amount of other ingredients to drastically alter the effects of a fixative polymer or
resin.
In this chapter we review the typical categories of styling and fixative products, present
some typical formulations, and speculate on some new formulation trends. At the end of
the chapter is a glossary of terms for your reference.
II.
Setting And Styling Aids
Formulation tools for preparing, designing, or stabilizing a coiffure are called setting, or
styling aids. The function of a setting or styling aid is to temporarily

 Page 106
hold a section of hair in place during the drying stage, to modify the feel and strength of
the hair, or to increase the interfibril interactions (1) during drying or after the hair has
dried. This is needed to create body, volume, or control when creating or modifying a
hair style. (Natural hair has a smooth, shiny cuticle, which allows the hairs to slide over
each other. Styling aid formulations help build the interactive forces between hair fibers
which prevent the smooth sliding of fibers over or past each other. Therefore, instead of
the hairs sliding over each other and resting flat against the scalp, the hairs can maintain a
fluffy and billowy position, using each other as supports. To promote this, the
formulations provide a type of roughness, or adhesion, on the hair surface.)
The cosmetic chemist continues to improve or modify styling products (consumable
tools) because, as the years go by, fashions change. This changes the needs of the hair
style and of the hair stylist. Hair styling and styling techniques cover a wide range of
applications to varied hair textures, involving styling manipulations/techniques. Hair
textures are manifested in degrees of damage, cross-sectional diameters of the hair shaft,
and density of hair in number of hairs per square inch (2). Hair damage is caused by a
variety of methods including perms, bleaches, colors, relaxers, chlorine, solar energy, and
mechanical action (brushing, pulling, etc.) Damaged hair is usually rough to the touch and
difficult to comb, producing tangles. Coarse hair has a higher percentage of cortex and
has more strength (structural modulus) and therefore more body. Fine (small cross-
sectional diameter) hair has less strength and body. The more hair there is on a head, the
more interactions there will be.
Therefore, styling products must be delivered in a form that will allow distribution of the
product throughout the hair. For instance, the physical form of the formula's ingredients
may change based on the level of damage that is present. The rougher the hair, the
smoother, creamier, or more detangling the product will need to be. The fineness of the
individual fibers may require lighter formulas as well as formulas that offer increased
body potential. A high density of the hair on the head may require extra detangling to
allow easier combing.
The final hair style and styling techniques will determine the type and level of ingredients
in the styling products. A flat, smooth, and soft style may use a low amount of resins and
a high level of softening or plasticizing additives. A blow-dry hair style may require
higher levels of antistatic ingredients to minimize static buildup during rapid and repeated
brushing during blow drying with high-temperature, low-humidity air. The use of a
curling iron may require a resin with a higher Tg (glass transition temperatureakin to the
melting point of a crystalline material; a polymer may be sticky at or above its Tg) or
some extra mold release compounds to prevent sticking to the hot curling iron barrel.

 Page 107
Styling products must vary in physical form, application performance, and the effect on
the hair or styling equipment in order to accomplish the desired style. Styling products
vary in clarity, viscosity, molding capability vs. flow-ability (wet holding), spreadability,
detangling, pH, color, mold release, stiffness, Tg of the resin, shine, tack, and dry times,
body when dry, smoothness, and water/resin/oil contents and ratios.
Many names have been used for these different versions of styling products: the
differences lie in the rheological properties (water or alcohol thin, thick but flowing, thick
but with high yield value/gel), solvents (alcohol vs. water), resin choice and
concentrations, and their mode of application: pour-on or spray-on liquid solutions,
glazes, gels, spray gels, shaping gels, working sprays, curl activators, shaping sprays,
spray gel (with actual gels), finishing sprays, shine and hold, creme gels, pomades, and
many more.
There are many styling techniques: wet sets (roller and pincurls), sculpting, finger waves,
wet look, root lift, scrunching, curling iron/marcel/hot iron, blow drying/diffuser/hot
lamps, curly look/curl activator, back combing/ratting/teasing (interfibril interactions are
critical with these techniques), braiding, pressing, singeing, polishing/shine, and
wrapping, to name a few that have been used. These techniques are applied to heads of
hair that are in various stages of condition. These conditions range from virgin to
multidimensionally treated hair. Part or all the hair may have damage levels ranging from
minimal (because the hair has had no treatments) to serve (sun-damaged, permed,
relaxed, tinted, bleached, chlorine pool exposed, and partial or mixed treatments such as
foiling, frosting, and highlighting). Since hair grows a half an inch per month (3) many of
these treatments are repeated at intervals ranging from every month to every 3 to 6
months, to maintain the look. This creates a difference between the quality of the hair at
the scalp end and at the distal ends of the hair. Because of the differences in the qualities
of hair, even hair on the same head, many products are designed to enhance their
properties on hair of different levels of damage and roughness, by making the product
flow smoothly and distribute without tangles.
Aqueous styling techniques generally affect the hydrogen bonds of the hair in contrast to
the effects of reactive treatments like perms, relaxers, hair dye, and bleaches, which
permanently and chemically alter the hair (disulfide bonds are the focus of most of the
changes or damage caused by reactive cosmetic products). Styling, on the other hand,
restructures and reorganizes the appearance of the hair by affecting the hydrogen bonds,
resulting in a change in the curl pattern of the hair.
When hair is modified by the addition of moisture or liquid water, the hydrogen bonds
are broken and the hair softens. In this state, the hair can be molded or distorted. In the
wet and soft state, the hair can be formed into a curled fashion. If the hair is held in this
curled position while it is dried, it will

 Page 108
hold a curled shape until the humidity rises too far or the hair is wetted. It is the job of the
styling product (mostly the resin/polymer) to retard the effects of the changing humidity.
The styling product will help hold the style longer and support the style (perhaps a hair
spray is used to do this). The same is true when curly hair is wetted and then reshaped
into a straight fashionthe hair will stay straight until the humidity rises when the hair will
revert to the natural permanent curly state.
In today's changing market, the styling product is sometimes relied on to perform the
entire job of maintaining the style. In some soft, flowable, and touchable hair styles that
may be shampooed and restyled daily, styling aids are thus used alone without the aid of a
spray to hold the hair in place.
Although the Tg and stiffness of a polymer or formulation are important, interfibril
interaction is the most important factor in styling the hair. High humidity curl retention
and degree of tackiness (ranging from slightly tacky to the touch through very stickyi.e.,
feels like glue in the hands and the hair sticks to the hand) are particularly important
when no hair spray is to be used on the top of the styling product. Volume and control
through interfibril interactions without excessive tack are the keys during building the hair
style.
The hair needs to be placed into the desired position and set into the curl pattern (or
straightened). The tools are applied (comb, dryer, curling iron) to separate the hair or
place the hair in the desired positions, seize the hair in place, and perhaps move the hair
again, etc., all without pulling or distorting the hair or allowing either tool or hands to
inadvertently stick to a section and pull it away, which would destroy the style.
Before beginning to formulate a styling aid, the formulator needs to ascertain what kind
of hair the product is intended for, what styling techniques may be used, and what the
final hair the styles may be. If it is determined how the consumer will measure the
efficacy or difference between a new and an old product, the formulator can develop
similar lab test methods and salon tests to simulate the same evaluations the consumer
would use at home. Skeletal formulas for some of the product types listed above follow.
Liquids, lotions, working sprays, curl activators, and shaping sprays can all be very low
in viscosityi.e., 5 to 1000 cps. They can be applied from a squeeze bottle, vial, or spray
pump directly onto the hair, and then dried to create the desired or needed effect. The
concentration of the polymers and ancillary ingredients will depend on the desired final
feel on the hair, the styling technique to be used (wet set vs. blow dry, etc.), and the
amount of product to be applied (0.5 to 18.0 g).
The viscosity of each of these types is usually determined by the polymers, solutions, or
emulsion formulations; no rheological additives are used. They are simply solutions or
emulsions that are watery or alcohol thin up to low-viscosity products that give none to
slight adhesion between hairs during the wet styling

 Page 109
stage (the hairs do not clump or hold together or hold hair in a particular shape). The
stiffness, curl retention, and flaking will depend primarily on the resin/polymer used. The
polymer film is then modified (usually plasticized and softened) by the ancillary
ingredients, including the fragrance and solubilizer.
The basic historical and current framework for these products is built around PVP,
PVP/VA, PVP/dimethylaminoethyl methacrylate copolymers, polyquaternium numbers 4,
11, 28, PVP/vinyl caprylactam/dimethylaminoethyl methacrylate terpolymers, and an
assortment of other polymers including proteins plus all the excipients such as
solubilizers, emulsifiers, antistats (alkyl quats), glycols, and concept (active) ingredients.
The level of each of the ingredients will determine if the product will be stiff, soft, sticky,
flexible, clear, or flaky.
For example, PVP (polyvinylpyrrolidone) polymers are very crispy in arid conditions.
(PVP's stiffness is related to its molecular weight; i.e., a K-value of 90 is stiffer gram per
gram than a K-value of 30) (4) but softer when exposed to high humidity. It is easy to
plasticize the dried resin film by adding humectants to the formulation such as polyols,
salts, or other hydrogen bonding molecules such as ethoxylates (i.e., ethoxylated fatty
alcohols used for solubilizers). As the product dries and the film concentrates, perhaps
over 10- or 20-fold, any ingredient at 0.5% or even less can dramatically affect the
attributes of the film and resin. Any ingredient that absorbs moisture or remains as a
liquid in the dried film will make the film more flexible and reduce flaking. The fatty type
(either nonionic or cationic) products may add a smoother feel or hand to the hair and
reduce static. Usually, combinations of the above are used to add smoothness, flexibility,
body, and feel to a hair styling product.
For the polymer to be effective, it must be able to adhere to the hair. If the adhesion to the
hair isn't adequate, flaking will result. This can be seen either on the comb or brush, on
the hair itself, or on the clothes. If the polymer is highly plasticized, the polymer film will
be soft (perhaps even tacky). Some degree of tack is usually desirable to indicate
successful styling and body building. In the future, the consumer (and professional) will
actually accept styling products with little or no tack time during the dry-down stage of a
styling product.
Generally, a styling product may not be tacky at all in the as is state. The water or solvent
content in the formula is high enough to prevent any adhesive properties at the onset of
application. However, as the water (or solvent) begins to evaporate, the concentration of
the resin (and ancillary ingredients) rises, the viscosity increases, and tackiness develops.
Depending on the properties of solvent, resin, and resin modifiers (ancillary ingredients)
at the varying reduced levels of solvent during the drying stages, the tack can last a short
time and have low amplitude (gram forcemeasured by pinching the fingers together
followed by separating the fingers and making an assessment of how hard it is to pull the
fingers apart, or making a fist, squeezing the product in the fold of

 Page 110
the elbow, or using measuring instruments (4); or, it can be sustained for several minutes
with very high amplitude (very sticky; high gram force of adhesiveness); or be sustained
for several minutes with low amplitude. Formulations can be made to alter the dry-down
characteristics in any of these combinations.
As previously mentioned, the hair is affected by moisture in the air as well as liquid
water. Polymers and additives are also affected by moisture and water. A good product
will be easy to apply to the hair for the targeted styling technique and hair style, be
compatible with the desired additives or system, and be able to be removed from the hair
in such a manner that buildup and an unnatural or unwanted look and feel won't be
produced.
Any hygroscopic material will either keep moisture in/on the fiber/resin longer or attract
moisture to the hair/resin. Generally, the higher the moisture level, the softer or more
flexible the resin or hair will be. An increase in moisture will cause the hair to revert back
to the natural/permanent shape determined by the disulfide bonds, resulting in either a
droop of the curl to a straight appearance or curl up from a straightened style (5). In
either case, the style that was intended would not be maintained. In addition, too much
hygroscopic material may cause the tacky stage to be prolonged to an undesirable length
of time (the intensity of the tackiness may also be increased). A slight amount of tackiness
is usually expected to indicate to the user that the product is working, but too much tack
will cause the hair to stick to the hands or implements to a point of making it difficult to
style the hair, or even pulling out hairs.
III.#Prototype Formulations
The product shown in Table 1 would be dispensed into the hand or directly on the hair
using a bottle with a small orifice or spray (as the molecular weight and concentration of
the resin increase, the spray will become coarser or not be sprayable).
The lotion shown in Table 2 would be applied from a bottle with a 1- to 3-mm orifice.
The product shown in Table 3 would typically be dispensed with a spray pump into the
hair. However, it could be applied via a squirt bottle or bottle with a dispenser with a 1-
mm orifice onto the hands or directly onto the hair. The benefit of distributing the
product directly to the hair is that the hands never touch the product. The product can be
evenly distributed to all portions or selectively to sections of the hair style merely by
spraying a fine mist. Previous methods required applying the solution to the hands
followed by distribution of the lotion throughout the hair before drying. The hands would
then be rinsed to prevent them from becoming sticky.
The formula shown in Table 4 uses a hair spray resin for styling, for a different feel from
the standard setting resin. This format has also been called a spray gel, but it contains no
rheological additive.

 Page 111
Table 1 Setting Lotion
% wt/wt
DI water Qs to 100
PVP K-30, -60, or -90 28
Preservative Qs
Solubilizer Qs
Fragrance Qs
Color Qs
pH 47
Viscosity 550 cps

Table 2 Blow-Dry Lotion

% wt/wt
DI water Qs to 100
PVP/dimethylaminoethyl methacrylate 416
Propylene glycol 0.21.0
Quaternium-26a 0.20.5
Solubilizer Qs
Fragrance Qs
Preservative Qs
pH 5.57.0
Viscosity 5500 cps
aQuarternium-26 (a monoalkyl quat) is added for
additional antistat properties needed for extra
brushing or manipulation during blow drying. This
lotion would be applied from a bottle with a 1- to
3-mm orifice.

The formula shown in Table 5 adds a film of nondrying and hygroscopic polyol
(propylene glycol and glycerin) to maintain moisture and softness plus a small amount of
resin to add some control.
This product can be applied using a spray pump (at the lower levels of glycols) or a bottle
with a 1- to 3-mm orifice either into the hands or directly onto the hair. This product type
was very popular for curly hair and for curly hair that had been permed to a larger curl
pattern with thioglycolates. Now it is seeing application to hair that has been permed,
colored, bleached, and highlighted, because of its softening attributes as well as its curl
activation. A curl that has been straightened out by mechanical and moisture forces (such
as sleeping on the hair and waking with one side crushed and flat, often referred to as
pillow hair or hat hair) can be reactivated to its curled position by spraying on a small
amount of this product type and manipulating the hair with the fingers to push the hair
back into the curled position.

 Page 112
Table 3 Working Spray (spray gel/no gel)a
% wt/wt
DI water 1060
SDA 40 Bb 1080
PVP/VA (50% in water, 70% PVP 30% VA
312
ratio
Glycerin 0.10.5
Solubilizer/preservative Qs
Cyclomethiconec 15
8100
Viscosity
cps
aThis is similar to the first spray gels that were
introduced as a new product category: a cross between
a setting lotion and a hair spray, a sprayed-on lotion that
contained no rheological additive to create a gel, in
contrast to the new versions, which are visually
obviously thick gels.
bBe aware that the levels of alcohol may be regulated
differently around the globe, possibly based on an
extension of the 1993 VOC regulations that originated
in California, as well as concerns or storage and
shipping due to flammability.
cCyclomethicone is added for antitack effect.

Table 4 Shaping Spray (spray gel/no gel)

% wt/wt
DI water Qs to 100
SDA 40B 1580
Ethyl ester PVM/MA copolymer 310
Aminomethyl propanol Qs~10-mole%
Quaternium-26 0.1
Preservative 0.0-Qs
Solubilizer/fragrance Qs
Viscosity 8100 cps

Quite often, products based on the formula shown in Table 6 can be used to create the
wet-look style. The product is applied and the hair is combed in place and allowed to dry
without moving the hair. The product dries with a high gloss and a low degree of
stiffness. Polymer and additive choice will affect the shine and stiffness. Because of the
high molecular weight of some of the polymers, the hairs will associate with each other
through adhesion, which will allow the tracks of the comb or fingers to show. Styling
damaged hair with these polymers is advantageous because these cationic polymers
associate with the anionic cysteic acid sites of the damaged hair and provide a smooth feel
during application, rinse out, or shampooing (6).
Products made from the base above could be used for wet set, blow dry, or wet-look-type
styling techniques. The wet set and blow dry types require more

 Page 113
Table 5 Curl Activator
% wt/wt
DI water Qs to 100
Propylene glycol 1030
Glycerin 1030
PVP/VA (50% active, 70% PVP 30% VA
210
ratio)
Preservative Qs
Solubilizer/fragrance Qs
10300
Viscosity
cps

Table 6 Sculpting Lotion

% wt/wt
DI Water Qs
Polyquaternium 11, 28, 4, 10, 7, etc. 0.12.0 (active)
Solubilizer/fragrance Qs
Preservative Qs
Concept ingredients Qs
Viscosity 1005000 cps

attention to antistat properties due to the excessive brushing or handling of the hair. Static
is somewhat attenuated by the use of cationic polymers. However, mono-or dialkyl quats
are added at 0.1% to 0.5% to drastically reduce static during the brushing stage. The alkyl
quats will add flexibility and additional smoothness to the hair. Propylene glycol and
other polyols or hygroscopic materials help dissipate charge either as water does or by
actually maintaining a higher level of water or moisture in (or on) the vicinity of the hair.
IV.
Styling Wet Hair
The previously discussed styling products provided relatively little holding or shaping
control to the style during the wet stage. After the styling products are applied to the hair,
the hair falls into place as dictated by its curl pattern and the force of gravity.
Cellulose or saccharide-type rheological additives (hydroxyethylcellulose, guar gums,
carboxymethylcellulose, hydroxypropylmethylcellulose, carrageenan, etc.) will usually
add adhesion between hairs, supply smoothness and detangling during distribution, and
prevent dripping. However, due to their ability to flow under merely the effect of gravity,
they are unable to hold the hair in place until it dries (some natural products like Karaya
and Xanthan as well as some syn-

 Page 114
thetic polymers as discussed above can provide moderate hold while wet if formulated
with that end in mind). Therefore, the hair must be held in place with curlers, clips,
brushes, or other devices to control the shape of the hair while it is dried. This section
will discuss formulations that supply a little to very much wet strength holding power;
i.e., these products could hold the hair in place until dry.
Low levels of hydroxyethylcellulose (or others derivatives of cellulose), some natural
gums, and low levels of polycarboxylic acid polymers can provide low-viscosity, easy-to-
spread hair-setting products that carry the active polymer to the hair and provide the
adhesion between the hairs as well as the slip and detangling effects. In most all cases, the
final pH is critical to create and maintain the viscosity over the projected shelf life of the
product. Always consult the ingredient manufacturer's literature to determine the optimum
pH for efficient rheological control and long-term stability and compatibility with active
ingredients.
To have gels that have a yield value sufficient to hold the hair in place (against the will of
the natural position of the hair or gravity), the formula generally needs a polymer system
that doesn't flow under its own weightfor example, the polycarboxylic acid polymers, i.e.,
carbomers and PVM/MA decadiene crosspolymers. Even though these two polymer types
create gels that do not flow under gravity, they do exhibit shear thinning. This allows
them to be easily spread across the hair shaft to produce a film as thin as desired. A thin
film is usually necessary for a natural look and feel, and to minimize flaking. This shear
thinning ability has allowed the creation of a true spray gela gel that is dispensed through
a pump sprayer which regains its gellike character on the hair.
These two categories (soft with flow and firm with ability to hold against gravity) can also
be used for blow dry, wet look, wet set, finger wave, and sculpting techniques. At the
onset of the introduction of blow drying, it was thought that anything greater than a low-
viscosity gel would increase excessively the dry time and heaviness of the hair. As the
blow dry technique, blow dryers and formulations improved, gels/glazes/lotions of all
viscosities have been successfully used for blow drying.
V.
Prototype Formulations
Below are prototype formulation examples.
The product shown in Table 7 is obviously a gel when viewed in a clear bottle. It sprays
as a fine mist and then works like a gel again when it contacts the hair. If the product is
sprayed onto all parts of the head of hair, spreading with the hands is eliminated. This
eliminates the sensation of tackiness on the hands.

 Page 115
Table 7 Spray Gel (true gel type)
% wt/wt
DI water Qs to 100
PVM/MA decadiene cross-
0.25
polymer
PVP K-30 2.0
Preservative/solubilizer/fragrance Qs
NaOH (10% solution) 0.5
pH 5.07.0
Viscosity 600010,000 cps
Calmar, Precision,
Pumps
Emson, Seaquista
aAdvances in pump and spray technology are very
rapid. Check with these suppliers and others for their
up-to-date sprayer for your particular formulation.

Table 8 Glaze
% wt/wt
DI water Qs to 100
Hydroxyethylcellulose (med. visc.
0.51.0
grade)
1.08.0
PVP, PVP/VA copolymer, etc.
active
Alkyl quat, i.e., quaternium-26 0.10.5
Preservatives/solubilizer/fragrance Qs
pH 5.87.0
7502500
Viscosity
cps

The glaze shown in Table 8 is an easy-to-spread flowable gel good for the wet look or
blow dry styling methods. Much higher levels of a higher viscosity grade cellulosics
would be slimy and difficult to spread.
The gel shown in Table 9 has a yield value sufficient to hold stubborn curly hair in a
straight position until it dries; it can also hold stubborn straight hair in a flat position or
finger wave until it dries. Because of the shear thinning ability, it spreads very thin, so it
works well as a blow dry product. These gels are normally produced as clear gels. In
today's market, which sports a significant level of people with chemically processed hair,
opaque gels are being made that are suspensions of esters, oils, or silicones at 0.05% to
15.0% incorporated into a base similar to the one in Table 9. These non-water-soluble
additives impart reduced tack, increased suppleness, sheen, smoothness, and flexibility to
the styled hair for people who have rough, fragile hair and have always steered away
from styling products because of their stiffness and tackiness.

 Page 116
Table 9 Gel
% wt/wt
DI water Qs
PVM/MA decadiene cross-
0.51.0
polymer
PVP K-30, -60, or -90 1.08.0
NaOH (10% solution) Qs to pH 5.07.0
Preservative/solubilizer/fragrance Qs
Additives Qs
Viscosity 50,000100,000 cps
Brookfield RVT #7 at 20
rpm

In all cases, the order of addition and processing variables can affect the clarity, viscosity,
and stability of the suggested formulations. In addition to what is discussed here, consult
the ingredient manufacturer's suggested protocols for ideas and limitations in formulation
conditions for combinations of materials to obtain the desired results. Stability and
performance are affected by the order of addition, pH, and type and duration of mixing.
VI.
Old vs. New Products
Wet and dry styling products include old and new ideas and slants on an old theme. With
today's lifestyles, hairstyles, and styling techniques, we are seeing new uses for old
products. Even the mousse technique or form wasn't new before it made the big hit in the
1980s for hair (shave cremes and mousse perms had been around for years). The curl
activator (propylene glycol/glycerin type) saw its heyday in the late 1970s and mid-1980s
for a wet look for curly perms.
If these products are looked at in today's light, the following can be noted: The curl
activator has taken on a new approach (with the same intention as beforeto moisten,
moisturize, and enhance the orientation of the curled hair). Today, these products are for
restyling hair the next day, or even just making it easier to form the curls into a more
organized, less frizzy format. Formerly, curl activators had high polyol levels to keep the
treated hair moisturized and flexible. They would exhibit deep luster or shine, but usually
be wet and never dry out.
Today, these same formulas exist, but we also see creations using lighter levels of polyols
with the addition of low levels of styling polymers and herbal extracts, proteins, and other
additives. These are intended to tame the wild hairs while giving just enough moisture to
yield that healthy, undamaged look and feel. These products could be put on as a blow
dry lotion or wet set lotion as well as be used to actually wet the hair temporarily to make
the hair curl up

 Page 117
Table 10 Curl Activator
% wt/wt
DI water Qs to 100
PVP/VA (50% in water, 70% PVP 30% VA ratio) 1.04.0
Preservative/solubilizer/fragrance Qs
Hydrolyzed vegetable protein Qs
Polyol 0.53.0
Polyquaternium-11 0.51.0
Concept ingredients Qs
Viscosity 550 cps

again to the conformation dictated by the disulfide bond linkageshence the term curl
activator. This has made a great hit in the after-perm market.
VII.
Prototype Formulations
The product shown in Table 10 could be dispensed from a spray pump or a small orifice
into the hands or directly onto the hair. Styling techniques could include squeezing,
pushing, and scrunching the hair in the palms of the hands or fingers in order to help the
water penetrate the hair and then push the hair into the curl pattern of choice.
Some other forms of styling products include the following products:
1. Shine products range from pump and aerosols to liquid drops of oils, esters, or
silicones that are applied as a modifier to any of the previously discussed styling aids to
add shine or enhance smoothness and remove tackiness of just about any style. One of
the drawbacks of these formulas is their high cost due to their lack of water. However,
since the activities are not water soluble and their incorporation into the typical styling
products would not result in clear products, or upon solubilization would lose their shine
and lubricity, these products have been marketed as anhydrous products diluted with a
solvent to aid their application and distribution to the hair. Since they are not water
soluble, quite often they can remove most if not all of the tackiness of the styling product
while at the same time, add shine.
Styling gels with a good yield value have also incorporated these esters/oils/silicones as
dispersions to yield a milky/icy/or opaque gel that provide styling control while adding
softness/less tack/and more shine.
2. Pomades may be petrolatum and microcrystalline wax-based products. They utilize a
stiff rheology and hydrophobic properties to hold curly hair in an uncurled position while
preventing water or moisture from entering the hair,

 Page 118
which would cause the hair to curl up again. A drawback is poor shampoo removability
and transfer to pillows and car windows. Incorporation of low to medium HLB (7)
surfactants into the petrolatum allows for enhanced removability. Another drawback is
the heaviness on fine or limp hair. In the mid 1980s through late 1990s, these pomades
saw several attempts to hit the fashion market againnot just for curly hair, but even for
straight hair. With increased processing of hairperms and color, and the attention to the
aging of Americakeeping hair feeling and looking natural and young has prompted the
resurgence and broadening the application of this line of products to a wider range of
users.
3. The grunge look was fashionable in the early 1990s, replacing the dry look. Products
were used to make the hair style look lived in instead of freshly washed. This was an
attempt to cover up the extensive damage due to cosmetic chemical treatments made on
the hairhighlighting, color, perms, and bleaches.
It was also a diversion from the preppy GQ look of extra clean to a rough and rugged,
street-tough look. For this modification of hair look and feel, products were based on
liquid pomades, either anhydrous, microemulsions (sometimes ringing gels) or solutions
of fatty ethoxylates. The microemulsions and solutions were much easier to remove than
the petrolatum grease products.
As the styles and fashion change, the needs of the hairstylist and consumer will change.
This demand will give the cosmetic chemist the opportunity to explore new combinations
of ingredients to produce hybrid or new formulations for specific effects.
VIII.
Aerosol Foam Mousses
Aerosol mousses are styling and/or conditioning aids that can be used on both wet and
dry hair, and that can be either washed out or left in the hair. They allow the hair to be
recombed or restyled several times without repeat application. The foam produced by the
aerosol gives a uniform coverage of the product for optimized benefits of ease of
combing, conditioning, and style retention.
Aerosol foams are of course not new to the cosmetic industry; shaving foams have been
around for many years. The characteristic mousse foam consistency was less common but
not new. The mousse product delivers what no other styling formula delivershold and
softness. It is fast (a dab of mousse works in seconds), and shapes a style in the time it
takes to run your fingers through your hair. The use of a mousse allows a consumer to
instantly change the look, the mood of her hair; and it gives volume to fine, thin hair. A
mousse can alter the direction of curls and waves, transform a dry look into a wet look,
tame unruly curls and waves, and take a style from casual to sophisticated.
Mousses are different from other styling aids in that when properly formulated, they don't
leave hair stiff or sticky. A mousse is applied by first discharging into the palm of the
hand an amount variously described in the

 Page 119
directions as the size of a ping pong ball, golf ball, egg, etc., depending on the length of
the hair and the particular formulation. The stiff foam retains its shape at this stage,
making measurement easy and fairly precise. With a little experience, the user soon learns
the correct amount for her hair. The foam is then spread evenly through the towel-dried,
shampooed hair, before combing; or to dry hair; and styled by any conventional
techniqueblow drying, finger drying, etc. Most mousses are designed to be used without a
rinsing step and include instructions to this effect. Once the hair is dry, the
styling/conditioning polymer provides the end style/holding benefit.
A.
History of Mousses
The story of the mousse begins in the early 1970s, when several companies developed
aerosol styling foam products; but they didn't develop a market for them at that time
because hair styling products did not readily incorporate their use. Helene Curtis was a
leader in this segment coming out with a brand called Balsam & Body, marketed to the
professional salon trade in mid-1973. Helene Curtis followed this product with other
brands such as Last Word and Heats On Self-Heating Foam Conditioner, which evolved
into La Forme (8). This product was applied to their hair when wet and left in.
The mousse (French word for foam) came to the retail sector of North America from
L'Oreal of France as a hair fixative/conditioner in the early 1980s (9). L'Oreal introduced
its product, called Valence styling mousse, in 1983a light, airy foam that melds the
negative charge of anionic polymers with the positive charge of cationic polymers. The
product, said to give hair a natural control, was available in soft and firm control versions
and sold for $6.95.
L'Oreal introduced a companion product which provided conditioning, called Flone
conditioning mousse. Unlike current mousses, this product was a conditioner, not a
styling aid. It was available as a moisturizing foam, which hydrates to restore and
maintain the moisture balance of dry to normal hair; and a bodifying version, which
added body, volume, and texture to hair. These products conditioned the hair in 1 to 3
minutes and had to be rinsed out.
The third and most popular mousse offering was the Freehold line. These mousses
touched off a stampede of imitations and me-too products by other manufacturers in 1983
(10). Within the space of 1 year, the mousse product had developed into a fast-growing
hair care market segment with 1984 domestic retail sales in the range of $100 million to
$150 million (11). In that first year, Freehold captured 43% of this market (12). By the end
of 1985, consumers spent over $100 million on mousses for 40 different kinds of
products. In 1986, mousses still remained popular, with nearly $200 million in retail sales.
By 1986, there were 50 different brands available and over 200 SKUs of mousse in the
market. Alberto Culver, Clairol, Revlon, Vidal Sassoon, and L'Oreal were among the top
brands. Although mousses were popular, research conducted by

 Page 120
Kline & Co. indicated that other product forms started to gain in popularity due to a
change in the hair styles.
Products were differentiated by styling, conditioning, bodifying/volumizing, hold factor,
moisturizing, adding color, adding sunscreen, adding shine, alcohol-free, and also by hair
type (10). Seemingly overnight, consumers began layering their styling aids, using
mousses and gels, and finishing off the hair style with a hair spray.
The year for styling aids was 1987. It started with mousse, and then consumers wanted
extra body and more and more hold. It was that year that styling mousses were
relaunched as alcohol-free products. At that time, the category became very crowded, and
changes in hair style trends led to the demise of the mousse as consumers returned to
more formal, less natural, more feminine hair which required more robust styling
products to hold their shape. In 1987, the styling spritz evolved and the mousse declined.
Beginning in 1987, mousses decreased because of changes in hair care practices and
environmental concerns about ozone depletion. In 1993, the California Air Resource
Board (CARB) regulated the amount of volatile organic content (VOC) for mousses from
a range of 12% to 27% down to 16%. Other states have followed suit, and the EPA has
proposed a consumer product rule to restrict the VOCs across the nation. The maximum
of VOCs in a mousse is 16%. To meet the current restrictions in the United States, for
VOCs, extra solvents such as water must be added at the expense of less propellant and/or
alcohol. The net effect of this change is a wetter foam.
B.
Theory of Product Performance
Mousses, setting lotions, styling sprays, and gels are all formulated with polymeric resins
as the active ingredients. These are long-chain molecules that form a film on hair. The
principal difference in polymers employed in mousses is that they are positively charged.
Hair is electronegative, so these polymers cling more tightly to the hair strands, are harder
to brush off, and form a more resilient film. This enables consumers to comb or brush
their hair and subject it to the heat of a blow dryer without removing the mousse or
leaving the hair stiff.
It is the choice of specific ingredients that makes one mousse different from another. The
first ingredient listed on most mousse cans is water. Water is still the best solvent for
mixing various chemical substances together. Alcohol can be used as a cosolvent to help
dissolve the ingredients in the water. Alcohol also helps to produce a quick-breaking
foam. Alcohol in leave-on products does not remove natural lipids or dry the hair, but
consumers have voiced their concerns in market research tests of alcohol drying out their
hair. These concerns have resulted in the introduction of alcohol-free mousses.
The next ingredient employed is the polymer or resin. Polymers are the

 Page 121
most effective and important functional component of mousses. They act primarily as the
conditioning and/or fixative agent and are therefore instrumental as film formers. While
the most common conditioning polymers are usually quaternized, this feature does not
appear to be required for mousses. Polymers containing tertiary amine groups which are
protonated at the pH of the formulated product are still cationic and therefore substantive
to hair (13).
The balance of properties may be shifted from conditioning toward setting by blending
the cationic resin with another film former to give a firmer hold. The polymer chosen
should be nonionic in nature and have good compatibility with the cationic resin. It is
also possible to combine the cationic polymer with an anionic polymer such as
monoesters of poly (vinyl methyl ether/maleic acid)e.g., Gantrez copolymersas evidenced
by an inspection of various mousse products on the market. L'Oreal's Freehold formulas
include a blend of two polymersa polymer with a positive (conditioning) charge, and one
with a negative (style and body building) charge. Researchers from L'Oreal showed that
cationic conditioning polymers could be mixed with anionic fixative polymers to give a
dual benefitconditioning and hold from the same formulation (14). Likewise, work at
Unilever discovered that conditioning and fixative properties could be conferred
simultaneously from a composition containing polyquaternium-10, and an anionic poly
(Potassium Methacrylate) (15), as well as work conducted at Dow Corning with
formulations containing carboxyfunctional silicone and a cationic polymer such as
polyquaterniums-4, -7, -10, and -11 (16).
Other ingredients listed on the mousse label are classified as plasticizers and conditioners.
These ingredients help determine the manageability of hair and/or the stickiness of the
formula; they have differing results depending on the proportions in which they are used.
Emulsifiers are used to help blend the product into a foam. These surface-active agents
are an integral component of foam product formulations. Because of their amphiphilic
nature, they tend to aggregate at the inferfacial region, the hydrophobic alkyl groups
extending into the oil phase, and the hydrophilic groups into the continuous aqueous
phase.
Substantial experimental evidence demonstrates that the surfactants complex to form
liquid crystal structures in the interfacial region (17). The choice of surfactant and its level
can alter foam stability. Mousses do not require lengthy foam stability; ideally, the foam
should break very quickly when worked into the hair. This may be achieved by using
lower amounts of surfactants and choosing ingredients that are nonionic in nature. The
surfactant's primary role is to reduce the surface tension-to-volume ratio of individual
microscopic bubbles formed by the dispensing unit.
For claims purposes or to penetrate a niche in the market, other ingredients may also be
used in mousse formulations. Many formulators include vitamins, silicones, sunscreens,
dyes, etc., to this end. These are the so-called claim ingredients utilized in virtually all
categories of personal care products.

 Page 122
C.
Formulation
Table 11 shows the essential components of an aerosol foam mousse. A delicate balance
exists between these ingredients. Any change in their ratios may cause the product to
separate into layers. Unless the alcohol content is very high, the propellant will normally
form a separate immiscible layer. Shaking the aerosol can immediately before use will
emulsify the ingredients. The consequences of nonhomogeneous concentrates that are not
shaken would include inconsistent product characteristics such as too liquid or soupy-
looking foam, too dry a foam, incomplete exhaustion, etc.
As the emulsion emerges from the nozzle, expansion of the vaporizing propellant droplets
produces the foam stabilized by the presence of the surfactant. The technology of aerosol
foam is quite complex. A number of variables can affect the texture and stability of the
foam. For a detailed discussion of the subject, the reader is referred to publications by
Sciarra and Stoller (18) and Johnsen (19). A typical mousse formulation is shown in
Table 12.
D.
Solvent
The solvent base for aerosol mousses is typically water. Products made in the past also
contained 4% to 15% SD alcohol 40 before the VOC reduction regulations. Recent
introductions have largely been alcohol-free systems. The net effect is a wetter foam. The
solvent concentrate and propellant form a two-phase system. The aerosol can must be
shaken immediately before use to recombine the layers. A surfactant or surfactant mixture
provides foam stability.
E.
Propellant
The selection of propellant used to prepare an aerosol foam is very important, as the
choice will dictate the foam's texture and stability. Foams can be made with very small
bubbles and thus appear relatively dry, or they can have large bubbles appearing coarse
and wet. Too much or too little propellant, coupled with unbalanced quantities of
surfactant or polymers, can damage the foam's characteristics. Halogenated propellants
such as 1,1-difluoroethane (HF-152a) generally produce foams with very small, uniform-
size bubbles. This is due to their pronounced surface activity resulting in low surface
tension. Hydrocarbons such as propane/isobutane mixtures (typically A-46 blend) tend to
give forms which are stiff due to their nonpolar nature. Using a blend of HF-152a and
hydrocarbon propellants yields foams of various appearance from lotionlike to stiff
semisolid, depending on the blend ratio. A traditional aerosol foam mousse would contain
5% to 15% w/w of a propellant blend such as propane/isobutane. Lower vapor pressure
propellant such as n-Butane (A-17) are also effective foam expanding agents because of
their slow release from the foam after discharge of the product from the can. By varying
the propellant system compo-

 Page 123
Table 11 Aerosol Foam Mousse
Solvent
Active ingredient(s)/polymer(s)
Propellant(s)
Emulsifier/surfactant
Preservative
Fragrance
Miscellaneous

Table 12 Ingredients by Weight (%)

Ingredient % by Weight
Water QS to 100%
SD alcohol 40 08
Propellant 815
Polymer 15
Nonionic emulsifier/surfactant 0.53.0
Corrosion inhibitor 01
Fragrance 0.10.5
Preservative 01
Miscellaneous/claim Ingredients 01

sitions, the physical properties of the resultant foams can be optimized for the particular
product application (20).
F.
Surfactant
The choice of surfactant in an aerosol foam mousse is also quite critical, since the foam
must have sufficiently initial stability yet break down fairly rapidly under the action of
rubbing through the hair. This short-term stability is achieved by reducing the level of
surfactant, adding a nonionic fatty-acid derived surfactant or long-chain fatty alcohol, or
using a surfactant with an HLB value in the range of 12 to 16. Commonly used surfactants
in an aerosol foam mousse are PEG-23-lauroyl ether (Laureth-23), laureth-7, PEG-150
distearate, oleth-20, quaternium-52, cocamine oxide, cocamide DEA, octoxynol-9,
emulsifying wax and cocamidopropylbetaine. Typical use levels are 0.5% to 3.0%;
preferred levels are 0.5% to 1.0%.
G.
Polymer/Resin
The polymer is the most effective and important functional component of the aerosol
foam mousse. Polymers act primarily as the conditioning and/or fixa-

 Page 124
tive agent. Cationic water-soluble polymers are preferred for conditioning mousses.
However, these polymers do not have good setting/hold properties. The difference
between a mousse and a hair spray lies in the solvent, the alcohol in the hair spray being
largely replaced by water. A key attribute for the mousse resin, then, is its need to be
compatible in aqueous solutions. Table 13 lists the hair fixative polymers commonly used
in mousse products.
For mousse applications, the carboxylated resins such as the ethyl ester of PVM/MA
copolymers (Gantrez ES copolymers) will require a greater degree of neutralization than is
usual for hair sprays. The nature of the neutralizing agent will also contribute to foam
attributes. These PVM/MA copolymers neutralized to 50% with aminomethyl propanol
(AMP-95) will produce a more stable foam than when this copolymer is neutralized with
ammonium hydroxide. This is due to the greater water solubility of the ammonia salt than
of the AMP salt (21). Research conducted by both L'Oreal and Unilever discovered that
conditioning and fixative properties could be conferred simultaneously by combining a
cationic polymer with an anionic polymer. Several patents cover these technologies and
have been discussed previously in this chapter. Dow Corning also has developed
formulations containing a carboxyl functional silicone and a cationic polymer.
Polyquaterniums-4, -7, -10, and -11 are claimed to give a conditioning effect along with
hair setting by means of a flexible film on the hair which allows combing without losing
hold, without flaking, and give retention of hair shape over extended periods of time even
under humid conditions.
H.
Polymer Quaternization
While the most common conditioning polymers used are quaternized, this feature does
not appear to be required in mousse formulations. Work completed by Petter and Murphy
(22) found no significant differences between the performances of quaternized and
unquaternized polymers.
I.
Additives
Other ingredients listed on a mousse label are classified as plasticizers, conditioners,
moisturizers, color enhancers, sunscreens, foam-in/wash-out hair color, botanicals,
vitamins, etc. These ingredients determine the manageability of hair and/or the stickiness
of the formulation, as well as for claim substantiation. The amounts of these ingredients
will impact the final formulation. Use them judiciously.
J.
Packaging and Delivery Systems
1.
Containers
The dispensing system plays a paramount role in aerosol foam mousses. Aluminum
dispensers remain popular because they do not experience the corrosion

 Page 125
Table 13 Hair Fixative Polymers Commonly Used in Mousse Products
INCI name Trade name Supplier
National
Polyquaternium-4 Celquat H 100, L200
Starch
Polyquaternium-11 Gafquat 734,755N
ISP,
Luviquat PQ-11
BASF
Ethyl ester of PVM/MA Gantrez ES-225
ISP
copolymer Omnirez 2000
Butyl ester of PVM/MA Gantrez ES-425
ISP
copolymer Gantrez A-425
Octylacrylamide/
Amophomer Amphomer LV- National
acrylates butylaminoethyl
71 Lovocryl-47 Starch
methacrylate copolymer
Polyquaternium-39 Merquat Plus 3330 Calgon
Polyquaternium-2 Merquat 295 Calgon
Vinyl acetate/crotonic acid National
Resyn 28-1310
copolymer Starch
VA/crotonates/vinyl National
Resyn 28-2930
neodecanoate copolymer Starch
PVP/VA E-735
PVP/VA E-635
ISP,
PVP/VA copolymer PVP/VA S-630
BASF
PVP/VA W-735
Luviskol VA 64
PVP/acrylates copolymer Luviflex VBM 35 BASF
PVP/dimethylaminoethylmeth-
Copolymers 845, 937, 958 ISP
acrylate copolymer
Guar hydroxypropyl Rhône-
Jaquar C135, C16S, C17
trimonium chloride Poulenc
Vinyl caprolactam/PVP/
Gaffix VC-713
dimethylaminoethyl methacrylate ISP
H2OLD EP-1
copolymer
Polyquaternium-28 Gafquat HS-100 ISP
PVP and dimethicone PVP/Si-10 ISP
Polyquaternium-28 and
Gafquat Hsi ISP
dimethicone
Polyquaternium-46 Luviquat Hold BASF

problems that may plague steel cans. Typically, organosol is used as the internal coating or
lining for product compatibility.
2.
Valve Assembly
A typical valve specification uses a stem with 2 × 0.5 mm orifices in a slotted housing
without a dip tube fitted with a vertical spout actuator. This inverted

 Page 126
configuration is convenient for measuring the foam into the hand and also avoids
problems that can occur when a dip tube is fitted for upright discharge. Most major valve
manufacturers can supply suitable valves to the manufacturer desiring to produce a
mousse.
IX.
Nonaerosol Foam Mousse
Nonaerosol foam mousse prototypes are another type of product. These products were
developed owing to the continued attack on aerosols as a class and to provide for
environmentally desirable options such as refillability. Several manufacturers have
developed packaging designed to dispense mousses without the aerosol. This product
form has similar ingredients to the aerosol mousse except it does not utilize propellants to
produce a foam. It uses special dispensing systems for the products to work. Examples of
these products are Airspray's Airspray Foamer and newer Jet Foamer with a flex-spout
head for precise dosages. EP Spray also has a system which utilizes a new actuator button
on its air powered barrier pack that delivers a foam without the use of propellants.
A.
Spray Mousses
Several new entries into this mature market have been spray mousses. These products are
dispensed as a spray or gel which foams up upon actuation. These products contain a
highly volatile liquid or liquefied gas such as n-pentane or isopentane which upon
actuation flash off and cause the resulting product to foam up in the hand or on the hair.
Examples of these products are Dep Corporation's DEP Mousse 'N Gel and Los Angeles
Research Packaging's L.A. Looks Gel 2 Mousse products.
B.
Formulations
Sample formulations are presented in Tables 14 to 21.
C.
Evaluation Methods
A formulator must be involved with the two criteria his product will be evaluated against
by the consumer: foam aesthetics and product performance. The former is critical in
getting the consumer to initially apply the product to their hair while the latter can assure
repeat usage.
D.
Foam Properties
Consumers generally evaluate a foam product by various subjective criteria. Some are
interested in how quickly a foam breaks (stability of the foam), others desire a rich
luxurious product, while still others want a stiff foam that

 Page 127
Table 14 Quick-Breaking Extrahold Styling Mousse
% by
INCI Name
Weight
QS to
Water
100%
SD Alcohol 40B 4.00
Polyquaternium-4 1.25
Polyquaternium-11 1.00
Amodimethicone (and) Tallowtrimonium
0.20
Chloride (and) Nonoxynol-10
PEG-150 Distearate 0.25
Quaternium-52 0.30
Hydrolyzed Wheat Collagen 0.20
Polysorbate-20 0.30
Fragrance 0.150.30
Isobutane/Propane Blend (A-46) propellant 8.00
Total 100.00

Table 15 Styling Mousse

% by
INCI Name
Weight
QS to
Water
100%
SD alcohol 40B 3.50
PVP/VA copolymer 4.00
Amodimethicone (and) tallowtrimonium chloride
0.15
(and) nonoxynol-10
Cocamine oxide 0.50
Cocamide DEA 0.10
Hydrolyzed wheat collagen 0.20
Panthenol 0.05
Fragrance 0.20
Isobutane/propane (A-46) propellant 8.00
Total 100.00

scrunches when they touch it. As stated previously in this chapter, the major ingredients
and their proportion in the formulation will have a major impact on the foam's
characteristics. The solvent, type of propellant, and selection of surfactant(s) can all alter
the foam stability. To produce longer-lasting, stable foams, a relatively high level of a
mixed surfactant system may be needed. Mousses do not require lengthy foam stability;
ideally, the foam should break very quickly when worked into the hair. This is achieved
by utilizing lower

 Page 128
Table 16 Hair Conditioning/Styling Mousse With Shine
% by
INCI Name
Weight
QS to
Water
100%
Polyquaternium-11 5.00
Vinyl caprolactam/PVP/dimethylaminoethyl
3.00
methacrylate copolymer
Oleth-20 0.50
Panthenol 0.05
Propylene glycol (and) diazolidinyl urea (and)
0.40
methylparaben (and) propylparaben
Dimethicone copolyol 0.10
Fragrance 0.15
Isobutane (and) propane (A-46) Propellant 10.00
Total 100.00

Table 17 Conditioning, Antistatic Mousse

(Note: Not a low-VOC formulation)
% by
INCI Name
Weight
Water QS to 100%
PVP/Dimethylaminoethylmethacrylate
10.00
copolymer
Emulphor ON-870 0.50
SD alcohol 40B 15.00
Fragrance 0.10
Isobutane (and) propane (A-46) propellant 15.00
Total 100.00

amounts of surfactant and choosing those which are nonionic in nature. Increasing the
proportion of alcohol will generally tend to decrease the stability of the mousse foam. The
perceived richness of a foam may be evaluated quantitatively by measuring the foam
density.
E.
Foam Density Measurement
A common procedure to measure foam density is to fill a wide-mouth glass jar of known
volume with foam. It is often necessary to attach a long tube (plastic straw) to the nozzle
of the sample can. The tubing allows the foam to fill the jar from the bottom, preventing
the entrapment of air in the sample. Excess foam is removed with a straight edge, and the
density is calculated by dividing the weight by the volume
Calculation for Density = M/V

 Page 129
Table 18 Bodifying Mousse
INCI Name % by Weight
Water QS to 100%
Oleth-20 0.50
Quaternium-52 0.50
Dimethicone copolyol 0.10
Polyquaternium-11 12.50
Panthenol 0.05
Hydrolyzed wheat collagen 0.20
DMDM hydantoin 0.20
Fragrance 0.15
HF-152 propellant 5.00
N-butane 5.00
Total 100.00

Table 19 Styling Mousse

INCI Name % by Weight
Water QS to 100%
Polyquaternium-46 5.00
PVP/VA copolymer 4.00
Hydroxyethyl cetyldimonium phosphate 2.00
Panthenol 0.20
Dimethicone copolyol 0.30
Aloe vera gel 1.00
Chamomile extract 1.00
Methychloroisothiazolinone (and) methylisothiazolinone 0.05
PEG-40 hydrogenated castor oil 0.35
Fragrance 0.10
Isobutane (and) propane (A-46) propellant 10.00
Total 100.00

where M = weight of the foam (in grams) and V = known volume of jar (in cc).
Propellant concentration has the most significant impact on foam density. An increased
propellant level leads to decreased foam density.
F.
Foam Stiffness Measurement
The stiffness or structural integrity of a foam may also be quantitatively evaluated in the
lab. Several methods are discussed in the literature. Sanders uti-

 Page 130
Table 20 Firm Hold Styling Mousse
(Note: Not a low-VOC formulation)
% by
INCI Name
Weight
QS to
Water
100%
Polyquaternium-4 2.00
Amodimethicone (and) tallowtrimonium chloride (and)
0.20
nonoxynol-10
Tallowtrimonium chloride and isopropyl alcohol 0.15
Oxtoxynol-9 0.30
Emulsifying wax, NF 0.10
SD alcohol 40B 15.00
Fragrance 0.15
Isobutane (and) propane (A-46) propellant 10.00
Total 100.00

Table 21 Non-Aerosol Styling Moussea

% by
INCI Name
Weight
QS to
Water
100%
PVP K-30 1.00
Polyquaternium-11 5.00
SD alcohol 40B 10.00
Cocamidopropyl betaine, 30% 0.50
PEG-40 hydrogenated castor oil 0.30
Citric acid, 50% aq. soln. 0.03
Propylene glycol (and) diazolidinyl urea (and)
0.30
methylparaben (and) propylparaben
Fragrance 0.20
Total 100.0
aThe formulation is designed for dispensing from a squeeze
pack such as the Supermatic Foamer or AirSpray Foamer
systems.

lized a Cherry-Burnell Curl Tension Meter (23), which measures the force required to
insert a standard knife into the foam at a fixed rate of speed. Breuer and Tsai (24)
developed an Instron method to quantitate stiffness. A quick and simple method is to
utilize a Brookfield RVT Viscometer. Foams are placed in jars as in the foam density
measurement and equilibrated at 25°C, and viscosities are measured using a #6 spindle at
20 RPM. To prevent channeling, only two revolutions of the spindle are run before a
reading is taken.

 Page 131
Calculation for viscosity or stiffness reading using Brookfield RVT Viscometer:
Spindle #6, at 20 RPM
Factor for spindle #6 = 500
Viscosity (cps) = dial reading × 500
Changes in the viscosity or stiffness of the foam can be brought about by changing the
concentrations of the mousse's major components. Increasing the alcohol level decreases
the stiffness. To increase the stiffness of the mousse foam, increase the propellant level,
or use a higher HLB surfactant.
G.
Product Performance
The performance properties of the mousse, whether conditioning or styling, can be
controlled by the choice of resin and its level. The marketing positioning of the product
will dictate the choice and level of resin. In evaluating the performance of a mousse, one
generally considers four major areas or properties: hold or high-humidity curl retention;
conditioning (i.e., lubricity, wet combing work, slip, etc.); buildup of resin on hair; and
tactile properties.
H.
High-Humidity Curl Retention Testing
High-humidity curl retention testing is done for styling products or combination
styling/conditioning products. This method subjects treated hair tresses to stressful curl
relaxation conditions, typically in high humidity and elevated temperature. It is a standard
test run in most hair care labs with minor variations. One such method is as follows:
1. European dark brown hair is subdivided into a series of individual hair swatches each
6.5 inches long, weighing 2.0 g. At least six hair swatches are necessary for each product
under evaluation. For claims support, normally 18 tresses are run for each product.
2. The hair tresses are all washed in 10% shampoo, rinsed thoroughly, and treated with
the test and control products. For mousses, 0.50 g of product is applied to each tress and
combed through the tress to distribute the product evenly.
3. Treated hair swatches are curled using a 5/8-inch outer diameter (OD) mandril; or
alternately a 5/8-inch curler and pinned.
4. Tresses are air dried overnight or placed under the hair dryer for 30 min on high.
5. The hair swatches are carefully unpinned and placed immediately onto a precalibrated
Plexiglas peg board.

 Page 132
6. Initial readings are recorded and then the hair tresses are placed inside the
preconditioned humidity chamber set at 80°F, 90% RH.
7. Swatch length readings are recorded at various prescribed time intervals, usually every
15 min. Humidity and temperature readings are also checked and recorded periodically.
8. Raw data are statistically analyzed at the 95% confidence level, and percent curl
retention is noted.
X.
Hair Characteristics Evaluation
The conditioning properties of a mousse formulation may be evaluated either objectively
or subjectively. Quantitative methods describing measurement of wet combing using an
Instron apparatus are described in the literature (25) and in Chapter 10 of this book.
Qualitative evaluations are also very valuable and can pinpoint various problems with the
formulation. Evaluations are done on both wet and blow-dried hair.
A.
Procedure
1. European dark brown hair is subdivided into a series of individual hair swatches each
6.5 inches long and weighing 3.5 g. A trained panel of five tests the samples.
2. The test and control samples are blind-coded prior to starting. Each panelist is given a
set of samples to test, and freshly shampooed hair swatches.
3. The panelist takes the first hair tress and immerses the swatch in distilled water for 10
sec. The swatch is removed after the 10 sec and squeezed between fingers to remove
excess water from hair. Half a gram of mousse product is applied to the tress.
4. As the product is massaged through the hair; the panelist observes the ease of
spreading/dispersion of the product through the hair and also how it feels on her
hand/hair. The feel is rated on a scale of 1 to 10: 1 = very, very slick, slimy; 5 =
conditioned feel (some slip); and 10 = very natural feel. All of the products are applied to
clean hair tresses and evaluated before proceeding to the next attribute.
5. Using a separate comb for each hair tress, the panelist uses the large-teeth side of the
comb to detangle each hair swatch. The swatches are rated for ease of detangling: 1 =
very difficult, unable to remove tangles; 5 = easy, some resistance; and 1 = very, very easy
to detangle.
6. Using the small end of the comb, the hair tresses are combed through and evaluated for
wet combability: 1 = very heavy drag (can't get comb through hair); 5 = moderate drag,
and 10 = no drag.

 Page 133
7. After finishing the comb drag evaluations, the combs are evaluated for residue or
foam: 1 = very heavy residue/foam; 5 = visible foam; 10 = no residue/foam.
8. Run hair between fingers and evaluate how it feels; clean feel, smooth feel, tacky/sticky
feel.
9. All of the hair swatches are blown-dried until dry. While drying hair, observe hair for
ease of drying. Note any short or long drying time.
10. Comb through the hair swatches four times with the large teeth of the comb, and
evaluate ease of combing: 1 = very heavy drag; 5 = moderate drag; 10 = no drag.
11. Run hair through fingers and evaluate how smooth/conditioned it feels: 1 = very raspy
feel; 5 = moderately smooth; 10 = very smooth.
12. After finishing the comb drag evaluations, the combs are evaluated again for
residue/flaking: 1 = heavy residue/flaking; 5 = visible flaking/residue; 10 = no
flaking/residue.
13. Using a curling iron, curl each hair tress for 30 sec. Evaluate visually the overall shine
of the hair/tress: 1 = dull; 5 = average shine; 10 = very, very shiny.
14. Break any crust on the outside of the curl. Comb through the tress with the large teeth
of the comb four times. Evaluate comb drag: 1 = very, heavy drag; 5 = moderate drag; 10
= no drag.
15. After combing and touching, each curl is evaluated for ease of styling. Remake the
curl and evaluate curl: 1 = straight, no curl; 5 = slight bounce; 10 = very tight, full curl.
16. Evaluate the overall fullness/body of the hair/curl: 1 = no body; 5 = fair body/fullness;
10 = excellent body (looks very full).
B.
Resin Buildup
Buildup of resin on the hair fiber is an extremely important consideration when
formulating a leave-on product, such as a mousse, which is intended for daily application.
Large degrees of resin buildup can be immediately detected by feeling the treated and
shampooed hair tress. Indications of gross buildup are a greasy, dirty, or matted feel.
Subtler degrees of buildup may be detected by wet chemical methods. For this test, virgin
piedmont hair is preferable. Hair swatches are prepared and treated with product. They
are shampooed and immersed for 10 sec in a diluted solution of water-soluble anionic
dye (Rubine dye). The swatch is then rinsed thoroughly and allowed to air-dry. Buildup is
evaluated by observing the degree of dye absorption by the treated tress; greater dye
pickup indicates larger degrees of buildup. These observations may be observed visually
or quantified by Hunter Colorimeter.

 Page 134
C.
Microbiological Testing
A most important part of the testing of water-based aerosol products consists of microbial
considerations, especially since the trend is toward alcohol-free products. The
preservation of the bulk concentrate needs to be considered prior to filling, to ensure that
the bulk product doesn't become contaminated while waiting to be filled. Challenge
testing and microbial counts should be conducted.
D.
Stability Testing
One of the most important considerations in the formulation of any product is its stability.
A comprehensive stability program should be conducted and include a study of both the
physical and chemical properties of the finished product in question as well as a critical
evaluation of all of the components. The main function of a stability program is to
determine the shelf life of the finished product. This can be determined in a variety of
ways, most typically by storing samples at room temperature and at elevated temperatures.
Results obtained from tests conducted at room temperature are the most reliable, but
elevated temperature stabilities give you information for other parts of the world, as well
as accelerating the stress on the system to give an early warning of potential problems.
A stability program consists of four major steps: the design of the experiment, preparation
of the samples, storage of samples at desired temperatures for a given period of time, and
removal of samples periodically and their subsequent analysis and evaluation. The
stability of aerosol products involves the stability of the concentrate as well as the stability
of the entire package. The stability is designed to determine the following: (a)
decomposition of the active ingredient(s); (b) flavor, odor, and color changes; (c)
development of toxic and irritating decomposition products; (d) stability of the container;
and (e) stability of the valve assembly.
A sufficient number of samples must be prepared to allow for testing over a period of at
least 1 year. The samples need to be stored at varying temperatures and to be prepared
similar to the way in which the product will ultimately be produced. Samples also should
be prepared in glass compatibility bottles or jars depending on product form to examine
the formulation without the effect of the container. Samples also should be stored upright
and inverted, to simulate real shipping/storage conditions in the field. Stability studies
should be run on all first production batches, pilot batches, and large-scale panel tests. An
example of a full-scale stability study for a new aerosol mousse product is described
below. Table 22 lists the number of samples needed for a 1-year study.
Testing should be done initially and at each of the time intervals. The samples should be
brought back to R.T. before testing. Testing normally done is percent weight loss, can
pressure, foam density, appearance/color of foam, fragrance

 Page 135
Table 22 Number of Samples Needed for a 1-Year Study
# Samples to # Total
Environment Retains Time intervals
test Intervals samples
1, 2, 3, 6, 12
R.T. 3 5 6 21
months
1, 2, 3, 6, 12
4°C 3 5 6 21
months
1, 2, 3, 6
38°C 3 4 6 18
months
45°C/50°C 3 3 6 12 1, 2, 3 months
Total: 72

evaluation, foam quality, pH, total can evacuation, evaluation of the inside lining/valve of
the can. In examining the can lining, visually inspect the can for pitting, detinning, rust,
enamel blistering, discoloration, softening, or lifting.
XI.
Voc Reduction
If you are formulating a hair spray in the United States, you need to keep the level of
volatile organic compounds (VOCs) in your formulation to an acceptable level. Volatile
organic compounds are defined by the California Air Resource Board (CARB) regulations
as any organic material containing organic side chains, with a vapor pressure of 0.1 mm
mercury or more at 20°C or 12 carbons or less if the vapor pressure is unknown. VOCs
commonly used in hair spray products are ethanol and hydrocarbon aerosol propellants.
Also, fragrance compounds are volatile by definition; however, under the CARB
regulations, up to 2% fragrance compounds are exempt from the calculations of VOC
content in products (26,27). VOC regulations were enacted upon as a result of attempts by
the State of California to comply with U.S. Environmental Protection Agency (EPA) and
Clean Air Act mandates to limit ozone levels in urban areas. To understand the regulatory
concerns about VOCs, you must first understand ozone's role in the Earth's atmosphere.
A.
Ozone
In the upper atmosphere, ozone (O3) is formed by high-energy ultraviolet (UV)
interacting with oxygen (O2). It is essential to protect the Earth against dangerous levels
of UV reaching the Earth's surface. Ozone that is near ground level (troposheric ozone) is
a troublesome pollutant, causing severe respiratory distress in sensitive individuals. VOCs
were chosen to be regulated because they react with the sunlight to form unwanted ozone
in the lower atmosphere and thus contribute to the formation of ground level ozone or
smog. The greatest

 Page 136
impact of this occurring, obviously, is in highly populated areas such as the San Francisco
Bay area, Los Angeles, New York City, or other large cities.
The percent of ozone generated by VOC's released from personal care products is
admitted low in comparison to other sources such as cars or refineries; however, state and
federal governments are beginning to regulate even this small source in their efforts to
bring troposphere pollution under control. As a result, self-pressurized aerosol and pump
spray product formulators need to find appropriate ingredients and componentry to
comply with the limits currently in force or proposed (28).
Table 23 outlines specific VOC limits already proposed or in effect as of October 1996.
Under these limits, manufacturers of hair care products and other personal care products
need to maintain records of products sold. Besides, the U.S., Canada, and several
countries in Europe are considering limiting VOC release. In Europe, the proposal to
lower VOC content is driven by concerns about hydrocarbon propellant flammability as
well as air quality (29).
B.
VOC Reduction in Hair Sprays
VOC reduction in hair sprays is achieved by the removal of alcohol in pumps, and the
removal of alcohol and/or propellants in aerosols. The removal of these essential
ingredients usually requires replacing them with ingredients that are not considered
VOCsnamely, water. But the addition of water creates several problems.
When formulating low-VOC hair sprays, a number of concerns must be addressed such
as decreased resin solubility, increased solution viscosity and surface tension, extended
dry times, a negative change in high-humidity curl retention (HHCR), a change in spray
characteristics, an increase in initial curl droop (ICD), an increase in tack, and a loss of
overall holding power. With aerosols, the water creates two additional problems: the
potential for can corrosion and solvent/propellant incompatibility.
For the formulator to succeed in its regulatory driven reformulation efforts, close
relationships with the suppliers of resins, solvents, packaging, and propellant are needed.
The industry has responded to the challenge of VOC reformulation with the introduction
of new low-viscosity/low-tack polymers such as Amphomer LV-71 (from National
Starch), Gantrez V-225 (from ISP), Stabileze XL-80W (from ISP), Amerhold DR-25
(from Amerchol), and Acudyne-255 (from Rohm & Haas). Where possible, lower-
molecular-weight polymers such as Lovocryl-47 (from National Starch), Gantrez A-425
(from ISP), and Luvimer 100P (from BASF) were introduced. Lower-viscosity/lower-
molecular-weight polymers such as Omnirez 2000 (from ISP) were also introduced.
Blends of polymers were also investigated to achieve the desired hair spray properties
impossible to achieve with a single resin

 Page 137
Table 23 Current Regulations Limiting VOC Levels (30)
Effective
State Product and VOC limit
Date
California 1993 Hair sprays, 80%
California 1994 Mousse, 16%, gels, 6%
Hair sprays, 80% mousses, 16% gels,
New York 1994
6%
Texas 1995 Hair sprays, 80%
Massachusetts 1995 Hair sprays, 80%
Hair sprays, 80% mousses, 16% gels,
New Jersey 1996
6% (30)
Oregon 1996 Hair sprays, 80%
Hair sprays, 80% mousses, 16% gels,
Maine 1996
6% (31)
1997 Hair sprays, 80% mousses, 16% gels,
EPA
(proposed) 6% (32)
1998
California Hair sprays, 55%
(proposed)
2003
New York Hair sprays, 55%
(proposed)

such as systems based on Amphomer LV-71 plus Resyn 282930 (from National Starch),
Gaffix VC-713 plus PVP K-30 (from ISP), and AQ Polymers (from Eastman Chemical)
plus PVP/VA Copolymer (from ISP). New valving, propellants, and packaging have also
been optimized for low-VOC systems (34).
C.
Corrosion
The aerosol industry is being driven toward lower volatile organic compound (VOC)
products due to regulatory and consumer pressures. The most economical way to reduce
VOCs is to add water, but this can create significant performance issues. For aerosols, the
water creates a potential for can corrosion which exponentially increase as the water
content increases (35). To address these issues, appropriate corrosion inhibitors and
preventive measures must be considered. This section of the chapter will highlight the
fundamentals of corrosion, selection/optimization of corrosion inhibitors, and other
considerations to consider in developing corrosion-resistant aqueous-based aerosols.

 Page 138
The main approaches to minimizing corrosion from the fluids inside the container are the
following (36):
1. Lowering the concentration of oxygen.
2. Lowering the concentration of corrosive ions such as chlorides and sulfates.
3. Optimizing the pH of the system while maintaining the product quality.
4. Utilizing a synergistic combination of corrosion inhibitors simultaneously.
The final approach to minimizing corrosion actually involves using each of these
approaches in concert.
XII.
Corrosion Process
The process of corrosion is electrochemical in nature. For corrosion to take place, four
things are needed: an anode (negative electrode), a cathode (positive electrode, an
electrolyte (a corrosive environment), and a circuit connecting the anode to the cathode
(37).
Corrosion of steel is a form of oxidation caused by a flow of electrons through the water
(electrolyte) from a negatively charged portion of the steel (the anode) to a positively
charged portion (the cathode). This results in conversion of metallic ion to iron oxide
(37).
In an aerosol, corrosion can be illustrated as seen in Figure 1 (38). The liquid content of
the can represents an electrolyte, and there are anodic and cathodic sites on the can wall.
Dissolution of the metal occurs at the anode, where the corrosion current enters the
electrolyte and flows to the cathode.
The reaction at the anodic sites is the oxidation of the metal, for example:

or

The oxidized form of the metal appears as the corrosion product. The electrons resulting
from the oxidation reaction migrate through the metal to the cathode, where they take part
in a reduction reaction such as:
Discharge of hydrogen ions takes places in many corrosion reactions; therefore, acidity of
a solution as represented by the concentration of hydrogen ions (pH) is a very important
factor to your aerosol product. The free electrons can react with any electron acceptor, but
hydrogen gases are typically often

 Page 139

Figure 1
Corrosion inhibition of aqueous-based aerosolscorrosion
cell.
found in corroded cans. Typically, acidic solutions are better electrolytes, allowing ionic
migration to take place relatively easily and resulting in more pronounced corrosion
effects (39).
A.
Fundamentals of Corrosion (37)
The mechanism of corrosion can occur in many forms. In aerosols, it can be uniform;
galvanic, or two-metal, corrosion; intergranular; or concentrated, and it can manifest itself
as crevice corrosion, pitting, selective leaching, or stress cracking.
Uniform corrosion is the most common form of corrosion. It is normally characterized by
a chemical or electrochemical reaction that proceeds uniformly over the entire exposed
area.
Galvanic, or two-metal, corrosion is also very common. It is based on the potential
difference between two metals or two sites on the same metal or alloy. This can occur if,
for example, the metallic compositions of the valve mounting cup and the can are
different. The rate of this type of corrosion can be influenced by the choice of inhibitors.
Crevice corrosion occurs in gasketed joints, underfilms, and curled or crimped areas.
Pitting corrosion is a form of extremely localized attack that forms deep holes in the metal
and often occurs at locations where the lining does not adhere well to the steel.
Concentrated cell corrosion occurs in localized areas where small volumes of stagnant
solution exists. These places include sharp corners, spot welds, lap joints, fasteners,
flanged fittings, couplings, and threaded joints.

 Page 140
Figure 2 illustrates the areas of a typical three-piece tinplate can most susceptible to
corrosion (35). Starting at the bottom of the can, there is a crevice where the bottom piece
joins the barrel. At this location, the materials are highly stressed. This combination of a
crevice point and high stresses in general accelerates crevice corrosion. The barrel of the
can is welded axially. Such welds often produce metallurgical structures and residual
stresses, which accelerate weld corrosion.
At the top of the can, the spray mechanism or valve assembly includes crevices associated
with the assembly itself and with the cap top or dome area. This crevice area is a location
of the type where corrosion is expected and which should be carefully evaluated. In
particular, vapor phase crevice corrosion is common in this area.
Other types of corrosion can be observed in the vapor phase area, the interfacial area, and
the liquid phase area. Depending on the type of product, you may see corrosion in one or
more areas.
XIII.
Other Considerations
In addition to proper neutralization levels in order to control pH, there are other
considerations which must be examined when developing new aqueous based aerosols. It
is important to carefully choose any ancillary ingredients to ensure that they do not
promote corrosion of the tinplate aerosol can (35,40). Ingredients to monitor include
fragrances, plasticizers, and nonfunctional additives. It is also recommended that only
deionized water be used for the aerosol product. The presence of ions, in particular
chloride, is known to accelerate corrosion. Excess oxygen should also be minimized
either by vacuum crimping or purging the air from the can before filling.
These considerations are important because oxygen is the most corrosive element inside
the aerosol container. The presence of oxygen actually accelerates the effects that chloride
or other ions might have by themselves. In aqueous solutions, the halides and some
compounds such as sulfate contribute to accelerating corrosion, and, particularly, they
promote localized corrosion such as pitting and crevice corrosion. Without oxygen, these
species are not so aggressive. However, in the presence of oxygen, these species
accelerate corrosion (41).
Another important point to remember is that cans are subjected to heating and cooling
during the normal life cycle of the product. Such thermal cycling can accelerate stress
corrosion cracking and should be evaluated.
As inhibitors are used, the electrochemical potential on the surface of the can changes.
While inhibitors may reduce the overall corrosion rate, they may shift the electrochemical
conditions of the product such that stress corrosion cracking or pitting may occur (39).

 Page 141

Figure 2
Potential corrosion sites in an aerosol can.
While it would be reasonable to assume that corrosion is accelerated at higher
temperatures, this is not always true. In some cases, corrosion has occurred only at room
temperature or at lower temperatures. So it is critical that stability testing be conducted at
various temperatures. It is recommended that testing be done at -20°C, 4°C, room
temperature (25°C), 38°C, 45°C, and 50°C. As the tin is perforated, the steel is more
exposed. Thus, corrosion reactions that occur on the steel alone, possibly due to stress
cracking, would not be immediately evident and should also be evaluated.
A.
Corrosion Testing Measures
While it has been traditional to evaluate corrosion using visual standards, in view of the
lack of prior history with some of the new lower VOC product forms, it is necessary to
be more thorough. This means that some of the specimens tested should be examined
using a scanning electron microscope (SEM) and cross-sectional optical metallography.
The concentrate solutions should also

 Page 142

Figure 3
Crevice cell test apparatusExploded view.
Courtesy of US Can.
be analyzed for tin and iron ions over time. The time frame recommended are (a) initially
and after 1 month; (b) 3 months; (c) 6 months; (d) 12 months, and (e) 24 months.
No one test satisfies all of the criteria for measuring corrosion, making formulation
selection based on corrosive potential difficult. But there are screening methods
developed by DuPont and US Can Corporation which are excellent screening tools for
quickly determining if a formulation will likely aggravate the system's stability against
corrosion.
US Can's method (39), the crevice cell test, is an electrochemical test that examines the
product's concentrate. This method simulates corrosion attack at the crevice sites of a
scored evaluation sheet of metal that simulates bending and/or breaking of the coating on
the tin can. Figure 3 shows the setup for conducting the crevice cell test.
The crevice cell test begins with a 4'' × 3'' tinplate sheet that has been scored with an X-
acto knife. The tinplate sheet is then placed on top of the PVC base, and the Pyrex o-ring
joint assembly is placed on top of the tinplate steel and tightened via a pinch clamp. The
product concentrate is then placed into the Pyrex tube. The concentrate should cover the
bottom of the carbon rod when the assembly is set up. The carbon rod is then submerged
via the rubber stopper into the product concentrate. The alligator clamps are attached to
the top of the carbon rod and to the corner of the tinplate. The experiment is then

 Page 143

Figure 4
Closed cell galvanic test apparatus. Courtesy
of DuPont.
run for 24 to 48 hours. At the end of the time period, the product concentrate is removed
and examined, and the tinplate is cleaned carefully. The tinplate is observed visually for
corrosion at the sites using the rating sheet for each site. The tinplate should also be
submitted for SEM analysis.
Boulder's method (39), the closed cell galvanic test, uses an electrical charge to accelerate
the corrosion in a tinplate can and therefore helps predict corrosion of both the vapor and
liquid phases. This test allows for the complete formulation, including the propellant, to
be tested for corrosion. Figure 4 shows a modified tinplate container used to form the
galvanic cell.
A metal wire is wrapped around the can body just below the dome area and represents the
anode. A steel electrode is inserted in the valve body in place of the diptube and
represents the cathode. Because there is no diptube, cans are filled with the concentrate
and chilled via a dry-ice bath; then, propellant is added via a cold filling process, and the
modified valves are quickly crimped onto each can. A DC power supply is then
connected to each can to begin the electrochemical process. The DC power supply
induces the flow of electrons from the anode to the cathode. Because the metal wire is in
direct contact with the outer wall of the can, the entire can wall becomes the anode.
Concurrently with the electron flow, positive metal ions leave the anode and travel
through the electrolyte. This positive metal ion migration is observed as corrosion.
Results from the crevice cell test and closed cell galvanic test can be used to select
formulations for long-term stability testing. In most cases, there is

 Page 144
good correlation between the test units and long-term stability. If the product fails the
screening tests, it will corrode in the oven or on shelf stability, but lack of corrosion does
not necessarily indicate a stable system.
B.
Selection/Optimization of the Corrosion Inhibitor
Before selecting a corrosion inhibitor, it is extremely important to determine the effects of
the inhibitor on the product's performance as well as the effects on the person using the
product. It is recommended that the toxicological profile of the inhibitor be assessed prior
to testing.
Inhibitors work differently: There are passivating and filming inhibitors (39). Passivating
inhibitors are also known as oxidizers. A strong oxidizing agent will form an oxide
coating at the anode, passivating the site from normal electrochemical activity. Some
typical examples of this type of inhibitor are phosphates and silicates.
Filming inhibitors form barriers between the metal surface and the aqueous environment
and can be organic or inorganic in nature. Examples of organic inhibitors are long-chain
molecules with a polar end that absorbs on the metal surface, and an organic end, which
repels the aqueous environment. Some typical examples are amines. Inorganic filming
inhibitors precipitate an insoluble layer on the surface of the metal and include
compounds such as bicarbonates and phosphates.
An inhibitor system should possess both head space and liquid-phase protective
properties, and there is no universally acceptable combinations known for low-VOC
formulations based on dimethyl ether/water formulations. Each formulation must be
tested. The inhibitors need to be evaluated alone and in combination to determine how
reliable the inhibitors might be over the range of conditions under which the aerosols will
be stored.
Formulations should be tested in ethanol/water systems propelled with either dimethyl
ether, hydrofluorocarbon-152a, hydrocarbon, or combinations thereof. No active
ingredients should be used initially. Typical usage levels to be examined are 0.1% to 0.5%.
Table 24 lists inhibitors which have been screened by both DuPont and International
Specialty Products in low VOC aerosol systems (36). From a practical point of view, the
optimum corrosion fix would involve the following:
1. Lowering the oxygen concentration to the lowest economically possible.
2. Lowering the corrosive on concentration of all ingredients to the lowest economically
possible.
3. Raising the pH as high as is consistent with the polymer, while maintaining overall
product performance.
4. Utilizing a synergistic combination of inhibitors simultaneously.

 Page 145
Table 24 Inhibitors
Passed
INCI Name Trade Name Vendor StabilityComments
Screening
Disodium oleamido EMCOL Failed
Witco No N/A
MIPA-sulfosuccinate 4161L screening tests
Polyglyceryl-4 oleate Witconol 14 Witco N/A N/A Not soluble
Acceptable for
MEA borate and 80% VOC and
Monacor BE Mona Yes Yes
MIPA borate 55% VOC-LP
inhibitor
Monacor Failed
Mona No N/A
2000 screening tests
Monacor Failed
Mona No N/A
3000 screening tests
Sodium Lauryl Hamposyl Vapor phase
Grace No No
sarcosinate L-30 corrosion
Aminomethyl Vapor phase
AMPD Angus Yes No
propanediol corrosion
Severe VP
Triisopropanol-amine TIPA Dow Yes No
corrosion
Dehyquart Passed 80%
Quaternium-52 Henkel, Inc. Yes Yes
SP VOC
Nitromethane Nitromethane Angus Yes No VP corrosion
Failed
Morpholine Morpholine Aldrich No No
screening tests
Acceptable for
Ammonium Ammonium 80% VOC and
Aldrich/Baker Yes Yes
hydroxide hydroxide 55% VOC-VP
inhibitor
Sodium Failed
Sodium nitrite No No
nitrite screening tests
Sodium Considerable
Sodium sulfite No No
sulfite corrosion
Acceptable for
Sodium
Sodium benzoate Yes Yes 80% VOC-LP
benzoate
inhibitor
Dimethyl
Oxaban A Angus Yes Yes VP inhibitor
oxazolidone
2-Dimethylamino-2-
DMAMP-80 Angus Yes Yes VP inhibitor
methyl-1-propanol
Aminomethyl
AMP-95 Angus Yes Yes LP inhibitor
propanol

 Page 146
5. Measuring the tin and iron ion concentration in the product concentrate initially and
over time.
6. Evaluating the corroded surfaces using an SEM and cross-sectional metallography.
7. Paying special attention to crevices and welds.
It has been demonstrated in the literature that acceptable long-term stability of 80% VOC
aerosol hair sprays is possible with an array of polymers and carefully chosen inhibitors,
with either hydrofluorocarbon-152a/hydrocarbon blends, dimethyl ether/hydrocarbon
blends, dimethyl ether, or hydrocarbon alone, and are on the market now. Work is still in
progress for 55% VOC systems.
XIV.
Finishing Products
When consumers go to purchase hair care products, they are met with a wide array of
choices, particularly in the hair fixative category. Hair sprays, mousses, gels, spray gels,
and styling lotions compete for shelf space, along with a number of other new products
that offer combined benefits of styling, conditioning, and/or protection all in one product.
Hair sprays can be defined in many ways, but essentially hair fixatives are products
designed to provide benefits that first enable the hair to be combed or set into a desired
style and then allow it to remain in that style for a considerable length of time. Today's
hair fixatives or styling products originated from liquid setting lotions which were
originally developed to strengthen and maintain a style. They differ from permanent
waving compositions in that they do not affect the internal structure of the hair. The
principal means of holding the set is to deposit on the hair a solution of polymeric
material which, after styling and drying, leaves a flexible film that ensures the
cohesiveness of the hold of the hair style and protects it from the humidity. In this section
of the chapter, hair fixatives such as styling spritzes, nonaerosol hair sprays, and aerosol
hair sprays will be discussed.
Early hair sprays utilized solutions of the naturally occurring resinous material shellac,
dissolved in alcohol. These products had severe limitations, however, in that the resin
was hard and brittle, making it difficult to remove from the hair by shampooing. For a
discussion on the history of hair sprays, the authors refer the reader to R. Lochhead's
History of Polymers in Hair Care (42).
Over the years, advances in polymer technology have led to the development of very
sophisticated hair fixatives from which excellent hair spray products can be formulated.
Such advances have made the fundamental requirements of a modern-day hair spray
mandatory, and the consumer expec-

 Page 147
tation today is of products with the following properties: they should (a) exhibit good
holding properties and style retention, (b) be easy to use, (c) provide a fine spray with a
gentle force, (d) give good coverage, and (e) not be too wet. In addition, a product should
not be tacky to touch, should dry quickly, and be stiff enough to hold the hair in place yet
allow for hair flexibility to touch. The product should not flake, and should be
substantive to the hair while easy to remove (43). Apart from these fundamental
performance attributes, the hair spray should be safe for its intended use, should be stable
and efficacious throughout the life of the product, and should comply with all regulatory
guidelines relevant to them.
A.
Formulation Considerations
1.
Regional Versus Domestic Market
The formulation you develop must meet the requirements of the region or country(s) for
which you are developing it. Regional differences in regulations, rates of taxation, cost,
and availability of raw materials will mean establishing a special formulation for each
region. For a regional or global formula, you need to consider:
1. Consumer needs
2. Application properties and after-feel
3. Visual effects
4. Cost of formula
5. Raw materials
6. Packaging
7. Product capabilities
8. Regulatory issues
9. Trade restrictions
a. Regulatory Issues Chapter 12 of this book covers domestic and international regulatory
issues; some examples are listed here for your reference.
United States: Self-regulated via CTFA, few restrictions on cosmetic ingredients.
Mexico: Same as United States, but Spanish-language labeling is required.
Japan: Stringently regulated. Cosmetic ingredients treated as pseudopharmaceuticals.
Raw materials need to be on the positive approval listing to use in country. Constraints on
usage levels.
Europe: Raw materials must be on the positive EINECS cosmetic directive or cannot be
used.
France: A dossier must be completed for all formulations, plus need 6-month stability
data at elevated temperatures.

 Page 148
Costa Rica: The most difficult market. Formulations need to be analyzed 10 times, and
results must be detailed and notarized.
Indonesia: Regulated via Ministry of Health Directorate General of Drug & Food Control.
Malaysia: Regulated via Ministry of Health under the Sale of Food & Drugs Ordinance
(1952).
Philippines: Regulated by the Bureau FDA, Cosmetic Drugs Administration.
Thailand: Regulated by the FDA Cosmetic Control Division.
Singapore: Regulated by the Ministry of Health, Pharmaceutical Dept. Cosmetic Control
Unit.
Vietnam: Regulated by the Ministry of Health. Requires Certificate of Analysis from the
Pasteur Institute.
b. Costs The costs of raw materials and packaging are important parameters to consider
when formulating a new product or restaging an old one. Several countries have been
researched, and the costs impact has been listed for your reference.
For Mexico: Cost is the greatest influence. Raw materials and packaging costs need to be
low in cost.
For Japan: This is an upscale market. Raw materials and packaging costs are not a
serious consideration.
For the United States: This is a mixed market. Raw materials and packaging are in
proportion to the price of the finished product.
2.
European Formulations
Bans or volatile restrictions on the use of chlorinated fluorocarbons (CFCs) and
methylene chloride, as well as heavy taxation of cosmetic alcohols (ethanols, propanols)
resulted in a change over from aerosols with CFCs, isopropanol, and methylene chloride
to aerosols with dimethyl ether (DME), with alcohol, with water, or based on
hydrocarbons. Some basic European aerosol formulations are outlined in Table 25.
3.
Asia-Pacific Considerations
In this region, LPG (hydrocarbon) is the main propellant used; Typically, 30% to 45% is
used. Some typical levels for this region are outlined in Table 26.
Hydrocarbon + DME blends are starting to be seen and funding for DME plants is being
developed, but at this time, LPG is the preferred propellant. The alcohol used in this
region could be any type or quality depending on the country. It is recommended when
you formulate any product to use SD alcohol 190-proof alcohol to verify that your
formulation will tolerate additional levels of water in the system.

 Page 149
Table 25 Some Basic European Aerosol Formulations
#1
DME 3050%
Alcohol 2468%
Water 018%
Polymer (solids) 28%
#2
Hydrocarbon n-Butane 4055%
Alcohol 2535%
Polymer (solids) 210%

Table 26 Typical LPG Levels by Country

Country % LPG Utilized
Australia 40%
China 30%
Japan 4045%
Korea 3035%
Taiwan 3035%
Thailand >30%

B.
Lower VOC Options
VOCs are not a problem in areas outside the United States for the moment, but if you are
formulating products for the U.S. or looking for lower cost options by adding water, hair
fixative products must meet the VOC regulations as stated in California by the CARB and
in other states as discussed previously in this chapter.
XV.
Market Positioning of Product
Hair fixative products are usually segmented according to holding power: light hold,
normal hold, or firm hold. Hair style fashions obviously have a great impact on the levels
of hold that are in vogue, but holding power does vary among countries. There are no
legislative guidelines with regard to resin level and description of hold for the product.
New twists and multifunctional formulas have emerged and are on the retail shelves.

 Page 150
A typical wish list of product objectives from Marketing might include:
1. Provides fast-drying firm hold for any style.
2. Helps preserve hair color vibrancy and add shine.
3. Enriched with sun screen, panthenol, and a natural antioxidant.
4. Actually creates a barrier of protection from the sun's UV rays.
5. Brushes out of hair easily while maintaining style.
Based on what marketing claims are desired, special additives may need to be added to
your formulations. You need to know what they are and if they are compatible with your
formula. For example, a hair spray formulation may include moisturizers, humectants,
conditioning agents, bodifying agents, gloss enhancers, protectants, sun screens,
antioxidants, etc.
A.
Plasticizer/Additive Criteria Selection
The degree of hardness of the polymer film can be modified by varying either the type of
resin used or the amount of plasticizer added. Plasticizers perform the important function
of softening and imparting flexibility to the film deposited on the hair by the spray.
Without plasticizers, the hair fixative in hair sprays would form a brittle film that would
give unacceptable performance. The plasticizer may also affect other performance
characteristics such as softening/imparting flexibility to the film, detactifying film,
imparting sheen/gloss, increasing lubricity/ease of combing, reduction of static charge,
improvement in tactile properties, reduction of surface tension of finished product, and
reduction of flaking/residue on hair. Final selection of the plasticizer should be based
upon its effect on the total performance of the spray. A suggested starting point would be
to add 0.1% to 0.5% of the plasticizer to the formula.
Tests to be performed to check the effectiveness of the plasticizer would be solubility,
film hardness, high-humidity curl retention, tack/dry time, hair characteristics, shine,
stiffness, combing ease, and flaking.
Plasticizers should be tested alone and in combination; sometimes a material may provide
good high-humidity curl retention (HHCR) but may not be ideal in other respects. For
example, a silicone material may not give favorable HHCR results, but it does impart a
good soft feel and manageability to the curls. By combining two plasticizers into the
formula, the desirable characteristics of both materials may be obtained.
1.
Degree of Neutralization
Film-forming properties of hair fixative resins containing carboxylic acid groups may be
altered by varying the degree of neutralization or the type of base used to neutralize the
resin. This resin type produces hard films with better adhesion to the hair than polymers
such as PVP or PVP/VA copoplymers

 Page 151
while having a higher degree of water resistance. These resins have to be neutralized and
by varying the degree of neutralization of the resin, the hardness, solubility, and
hydroscopicity of the resin can be modified. The greater the degree of neutralization, the
more flexible the film. The most commonly used neutralizer is 2-amino-2-methyl-1-
propanol (AMP).
This ingredient not only acts as a neutralizer, but has plasticizing characteristics as well.
Other commonly used neutralizers are the following:
Aminomethyl propanediol (AMPD)
Triisopropyl amine (TIPA)
Dimethyl stearamine (DMS)
Dimethyl hydrogenated tallow amine (DMHTA)
Triethanolamine (TEA)
Sodium hydroxide (NaOH)
Potassium hydroxide (KOH)
Diethylpropylamine (DEPA)
Unneutralized or improperly neutralized resins give hard, water-resistant films which
cannot be washed easily off the hair. Partial neutralization is necessary to make resins
removable by shampoo. The degree of neutralization must be balanced to yield good hold
(HHCR) and removability.
Neutralization will affect the following properties:
Polarity
Solubility in solvents
Film clarity
Hardness/flexibility of film
Tackiness of film
Removability
High-humidity resistance
Stiffness
Compatibility with propellants
Typically, neutralizing with inorganic bases such as NaOH or KOH can produce stiffer
films on hair than with organic bases. To increase hydrocarbon compatibility, use long-
chain amines or blend AMP-95 with a long-chain amine such as TIPA, DMS, or DMHTA.
DMS or potassium hydroxide (KOH) should not be used in 80% VOC or lower hair spray
products as it results in white, opaque dried films, which translates to dullness/flaking on
hair.
Calculations for percent neutralization:
Parts by weight (g) of base required = A × B × C × D/1000
where A = parts by weight (g) of resin solids used; B = Acidity (mEq/g); C = equivalent
weight of the base; and D = % neutralization required (in dec-

 Page 152
Table 27 Typical Neutralization Levels
Trade
INCI name Typical Preferred
Name
Luvimer
Acrylates copolymer 100% 100%
100P
Luvimer
100% 100%
36D
Luvimer
100% 100%
30E
Luvimer-
75% 75%
Low VOC
Ultrahold
Acrylates/acrylamide copolymer 80100% 80100%
8
Acrylates/hydroxyester acrylates Acudyne
4060% 50%
copolymer 255
Gantrez
ES-425
Butyl ester of PVM/MA copolymer 725% 1020%
Gantrez A-
425
Gantrez
ES-225
Ethyl ester of PVM/MA copolymer 725% 1020%
Omnirez
2000
85100% 90100%
for high for high
Amphomer
Octylacrylamide/acrylates/butylaminoethyl VOC; VOC;
Amphomer
methacrylate copolymer 90100% 95100%
LV-71
for 80% for 80%
VOC VOC
80% for 80% for
Lovocryl-
80% & 80% &
47
55% VOC 55% VOC
Luviflex
PVP/acrylates copolymer 80% 80%
VBM 35
Advantage
VA/butyl maleate/isobornyl acrylate CP
1550% 1520%
copolymer Advantage
Plus
Resyn
281310
Vinyl acetate/crotonic acid polymer 8090% 8090%
Luviset
CA66
Vinyl acetate/crotonic acid/vinyl Resyn 8090% 8090%
neodecanoate copolymer 282930

imal). Typical neutralization levels for various polymers are listed in Table 27 for your
reference.
B.
Resin Selection
The most important raw material in any styling product is the resin. Its main job is to weld
or hold the style in place. The type of film a hair fixative product forms depends on
whether it is used as a holding aid or as a finishing spray. The amount of resin used
affects the degree of holding power. A higher level of resin forms a harder film and
produces a firm hold; a lower level forms a softer film that is more suitable for a finishing
spray.

 Page 153
Once the formulators have decided which particular resin is suitable for their application
needs, they must then decide on what level of resin is suitable for the product. Hair style
fashion has the greatest impact on the amount of resin required. The amount of resin can
also vary dramatically depending on which country or region you are developing the
product for. When choosing a resin, keep in mind your customer profile and the other
products already in these markets. Some typical resin levels by percent solids-basis
according to product type are outlined in Table 28. In its simplest form a hair spray
consists of the items listed in Table 29.
1.
Resin Selection/Amount
The commercial success of a styling product depends on the ability of the polymer to be
solubilized in the hair care formulation and display useful performance characteristics,
particularly a set of multifunctional properties. The hair fixative resin can be used in a
variety of compositions in an amount of about 0.25% to about 12% by weight on a
percent solids basis. The preferred amount will depend on the particular personal care
product being formulated. Some general guidelines are illustrated in Table 30. Table 31
lists the hair fixative polymers commonly used in hair spray products.
Table 28 Typical Solids-Basis Resin Levels by Product Type
Product Type Light Hold Normal Hold Firm Hold
Aerosol hair sprays 2% 45% 68%
Pump hair sprays 34% 57% 812%
Styling spritz 23% 46% 710%

Table 29 Contents of Typical Hair Sprays

Aerosol Nonaerosol
Fixative polymer Fixative polymer
Solvent Solvent
Adjuvants Adjuvants
Propellant
Valve system Pump system

Table 30 Preferred Resin Levels by Personal Care Product

Type
Personal Care Product Type Resin Use Level
Hair sprays 212%
Styling spritz 36%
Innovative pump or aerosol hair spray 516%

 Page 154
Table 31 Hair Fixative Polymers Commonly Used in Hair Spray
Products
INCI Name Trade Name Vendor
PVP/VA E-
735
PVP/VA E-
635
PVP/VA copolymer ISP
PVP/VA S-
630
PVP/VA
W735
Luviskol VA
BASF
Grades
Gantrez ES-
225
Ethyl ester of PVM/MA copolymer ISP
Omnirez
2000
Gantrez ES-
425
Butyl ester of PVM/MA copolymer ISP
Gantrez A-
425
Resyn 28-
1310 National
Vinyl acetate/crotonic acid copolymer
Luviset Starch BASF
CA66
Vinyl acetate/crotonic acid/vinyl Resyn 28- National
neodecanoate 2930 Starch
Luviskol
PVP/VA/vinyl propionate BASF
VAP
Amphomer
Octylacrylamide/acrylates/butylaminoethyl Amphomer National
methacrylate copolymer LV-71 Starch
Lovocryl-47
Luviskol
VA/vinyl propionate/crotonic acid BASF
CAP
Gaffix VC-
VCL/PVP/dimethyl-aminoethyl 713
ISP
methacrylate copolymer H2OLD EP-
1
Advantage
CP
VA/butyl maleate/isobornyl acrylate ISP
Advantage
copolymer
 Plus
Amerhold
Acrylates copolymer Amerchol
DR-25
Luvimer
100P
Luvimer
Acrylates copolymer 36D BASF
Luvimer 30E
Luvimer
Low VOC
AQ 38S
Diglycol/CHDM/isophalates/SIP Eastman
AQ 55S
copolymer Kodak
AQ 48 Ultra
Acudyne
Acrylates hydroxyacrylates copolymer Rohm & Haas
255
Propriety
Acrylates copolymer SC Johnson
Blend
Methacryloyl ethyl betaine/methacrylates Diaformer
Sandoz
copolymer Z400
Methacrylates/acrylates copolymer/amine Diahold A-
Sandoz
salt 503
Yukaformer
Methacryloylethyl betaine/methacrylate
AM-75 Mitsubishi
copolymer
Amphoset
AMP-acrylates/diacetone-acrylamide Plas-cise L- Goo Chemical
copolymer 53P Ltd.
AMPD-acrylates/diacetone-acrylamide Plas-cize L- Goo Chemical
copolymer 53D Ltd.
Plas-cize L- Goo Chemical
Acrylates/methacrylate polymers
8011C Ltd.
Ultrahold 8
Acrylates/acrylamide copolymer Ultrahold BASF
Strong

 Page 155
C.
Propellant Selection
The formulator must determine the best propellant to use and how much. High-pressure
propellants, such as carbon dioxide, nitrous oxide, and compressed air, are used for a
significant number of aerosol products, especially in Europe.
The bulk of all aerosols are pressurized with low-pressure propellants, basically:
Hydrocarbons-LPG
Dimethyl ether
1,1-difluroethane (HFC-152a)
All of these propellants have air-free pressure in the range of 17 to 109 PSIG at 70°F.
Water solubility is very poor, except with dimethyl ether, which can dissolve up to about
35% to 40% in water.
Tests that need to be conducted on the finished aerosol formulations are as follows:
compatibility, pressure at 70°F, weight loss, net weight, spray rate, spray pattern, particle
size distribution, flammability, and freeze/thaw stability.
The primary purpose of the propellant is to provide pressure to the gaseous phase of the
dispenser so that the product can be dispensed upon actuating the valve. Other functions
include diluent, solvent, and spraying or foaming agent. The most common propellants
are propane, isobutane, n-butane, dimethyl ether, hydrofluorcarbon-152a, carbon dioxide,
nitrous oxide, nitrogen, and compressed air.
Some gas-liquids are sometimes called propellants, but are not really, such as n-petane or
iso-petane. They are actually very volatile liquids.
If the propellant is soluble in the concentrate or base, it will often cause the emerging
liquid stream to break-up, producing a spray. Generally:
Lower-pressure
Higher-pressure gases
propellants
Allow the use of
Produce fine sprays valves with large
orifices
Compensate for the
vapour tap (VT)
Large amounts of lower pressure propellant Lower the overall
will sometimes give a smoother, less blasty viscosity
spray. Reduce the foaming
 potential of your
system

Propellant formulation aspects may affect your propellant selection. The 80% VOC hair
sprays can no longer accept the usual 20% to 25% A-31 propellant load without cloud-
pointing and going to two phases. This can be avoided by using 30% to 35% dimethyl
ether (DME) or blends of DME and

 Page 156
hydrocarbon, or a small amount (15%) of a high-pressure hydrocarbon such as A-70.
The goal of the formulator is to keep the cloud point below 0°C (or other appropriate
temperature as deemed important by your company) and the product in a single phase.
Typically > 15% hydrocarbon is unacceptable. For 80% VOC systems; high-pressure
hydrocarbon (A-70 propellant), dimethyl ether, or hydrofluorocarbon-152a is
recommended. For 55% VOC systems; dimethyl ether, dimethyl ether/HFC-152a blends,
or hydrofluorocarbon-152a propellant used alone are recommended.
Selection of the valve system also has an effect on the propellant choice. If a valve with a
large orifice is needed in order to reduce cloggage, filming on the actuator, etc., then the
propellant pressure should be reduced to as low as practical to keep the delivery rate from
becoming excessive.
D.
Packaging Selection
1.
Valve Requirements
Over 90% of all aerosol valves used in the United States are made by Precision, Seaquist,
and Summit. Specialty valves utilized for hair fixatives are made by Newman-Green,
Bespak, Emson, Coster, and Beard. There are several basic valve styles which will work
with a given system; the formulator needs to choose between a toggle action valve (Tilt
action) or regular (vertical) reciprocating action type.
Parameters that are important when choosing a valve system are spray character, spray
pattern, particle size distribution, and spray rates. The spray pattern becomes the most
important parameter of the dispenser. It is measured by cone diameter and uniformity of
the spray. Generally the diameter is readily measured from 6 to 12 inches. If your label
copy suggests a spraying range, it is best to use the midrange point.
a. Vapor Tap Valves During use, the vapor tap steals first the entrapped air, reducing the
pressure in the can, and then the more volatile propellant if a blend is utilized. To check
this, you need to check the spray rate and spray pattern throughout the use of the can.
The delivery rate will normally decrease somewhat as the product is used up, especially
with a VT valve. Sprayouts are always run to determine the total amount that can be
dispensed, under similar consumer use conditions. For foam products and products with
a vapor tap, the sprayouts should be done gradually with shaking in between and periodic
warming of the can back to 70°F.
The swelling of the gasket material must also be checked to ensure a proper seal. This
testing is typically done by the valve manufacturer. Normally 3% to 6% minor swelling is
acceptable. For dimethyl ether, gasket swelling can be especially troublesome and extra
care and testing may be appropriate.

 Page 157
Table 32 Anhydrous Aerosol Hair Spray Prototype
Formula
Ingredient % by Weight
SD 40 B alcohol 69.67
Aminomethyl propanol (AMP-
(as needed) 0.23
95%)
Resin (% solids) 5.00
Phenyl trimethicone 0.10
Isobutane/propane blend (A-40) 25.00
Total 100.00
Actuator: Excel 200
Valve: Seaquist NS-34
Misty
Stem:0.013'' Orifice: 0.016'' Misty
Body: Capillary
V. tap: 0.013"
ID tubing: 0.040"

b. The Actuator The actuator is used to turn on the aerosol valve. The most important
character of the actuator is the terminal orifice. This is part of the dynamic fluid control
system. Straight taper orifices generally lead to narrower sprays, standard taper orifices
lead to somewhat wider sprays, and reverse taper orifices lead to the widest spray. A
mechanical break-up actuator also breaks up the spray to yield a finer spray. This type of
actuator is usually recommended for lower VOC hair spray systems or systems that
contain water.
2.
Prototype Formulations
In its simplest form a hair spray consists of a fixative polymer(s), solvent(s), adjuvants,
propellant, and valve system for aerosols; a fixative consists of polymer(s), solvent(s),
adjuvants, and pump sprayer system for nonaerosols. Prototype hair spray formulations
examples are listed in Tables 32 to 39.
E.
Innovative Products
The Innovative Product clause was part of the regulations adopted by the California Air
Resources Board in 1990. The current interpretation of this clause is that higher VOC
levels (i.e., > 80% or 55%) will be tolerated in formulations provided it can be proved
that the quality of VOCs emitted over a given period of time is equal to or less than that
emitted by a product of similar efficacy that is in compliance with the CARB mandate.
The burden of proof of similar efficacy lies solely with the manufacturer, and there are
guidelines which are available from the CARB. The superconcentrated hair spray with a
low flow rate

 Page 158
Table 33 Stiff Feel Anhydrous Aerosol Hair Spray
Ingredient % by Weight
SD 40 B alcohol 69.67
Aminomethyl propanol (AMP-
(as needed) 0.23
95%)
Resin (% solids) 5.00
Gum rosin 0.40
Phenyl trimethicone 0.10
Isobutane/propane blend (A-40) 25.00
Total 100.00
Actuator: Excel 200
Valve: Seaquist NS-34
Misty
Stem: 0.013" Orifice: 0.016" Misty
Body: Capillary
V. tap: 0.013"
ID tubing: 0.040"

Table 34 80% VOC Pump Hair Spray Prototype Formula

% by
Ingredient
Weight
SD 40 alcohol 80.00
Water 11.20
(as needed)
Triisopropylamine
0.60
Resin (% solids) 8.00
Quaternium-26 0.10
Dimethicone copolyol 0.10
Total 100.00
Pump Sprayer: Seaquist Euromist II (160 1 output)
Calmar Mark II or IV
Actuator: 0.014" × 0.010" deep

valve system that delivers the same number of grams of resin to the hair as an 80% VOC
product is one optioni.e., Rave Micro-Spray.
VXI.
Forecast for Future Needs
There is a growing need for antiaging hair care products in many regions around the
globe with larger portions of the population getting older. Products will be needed to treat
and maintain this hair. Healthy, shiny hair will also continue to be a megatrend, so there
will be a need for hair protectants, restorers and restructurizers, and products to promote
shine. Color products and treat-

 Page 159
Table 35 80% VOC Aerosol Hair Spray Prototype Formula
Ingredient % by Weight
SD 40 alcohol 45.00
Water 11.13
Aminomethyl propanol (AMP-95%) (as needed) 0.37
Resin (% solids) 8.00
Dimethicone copolyol 0.10
Lauramide DEA 0.10
Ammonium hydroxide 0.10
MEA borate and MIPA borate 0.20
Dimethyl ether 35.00
Total 100.00
Actuator: ST-150
Valve: Seaquist ST-74
Misty
Stem: 0.018"
Orifice: 0.020"
Body: capillary (under
development)
V. tap: 0.013%"
ID tubing: 0.030"

Table 36 80% VOC Single-Phase Hydrocarbon Aerosol Hair

Spray Prototype Formula
Ingredient % by Weight
SD 40 alcohol 65.00
Water 11.13
Aminomethyl propanol (AMP-95) (as needed) 0.37
Resin (% solids) 8.00
Dimethicone copolyol 0.10
Lauramide DEA 0.10
Ammonium hydroxide 0.10
MEA borate (and) MIPA borate 0.20
Propane/isobutane blend (A-70) 15.00
Total 100.00
Valve: Precision Aquasol Actuator: Precision MBUB
Stem: 2 × 0.020" Orifice: 0.016" CO2
Body: 0.023"
V. tap: N/A
Chamber 2 × 0.010"
ID tubing: 0.060"

 Page 160
Table 37 55% VOC Pump Hair Spray Prototype Formula
% by
Ingredient
Weight
SD 40 alcohol 55.00
Water 40.52
Triisopropylamine (as needed) 0.38
Resin (% solids) 4.00
Quaternium-26 0.10
Total 100.00
Pump sprayer: Seaquist Euromist II (160 mcl
output)
Actuator: 0.018" × 0.010" deep

Table 38 55% VOC Aerosol Hair Spray Prototype Formula

Ingredient % by Weight
SD 40 alcohol 20.00
Water 39.17
Aminomethyl propanol (AMP-95) (as needed) 0.23
Resin (% solids) 5.00
Ammonium hydroxide 0.20
MEA Borate (and) MIPA borate 0.40
Dimethyl ether 35.00
Total 100.00
Valve: Seaquist ST-74 Valve Actuator: ST-150 Misty
Stem: 0.018" Orifice: 0.023"
Body: Capillary
V. tap: 0.015"
ID tubing: 0.050%

ment of colored hair will continue to be important for the aging consumer who wants to
look young. This product category grew 13% to 15% in 1995, and we think there is
significant expansion potential in the future. There will be a continued focus on
environmental and ecological market trends. Lower-VOC products will continue in the
U.S. and other regions such as Canada and Europe, which have started investigating
VOCs. Other environmental trends that will continue are natural, non-animal-derived,
non-animal-tested, recyclable/refill-

 Page 161
Table 39 Styling Spritz Prototype Formula
% by
Ingredient
Weight
SD 40 alcohol 63.25
Water 20.00
(as needed)
Aminomethyl propanol (AMP-95)
0.35
Resin (% solids) 8.00
Lauryl pyrolidone 0.30
Dimethicone copolyol 0.10
Total 100.00
Pump Sprayer: Seaquist Euromist II (160 1
output) Calmar Mark II or IV
Actuator: 0.018" × 0.010" deep

able, and alcohol-free. As we have seen in the past, stiff hair/high hold and soft natural
hold with movement will continue as consumers search for products that are right for
them and also fashionable.
Acknowledgments
The authors wish to acknowledge their colleagues Brenda Hamilton, Greg DuBrowny,
Alfons Holzli, and Ed Walls, Jr. for their assistance in providing information on
corrosion. They also wish to acknowledge Maria Boulden and her staff from Dupont
Fluorochemicals Laboratory, and Walter Dow from US Can for their continued support
and assistance in corrosion programs; to Montefort Johnsen for his guidance in
preventing corrosion of aqueous-based aerosols; and to Dr. Robert Lochhead for
providing information on the history of polymers in hair care.
Glossary of Terms
Creme gel A gel comprised of a dispersion or emulsion of components usually contained
in a creme, but gives similar spreading and feel of either a creme or a gel, and some
holding power or stiffness usually attributed to a styling gel.
Curl activator A preparation that is added to the hair to help fashion the hair into distinct
curls either after shampooing or after the hair has been dry in order to reactivate the
permanent curl of the hair and override the existing set curl pattern.

 Page 162
Finishing spray A hair spray used to fix the hairstyle in place at the end of the styling
activities.
Flowability The ability of a product to spread from a dispensed pile of material to a flat
puddle.
Gel A viscous to highly viscous nonflowable solution of resins in a base that will hold its
own shape; sometimes viscous bases of flowable rheological additives are termed gels.
Glaze A low to medium viscous solution of resins in a rheological base; may be flowable
or nonflowable.
Interfibril interactions The hair cuticle is smooth in the natural statea smooth surface will
prevent interactions between hairs. To increase body, one can coat the hair with resins etc.
to decrease the smoothness of the surface of the hair to increase the drag when one hair
fiber contacts another; this slows down the slippage or sliding of one hair fiber against the
other.
Molding capability The ability of a product to hold the hair in a particular position until
dry (the gel has a high enough yield value to hold its own shape while wet), such as a
finger wave or repositioning a cowlick.
Mold release An additive that prevents material from sticking to the mold, such as hair
sticking to the curling iron.
Plasticizer An additive that makes a resin more flexible; prevents flaking.
Pomade Typically a thick paste comprised of a combination of petrolatum,
microcrystalline or natural wax, lanolin, etc., used to hold hair in place or coat the hair to
give heaviness, coating, or holding power.
Root lift Applying styling product or scrunching technique to develop direction (usually
height) in the hair section at the scalp base.
Scrunching Squeezing and pushing a section of hair with the hand in a crumpled fashion
to develop a deeper or more curl while drying.
Shaping spray A hair spray type formula, perhaps either wetter or with less tack and
perhaps lower resin activity that is sprayed onto the hair before or during the drying and
styling process. The hair is touched and moved while (or after) the resin is dried.
Shine spray A sprayable solution of esters, silicones, or oils designed to impart shine to a
finished hairstyle, but may be added at any time of the hair regimen to give shine,
suppleness, antitack, and detangling.
Singeing Twising a hair strand followed by burning the loose hair with a candle flame.
Spray gel An alcoholic or aqueous solution of resins that are sprayed onto the hair during
the styling process to set the hair.
Spray gel with gel (true spray gel) A visually obvious gel that can be dispensed through a
spray pump.

 Page 163
Structural modulus A general term to relate to twisting, bending, or stretching forces
needed to effect change on the hair.
Tack and dry time The period from time of application of a product to the time it stops
being tacky or to the time it dries.
Teasing/ratting Pushing some of the section of hair closer to the scalp in order to create a
foundation of nonmovable hair at the base to develop rigidity and volume in a hair style.
Tg A temperature range through which the amorphous/noncrystalline polymer passes
from a rigid and brittle solid to a soft and rubbery mass. A polymer may be sticky above
the Tg (44).
Wet look A dried style in which there is a high gloss achieved due to the hair being
aligned as well as the resin/fixative product being undisturbed and existing in a
continuous film; sometimes a formulation that does not dry (high in polyol), looks and is
wet.
Working spray A liquid sprayed onto the hair during the drying stages of the hair style;
could contain either hair spray or setting resins in alcohol or aqueous base.
Yield value The force that is required to make a gel matrix flow; insufficient yield value
will allow suspended items to float or sink, dispersed oils to coalesce and float. A yield
value allows a thick system to be thick at rest and then spread thin upon application.
References
1. Lochhead, R. Y., Hair care gels. Cosmetics & Toiletries 1987; 102(10).
2. Robbins, C. R., Chemical and Physical Behavior of Human Hair. 2d ed. New York:
Springer-Verlag, 1988.
3. Frangie, C., Milady's Standard Textbook of Cosmetology, 1991 ed. New York: Delmar
Publishers, 1991:49.
4. Jachowicz, J., Yao, K., Dynamic hair spray analysis. I. Instrumentation and preliminary
results. JSCC 1996; 47(2):7384.
5. Willit, A. F., Physics of Hair. 2nd ed. San Francisco: Willat, 1960.
6. Robbins, C. R., Chemical and Physical Behavior of Human Hair 2nd ed. New York:
Springer-Verlag, 1988.
7. Griffin, W. C., The HLB System. 1993 ed. Delaware: ICI Americas Ainc., 1993.
8. Jacobsen, M., The hair care market. HAPPI 1983; Nov.:37,39.
9. Johnsen, M., Foamsa classical aerosol domain. Spray Technology and Marketing 1995;
June:48.
10. Vogel, M., The hair care market. HAPPI 1986; Nov.:30.
11. Lord, S., American hair report. Vogue, 1985; July:202210.
12. Aerosol Age. November 1985.

 Page 164
13. Petter, P., Murphy, E. J., Formulating aerosol foam mousse products for hair care.
Aerosol age 1983; Dec.:38.
14. Grollier, J. F., Mandrange, A., Chaily, M., Aerosol hair conditioner foam conditioning
cationic and anionic polymers. Ger Offen Patent DE 3,217,059. 1982. L'Oreal SA.
15. Channer, R. V., Lewis, M. R., British Patent 2,025,228. 1980. Unilever Ltd.
16. Horman, G. R., Cornwall, S. M., European Patent Application 219,830. 1987. Dow
Corning.
17. Jederstrom, G., Rydhy, L., Friberg, S., Liquid crystalline phases in aerosol
formulation. II: Influence of liquid crystalline phases on foam stability. J. Pharm. Sci.
1973; 62(12):19791980.
18. Sciarra, J. J., Stoller, L., The Science and Technology of Aerosol Packaging. 1st ed.,
New York: John Wiley & Sons, 1974:4347.
19. Johnsen, M. A., The aerosol Handbook. 2nd ed., Wayne Dorland Co., 1982.
20. Bartlett, P. L., Aerosol foams and the role of propellants. Aerosol Age 1986; Feb:3235.
21. Oteri, R., Johnson, S. C., Haldar, R., Formulating the Mousse Technical Bulletin. GAF
Corp., 1985:5.
22. Petter, P., Murphy, E. J., Formulating aerosol foam mousse products for hair care.
Aerosol Age 1983; Dec.:36,38,56.
23. Sanders, P., Stiffness measurement of aerosol foams. Aerosol Age 1963; 8(7):33.
24. Breuer, M., M., Tsai, H. C., Measuring the viscelectric properties of aerosol shaving
foams. J. Soc. Cosmet. Chem. 1984; 35:5971.
25. Garcia, M., Diaz, J. J., Combability measurements on human hair. Soc. Cosmet.
Chem. 1976; 27:379398.
26. California Air Resource Board. A Proposed Regulation to Reduced Volatile Organic
Compound Emissions From Consumer Products. October 1990.
27. CARB. Statewide consumer product VOC standards. Aerosol Age 1990; 12:14.
28. Price, S. N. C., Keeping VOC's under control. Cosmet Toil 1995; 110(6):42.
29. Guth, J., Addressing the low VOC hairspray issuenew options. Cosmet Toil 1993;
108(11):97.
30. Rocafort, C., Polymers in hair care. Spray Technol Marketing 1995; 5(5):34.
31. San Giovanni, M., Sprays under pressureNJ content limits for consumer products.
Spray Technol Marketing 1995; 5(4):26.
32. HAPPI Regulations. HAPPI 1995; 32(8):32.
33. Jass, H. E., Regulatory Review, The EPA. Cosmet Toil 1995; 110:27.
34. Rocafort, C., Polymers in hair care. Spray Technol Marketing 1995; 5(5):2834.
35. Johnsen, M. A., Corrosion inhibition of aqueous-based aerosol hair sprays. Spray
Technol Marketing 1992; June:35.
36. Rocafort, C. M., Preventing corrosion in aqueous based aerosols. Spray Technol
Marketing 1995; Dec.:2630.
37. Smith, R. J., Chasten, C., Corrosion protection for miter gates. ASTM Standardization
News 1993; May:5253.
38. Walls, E. W., Hamilton, B., Formulating 80% VOC aerosol hair sprays with PVM/MA
copolymers. Spray Technol Marketing 1994; Feb.:15.

 Page 165
39. Boulden, M. E., Corrosion inhibitors for water-based aerosol formulations. Spray
Technol Marketing 1993; April:3031.
40. Morowsky, N., Martino, G., Bushy, C., Corrosion study of 80% VOC aerosol hair-
sprays containing water. Spray Technol Marketing 1993; May:64.
41. Johnsen, M. A., Corrosion inhibition of aqueous-based aerosol hair sprays. Spray
Technol Marketing 1992; June:38.
42. Lochhead, R., The history of polymers in hair care (1940-present). Cosmet Toil 1988;
103(12):2350.
43. Zviak, C., The Science of Hair Care. New York: Marcel Dekker, 1986:153.
44. Kirk-Othmer. Encyclopedia of Chemical Technology. 2nd ed. New York: John Wiley,
1968:252.

 Page 167

6
Hair Waving
Edward T. Borish
Zotos Corporation, Darien, Connecticut
I.
Objective
The art of hair waving has been practiced for well over 20 centuries. The previous works
of Zviak, Robbins, and others have contributed much to the practice and understanding
of hair waving (1,2). However, with the rapid pace of advancements in science and
technology during the 20th century, our understanding of waving and the practice of
waving have evolved even during the past decade. It is the purpose of the current work to
continue what these others have begun and, like them, not to present a conclusive final
word but to put into perspective recent developments and to provide stimulation for
continuing advancements in the principles and practice of hair waving.
II.
Historical Perspective
The history of permanent waving has been detailed elsewhere (13) and is considered here
only briefly for perspective. Permanent hair waving during the past 50 years has been
based on only two classes of compoundsthioglycolates and bisulfites. And only two
members of the former have gained any substantial commercial prevalence. These are
thioglycolic acid and its salts and the glyceryl ester of thioglycolic acid. This may seem
startling when one considers the wide range of thioglycolate derivatives and other sulfur-
containing reducing agents as well as non-sulfur-containing reducing agents that are
commercially available.
It is interesting to consider a series of systematic studies of the reactivity and toxicology
of about 40 mercaptans published between 1958 and 1961

 Page 168
(46). Of all the compounds tested, and considering efficacy, damage, convenience, and
toxicology, no better overall waving agent than thioglycolic acid could be found at that
time. Perhaps it should not be surprising then that past advances in practicing hair waving
have not been in the use of revolutionary new waving (reducing) agents. New reducing
agents have been invented, and, in fact, hydrides and phosphines in hair waving were
patented respectively in mid-1950 and 1960 (7,8). Commercially, however, advances have
occurred through more judicial use of existing materials stemming from a better
understanding of the fundamental principles of hair waving. Indeed advances in past
decades have been in many cases through the combined use of thioglycolate with other
additives and to some degree in new methods and techniques.
It is important to remember that unlike other cosmetic, permanent hair waving does
indeed effect a permanent change in the hair. In certain countries hair waving
preparations are regulated as drugs. It is a credit to the voluntary self-regulation of the
cosmetic industry in the United States that this is not the case here. Nonetheless, it is
largely the inherent reactivity of waving agents and the need to target hair protein
exclusive of that in skin that has kept new actives from gaining commercial acceptance.
III.
Chemical Dynamics of Hair Waving
A.
Thermodynamics
Hair is comprised largely of alpha-keratin protein, the properties of which are largely
dependent on the presence of cystine sulfur-sulfur crosslinks. Thus, based on current
teachings in chemistry and biochemistry, to permanently wave (rearrange or denature)
hair it is necessary to break a certain number of these disulfide linkages. In this lies the
foundation for the current state of the art in permanent hair waving as being based on
sequential steps of reductive cleavage of cystine sulfur-sulfur crosslinks, molecular and
macroscopic rearrangement, and reoxidation. In fact this has been the basis for the
practice of hair waving for nearly a century and may very well be for some time to come.
It is important to remember that permanent hair waving is not a simple process, nor is
hair simply strands of protein. Describing hair, for example, as a ladder of protein strung
together by rungs of cystine sulfur-sulfur crosslinks is a model that is helpful for
understanding certain aspects of hair and waving but does not represent a complete
picture. A much more detailed treatment is found in the first two chapters of this volume.
Indeed hair is a complex biological structure consisting not only of protein but also lipids,
fatty acids, and other inorganic and organic matter. Moreover, in complexity, the structure
of hair rivals that of the organ skin of which hair is an appendage.
Although the overall chemical process describing the permanent waving of hair is fairly
well established and generally accepted, the interactions of wav-

 Page 169
ing chemicals with hair on the molecular and macroscopic levels are still not well
understood, nor are the physical and chemical changes that occur in hair during waving.
Nonetheless, our understanding of the processes and refinement in the practice of hair
waving has continued to increase over the years, even during the past decade.
The kinetics and thermodynamics related to permanently hair waving have been
addressed by many (928). In terms of the ideal commercial waving agent, it might be
characterized as follows. It should not reduce hair, and it should do so very fast! This
may seem ridiculous, but consider cystine and thioglycolic acid. If we assume that the
reduction potential for S-S crosslinks of cystine in hair is similar to that for free cystine
(29), then we can calculate the potentential (E) for the reduction of hair by what is
probably the best overall waving agent known to date. When we do this we find that E <
0! That is to say, the reduction of hair by thioglycolic acid does not go spontaneously to
completion. But should this be surprising? More importantly, is this bad? No. In fact it is
probably critical to the success of thioglycolic acid as a waving agent.
The reduction of hair with thioglycolic acid has been considered as an equilibrium
process (Fig. 1). Equation (1) shows the reversible reaction of a thiol (R-SH) such as
thioglycolic acid with sulfur-sulfur cystine crosslinks in hair keratin (K-SS-K) to form a
mixed disulfide (K-SS-R) and a free keratin cysteine (K-SH). The equilibrium expression
associated with this step is shown in Equation (2). Reaction of the mixed disulfide with
additional thiol gives the disulfide of the reducing agent and another free hair keratin
cysteine (Eq. (3)). The equilibrium expression for this step is Equation (4). The overall
process which is the sum of equations (1) and (3) is Equation (5), and the associated
equilibrium expression is Equation (6). Reduction of hair with bisulfite like thioglycolate
is an equilibrium process. Bisulfite reacts with sulfur-sulfur crosslinks in hair to form a
free hair keratin cysteine and a thiosulfate group , which is analogous to the mixed
disulfide for thiols. However, unlike the mixed disulfide, the thiosulfate group does not
react with additional bisulfite. Thus the reaction of hair with bisulfite is essentially the
same as the first step for thiols and is described by an equation and equilibrium
expression analogous respectively to Equations (1) and (2).
Since the reduction of hair with thioglycolate is an equilibrium process, the rate and
extent are modulated by the concentration of the reactant thioglycolic acid and the product
dithioglycolic acid (Fig. 2) (23). This of course is the basis for self-timing or stop action
claims made by a number of permanent wave manufactures. However, there are at least
two other, not unrelated reasons for waving systems to be based on an equilibrium
process rather than one that goes to completion. In practice it is found that hair reduced
beyond a certain point does not recover sufficiently when reoxidized (19,27,30). Thus if
one uses a waving agent that goes to completion, one needs to know very accurately

 Page 170
(1)

(2)
(3)

(4)
(5)

(6)
Figure 1
Thermodynamics of hair waving.
the amount of hair being waved to avoid overprocessing. In pratice of course this is quite
impractical. Thus a less effective waving agent (that is to say, one that goes to equilibrium
rather than to completion) seems more desirable to prevent overprocessing and to be
more generally applicable to the wide range of hair encountered in practice. I believe that
this at least in part accounts for the (effectiveness) commercial success of thioglycolic
acid and the thioglycolates in general.
However, it does not explain why cysteine itself has not gained popularity in commercial
waving preparations. After all if an equilibrium process is desirable, then cysteine should
be ideal. In fact, the reduction potential for the cysteine-cystine couple is equal to or even
more favorable than that for thioglycolic acid. However, cysteine alone does not produce
a wave of sufficient strength or duration to be commercially acceptable. The reasons for
this are not completely obvious. But clearly, reducing power alone is not the only factor
determining the effectiveness of a waving agent. Absorption or penetration is critical and
can dramatically influence the precise mechanism by which a given waving agent reduces
hair.
B.
Kinetics and Mechanisms
Studies on the kinetics of hair waving have demonstrated two different mechanisms by
which hair is reduced by thiols and sulfite which are essentially limiting cases of the same
process. In one case, the rate of reduction is faster than

 Page 171

Figure 2
Effect of thioglycolate disulfide concentration during waving.
penetration, so diffusion of the reducing agent is rate-limiting. Under these conditions the
reduction is seen to take place along what is called a moving boundary where ahead of
the boundary the hair is unreduced and behind, reduction follows pseudo-first-order
behavior. This is termed a moving boundary mechanism. In the other extreme,
penetration of the waving agent is rapid compared to reduction, and as such, equilibrium
is established between reducing agent absorbed into the hair and that remaining in the
waving solution. In this situation and where the reducing agent is in large excess, pseudo-
first-order kinetics are observed.
Thioglycolate (12) below pH 910 and bisulfite (9) follow pseudo-first-order kinetics (Fig.
3), where the rate of the reaction with hair has been found to be given by Equation (7)
where t is time, B is the amount of sulfur-sulfur cystine bonds, and kap is the apparent
pseudo-first-order rate constant. In Equation (7) kap is an apparent rate constant because
under pseudo-first-order conditions the concentration of the reducing agent is very high
compared to B and is essentially constant during the reaction. Thus kap includes the
concentration of the reducing agent as shown in Equation (8), where A is the
concentration of the reducing agent and n is the order of the reaction in A. For n = l, k is
the second-order rate constant for the reaction of the reducing agent with hairi.e., that for
the forward reaction of Equation (1). For thioglycolate (12) where n = l, k = 4 × 10-4 M-1
sec-1.
Above pH 10 the deprotonated thiolate anion, which is the active reducing species, begins
to predominate, and so the rate of reduction relative to absorption increases and under
these conditions the reduction follows moving

 Page 172

(7)
(8)
(9)
Figure 3
Kinetics of hair waving.
boundary kinetics (12). However if the hair is oxidatively pretreated with hydrogen
peroxide at pH 11, then reduction with thioglycolate reverts to pseudo-first-order
conditions and is very rapid. This is attributed to a higher rate of diffusion for
thioglycolate in oxidatively treated hair (12). This is consistent with observations in
practice that oxidative coloring or bleaching hair reduces the contact time necessary for
the reducing agent during subsequent waving. Thus permanent waves for tinted or
bleached hair often use lower concentrations of reducing agent and shorter application
times.
The mechanism of reduction of hair with bisulfite is more complicated than thioglycolate,
even though the overall process is apparently simpler. Although bisulfite reduction
follows pseudo-first-order kinetics, indicating a first-order dependence on hair keratin
cystine, the reduction follows saturation kinetics becoming independent of bisulfite
concentration between 0.001 and 0.1 M. This has been interpreted to mean that some site
(or sites) in hair becomes reversibly saturated with bisulfite prior to reduction. In this case
kap for bisulfite in Equation (7) would take the form of Equation (9), where A is the
concentration of, in this case, bisulfite, K is the equilibrium constant for the binding of
bisulfite to some site in hair, and k is the first-order rate constant for reduction. From
Equation (9) it can be seen that at high concentrations the rate becomes independent of A
while a low concentrations the rate with be linearly dependent on A as has been
demonstrated (9).
Sodium sulfide (9) and dithiol compounds capable of forming five or six membered rings
such as dithiothreitol reduce disulfide bonds in hair much more rapidly than thioglycolate
and follow moving boundary kinetics (13). Little is known concerning the kinetics of hair
reduction by cysteine or the glyceryl ester of thioglycolate.
IV.
Changes in Hair Caused by Waving
Waving of hair results in chemical, physical, and structural changes in hair. Not all of
these are undesirable or detrimental, nor are they necessarily irreversible. Hair waving
with alkaline thioglycolate has long been known to be accompa-

 Page 173
nied by swelling of the hair shaft (10,3137). Recent studies dealing with the physical
deformations in the hair shaft during waving have focused on the lateral or crossectional
swelling (Fig. 4) (35) and longitudinal contraction (Fig. 5) (36). The two papers are in
general agreement and show that the majority of physical deformation during a permanent
wave may occur during the rinsing step following waving and preceding neutralization!
Although rinsing of the waving agent may seem necessary, pure water may not be the best
candidate for this purpose. Rinsing with pure water after saturating hair with wave lotion
sets up a powerful osmotic gradient. The result is rapid deformation (lateral swelling and
longitudinal contraction) of the hair shaft which is not entirely alleviated after neutralizing
resulting apparently in permanent damage. By using a salt or buffer solution, the osmotic
gradient is significantly reduced and damage from osmotic shock is thus minimized. It is
interesting to note that sodium thioglycolate which has long been known (37) to produce
more damage and less curl than ammonium thioglycolate also causes greater physical
deformation to the hair shaft on rinsing.
Another significant change that occurs in hair that is waved is its odor. Hair that is waved
takes on a disagreeable sulfurous odor that seems to persist for days, weeks, or longer
and appears to be more pronounced for waves based on GMT than TGA or sulfites. The
exact identity of the compounds responsible for this odor are uncertain. However,
evidence tends to suggest that certain

Figure 4
Changes in hair length during hair waving.

 Page 174

Figure 5
Osmotic swelling during hair waving.
compounds, possibly the actives themselves, become bound physically or chemically into
hair during the waving process. This possibility is consistent with the observations of a
number of investigators (24,38,39).
Although the waving agent is often thought to cause the majority of the damage occurring
during the permanent wave process, other steps in this process also contribute. The
neutralization step is no exception. Changes in the chemical composition and strength of
hair can occur during exposure of hair to peroxide during neutralization. In fact,
Feughelman has indicated that under certain circumstances, more structural and physical
damage is done to hair during hydrogen peroxide oxidation than by thiol reduction (27).
Although free radicals have been implicated in hair waving, convincing evidence for their
participation has yet to be found. However, thiols and hydrogen peroxide are known to
promote the formation of superoxide and hydroxyl radicals, and the destructive influence
of these oxyradicals on biological systems including proteins is well established (40,41).
Changes in hair amino acids and lipids resulting from waving have been demonstrated by
a number of methods including amino acid analysis, FTIR, ESCA, and colorimetric,
electrophetic, and electrochemical methods (1719,24,30,42). Using amino acid analysis,
for example, the major products resulting from cystine loss during waving were found to
be cysteine, cysteic acid, and mixed disulfides. FTIR has the advantage of not requiring
chemical digestion prior to analysis, and shows that cystine monoxide and dioxide are

 Page 175
also formed during waving. Hydrolytic methods used for amino acid sample preparation
likely account for oxides other than cysteic acid not being found.
Although hair is largely protein, a small but significant part of hair is comprised of lipids
(18). These lipids are part of the follicular cell membrane and as such are part of the cell
membrane complex of keratinized hair. The cell membrane complex forms a continuous
network and is responsible for the adhesion of these cell in the hair fibers. Internal hair
lipids originating from the cell membrane complex are lost during waving with the extent
increasing with increasing pH from pH 7.5 to 9 (18).
V.
Formulations and Factors Affecting Waving
Commercially available hair waving preparations generally consist of two components
regardless of whether the product is a home perm or a professional perm intended for use
in a salon. The first is a waving lotion containing, most importantly, a reducing agent. The
second is generally referred to in the industry as a neutralizer and contains, most
importantly, an oxidizing agent. The differences between home and salon perms are
primarily quantitative rather than qualitative. However, there are some exceptions, and
certain types of perms are not available in the home perm market. Conversely, while
certain types of perm formulations enjoy popularity in the home perm market, they may
not have a presence in the salon market.
In the United States today only hydrogen peroxide enjoys any substantial commercial
popularity as the active oxidant in hair waving neutralizers, although in the past bromates
were also used commercially. However, hydrogen peroxide is cheaper, faster, effective at
lower concentrations, and leaves hair feeling softer that bromates. Another reason for the
popularity of hydrogen peroxide is safety. Hydrogen peroxide has an excellent safety
profile while that of bromates has been questioned. However, recent investigations
indicate that bromates can be used safely.
Commercial waving lotions for the home and the salon market, regardless of the identity
of the active, are formulated near or above neutrality up to a pH of about 10. However,
waving lotions in home perms are generally formulated at lower levels of reducing agent
for safety since they are intended to be used by the general population rather than a
trained salon professional. Therefore, waving lotions, regardless of the market, contain
some kind of alkali such as ammonia (and/or an ammonium salt), amines, or sodium
hydroxide (and/or an alkaline sodium salt such as sodium borate). The most popular
alkali in wave lotions regardless of market is probably ammonia or ammonium
hydroxide. Hydroxides of alkali metals or alkali earth metals such as sodium or calcium
are generally not used in wave lotions. Thioglycolic acid salts of these metals, for reasons
that are not completely well understood, tend to cause severe physical

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deformation when used to reduce hair. However, amines such as the ethanolamines are
popular, particularily for low odor or mildness claims. There is a mildness associated with
amine-based formulations because of negative consumer perceptions associated with
ammonia as a harsh chemical since it is often used in hard surface cleaners. Also, because
of the high volativity of ammonia, products formulated with ammonia often have a sharp
distinctive odor. However, this negative consumer perception is largely just
thatperception. The alkalinities of ammonia and ethanolamine are quite similar. Thus
while wave lotions made with an ethanolamine may not smell as sharp as those with
ammonia, the volatility of ammonia helps provide a stop action or self-regulating/timing
benefit. As the ammonia evaporates during the processing, the pH drops, moderating the
activity of the wave lotion with time.
On the other hand, neutralizers are formulated at an acidic pH. This is largely due to the
inherent instability of hydrogen peroxide at alkaline pH. Formulating neutralizers at
neutral to acidic pH is also helpful in removing any residual alkali that may be left in the
hair due to incomplete rinsing of the waving lotion. Commercial neutralizers therefore
contain some organic or inorganic acid such as citric or phosphoric.
In addition to the active ingredient and pH regulators, other ingredients are often added to
hair waving components. These include fragrances, opacifiers, and ingredients to modify
penetration of the waving agent and to help compensate for the damage caused by the
physical deformation and chemical changes that occur in hair during waving. These
compounds consist of perfumes, surfactants, solvents, and conditioning agents including
humectants, emollients, and quaternary ammonium and polymeric quaternary ammonium
compounds.
Permanent waves are probably among the most challenging cosmetics to fragrance and
not just because of the offensive odors often associated with waving caused by certain
ingredients. Fragrance can be formulated into the wave lotion and/or the neutralizer.
Because of the extremes of pH and the reactive nature of wave lotions and neutralizers,
obtaining stable fragrances is challenging. However, this is further complicated since the
fragrance not only must mask the base odor but should also cover the odors associated
with hair during perming as well as post perm sinced permed hair is, in general, not
shampooed for 24 to 48 hours after perming. Thus, the ideal perm fragrance should be
persistent without being overpowering for several days and must mask not only base
perm odor but also odors associated with permed hair which, although sulfurous, are not
identical to those of the wave lotion. It is therefore important that while screening
fragrances, evaluations be made out of bottle but also during and after the perming
process.
In the past floral and in particular rose notes were rather popular in the fragrancing of
wave lotions. This was primarily due to the ability of these fra-

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grance raw materials to withstand the aggressive environment of perm lotions. However,
as fragrance trends and technology have advanced, a wider range of fragrances are now
available for permanent waves, and fruity and fruity/floral fragrances are currently
popular. However, since perms are generally aqueous solutions, fragrance oils must be
solubilized, and nonionics including tweens, bridges, and tritons are typically used.
Opacifiers are often added to wave lotions and neutralizers and have both real and
perceived benefits. In general, cosmetic formulations that are opaque are associated with
milder, more conditioning products. Thus, perms are often opacified to help compensate
for harshness and support conditioning claims. Opacifiers are typically acrylate polymers
or derivatives of fatty alcohols, acids, and amines. Another reason for perm solutions to
be opaque is to help visualize the material during waving.
Another important area in permanent waving is conditioners. Conditioners not only help
compensate for damage to the hair that occurs during perming but also can help to direct
or modify the perm process. Cationic polymers are often formulated into waving lotions
to help maintain uniformity in the hair during reduction or processing. Areas of the hair
shaft where damage has been caused by previous combing, styling, environmental insult,
or previous treatments like coloring tend to allow greater penetration of the wave lotion
(more porous) than adjacent normal areas. These damaged areas also tend to have a
higher negative charge than adjacent normal areas. Cationic polymers tend preferentially
to target these more negative areas and thereby help to protect these areas by moderating
penetration of the waving lotion in these areas. Thus, the penetration of the wave lotion is
more uniform or the condition or porosity can be said to be normalized or equalized.
Simple quaternary amines would function similarily but tend to be incompatible with
wave lotions, forming insoluble precipitates. However, quaternary amines are used in
neutralizer formulations and humectants like glycerin, and fatty alcohols and derivatives
can be used throughout the perming process.
Waving formulations can be and have been categorized in various ways depending on the
goal of the author. Here they are grouped based on the main waving active. As such, there
are in general three basic types of waving formulations which currently enjoy substantial
commercial popularity, and even these are all based on related sulfur chemistry: (a)
alkaline waves, (b) acid waves, and (c) bisulfite waves. Each is based on a different
though related sulfur-based ingredient technology. However, functionally and
mechanistically there seem to be some distinct differences.
Alkaline waves are formulations based on using thioglycolic acid. This label may seem
contradictory but is derived from the pH of the formulation. These formulations are
generally at pH 9 or above. Examples of this type that

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are commercially available are Ogilvie Conditioning Home Perm and, in the salon market,
Luxuriance by Helene Curtis and Design Freedom by Zotos. A subset of alkaline waves
are exothermic waves. These formulations involve the use of a third component, which is
hydrogen peroxide. At the time of use the hydrogen peroxide is added to the thioglycolate
lotion, resulting in conversion of part of the thioglycolate to dithioglycolate. Since this
reaction is exothermic addition of the peroxide activator generates heat and the wave
lotion is warmed to 1218°C higher than the original temperature. The heat generated
accelerates the approach to equilibrium between the waving agent and hair while the
dithioglycolate inhibits the the level of reduction providing stop action or self-timing
claimed by manufacturers. These waves are generally stronger and tend to be preferred
for hard-to-wave hair. Examples of commercial products include Precisely Right by
Ogilvie in the home perm market, Feels So Lively by Zotos, Therma Vantage by Matrix,
and Even Heat by Helene Curtis.
If the carboxylic acid of thioglycolic acid is replaced by the electron-withdrawing glyceryl
ester to give glyceryl monothioglycolate (GMT), the acidity of the thiol proton of nearly
7! This allows the wave to be formulated at a lower pH, resulting in less damage to the
hair. Although acid waves are an important part of the professional salon market, there
are no acid perms in the home perm market. This may be due to possible issues
concerning safety as well as odor. Examples of salon acid waves include Quantum by
Helene Curtis, Acclaim by Zotos, and Opticurl by Matrix.
Acid waves are the class of hair waving formulations based on using the glyceryl ester of
thioglycolic acid (GMT). This may seem a bit misleading since the majority of GMT
products currently available are neutral or slightly alkaline (ca pH 78). However, the first
GMT-based formulations to be commercially available, which were in Germany in the
early 20th century, had a pH < 7 (ca pH 67). They required the use of a dryer to generate
sufficient heat to produce an acceptable curl (accelerate and improve waving). Over time,
the dryer was eliminated, resulting in a more convenient process though one requiring a
higher pH to compensate. The label acid wave, however, has generally been retained in
the industry to distinguish waves based on GMT from those based on thioglycolic acid
(or alkaline salts thereof) or alkaline waves.
The name acid wave is, however, more than a label and has some equity in the hair
waving industry. The lower pH required for GMT formulation is likely to be at least in
part responsible for these formulations being less damaging than alkaline or thioglycolic
acid formulations. The pH constraints of these formulations are dictated by the intrinsic
acidities (pKa) of the thiol proton in TG and GMT since the mercaptide ion is the active
species responsible for reducing cystine sulfur-sulfur crosslinks during hair waving. The
pKa of the

 Page 179
thiol proton of thioglycolic acid is around 10. Thus at a pH greater than 9, significant
amounts of free mercaptide ion are present. However, as the pH approaches the pKa, the
mercaptide anion begins to be the predominant species; higher pHs would result in no
further increase in the level of cystine reduction at equilibrium. In fact higher pHs could
compromise waving since back-reaction of the reduced cysteine in hair on dithioglycolate
will begin to compete with the reduction of cystine in hair as the pKa (1011) of the
cysteine thiol proton is approached (16). In addition, as the pKa of the cysteine thiol is
approached, increased coulombic repulsion of reduced and deprotonated cysteine
promotes swelling and greater hair damage. Furthermore, degradation of hair protein
amide linkages might occur, resulting in irreversible hair damage.
Bisulfite formulations are based on using alkaline salts of sulfurous acid. These
formulations generally do not provide a strong enough curl for the professional market.
Even in the home market they are not a major player compared to thiol-based
formulations again because they generally produce less curl than thiol-type waves.
However, Heat-Activated Whisper Wave by Ogilvie is probably the best-selling bisulfite
perm. This unique product, like the exothermic perms above, takes advantage of the heat
produced when hydrogen peroxide is combined with the wave lotion just before use to
improve the efficiency of perming.
One feature that distinguishes bisulfites from thiols is that bisulfites can provide
permanent set without peroxide reoxidation (15). This is accomplished through rinsing
which removes free waving agent and drives Reaction (1) to the left in the case of
bisulfite. In general, this is not possible for thioglycolates since it is difficult to have
Reaction (1) in the absence of Reaction (3). However, it has recently been shown (27) that
this type of reaction can be utilized if conditions are controlled to maintain low levels of
reduction.
Temperature, concentration, and pH are all known to have dramatic effects on waving.
For thioglycolate, pH increases waving effectiveness or power by increasing the
concentration of the thiolate anion, which is the active reducing form of the thiol.
However, reduction by thioglycolate continues to be accelerated with increasing pH even
after deprotonation of the thiol is complete (10). This is probably due to a higher rate of
penetration as evidence by changes in mechanism over the pH range 913 (10). For sulfites
(15,16) a maximum in waving is seen at neutral pH and is apparently the result of a
number of competing factors all of which are still not clear. Temperature increases the
rate of hair reduction by both thioglycolate (10) and bisulfite (9). However, temperature
does not change the mechanism by which hair is reduced by thioglycolate or bisulfite
(9,10). Exothermic waves tend to be favored for yielding stronger, longer-lasting curls
even on more resistent hair. They take advantage of the temperature effect.

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VI.
TESTING
A.
Safety Testing
The Cosmetic, Toiletry and Fragrance Association (CTFA) has extensively reviewed the
available literature published and unpublished pertaining to thioglycolates and the Expert
Panel on Chemical Ingredient Review (CIR) issued its final report on thioglycolates Aug.
30, 1990 (43). Generally, the finding of the CIR was that commercially used thioglycolates
may be safely sued at infrequent intervals; however, hairdressers should avoid skin
contact. The CIR found that skin testing for irritation and sensitization of these
thioglycolates depends upon the type of system used. Sensitization or the process of
developing an allergic reaction is a complex physiological process. In the broadest sense,
any chemical capable of modifying protein could be a potential sensitizer. Thus, due care
must be taken in demonstrating that waving systems based on the current state of the art
have the possibility of causing sensitization since hair and skin are both protein, and a
system which selectively targets hair and not skin is difficult to envision. However, it
seems clear that the precise method of use is critical in defining safe use and in
developing testing protocols.
In the United States permanent waves are regulated by the federal Food and Drug
Administration as cosmetics under the Food, Drug and Cosmetic Act of 1938 and as
ammended (21 USC). Clearly it is important for anyone who is producing or is intending
to produce permanent waves in the United States to be familiar with this and other federal
and state regulations. Another important consideration that might not be so obvious is that
for the sale of products outside the United States there are other regulations that may be
quite different from those in the United States. Although a full discussion of domestic and
and foreign regulation pertaining to perms is well beyond the scope here, some illustrative
examples may be helpful.
In Japan, for example, both the identity and concentration of active reducing agents in
perms are regulated and require preapproval by the Ministry of Health. There are also
limits on actives and their use levels imposed in other countries, but it is also important to
remember that use of ingredients other than the active may also be limited by regulation.
In the European Union (EU), formerly the European Economic Community (EEC), not
only are the levels of thioglycolate limited, but pH limitations are also imposed and differ
depending on whether intended for use by professionals or the general public. The EU
also imposes limits on ammonia and hydrogen peroxide concentrations that can be used.
The EU also stipulates certain conditions and warnings that must be printed on the label
which depend on the identity, concentration, and intended use.

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B.
Performance
Ultimately the only way to be absolutely sure of the commercial success of a product is to
sell it. Short of this, subjective evaluations testing using volunteer consumers are
probably the most widely used and accepted method for predicting success (1,2).
Nonetheless, an important part of initial developmental testing is tress evaluation. This
involves testing the efficacy of a prototype on samples of authentic human hair which is
available commercially from a number of sources. In this way, optimization of prototypes
can, to a large extent, be accomplished prior to consumer exposure. There are a number
of methods detailed in the literature for measuring efficiency of waving formulations on
hair tresses. One such approach is that of Kirby (44), but others involve similar principles
and can be modified and customized to meet the needs of the individual formulator. The
general approach is to roll or wrap the tress on some device so that the hair tress is
subjected to stress representative of that encountered in waving. The tress is then exposed
to a given formulation, and after rinsing the tress can be evaluated wet or dry. Evaluation
can be qualitative by visual and tactile inspection or can be quantitated by, for example,
measuring the degree to which the tress is shortened by the waving process as a measure
of curl strength.
Conditioning attributes can also be quantitated. An important technique for assessing the
overall condition of waved hair is the liquid retention method (45). Here again the exact
protocol can be modified to suit the exact needs of the formulator. However, the
underlying principle is that the porosity or the tendency of hair to absorb moisture
increases with damage. Instrumental methods also provide important insight into the
chemistry and physics of waving and therefore provide important information for
directing new developments in hair waving.
A number of methods involving intermittent stress and modulus measurements and
bending relaxation have been developed (2,10,25,26) and provide useful information for
predicting set retention. Single-fiber her tensile kinetics (SFTK) has also proven useful in
predicting product performance for thiol based formulations including waves and
depilitories (10,1214).
Electron spectroscopy for chemical analysis (ESCA) and Fourier transform infrared
spectroscopy (FTIR) (17,30,46) are powerful techniques requiring only minimal sample
preparation. Thus, modifications that are sensitive, for example, to chemical hydrolysis be
can detected by these method. In fact, FTIR can be used to quantitate certain sulfur oxides
which represent damage caused by waving (Fig.6).
Fluorescence techniques (47) have been used to demonstrate quantitative differences in
damage caused by various treatments, and could provide useful information about
damage caused by waving. Fluorescence probes specific to thiols have been developed
and used in conjunction with microscopy; the de-

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Figure 6
Changes in FTIR spectrum of hair during
hair waving. Solid line, untreated; dotted line,
reduced (ammonium thioglycolate, pH 8);
dashed and dotted line, reoxidized (2.5%
hydrogen peroxide).
gree and location of reduction caused by sulfur-and phosphorous-based reducing agents
have been visualized (48). Results are consistent with kinetic studies and could provide
insight useful in developing new waving systems.
VII.
Production
Manufacturing permanent waves is generally simpler than for other cosmetics or personal
care products. Most perms including wave lotions and neutralizers are essentially aqueous
solutions. Thus, perm formulations usually don't require specialized mixing equipment
such as homogenizers or mills used in producing emulsions which form the basis of
many cosmetic products. However, there are a number of important considerations
regarding materials for manufacturing and packaging permanent waves.
As previously discussed, perms are formulated with reactive materials and at extremes of
pH. It is therefore important that manufacturing, storage, filling, and packaging materials
be unreactive and free of impurities. Thus, even trace amounts of free metals should be
avoided, and nonmetalic materials including plastics or fiberglass are often used in
manufacturing and handling perms. For example, redox active transition metals such as
copper or iron are well known to react with thiols or hydrogen peroxide and can catalyze
their decomposition.

 Page 183
Metalic components can be used but should be of high quality such as 316 stainless steel
or equivalent, and should be appropriately passivated to eliminate any surface metal
contamination. Thioglycolic acid forms an intense purple complex with iron. Thus even
trace iron contamination can cause discoloration of thioglycolate-based waves. Although
such low-level iron contamination may not initially interfere with product performance, it
can accelerate the autoxidation of thioglycolate resulting not only in poor performance but
also in paneling of the wave lotion bottle. Similarly for peroxide neutralizers
contamination not only compromises performance but causes swelling of the neutralizer
bottle, resulting from oxygen produced via hydrogen peroxide decomposition.
During manufacturing, filling, or even storage for short periods of time, it is not generally
necessary to exclude air as opposed to other reactive products such as hair color where air
is excluded with nitrogen blanketing. Although thiols are thermodynamically unstable in
the presence of oxygen, this autoxidation is kinetically slow. However, it is desirable to
exclude air during longterm storage of thiol-based raw materials and finished bulk wave
lotion.
Perms today are virtually all packaged in plastic bottles although in the past glass bottles
were used. Although this change was probably for ease of manufacturing and handling
and cost, glass is probably not the packaging material of choice for reasons of
compatibility. Glass that is used in mass production of jars and bottles can be
contaminated with relatively high levels of metalin particular, iron. Another important
implication is that while glass is often the material of choice for conducting lab studies,
such as stability, before packaging has been identified, such contamination can contribute
to instability of wave lotions and neutralizers unless appropriate steps to eliminate
contamination are taken. Furthermore, the surface structure of glass itself is known to
contribute to decomposition of hydrogen peroxide. Perm neutralizers are generally sold in
high-density polyethylene (HDPE), acid waves are usually sold in HDPE and low-density
polyethylene (LDPE), and alkaline waves are generally packaged in polyvinyl chloride
(PVC) or polyethylene terephthalate (PET). The choice of packaging is dictated by factors
including cost and compatibility. HDPE is the least expensive while PET is the most,
although increased usage of PET resulting from environmental advantages has resulted in
more competitive cost for PET. On the other hand, HDPE is a poorer oxygen barrier than
either PVC or PET. Thus for alkaline waves, which are prone to autoxidation, PVC and
PET are the packaging materials of choice for long-term stability. For acid waves the
active reducing agent GMT is an ester which is susceptible to hydrolysis under typical use
conditions; it is a water-based, slightly alkaline formulation. For this reason, the GMT is
combined with the rest of the formulation at the time of use, since commercial GMT is
nonaqueous and slightly acid autoxidation is less of a concern and GMT can be packaged
in HDPE or LDPE tubes or bottles. For acid waves where the sole source of reducing
agent is a

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GMT additive, the remainder or the bulk of the formulation can be packaged in a HDPE
bottle. However, in many cases TGA or ATG is added to the bulk lotion to enhance the
curling characteristics of the perm. This is often true for resistant or extra-body formulas.
In these cases PVC or PET should be considered for the bulk of the formulation.
VIII.
The Market
The professional permanent wave market is tremendously fragmented. There are
hundreds of brands being sold by about 100 manufacturers with industry gross sales of
approximately $300MM. This market is very trend-oriented, with dozens of new
introductions each year. It is also a growing market, largely at the expense of the home
perm market. With less time and more income women seem more willing to spend the
extra money on salon perms. Almost every other woman currently is a permer. The
average factory cost of professional perm is about half that of a home perm. This means
that about 80% of all perm sales are in the professional market. There are only a handful
of manufacturers of home permanents and a dozen or so major home permanent wave
brands. Changes in lifestyle with more women working and less free time have led to
fewer women with the skill or the need to roll hair for home perms. However, current
economic trends may change this. Although the home permanent wave market is much
smaller than the professional business, it remains profitable, and there will likely always
be a segment of the population who by their very nature will remain home permers.
IX.
The Future
Although the thioglycolates and sufites are the principal actives to be commercially
important at this time, the search for new ones goes on. One recent development in the
United States is the introduction in the professional market of products utilizing
technology other than acid or alkaline perms. These formulations include cysteamine as
well as thiolactate, and mark the first time in nearly a century that permanent waves based
on a reducing agent other than thioglycolates have been successfully introduced. These
products are distinctly different from those based on thiolycolates. The technology
utilized in these products is described in U.S. Patents 5,260,054; 5,382,426; 5,225,191;
5,332,570; and 5,362,487 (4953) and cover cysteamine, cysteamine derivatives, and
combinations with other perming agents including thioglycolate and sulfites. These
products claim to be able to be used on a wider range of hair types (normal to bleached),
leave permed hair in a condition more like virgin hair, and eliminate the odors associated
with thioglycolate perms.

 Page 185
Another significant recent development (54) is described in U.S. Patent 5,165,427. This
patent describes a cysteine-based technology which overcomes the main disadvantage of
cysteine perms (weak curl formation), while maintaining the advantages of mildness and
low odor associated with cysteine. Three other compounds that claim to have some
advantage and which are covered by patents are thioglycerol alkyl ether, 1-phenyl-2-
mercaptoethanol, and certain quaternary aminomercaptans (5558).
One of the holy grails in hair waving is a nonchemical process, and two approaches that
have been pursued are the use of enzymes and polymers. Although chemical reducing
agents are effective in reducing disulfide bonds, their use also causes a number of side
reactions resulting in other, undesirable changes in hair. The benefit of enzymes is that
they catalyze a specific chemical reaction, thereby preventing undesirable side reactions
and damage. Patents cover the use of protein-disulfide isomerase (59) and (60,61)
thioredoxin. The benefit of a polymer-based perm is that the hair can be permanently
reconfigured without reducing the disulfide bonds in hair. U.S. Patent 5,362,486 (62)
deals with in situ polymerization of hair.
Current public awareness of environmental issues has fueled the recent trend to a
healthier environment and has had a powerful impact on the cosmetics industry. Natural,
nonchemical and environmentally friendly claims are appearing everywhere in advertising
and package copy. It is not surprising then that natural ingredients are being patented
including not only the enzymes already mentioned but also other natural materials such as
glutathione (63) and pantethine (64).
Another avenue of advancement is the combining of services or technologies. A number
of patents and applications describe methods for combining waving and coloring (6567).
Damage to hair by peroxide neutralizers seems to be circumvented by a number of
patented systems using nonperoxide neutralizing. These include disulfides and
succinimides (63,68,69). Another approach is by using vinyl functional silicones (7072),
which possess the advantage of serving to crosslink reduced hair but also simultaneouly
providing conditioning.
A number of recent studies indicate the potential for possible improvements in hair
waving formulations by using micelles, emulsions, microemulsions, and liquid crystals
(7375). The rate and extent of cystine reduction in hair can be increased using micelles
and to an even greater extent using a microemulsion.
Two methods for eliminating perm odor are described in patents assigned Shiseido and
Aveda (7678). One involves the covalent bonding of fragrance compounds having
olefinic or unsaturated sites into permed hair.
The use of ethoxylated mercaptans in waving is described in U.S. Patent 5,241,973 (79).
Stronger and longer-lasting waves are obtained by using mono-

 Page 186
or dimercaptopolyoxyethylene compounds in the molecular weight range 200 to 800. The
use of these materials also provides for permanent conditioning.
X.
Conclusions
To remain a constant is change. Although change in the permanent wave industry is
perhaps slow compared to other industries and segments in this industry, it is not for lack
of effort as evidenced by the wide range of publications, patents, and products available.
It is a profitable though relatively small industry and therefore tends to be lacking in
corporate funding compared to other categories.
This, coupled with inherent difficulties of the process and reactivity of waving actives,
makes new development particularly challenging. However, it is clear that we have seen
and will continue to see new innovations in the principles and practice of permanent hair
waving as we approach the 21st century.
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24. Gumprecht JG, Patel K, Bono RP. Effectiveness of reduction and oxidation in acid
and alkaline permanent waving. J Soc Cosmet Chem 1977; 28:717732.
25. Wortman F-J, Souren J. Extensional properties of human hair in permanent waving. J
Soc Cosmet Chem 1987; 38:128140.
26. Wortman F-J, Kure N. Bending relaxation properties of human hair and permanent
waving performance. J Soc Cosmet Chem 1990; 41:123139.
27. Feughelman M. A note on the permanent setting of human hair. J Soc Cosmet Chem
1990; 41:209212.
28. Feughelman M. A comment on Bending Relaxation Properties of Human Hair and
Permanent Waving Performance. J Soc Cosmet Chem 1991; 42:129131.
29. Clark WM. Oxidation-Reduction Potentials of Organic Systems. London: Baillire,
Tindall & Cox, 1960:471487.
30. Zahn H, Hilterhaus S, StruBmann A. Bleaching and permanent waving aspects of hair
research. J Soc Cosmet Chem 1986; 37:159175.
31. Eckstrom, MG, Swelling studies of single human hair fibers. J Soc Cosmet Chem
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32. Powers DH. Barnett G. A study of the swelling of hair in thioglycolate solutions and
its reswelling. J Soc Cosmet Chem 1953; 4:92100.
33. Herman KW. Hair keratin, reaction, penetration and swelling in mercaptan solutions.
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34. Shransky A. The osmotic behavior of hair during the permanent waving process as
explained by swelling measurements. J Soc Cosmet Chem 1963; 14:427432.
35. Nothen J, Bollert V, Blankenburg G, Hocker H. The influence of the osmotic swelling
behaviour on the quality of the permanent wave. Proceedings of the 16th IFSCC
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36. Garcia ML, Nadgorny EM, Wolfram LJ. Physiochemical changes in hair during
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37. De Navarre MG. The Chemistry and Manufacture of Cosmetics New York: Van
Nostrand, 1941:471481.
38. Storrs FJ. Permanent wave contact dermatitis: contact allergy to glyceryl
monothioglycolate. J Am Acad Dermatol 1984; 11:7485.
39. Morrison LH, Storrs FJ. Persistence of an allergen in hair after glyceryl
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radicals and biological damage. In: Rotilio G, ed. Superoxide and Superoxide Dismutase
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Ann Intern Med 1987; 107:526.
42. Burkinshaw SM, Joy MA, Lewis DM. Hair analysis by derivative FTIR spectroscopy
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43. Elder RL. Final report on the safety assessment of ammonium and glyceryl
thioglycolic and thioglycolic acid. J Am Coll Toxicol 1991; 10:135192.
44. Kirby DH. A method for determining the waving efficiency of cold permanent wave
lotion. Proc Sci Sect Toilet Goods Assoc 1956; 26:1215.
45. Valko EI, Barnett G. A study of the swelling of hair in mixed aqueous solvents. J Soc
Cosmet Chem 1952; 3:108117.
46. Robbins CR, Bahl MK. Analysis of hair by electron spectroscopy for chemical
analysis. J Soc Cosmet Chem 1984; 35:379390.
47. Sukhvinder SS, Robbins CR. A sensitive technique using dansyl chloride to assess
hair damage. J Soc Cosmet Chem 1989; 40:287296.
48. Evans DJ. A method for determining the penetration of reducing agents into wool
using fluorescence microscopy. Text Res J 1989; 59:569576.
49. Borish ET, Nandagiri A, Abbott R, Nardone R. Cysteamine permanent wave
composition and method. U.S. Patent 5,260,054 (1993), Helene Curtis.
50. Nandagiri A, Abbott R, Nardone R, Borish ET. Cysteamine permanent wave
composition and method. U.S. Patent 5,382,426 (1995), Helene Curtis.
51. Nandagiri A, Abbott R, Nardone R, Borish ET. Cysteamine permanent wave
composition and method. U.S. Patent 5,362,487 (1994), Helene Curtis.
52. Bergstrom JM. Wilmott JM. Reducing solution for permanent wave. U.S. Patent
5,332,570 (1994), Dowbrands.
53. Arnaud L. Cosmetic reducing compositions for the permanent deformation of hair
based on an ester of thioglycolic acid and an N-(C2-C4) acyl cysteamine. U.S. Patent
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54. Borish ET. Cysteinamide-containing permanent wave composition and method. U.S.
Patent 5,165,427 (1992), Helene Curtis.
55. Naito S, Ohshima K, Hair waving agent. U.S. Patent 4,935,229 (1990), Kao.
56. Naito S, Ohshima K. Hair waving agent. U.S. Patent 4,935,230 (1990), Kao.
57. Yoshioka I, Kamimura Y, Kitano M, Goto Y. Permanent waving composition
comprising quaternary amminomercaptan compounds. U.K. Pat. Appl. 2223242 (1990),
Nippon Shokubai Kagaku Kogyo.
58. Yoshioka I, Kamimura Y, Kitano M, Goto Y. Permanent waving composition. U.S.
Patent 5,116,608 (1992), Seiwa Kasei.
59. Brockway BE. Treatment of hair. U.S. Patent 4,853,215 (1989), University of Reading
of Whiteknights House, Reading, England.
60. Pigiet VP. Use of thioredoxin, thioredoxin-derived or thioredoxin-like dithiol peptides
in hair care preparations. U.S. Patent 4,935,231 (1990), Repligen.
61. Pigiet VP. Use of thioredoxin, thioredoxin-derived or thioredoxin-like dithiol peptides
in hair care preparations. U.S. Patent 4,919,924 (1990), Repligen.
62. Nandagiri A, Hutter J, Galleguillos R. In-situ polymerization of oligomers onto hair.
U.S. Patent 5,362,486 (1994), Helene Curtis.
63. Siuta-Mangano P. Crosslinking of hair thiols using glutathione disulfide. U.S. patent
4,812,307 (1989), Chesebrough-Ponds.
64. Smith WP, Hawkins GR, Yeung D. Pantethine component for hair permanent waving.
U.S. Patent 4,851,215 (1989), Richardson-Vicks.
65. Pontani S. Method and composition for simultaneously permanenetly waving and
dyeing human hair. U.S. Patent 4,630,621 (1986).
66. Cohen D, Wolfram L. A process for simultaneously waving and coloring hair. Eur.
Pat. Appl. 87113711 (1987), Bristol-Myers.
67. Brown K, Iscowitz S, Masoni J, Wolfram L, Mayer A. Process for dyeing of waved or
relaxed hair. Eur. Pat. Appl. 88310817 (1988), Bristol-Myers.
68. Siuta-Mangano P, Edelstein H. Crosslinking of hair thiols. U.S. Patent 4,793,993
(1988), Chesebrough-Ponds.
69. Siuta-Mangano P. Crosslinking of hair thiols using cystamine. U.S. Patent 4,795,629
(1989), Chesebrough-Ponds.
70. Halloran JH, Dehli GJ. Permanent waving with silicones. U.S. Patent 5,300,285
(1994), Dow Corning.
71. Halloran JH, Swihart TJ. Permanent waving with silicones. U.S. Patent 5,279,818
(1994), Dow Corning.
72. Varaprath PJ, Vincent JM. Permanent waving with silicones. U.S. Patent 5,279,818
(1993), Dow Corning.
73. Parra JL, Garcia Dominguez JJ, Comelles F, et al. Use of microemulsions as vehicles
for nucleophilic reagents in cosmetic formulations. Int J Cosmet Chem 1985; 7:127141.
74. Solans C, Parra JL, Erra P, Clausse M, Touraud D. Influence of microemulsion
structure on cystine reactivity with keratin fibres. Int J Cosmet Chem 1987; 9:215222.
75. Erra P. Solans C, Azemar N. Parra JL. Touraud D. Clausse M. Reactivity of hair
cystine in microemulsion media. Int J Cosmet Chem 1990; 12:7180.
76. Shansky A, Purohit PC. Process of incorporating essential oils into hair fibers and

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permanent waving process and compositions thereof. U.S. Patent 4,832,947 (1989), A-
Veda.
77. Kubo S, Nakamura F. Waving lotions for cold waving. U.S. Patent 4,547,365 (1985),
Shiseido.
78. Kubo S, Nakamura F. Waving lotions for cold waving. U.S. Patent 4,548,811 (1985),
Shiseido.
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enhancements. U.S. Patent 5,241,973 (1993), Shiseido.

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7
Hair Coloring
Keith C. Brown
Clairol, Inc., Stamford, Connecticut
1.
Introduction
There is an extremely wide variety of human hair colors, varying from the palest
Scandinavian blonds to the dark blue-black of the Far East. Even so, individuals appear
to have been dissatisfied with their own particular shading throughout recorded history.
Early hair colorants were obtained from natural sources, but in modern times organic
chemistry has provided a range of synthetic dyes that will produce essentially any color
change that a user could desire. However, as with any other cosmetic treatment, there is a
constant change in consumer needs and desires, especially for a population whose
average age is increasing. The challenge to the hair dye formulators and marketers is,
therefore, to produce materials that satisfy current needs while developing novel products
to satisfy future trends.
Two aspects of hair coloring will not be covered to any great depth in this chapter.
Regulatory requirements for products vary by country, and in many cases they are
currently undergoing revisions. This short review, therefore, will only touch on general
trends, especially as they impact the U.S. market. Toxicology of hair dye ingredients is
also an important and rapidly changing topic. As well as being beyond the technical scope
of this chapter, it is not a topic that could be condensed to a reasonable length and still be
given the depth of coverage necessary for such a complex subject.
To appreciate the strengths and weaknesses of current commercial hair dye products, an
understanding of the natural hair coloring process is required.

 Page 192
This will be reviewed first, although surprisingly little is known of the detailed
biochemistry, despite years of study.
II.
Natural Coloration Of Hair
The color of human hair is due to the presence of melanin pigments. These pigments are
widely distributed throughout the animal and plant kingdom; they appear also, for
example, in squid ink, bird feathers, and the colors of various mildews and molds. In
hair, the pigments are located only in the cortex. In broad terms it appears that the blond,
gray, brown, and black shades are due to eumelanin, and the red and yellow shades are
due to the pheomelanin pigments. While these two classes of pigments may have distinct
and separate biosynthetic sources, current theories tie the biosynthetic routes closely
together.
A.
Eumelanins
1.
Structure and Properties
Eumelanin is the generic term for a variety of dark-colored natural pigments. These
pigments are generally intractable solids which are insoluble in all solvent systems.
Surprisingly, however, these materials can be quite reactive under some conditions. Even
so, except by the classical degradative methods of organic chemistry, structural
information has been difficult to generate. In addition, the natural pigments are always
combined with proteinaceous materials, and separation can be difficult and frequently
incomplete. Thus, the interpretation of any results must be treated with caution, and
particular attention must be paid to the source of the eumelanin, the extraction and
separation methods, and finally any treatments used to solubilize the material or otherwise
prepare it for analysis. Given these caveats, it is not surprising that much of the early
work on structure elucidation of eumelanins is now considered unreliable.
Eumelanin is a polymeric pigment derived from 5,6-dihydroxyindole which is itself
derived enzymically from tyrosine. While it was originally considered to be a structure in
which the indole units remained basically unchanged, there is evidence now that a
significant fraction of these units do not resemble the dihydroxyindole component. For
example, oxidative degradation of the melanin with H2O2 or KMnO4 gives a mixture of
pyrrole carboxylic acids including the 2,3,4,5-, 2,3,5-, and 2,3- derivatives, but the overall
recovered yield is extremely low, suggesting that only a small fraction of the units had
remained in the indole form. Elemental analysis is likewise quite dissimilar from that
expected for a dihydroxyindole polymer, although additional problems are associated
both with the hygroscopic nature of the eumelanins and with proteinaceous contaminants,
so literature results are variable.

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Eumelanins give an e.s.r. spectrum suggesting the presence of a radical in the polymer.
However, the calculated spin density is extremely low (1 spin per 100200 monomer units),
and therefore, while much has been made of the free radical properties in terms of
structural significance, this clearly represents only a small and possibly atypical part of the
polymer. Other spectroscopic tools seem to be of little value in structural elucidation since
only broad bands are observed in UV/VIS and IR spectra.
In general, the properties of hair eumelanin have received little study due to the
difficulties involved in removing the melanin granules from the hair by processes other
than those involving vigorous chemistry. It is quite surprising that the ready dissolution of
hair eumelanins by hydrogen peroxide has not been used more often in structural
determinations. Systematic studies have been undertaken on synthetic melanins, but this
work, while obviously relevant, is beyond the scope of this chapter.
2.
Biosynthesis
The initial theory of eumelanin biosynthesis comes from the works of Raper (1) and
Mason (2), who postulated that the amino acid tyrosine [1] was converted to eumelanin
through a number of stages some of which were controlled enzymically. In general terms,
as shown in Figures 1 and 2, tyrosine [1] is first hydroxylated to 3,4-
dihydroxyphenylalanine (DOPA) [2]. Oxidation to

Figure 1
Early stages of melanogenesis.

 Page 194

Figure 2
Later stages of melanogenesis.
dopaquinone [3], followed by cyclization to leucodopachrome (cyclodopa) [4] and
further oxidation, gives dopachrome [5]. Decarboxylation of dopachrome gives 5,6-
dihydroxyindole [6]. Oxidation of [6] gives the quinone [7], which then polymerizes to
melanin presumably through a number of oligomeric stages. The enzyme tyrosinase is an
important catalyst in some of these steps.
A number of studies have shown that this is an oversimplification of the process, since it
would lead to a homopolymer of 5,6-dihydroxyindole. For example, Ito (3) has suggested
that carboxy-containing intermediates such as 5,6-dihydroxyindole-2-carboxylic acid are
also involved in the polymerization reactions as shown in Figure 2. Probably the best that
can be said with confidence is that eumelanin is a nonhomogeneous polymer
biosynthesized from tyrosine through DOPA, 5,6-dihydroxyindole, and other related
metabolites.
B.
Pheomelanins
1.
Structure and Properties
Pheomelanin pigments are largely responsible for the red and yellow colors of hair and
feathers. While they are obviously different in color from the eumelanins,

 Page 195
they are also characterized by a significant solubility in aqueous or aqueous alkaline
systems. The pheomelanins also show, by elemental analysis, considerable sulfur content
in contrast to the eumelanins. Typically, the sulfur:nitrogen ratio is about 1:2. Evidence
from chemical degradative studies suggests that pheomelanins contain benzothiazine units
such as [8]. Pheomelanins appear to be more stable toward chemical and photochemical
bleaching than eumelanins (4).
2.
Biosynthesis
Pheomelanins are now believed to be formed by a biosynthetic route closely related to
that for the eumelanins (Figs. 1, 2). Dopaquinone [3] reacts with the amino acid cysteine
to give cysteinyldopas [9], which can then cyclize to the various 1,4-benzothiazines [8]. In
this route mixed melanins can be formed by reaction of dopa with cysteinyldopa (5), and
the presence of cysteine or other thiols can trigger a change from eumelanin to
pheomelanin formation. Both of these processes are suspected to occur in nature. A much
expanded version of this whole process is described by Prota (6).
C.
Hair Color
The natural color of hair is determined by its melanin content. Both the total amount of
melanin and the proportions of eu- and pheomelanin (individually or mixed) control the
final color. Dark hair contains significantly more melanin than light hair; in fact, black
hair may contain up to 4% total melanin. Color is also determined by the sizes of the
particles of eumelanin pigment and their distribution density in the hair. In contrast, red
hair tends to have color which appears more diffuse possibly because the pigment
particles are smaller and more irregularly shaped. Although some of the perceived color
may be due to specific chromophores in the melanins, it is likely that most of the color is
due to light scattering by the pigment particles.
A second major contributor to hair color is age. With aging, hair becomes gray due to
absence of the melanin pigments. This process has received little study and significantly
less is known about the biochemical causes of hair graying than is known about melanin
formation. Current theories suggest that inhibition of tyrosinase activity and accumulation
of metabolites in the melanocyte may contribute to graying. However, considerable
advances will need to be made in this area before any realistic attempts can be made to
develop products either to delay the onset of graying or to repigment already gray hair.
For the moment, then, changing one's hair color requires either changing or removing the
natural melanins or adding other colored materials to supplement, or mask, the natural
melanin color. Products are available to perform each of these processes, but it is
interesting to note that, whereas nature uses only one or two coloring species to produce
an endless variety of hair colors, the hair color chemist needs many colorants to produce
even a limited number of hair shades.

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III.
Bleaching
Probably the simplest method of changing the hair's natural color involves either partial
or total decolorization of the natural melanin. In essence, the process can give
progressively lighter colors until finally white or blond shades are produced. While
recipes for bleaching have existed for centuries, the preferred current method involves an
alkaline solution of hydrogen peroxide.
A.
Effect on Melanin
Hair bleaches consist of solutions of up to 12% hydrogen peroxide. While most active at
alkaline pH, peroxide is preferably stored in acid solution, so, immediately prior to use,
the peroxide must be mixed with an alkali-containing base to give a final pH around 10.
Usually, thickeners are incorporated into the base or peroxide to give the desired stay-put
consistency. Ammonia is the preferred alkalizer, and it appears that it is an essential part
of the formulation since less bleaching occurs if other amines or alkaline agents are used
to maintain the pH. In addition, bleaching markedly decreases with decreasing pH. If
extensive bleaching is required or a frosting/streaking effect is desired, peroxide alone is
too slow. In these cases, a bleach booster is added to the peroxide. The booster is usually
a mixture of ammonium and potassium persulfates, added as a powder to the peroxide
solution. Generally, the mixture is then applied to hair as a paste. Alkaline pH is
controlled by metasilicates mixed in with the persulfates, and ammonia is supplied by the
ammonium salts. Bleaching times of 1 or 2 hours are required to decolorize dark hair with
these mixtures, and the aggressive nature of the bleaching mixtures can result in
significant damage to hair during this time. In addition, the resulting hair color tends to be
flat and uniform and difficult to control exactly; most users then treat the hair with a toner
(a dilute solution of dyes) to moderate this peroxide-blonde look.
Although peroxide solutions are only active for bleaching in alkaline solution, they are
not stable for long-term storage under these conditions and are generally supplied at pH 3
to 4. Even at this pH, they are susceptible to catalyzed decomposition processes caused by
heat, light, and trace metals or other contaminants that can participate in redox reactions.
Moreover, considerable pressure can be generated by the released oxygen resulting,
ultimately, in rupture of the container. Metal chelating agents and other stabilizers must
therefore be added to control this chemistry.
Persulfates react slowly with water and are therefore supplied as dry powders either in
single-use foil packettes or in larger drums for salon use. Recent formulation
developments have attempted to limit user contact with the powdered persulfates, which
can be irritating when inhaled. For example, the persulfates can be encased in a water-
soluble package. Some of the versatility of this system is, however, lost with such
products.

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B.
Mechanism of Bleaching
There have been some studies on the factors that control the bleaching process both on
hair (7) and isolated eumelanin granules (4,8,9). In general terms, it appears that two
distinct steps are involved in bleaching: a fast dissolution step in which the granules
disperse and dissolve, followed by a much slower, decoloration step. Dissolution appears
to be specific to peroxide, and occurs maximally at about pH 11. A number of other
oxidants are able to decolorize the solution. It is surprising that the very unreactive
eumelanins can be so readily dissolved by hydrogen peroxide. Dissolution is
accompanied by a significant color change from black to brown, which can result in the
unwelcome perception of reddening that frequently occurs during the bleaching of dark
hair. The chemical steps involved in these processes are unknown, although it has been
argued that dissolution must involve destruction of the various cross-links that maintain
the pigment particles, whereas decolorization involves more extensive breakdown of the
polymeric structure. The efficiency of the peroxide-persulfate mixtures for bleaching may
well be due to different, but complementary, reactivity in these two processes.
The chemistry of these interactions remains, however, unclear. It is also of interest that
red hair is much more resistant to bleaching than brown hair. In view of the importance
of melanin bleaching in hair coloring processes and of the accompanying damage to hair
during bleaching, these processes must continue to receive study so that more effective
and efficient systems can be developed.
C.
Effect on Hair
There is no doubt that the major reaction between hair and hydrogen peroxide involves
decolorization of the melanin. However, there is also some reaction with the hair keratin
producing oxidative or bleaching damage. It appears that the damage is largely a result of
oxidation of cystine to cysteic acid (8) with a consequent weakening of the hair structure
due to loss of the disulfide crosslinks and an overall increase in its hydrophilic nature.
Other amino acid residues are only affected to a minor degree by bleaching with peroxide
(10). These effects are largely perceived by the user as an unwanted change in feel and
combability of the hair. In particular, the hair feels more brittle and is more liable to
break. It is also more sensitive to humidity and much more porous, and therefore will
absorb larger amounts of water. Further chemical treatments, such as dyeing and
permanent waving, exaggerate these effects. A number of techniques have been
developed by the cosmetic chemist to demonstrate and quantitate the results of bleaching
with a view to modifying formulas to reduce or repair damage (11). However, the
preferred method at present is to condition the hair after bleaching or to include
conditioners in the products. Conditioning

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some of these aggressive and reactive mixtures is not an easy task. It is clear that many of
these problems would be solved by a bleaching system that has greater selectivity for the
melanin.
IV.
Hair Coloring
Nature produces the wide variety of hair colors with only one or two colorants. There
have been many attempts to mimic these processes using synthetic or natural chemicals,
and the processes have received wide patent coverage. However, most hair coloring has
had to rely on mixing a number of coloring agents to give a desirable shade. Typically,
products may contain up to 10 or 12 individual dyes of various hues, and the
development chemist has to manipulate the proportions to maintain an acceptable color
through not only the dyeing step, but also through subsequent grooming, shampooing,
and environmental exposure.
Hair coloring products can be divided into a number of categories, conventionally
characterized by the length of time the color will remain on hair. Thus, products are
available that will last essentially indefinitely, through a few shampoos, or that will be
removed by a single shampoo. These product types will be described separately since the
chemistry and physics of the processes are quite distinct, and the effects desired and
expected by the product user are different. The dyes currently in use in each of these
product types have been described in detail by Corbett (12) and Zviak (13). They will
only be referred to in general terms in this review.
A.
Oxidation Dyeing
Oxidative or permanent dyes are the most important class of hair dyes, especially in the
United States. Color is produced inside the hair fiber by hydrogen peroxide-induced
coupling reactions of aromatic amines and phenols. Since H2O2 is used, it will
concurrently bleach the hair's melanin, and shades lighter than the natural hair color can
thus be obtained.
Oxidative hair dyes require three major components for the dyeing process. The primary
intermediates are amino and hydroxy aromatic compounds that form color on oxidation.
Most commonly used are ortho and para aminophenols and phenylenediamines,
although there are a number of similarly substituted heterocycles that are equally
effective. Couplers will not produce color when oxidized themselves, but they are able to
react with the products from oxidation of the primary intermediates to form dyes. Typical
couplers are phenols, meta-aminophenols, and meta-diaminobenzenes. The final
component is the oxidant, which is almost always hydrogen peroxide, although solid de-

 Page 199
rivatives such as urea peroxide, and peroxide generators such as perborate can be used
with equal effect. Oxidative dyeing is usually carried out under alkaline conditions
preferably at pH 9 to 10 which is achieved by ammonia or less commonly and effectively,
by alkanolamines. At the time of dyeing, the alkaline solution containing the dye
components is mixed with the peroxide, which is stabilized for storage and at a pH of 3 to
5. The resulting mixture is then applied to hair for 20 to 40 minutes before being rinsed
off with water.
Surfactants in the dye base help to remove dye deposited on the hair surface, which
contributes to a poor feel and dull appearance. These surfactants also guide the home user
during product application to ensure uniform hair coverage. Typical surfactants may be
soap-based oleic acid derivatives or, more recently, the nonionic ethoxylated phenols.
Most dye ingredients are only slightly soluble in water, and therefore organic solvents are
required to dissolve them during product manufacture and to maintain solution during
storage. Glycols and alcohols are used for this purpose. The dyes are also sensitive to
oxidation, and antioxidants must be added to prevent the formation of dark-colored
product during both manufacture and storage of the product. Sodium sulfite is the most
commonly used antioxidant, and a nitrogen blanket may be used during manufacturing.
The dyeing process is generally repeated every 30 to 45 days as new growth dictates.
Since some users customize their own shade by combining two or more of the
commercial shades, the effectiveness of antioxidants is severely taxed by storage of the
half-full bottles of dye during this time.
Contamination of any of the ingredients by metal salts can cause serious problems when
the dye solutions are mixed with peroxide and applied to the headprincipally rapid heat
generation and foaming. Low-level metal contamination is controlled by sequestering
agents such as salts of ethylenediaminetetraacetic acid. Gross contamination is controlled
by raw material specifications and careful quality assurance checks. Obviously, exposure
to any of the particularly reactive metals during product manufacture is also unwise, and
stainless-steel equipment is commonly used.
Consistency and viscosity of the product are critical. The solutions are required to have
sufficient viscosity to remain localized on the hair (at the roots, for example, when
coloring new growth) and yet be liquid for pouring and mixing. Liquid dye products,
therefore, are generally relatively thin, so they can be manufactured easily and poured
from the container. Gentle mixing by inverting the peroxide container several times gives
a uniform solution of dye and peroxide which must then thicken so that when applied to
the hair, dripping and running are minimal. Polymer systems which respond to the pH
change or physical stress are appropriate. Gel products, in which the viscous dye product
is squeezed from a tube into the peroxide, must dissolve and mix readily and yet remain
thick for the application. Again, appropriate polymer systems are used.

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The product containers and dispensers are very important components since, next to the
final dye result, they represent the major interaction of the product with the consumer.
The dye container must be impermeable to oxygen penetration to control premature dye
oxidation, and be an effective barrier to loss of ammonia, water, and solvent. Glass
clearly was the material of choice, but now most manufacturers are using one of the rigid
plastics. Metal caps, unless lined, are not recommended. The peroxide container should
be opaque to prevent peroxide photodecomposition and comfortably shaped and
deformable for squeezing by the user to give easily controlled dispensing. Plastics readily
serve these purposes.
To summarize then, an oxidative dye formulation must contain the following types of
ingredients:
Alkalizer
Surfactants
Solvents
Foam booster/thickeners
Antioxidants
Dye intermediates
Metal chelating agents
and packaged separately:
Hydrogen peroxide
Stabilizer
The formulation and manufacture of oxidation dye products are clearly complex
processes involving considerable expertise. Equally, quality control is also very
specialized. As well as factors such as pH and viscosity which must be within tight
specifications, the final dyeing result is of paramount importance. Generally, the sample is
dyed onto a hair tress under controlled conditions relative to an acceptable standard and
the variation judged by the eye of an experienced color matcher. Instrumental control,
which is obviously desirable, is also used. All data are complicated by gradual color
changes in the standard dyeings and, frequently, by time-dependent color changes in the
formulations. When this is coupled with the 20 or 30 shades that typically constitute a
retail line of products, and the number of product lines that are marketed, it is surprising
that product consistency can be obtained. In fact, in most cases, the overall variation in
product is quite small and the consumer is tolerant of this variation.
The chemistry of this system has received considerable study both from the viewpoint of
the types of colors that can be achieved and from the complex reaction mechanisms that
are occurring. Consequently, there has been a great

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advance in the understanding and control of oxidative dye chemistry in the last 20 years.
A number of review articles have been written describing the chemistry (1417). In
general, as shown below, the primary intermediate is oxidized to a reactive imine [10]
which then attacks electrophilic sites on the color coupler to
give a diphenylamine derivative [11]. The diphenylamine is then oxidized to the indo dye
[12], which is the basic chromophoric unit of the oxidation dye system. In general, blue
indo dyes are formed from mixtures of p-diamines and m-diamines or
phenols, reds from p-diamines or p-aminophenols and m-aminophenols and
yellow/browns from p-diamines and p-aminophenols and resorcinols . Thus, a
full range of shades can be formulated with these relatively simple mixtures.

The effects on overall color yield of a number of the system's variables have also been
studied (18) with a view to achieving better color control and to better relate solution
chemistry to dyeing results. In general, up to a point, higher concentrations of dye and
peroxide will give more intense color, as will an increase in application temperature. The
effects of pH are complex, since bleaching is markedly reduced at lower pH while dye
intensity can be stronger although the color is usually drabber. Surprisingly, though, most
of this information has been obtained using oxidants other than hydrogen peroxide, and
its final applicability to dyeing technology is open to question.
Little is known about the chemistry using H2O2 although in some cases products similar
to those formed by, for example, K3Fe(CN)6 oxidation, have

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been isolated from H2O2 reactions. Part of the difficulty is due to the instability of the
indo dyes in solution to excess H2O2 making quantitative reaction kinetics and product
isolation complex. The apparent stability to H2O2 of the indo dyes inside the hair raises
the question of the involvement of the substrate in the chemistry. In any event, it is clear
that overall color produced by the dyeing system depends on three competing processes:
Melanin decolorization by peroxide
Color formation by peroxide
Dye destruction by peroxide
All of these processes contribute to the success of the oxidative products. Without the
effect of color loss due to dye decomposition, color intensity would build up on
subsequent applications, resulting in progressively darker color along the hair shaft. Dye
loss, therefore, gives a more acceptable blend of new and redyed color. In addition, this
dual role of peroxide activity also explains why more intense color is not always
produced at increased peroxide concentrations.
It is clear that the dye intermediates have some affinity for hair and can readily diffuse
into the swollen fiber. Water is suspected to be the major carrier of the dyes. Surprisingly,
the phenolic compounds produce strong dye colors even though at the alkaline pH values
of the dye solutions, they are at least partially in the anionic phenolate forms which would
be expected to show some electrostatic repulsion from the negatively charged fiber
surface. It must be assumed that the chemical reactions set up concentration gradients that
force the materials into the hair regardless of charge, or that it is only the neutral phenol
form that can diffuse.
Oxidative colors are stable to shampoo, and the hair only requires redyeing to cover new
growth. Thus, applications are generally 4 weeks apart. Even so, there is a slight color
loss (or shift in shade) due to photolytic or chemical reactions of the indo dyes. Some of
these reactions have been studied in detail with a view to understanding and controlling
the processes.
Removal of these colors from hair is not easy, and no acceptable process is currently
available in case the user is not satisfied with the dyeing results. This may represent the
biggest single drawback of oxidative dyes.
As expected, the process produces a certain amount of oxidative damage to the hair, and
most products contain a conditioning agent to modify the effects of the damage, which is
particularly evident on combing the hair after dyeing. In addition, less damaging formulas
are available. They operate at lower pH and tend to impart less color. Such products have
specific but limited appeal since bleaching does not occur and generally somewhat drab
colors are produced.

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An alternative type of damage occurs in darker shades of the oxidative dyes. Heavy dye
deposition from these shades can give the appearance of hair damage by changing the
tactile properties of the hair. This problem has not been dealt with to any extent by current
products.
For users who require very blond color, it is frequently not sufficient to use the oxidative
products already described. Instead, a two-step procedure is used. The hair is initially
bleached with a mixture of potassium and ammonium persulfate and H2O2 to the shade
approximately as desired, and then slight color is imparted by adding toner, which is a
dilute solution of dyes. This double processing gives pale blond colors and can be quite
damaging to the hair since the bleaching mixture may contact the hair for upwards of 1
hour. Generally, after the first use of these products, subsequent treatments are only
applied to the new growth areas (root application) for this length of time to limit
cumulative damage. The chemistry of the peroxide/persulfate interaction is not known.
While the shampoo-in, liquid tint is very popular in the United States, other product
forms are equally popular in various foreign markets. Dyeing gels supplied in a tube are
convenient provided they readily mix with available peroxide solutions and yet retain
some consistency on the head. In some Far Eastern countries, the dyeing product is
supplied as a powder, consisting of a solid perborate oxidant mixed with the dye
intermediates and surfactants. As far as is known, the chemistry involved is similar to that
for the liquid products.
Recently, products that color in significantly shorter times have been developed to satisfy
various specialized marketsprincipally, 5-minute coloring for the male market. Higher dye
loadings will result in this faster coloring, but the short exposure time gives only
insignificant bleaching. This approach is therefore not likely to appeal to the general U.S.
market. Other specialized applications involve dyeing after permanent waving or hair
straightening where less aggressive products are required even with shorter exposure
times. Various peroxide decomposition catalysts have been suggested for these cases,
sometimes together with lower pH dye products. Alternatively, the user must wait for
several days before dyeing to allow the scalp to lose its sensitivity. It should be noted that
permanent waving and hair straightening chemicals will produce some irreversible color
loss from dyed hair, and thus dyeing should never precede these treatments.
As far as is know, color is produced in the hair by working in from the outside to the
inside and it may not be evenly distributed throughout the cortex, especially in the early
stages of dyeing. This may be a problem with products that recommend shorter dyeing
times. However, most products do attempt to dye evenly along the hair shaft, which
results in the rather flat dyed look frequently associated with hair dyeing. Modern
products attempt to deal with this problem, but in cases where significant color change is
involved, the problem persists.

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From the consumer's point of view, the use of permanent dyes requires a continuing
commitment of time. Additionally, the dyes cannot be removed readily, and so the color
will persist until the hair grows out. During hair growth, new undyed roots will appear,
resulting in a definite color demarcation line which must be redyed at intervals. Salons
may use a specialized root application technique to do this by applying the product to the
root area first and then only applying to the remaining hair toward the end of the dyeing
process. This evens out the color take and attempts to blend the newly dyed hair to the
older, previously colored hair. This is less easy to do at home. Even so, most users do
appear to use a simplified version of this technique. However, to overcome some of these
drawbacks, semipermanent dyeing products were developed. They require less skill in
application and are more readily removed.
B.
Semipermanent Colorants
This class of hair colorant will generally last through a number of shampoos before
needing reapplication. Usually, intensity of the imparted color is relatively low, and
therefore the color is only really noticeable on gray hair. Hence the major uses of such
colorants have been for gray coverage or gray blending on users who have a limited
amount of gray hair. However, in recent years, products have appeared that contain higher
dye loadings and will give quite intense coloration. These products appeal particularly to
the younger, nongray users who desire highlights or brightening of their own hair color.
The dyeing processes involve no chemical reactions, but rely on the diffusion of colored
molecules from solution into the hair cortex. Therefore, little or no damage is done to the
hair by these products.
Semipermanent products consist of a number of dyes, blended to give the desired shade,
and dissolved or dispersed in a detergent base. They are usually applied to the hair as a
shampoo and left in contact for 10 to 40 minutes before being rinsed off with water. In
order to obtain a shade balanced between the relatively undamaged and therefore less
porous root end and the more damaged tip of the same hair, several dyes of the same
approximate color are used. These dyes differ in molecular size. The larger molecules
tend to be retained by the tip end, whereas they do not penetrate the root. The smaller dye
molecules are retained by the root end but diffuse freely in and out of the tip ends. It
should be noted that this differentiation continues through the subsequent color loss by
shampooing and can result in significant shade changes from poorly formulated products.
Typical dye components comprise yellow to orange ortho- and para-nitroanilines and
nitrodiphenylamines, yellow to violet nitrophenylenediamines and nitroaminophenolic
ethers, and violet to blue amino and hydroxyan-

 Page 205
thraquinones. Occasionally, azo dyes are used, but usually they have significantly
different solubility, diffusion, and photochemical properties from the other dyes.
Nitrophenols are used infrequently because of the strong color change associated with
phenol ionization at pH 9 to 10. At first sight, it may seem surprising that such a variety of
colors are available from this relatively simple series of structures. It is indeed fortunate
that minor structural changes can result in significant spectral shifts. For example, N-
alkylation of nitroanilines and nitrophenylenediamines shifts the visible absorption
maximum to longer wavelength in a predictable manner (19) and results in a
bathochromic shift of 20 to 30 nm for each substituent added. Thus, 2-nitro-1,4-
phenylenediamine is orange ( 472 nm in ethanol), and the N1,N4,N4 trisalkyl derivatives
are violet ( ~ 550 nm in ethanol). In addition, such spectral shifts are relatively
independent of the chemical nature of the substituents, giving the formulator an
opportunity to fine-tune characteristics of the dye such as solubility, partition coefficient,
light fading, and shampoo removability as well as control the color by selection of a
particular substituent. For this reason, a wide variety of substituent types have been
patented for these series of compounds in the last 15 years. In actual dyeing practice,
though, alkyl, monohydroxyalkyl, and polyhydroxyalkyl are the most widely used
substituents (12) since they offer a compromise between solubility, affinity for hair, and
availability. Experience suggest that these effects are also present in the other series of
dyes. Again, relatively simple alkyl and hydroxyalkyl substituent are the only ones to gain
practical exploitation. Examples of dyes currently being used in these products are shown
below:

 Page 206

The coloring solution is adjusted to pH 9 to 10 with ammonia or an alkanolamine.

However, it has been found that many of the nitro dyes will undergo a reaction on storage
in alkaline solution during which the amino group ortho to the nitro group is replaced by
the amino group of the alkalizing base (amine exchange). This reaction can result in a
significant color change. Moreover, some alkanolamines are quite reactive reductants for
nitro groups again resulting in unwanted color changes during storage (20). A
combination of these two effects can be quite spectacular, and much care has to be taken
to select compatible dyes and alkalizers. Dyeing at lower pH gives much weaker color
take, possibly because the hair is less swollen and therefore the diffusion process occurs
more slowly.
The semipermanent dyeing systems are typically supplied as thickened liquids (lotions),
but aerosol foams and mousses are also quite common and equally useful and effective.
Thickening is achieved by cellulosic and other common viscosity increasing agents as
well as by the addition of surfactants and various alkanolamides. Antioxidants are not
usually required in these products since the dyes are relatively stable toward oxidation. In
fact, some of the dyes may be used in oxidative dye products to give brighter dyeing
results.
Manufacturing requirements are considerably less stringent for these products, although
metal contamination should be mimimized so that the user need not be concerned if they
later use a permanent dye product or a permanent wave. The dyes are normally
predissolved in the organic components by heating and then added to the aqueous phase
to form a stable emulsion. Quality control is readily amenable to chromatographic
separation and quantitation, although dyeing on hair tresses is probably also done as the
ultimate test by most manufacturers. Overall, therefore, the semipermanent products are
somewhat easier to manufacture than oxidative dyes, but it is selection of the dye

 Page 207
components that is critical to their success. Many of these materials are expensive and
difficult to synthesize.
To summarize therefore, semipermanent dye products are formulated with the following
types of ingredients:
Solvents
Surfactants
Foam stabilizer/thickener
Alkalizing agent
Dyes
Probably the major consumer-perceived drawback of these dyes is their inability to
lighten hair. Since they can only add color to hair, shades lighter than the original are not
available. In addition, the ease of removal by shampooing which was a considerable asset
when these dyeing systems were developed, since 4 to 6 weeks of satisfactory coloring
was obtained when shampooing was done weekly, can be a problem for daily
shampooers. Given typical dye removal in six to eight shampoos, the coloring could need
renewal every week.
It is clear that the semipermanent dyes have some inherent affinity for hair. During the
dyeing process a considerable fraction of the total dyes do deposit either in the hair or on
the hair surface, and penetration through the diameter of the hair shaft appears to be
uniform. This property, and the corresponding ease of removal by shampooing, is related
to structural features of the dyes. In general terms, it seems that the water-insoluble azo
and anthraquinones are relatively difficult to remove from hair but that the
nitrophenylenediamines shampoo out quite easily. This difference is magnified on hair
damaged, for example, by waving or straightening, and in such cases, the effects of
different dye removal rates can become very evident. A loose correlation exists between
the degrees of affinity for hair and the dyes partition coefficients, but such connections
are somewhat empirical.
It is common practice to increase affinity (or, more likely, penetration and color take) by
increasing the dyeing temperature. Hair dryers or even a plastic cap will suffice to extend
shampoo resistance of these dyes. However, the goal of a longer-lasting semipermanent
product, based on these kinds of dyes and not employing peroxide or ammonia, still
eludes the formulator.
C.
Temporary Colorants
The previously discussed coloring systems are used by consumers who wish to change
their hair color on a long-term basis. However, there are a significant number of people
who desire a color change for a single event, and wish to remove that color at the
following shampoo. Alternatively, users who shampoo infrequently may wish to use an
easy, quick-to-apply colorant, and do not object

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to reapplying it after every shampoo. Temporary colorants or color rinses satisfy these
users. Probably their primary uses are in masking unwanted gray in light-colored hair, in
covering yellow in gray hair, and in giving party colors.
Coloration occurs by deposition of disperse or acid dyes on the surface of the hair. These
dyes have little affinity for the hair, and tend to be quite soluble in the aqueous carriers.
Complexation or precipitation is therefore required to deposit the dyes, and cationic
surfactants or cationic polymers are frequently incorporated into formulations for this
purpose. However, it is clear that long-term storage of single solutions containing both
dye and precipitant is a problem. In some cases, high surfactant levels are used to
disperse the precipitate or complex into a more stable form. Examples of typical dyes are
shown below:

Generally, the temporary dyeing process is associated with some other kind of hair
grooming (e.g., setting), and reagents for this process will also be contained in the
formula. Depending on the particular product, a rinsing step may be involved. Coloration
can be done quickly, but the dye is readily removed by shampooing, and to a lesser extent
by rubbing and a water rinse. These products are marketed as simple, easy-to-apply, no-
risk, no-commitment rinses, and U.S. companies frequently use only certified dyes (as
shown above). This permits the products not to carry the patch test and warning labels
required on other hair dyeing products and further enhances their safe and easy-to-use
image.
Current temporary products are thin liquids which run and drip during use. In addition,
the dyes readily stain the scalp and skin so the application can turn out to be quite messy
and unpleasant even though it is quick. This is surprising

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in products that may represent a consumer's first exposure to hair coloring. There is
clearly the need for temporary products with improved application procedures and better
dyeing properties. Unfortunately, this category represents only a small fraction of hair
color sales, and therefore it does not receive the technical attention it needs.
D.
Progressive ColorantsThe Male Market
Color changes produced by the previous products are relatively instantaneous and can be
quite noticeable. However, a substantial number of users prefer a colorant that produces
color in barely perceptible amounts after each application. Over a period of time, and
with frequent use, the color change is, however, significant.
The most common components of these products are salts of lead and bismuth (acetate,
citrate, etc.) dissolved in an aqueous base. They are believed to form metal sulfides in the
hair's cuticle by slow interaction with cysteine residues. However, the colors produced
tend to be inconsistent and sometimes undesirable, and are difficult to remove. The shade
range is also very limited.
A second approach to producing this effect involved the autoxidation of polyhydric
phenols (especially trihydroxybenzenes, but also some dihydroxybenzenes and
aminophenols). While the various systems have been known for some time, it is only
recently that this technology has been exploited. It is usually desirable to add other color-
forming materials to these systems to develop acceptable shades. Even so, the shade range
is generally quite limited since the oxidation products are drab browns or yellow. In
addition, although intense coloration is achievable with relatively few applications, the
color continues to develop for some time after application, and is therefore difficult to
control and reproduce.
These hair dyeing processes are particularly suited to the male market since it is generally
believed that only a few generic shades (light, medium, dark brown, etc.) are needed to
satisfy men. In contrast, a typical women's line of colorants may contain upwards of 20 or
30 shades. Furthermore, most men may be unwilling to spend the 30 to 45 minutes
required for dyeing with the typical permanent and semipermanent dye products. For this
reason, products using conventional dyeing technology, but dyeing in only 5 minutes,
have recently appeared on the market. These products necessarily involve a compromise
in color rendition (weaker and drabber) and possibly in subsequent wearing properties
(more prone to light- or shampoo-induced color changes). However, they are marketed
specifically at men, where these disadvantages may not be so relevant.
Except for some teenager-oriented products, bleaching products have not been aimed at
the male market specifically. There is good reason to expect increased marketing of hair
coloring to men in the next few years with products designed to appeal more specifically
to the male user.

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E.
Melanin-Based Colorants
There are considerable opportunities for the innovative hair dye chemist in the area of
coloring processes based on melanin and melanin precursors. Indeed, this area has
received increased attention in the patent literature during the last few years. It appears
that the major focus is on practical dyeing systems based on 5,6-dihydroxyindole (DHI),
probably since it represents the closest isolatable intermediate to melanin in the natural
pathway and therefore presumably requires the least chemistry for conversion. However,
few technical papers on the hair dyeing potential of this intermediate have been published
(21). Apart from the difficulty in synthesizing and isolating this reactive chemical, storage
stability also seems to be a problem. Early work showed that color formation from DHI
was relatively slow and gave gray to black shades that lacked warm tones. It has been
shown that a variety of oxidants accelerate color formation sometimes with the
development of warmer tones in the shade produced. Among the oxidation systems
covered are metal ion-catalyzed autoxidation (22) and iodide-hydrogen peroxide
combinations (23). The melanins formed by these systems appear to be quite similar to
natural eumelanin in properties and reactivity. However, to produce an acceptably wide
range of shades, other dyeing materials must be added to the coloring systems.
Tyrosine and DOPA have also been claimed as dye ingredients using enzymatic (24) or
chemical oxidation (25,26) to produce the melanin. These materials are more readily
available and more stable than DHI, but it is not known whether the chemistry involves
the formation of DHI or is at all related to the natural pathway. Similar questions arise
about coloring systems based on related compounds such as dopamine (26), epinephrine
(27), and 5,6-dihydroxyindole-2-carboxylic acid (28,29). One recent patent does,
however, claim to have partially resolved this problem by obtaining high conversions of
DOPA to DHI during the hair dyeing process (30).
The utilization of preformed melanins, either chemically produced or isolated from
natural sources, is limited by insolubility. Preferred applications so far are therefore in
cosmetics where pigments are currently used, e.g., eyebrows (31), or in sunscreen
products (32).
With all this diverse and extensive patent activity, it might be expected that the market
would be flooded with products based on this technology. This has not been the case.
While cost of raw materials is certainly one major hurdle, it seems clear that there are also
significant technical barriers to be overcome in this area. In addition, consumer appeal
may be limited since most processes do not involve or tolerate hydrogen peroxide and
consequently do not lighten hair. A full shade range is, therefore, not available.
On the technical side, almost all attention seems to have been concentrated on the two
stable and isolatable intermediates in the melanin biosynthetic pathway (DOPA and DHI).
Even so, most color formation processes from

 Page 211
DOPA and to a greater extent tyrosine are especially poor, with only weak colors
produced over long exposure times.
F.
Natural Colorants
Some natural colorants that have been used for dyeing hair for centuries are still in use
today. The most widely used is henna, which imparts a strong orange/reddish color to
hair. While this may be good for giving red highlights to dark hair, the overall color tends
to be too unnatural and brassy for gray hair. The coloring species in natural henna is
lawsone, 2-hydroxy-1,4-naphthoquinone [13] which occurs at concentrations of 0.51.0%
in the plant. Other vegetables dyes such as chamomile are little used for dyeing.

Natural extracts appear to have greater use in some Asian countries, where the main
purpose is to blacken graying hair. Primary among these are the extracts of nutgall (active
colorants gallic acid [14] and other tannin precursors), logwood (active colorant
hematoxylin [15], and brazilwood (active colorant brazilin [15]. As with all of these types
of natural coloring systems, a very limited color range is obtainable, although color
intensity can be very strong. Given a choice, most users seem to prefer the predictability
and versatility of systems based on synthetic dyes.
G.
Miscellaneous Colorants
The patent literature is replete with hair coloring systems that have not achieved
commercial importance. Generally, this is not because of ineffectiveness at col-

 Page 212
oring, but rather the use of expensive components or development of unwanted side
effects. For example, cationic dyes are known for their rapid color take and strong
affinity for hair. However, with variably damaged hair, color can become patchy and
unpleasant looking. This may be moderated by incorporating polymers into the system,
but exploitation has been very limited.
Despite extensive patent coverage, products containing colored polymers have not
reached the market. While cost is certainly a factor, it seems inherent that any polymer
coating on the hair shaft has to substantially change the feel and properties of the hair.
Again with such a varied surface, it may also be impossible to obtain coherent coverage,
and thus the color will appear patchy.
H.
Consumer's Choice
So far, the various hair coloring products have been described and categorized largely by
their technical limitations. It is unlikely that a consumer would use such rationalization in
selecting a product. Instead, some stimulus prompts the desire to color hair, and the task
becomes selection of the most appropriate colorant. It is probable that the most common
reason for coloring is the onset of graying.
With the presence of a small amount of gray hair, the user prefers to blend the gray and
natural color so the gray is merely less visible. Temporary and semipermanent products
can do this very effectively while doing little to change the overall hair color. The
frequency of shampooing and need to reapply color then determine the better choice of
product. It should be noted that many users who are totally gray can also use these
products to good effect.
If the user has a considerable amount of gray hair, blending requires not only adding
color to the gray hair but also removing or changing the color of the nongray hair to
ensure a better match. Only the permanent dye products will perform this task
satisfactorily, and the user is then left with the selection of preferred product form (lotion,
cream, gel) and mildness (nonammonia products are milder).
The other major consumer-determined selection is the shade to use. While this depends
on many factors, including original hair and skin color, it is generally considered
preferable to use a shade somewhat lighter than the natural color as a starting point.
For the user who desires marked color change, the choice of product is dictated by the
length of time for which the color change is required. These properties have been
described in the previous sections and will not be discussed further here.
Whether male users apply different criteria in selecting a product is open to question.
However, some of the factors that influence the types of products available for the male
market have been described earlier. Apart from personal

 Page 213
preference, there is no reason similar products should not be used interchangeably
between the sexes.
On a worldwide basis, products seem to be differentiated more along the lines of
appropriate shades than on the type of product. There is evidence to suggest, however,
that in some countries the usage of semipermanent products is increasing relative to other
colorants. This probably reflects the brighter colors available from this type of product
and the preference of that particular population for this effect.
I.
Safety and Regulatory Issues
Regulations are covered in another chapter of this volume. However, there are some
regulations that are specific to hair dyeing. These are described in general terms and very
briefly here.
Hair coloring products in the United States are regulated under the hair dye exemption to
the Federal Food, Drug and Cosmetic Act. This act classified cosmetic products as
adulterated, and therefore not permitted to be sold if other than approved colorants were
used. Hair dyes are specifically exempted from these adulteration provisions of the Act if
they use coal tar derivatives as the hair colorants and they carry a statutory warning
statement and instructions to perform a skin patch test 24 hours prior to using the
product. Hair coloring products in the United States, therefore, either use approved
(certified) dyes and carry no warning and patch test requirement, or use coal tar
derivatives and carry the statutory warning and patch test requirements. Henna and lead
acetate are included in the list of approved colorants.
The patch test is particularly relevant to oxidative hair dyes since p-phenylenediamine, a
major component of these products in the United States and many part of the world, is a
known sensitizer that is capable of producing contact dermatitis. Current practice of the
patch test involves applying the dye mixture, with peroxide if appropriate, to a sensitive
area of skin (inside forearm, for example). The area is then left undisturbed and
uncovered for 24 to 48 hours. If no reddening occurs, the consumer can safely use the
product. If, however, itching or reddening occurs, the consumer is warned not to use the
product since a more severe reaction could occur with more extensive application and
exposure. While consumer compliance with this protocol is difficult to assess, it is
probably fairly high since the overall incidence of allergic dermatitis to hair dye products
is low.
Retail cosmetic products in the United States have also been required to carry ingredient
listings since 1977, and many manufacturers have also participated in the voluntary
ingredient registration program initially started in 1972. These regulations, and those
currently in effect in many other countries, have been reviewed (13).

 Page 214
Toxicology of hair dye ingredients has received considerable publicity and much effort
has been directed towards testing protocols to establish product safety. A review of this
information is well beyond the scope of this chapter, and there are many technical articles
which deal with the general, historical, and detailed aspects of hair dye safety. This large
volume of data suggests that current hair dye products are extremely safe and present no
risk to the users when used as recommended.
V.
Future Prospects
While the steady improvement in current hair dye products is likely to continue, it seems
that major breakthroughs into new dyeing techniques will only occur when there is a
better understanding of the properties and structures of natural melanins. This
information could allow us to develop specific bleaches which will only attack melanin
and not hair keratin, or enable us to sensitize the melanin so that it can be decolorized or
altered at will by specific triggering devices. Along these lines, the use of lasers to bleach
hair has been suggested (33,34). While these processes are apparently effective and
require very short exposure times, exploitation of such findings must await the
development of more suitable equipment so that the process can be operated in a
controlled and safe manner. In addition, being able to produce a wide variety of hair
colors with a single component is an attractive proposition to most formulators.
Furthermore, an understanding of the biochemical mechanisms by which animals can
alter their hair color opens up a totally new area for the hair dye chemist. In the
meantime, current products offer the consumer a wide variety of effects that are based on
well-established chemistry and can be readily performed by the home user.
References
1. Raper HS. Biochem J 1927; 21:89.
2. Mason HS. J Biol Chem 1948; 172:83.
3. Ito S. Biochim Biophys Acta 1986; 883:155.
4. Wolfram LJ, Albrecht L. J Soc Cosmet Chem 1987; 38:179.
5. Ito S, Novellino E, Chioccara F, Misuraca G, Prota G. Experientia 1980; 36:822.
6. Prota G. Melanins and Melanogenesis. San Diego: Academic Press, 1992.
7. Bollert V, Eckert L. J Soc Cosmet Chem 1968; 19:275.
8. Wolfram LJ, Hall K, Hui I. J Soc Cosmet Chem 1970: 21:875.
9. Zahn H, Hilterhaus, S, Strussmann A. J Soc Cosmet Chem 1986; 37:159.
10. Chao J, Newsom E, Wainwright IM, Mathews RA. J Soc Cosmet Chem 1979; 30:401.
11. Jachowicz J. J Soc Cosmet Chem 1987;38:263.

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12. Corbett JF. Rev Prog Coloration 1985; 15:52.
13. Zviak C. The Science of Hair Care. New York: Marcel Dekker, 1986.
14. Corbett JF. J Soc Cosmet Chem 1973; 24:103.
15. Brown KC, Corbett JF. J Soc Cosmet Chem 1979; 30:191.
16. Brown KC. J Soc Cosmet Chem 1982; 33:375.
17. Brown KC, Corbett JF. J Soc Cosmet Chem 1986; 37:1.
18. Brown KC, Pohl S, Kezer AA, Cohen D. J Soc Cosmet Chem 1985; 36:31.
19. Corbett JF. J Soc Cosmet Chem 1984; 35:297.
20. Bil M, Corbett JF. Dyes Pigments 1981; 2:215.
21. Brown KC, Mayer A, Murphy BP, Schultz T, Wolfram LJ. J Soc Cosmet Chem 1989;
40:65.
22. Bristol-Myers. British Patent 2,132,642 (1986).
23. L'Oreal. U.S. Patent 4,804,385 (1989) and some later patents.
24. Peck SM. U.S. Patent 2,539,202 (1951).
25. Goshen College. U.S. Patent 4,453,941 (1984).
26. Repligen. U.S. Patent 4,746,322 (1988).
27. Clairol. U.S. Patent 4,904,274 (1990).
28. Kao. Japanese Patent 01-33210 (1991).
29. Bristol-Myers. European Patent 342,034 (1989).
30. Clairol. U.S. Patent 5,273,550 (1993).
31. L'Oreal. U.S. Patent 4,961,754 (1990).
32. Advanced Polymer Systems. U.S. Patent 4,806,360 (1989).
33. Clairol. U.S. Patent 4,792,341 (1988).
34. Wella. PCT Application WO 91-06279 (1991).

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8
Fragrance for Hair Care Products
Peter Dichter
Peter Dichter and Associates, New York, New York
A new shampoo was being developed. A great deal of care went into this development.
The formulation was unique in many ways. The packaging was costlier than average. The
advertising and promotional budgets were the highest in the history of the company. Even
the color of the product had been carefully researched. On the day of the product launch,
key executives from the company were placed in various stores throughout the home city
to observe consumers and note their reactions to the product. Would they reach for it
amidst all the competition? Would all their investment in time, energy, and money pay off
in sales? Well, one executive (whom we'll call Peter) related his day, a day that reflected
the day of the other executives as well.
It was about 10:00 A.M. when the first woman stood in front of the Hair Care section
and paused. She scrutinized the shelves. She reached out. She chose our Shampoo.
Then she opened the cap and smelled it! And she closed the cap and replaced it on the
shelf. I would have thought she was some kind of weirdo, except that almost every
other person who bought a Shampoo that day did the same thing, not only to our
product, but to others, as well.
Peter's story can be verified by you. Observe for yourself the buyers of hair care
products. In fact, observe the buyers of virtually any toiletries or household product.
Don't you smell a product before you use it? Sure you do. And all the money and effort
that had gone into the creation of that shampoo was wasted because no one had bothered
to create a fragrance that would be as positive as the product's promised performance.

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Fragrance plays a critical role in hair care products. It can inspire the first purchase,
communicate through your senses that the product is doing its job, give you overall
positive feelings about the product, and maintain brand loyalty. From a marketing point
of view, it can reinforce a strategy. From an esthetic point of view, a nice aroma is a turn-
on. Why?
Our sense of smell is highly underrated. It may be the most primitive sense of all, yet it
has psychological overtones our other senses lack. The sense of smell brings back
memories and experiences like no other sense. I remember my sister-in-law passing a
flower store with me and suddenly recalling her days as a piano student. It's the
eucalyptus. His place always smelled of eucalyptus. I hated my lessons and to this day I
hate the smell of eucalyptus. The memories evoked aren't always pleasant, obviously.
Your sense of smell is keener in the summer than in the winter. Left-handed people smell
differently from right-handed people. Our sophisticated machines that can break down all
the chemicals in a rose can't exactly duplicate that smell. So this sense, so many times
summarily dismissed as primitive, is actually a lot more complex than we realize. Maybe
that's why perfumes have had such a fascinating history. The very word perfume derives
from the Latin through smoke because of its use during religious ceremonies. Ancient
Egyptians put bottles into tombs to make passage to the afterlife more pleasant. The Bible
has multiple references to fragrant oils like frankincense and myrrh.
The creation of a fragrance is no mean feat. A perfumer has at his or her disposal
extractions of flowers (petals and stems), roots, barks, spices, herbs, animal exudates,
resins, fruits, mosses, and synthetic chemicals, but putting them together into a pleasant-
smelling, appropriate, and stable scent takes a great deal of skill. Picture yourself as a
perfumer blending jasmine from France, lemon oil from Argentina, cinnamon from
Madagascar, pine needles from Russia, orange oil from the United States, sage oil from
Spain, sandalwood from India, and rose oil from Morocco. Did you know it takes 4,000
pounds of rose petals to make a single pound of rose oil? But because that pound costs
$3000, its use must be carefully considered since a perfumer must also work within the
confines of cost parameters.
But we're getting ahead of ourselves. Let's go back to the beginning. Let's say that this
time Peter and his company are well aware of the role fragrance plays in hair care
products. And they are developing a whole line. As always, marketing and R&D develop
the products with a specific consumer strategy in mind, and ultimately the development of
the fragrance will be based on that strategy. And so the process of fragrance development
is put into motion and a selected number of fragrance houses with their perfumery
resources will be called in to create the ideal scent. Ostensibly the creation of the ideal
scent is a combination of the perfumer's artistry, imagination, and inspiration, but in
actuality that ideal scent is the product of a great deal of planning

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on many levelsand there's a lot of trial and error, to boot. Many elements are involved and
each must be treated separately as well as within the framework of the larger context.
Fragrance development begins with the profile (Fig. 1), which is essentially a blueprint
containing these elements:
1. Name and address of the company and the person issuing the profile
2. Product(s) to be fragranced
3. Type(s) of fragrances desired
4. Cost parameters
5. Base(s) to be fragranced (sent under separate cover)
6. Percentage of fragrance desired in each base
7. Number of fragrance submissions allowed for each product
8. Form and quantity of the submissions
9. Other pertinent data: timing, method of delivery, stability requirements, accompanying
documents, special requests
The ideal profile is rare since it should provide the marketing strategy, the target
competition, and the method of determining the winning fragrance, and it rarely does.
Therefore it is up to the account executive (the fragrance house's saleperson) acting as
liaison between the fragrance house and the client to fill in the blanks. Through
conversations with client personnel and a knowledge of client tastes and goals, the
account executive can communicate important, subtle, unwritten data to the key people of
his or her company.
For this reason, the A/E has assembled Odor Inc.'s marketing group, evaluators, and the
chief perfumer to discuss the new profile from Winnifred Tresses.
Winnifred Tresses with its present lines skewed towards an older, more conservative
audience, would now like to target the young. Younger users tend to be more
adventuresome in their product choices and in the composition of those products.
They are frequent users of Hair Care products, toomany teen-agers wash their hair
every day, perhaps more than once a day. The good news from the corporate point of
view is that young consumers use up products at a much faster rate and are willing to
experiment with new products. Of course, the bad news is that they have limited or no
brand loyalty so each aspect of a new product must please them a great dealand
 fragrance is an element they notice immediately. If the in-shower experience is
important to any user of hair products, it is critical to the teen.
There may appear to be a dichotomy here. Is it possible to create a conservative fragrance
for a venturesome consumer? A soft light floral may be as inappropriate as a powerful
fragrance that smelled like chocolate fudge.

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Figure 1 A typical profile as issued by the manufacturer to the fragrance supplier.

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At this point, the evaluation group asks a critical question: Who is going to evaluate the
fragrance we submit? The target group (teens), or an in-house panel from Winnifred
Tresses? If it is the target group, it would be wiser to err on the side of the chocolate
fudge fragrance. If it is in-house, a less dynamic fragrance would win. In this case, an
internal panel will screen the fragrances, which will then be sent on to a panel of teens.
Therefore, from Odor Inc.'s vantage point, a compromise is clearly in order.
Enter the marketing group, counterparts to the marketing group of Winnifred.
Winnifred Tresses has been a leader in hair care, but they haven't had a real success for
a few years and their share of market is slowly declining. As a result, they are losing
space and positioning on the shelf. Their key problem is that their present users are
getting older, and they haven't been able to attract a younger audience. They are a
midpriced line and want to avoid getting into the price-value segment of the
marketplace. In the past, this company has chosen low-impact fragrances with minimal
substantivity. This is in keeping with the conservative imagea tremendously offbeat
fragrance, even if right for the teen market, will be difficult to get through their panel.
Yet each of their present products contains a fragrance appropriate to the marketing
strategy of that product, indicating that they appreciate the value of a well-chosen
scent. What's their competition doing that Winnifred isn't?
Although fragrance is the main concern of Odor Inc.'s marketing group, packaging,
advertising, and demography are also topics of discussion. Imagine being surrounded by
a dozen or more hair products that represent the current marketplace. Technically, all
these products represent competition, but those specifically aimed at the younger segment
of the market will be analyzed more carefully. This includes not only present competition,
but also two soon-to-be competitors scheduled for introduction within a short time. One
of them has been in test market, so marketing has obtained the products. The other is
known by its trendy strategies, and while nothing is known about the fragrance, an
educated guess may be possible based on other products within that company's lines. For
odor evaluation purposes, shampoos are the products of choice because in most cases
their relatively bland basenotes don't tend to interfere seriously with the fragrance. All the
shampoos will be smelled from the container, to simulate the store experience; in water, to
simulate the in-shower experience; and on a swatch of hair, to evaluate retentive qualities.
Here are the evaluation group's descriptions of two of those shampoos:
1. A green herbaceous topnote introduces a fruity floral midnote. Musky basenotes
complete the theme.

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2. A clean, apple-y herbal bouquet with underlying support from sweet woods and subtle
vanillic sweetness. Reminiscent of Clairol's Herbal Essence.
At this point, a brief overview of fragrance terminology is in order:
Topnote: This is the initial note of the fragrance, the first impression. These are the most
volatile notes, evaporating quickly and disappearing after about 15 minutes. Typical
contributors to these notes are citruses, aldehydes, fruity notes, herbaceous notes (like
camomile), and light florals (like lily-of-the-valley).
Midnote: The notes that go into the midnote serve to support the topnote and give the
fragrance its heart. These notes become apparent after about 15 minutes to half an hour.
These could be rich florals (like rose or jasmine), spice notes (like cinnamon), mosses or,
woody notes (like patchouli).
Basenote: Sometimes known as the bottom note, or the drydown, this note is a
combination of heavier ingredients that give a fragrance depth and make it longer-lasting:
animal notes (like musk), resinous notes (like myrrh), powdery notes (like vanillin).
While midnotes and basenotes may mean more when describing designer perfumes rather
than toiletries, an understanding of them contributes to a more thorough evaluation of the
fragrance of a hair care product.
Picture a fragrance as a three-tiered pyramid. Visualize the interrelationship of all the
notes. Can you see how the same topnote might smell different with different midnotes,
for example? And the slow process of evaporation reveals new layers of fragrance.
Armed with this information we now return to the meeting at Odor, Inc. The analysis of
Winnifred's previous products and their competition has just led to a fragrance direction.
Many fragrance types have been eliminated, and the result is that the perfumers will be
asked to create a light floral fragrance with offbeat herbaceous undertones. The key will
be the herbaceous undertonesthere are dozens are herbal notes the perfumers can choose
from and they can range from green, grassy notes to cooking herb notes.

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Perfumers have hundreds of ingredients to choose from, and a large number of these
ingredients are available in different forms and grades with different subtle nuances.
Geranium could be Egyptian, Algerian, Chinese, or Bourbon, and the choice of which of
these to use will be based not only on aromatic qualities but on cost, availability, and the
medium it will be used in. The choice of ingredients is also based on safety.
In terms of safety, the most common concerns involve irritationallergies, photosensitivity.
There are ingredients known to cause skin irritation among a large enough segment of the
population that their usage is undesirable. Sometimes the usage is perfectly safe in low
levels. And, of course, there are no ingredients that will be nonirritating to everyone; there
are always some people who are allergic to something. Fortunately, all the ingredients the
perfumer works with have been prescreened by the fragrance industry's own screening
arms: the Research Institute for Fragrance Materials (RIFM), and the International
Fragrance Association (IFRA). RIFM is basically a testing/technical arm; IFRA establishes
policy regarding raw materials. Every perfumer receives periodic bulletins concerning the
sensitivity levels, toxicological information, and general health and safety data on various
raw materials. A typical RIFM bulletin will include the following:
The members of the board of IFRA approved the following recommendations of the
Technical Advisory Committee of IFRA.
METHYL ETHYL ALDEHYDE (fictitious) The committee recommends that Methyl
Ethyl Aldehyde should not be used as a fragrance ingredient at a total level greater than
0.5%, individually or in combination, in fragrance compounds.
This recommendation is based on extensive data from sensitization studies.
Learning of this, the perfumer will limit his use of Methyl Ethyl Aldehyde accordingly.
Occasionally, a raw material will be found to be irritating at any level, and RIFM will
recommend that it not be used at all. In these cases, the ingredient will be thrown out by
the fragrance house and will be unavailable for use in any fragrance compound. If it is a
part of existing compounds, a substitute will be found and the formulas changed
accordingly.
All raw materials available to the perfumer are prescreened for quality before the
perfumer can use them. Natural materials, especially, are subject to the vagaries of nature
and vary in quality from year to year much in the same way that different vintages will
yield different qualities of the same wine. Machines like the gas-liquid chromatograph
(GLC) graph each material. The graph is then compared to the raw material standard. The
GLC and others, like the mass spectrometer and infrared spectrometer, help the perfumer
and quality-control

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personnel detect impurities and determine the grade of the material. Probably the most
fascinating aspect of this is that two graphs can match and yet, because of the complex
chemicals that make up each ingredient, there can be a difference in aroma. The ultimate
arbiter is still the human nose, and by and large there has never been a machine that can
match it for accuracy.
All this serves as an indicator that a perfumer has to be more than a creative artist; the
perfumer must also be well-grounded in chemistry. So it is very important to be familiar
with the customer's base. After all, a great fragrance is wasted if it proves to be unstable
in the final product, and while a perfumer cannot guarantee fragrance compatibility, there
are certain do's and don'ts that are known from the outset. For example, oil-based
productsmineral oil, etc.are well-known for perfume insolubility so that certain resinous
materials or crystals which have low solubility characteristics will be avoided. And
solvents can affect substantivity, diffusion, bloom in water, aerosol dispersion, and
solubility in suspensions. Certain actives like protein and polymers affect stability. Highly
volatile materials diffuse well in water. In short, knowing that there is going to be a
reaction between a fragrance and the active ingredients of a product, a perfumer tries to
eliminate or minimize any unwanted side effects.
For instance, many raw materials are susceptible to discoloration as a result of sensitivity
to light or heat. And since the physical appearance of hair care products is part of their
mystique, color stability is critical. However, these raw materials aren't necessarily
discarded because, based on end-use levels, traces of these ingredients can contribute to
the overall character without causing discoloration. For example, vanillin in a typical
shampoo fragrance at 0.5% when extrapolated into in-use percentages probably won't
cause a color change. As a last resort, there are antioxidants like butylated hydroxy
toluene (BHT) which may be used to retard discoloration.
Let's see how a perfumer would approach each of the key hair care products.
Shampoos
Shampoos are usually the easiest of the hair products to fragrance. The basic formulations
have certain ingredients in common, and the pH usually runs around 6.0. There are still
caveats, however. The aroma out of the bottle is not the only one that counts. The bloom
in water is more important in the long run, and the degree of substantivity on the hair
influences the overall perception. There may be additives in the base which can create
problems of odor and reactivity, and these must be dealt with individually. Where there
are pungent base notes to contend with, a perfumer might build up the middle notes of
the fragrance, reduce the basenotes (letting the shampoo formulation itself perform as a
fixitive), develop the topnotes for their identifiable characteristics, and minimize but not
compromise potentially volatile materials.

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Conditioners
When applying a fragrance type to a conditioner, the fragrance created for the shampoo
will often suffice. However, the base odor and fragrance level may necessitate
modification (in general, fragrance levels in conditioners tend to be lower than those of
shampoos). A conditioning agent such as a quaternary ammonium derivative contributes
to the base odor and has the potential to react with those perfume ingredients subject to
oxidation. Although the aroma impression should be the same as the shampoo, sometimes
ingredients need to be eliminated: bloom in water is usually less important, for instance,
so certain notes are unnecessary. At the same time, the topnotes may have to be pushed.
Much depends on the fragrance type; in general, the heavier the fragrance, the less
modification will be necessary.
Aerosol Hair Sprays
The perfuming of aerosols involves a great variety of interrelated problems. The
individual components such as the chemistry and odor of the base, the propellant, and the
container must all be considered. Problems encountered include solubility, color,
chemical activity, physical compatibility, and, of course, the olfactory characteristics of
the spray when compared to the same product in liquid form. For example, the possible
catalytic effect of the presence of propellant under high pressure can create conditions
favorable to chemical activity. Temperature, pH, and the formation of electrochemical
potential in the presence of metals can easily produce a change in odor and chemical
activity of the product. There may be mercaptans in the propellant. Even the valve gaskets
have to be considered since they often react with fragrance to cause an off-odor. Certain
ingredients react with the container. And a perfumer always faces the problem that a spray
tends to deliver the top, mid, and bottom notes all at once, completely disorienting the
balance of the fragrance. In some cases, notes will have to be added that mask many of
the unpleasant basenotes without altering the character of the fragrance.
Nonaerosol Sprays
While pump sprays are less difficult to work with than aerosols, a perfumer must
consider foremost the initial burst of the formula basenotes which must be effectively
neutralized. This is made more difficult because the fragrance level is generally low (0.1%
to 0.3%). Residual characteristics should be reduced since the spray pattern will diffuse
background notes too soon and distort the fragrance balance. Again, the topnotes must be
enhancedsometimes by as much as 20% to 30%. The addition of a diffusive masking
agent such as amyl acetate can alleviate some of the problems and not interfere with the
basic fragrance character.

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Permanent Waves and Dyes
Both of these formulations contain overpowering and offensive notes that can't be
completely covered but can be masked to make them more tolerable. With perms, there is
also the problem of fragrance exposure to extreme heat making stability even more
difficult; fragrances react poorly to light and heat in general, let alone under such severe
conditions. Unsaturated chemicals could be subject to reductionthe breaking of the double
bondwhich not only changes the chemical nature of the base, but has a destructive effect
on the odor as well. Some fragrances that mask beautifully when first mixed with the base
seem to disappear completely after a few days of stability testing. Obviously, the
enormous range of fragrances available for shampoos has been drastically cut by the time
you get to perms and dyes.
It is amazing that with all these caveats, perfumers still manage to create aromas that smell
good and are stable as well. Figure 2 shows a formula that has been created for the
Winnifred project and the changes that were made in it for each vehicle. This formula and
a few others are assigned code numbers and sent to the lab technicians, who make a small
quantity of fragrance oil according to the formula. The oil is then given to the applications
lab, where it is put into the customer base, in this case, shampoo, and sent on to the
evaluation group. Since every fragrance shown to them can't be submitted to the client
(Winnifred has asked for only one submission), it is up to the evaluators, who are part
noses and part diplomats, to screen out the array of fragrances the perfumers have created
without offending them. The primary function of the evaluator is to interpret whether a
fragrance has the specific characteristics that the profile indicates. Since more than one
fragrance can meet these requirements, the screening process narrows down the number
to those perceived as the best for the project and places them in a small market research
study. This study is usually conducted in-house but may be expanded to an outside study,
if required. A typical questionnaire can be seen in Figure 3.
The market research study is based on what aspects of the product/fragrance relationship
are most critical to the client. For example, for an initial fragrance impression (like/dislike;
how much), a simple monadic study may be all that is required. Many times, however,
paired comparison studies are done against other fragrances that are being evaluated or
against a target fragrance you are challenged to surpass. Many times, panelists are asked
to evaluate not only their first impressions, but impressions of the fragrance over a period
of time. Often, preferences are simply stated using a 1-to-5 or 1-to-10 scale, with the high
number being the best; but sometimes the evaluator will solicit comments from the
panelist that may indicate that all is not necessarily what it seems. Sometimes more than
one aspect of the fragrance will be studied (strength perception, freshness,
appropriateness, etc.), so that a more compre-

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Figure 2
A fragrance formula including the variations needed for each of the hair care products.

 Page 228

Figure 3
A simplified evaluation form, seeking overall consumer impression.

 Page 229
hensive view of the fragrance is possible. And so, armed with panelist preferences
combined with personal intuition, the fragrances are ranked in order of preference.
But there is another critical criterion: how did the fragrances fare in stability? While the
fragrances were being ranked in the market research study, they had been concomitantly
placed in stability; a wonderful fragrance that is unstable is useless. Although stability
requirements may vary from client to client, generally both the fragranced and the
unfragranced bases are put into an oven at around 37°C and checked at weekly
intervalsideally, for a month, although some testing may continue even after the product
has been submitted to meet the client's time requirements. At the same time, identical
samples are left at room temperature, and it is these samples that are checked against the
oven samples to see if any significant changes have taken place.
In some cases, UV light testing may be required, so the products will be exposed to UV
light for 8 hours or more. This procedure accelerates the effect of exposure to sunlight. It
provides a good prediction of the color and/or odor stability of a fragrance in the real
world, whether the product is actually worn outdoors or just left in a clear package stored
near a window. The more transparent the package, the more this test is necessary.
In short, the purpose of stability testing is to try to simulate in a brief time what will take
place over a 2-year period. The oven accelerates the real world by placing the product
under abnormal stress conditions in the hopes of duplicating the conditions of storage,
shipping, shelf life, and customer usage.
Sales, marketing, perfumery, evaluation, research, and stability have narrowed down the
fragrance to the one coded (OLXXX) Malibu Summer (the reasons for the choice can be
seen in Fig. 4). It will now be submitted to Winnifred Tresses after it is reviewed by the
R&D/quality control group, who will issue a material safety data sheet (MSDS) outlining
the fragrance's physical characteristics and health and safety information (Fig. 5); a
specification sheet, which includes the results of gas chromatography, flash point,
refractive index testing, and specific gravity analysis; and brief descriptions of the color,
odor, and general appearance, all in an effort to guarantee equivalent quality and
uniformity of every future batch. Lastly, they issue a certificate of analysis listing and
verifying each of the specification requirements of the client (Fig. 6).
At one time, this would have been the extent of their responsibilities, but now they must
be up-to-date on environmental issues, as well. Various federal and state regulatory
agencies are expressing concern that the quantity of volatile organic compounds (VOCs)
released during the application of many personal care products is adversely affecting the
environment, depleting the ozone layer, and enhancing the greenhouse effect on global
warming. Restriction of VOCs affects product formulations; e.g., lower quantities of
solvents such as ethanol are being explored along with their effects on drying time,
polymer types and spray

 Page 230

Figure 4 This panel test summary is a compilation of results from all of the questionnaires
and is scored numerically to give a quick overview of the key attributes.

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Figure 5
An MSDS is required by law to accompany each fragrance submission. It explains
what the product is, the potential hazards and what to do in case of emergency.

 Page 232

patterns. All this information is being relayed to the perfumers, who must learn to work
within these confines and still achieve fragrances with sparkle and lift.
A lot of work has gone into Malibu Summer, but the end result is a fragrance that Odor.
Inc. is proud to submit to Winnifred Tresses.

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Figure 6
The Certificate of Analysis reports the chemical specifications of the fragrance.

 Page 234

FRAGRANCE DESCRIPTION
Malibu Summer (OLXXX)
Topnote:Coriander, Marigold, Muguet, Peche
Hyacinth, Jonquille, Orange Flower,
Middle:
Ylang Ylang
Bottom: Labdanum, Oak Moss, Musk

A fresh floral topnote is balanced by a herbaceous quality enhanced by subtle

fruitiness. Rich middle notes are based on floral complexity and hints of woody notes.
The deep bottom notes add touches of sensuality and warmth.
Who could resist a shampoo like that? So remember, the next time you open up a hair
care product and inhale its aroma, just think of how complex its creation was. Then take
another whiff, just for the pure pleasure of it.

 Page 235

9
Ethnic Hair Care Products
Ali N. Syed
Avlon Industries, Inc., Chicago, Illinois
The ethnic hair and hair care is served by products and services devoted to the care of
excessively curly hair. Primarily, it is the African-American segment of the population that
has the type of hair for which ethnic products are designed, although some Caucasians
with naturally curly hair can also use these products. Worldwide, this same industry is
devoted to many others with similar hair textures, such as Africans, African-Caribbeans,
and segments of South American and Middle-Eastern populations.
The birth of the ethnic hair care industry in America began around the beginning of the
20th century. Since that time, the ethnic health and beauty aids industry (in which hair
care is a large part) has experienced tremendous growth, and is now estimated to be
around $1.5 billion (in 1991 wholesale figures). The phenomenal growth enjoyed by the
industry since its inception can be largely attributed to two factors. (a) scientific
innovations in the development of chemical treatments for excessively curly hair; and (b)
hairstyle trends within the African-American population which spurred the birth of new
products and even whole new categories of products. As the manufacturers of ethnic hair
care products prospered domestically, international markets were also opened. Thus,
today many of the leading U.S. manufacturers are participating in growing international
markets such as Africa, Europe, Canada, and Latin America.
While most consumer industries address general populations (clothing, food,
automobiles, etc.), the hair care industry is split into general market and ethnic market
segments. This segmentation is not merely a marketing figment, as with some other
product categories; rather, the ethnic hair care segment has a legitimate reason for being.
Excessively curly hair does require

 Page 236
different handling, different styling techniques, and different product formulations from
other hair textures.
1.
A Description Of Excessively Curly Hair
Excessively curly hair, in comparison to straight hair, is similar in amino acid content but
varies considerably in diameter at various points along the hair shaft. This variation in
diameter lends to the idea that excessively curly hair is twisted at various spots, the
diameter at the twisted region being very small. Kamath et al. (1) used the scanning
electron microscope technique to examine the physical shape of excessively curly hair and
found the excessively curly hair fiber twisted at various regions (Fig. 1).
They further examined many cross sections in the region of the twist and found
considerable variation in cross sections within a relatively short distance in the twisted
region. They also used optical microscopy to determine ellipticity for excessively curly
hair and found it to be much higher than in Caucasian hair. According to Kamath, the
ellipticity is defined as the ratio of major axis to minor axis, and Caucasian hair has an
ellipticity value of 1.4, whereas ellipticity for excessively curly hair is around 1.895, as
shown in Figure 2.
Leon (2) made another interesting observation, while working on the structural aspects of
keratin fibers. He discovered that excessively curly hair contains a higher proportion of
orthocortical cells than straight Caucasian hair. The cuticle of Caucasian hair is six to eight
layers thick, whereas the cuticle of excessively curly hair is of variable thickness with six
to eight layers at the end

Figure 1
Excessively curly hair fiber. (Courtesy of Journal of the Society of Cosmetic Chemistry.)

 Page 237

Figure 2
Ellipticity of Caucasian and curly hair.
of the major axis of the fiber and then reducing to one to two layers at the ends of the
minor axis. Therefore, excessively curly hair resembles a twisted oval rod, whereas
straight Caucasian hair resembles a cylinder. The tensile properties of excessively curly
hair indicate that it has lower strain values at break point when compared to Caucasian,
straight hair (3). One reason that comes to mind is that twisted regions along the hair axis
are more prone to damage and hair fiber break at a relatively lower strain or extension.
African-American hair and scalp tend to be dry compared to Caucasian hair and scalp.
For African-Americans, the sebaceous glands within the scalp are often less active and
secrete an inadequate amount of sebum. Therefore, the scalp is relatively dry and so is the
hair since there is less natural oil to be distributed along the hair shaft (4). The water
content in African-American hair is slightly less than in Caucasian hair, as measured via
differential scanning calorimetry (5). It grows from the scalp into small twisted spirals
due to the configuration of the hair follicles. The tight curl pattern makes excessively
curly hair particularly susceptible to breakage when mechanically manipulated (i.e.,
combing and brushing). The combing difference of excessively curly hair as compared to
Caucasian hair is shown in Figure 3 (6).

 Page 238

Figure 3
Dry-combing comparison of African-American vs.
Caucasian hair.
Therefore, the curlier the hair, the more difficult it is to comb, making stylability limited
in the sense that many of the most popular styles cannot be achieved without special
handling. To achieve the widest variety of hairstyles, excessively curly hair is often
straightened, either by pressing or lanthionization (relaxing).

 Page 239

II.
Straightening Curly Hair
A.
Pressing
Pressing is a process whereby excessively curly hair is straightened with the use of high
heat, oils, and metal implements. This practice dates back to the beginning of the 20th
century and was popularized by the renowned Madame C. J. Walker, who is credited with
the origination of the ethnic hair care industry (7). She first developed an ointment that
gave African-American hair a special gloss and softness. It was applied, and then metal
pressing combs or round tongs (called pullers) were used to straighten the hair section by
section. After straightening, the hair was curled with hot metal curling irons.
Early in the history of pressing, the implements were heated on household stoves to
temperatures of about 350°F, and the pressing oils used were heavy and often petrolatum-
based. Since then, improvements include: (a) better-designed implements (combs, flat
irons, and curling irons); (b) the invention of the marcel stove to heat the implements; and
(c) electrically heated implements. Also, pressing oils have been upgraded to lighter,
smoke-free cremes and lotions that leave hair silky-feeling and nongreasy. With little
change in methodology, pressing is still used today among a relatively small segment of
the market that prefer not to permanently alter their natural hair textures.
Two formulas for pressing cremes and one formula for pressing lotion are provided
below. Formula 1 will yield more natural luster to hair, whereas Formula 2 will give a
higher gloss to the hair. Formula 3 will impart more body with less greasy after-feel of the
hair.
Pressing Creme/Lotion
Formula Formula Formula
1 2 3
A. Hydrolyzed vegetable shortening 73.05% 60.25% -
Castor oil 5.00 20.00 2.00%
Corn oil - - 20.00
Lanolin 2.00 - -
Beeswax 7.00 5.00 -
BHA 0.10 - 0.10
Phenyl dimethicone 2.00 2.00 0.20
Stearoxytrimethylsilane (and) stearyl
- 2.00 -
alcohol
B. Water 10.00 10.00 73.98
 Methylparaben 0.20 0.20 0.20
Imidazolidinyl urea 0.25 0.25 0.25
Sodium borate 0.40 0.30 -
Carbopol 940 - - 0.50
Laureth-16 - - 2.50
Triethanol amine (85%) - - 0.47
Fragrance - - 0.20

(table continued on next page)

 Page 240
(table continued from previous page)
Formula 1 Formula 2 Formula 3
Procedure: Place A in a stainless-steel container. Heat to 78°C
while stirring with Lightnin' mixer. Weigh B; place in separate
container. Blend B using Lightnin' mixer while heating to 80°C.
Once A and B reach specified temperatures, add B to A; mix for 10
minutes. Cool mixture to 55°C. Pour into containers while still hot.
Cool mixture further to 25°C by passing it through cooling tunnel
where temperature is maintained at 5°C. For Formula 3, cool
mixture of A and B to 25°C and fill in containers.

B.
Chemical Relaxing
Hair relaxing, or lanthionization, is a chemical process whereby excessively curly hair is
permanently straightened. The first relaxers were developed around the 1940s. They were
crude concoctions of sodium hydroxide or potassium hydroxide (lye) mixed into potato
starch, and were highly irritating to the scalp. Although irritating, chemical relaxers
provided a more permanent way to straighten the hair and to address the problem of
reversion associated with hair pressing.
During the 1950s, more advanced relaxer formulas were developed that placed the active
straightening agent (approximately 3.25% sodium hydroxide) in a creamy base of
petrolatum, fatty alcohols, and emulsifiers (8). While not as irritating as the first relaxers,
this formula still sensitized the scalp. Therefore, a petrolatum pomade called base was
applied to the scalp before relaxing, to help protect the scalp. This form of relaxer became
very popular because for the first time, excessively curly hair could be wet-set and styled
in a wide variety of looks. It truly revolutionized ethnic hair care, not only because it
expanded hair styling, but also because the hair no longer reverted to its natural state in
humid weather or when it was shampooed. High heat was no longer necessary to
straighten or curl the haironly regular touchups every 8 weeks or so to treat newly grown
hair.
Advancements in hair relaxers have been steady and significant since the 1950s, starting
with the introduction in 1965 of No Base Relaxers (which required no separate
application of petrolatum base to the scalp) (7). Other notable innovations include the
following: Blow-Out Relaxers, which relaxed the hair minimally for more manageable but
very natural-textured looks; Texturizing Relaxers like Blow-Out Relaxers) that left the hair
with a wavy texture rather than a straight one; No Lye Relaxers (9), formulated primarily
with guanidine hydroxide, that maximized scalp comfort without sacrificing straightening;
and Conditioning-Relaxers (1012) with Pre- and/or Post-Conditioners (13) that treat and
repair the hair shaft before, during and after the (1012) relaxation process. For many
years now, relaxers have been the predominant method of straightening excessively curly
hair and are currently the treatment of choice for the majority of African-American
women.
1.
Chemistry of Lanthionization
According to Wolfram (14), lanthionization is accomplished via metal hydroxides or
guanidine by changing one-third of the cystine contents of hair to lan-

 Page 241

Figure 4
Chemical structure of keratin showing peptide, cystine, and salt linkages.
thionine, along with minor hydrolysis of peptide bonds. The possible reaction mechanism
is offered by Hsiung (15) and Tolgyesi and Fang (16). The simplified version of the
chemical reaction is shown in Figure 4.
Sodium hydroxide, guanidine hydroxide, potassium hydroxide, and lithium hydroxide
have all been used in relaxers as active straightening agents. Sodium hydroxide, and
guanidine hydroxide have proven to be the most effective (17). Relaxers containing
sodium hydroxide are categorized in the market-place as lye-based relaxers; guanidine
hydroxide formulations are called no-lye relaxers.
Guanidine hydroxide relaxers are less irritating to the scalp than lye-based relaxers;
therefore many consumers prefer them. This category of relaxers may be deemed slightly
less convenient to use since it requires mixing a creme relaxer (containing calcium
hydroxide) with a liquid activator (containing guanidine carbonate). See the upcoming
section on Relaxer Product Formulation for more details.
2.
How Relaxers Are Applied (18)
The application method for creme relaxers is fairly straightforward. Petrolatum jelly is
applied to the hairline and ears for protection, and the hair is parted into

 Page 242
four equal sections. The creme relaxer is applied with a small brush or the back of a
rattail comb, beginning in the nape area and working toward the forehead. Section by
section, the creme is applied only to the virgin portions of the hair. Then the creme is
smoothed with the back of a rattail comb, section by section, to achieve the desired
degree of straightening before the hair is thoroughly rinsed with tepid water. The time of
application and smoothing is limited according to hair texture and condition to avoid hair
damage and scalp irritationapproximately 13 minutes for fine hair, 15 minutes for medium
hair, and up to 18 minutes for coarse, resistant hair.
The formulation and manufacturing of relaxers is a complicated task, and the following
points must be kept in mind during the product development of relaxers:
1. They should be able to straighten hair effectively within optimum time limit of 13 to 18
minutes.
2. They should contain an adequate amount of oils and/or petrolatum to protect against
the irritation of sodium hydroxide. The usual amount of oil phase including fatty alcohol
is 35% to 45% in a no-base relaxer.
3. They should contain an adequate amount of emulsifiers to form a stable emulsion
where required oil contents are high, as mentioned in 2. These emulsifiers should also be
stable in a highly alkaline medium at a pH of 12 to 13.
4. A stability study must be conducted at room temperature and at 45°C including two
freeze-thaw cycles.
5. They should form a fluffy and smooth creme in order to achieve maximum ease of
application and should not become pasty, which would hinder the smoothing process.
6. They should rinse easily from hair using tepid water.
7. They should not damage hair or reduce tensile strength of hair beyond acceptable
levels when compared to leading national brands.
3.
Lye Relaxers
Lye-based relaxers generally contain sodium hydroxide as an active straightening agent. A
typical formula contains 3035% petrolatum and/or mineral oil, 610% fatty alcohols as
thickeners, 2.54% alkali-stable emulsifiers, 1.852.40% active sodium hydroxide, and
remaining amount of water to equal 100%. The mild-strength relaxer may contain a
1.852.00% concentration of sodium hydroxide, 2.062.20% for normal strength, and
2.252.40% for resistant strength. These three strengths, mild, normal, and resistant, are
used to straighten fine, medium, and coarse textures of hair, respectively.
Caution must be observed while determining the optimum ratios of oils, petrolatum,
thickeners, emulsifiers, active straightening agent, and water, in

 Page 243
order to achieve above-mentioned performance objectives. For example, if too little
petrolatum and/or mineral oil is added to the formulation, the resulting relaxer would be
irritating to the scalp because of lack of a protective barrier against the irritation of the
sodium hydroxide. Conversely, if too much petrolatum/mineral oil is added to the
formulation, the resulting relaxer would be too slow in acting and would have inadequate
straightening power. It may also be hard to stabilize because of a high oil to water phase
ratio (19).
The concentration and type of emulsifiers used in relaxers also have a profound impact
on the stability, irritation potential, and straightening ability of the relaxer cream.
Formulas 4 to 6 mentioned here are for normal-strength sodium hydroxide relaxer.
Formula 4 is a conventional relaxer, whereas Formulas 5 and 6 are conditioning relaxers
containing a cationic polymer. Most cationic polymers are not stable at high pH levels
except the patented polymers of Formulas 5 and 6.
No-Base Lye Creme Relaxer
Formula 5 Formula 6
Formula 4
(11) (12)
A. Petrolatum and/or mineral oil 30.035.0% 30.035.0% 30.035.0%
Fatty alcohols
6.010.0 6.010.0 6.010.0
and/oremulsifying wax
Emulsifiers 2.54.0 2.54.0 2.54.0
Simethicone 0.1 0.1 0.1
B. Deionized water 48.458.9 42.753.2 42.753.2
Propylene glycol - 5.0 -
Sodium lauryl sulfate 0.3 - -
Polyquaternium 6 or 7 - 1.0 -
Polyamines - - 1.0
C. Sodium hydroxide* 2.2 2.2 2.2
Procedure: Place A into a double-motion sweep mixer; heat to 80°C
during mixing. Place B into a tank with a Lightnin' mixer; heat between
75 to 78°C during mixing. Add B to A; mix for 30 minutes. Cool
mixture to 50°C, and add C. Further cool batch to 25°C, and mill using
a colloid mill, Sanolator, or Versator. Analyze finished product for
viscosity, sodium hydroxide content and particle size.
* Percentage of sodium hydroxide may vary depending upon relaxer
strengthi.e., mild, normal, or resistant.

4.
No-Lye Relaxers
When the active ingredient (sodium hydroxide) present in lye relaxers is replaced by
freshly prepared guanidine hydroxide, these relaxers are called no-lye relaxers. The
irritation potential of no-lye relaxers is significantly lower

 Page 244
than lye relaxers containing sodium hydroxide. No-lye relaxers are generally available in
two components. Component A is usually a cream containing calcium hydroxide, water,
oils, emulsifiers, and thickeners. Component B is a concentrated solution of guanidine
carbonate. Upon mixing Component A and Component B, guanidine hydroxide is
produced according to the chemical equation shown below:

Generally, Component A cream contains 5.0% calcium hydroxide and Component B

activator contains a 25% solution of guanidine carbonate in water. The Component A is
mixed with Component B in a ratio of 3.28:1. This freshly prepared guanidine hydroxide
(no-lye) cream is then applied to hair in the same manner as lye relaxers. Once the two
components are mixed, they must be used the same day to avoid any chemical
deterioration of guanidine hydroxide. No-lye relaxers are generally marketed in two
strengthsnormal, for fine to medium hair, and resistant, for coarse hair. The application
time is in the range of 13 to 18 minutes depending upon hair texture. Formula 7 is a
conventional no-lye relaxer whereas Formulas 8 and 9 are conditioning no-lye relaxers
containing patented cationic polymers for conditioning hair during straightening
(relaxing) process. Formulas 10 and 11 are liquid activators; Formula 10 is more viscous
than formula 11 for ease of transferring into Component A cream.
No-Lye Creme Relaxer
Part A: Creme Relaxer
Formula 7 Formula 8 Formula 9
(9) (12) (11)
A. Petrolatum and/or mineral oil 30.035.0% 30.035.0% 30.035.0%
Fatty alcohols
6.010.0 6.010.0 6.010.0
and/oremulsifying wax
Emulsifiers 2.54.0 2.54.0 2.54.0
Simethicone 0.1 0.1 0.1
B. Deionized water 43.954.4 42.953.4 42.953.4
Propylene glycol 2.0 2.0 2.0
Polyquaternium 6 or 7 - 1.0 -
Polyamines - - 1.0
Calcium hydroxide 5.0 5.0 5.0
Procedure: The no-lye cream relaxer is manufactured similarly to
sodium hydroxide no-base relaxers. The finished product is analyzed
for calcium hydroxide content and viscosity.

 Page 245
Part B: Liquid Activator
Formula 10 Formula 11
Water deionized propylene glycol 74.8 75.0
Xanthin gum 0.2 -
Guanidine carbonate* 25.0 25.0
Procedure: Add water and dissolve ingredients at 45°C using a high-
shear Lightnin' mixer until all guanidine carbonate has dissolved.
Analyze for guanidine carbonate contents.
* Amount of guanidine carbonate may vary depending upon the
desired strength of relaxer.

C.
Neutralizing Shampoo
All relaxer treatments, whether containing alkali metal hydroxides or guanidine
hydroxide, are very high in pH. They leave the hair in a highly alkaline state, which could
be as high as pH 12.0.
To bring the pH of hair back to a pH balance of 4.06.0, neutralizing shampoos are usually
used after the cream relaxer is rinsed from the hair. These shampoos are acidic in nature
and generally have a pH of 4.5 to 6.0. To date, no chemical literature is found on this
subject. Today's state-of-the-art formulations of neutralizing shampoos place more
emphasis on conditioning and detangling without presenting any evidence that the pH of
hair has returned to its approximate natural state of 4.06.0. The conventional and
advanced formulations are shown in Formulas 12 through 14. Formula 12 is just a low-
pH acidic shampoo whereas Formulas 13 and 14 are mixtures of anionic, amphoteric
detergents complexed with cationic polymers to provide detangling and softness to hair at
a pH of 5.0 to 5.5.
Neutralizing/Normalizing Shampoo
Formula Formula Formula
12 13 14
A. Water deionized 85.6 77.1 77.4
Methylparaben 0.2 0.2 0.2
Imidazolidinyl urea 0.3 0.3 0.3
Disodium EDTA 0.2 0.2 0.2
Citric acid 0.5 0.5 0.2
B. Polyquaternium-10 - 0.5 -
Polyquaternium-6 or -7 - - 0.5
C. Disodium
- 8.0 8.0
cocoamphodipropionate
 Ammonium lauryl sulfate 10.0 10.0 10.0
Lauramide DEA 3.0 3.0 3.0
D. Fragrance 0.2 0.2 0.2
pH of the formula is adjusted from 5.0 to
5.5

(table continued on next page)

 Page 246
(table continued from previous page)
Formula 12 Formula 13 Formula 14
Procedure: Heat A to 78°C while dispersing B in A. At 7880°C, add
C; mix for 20 minutes. Cool batch to 50°C; add D. Cool to room
temperature. Adjust pH of formula from 5.0 to 5.5 if needed.

D.
Permanent Waving
In the 1970s, the relaxer market reached the point of saturation, and the relaxed look
became a very common hair style. One of the disadvantages of relaxed hair is that the
patron has to dry her hair anywhere from 1 to 1 1/2 hours under the dryer to set the hair
in a curly formation. Therefore, the idea of permanent waving African-American hair
became popular overnight, in the late 1970s. These permanent waves were called curly
perms and they left hair frizzy-looking and dry. To combat dryness and frizzy looks, one
had to use glycerine-based hair sprays and lotions, known as curl activators, on a daily
basis. In 1980, the permanent wave process was quickly improved by straightening the
hair first with thioglycolic acid creams before wrapping the hair on permanent wave
rollers. Daily maintenance products were improved as well to improve the look and the
feel of the hair to less greasy and wet. Because of these improvements, the permanent
wave market experienced a tremendous growth, which continued well into the mid to late
80s. Many consumers enjoyed this carefree style, which required little maintenance.
However, many problems associated with curly perms caused the market to mature and
then decline. The associated problems are as follows:
The new growth was permed every 12 weeks and the previously curled hair was also
treated with wrapping lotion (called booster) containing approximately 4.0% thioglycolic
acid at a pH of 9.0. With each repeated treatment, previously curled hair lost additional
cystine bonds and suffered greater damage. Therefore, perming hair over a period of time
made hair very dry, and previously permed hair ends became straight and stringy or
broke off all together.
Ammonium thioglycolate is extremely drying to excessively curly hair and scalp. For hair
and scalp moisturization, consumers had to apply large quantities of glycerin-rich creams,
lotions, and sprays on a daily basis. These products gave hair a buildup which was sticky,
greasy in feel, and stained clothing collars and pillows.
To offer economy to hair stylists, manufacturers packaged the professional perm
components in bulk sizes. The large, bulk-size cremes and lotions containing ammonium
thioglycolate could not be packaged airtight, and they started to decrease in pH and
thioglycolic acid content. Therefore, at the salon level, permanent wave products were
subject to inconsistent performance, yielding unpredictable results.

 Page 247
Styling versatility was limited to curly or wavy looks. When sleeker styles became
popular, permed hair could not make the transition as well as relaxed hair. To make
matters even worse, permed hair could not be relaxed by sodium hydroxide or guanidine
hydroxide relaxer formulas without causing excessive hair damage. Therefore, consumers
had to grow enough new hair and then cut off the permed portion before relaxing; not a
very pleasant situation.
Although there is a tremendous decline in the popularity of perms in recent years, there
remain a loyal group of users in the market place.
The perming process, known as redox, has two basic phasesreduction and oxidation.
During the reduction phases hair goes through two distinct steps. In the first step, the
newly grown curly portion of the hair is straightened by using a rearranger or reducing
creme containing ammonium thioglycolate. The 20% of cystine bonds of newly grown
hair change to cysteine (14). In the second step of reduction, the newly straightened hair
and previously permed (old) hair are treated with booster or reducing lotion containing
4.0% thioglycolic acid. At this stage, as much as 40% of the cystine bonds may reduce to
cysteine bonds (14). It is in this phase that the hair assumes its new configuration. In the
oxidation phase, 8090% of the broken cystine bondsi.e., cysteine bondsare re-formed to
lock in the new curl formations (14).
1.
Chemistry of Perming Excessively Curly Hair
The chemistry of perming excessively curly hair is very similar to perming Caucasian
hair, except that the curly hair is first straightened with the use of a creme containing
ammonium thioglycolate at pH of 9.3 to 9.5, then retreated with a lotion containing 5%
ammonium thioglycolate and wrapped on rollers. Anywhere from 20% to 40% of cystine
bonds change to cysteine; the lower figure represents untreated hair, and higher figure
represents previously permed hair. Once the S-shape curl is formed, the lotion is rinsed
and hair is oxidized using a neutralizer containing 1013% sodium bromate at a pH of 6.5
to 7.0.
2.
How to Perm Excessively Curly Hair (18)
The permanent waving of excessively curly hair is generally conducted in three steps:
1. A rearranger creme containing high levels of ammonium thioglycolate adjusted to a pH
of 9.3 to 9.5 is applied to new growth of the freshly shampooed hair. Its purpose is to
straighten hair in preparation for wrapping hair onto perm rollers. A rearranger creme can
also be called reducing creme and it consists of two strengths. The normal strength is
formulated to straighten fine to medium and color-treated hair. It contains 6.9% to 7.1%
active thioglycolic acid at a pH

 Page 248
of 9.3 preferably. The resistant strength is formulated to straighten coarse, resistant hair
and contains 7.3% to 7.5% active thioglycolic acid at a preferred pH of 9.3.
2. Once the rearranger creme has straightened the excessively curly hair and it is rinsed
out, booster or reducing lotion is applied. The hair is then wrapped on the desired
diameter roller and processed under a heated dryer for 15 to 20 minutes. A few rollers are
unwound to ensure the formation of an S pattern, and the hair is rinsed. The curl booster
or reducing lotion contains 3.6% to 4.0% thioglycolic acid at a preferred pH of 9.0.
3. A neutralizer or oxidizing lotion containing sodium bromate is applied and left on the
hair for 15 to 20 minutes. The perm rollers are removed and the hair is rinsed. The
neutralizer contains 1013% of sodium bromate at a preferred pH of 6.8. It is advisable to
use neutralizer containing sodium bromate on excessively curly hair since this type of hair
is generally dark in color and the sodium bromate of the neutralizer does not lift the
natural color of the hair, as can happen with hydrogen peroxide-based neutralizers.
Following redox processing, glycerine, propylene glycol, and quaternary ammonium
compound-based sprays, lotions, cremes or gels are applied to moisturize and style the
hair.
3.
Permanent Wave Product Formulation
Formulas 15 through 22 are for the basic components of a permanent wave system. The
first two formulas are for rearranger/reducing cremes; Formula 15 contains ammonia and
offers greater straightening action than Formula 16, which contains an amine. Formula 17
is a geltype formula where gel is prepared using a carbomer-type polymer, with the same
levels of ammonium thioglycolate and ammonia or ethanolamine as prescribed in
Formulas 15 and 16. The gel formulations tend to migrate undesirably onto the area of
previously permed hair during application and therefore are not well accepted.
Reducing Creme/Rearranger Creme
Formula 15Formula 16 Formula 17
A. Emulsifying wax N.F. 10.00% 2.00% -
Fatty alcohol 1.00 1.00 -
Glyceryl stearate SE 1.00 1.00 -
Mineral oil 1.00 1.00 -
Emulsifying wax (evanol) - 8.00 -
B. Water 64.57 69.80 77.27%
Carbomer 940 - - 1.50
Trisodium HEDTA - 0.20 0.20
(table continued on next page)

 Page 249
(table continued from previous page)
Formula Formula Formula
15 16 17
Tetrasodium EDTA 0.40 - -
Sodium lauryl sulfate 0.50 0.50 0.20
Glycerin 2.00 - 2.00
Azulene (25%) 0.03 - 0.03
C. Perfume 0.20 0.20 0.50
Ammonium thioglycolate (60%) 14.00 14.00 14.00
Diammonium dithiodiglycolate
1.00 - 1.00
(40%)
Aqua ammonia (26%) 4.30 - 1.00
Ethanolamine (to adjust pH to
- 2.30 3.30
9.3)
Procedure for Formula 15 and 16: Place B in a kettle equipped
with a double-motion sweep mixer and heated to 7880°C during
mixing. In separate tank with Lightnin' mixer, blend A and heat to
7880°C. Add A to B; mix for 15 minutes. Cool mixture to 45°C
before adding C. Further cool batch to 25°C; then test for pH,
viscosity, and thioglycolic acid content before filling and
packaging. Adjust pH from 8.9 to 9.3. Adjust thioglycolic acid in
the range 6.907.10 for normal strength and 7.307.50 for resistant
strength.
Procedure for Formula 17: Place water of Phase B into a kettle
equipped with a double-motion sweep mixer and a Lightnin'
mixer. Disperse carbomer 940 into water using Lightnin' mixer.
Once the dispersion is complete, add remaining Phase B
ingredients. Warm to 50°C and add C. Mix for 30 minutes and
cool to 25°C; then test and adjust for pH, viscosity, and
thioglycolic acid content.

Formulas 18 and 19 are for curl booster/reducing lotion. Formula 18 contains ammonia
and produces a tighter curl whereas Formula 19 does not have ammonia odor and may
produce a looser curl pattern.
Reducing Lotion/Curl Booster
Formula 18 Formula 19
A. Emulsifying wax N.F. 3.0% -
Fatty alcohol 2.0 1.0%
Glyceryl stearate S.E. 1.0 1.0
Mineral oil 1.0 1.0
 Emulsifying wax (evanol) - 3.0
Water deionized 83.5 82.2
Tetrasodium EDTA 0.3 0.3
B. Perfume 0.2 0.2
Ammonium thioglycolate (60%) 7.0 8.5
Diammonium dithiodiglycolate - 0.5
Aqua ammonia (26%) 2.0 -
Ethanolamine (to adjust pH to 9.0) - 2.3
Procedure: Mix and combine ingredients as directed for reducing
cremes. Adjust pH from 8.5 to 9.0. Adjust thioglycolic acid content
from 3.60% to 4.00%

 Page 250
Formulas 20 through 22 represent neutralizing solution/oxidizing solution where sodium
bromate is used in the range of 10.0% to 13.0% along with various levels of urea as a
flame retardant
Neutralizing Solution/Oxidizing Solution
Formula Formula Formula
20 21 22
A. Water deionized 84.0% 81.5% 79.5%
Polyquaternium 6 1.0 - -
Polyquaternium 10 - 0.5 0.5
B. Urea 5.0 5.0 10.0
Sodium bromate 10.0 13.0 10.0
Disodium phosphate to adjustpH to
6.87.0
Procedure: Disperse A in water using a Lightnin' mixer. When
polymer is completely dispersed, add B one at a time, until a clear
solution is achieved. Adjust pH; analyze the sodium bromate content
before filling and packaging. At 25°C, pH should be 6.87.0; sodium
bromate should be 1013%

III.
Maintenance
A.
Styling and Maintenance Products
There is a wide variety of maintenance products available for permed excessively curly
hair. The most commonly used products are instant moisturizing sprays and curl
activators, which are formulated in creme or gel form. These products contain adequate
amounts of glycerine and propylene glycol as moisturizers. Formulas 23 and 24 are
instant moisturizers with different degrees of moisturizing ability. Formula 23 is
appropriate for dry and damaged hair since it contains a higher amount of glycerine;
Formula 24 is light in feel and is more appropriate for normal hair. The curl activators are
applied to hair after instant moisturizers and can be formulated as gels or cremes.
Formulas 25 and 26 are light gels capable of imparting a wavy look; Formulas 27 and 28
contain higher amounts of emollients and therefore are more suitable for drier hair.
Instant Moisturizing Spray
Formula 23 Formula 24
A. Water deionized 70.7 70.8
Preservatives 0.5 0.5
 Glycerin 18.0 12.0

(table continued on next page)

 Page 251
(table continued from previous page)
Formula 23 Formula 24
Propylene glycol 10.0 8.0
Stearalkonium chloride 0.5 0.5
B. Hydrolyzed animal protein 0.1 -
Hydrolyzed silk - 0.1
Sodium PCA 0.1 -
Fragrance 0.1 0.1
Procedure: Disperse A in water; heat at 7880°C while mixing with
Lightnin' mixer. Cool to 50°C; add B. Cool batch to 25°C before
filling and packaging.

Curl Activator
Gel Creme
Formula Formula Formula Formula
25 26 27 28
A. Water 76.0% 73.0% 65.4% 58.9%
Carbomer 0.5 0.5 - -
PEG-75 lanolin 2.0 - - -
Glycerin 20.0 25.0 22.0 27.7
Preservatives 0.6 0.6 0.6 0.6
Triethanolamine 0.5 0.5 - -
Simethicone 0.1 0.1 0.1 0.1
Acetamide MEA - - 2.0 2.0
B. Hydrolyzed silk 0.1 0.1 0.1 0.1
Sodium PCA - - 0.1 0.1
Fragrance 0.2 0.2 0.2 0.2
C. Cetyl alcohol - - 1.0 4.0
Mineral oil - - 2.5 5.0
Emulsifying wax
- - 6.0 -
N.F.
Glyceryl stearate
- - - 2.0
S.E.
Procedure: Mix A in tank with Lightnin' mixer; heat to 80°C. Mix C
in tank with double-motion mixer; heat to 80°C. Add A to C; mix for
15 minutes; then cool to 50°C. Add B to AC; cool to 25°C. Adjust
pH to 5.5, if necessary.

B.
Cleansing
The African-American or excessively curly hair is generally dry and very difficult to
comb during wet and dry stages. Epps and Wolfram have shown that excessively curly
hair may require twice the work to comb wet and 11 times more work to comb when dry,
compared to Caucasian hair (7). Therefore, it is evident that excessively curly hair is very
difficult to comb and requires special

 Page 252
handling during shampooing and towel drying. Another important factor is that
excessively curly hair does not become coated with sebum secretions as readily as
naturally straight Caucasian hair; therefore, the hair is shampooed on a weekly or every-
other-week basis. Finally, while formulating a shampoo for excessively curly hair, one
must incorporate detangling characteristics along with mild detergents in order not to
aggravate the dry scalp of African-American patrons. Formulas 29 and 30 contain cationic
polymers at 1.01.5% level, along with mild amphoteric detergents. These formulas are
excellent for cleansing, conditioning, and detangling excessively curly hair on a weekly
basis (20,21).
Detangling Shampoo
Formula Formula
29 (20) 30 (21)
A. Water deionized 77.5% 75.0%
Methylparaben 0.2 0.2
Imidazolidinly urea 0.3 0.3
Disodium EDTA 0.2 0.2
Citric acid 0.5 0.5
B. Polyquaternium-10 1.5 1.5
C. Disodium cocoamphodipropionate (and)
10.0 -
sodium lauryl sulfate (and) hexylene glycol
Sodium lauryl sulfate - 3.0
Disodium cocoamphodipropionate - 8.0
Trideceth-7 carboxylic acid - 7.0
Lauramide DEA 5.0 3.0
Polysorbate-20 3.0 -
D. Glycol stearate 2.0 1.0
E. Fragrance 0.3 0.3
Procedure: Heat A to 80°C while dispersing B in A. At 80°C, add C
and D; mix for 30 min. Cool to 50°C; add E. Cool to room
temperature.

C.
Conditioning
Epps and Wolfram have shown that African-American hair is more difficult to comb and
requires much higher forces to comb. The excessive grooming of hair causes damage to
hair cuticles, as evident from the study conducted by Kelly and Robinson (22). They
found that shampooing and towel drying inflect some damage to the cuticles, but wet
combing or brushing greatly increases the cuticular damage. It is therefore incumbent
upon a formulating chemist to reduce the work required to comb hair in order to
minimize wet combing or brushing damage. Therefore, a conditioner formulated for
African-American hair must be

 Page 253
very rich in quaternary ammonium compounds to facilitate ease of wet combing while
minimizing combing or brushing damage. Various emollients like mineral oils or esters
such as isopropyl myristate should be incorporated in the formulations to reduce natural
dryness of the African-American hair and scalp. Also, moisture binding ingredients like
sodium PCA, panthenol, glycerine, and chitosan, etc., should be utilized to enhance
moisture contents of naturally dry African-American hair. Formulas 31 and 32 provide
hair with one or more of the following functions: ease of wet and dry combing; smooth,
seal, and realign damaged areas of the hair shaft; minimize porosity; impart sheen and
silky feel to hair; provide some protection against thermal and mechanical damage;
moisturize; add volume and body; and eliminate static electricity. These formulations can
adsorb more onto the hair if kept on the hair with a plastic cap for 20 to 30 minutes under
a warm dryer (23).
Remoisturizing/Deep Penetrating Conditioner
Formula 31 Formula 32
A. Water deionized 87.7% 86.2%
Methylparaben 0.2 0.2
Imidazolidinyl urea 0.3 0.3
Panthenol 0.5 0.5
Sodium PCA 0.5 0.5
Polyquaternium-10 - 1.0
B. Cetearyl alcohol 6.0 8.0
Stearylakonium chloride 0.5 0.5
Dicetyldimonium chloride 1.0 1.0
Mineral oil 2.0 1.0
Polysorbate-20 0.5 0.5
Propylparaben 0.1 0.1
Octyl dimethyl PABA 0.5 -
C. Fragrance 0.2 0.2
Procedure: Mix A; heat to 80°C. Add B to A at 80°C. Mix for 30
min; then cool to 50°C. Add C to AB; cool to 25°C.

D.
Blow Drying
The process of blow drying involves repetitive combing in the presence of moderately
hot air. Since African-American hair is more difficult to comb, even after chemical
straightening, the magnitude of combing forces applied during blow drying is normally
higher than for Caucasian hair. Therefore, the potential for excessive damage during this
process gives conditioning an even greater importance.

 Page 254
Blow drying products were designed to minimize combing force exerted in the blow
drying process and help to protect hair from heat and dehydration. Specifically, laminate
and spray lotions were developed to seal hair cuticles and minimally coat the hair shaft so
that styling combs and brushes would glide easily through hair. Formula 33 is a
conventional blow drying lotion with some hold and moderate ease of wet combing.
Formula 34 provides some hold and extra ease of wet combing with the incorporation of
an amino-functional silicone polymer (24).
Blow Drying Lotion
Formula 33 Formula 34
A. Water deionized 98.8% 97.2%
Methylparaben 0.2 0.2
Imidazolidinyl urea 0.3 0.3
B. Polyquaternium-11 (20%) - 1.0
Polyquaternium-10 - -
Polyquaternium-5 0.1 -
C. Quaternium-18 0.3 -
Amodimethicone (and) tallowtrimonium
Chloride (and) nonoxynol (10) - 1.0
D. Polysorbate 20 0.2 0.2
Fragrance 0.1 0.1
Procedure: Heat A to 80°C; add B and C. Mix for 30 min, then cool to
50°C. Premix D separately; add to ABC at 50°C. Mix for 15 min, then
cool to 25°C.

E.
Laminates
The primary purpose of laminates is to provide ease of wet combing to hair during blow
drying, thus helping to reduce combing damage. They are also used on dry hair to
provide some extra shine to dull and dry hair. The formulas for laminates vary in
viscosity and coverage. Formula 35 provides a heavier and more substantive coverage
which is desirable for dry and dull hair. Formula 36 is less viscous and less substantive,
which leaves hair more free-flowing and manageable.
Laminates
Formula 35 Formula 36
Cyclomethicone 70.0% 85.0%
Dimethicone 30.0 -
Dimethiconol - 15.0
Procedure: Add ingredients to tank in listed
sequence at 25°C. Mix until uniform; fill into
appropriate dispenser

 Page 255
F.
Setting
Like clothing fashions, hair styles are cyclical too. Various hair-setting techniques have
come, gone, and returned again with great vigor to the ethnic market. Some styles are
achieved with rollers and others are accomplished by various molding techniques, such as
finger waving and wrapping, which use the head as a foundation. Whether setting or
molding, the basic components are clean, wet hair and a styling fixative. Setting lotions
and styling gels are manufactured in a number of formulas ranging from light hold to a
very firm, freeze hold.
It is important to minimize the use of ingredients like ethyl alcohol or isopropyl alcohol
which are drying to hair when added to setting products for excessively curly hair. And,
with any such products, a formula that flakes inordinately will not have strong market
appeal. Therefore, the amount of fixatives, such as carbomers, must be carefully selected,
and balanced by plasticizers such as propylene glycol or glycerin. Formula 37 features
cationic polymers as setting agents and conditioners while providing a gentle hold. Styling
gel Formula 38 offers a light hold, Formula 39 offers a firmer hold.
Setting Lotion
Formula 37
A. Water 94.0%
Methylparaben 0.2
Imidazolidinyl urea 0.3
B. Polyquaternium-10 0.2
Polyquaternium-11 (20%) 5.0
C. Polysorbate-20 0.2
Fragrance 0.1
Procedure: Heat A to 80°C. Disperse B
in A. Cool AB to 50°C. Add premixed
C, then cool batch to 25°C.

Styling Gels
FormulaFormula
38 39
A. Water 94.6% 90.9%
Methylparaben 0.2 0.2
Imidazolidinyl urea 0.3 0.3
B. Carbomer 1.0 1.0
C. Vinyl caprolactum/PVP dimethyl amino ethyl
- 3.7
methacrylate copolymer
 Glycerin 2.0 2.0
D. Triethanolamine 1.3 1.3
Hydrolyzed animal protein 0.5 0.5
Fragrance 0.1 0.1

(table continued on next page)

 Page 256
(table continued from previous page)
Formula 38 Formula 39
Procedure: Heat A to 75°C. Disperse B in A. When completely
dispersed, add C to AB at 75°C. Mix for 20 min, then cool to
50°C. Add D; mix for 20 min, then cool to 25°C.

G.
Finishing
Oil-based pomades, creams, and lotions are used copiously in ethnic hair market to
enhance manageability, provide sheen to hair, and alleviate dryness of the scalp. These
products are often used in conjunction with various styling methods such as pressing,
blow drying, thermal curling, and setting. Hair dressings of this type are also applied to
the scalp by consumers to alleviate dry and itchy scalp conditions.
Formulas 40, 41, and 42 represent three popular product types in this category. The
pomade is the heaviest form, containing no water for excessively dry hair and scalp. The
other two, a creme and a lotion, are emulsions which are lighter in feel, preferred by
consumers who desire less oily and more free-flowing hair styles.
Oil Moisturizing Creme Hair
Pomade
Lotion Dressing
Formula
Formula 41 Formula 42
40
A. Petrolatum 59.8% 7.0% -
Mineral oil 39.0 25.0 40.0%
Polyethylene 1.0 - -
Propylparaben 0.1 0.1 0.1
Beeswax - 6.0 10.0
Stearic hydrazide - 0.1 0.1
Sorbitan
- 1.0 -
sesquiolente
Polysorbate-80 - 0.5 -
Glyceryl stearate
- - 1.0
S.E.
Stearic acid - - 1.0
Paraffin - - 3.0
B. Water deionized - 58.7 43.1
Methylparaben - 0.1 0.1
Imidazolidinyl
- 0.3 0.3
 urea
Sodium borate - 1.1 1.2
C. Fragrance 0.1 0.1 0.1
Procedure: Mix A; heat to 80°C. Add B to A; mix for 15 min. Cool
to 50°C; Add C. Mix for 15 min. For pomade, pour in jars at 50°C.
Cool oil moisturizer or creme hair dressing to 25°C before filling in
containers.

 Page 257
Oil sheen spray is another form of hair dressing, demanded by consumers who desire a
higher degree of hair sheen. It is customarily applied after the hair has been styled
through completion. Formula 43 is one example of a standard oil sheen formula.
Oil Sheen Spray
Formula 43
A. C911 isoparaffin 49.3%
Isodecyl oleate 2.5
SDA-40 10.0
C1215 alkyl benzoate 4.0
Fragrance 0.2
Propylene glycol -
B. Isobutane 19.0
Propane 15.0
Procedure: Mix A at 25°C, adding in listed
order. Use A as concentrate; pressurize
with B (propellants).

As a final step, a finishing spritz or holding spray is often applied. Such products when
marketed to the ethnic market must be formulated carefully so that they do not dry hair
significantly. This is accomplished by using less ethanol and more ethanol-soluble
emollients or oils. An example of finishing spritz is provided in Formula 44.
Finishing Spritz
Formula 44
A. SDA 40 82.5%
Butyl ester of PVM/MA copolymer 6.0
B. AMP 0.2
Isopropyl myristate 0.5
C. PPG-12/PEG-50 lanolin 0.5
Dimethicone 0.1
Benzophenone-4 0.1
Water 10.0
Hydrolvzed silk 0.1
Procedure: Mix A at 25°C. Once clear, add B. Mix
for 15 min; add C. Mix for 15 min, then pour into
containers.

 Page 258

IV.
Conclusion
In spite of the fact that there is a dearth of research conducted in ethnic hair care category,
its vitality and growth are based upon the skill and foresight of formulating chemists who
dare to innovate and develop new products, or adapt existing products, which promote
the health of excessively curly hair and, at the same time, increase the stylability of the
hair and create and support new hair-styling trends.
References
1. Kamath YK, Hornby SB, Weigman HD. Mechanical and fractographic behavior of
negroid hair. JSCC 1984; 35:24.
2. Leon NH. Structural aspects of keratin fibers. JSCC 1972; 23:435.
3. Avlon Industries. R&D Laboratory Report. Stress-strain curves for African-American
hair.
4. Syed AN. Is African-American hair really different? Part I. Shop Talk, April 1991.
5. Avlon Industries. R&D Laboratory Report. Comparison of water contents in African-
American hair against Caucasian hair via differential scanning calorimetry. May 1993.
6. Avlon Industries. R&D Laboratory Report. Comparison of wet and dry combing of
African-American hair vs. Caucasian hair. December 1993.
7. Parks C. Living legends in cosmetology. Shop Talk 1993; 12(1).
8. Childrey HM, Jr, Doty E. Hair straightening preparation. U.S. Patent No. 3,017,328
(Jan. 1962).
9. DeLa Guardia MJ. Hair straightening process and hair curling process and
compositions thereof. U.S. Patent No. 4,304,244, assigned to Carson Products Co. (Dec.
1981).
10. Hsiung DY, Mueller WH. Hair conditioning waving and straightening compositions
and methods. U.S. Patent No. 4,175,572, assigned to Johnson Products Co. (Nov. 1979).
11. Syed AN. Hair softening method and composition. U.S. Patent No. 4,579,131,
assigned to Avlon Industries, Inc. (April 1986).
12. Khalil EN, Syed AN. Stable hair relaxer. U.S. Patent No. 4,390,033, assigned to
Johnson Products Co. (June 1983).
13. Syed AN, Gross KW. Pre-shampoo normalizer for a hair straightening system. U.S.
Patent No. 4,602,648, assigned to SoftSheen Products Co. (July 1986).
14. Wolfram LJ. The reactivity of human hair. A review. In: Orfanos, Montagna, Stuttgen,
eds. Hair Research. Berlin: Springer-Verlag, 1981.
15. Hsiung DY. The Hair Straightening, Chemistry and Manufacture of Cosmetics, Vol. 4.
Orlando: Continental Press, 2nd ed., p. 1155.
16. Tolgyesi E, Fang F. Action of nucleophilic reagents on hair keratin, In: Hair Research.
Berlin: Springer-Verlag, 1981:116117.
17. Zviak C. Permanent waving and hair straightening. In: The Science of Hair Care. New
York: Marcel Dekker, 1986:207.

 Page 259
18. Avlon Product Information & Instructions, 1992, p. 11.
19. Khalil EN, Syed AN. A stable hair relaxer. U.S. Patent No. 4,237,910, assigned to
Johnson Products Co. (Dec. 1980).
20. Khalil EN, Syed AN. Low irritation conditioning shampoo. U.S. Patent No. 4,205,063,
assigned to Johnson Products Co. (May 1980).
21. Gerstein T. Shampoo conditioner formulations. U.S. Patent No. 3,990,991, assigned to
Revlon, Inc. (Nov. 1976).
22. Kelly SB, Robinson, VNE. The effect of grooming on the hair cuticle. JSCC 1982;
33:203215.
23. Lötzsch KR. The radiometric technique. Explained by the example of adsorption and
desorption of 14C-labelled distearyl-dimethylammonium chloride on human hair. In:
Orfanos, Montagna, Stüttgen, eds. Hair Research. Berlin: Springer-Verlag, 1981:645.
24. DeMarco R. Hair conditioning composition and process. U.S. Patent No. 4,529,586
assigned to Clairol Incorporated (July 1985).

 Page 261

10
Objective and Instrumental Methods for Evaluation of Hair Care Product
Efficacy and Substantiation of Claims
Marion K. Ishii*
Helene Curtis, Inc., Chicago, Illinois
I.
Introduction
Over the years, scientists developed many test methods to evaluate the efficacy of hair
care products, so consumers were offered trustworthy products that performed as
claimed. This was accomplished by translating consumers' perceived attributes into
scientifically measurable properties and correlating these laboratory test data with real-life
results from expert panels or beauty salon tests.
In the early years, chemists used simple methods to subjectively assess hair care product
efficacy based on their internal standards. During this period, some ambitious advertising
agencies made enticing product claims based on promises and not on accurate product
performance data. This practice appalled pioneer cosmetic chemists, who had founded
the Society of Cosmetic Chemists (SCC) in 1948. They realized there was an urgent need
for developing standard objective evaluating methods available for all cosmetic
laboratories. So they started an ambitious program to develop standard methods similar in
concept to those of the American Society for Testing and Materials (ASTM). Sub-
committees were formed to establish tentative techniques and methods for evaluating
cosmetic products. The committee hoped that, after the SCC members had reviewed these
methods, they could become the Official SCC Methods (1). Whatever the reason,
agreement regarding standard methods was not reached at this time.
*Retired

 Page 262
Scientists agreed there were common problems involved in gathering scientific data to
show that a product performed as claimed in its advertisement. The complexity of
product performance evaluation was aptly described by Wilkinson (2):
What is this thing we call Evaluation Science? Essentially it is a measurement science, but within
boundaries very different from those of metrology. It subsumes not only measurement of physical
parameters and chemical analysis but also physiological and even psychological quantification; it
makes great call on statistics not just as a science but as a philosophy. It operates in a dual
atmosphere of science and marketing, needing a degree of understanding of that complex animal, the
consumer, which far outreaches that of many other scientific research workersand probably that of
many marketing managers. It needs an understanding, always inadequate, of the emotional content of
product judgments. Not in order that this content can be disregarded, but so that it can be given
proper weight when this is due.
Later, leading cosmetic scientists once again approached the subject of a standard
methods handbook. They wanted the international scientists to exchange information on
standardized procedures and to adopt them in their laboratories. These proposals were
included as one of the aims in the Constitution of the International Federation of the
Societies of Cosmetic Chemists (IFSCC) (3).
Over the years, scientists have independently developed many hair test methods for their
own laboratories (4,5) because an official standard hair test methods handbook was not
available. These methods were helpful in providing scientific evidence to substantiate
product claims (6,7).
The purpose of this chapter is to bring together in one place a brief review of hair care
test methods and their areas of usage reported by investigators, and to provide a set of
references. Readers interested in product evaluation can choose from a variety of old and
new methods for documenting claims. Most of the techniques and methods discussed
simulate normal use conditions so that the laboratory data will correlate with those of the
panel or salon test results. This is in keeping with the communication networks' standards
for claims requiring product performance documentation based on normal-use conditions
and on the benefits being perceptible to the consumer.
Recommendation of one method over another is not made, but suggestions for
conducting specific tests are offered. For simplicity's sake, the discussion is arranged in
the following order: background, conventional methods (hair cleansing, condition,
manageability, body), other verification methods, conclusion, and references.

 Page 263

II.
Conventional Methods
The order of presentation is not based on importance, but the methods are grouped by
areas of assessment.
A.
Shampoo Performance
Many methods have been developed for measuring foam generated by a shampoo and for
evaluating its cleansing ability on hair. These methods were developed to objectively
simulate consumers' perception of a shampoo's foam characteristics and its cleansing
ability.
1.
Foam Generation
One of the earliest methods for measuring the foaming capabilities of soaps and
detergents was developed by Ross and Miles (8). For many years, their Pour Foam Test
was the accepted method for measuring foaming performance. Later, some investigators
modified this method (9,10) while others developed their own foam generator. Barnett
and Powers (11) devised a Latherometer consisting of a series of plungers, each equipped
with a stainless-steel screen at the end, which moved in and out of the shampoo solutions
to drive air into the solution and to generate foam. They studied the effects of soft or hard
water and additives on foam characteristics (development, volume, and stability). Neu
(12) and Bromley (13), independently, chose a kitchen food mixer to produce foam and
found that the foam characteristics were similar to those observed in practice.
A German group (14) developed an elaborate foam-testing apparatus with a variable
temperature control (room to 90°C) and a constant-speed rotating brush. Unlike the
plunger system, which moved vertically, the brush system had a horizontal frictional
motion, so that foam was created slowly and was not disturbed. The foam created by this
system was similar to that produced in practice. Soon, a similar friction foam apparatus,
Ehmeda-Reibschaumgerat (15), became commercially available. Later, a Japanese
manufacturer (16) introduced a modified version of the Wilmsmann friction foam
apparatus. It had a variable temperature control (room to 70°C) and a variable speed (300
to 2500 rpm) brush.
In contrast to the elaborate frictional-foam apparatus, the simple method of Sorkin et al.
(17) called for rotating a glass-stoppered cylinder containing a diluted test shampoo for a
precise number of times, then determining the foam level. The authors claimed the
method was fast, was reproducible, and reflected the performance of a shampoo on hair.
Other workers have widely criticized this cylinder shake test because they thought it was
unreproducible and unrealistic. Rather than measuring the generated foam. Hart and
DeGeorge (18) proposed measuring the lathering properties of shampoos. Their method
called for generating lather with a kitchen blender then measuring the lather drain time.

 Page 264
Another research group (19) designed and made a semiautomated lather generator which
mimicked practical shampooing. It had four vertically aligned and interconnected jacketed
glass cells containing an arrangement of inward-protruding simulated fingers and a
heavy-duty nylon-bristled beaker brush. The test protocol called for pouring the test
solution in each cell, adding artificial sebum, generating the lather, and reading the foam
volume. They believed this apparatus overcame the limitations of other testing techniques
used in the industry.
2.
Detergency
Early evaluators adapted the testing techniques for evaluating the cleansing power of
shampoos from the textile and detergent industries. For example, Barnett and Powers (20)
used unscoured wool yarn as the substrate for determining the relative cleansing
performance of shampoos. To simulate real life, Neu (21) degreased salon hair sweepings
with solvent and then regreased the hair with a known amount of the extracted grease.
After applying a test shampoo to soiled hair, he manipulated the hair using a squeezing,
rubbing, and mixing action. The cleansing ability, assessed after solvent extraction of hair,
correlated well with the salon results.
A practical approach taken by Brasch and Amoore (22) required tying standard unscoured
raw wool yarn to the underside of the hairdresser's fingertips. A subject's head was
shampooed with the prepared fingers in a standard manner, and the cleansing ability was
determined on the wool yarn based on the weight loss and detergent retention. The
method of Thompson et al. (23) required soiling a known amount of hair with artificial
sebum (24) and cleansing the soiled hair with methods intended to simulate real-life
conditions (bath process, finger squeeze, controlled pressure). The residual sebum
components in the hair extractant were analyzed by gas chromatography. Other
investigators (2527) also studied the effect of surfactants on sebum removal from hair
using the extraction process.
Foam generation and hair cleansing methods require either simple apparatus, readily
available in a laboratory, or elaborate instrumentation. Given these options, many
laboratories routinely use a simple method, such as the modified Ross-Miles foam test,
for shampoo screening, while the cleansing ability of shampoo is assessed by treating
uniformly soiled hair using controlled experimental conditions (amount of product, water
temperature, rinse time, etc.). Cleansing efficacy would be evaluated by hair surface
analysis (e.g., scanning electron microscope or other instruments covered later in section
III).
B.
Hair Condition
Consumers sensorially assess the condition of their hair after a hair care treatment.
Cosmetic scientists have developed an assemblage of objective test meth-

 Page 265
ods to measure consumer-perceived hair condition attributes such as feel, appearance,
ease of combing, etc. Due to the interrelatedness of these hair properties, a single test
cannot measure all of the hair attributes described by the consumer. The following series
of techniques and methods are discussed separately, but they are all associated with hair
condition.
1.
Detangling Property
The first physical behavior a consumer perceives after a hair treatment is how well a
comb detangles and releases the hair ends. Many laboratories have attempted to translate
this detangling process into a physically measurable propertybut could not obtain
reproducible detangling results because of the lack of a standardized way to uniformly
tangle hair.
One group was successful in devising a novel apparatus to uniformly tangle hair and then
measure the detangling property (28). Their setup had one microprocessor-controlled
robot which tangled the hair in a standardized manner and another robot which detangled
the hair swatches. Using this setup, they obtained reproducible detangling results on
cosmetic-treated hair.
Most laboratories do not have the extravagance of an instrumentation worker who can
design and build special apparatus. A simple technique which generated a relatively
uniform level of tangling (29) yielded fairly reproducible detangling results. This method
called for manually combing a wet tress until tangle-free and then carefully dipping the
tress in water three times to tangle the tip end. The tangled tress was instrumentally
combed using a comb attached to a universal tensile tester. By repeatedly tangling and
detangling a tress, the evaluators obtained test parameters such as average value, peak
force, and work required to detangle a tress.
2.
Combing Property
An improvement in combing after a treatment is perceived by consumers as their hair
being in better condition than before product usage. Recognizing the importance of
combability, early workers routinely evaluated the ease of combing subjectively on
untreated and treated hair. Later, some workers objectified this hair resistance to comb
indirectly by measuring the changes in hair raspiness as the comb moved through the hair.
For example, Waggoner and Scott (30) used an electronic comb for measuring the
vibrational frequencies generated by the comb tooth-hair interface friction.
Newman et al. (31) were the first team to report on a quantitative method for measuring
the combing force on hair. Their custom-made apparatus had a strain gauge transducer,
synchronous motor, dowel for attaching a tress, and a stationary comb. By this setup, they
obtained both wet and dry combing measurements of hair treated with various hair care
formulations. Later, Garcia and Diaz (32) equipped a conventional tensile tester with a
comb attachment and conducted a detailed study on the effect of conditioning treatments
on hair com-

 Page 266
bability. Others (3335) have conducted similar tests using automated instrumental
combing systems for quantifying the combing properties of cosmetically treated hair.
Most instrumental combing started by inserting a comb (hard rubber, stainless steel, etc.)
close to the root end of a hair tress suspended from a force measuring device. The tress
was moved up at a constant speed, and hair was pulled through the comb until the tip end
cleared the comb (see Fig. 1) (36).
Kamath and Weigmann (37) departed from the conventional one-comb system by
mounting two combs 100 mm apart on a tensile tester's crosshead. By this setup, they
found decreased tangling of hair and increased smoothness in combing. Bauer et al. (38)
used two different combing apparatus for measuring the ease of combing of dyed hair.
They used a tensile tester with dual comb setup for slow combing, and a custom-built
machine for simulating real life combing of hair. By using this approach, they identified
the dye products which underperformed in combing.
Other laboratories developed a more sophisticated combing system. For example, Busch
(39,40) reported using an elaborate, computerized, robotized,

Figure 1
Instrumental dry combing test conducted
in a controlled environment (36).

 Page 267
dual-comb testing system. Another laboratory reported developing an automated in vitro
testing system, intended to simulate real-life shampooing, tangling, and untangling hair
(41). This system had a microprocessor-operated robot which controlled the shampooing,
massaging, and rinsing steps. A second robot simulated the usual untangling motions used
by a hairdresser. Unlike the normal scalp-to-tip combing motion, this involved first
combing the tangled lower tip portion of a tress, then positioning the comb to a higher
uncombed section and combing through. This combing process continued until the whole
tress could be combed from root to tip in one stroke. By this system, the evaluators
simulated the real-life assessment of hair treated by the various conditioners.
Gikas (42) devised a combing device which continuously monitored the magnitude of
force applied to either hair tress or on-head hair during the combing stroke. By this
apparatus, when high force applied in the combing process was detected, the force could
be reduced to prevent hair damage.
For correlating in vitro and in vivo combing test results, Wedderburn and Prall (4)
devised a portable comb system equipped with a piezo electric transducer. A more
elaborate system, reported by Sakamoto (43,44), had a strain gauge installed in the comb
handle and was interfaced with a computer. His salon and laboratory combing studies on
hair treated with various products showed good correlation.
Wet and dry combing test results can be used for documenting product performance and
patent claims for a variety of products (e.g., shampoos, conditioners, perms).
3.
Friction
Usually hair feel is judged subjectively by sliding the fingers over hair or by rubbing
fibers between fingers. Scientists translated this subjective evaluation into an objective
measurement of frictional property. This is the force resistance to relative motion between
two surfaces in contact and is proportional to the normal force. The proportionality
constant is the coefficient of friction.
The force required to start the sliding motion determines the static coefficient while the
force required to maintain the sliding motion determines the kinetic coefficient. Most
friction methods used in the cosmetic industry are a modification of the classical works of
Schwartz and Knowles (45). Their capstan method called for draping a single fiber, with
equal weights at both ends, over a cylindrical mandrel (wrap angle of 180°) and placing
one weighted end on a torsion balance. The torsion balance read the frictional force
developed by the revolving mandrel rubbing against the fiber. They used interchangeable
mandrels such as glass, aluminum, hard rubber, etc., for evaluating the frictional property
of shampooed, waved, or bleached-waved hair.
The method of Nagai et al. (46) measured the resistance to the movement of a single fiber
placed at right angle to either a static bundle or a rotating bun-

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dle of hair. They were able to show a good correlation between in vitro friction tests and
in vivo panel or use tests based on feel. The friction test of Scott and Robbins (47) used a
tensile tester equipped with two mandrels on the crosshead. The root end of a fiber was
attached to the load cell, the middle section was draped around the mandrels (wrap angle
of either 97°, 210°, or 348°), and the tip end was weighted. This sensitive method showed
differences among the various shampoo types.
Fair and Gupta (48) modified the twist method of Lindberg and Gralen (49). They
attached hair fibers to a tensile tester, draped the strands over frictionless pulleys, then
crisscrossed them. After twisting the hair two turns, they placed a weight on the tip ends
and then took measurements. These interfiber friction measurements correlated well with
the morphological changes in hair. Another study involved the investigation of the
combined effects of chlorination and either bleaching, dyeing, or permanent waving on
the inter fiber friction (50).
Early evaluators, who utilized a tensile tester in conjunction with a mandrel system,
usually built their own mandrel-motor attachment similar to that shown in Figure 2 (51).
Later, researchers used commercially available apparatus for measuring the coefficient of
friction of hair (52,53).
An unconventional instrumental method reported by a Japanese group (54) compared the
effects of shampoos and conditioners on the frictional drag on hair. This technique
involved passing water (wet test) or air (dry test) through a circular tube filled with a
bundle of hair. The resistance to flow through the hair was calculated from pressure drop
of the fluid. They interpreted the values of pressure drop measured in air or water as the
frictional drag of dry or wet hair, respectively.
More recently, a Japanese manufacturer (55) introduced an easy-to-use, portable static
friction measuring device (Heidon Tribogear). The measurements are reproducible and
sensitive so that even difference between the scalp hair and the end hair (aged) is
demonstrable.
Workers in friction testing offer the following recommendations:
Equilibrate hair and conduct the test in a controlled temperature and humidity
environment.
Use oriented hair (root to tip), and test it in one direction.
Load the tip end of a fiber with weight below the yield point of the fiber.
Use the wrap angle (less than 360°) proper for the hair condition (wet, dry, bleached-
waved hair)
Choose the mandrel composition that is most sensitive for detecting differences on treated
hair.

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Figure 2
Diagram of a typical apparatus for measuring the coefficient of kinetic
friction of hair (51).
The friction test is considered more sensitive than the combing test and can usually
differentiate performance of similar formulations, such as shampoos. Whether these small
differences represent consumer-perceptible properties is a judgment that must be made by
the particular group conducting the study. Correlation with real life is a desirable but
elusive goal.
4.
Luster
Luster or sheen is considered one of the desirable properties of hair, as it implies health
and beauty. This optical reflection occurs when a beam of light falls on a surface and is
either reflected, absorbed, scattered, or combined. Thompson and Mills (56) created their
own apparatus for measuring luster on hair. They aligned hair fibers by stretching them
over a cylinder and catching the ends between two combs. An incident beam of light was
focused at a certain point, and the sample holder was rotated until it was aligned with the
optical system for maximum reading.
An excellent article by Stamm et al. (57) detailed their goniophotometer method for
measuring luster. This method required a goniophotometer and lin-early polarized parallel
white light incident obliquely on the surface of a parallel oriented taut hair fibers to
record the scattered and specularly reflected light from the fibers as a function of the
angle of observation and direction of polarization in the exit beam.
Guiolet et al. (58) used a computerized photogoniometer enclosed in a constant
temperature and humidity chamber. By computer analysis of the gen-

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erated curve, they obtained detailed information regarding the structural parameters of
hair surface, luster, and pigmentation. Reich and Robbins (59) took goniophotometric
measurements to follow changes to the hair surface such as deposition (soiling), particle
removal (cleaning), and interactions on the fiber surface. Their instrumental method
showed excellent correlation with the subjective evaluations of hair shine.
Some laboratories used a custom-built, portable goniophotometer (60,61) which could be
interfaced with a computer. Both hair luster and hair lightness were measured by placing
the opening of the apparatus over a flat tress and allowing the light striking the hair to be
reflected back into the chamber to the photocell. Luster was expressed as the contrast
ratio (ratio of the specular intensity to diffuse intensity). Readings taken at specified test
areas before and after the treatment provided a fast way to screen luster-enhancing
products.
More recently, luster has been measured by an image analyzer (62). By this method, luster
was the contrast value of the shiny, highlighted areas and the dark portions of hair. Maeda
et al. (63,64) validated their image analysis luster method by conducting hair luster
correlative study using the visual evaluation, goniophotometry, and color image analysis.
The consensus among scientists is that specularity, fiber straightness, light scattering,
degree of alignment, and hair color all contribute to the discernment of luster. All these
facts must be considered when taking luster measurements on hair to substantiate claims
for luster enhancement products.
5.
Tensile Property
Hair is mechanically abused by excessive back-combing or repeated hot iron treatments
and chemically modified by cold waving, chemical straightening, bleaching, or oxidative
dyeing. Depending on the extent of modification, people refer to such changes as hair
damage. The conventional method for evaluating this change in hair fibers is the stress-
strain test conducted on a tensile tester using either wet or dry fibers.
Speakman (65) has been credited for developing the mechanochemical method for
determining the changes in wool fibers produced by physical or chemical treatment. He
identified three distinct regions in the stress-strain curve: the linear region (Hookean
region); the yield region; and the postyield region (see Fig. 3). Decrease in any of these
three regions signified the treatment as damaging to the fiber. Speakman expressed the
change in work required to stretch a treated fiber 30% as a percentage of the before
treatment value. The method of Sookne and Harris (66) used the ratio of the treated value
and the initial value, and called it the 30% index.
Early hair care chemists adapted these wool mechanical test methods to human hair. For
example, Reed et al. (67) studied the role of hydrogen bonds and salt linkages in the cold
waving process using the 20% index to assess the

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Figure 3
A typical stress strain curve (72).
changes in hair. Hamburger and Morgan (68) analyzed the particular bonds in play during
a cold wave process by immersing hair in wave lotion using variable timing and
immediately elongating the fibers on a tensile tester. They also elongated similarly treated
fibers after water rinsing and after neutralization. By comparing the postyield slope from
the stress-strain curve, they assessed the extent of hair modification after various steps in
the waving procedure (after reduction, water rinse, and neutralization).
Other investigators used 12-fiber bundles, instead of single fibers, for studying the effects
of various mercaptans (69) or the effects of bleaches (70) on hair and assessed the
changes using the 20% index. Some people adapted similar tensile tests but used single
fibers and different test parameters for expressing the changes in the tensile property.
Deem and Rieger (71) used the hysteresis ratio between the work of unloading and
loading of hair fibers, while Beyak et al. (72) measured the change in yield point of
untreated and chemically treated single hair fibers. They also determined the effect of
light radiation on hair based on the yield point (73). Other workers (74) evaluated the
damaging effect of bleaching and repairability of hair by commercially available products
using the 20% extension index.
Often hairdressers evaluate the quality of hair fibers by stretching them and observing the
breakage behavior. This action is simulated in the laboratory

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by elongating a fiber on the tensile tester until it breaks. This conventional tensile break
test calls for cutting hair to a specified length and measuring the dimension of each fiber
before testing (75).
Hayashi and Ito (76) circumvented the measuring of fiber dimension by using short,
adjacent sections (2 cm) for measuring the break force on similar fibers for both the
untreated and treated fibers.
Another group (77) selected Korean hair fibers with diameter between 80 to 90 m and
treated them in either ginseng saponin or collagen hydrolysate solutions. They found that
fibers immersed in saponin for 30 minutes had higher break strength than collagen
hydrolysate-treated fibers. Later, Kim et al. (78), using bleached hair with similar
dimensions, measured the change in work after 20% extension. The hydrolyzed ginseng-
saponin quaternary was found to be more effective than ginseng saponin or other
conditioning agents in strengthening the structure of bleached hair.
Kamimura et al. (79) proposed the one-point tension test, using 1-mm fibers of known
cross-sectional area in the tensile break test. Their results showed progressive damage as
the testing moved toward the tip ends. Wolfram's group (80) measured both wet and dry
mechanical properties of bleached hair of known fiber dimension and found that
bleaching had a significant effect on the wet tensile properties while it had a slight effect
on dry hair. Other wet tensile tests conducted on reduced and alkylated hair showed such
treatment stabilized the mechanical properties (81). Cannell and Carothers (82) showed
correlation between the change in disulfide bonds during permanent waving and the
postyield slope of the stress-strain curve.
Yquel (83) reported on an instrument capable of automatically carrying out tensile
measurements on a group of samples without the intervention by an operator. This
instrument eliminated manual operation by allowing for all the necessary test parameters
of obtaining transverse dimension of fibers, measuring the elongation and tensile stress
properties. Compared to the tedious, time-consuming, conventional tensile test, this
system offered considerable savings in both time and manpower.
Another method frequently used to evaluate fiber property called for imposing a constant
low strain on a fiber while immersed in various solutions and monitoring the stress
relaxation at designated intervals. Instead of a single fiber, McDonough et al. (84)
stretched a 12-fiber bundle 20% at 85% relative humidity using their Constant Rate of
Elongation Tester. They studied the decay behavior of the bundles after immersion in
either water, mineral oil, or waving lotion.
Some workers (85) used an in-house-built extensiometer for studying the stress relaxation
of chemically treated hair. They compared the mechanical changes in hair based on the
relaxation modulus of hair before and after a treatment. A group in Japan (86) studied the
extension-recovery behavior of physi-

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cally abused hair by extending a preconditioned dry fiber 40% and keeping the strain
constant for 5 minutes, then removing the load. They showed that hair damaged by
brushing did not recover to the normal level during unloading.
Other investigators (87) modified the conventional stress-relaxation method by
interjecting a cycling operation and evaluated the aggressiveness of wave lotions and the
extent or rebuilding after neutralization. This intermittent stress relaxation process called
for the application of an intermittent low strain on a single fiber during an immersion
waving process in diluted lotion and neutralizer (simulating on-head concentration).
Using normalized stress values, they showed relative stress decay and rebuilding of hair
(see Fig. 4). Chemical stress relaxation processes exploring the reduction kinetics of hair
are found in excellent articles by Wickett et all (8891). They investigated the effect of
various test parameters (e.g., pH, temperature, concentration of reactant) on the reduction
rate of hair. This technique was also applied to the study of hair depilation.
The hair loop test of Szadurski and Erlemann (92) consisted of looping a single fiber
around a horizontal pin located on the lower side of a glass cell and clamping both the
root and tip ends to the load cell of a tensile tester. By this unconventional method, they
monitored the changes in hair during an immersion waving process.
Den Beste (93) took a different approach to physical testing with his custom-built
sensitive Intermittent Modulus Device. He mounted a fiber in this device,

Figure 4
Intermittent stress relaxation of normal hair in an acid or alkaline
immersion waving process (87).

 Page 274
elongated it 0.5%, and continuously followed the changes in the fiber length during an
immersion waving process. This device was also used for showing the relative hair
strength loss on fiber elongation after various hair relaxer treatments (94). A similar
device was built for Garcia et al. (95), and they called it the Differential Extension (DE)
instrument. With the DE, they showed sodium thioglycolate-treated fibers contracting
more than ammonium thioglycolate-treated fibers when they were rinsed in water. This
fiber length contraction was eliminated when water rinsing was replaced by either 7%
NaCl or pH 3 buffer.
Another variation of the tensile test evaluated the resistance of cosmetic-treated hair to
repeated mechanical strain (96). By subjecting a treated fiber to progressively increased
elongation cycles on a tensile tester until breaking, investigators found that certain
materials such as polymers strengthened hair.
Fiber experts suggested the following testing conditions for maximizing reproducibility:
Use several lots of single-donor hair.
Prepare short test fibers from hair cut as close to the scalp as possible.
Control the amount of product, processing time, and temperature.
Control the temperature and humidity in the dry tensile test.
Use diluted wave lotion for immersion study, which gives realistic hair reduction level
similar to the level found in hair waved under practical conditions.
6.
Swelling Behavior
There are direct and indirect techniques for measuring the changes in swelling
characteristics of chemically treated hair.
a. Microscopic. Eckstrom (97) provided a detailed description of his test cell and
microscopic technique for conducting hair swelling experiments. He related the degree of
swelling to the degree of penetration of the reducing solution and to the reduction level in
hair. Herman (98) also showed the relationship between swelling and penetration of
mercaptan solutions into hair.
Shansky (99) studied the osmotic behavior of hair by taking microscopic swelling
measurements in an intracell waving process. His experiment, using various
concentrations of salt solutions as the rinsing medium rather than water, showed that a
sodium chloride rinse equalized the osmotic pressure of a reducing solution on the inside
of hair. Others (100) measured the diameter of chemically treated fibers after exposure to
known concentration of lithium bromide and found that damaged fibers were more
susceptible than normal fibers to the hydrogen bond rupturing effect of lithium bromide.
A German team (101), using their newly developed Fiber Swelling Analyser, measured
the diameter of fibers after exposure to various solutions in the waving cycle. Their

 Page 275
results confirmed the previous finding (99) that rinsing reduced hair with sodium chloride
solution instead of water reduced osmotic swelling.
b. Liquid Retention. Some scientists adopted a simple, indirect way to evaluate the
swelling property of hair. This was the liquid retention technique developed by Valko and
Barnett (102). This centrifugal method was not as tedious or as time-consuming as the
microscopic procedure. Swelling measurements, by this method, required soaking
preweighed hair in a test solution, then centrifuging and weighing. For example, the
swelling behavior (in water) of two types of hair waved with either acid or alkaline perm
was demonstrated in a relatively short time (see Fig. 5) (103).
Powers and Barnett (104) used this technique to evaluate the swelling of hair immediately
after treatment in different mercaptan solutions and neutralizers (deswelling). Hall and
Wolfram (81) treated reduced hair with a series of alkylating agents and measured the
liquid retained after equilibrating the treated hair in water or aqueous alcohols. They
identified the agents that increased and those that decreased hair swelling.
c. Alkaline Solubility. The alkaline solubility test was developed by wool chemists who
used it as a criterion of changes in the physical and chemical properties of wool. For
example, Harris and Smith (105) based their method on the fact that chemically treated
fibers placed in a given alkaline solution for a

Figure 5
Liquid retention of acid or alkaline waved Caucasian and
Oriental hair (103).

 Page 276
given time and temperature will show either increased alkaline solubility for fibers with
increased breakdown of peptide or disulfide bonds and decreased alkaline solubility for
cross-linked fibers.
Hair chemists adapted the alkaline solubility test for assessing damaging effects of
previous hair treatment (weathering, physical, or chemical treatment). Experimenters used
the alkaline solubility test (106) for assessing changes in hair after treatment in hydrogen
peroxide (70) or hair dyes (38). They showed, for example, a linear relationship between
bleaching time and alkaline solubility. Okumura et al. (86), investigating the effect of
brushing on Japanese hair, observed increased cuticle damage with increased number of
brush strokes. This finding was reflected in an increase in alkaline solubility as measured
by the method of Erlemann and Beyer (107).
d. Moisture Regain. Hair is hygroscopic, adsorbing water vapor in a moist atmosphere
and losing it in a dry one. Chamberlain and Speakman (108) found an interesting
phenomenon while investigating the moisture regain in hair. When they exposed hair in
an ascending order of relative humidity and then reversed the humidity to a descending
order, they obtained a hysteresis curve. This finding meant that, at any relative humidity,
the hair contained less moisture when it was allowed to absorb moisture from the dry
state than desorbed from the wet state. Stam et al. (109) conducted a more detailed
investigation of the changes in hair by measuring the fiber diameter, length, cross-
sectional area, and hair volume at different relative humidities. Their hysteresis curve was
similar to that obtained by Chamberlain and Speakman (108).
Others studied the moisture regain property of treated hair. For example, Breuer (110)
measured the moisture regain of acid-treated hair in ascending relative humidities and
found less moisture regain in acid-treated hair than in untreated hair. Korean scientists
(77) found that ginseng saponin-treated hair was less hygroscopic and that collagen
hydrolysate-treated hair was more hygroscopic than untreated Korean hair. Later, Kim et
al. (78) found that hair immersed in hydrolyzed ginseng saponin quaternary had higher
moisture regain than ginseng saponin or other conditioner-treated hair.
Recently, Drozdenko et al. (111) proposed using an electric hydrometer for measuring the
hair moisture content. Their hair moisture measurements with an evaporimeter showed
longer moisture retention by the product-treated hair than by the untreated hair, and also a
high level of reliability with the gravimetric measurements.
Hair is quite resistant to dry heat, so hair damage was not detected in hair subjected to
either hair dryer or heated rollers (112,113). However, repeated applications of a hot
curling or pressing iron can be damaging to fibers. Bories et al. (114) determined the
effects of temperature (20°C to 200°C) on hair structure and moisture content by use of
electron microscopy, differential colorimetry, and x-ray diffraction. They found that
below 140°C, hair modification was

 Page 277
reversible, which correlated with the increasing loss of free water. But as the temperature
increased above 140°C, permanent changes occurred ranging from cuticle damage to the
total degradation of the hair structure.
Product evaluators assessed hair altering products for product performance and for hair
damage using the aforementioned methods. Others, for example, Jachowicz (115),
attempted to repair damaged hair either by producing crosslinking in situ or by surface
polymerization. In this excellent article, he also discussed the structural changes in
damaged hair and reviewed other methods for detecting hair damage.
Hair condition assessment is facilitated by using a combination of test methods. For
example, the multitest results presented in Table 1 show that hair waved with an alkaline
thio system had stronger wave levels than hair waved with the bisulfite system. However,
this was accompanied by increased hair porosity (higher liquid retention) and reduced
tensile strength (116).
C.
Hair Manageability
Consumers react negatively to a product if their dry hair balloons out and is
unmanageable. The characteristic of hair manageability is not a single measurable attribute
but involves a complex conglomerate of hair properties (117). Robbins et al. (118)
defined manageability as the ease of arranging hair in place and its temporary ability to
stay in place. Robbins and Reich (119), based on a consumer survey, identified three
types of manageability: style arrangement, style retention, and flyaway hair.
1.
Style Arrangement
The ease of style arrangement is determined by hair condition and combing ease. Methods
for determining hair condition and combing were discussed in III.B.2.
Table 1 Hair Characteristic and Condition of Waved
Hair
Dry wavea Liquid retentionb % Tensilec
°/cm change from untreated g/denier
One Three One Three
Three waves
wave waves wave waves
Alkaline
36 67 30 77 1.04
thio wave
Bisulfite
30 42 19 48 1.22
wave
a Measured with angle of curvature device (127).
b Tested after wave in water (102).
c Tested in water.
Source: (116)

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2.
Style Retention
Style retention is influenced by static friction (discussed previously in III.B.3), hair type,
fiber texture, and configuration.
a. Hair Texture. How a product performs on hair is influenced significantly by its
individual fiber diameter. Cottington et al. (120) showed a direct relationship of fiber
diameter to hair body, combing ease, and abrasion resistance when other properties were
equal. Methods for determining hair fiber dimension, suggested by Robbins (75), are
linear density, microscope (light or electron), vibrascope, micrometer caliper, and laser
beam diffraction. Some researchers are now using an optical micrometer (121) for
determining the diameter of the hair fibers.
b. Hair Curvature. The natural conformation of human hair ranges from straight to very
curly. The desire to change the contour of hair has existed throughout civilization. People
wanted to impart waves to straight hair and straighten very curly hair. They thought these
configurational changes improved hair style retention.
Traditionally, curls were generated in hair by a permanent waving process. For evaluating
the hair curvature, early investigators used a numerical method of rating laboratory
waves. Reed (122) proposed the use of photographic standards of waved tresses having a
scale of 1 to 5; a higher rating indicating increased degrees of curls.
Kirby (123,124) thought the curls generated by rod waving could not be measured
accurately because the curls were not uniform. So, to produce uniform curls, he adapted
the pegboard method developed in the laboratories of Arthur D. Little Inc. (125). Instead
of the traditional, overlapped wrapping of hair on a perm rod from the ends toward the
scalp (croquignole), the hair was interlaced between two rows of removable pegs on the
pegboard, and a strip of white blotting paper was then wrapped over the wound hair. This
provided a means of completely staturating hair with wave lotion and prevented pooling
of the lotion. The wound and wave-lotion-saturated hair was then placed in a covered
container, and this in turn was placed in a constant temperature bath at 25°C. At the end
of the designated waving time, the wound hair was rinsed in water then followed by
neutralization and a final water rinse. After the pegs were removed, the curl was allowed
to relax in water before the linear length was measured. The percent waving efficiency
was calculated based on the straight hair length, the distance between two designated test
pegs, and the distance between the undulations formed at the two designated pegs.
Tsujino and Sakata (126) used the Kirby method for evaluating the effect of a biochemical
oxidizer, the enzyme uricase, instead of a chemical neutralizer in the permanent waving
process. The waving efficiency was evaluated according to the Kirby method (123,124).
The waved hair was subjected to surfactant solution at elevated temperature to accelerate
the wave loss. The percent

 Page 279
wave retained was calculated based on the initial curl length and the after-relaxation curl
length. These investigators claimed that their state-of-the-art waving system performed
similarly to that of control and it also manifested softness in the waved hair.
Rather than assess the waving efficiency based on the length of a curled tress, Den Beste
(127) built a total angle of curvature device for measuring the actual curvature in a tress.
Using a silhouette of a waved tress, he traced the curvature of each strand using the angle-
measuring probe. A dial on the device showed the accumulated angle of curvature for the
whole tress, from which the wave level was calculated as the average curvature (total
angle/number of strands measured).
Some evaluators processed hair by immersion to ensure uniform treatment. For example,
Japanese chemists (128) wrapped a single fiber around a Monel bolt (1-mm screw pitch,
7-mm diameter) and immersed this in a controlled amount of permanent wave lotion for a
given time. This was followed by neutralization and water rinse. The dry test fibers were
unwound, hung in front of a measuring grid, and photographed immediately, then again
after 1 week, and after 2 weeks. The results showed better curl generation in fibers
reduced with lotion containing keratin polypeptide and neutralized with oxidizer
containing keratin polypeptide than in the control fibers. Other investigators (129)
conducted similar tests but wound a 10-fiber bundle around a glass rod (10-mm diameter)
without overlapping and immersed the wrapped samples in wave lotion or other test
solutions. The waving efficiency was calculated based on the straight hair length and the
waved hair length.
A simple procedure for measuring the curvature of hair offered by Robbins and Reich
(119) was based on the curled hair length; the taut, straight hair length; and the number of
undulations. Marti (130) proposed his test tube test curl as a quick screening method for
perm lotions. The method called for winding a 12-fiber bundle around an aluminum
mandrel, then reducing and oxidizing the hair. The waving efficiency was assessed based
on the curled hair length and curl diameter.
The methods for measuring the curliness of hair vary from single fibers, fiber bundles,
and standard tresses; the curl imparting devices and curl measuring techniques range from
simple to complex. Irrespective of the devices chosen for imparting curls to hair, it is
important to control the lotion-to-hair ratio, and the treatment temperature and time. If
using an immersion technique, hair should be treated in diluted wave lotion and
processed for a specific time so that the reduction level in hair is similar to that found in
an on-head processed hair. This practice should provide good correlation between
laboratory and salon test results. Care must be taken in interpreting the waving efficiency
of a product on repeatedly waved hair, because hair subjected to repeated alkaline waving
tends to form progressively more shallow curls.

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3.
Set Retention
Most evaluators use conventional techniques for measuring the set-holding property of
hair (81,131134). The protocol calls for tresses of specified hair length and weight to be
wrapped on rollers of known diameter. After equilibrating in a given humidity, rollers are
removed and the initial curl length is measured. The tresses are then exposed to high
humidity, and the curl length is measured at appropriate time intervals. The set retention
efficacy is expressed as % curl retention.

where L = length of hair fully extended, Lo = length of hair before exposure to high
humidity, and Lt = length of hair after exposure at time (t).
Diaz and Wong (135), in addition to the conventional equation, described the set
relaxation process over a wide range of humidity, by the expression Y = ATB. The Y was
the amount of set remaining after exposure to humidity for time T, and A and B were
constants. They suggested using the integrated form of the equation for evaluating the
setting efficacy.
Some chemists modify the test substrate or used other setting and measuring devices for
investigating the set-holding property of hair. Reed and Bronfein (136) tried to eliminate
many of the variability connected with curl retention measurements. One of the variables
they thought was the technique of hair preparation. Instead of setting hair by the
conventional overlapping roller wrap (see Fig. 6), they rolled uniform hair swatches into
two-dimensional pin curls (see Fig. 7) for studying the effect of hair sprays on set
retention. A novel method of Stavrakas et al. (137) required preparing special tresses
which could be clamped on the tensile tester at both the scalp and tip ends. For this test,
hair was set on a glass tubing and the work required to straighten the dry curl was
measured with a tensile tester. By normalizing the test parameters and calculating the curl
strength index, they found that both water-set and hair-spray-treated tresses had
considerably lower curl strength than permed tresses.
Instead of setting hair in coils, some laboratories set hair swatches on pegboards (see Fig.
8) (138,139). This technique imparts uniform curl configuration and allows uniform
spraying of products. The curl droop measurements with time are made on curls hanging
on a calibrated Plexiglas rack in a controlled temperature and humidity chamber.
Differences in set-holding property among resins were shown by using this method,
which is claimed to mimic actual use conditions.
To avoid interfiber interactions, Robbins (140) used single-fiber coils for measuring the
set retention properties and concurrently studied the load elongation and creep behavior
of single-fiber coils. From these studies, he con-

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Figure 6
Roller-set tresses (122).

Figure 7
Pin curls (122).
cluded that water-set fiber coils were not elastic and that thicker fibers resisted uncoiling
better than thinner fibers.
The holding power of hair styling products was evaluated by Mathews and Cannell (141)
using an unconventional technique. Untreated and styling aid-treated roller-set tresses
were compressed by a compression tester, and the efficacy of a styling aid, the hold
factor, was calculated using the ratio of work of deformation of the treated curl and of the
water-treated curl.
Although roller-setting of hair simulates the real-life situation, the curl droop taking place
under static condition is not realistic. So, to account for the stress experienced by hair
during real-life experience, experimenters developed the Dynamic Set Retention Test
(142). This procedure calls for setting small,

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Figure 8
Peg-board-set tresses (142).
dual-tabbed tresses on peg boards, then equilibrating the set tresses at a specified
temperature and humidity and measuring the initial curl length. Both the force required to
straighten out the curl with a tensile tester (see Fig. 9) and the set relaxation with time (see
Fig. 10) are measured. By this method, they obtained a better understanding of product
performance of styling aids in a dynamic condition than by the conventional static set
retention method.
Bauer et al. (38) also thought the conventional set retention test was unrealistic because
each styled swatch was studied independently and did not account for hair interaction as
observed in real life. So, they prepared half-head model by mounting six swatches on
each side of a simulated head. After concentrically winding each swatch, they brushed
each set of six dry swatches into a single curl. This test head was subjected to simulated
natural head movements and brushing during the test investigating the setting behavior of
waved, bleached, or dyed hair.
Experts offered some guidelines for conducting set retention studies:
Prepare standard hair assembly of known hair length and weight.
Control the product-to-hair ratio, mode of product application, treatment time, and
temperature.
Use standardized setting devices.

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Equilibrate set hair at lower humidity (~20% to 45% relative humidity) than that used for
relaxing the curls (~65% to 95% relative humidity).
Use accurate measuring device (e.g., cathetometer, calibrated moisture-resistant grid) for
taking curl droop readings.
4.
Static on Hair
Consumers think flyaway hair causes difficulty in combing and style manageability. This
ballooning of hair is caused by the repulsive forces of static charge generated when hair is
combed or brushed. Hair can become damaged if it is subjected to constant static charge
buildup (143).
Scientists have developed either direct or indirect ways to measure the charge generated
by combing of hair. The method of Mills et al. (144) measured the static charge on the
comb after it was passed through hair. This indirect measurement could be taken because
the charge produced on hair was equal but opposite in sign to that produced on the comb.
Hair was combed in a standard fashion using a comb with a copper wire leading to an
oscillograph, while a camera attached to the oscillograph photographed the appearance of
both the experimental and control tresses. They demonstrated the effectiveness of a
cationic creme rinse in reducing the static charge on hair in both an in vitro tress study
and by in vivo tests on heads. The technique of Barber and Posner (145) called for
measuring the distance at which a freely suspended gold leaf began to be attracted to a
comb after combing hair. They found that the charge

Figure 9
Curl strength of peg-board-set tresses (142).

 Page 284

Figure 10
Dynamic curl retention of peg-board-set tresses (142).
on hair decreased either with an increase in relative humidity or by a cationic detergent
treatment.
Lunn and Evans (146) conducted a comprehensive study investigating the effects of
variables such as comb material, number of manual comb strokes, and commercial creme
rinse products by manually combing hair and measuring the charge in a Faraday cage
connected to an electrometer.
Sakamoto et al. (43,44) devised a Faraday cage charge tester and a comb electrode
detector interfaced with a microcomputer. They measured the amount of initial electrical
charge, the decay, and the amount of induced electricity on the comb after combing
different hair types. Jachowicz et al. (147,148) made a device with an exchangeable
contact probe. Their results showed that the static charge could be suppressed by
reducing the difference in work functions between the contact probe material used and
hair. In practice, this was accomplished either by choosing the proper comb material or
by modifying the hair surface.
Some laboratories used commercially available apparatus for electrostatic testing
(149,150). For example, tests were conducted using the Static Decay Meter with a control
unit and Faraday test cage inside an automatically controlled humidity chamber (151).
Most evaluators conduct combing and static tests separately for evaluating product
performance. In reality, when a consumer combs her hair repeatedly in a low-humidity
environment, the combing and ballooning of hair occur together and not in two acts. So,
some scientists tried measuring both the ease

 Page 285
of combing and the charge distribution along the hair tress simultaneously during the
combing operation. Lunn and Evans (146) inserted both a hard rubber comb and a metal
comb in a tress attached to a tensile tester load cell. As the hair was combed, the charge
generated on the fibers was sensed by a detector electrode and read by an electrometer.
Unfortunately, simultaneous combing force and electrostatic measurements could not be
taken due to interference from the metal comb.
Other workers were successful by incorporating a detector for measuring electrical charge
on the comb in the automated in vitro testing system (41) described in Section III.B.2.
Testing was conducted in a constant-temperature and-humidity chamber. As the tress was
combed on the downstroke, both the charge generated on the comb and the combing
force were read and transmitted to a computer. Their laboratory test data correlated well
with their on-head test results. Jachowicz et al. (148) used a specially constructed
apparatus for measuring both the combing and charge distribution simultaneously. The
setup consisted of a combing system attached to a tensile tester and a charge probe
interfaced with a computer. Experiments conducted at 25% to 30% relative humidity
showed three distinct charge density distribution profiles, corresponding to the upper,
middle, and tip portions of a hair tress during combing. This finding was different from
the single peak charge-density profile obtained by Lunn and Evans (146) at 50% relative
humidity.
Whether one uses custom-made or off-the-shelf equipment, some general testing
techniques are suggested:
Use clean hair free of sorbed material such as polymer.
Use properly oriented hair tresses (153).
Comb or brush hair in one directione.g., scalp to tip.
Use efficient and reliable apparatus.
Follow strict experimental protocols (e.g., type of comb, combing speed, number of
strokes).
Conduct the test in a strictly controlled temperature and humidity environment.
5.
Hair Body
Various methods are reported on ways to assess hair body. They were developed by
scientists according to their interpretation of what constituted hair body. For example,
Hough et al. (154) proposed the following definition for this complex hair property: Body
is a measure of a hair mass's resistance to and recovery from externally induced
deformation.
Based on their study, factors that governed hair body were hair density, curvature,
stiffness, diameter, and fiber interactions. In practice, women judge hair body visually
and tactilely and describe it with three major words: springiness, volume, and stiffness
(4). These attributes tend to overlap, and they

 Page 286
cannot be measured by a single method. To simplify the discussion, the hair body
methods will be presented in two sections: (a) hair bulk and resiliency, and (b) stiffness.
a. Hair Bulk and Resiliency. Yin et al. developed the Omega Loop Test (155) to measure
the structural strength and resiliency of a hair mass. In this test, a hair tress held in the
shape of the Greek letter omega was repeatedly compressed to a given strain and then
allowed to recover. The differences between treatments were compared based on the
average force and work values. The method by Garcia and Wolfram (156) used a special
ring attachment on a universal tensile tester. They suspended a hair swatch from a tensile
load cell and continuously recorded the forces required to pull the hair swatch through a
Teflon ring. The work of passage through the ring measured the compressibility of a hair
mass. Also, the successive passes of the swatch through the ring were used as a measure
of resiliency or recovery from deformation of a hair mass. This sensitive method was
claimed to quantify changes in the bulk properties of cosmetically treated hair (shampoos,
hair sprays, conditioners, waving lotions, etc.).
Robbins and Crawford (157) modified the method of Garcia and Wolfram by replacing
the Teflon ring with sets of very thin circular templates formed from a butyrate plastic
sheet (see Fig. 11). The support apparatus to hold the

Figure 11
Typical template (157).

 Page 287

Figure 12
Tensile tester modified to measure the
work to pull a hair swatch through
the templates (157).
templates was mounted on the tensile tester crosshead. The scalp portion of a hair swatch
was attached to the load cell, and hair was allowed to hang free through the template hole
(see Fig. 12). The template hole size was progressively decreased after each tensile test
pull through of hair. These workers suggested that the maximum tress diameter obtained
by their method was a measurement of hair assembly bulk. They studied the effects of
hair curvature, weight, friction, and body shampoos on hair body using the maximum
tress diameter as a measure of hair assembly bulk. Later, Thomson et al. (158) used the
template test method to evaluate organosiloxanes as hair body and volume conferring
agents. They found that the trialkoxy aminosilanes increased the body and volume
characteristics on hair tresses; this was confirmed by half-head salon studies.
The radial compression method of Weigmann et al. (159) was developed to simulate the
in vivo evaluation of hair body. Their device consisted of a stand with a horseshoe
bracket equipped with a low-friction pulley on each end (see Fig. 13). This was mounted
on a tensile tester crosshead so that as the crosshead

 Page 288

Figure 13
Diagram of the apparatus for radial
compression of a fiber bundle (159).
moved downward, the hair swatch, suspended between the pulleys, remained stationary.
This motion radially compressed the swatch and allowed a recording of the force of
compression. The recovery of the swatch from this deformation was recorded by
reversing the crosshead to an up movement. By this method, they demonstrated the
changes in compression and recovery of cationic polymer-treated hair.
Robbins (160) proposed a simple method to measure the bulk of hair fibers based on
their frictional behavior. The method called for randomly dropping short hair fibers (1- to
2-inch length) into a large graduated cylinder. The fiber sample with the higher interfiber
friction was interpreted as providing a larger volume and more body.
Clark et al. (161) developed a technique to measure hair body based on the volume
occupied by the hair. Their method consisted of measuring and recording the area of the
test tress and a control tress using an image analyzer and camera. Hair body, by this
method, was the ratio of the test tress area to the control area. Test data from this
instrumental method correlated well with the panelists' visual assessment of tress hair
body.
The springiness described by consumers as one attribute of hair body was simulated by
an ingenious dynamic curl bounce or curl elasticity

 Page 289
method developed by scientists from Switzerland (162). They hung triplicate curls on a
calibrated grid propped between two sliding frames. An unlocking of the grid allowed the
grid to drop (like a guillotine), hit the bottom of the frame, and simultaneously switch on
a light bulb, indicating the start of the curls' vertical movement. A camera connected to a
video recorder system continuously filmed the curls' oscillations (see Fig. 14). Then data
from the film frames were processed by a computer to yield curves showing oscillating
cycle amplitude versus time. They reported good correlation between this in vitro bounce
test data and the hair dresser's ratings relative to hairstyle hold and flexibility properties.
b. Stiffness. Fiber stiffness is an important property which affects hair body, combing,
style manageability, and curl retention. The methods for measuring this parameter involve
either bending, torsional, or stretching stiffness.
i. Bending Stiffness. A simple method developed by Scott and Robbins (163,164)
measured the stiffness or resistance to bending of individual fibers. This balanced fiber
method required draping a fiber weighted on each end over a fine wire and measuring the
distance between the vertical legs. The stiffness index, the distance between the legs, was
used for comparing the effects of various treatments. They found that the fiber stiffness
progressively decreased as the reduction time was increased in permanent waving while
fiber stiffness increased when a monomer was used for intrafiber polymerization.
Others (165) used the balanced fiber method (see Fig. 15) to investigate the bending
properties of hair under various conditions of the permanent waving processes. They
calculated the permanent set values from the fiber stiffness

Figure 14
Bounce test for evaluating curl springiness (162).

 Page 290

Figure 15
Diagram of the device for measuring
the bending stiffness of hair, built
according to the description by
Scott and Robbins (165).
in the reduced and oxidized states based on the linear viscoelastic theory as expressed by
Denby's equation.
Busch measured the bending modulus by generating vibration by a loud speaker and
determining the hair resonance vibrations via light reflection (166). He observed that
waving of hair manifested stiffness in hair while bleaching increased flexibility in hair.
ii. Torsional Stiffness. Bogaty (167) applied the classical physical theory of springs to
develop methods for measuring the torsional rigidity of helical coil configured hair. These
methods were needed because torsional deformation played an important role both in
impartation and in maintenance of hair styles. He used a custom-built apparatus for
developing two different methods.
In the torsion pendulum method, a single, dry fiber was suspended and allowed to
equilibrate in a constant-humidity jar. Testing began with a rotating electromagnetic field
bringing the pendulum into motion.
The second method for testing wet fibers was the direct twist method, based on the
principle of a technique by Morton and Permanyer (168,169). By this method, a test fiber
mounted in series with a reference wire (tungsten) was allowed to twist and the total twist
was read on the counter attached to the motor (see Fig. 16).
These two methods were used over a wide range of humidities for studying the torsional
properties of waved and unwaved single fibers. The investigation showed that torsional
stiffness and mechanical creep of hair were sensitive to moisture.
Later, Wolfram and Albrecht (170) had a similar torsion apparatus built, with a slight
modification. By a simple capillary insertion, they were able to use just the torsion
pendulum technique for testing fibers both in air and in liq-

 Page 291

Figure 16
Sketch of the apparatus used for torsion measurements by the direct twist
method. Small sketch shows detail of the collar with indicating pin passing
through the circular measuring scale (167).
uids. Tests showed that the hair cuticle was plasticized by water more than the cortex and
that dry heat increased torsional rigidity. They also found that chemical modification was
related to configurational stability and could be used to predict setting behavior of hair.
Ganslaw and Koehlet (171) followed a practical approach by measuring the torsional
property of hair with a torsional braid analyzer (see Fig. 17), similar to that described by
Gillham (172). Their method involved mounting a pretwisted swatch in the torsional
braid analyzer, then allowing it to untwist freely and recording the rate of untwisting as a
function of time. They showed excellent correlation between twist retention and
traditional curl retention by using helically configured hair. Moreover, the twist retention
test was able to distinguish statistical differences between fixatives using small sample
numbers while curl retention test could not, even with large sample numbers.
iii. Stretching Stiffness. During the development of the balanced fiber method for
measuring bending stiffness, Scott and Robbins (164) also con-

 Page 292

Figure 17
Schematic diagram of the Torsional Braid Analyzer (171).
ducted tensile tests on the same test fibers. They wanted to test the strength of fibers by
bending and by stretching to see how well one measurement predicted the other. The
findings showed satisfactory relationship between the bending stiffness indices and
Hookean slopes of the stress-strain curve. So, they concluded that tensile measurements
could be used to estimate bending strengths. Robbins and Reich (34) also used the tensile
tester for determining the relation of hair fiber stiffness and combing. They found that
increased fiber stiffness lowered the force required to comb hair.
To obtain good hair manageability, related hair properties, discussed previously, need to
be in balance. For example, too much body (through increased curvature) can make hair
difficult to comb, retain style, and manage.
Robbins and Scott (117) undertook an ambitious task of developing algebraic expressions
for predicting changes in the behavior of hair assemblies from combinations of single
fiber properties such as static friction, kinetic friction, stiffness, static charge, curvature,
weight, and diameter or cross-sectional area. They suggested that these equations can
guide chemists in developing and documenting different hair products. By this approach,
products claiming extra body could be expected to perform differently from regular
formula.

 Page 293

III.
Other Verification Methods
There are other qualitative and quantitative test methods which can be used in
conjunction with the previously discussed conventional methods to verify test results. A
few of them are presented here in summary form with references.
Properties Methods References
General appearance,
Scanning
productdeposition,
electronmicroscopy (173,174)
substantivity,distribution,
(SEM)
or buildup
(175,176)
(177,178)
(179,180)
(181,182)
(183,184)
Wavelength
spectroscopy,
(185)
energydispersion,
spectroscopy
Reflectometry (186)
Spectrophotometry (187)
Liquid scintillation (188,189)
spectrometry (190)
Liquid membrane
(191)
wettabilityscanning
Microfluorometry (192)
X-ray photoelectron
(193,194)
spectroscopy(XPS)
Electrokinetics (EK) (193,194)
Electron
spectroscopy
(195,196)
chemicalanalysis
(ESCA)
Pyrazol red dye (197,198)
SEM and image
Structural changes orhair
analysis orhair (199201)
damage
damage
Polarization microscopy (35,202,203)
Fourier transform
infraredspectrometry (204,205)
 (FTIR)
Spectrofluorometry (206)
Penetration of reducing agent Qualitative (visual) (207,211)
Reduction level Quantitative analyses (80,212217)

Whichever method is used for product evaluation, it is important that all experimental
conditions be carefully controlled. Reproducible laboratory results can be obtained by
following suggestions offered by hair experts:
Use multitest approach for evaluating products (e.g., combination of combing, static, and
retention tests).

 Page 294
Use hair certified to be chemically untreated oriented root to tip and to have little natural
wave.
Accurately measure fiber dimension (75) for single-fiber studies.
Use reliable test instruments (e.g., tensile testers in varying price range are available)
(217221).
Control the amount of product-to-hair ratio (based on objective [realistic] or exaggerated
test condition).
Uniformly manipulate hair (after application of shampoo, conditioner, etc.) and time the
product contact on hair.
Rinse hair with constant-temperature water (e.g., use equipment similar to that shown in
Figure 18)(36).
Test hair in environmentally controlled temperature and humidity facility.
Use proper statistical treatment of test data.

Figure 18
Controlled temperature and flow water
rinsing apparatus (36).

 Page 295

IV.
Conclusion
Evaluation science has made great strides so that the product performance claimed is
close to what the end user will perceive. Performance testers do not depend on just a
single test for evaluating product efficacy but use a battery of techniques and methods.
This conglomerate approach is intended to match the consumers' multiple sensory means
of product assessment.
To assure that the laboratory results are relevant in the real world, the in vitro test results
must be correlated with the in vivo results such as the salon, sensory panel, and self-
application panel results.
Acknowledgment
The author gratefully acknowledges the contributions of the past and present dedicated
scientists who made this chapter possible.
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11
Consumer Research Techniques
Ralph Blessing
Helene Curtis, Inc., Chicago, Illinois
Hair Care consumer product testing can be extremely challenging and complex because
there are many factors that make it different from other types of product testing. The
products typically deliver not only functional benefits like cleaning and hold, but also
psychological benefits. Hair often acts as an ornament to express one's individual
personality. People can change their hair's appearance easier than other aspects of their
physical being by changing the hair length, chemically treating and coloring the hair, or
changing the style they wear.
Product aesthetics, like fragrance, can often be as important as functionality, and
preferences vary widely. Needs, tastes, styles, and preferences change over time culturally
and as consumers age. For example, as the baby boomers in the United States become
older, hair color, products that moisturize, and products that can grow hair or retard hair
loss are becoming much more important.
Before any discussion can begin about how to do product testing in hair care, it is very
important to understand the product characteristics and user dynamics that can influence
the test design and analysis of results. Some of the more common issues and their
implications are detailed below.
I.
Factors to Consider When Developing a Testing Plan
A.
Evaluation
Many hair care product performance characteristics are difficult to measure accurately
using laboratory or sensory instruments. Marketplace decisions often

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require understanding of product performance or preference. For example, a lab
instrument or trained sensory panel may indicate that a new product delivers more shine
than other products. The shine difference, however, may be so small that consumers
simply don't notice it (or don't care).
It is important to determine what the objective is and how difficult it will be to measure
before mapping out a testing plan. Whenever possible, consumer results should be
compared with sensory or instrument results to better calibrate in-house testing
techniques. The groups in the organization that do various types of testing need to work
together so that R&D, marketing, or other decision makers get the best possible
information and consumer insight.
B.
Fragmentation of Preferences
There is a very high level of fragmentation in the hair care category. Because hair, hair
styles, and tastes vary so widely, preferences also differ significantly. Rarely does one
formula satisfy a wide group of consumers. For each product there is a need to
understand who the target is and what their expectations are. For example, if the company
is developing an extramoisturizing shampoo, considerations should be given to testing the
products among current users of extramoisturizing shampoos or people with dry hair.
Other factors to determine among your target group include what existing products they
prefer and what drives those preferences. Their reactions will likely be quite different
than people who have thick, oily hair who may want more body or cleaning.
Some factors that cause fragmentation to consider are listed below:
1.
Demographics
Age
Sex
Race/ethnicity
Region (hard vs. soft water)
Family size; who uses/shares
Who decides/influences brand/product choice
2.
Habit and Practices
Products used to style hair
Frequency of product use
Is hair permed or color-treated? When?
Use of heat appliances
Way hair is typically styled
3.
Hair Types
Length (short to long)
Oily to dry

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Amount of curl
Amount of split ends
Shininess
Thickness
Texture
Density
Manageability
Sensitivity to humidity
Softness
Amount of body
Scalp condition (oily/dry, flakes)
Ability to hold a curl
Ease of styling/holding a style
Quantity of hair/degree of balding
Softness
Hair color (gray, white, blond, brunette, red, etc.)
4.
Forms/Flavors of Products Used
Dry, normal, oily
Body, moisturizing, highlighting, for permed hair
For color-treated hair, dandruff, dry scalp
Baby/tearless, sensitive, extra cleaning
Liquid, spray, leave-in, foam/mousse, gel
Spray (nonaerosol, aerosol)
Hold level for styling products (soft, extra, ultra)
Fragrance; scented vs. unscented
Conditioner forms (hot oil, muds, intensive treatments)
Brand(s) used
C.
Product Characteristics
Product characteristics such as fragrance, color/appearance, consistency and texture can
all significantly impact perceptions about product performance. When testing different
formulas, it is important to keep as many product characteristics constant as possible.
Also, reactions to all product characteristics, even if they are not a focus of the project,
should be measured to provide understanding for what is driving reactions to the product.
For example, different chemical bases can often change fragrance characteristics. Efforts
should be made to ensure that the fragrance has a consistent odor and strength to the
respondent or it may halo other measures.
Some product characteristics, by type of product, that can be measured are detailed in
Table 1.

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Table 1 Measurable Product Characteristics
Shampoos/conditioners Hair spray or styling products
Aesthetics/functionality
Lather (amount, type, creaminess,
Drying time (too fast, too slow)
speed)
Consistency (too thick, too thin,
Hair feel (stickiness)
feel)
Fragrance (intensity, type) Fragrance (intensity, type)
Ease of dispensing, using productEase of dispensing, using product
Spreadability, ability to control
Spreadability
location
Appearance/color of product
Performance/end benefits
Amount of cleaning/conditioning Amount of hold
Rinsability Rinsability
Shine/highlights Shine/highlights
Impact on body (add, subtract) Impact on body (add, subtract)
Softness Softness
Scalp effects Scalp effects
Manageability/combability Manageability/combability
Ease of styling Ease of styling
Damage repair Damage repair
Moisturizing/drying Moisturizing/drying
Effects on curls, perm or color Effects on curls, perm, or color
Buildup over time Buildup over time

D.
Packaging
Packaging functionality and appearance can also significantly affect overall perceived
product performance. Products should be developed as a system, which combines the
optimal packaging and formula. Key packaging elements to consider include size of
bottle, shape, type of orifice (flip top, screw top, disk top etc.), size of orifice, type of
spray (for spray products), spray insert, etc. Again, asking consumers their reaction to
packaging functionality as well as product performance and sensory characteristics is
advised.
To isolate product formula differences, it is important to keep the package shape, color,
size, and instructions the same. Remember, the product color and package color can
interact. Consumer reactions to a formula in a white package can be different than in the
final colored package.
E.
Consumer Testing
When using consumers, it will be important to determine how much to direct their hair
care habits and practices. Hair care products are often used in com-

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binationa woman may first shampoo, then use conditioner, then mousse, and then spray.
In early formula development and small-scale testing, it may be necessary to control the
products used before and after the test products/categories. For example, if conditioners
are being tested for improved combability, the hair may need to be washed first using one
specific formula of shampoo. For largescale testing, there may be the need to break the
sample out by specific sub-groups (e.g., women who used a conditioner seven times in a
week vs. one to six times, etc.), depending on the issue.
The type of product, consumer, and issues are all key factors affecting how long the test
should last. It can take many uses before a consumer can accurately judge the
performance of a specific hair care product. As a general rule, product aesthetic issues
like fragrance appeal or consistency can be addressed in shorter tests (as little as one sniff
per use), while product performance measurement (shine, body, buildup, etc.) will take a
lot longer. A test for a daily hair care product, like shampoo, that is measuring
performance should last at least 7 days.
F.
Effects of Time
Product appearance and performance can change over time, or be different from batch to
batch. Many hair care product formulas can change over time, due to their chemical
nature and exposure to heat, cold, sun, etc. The changes can affect both aesthetics
(different color, different consistency) and clinical and/or perceived efficacy. Similarly,
formulas rarely turn out exactly the same from batch to batch, or when comparing pilot
lab formulas to final large-scale production batches.
Ideally, the formula that best represents what the average consumer will experience
should be tested. If there is a likelihood of a lot of variability, it should be built into the
study through larger samples, multiple batches, or deliberately varying the key variables.
Sometimes the product may require agingto simulate the product experience a consumer
will have after the product goes through the distribution and retail channel.
II.
What Issues can Product Tests Help Address?
There can be several different reasons why hair care product tests are conducted: (a) to
help formulators develop a product to meet specific objectives; (b) to make an in-market
decision; (c) to determine product integrity; and (d) to support or challenge product
claims. Each issue may require different test methodologies, action standards, and types
of analysis.
Because of the complex nature of legal product claims research, it will not be addressed in
great detail here. It is critical that legal counsel be involved

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in any design, execution, and reporting of claims-related research. However, the general
principles described in this chapter will usually be a part of a legally valid product/brand
claim test.
A.
Help Guide Marketers and Formula Developers
Most product testing is done primarily to aid the formula developer in coming up with a
final recommended formula. Some questions the research may be asked to address
include:
What are the strengths and weaknesses of current products on the market?
What are unmet consumer needs?
What is the best product? Why?
What performance and aesthetic cues do consumers use to evaluate each type of product?
What performance trade-offs are the target consumers willing to make? (e.g., more hold,
but stickier hair feel)?
How do different prototypes perform vs. performance objectives? Which ones should be
pursued?
How do changes of ingredients, packaging, or sensory characteristics affect performance?
What are the price/performance trade-offs target consumers are willing to make?
Often R&D has instrumentation, sensory, clinical, and salon testing facilities available to
conduct very preliminary testing to narrow options. Again, however, they may not
correlate very well with consumer preferences. Formula development testing should
include a wide variety of diagnostic questions. Preference or liking may or may not be
asked.
B.
Make an In-Market Decision
A second major use of product testing is to make a final in-market decision. The decision
is usually one of two types: (a) should we upgrade to a new, superior formula, or (b)
should we replace our current product with a lower-cost option.
Before changing a formula or package that is being manufactured, it should be tested
among the appropriate target group to confirm the correct decision is being made. It is
important to determine the level of risk, and reward, that making a correct or incorrect
decision entails. It is also important that all the key internal players agree to a specific
action standard.
Making a decision to upgrade can be fairly straightforward if the upgrade
formula/package costs the same as or less than the current product. The key question to
determine then is if the new formula is actually perceived to be bet-

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ter among the relevant target audience or user group. For products with very distinctive
characteristics and a loyal user base, consider branding the test (i.e., testing among current
brand users with the product including the brand name). The classic example is New
Coke, which was preferred in blind label taste tests, but which was not preferred by Coke
drinkers when identified by brand.
The decision and testing methodology becomes much more complex when the upgrade
costs more money than the current product. In that situation it is critical that the decision
makers agree to the test design and an action standard before a study is fielded.
A company is considering upgrading their moisturizing shampoo. Recently several
competitors have come out with new formulas that R&D feel are superior. R&D has
developed several new prototypes that range in cost from parity to 20% more
expensive than the current formula. The company decides to field two studies:
Study 1: Competitive Product TestThe company tests the key competitors, its current
formula, and some prototypes among moisturizing shampoo users (a) to determine if
the new formulas are superior to their current product, (b) to select a gold standard,
and (c) to provide guidance to R&D in developing its new prototypes.
Study 2: Upgrade Product TestAfter getting the results of the competitive test, the
company decides to test current, the competitive gold standard and several of the new
prototypes among target users of their brand. Given the brand's promise of superior
performance, the goal is to identify a formula that is superior to the gold standard and
noticeably better than current.
The action standard thus requires that for a new prototype to be recommended it must
be rated significantly better than current overall at the 95% confidence level. If two
prototypes are rated parity to each other and superior to current, the lower cost option
will be selected. If the prototype is superior to current, but only parity or less vs. the
gold standard competitor, the company would switch to the new formula in the short
term, but continue to work on better prototypes. In this case the company is deciding
that performance is more important than cost of the product.
When deciding to change to a lower-cost formula, the action standard and type of
statistical analysis change. The goal becomes parity (or better), not superiority. Testing for
parity requires a different type of statistical analysis. The key determination is how strict
an action standard to set. Usually the action standard can range from the 80% to 99%
confidence level that the new formula is at least as good as current. Higher standards are
recommended when there is a very loyal, profitable user base and/or the product has very
distinctive prop-

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erties to which the users are sensitive (typically fragrance, appearance, or consistency).
Any time an existing product is changed, there must be a high degree of confidence that
the product performs equal to or better than the current product overall, and on key
attributes among likely product users.
Keeping existing users loyal is more profitable because it is less expensive than gaining or
regaining trial. Satisfying consumer product expectations, especially consumers already in
a brand's franchise, is critical for the long-term health of a brand. Often there is a
tendency in organizations to have too loose an action standard for product tests that
involve cost reductions.
The issue should be looked at on a user basis, rather than strictly on unit sales. For most
brands, there is often a simple but dramatic 80/20 rule20% of the brand's users account
for 80% of the volume. It is critical to understand how that 20% of the brand's users (who
account for 80% of the volume) react to the lower-cost option. As the simple example
below demonstrates, the loss of only 4 of 100 users (4%) can result in a 15% loss of
volume. Again, loyal users are most likely to notice and react to any negative changes in
the product.
Volume Units per No. users lost for volume decline of
Users
(units) user 15%
20 80 4.00 4 users of 100 (4%)
80 20 0.25
100 100

C.
Product Integrity
Besides meeting a target group's expectations, products must also meet various legal and
practical integrity issues including packaging functionality, fragrance stability,
preservative effectiveness, safety requirements, and shelf-life integrity (both package and
product). A thorough understanding of legal requirements and accepted industry practices
is required. Usually, product integrity testing is conducted by R&D internally or through
very specific testing methodologies. Before any product is tested among consumers, it
should pass required product integrity and safety tests.
Appendix A contains the Council of American Survey Research Organizations (CASRO)
survey reporting guidelines for general health, safety, and security guidelines for
consumer product testing. These guidelines should always be adhered to for any
consumer product test.
Sometimes a series or combination of physical property changes is observed in stability
testing. No easy or economical fix is possible, nor is the

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product unsafe or clinically less efficacous. Consumer testing can determine if perceived
product performance and appeal have been affected. For example, a conditioner either
thickens or thins 30% over a 6-month period; how is perceived product performance
affected?
Similarly, testing of specification ranges can help the manufacturer determine how tight
quality control (QC) needs to be. Specifications that are too strict can lead to higher
production costs due to high quality-control costs, higher rejection/rework rates, etc. If
the specification or quality control range is too broad, actually marketplace product may
not be consumer accepted. This is especially critical when multiple manufacturing
locations or production lines are making the same product. Just like McDonald's French
fries, consumers expect nationally branded hair care products to consistently look, smell,
feel, and perform the same.
D.
Legal Claims Substantiation and Challenges
Product testing is often required in claims substantiation either to make a claim, to defend
a claim when it gets challenged, or to challenge a competitors claim. The legal claims area
is very complicated and changing. It requires expert input from your legal, marketing,
marketing research, and R&D departments. Advertising agencies may also frequently be
involved.
Claim substantiation can be required for advertising, package copy, consumer promotion
material, public relations, and even sales materials. Claims can be challenged not only by
competitors, but also by the TV networks, magazine publishers, federal and state
governmental bodies, and consumer groups. Each network will provide its current
requirements for claims substantiation.
Claims substantiation and challenges can require many different types of data from
instrumentation to consumer preference testing. The test needs to be fair, valid, accepted
in the industry, and conducted among a sample representative of the users for that
product. Each regulatory body has developed strict guidelines on acceptable standards.
Again, expert counsel throughout the development process is recommended. Legal claims
substantiation consumer tests often require larger sample sizestypically at least 300
respondents for a preference test and 500 or more respondents for monadic or monadic
sequential testing. Most regulatory bodies prefer or require blind preference tests.
Typically, for consumer preference claims, the requirement is for a nationally
representative (or relevant target) sample, with blind label exposure to the products.
Superiority claims often require a significant difference in preference among the total
sample at a 95% confidence level. The order of product exposure must be rotated evenly,
since typically the product a consumer sees first will get better ratings. Regulatory bodies,
and a competitor who challenges a claim, are very sophisticated at detecting any attempts
to rig the results, so care must be taken that the design is legitimate.

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Independent third-party testing firms are well equipped to minimize the charge of bias in
your test design. A list of qualified firms is attached as Appendix B. It is important, and
only fair, when dealing with a third party that they be notified of the purpose of the test
before it is fielded. They can then add expertise. Some product testing services, however,
will not perform legal claims testing. If a claim is challenged in court, all related research
learning must be produced. Before any product testing that will be used for claims
substantiation, it must be determined what information to collect and what information
not to collect (i.e., don't ask a question if you can't live with a possible answer).
III.
Types of Consumer Product Tests
A.
Qualitative
Qualitative research is characterized by having a small sample that is not projectable or
nationally representative. It can, however, generate in-depth consumer feedback on
specific issues. Thus, it is primarily used for exploratory research where there is often a
lack of basic knowledge. For example, R&D may be exploring a new type of package to
deliver a product. Qualitative research can help R&D gain insight into potential issues or
benefits that the new package type offers.
The major caution with qualitative data is not to rely on the information to make major
marketplace decisions. Because of the small sample size and nonprojectable nature of
qualitative research, it may not correlate with subsequent quantitative testing. Care must
also be given in how consumer comments during a qualitative session are interpreted.
Having a professional moderator or market research professional summarize the results
can help maintain necessary objectivity.
Qualitative research can take many different forms, driven in part by how many
consumers participate in a session. The following are the most popular forms of
qualitative research.
1. One-on-Ones: One respondent is interviewed at a time. Excellent when interview is
brief, topic is personal, or when looking for a reaction to a product without group bias.
2. Triads: Three consumers are interviewed at a time. Similar to one-on-ones, but allows
for some group dynamics and is still it easy to manage.
3. Focus Groups: Five or more consumers are interviewed at a time. Focus groups are
best used when planning a longer (i.e., 1 1/2 to 2 hours), more detailed discussion where
group dynamics allow ideas to build. Groups can be more difficult type to manage, and
modera-

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tor should involve all participants and not let most vocal group members take over.
Because hair care product tests often require consumers using the product for several
days, the test design may combine different types of qualitative research. For example, the
new package form project may start with focus groups to discuss the new idea.
Respondents are given the package to try at home for several days, and then come back
for one-on-one interviews to provide their reactions.
B.
Quantitative-Monadic Product Tests
Monadic tests require a respondent to only use one product. After using the product for a
specified period of time, they are typically asked overall satisfaction, likes/dislikes, ratings
on different attributes, and comparisons to products currently used. The advantages of a
monadic design are (a) it is simple to design and execute, (b) it allows building a database
so that results can be compared over time without retesting the same product, (c) there are
fewer issues about product rotation biases, (d) it can be quicker than having consumers
use multiple products, and (e) it may be the only technique for some hair care products
that have long purchase cycles (e.g., hair color).
A major shortcoming of monadic tests is that they may be less sensitive than tests where
consumers compare two or more products. Sample-to-sample variations become more of
a concern. Since only one product is being tested per respondent, the testing can also
become very expensive. Also, time-related changes such as climate, the competitive set,
and changing expectations/needs can all affect benchmarks.
Example: R&D has been asked to develop a new shampoo and conditioner in one. They
recognize that the project will be ongoing, covering several years. They also have many
different prototypes at various stages of development. Monadic product tests are
conducted among each of the prototypes when they are deemed ready, as well as
competitors to establish a benchmark.
C.
Monadic-Sequential Product Tests
In a monadic sequential design, each respondent evaluates two or more products
sequentially. After using each product, the respondent rates the product on absolute
scales, rather then comparing it to the other products (e.g., overall how would you rate
product Xexcellent, very good ). Preference questions can also be added at the end of the
study. Products in a sequential monadic test need to be rotated to avoid position bias.
Monadic sequential tests allow for the efficient testing of many different prototypes in one
test. While requiring more time than a monadic test, they are

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usually less expensive. The one major disadvantage is the difficulty comparing scores to
other tests or a benchmark. Each study is unique to itself, so a benchmark product should
be included in each study. Because hair care consumer product tests often require long
usage periods, most test designs require consumers to only evaluate two products. Some
issues, usually related to aestethics (e.g., fragrance, color, consistency), can permit
consumers evaluating three or more products in a study.
Example: R&D has three different prototypes (A, B, & C) that they would like to
compare vs. the current product (D). In the test design each respondent will rate two
products. They will use the first product for 10 days, rate it, and then use the second
product for 10 days and rate it. Product order will be rotated, requiring 12 different
rotation patterns (see below). To generate an ending sample of 300 responses per product,
a total of 600 consumers are required (half as many as in a monadic design). To make
sure each product is used equally in the first or second position with every other product,
a fairly detailed rotation pattern is required, as detailed below:
Product Used
1st 2nd 1st 2nd 1st 2nd 1st 2nd
A B C A A D D B
B A B C D A C D
A C C B B D D C

There are many other types of experimental designs that fully or partially pair different
products with each other. The final design will depend on the number of variables and
number of prototypes being evaluated. Many extremely sophisticated analyses can now
help the researcher isolate the affects of changing single variables (e.g., percent of an
ingredient) can have.
D.
Paired Comparison Product Tests
Unlike monadic designs, in a paired comparison test consumers compare two products to
each other. They use both products before they answer any questions. The advantages of
a paired comparison test are (a) it is highly sensitive to product differences, (b) it is easier
to understand and explain which product is better, and (c) it is often the required type of
research in claims support (consult with your legal counsel).
The paired comparison methodology can be harder to use when you have three products
and should not be used to test four or more products. Testing more than two products can
generate very confusing results such as A is

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preferred vs. B, B is preferred vs. C, but C is preferred vs. A. A second disadvantage is
that halo effects are more prevalent, so it is harder to get a good diagnostic read on
individual product/performance characteristics. For example, fragrance can have a
powerful halo effect on how consumers rate other attributes. To the consumer the product
is better, but the chemist gets little guidance on true product performance differences and
where to focus efforts. Similar to monadic sequential designs, paired comparison scores
are difficult or impossible to compare to benchmark or other historical results.
Example: R&D has developed a new conditioner formula that they believe performs as
well as or better than current, and costs $0.05 less per 15 oz. The company needs to
decide if it should switch. A paired comparison test is set up with current users of the
product. Each respondent gets two bottles of conditioner (again, order of exposure is
rotated). Respondents are asked to use each product for 10 days. After using both
products, they are asked which product they preferred (and why), as well as preference
on individual attributes. The company will switch to the new formula if it is parity or
better than current at a 90% confidence level.
E.
Concept-Aided (with any methodology)
Concept-aided tests differ from blind tests by first exposing consumers to the brand
concept positioning behind the product. For example, instead of receiving a bottle labeled
Shampoo, it might be labeled extra moisturizing shampoo. Prototype labels, ad copy, or
mock-up commercials can be used. Conceptaided testing is only recommended for a
distinctive or niche product promise (or user base) or when it is critical that consumers
know what brand or type of product they are using.
Often, this type of testing is unnecessary and discouraged because it can build bias into
the responses. Including a brand name in a multiple-product test, for example, can cause
consumers to try guessing which product they are using is current. They are no longer
reacting to each prototype in an unbiased way.
F.
Concept and Use/Simulated Test Market Consumer Tests
Concept and use testing is an excellent methodology to determine if a new product (either
a brand or line extension) should be introduced in the marketplace. It helps you
determine it the product matches, or lives up to, the expectations that a new concept
generates.
There are very good norms for the after-use tests that can help predict the likelihood that
the product will generate enough repeat consumer business to keep it on the market.
Several different models also exist that use the concept and use results, along with
marketing assumptions, to generate initial consumer sales volume and cannibalization
predictions. These tests are often called simulated test markets. As the name implies, there
are two parts to a concept

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and use test. In the first phase, consumers are shown a concept for the new idea, typically
in a mall research facility. They are then asked several questions to determine how
interested they are in the idea. Those exhibiting a predetermined level of interest are given
a prototype to take home and use for a specified period, typically 14 days for an
everyday-use hair care product. Respondents are then called back and asked how likely
they would be to buy the product again, what they liked and disliked about the product,
and how it performed versus their expectations (better, same, or not as good as).
The disadvantages of concept and use testing are they are time-consuming (usually 12 to
16 weeks) and expensive, because of the two-step process and monadic product
placement. A concept and use test can typically cost from $30,000 to $60,000 or more.
G.
Test Market
The most expensive and real-world form of testing is a test market or in-store placement
test. When a product decision is extremely high risk financially, there is little risk of
competitive preemption and not time-urgent, a test market may provide the most accurate
read on how consumers react to the new product. Test marketing allows the measurement
of both attitudes (likes, overall rating, intended behavior) and actual behavior (trial,
source of volume, repeat and depth of repeat).
There are many ways to execute a test market or in-store placement test. The market
research department should be responsible for setting up the test and action standard.
Appendix B includes a list of leading test market research firms in the United States.
In the hair care category in the United States, test markets are very rare for several
reasons. The market changes very rapidly so the data quickly become out-of-date,
competition for ideas is fierce, and competitive firms copy each other very quickly. Also,
test marketing is very expensive, with costs of over $1 million. Instead, companies rely on
simulated test market models. A recent trend among global companies is to use a smaller
foreign country as the test market.
IV.
Measurement and Scaling
The purpose of this section is to discuss basic concepts of psychological scaling, as
related particularly to the study of consumer perception, preference, and motivation.
A.
Attitude Measurement
All attitude measurement procedures are concerned with having peopleconsumers,
purchasing agents, marketing managers, or whateverrespond to

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certain stimuli according to certain sets of instructions. The stimuli may be alternative
advertising copy themes, concepts, products, package designs, salespeople's
presentations, and so on. The response may involve which concept is more pleasing than
another, which adjectives best describe a product, and so on.
Attitudes toward products may be defined operationally as numerical ratings on various
types of scales. Scales can be classified into the following major categories: nominal,
ordinal, interval, and ratio. Each scale possesses its own set of underlying assumptions
regarding the correspondence of numbers with real world entities.
Nominal scales are the least restrictive of scales. In this type of scale the numbers serve
only as labels or tags for identifying objects, properties, or events. It should be clear that
nominal scales permit only the most rudimentary of mathematical operations. We can
count the number of stores that carry each brand in a product class and find the modal
(highest number of mentions) brand carried. Also, we may make various contingency
tests having to do with the likelihood that a member of one category is also a member of
another category, but the usual statistical operations (calculations of means, standard
deviations, etc.) are not empirically meaningful.
Ordinal scales are, as the name suggests, ranking scales. These scales require the ability
to distinguish between elements according to a single attribute and direction. For example,
a person may be able to rank a group of shampoo brands according to cleaning ability.
One might assign the number 1 to the highest-ranking shampoo, number 2 to the second-
highest-ranking shampoo, and so on. Note, however, that the mere ranking of brands
does not permit us to say anything about the differences separating brands with regard to
cleaning ability. We do not know if the difference in cleaning ability between the brand
ranked 1 and the brand ranked 2 is larger, less than, or equal to the difference between the
brand ranked 2 and the brand ranked 3. Thus, any series of numbers that preserves the
ordering relationship is only as good as our original number assignment involving
successive integers.
An ordinal scale possess all the information of a nominal scale in the sense that equivalent
entities receive the same rank. Notice, however, that in dealing with ordinal scales,
statistical description can employ positional measures such as the median, quartile, and
percentile, or other summary statistics that deal with order among entities. The usual
arithmetic averaging operations cannot be meaningfully interpreted with ranked data, and
the practice of calculating an overall index ranking (a weighted ranking of a set of' brands
according to several properties) is often suspect from an interpretative point of view.
Interval scales approach the typical conception of measurement in that an interval scale
does possess a constant unit of measurement. Interval scales permit one to make
meaningful statements about the differences separating two objects. However, the zero
point of this scale is arbitrary. Most ordinary statisti-

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cal measures to be discussed later (such as arithmetic mean, standard deviation, and
correlation coefficients) require only interval scales for their computation.
Ratio scales represent the elite of scales, in that all arithmetic operations are permissible
on ratio-scale measurements. These scales posses a unique zero point and are the scales
usually found in the physical sciences (e.g., scales for measuring length and weight). As
the name suggests, equal ratios among the scale values correspond to equal ratios among
the entity being measured. All types of statistical operations can be performed on ratio
scales. These scales, despite their mathematical appeal, are far less typical in product
testing.
B.
Ranking Methods
Ranking procedures require the respondent to order stimuli with respect to some
designated property of interest. For example, each respondent might be asked to rank the
shampoos with respect to some property, such as cleaning, fragrance, etc. Ranks can then
be compared to evaluate products' performance (see statistical section).
C.
Rating Methods
Rating methods, as used in both marketing research and the behavioral sciences,
represent one of the most popular and easily applied data collection methods. Rating
methods can take several forms: numerical, graphic, or verbal. Often two or more of
these formats appear together, as illustrated in Figure 1. As shown in panel (a) of the
figure, the respondent is given both a series of integers (1 through 7) and a limited set of
verbal descriptions of the degree of gentleness-harshness. He would then be asked to
circle the number associated with the descriptive statement that comes closest to how he
feels about the gentleness-harshness of the brand(s) being rated. In panel (b) of Figure 1,
he need only check the category appropriate for expressing his feelings about some
attitude statement. (For example, How much do you agree or disagree that this shampoo is
appropriate for the entire family?) In Panel (c), two variations of a scale with both
numerical assignments and a (complete) set of descriptive statements illustrates another
typical rating device. Panel (d) represents a scale used to evaluate directional product
attributes. This is a balanced odd-interval scale. The middle dimension is usually just
about right while the anchors represent product criticisms.
Guilford, among others, lists a large number of do's and don'ts regarding rating scales,
which the interested reader might examine (1).
1.
Direct-Judgment Methods
In direct-judgment methods the respondent is asked to give a numerical rating to each
stimulus with respect to some designated attribute. In the unlimited-response

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Figure 1
Examples of rating scales used in marketing research.
category subcase, the respondent is free to choose his own number or, in graphical
methods, to lay off a tic mark along some line that reflects his judgment about the
magnitude of the stimulus relative to some reference points. This is illustrated in panel (a)
of Figure 2 for the rating of brand A. The limited-response category subcase is illustrated
by panel (b) in Figure 2. Here the respondent is limited to choosing one of seven
categories. We note that in this instance the direct-judgment method is nothing more than
a straight rating procedure, with the important addition that the ratings are now treated as
either interval- or ratio-scaled data (depending upon the application) rather than as simple
rankings.
2.
Constant Sum
Constant-sum methods, primarily because of their simplicity and ease of instructions,
have become quite popular in marketing research. In constant-sum methods the
respondent is given some number of pointstypically 10 or 11 or

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Figure 2
Some illustrations of direct-judgment and constant-sum methods.
100and asked to distribute them over the alternatives in a way that reflects their relative
magnitude regarding some attitudinal characteristic.
Panel (c) of Figure 2 shows an illustration of the constant-sum procedure. Constant sum
forces the respondent to allocate his evaluations and has the effect of standardizing each
scale across persons, since all scores must add to the same constant (e.g., 10 or 100). As
such, the constant-sum procedure requires the respondent to make a comparative
evaluation of the stimuli. Generally, it is assumed that a subjective ratio scale is obtained
by this method.

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Some of the problems associated with direct-judgment and constant-sum methods are:
1. Respondents' subjective scale units may differ across each other, across testing
occasions, or both.
2. Respondents' subjective origins (zero points) may differ across each other, across
occasions, or both.
3. Unit and origin may shift over stimulus items within a single occasion.
These problems should not be treated lightly, particularly when data for several subjects
are being averaged.
In addition, researchers should be aware of the constraints placed on the subjects'
response format. For example, if the respondent is asked to rate dishwashing detergents
on a 5-point scale, ranging from 1 (gentlest) to 3 (neither harsh nor gentle) to 5 (harshest),
the task, in a sense, may not be able to be carried out. That is, one's subjective distance
between the harshest detergent and the neutral detergent(s) may not equal one's
perception of the distance between the neutral detergent(s) and the gentlest detergent.
Most direct-judgment methods have the virtue of being easy to apply. Moreover, little
additional work beyond averaging is required to obtain the unit of measurement directly.
Indeed, if a unique origin can be established (e.g., a zero level of the property), then the
researcher obtains both an absolute origin and a measurement unit. As such, a subjective
ratio scale is obtained.
D.
Semantic Differential
The semantic differential is a type of question that results in (assumed interval) scales that
are often further analyzed by such techniques as factor analysis (2). Essentially, the
semantic differential procedure enables the researcher to probe into both the direction
and the intensity of respondents' attitudes toward such concepts as advertising image,
brand or service image, and so on. One way this is done is to ask the respondent to
describe the brand by means of ratings on a set of bipolar adjectives, as illustrated in
Figure 3.

Figure 3
 Shampoo profile obtained by means of the semantic differential.

 Page 322
As shown in Figure 3, the respondent may be given a set of pairs of antonyms, the
extremes of each pair being separated by, say, seven (assumed equal) intervals. For each
pair of adjectives (e.g., strong-weak) the respondent is asked to judge the product along
the 7-point scale with descriptive phrases such as:
Extremely strong
Very strong
Slightly strong
Neither strong nor weak
Slightly weak
Very weak
Extremely weak
By assigning integer values, such as +3, +2, +1, 0, -1, -2, -3, to the seven gradations of
each bipolar scale in Figure 3, the responses can be quantified under the assumption of
equal-appearing intervals. These scale values, in turn, can be averaged across respondents
to develop semantic differential profiles. For example, Figure 4 shows the average-
respondent profiles of two products: X and Y. We note that product X is perceived as very
weak, unreliable, old-fashioned, and careless, but rather warm. Product Y is perceived as
strong, reliable, and careful, but rather cold as well; it is almost neutral with respect to the
modern-old-fashioned scale.
E.
Paired Comparisons
As the name suggests, paired comparisons require the respondent to choose or prefer one
of a pair of stimuli/products that has more of, dominates, precedes, wins over, or exceeds
the other with respect to some designated

Figure 4
Average-respondent profile comparisons of companies X and Y via the
 semantic differential.

 Page 323
property of interest. A typical question may read, Which of these two products do you
prefer.
Preference measurement typically involves two steps. First, the respondent is asked
whether or not he noticed any difference between products. For example:
Now, I'm going to ask you about several Yes.......................
characteristics of the products you used. Did you 1
notice a difference between the two products on No .......................
OVERALL EFFECTIVENESS or not? 2

Step 1 is done in order to minimize any error associated with random guessing at the next
step. Step 1 also allows us to estimate the proportion of the population that truly can and
cannot discern differences among products.
If the answer is yes in Step 1, the respondent is asked for his preference in Step 2:
Product A 1
Which one product did you like BETTER on OVERALL Product B 2
EFFECTIVENESS? Liked both the
same3

Taking this one step further, if the respondent chooses to say liked both the same in
response to the second question, they might be asked a third question: If you saw both
products side-by-side in a store, both at the same price, which one would you be more
likely to buy?
At this point, an answer of liked both the same can be accepted. Forcing preference is a
matter of degree. While this procedure is somewhat more forcing than the ask one
approach, the benefits of uncovering additional preferences when they exist and
minimizing the number of respondents saying liked both the same as an easy out have
significant merit. Essentially, this procedure allows for the recording of a strongly felt
position of ambivalence, a true nonpreference, which a true forced choiced ignores. At
this point, it should be believed that one truly has nonpreferrers, and they will be handled
as such in the statistical analysis.
Preference can also be obtained on the relevant product attributes. For example, For each
of the qualities listed below, indicate which of the two products you prefer on that quality.

 Page 324
Prefer product Prefer product Liked both
Attribute
tested first tested second the same
Fragrance
Texture

References
1. Guilford JP. Psychometric Methods. New York: McGraw-Hill Book Company, 1954.
2. Osgood CE, Suci GJ, Tannenbaum PH. The measurement of Meaning. Urbana, IL:
University of Illinois Press, 1957.
Appendix A:
Casro Code of Standards for Survey Research
Introduction
This Code of Standards for Survey Research sets forth the agreed upon rules of ethical
conduct for Survey Research Organizations. Acceptance of this Code is mandatory for all
CASRO Members.
The Code has been organized into sections describing the responsibilities of a Survey
Research Organization to Respondents, Clients and Outside Contractors and in reporting
study results.
This Code is not intended to be, nor should it be, an immutable document. Circumstances
may arise that are not covered by this Code or that may call for modification of some
aspects of this Code. The Standards Committee and the Board of Directors of CASRO
will evaluate these circumstances as they arise and, if appropriate, revise the Code. The
Code, therefore, is a living document that seeks to be responsive to the changing world of
Survey Research. To continue to be contemporary, CASRO advocates ongoing, two-way
communication with Members, Clients, Outside Contractors, Consultants and
Interviewers.
1.
Responsibilities to Respondents
A.
Confidentiality
1. Since individuals who are interviewed are the lifeblood of the Survey Research
Industry, it is essential that Survey Research Organizations by responsible for protecting
from disclosure to third partiesincluding Clients and members of the Publicthe identity of
individual Respondents as well as Respondent-identifiable information, unless the
Respondent expressly requests or permits such disclosure.

 Page 325
2. This principle of confidentiality is qualified by the following exceptions:
a. The identity of individual Respondents and Respondent-identifiable information
may be disclosed to the Client to permit the Client: (1) to validate interviews and/or (2)
to determine an additional fact of analytical importance to the study. In these cases,
Respondents must be given a sound reason for the re-inquiry. In all cases, a refusal by
Respondent to continue must be respected.
Before disclosing Respondent-identifiable information to a Client for purposes of
interview validation or re-inquiry, the Survey Research Organization must take
whatever steps are needed to ensure that the Client will conduct the validation or
recontract in a fully professional manner. This includes the avoidance of multiple
validation contacts or other conduct that would harass or could embarrass
Respondents. It also includes avoidance of any use of the information (e.g., lead
generation) for other than legitimate and ethical Survey Research purposes or to
respond to Customer/Respondent complaints. Assurance that the Client will respect
such limitations and maintain Respondent confidentiality should be confirmed in
writing before any confidential information is disclosed.
b. The identity of individual Respondents and Respondent-identifiable information
may be disclosed to other Survey Research Organizations whenever such
organizations are conducting different phases of a multistage study (e.g., a trend
study). The initial Research Company should confirm in writing that Respondent
confidentiality will be maintained in accordance with the Code.
c. In the case of research in which representatives of the Client or others are present,
such Client representatives and others should be asked not to disclose to anyone not
present the identity of individual Participants or other Participant-identifying
information except as needed to respond, with the Participant's prior specific approval,
to any complaint by one or more of the Participants concerning a product or service
supplied by the Client.
3. The principle of Respondent confidentiality includes the following specific applications
or safeguards:
a. Survey Research Organizations' staff or personnel should not use or discuss
Respondent-identifiable data or information for other than legitimate internal research
purposes.
b. The Survey Research Organization has the responsibility for ensuring that
Subcontractors (Interviewers, Interviewing Services and Validation, Coding, and
 Tabulation Organizations) and Consultants are aware of and agree to maintain and
respect Respondent confidentiality whenever the identity of Respondents or
Respondent-identifiable information is disclosed to such entities.
c. Before permitting Clients or others to have access to completed questionnaires in
circumstances other than those described above, Respondent names and other
Respondent-identifiable information (e.g., telephone numbers) should be deleted.
d. Invisible identifiers on mail questionnaires that connect Respondent an-

 Page 326
swers to particular Respondents should not be used. Visible identification numbers
may be used but should be accompanied by an explanation that such identifiers are
for control purposes only and that Respondent confidentiality will not be
compromised.
e. Any Survey Research Organization that receives from a Client or other entity
information that it knows or reasonably believes to be confidential Respondent-
identifiable information should only use such information in accordance with the
principles and procedures described in this Code.
f. The use of survey results in a legal proceeding does not relieve the Survey Research
Organization of its ethical obligation to maintain in confidence all Respondent-
identifiable information or lessen the importance of Respondent anonymity.
Consequently, Survey Research firms confronted with a subpoena or other legal
process requesting the disclosure of Respondent-identifiable information should take
all reasonable steps to oppose such requests, including informing the court or other
decision-maker involved of the factors justifying confidentiality and Respondent
anonymity and interposing all appropriate defenses to the request for disclosure.
B.
Privacy and the Avoidance of Harassment
1. Survey Research Organizations have a responsibility to strike a proper balance between
the needs for research in contemporary American life and the privacy of individuals who
become the Respondents in the research. To achieve this balance:
a. Respondents will be protected from unnecessary and unwanted intrusions and/or
any form of personal harassment.
b. The voluntary character of the Interviewer-Respondent contact should be stated
explicitly where the Respondent might have reason to believe that cooperation is not
voluntary.
2. This principle of privacy includes the following specific applications:
a. The Research Organization, Subcontractors and Interviewers shall make every
reasonable effort to ensure that the Respondent understands the purpose of the
Interviewer/Respondent contact.
(1) The Interviewer/Research Company representative must provide prompt and
honest identification of his/her research firm affiliation.
(2) Respondent questions should be answered in a forthright and non-deceptive
 manner.
b. Deceptive practices and misrepresentation, such as using research as a guise for
sales or solicitation purposes, are expressly prohibited.
c. Survey Research Organizations must respect the right of individuals to refuse to be
interviewed or to terminate an interview in progress. Techniques that infringe on these
rights should not be employed, but Survey Research Organizations may make
reasonable efforts to obtain an interview including: (1) explaining the purposes of the
research project; (2) providing a gift or monetary incentive adequate to elicit
cooperation; and

 Page 327
(3) re-contacting an individual at a different time if the individual is unwilling or
unable to participate during the initial contact.
d. Research Organizations are responsible for arranging interviewing times that are
convenient for Respondents.
e. Lengthy interviews can be a burden. Research Organizations are responsible for
weighing the research need against the length of the interview and Respondents must
not be enticed into an interview by a misrepresentation of the length of the interview.
f. Research Organizations are responsible for developing techniques to minimize the
discomfort or apprehension of Respondents and Interviewers when dealing with
sensitive subject manner.
g. Electronic equipment (taping, recording, photographing) and one-way viewing
rooms may be used only with the full knowledge of Respondents.
II.
Responsibilities to Clients
A. Relationships between a Survey Research Organization and Clients for whom the
surveys are conducted should be of such a nature that they foster confidence and mutual
respect. They must be characterized by honesty and confidentiality.
B. The following specific approaches describe in more detail the responsibilities of
Research Organizations in this relationship:
1. A Survey Research Organization must assist its Clients in the design of effective and
efficient studies that are to be carried out by the Research Company. If the Survey
Research Organization questions whether a study design will provide the information
necessary to serve the Client's purposes, it must make its reservations known.
2. A Research Organization must conduct the study in the manner agreed upon.
However, if it becomes apparent in the course of the study that changes in the plans
should be made, the Research Organization must make its views known to the Client
promptly.
3. A Research Organization has an obligation to allow its Clients to verify that work
performed meets all contracted specifications and to examine all operations of the
Research Organization that are relevant to the proper execution of the project in the
manner set forth. While Clients are encouraged to examine questionnaires or other
records to maintain open access to the research process, the Survey Research
Organization must continue to protect the confidentiality and privacy of survey
 Respondents.
4. When more than one Client contributes to the cost of a project specially
commissioned with the Research Organization, each Client concerned shall be
informed that there are other Participants (but not necessarily their identity).
5. Research Organizations will hold confidential all information that they obtain about
a Client's general business operations, and about matters connected with research
projects that they conduct for a Client.
6. For research findings obtained by the agency that are the property of the

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Client, the Research Organization may make no public release of revelation of
findings without expressed, prior approval from the Client.
C. Bribery in any form and in any amount is unacceptable and is a violation of a Research
Organization's fundamental, ethical obligations. A Research Organization and/or its
principals, officers and employees should never give gifts to Clients in the form of cash.
To the extent permitted by applicable laws and regulations, a Research Organization may
provide nominal gifts to Clients and may entertain Clients as long as the cost of such
entertainment is modest in amount and incidental in nature.
III.
Responsibilities in Reporting to Clients and the Public
A. When reports are being prepared for Client confidential or public release purposes, it
is the obligation of the Research Organization to ensure that the findings they release are
an accurate portrayal of the survey data, and careful checks on the accuracy of all figures
are mandatory.
B. A Research Organization's report to a Client or the Public should contain, or the
Research Organization should be ready to supply to a Client or the Public on short notice,
the following information about the survey:
1. The name of the organization for which the study was conducted and the name of
the organization conducting it.
2. The purpose of the study, including the specific objectives.
3. The dates on or between which the data collection was done.
4. A definition of the universe that the survey is intended to represent and a
description of the population frame(s) that was actually sampled.
5. A description of the sample design, including the method of selecting sample
elements, method of interview, cluster size, number of callbacks, Respondent
eligibility or screening criteria, and other pertinent information.
6. A description of results of sample implementation including (a) a total number of
sample elements contacted, (b) the number not reached, (c) the number of refusals, (d)
the number of terminations, (e) the number of noneligibles, (f) the number of
completed interviews.
7. The basis for any specific completion rate percentages should be fully documented
and described.
 8. The questionnaire or exact wording of the questions used, including Interviewer
directions and visual exhibits.
9. A description of any weighting or estimating procedures used.
10. A description of any special scoring, data adjustment or indexing procedures used.
(Where the Research Organization uses proprietary techniques, these should be
described in general and the Research Organization should be prepared to provide
technical information on demand from qualified and technically competent persons
who have agreed to honor the confidentiality of such information.)

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11. Estimates of the sampling error and of data should be shown when appropriate,
but when shown they should include reference to other possible sources of error so
that a misleading impression of accuracy or precision is not conveyed.
12. Statistical tables clearly labelled and identified as to questionnaire source, including
the number of raw cases forming the base for each cross-tabulation.
13. Copies of Interviewer instructions, validation results, code books, and other
important working papers.
C. As a minimum, any general public release of survey findings should include the
following information:
1. The sponsorship of the study.
2. A description of the purposes.
3. The sample description and size.
4. The dates of data collection.
5. The names of the research company conducting the study.
6. The exact wording of the questions.
7. Any other information that a lay person would need to make a reasonable
assessment of the reported findings.
D. A Survey Research Organization will seek agreements from Clients so that citations of
survey findings will be presented to the Research Organization for review and clearance
as to accuracy and proper interpretation prior to public release. A Research Organization
will advise Clients that if the survey findings publicly disclosed are incorrect, distorted, or
incomplete, in the Research Organization's opinion, the Research Organization reserves
the right to make its own release of any or all survey findings necessary to make
clarification.
IV.
Responsibility to Outside Contractors and Interviewers
Research Organizations will not ask any Outside Contractor or Interviewer to engage in
any activity which is not acceptable as defined in other sections of this Code of Standards
for Survey Research or related CASRO publications.
The Council of American Survey Research Organizations (CASRO), established in 1975,
is the national trade association for commercial survey research firms in the United States.
CASRO's mission is to provide the environment and leadership that will promote the
profitable growth of the survey research industry in an ethical and professional manner.
As a condition of membership, CASRO members subscribe to the Code of Standards for
Survey Research. This Code describes the research company's responsibilities to
respondents, to clients, to outside contractors and interviewers, and in reporting to clients
and the public.
CASRO works to fully serve our members, the industry and the public. Our volunteer
committees are: Annual Workshop, Budget/Finance, Business Practices, Educational &
Professional Training, Financial/Compensation Survey, Government Affairs, Public
Relations, Membership Services, Past Chairs Council, Survey Research Quality, and
Standards. We have a Code of Business Practices that serves as a guideline for our
members. We work with other industry associations to improve the entire survey process.
And we serve as a watchdog for any proposed changes in government regulations or
legislation that could affect the research industry.

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These Data Collection Guidelines were produced, as a membership service, by the
CASRO Survey Research Quality Committee and approved by the CASRO Board of
directors in the Fall of 1988.
Please direct questions about these Guidelines or about CASRO in general to: Diane K.
Bowers, Executive Director, CASRO, (516) 928-6954.
Appendix B:
Information Sources
Listed below are the names of several different companies that can provide expert advice
and service for product testing issues. The list is not comprehensive, but can be a starting
point if additional information or ideas are needed.
General Information/Guidelines
Council of American Survey Research Organizations (CASRO)
3 Upper Devon, Belle Terre, Port Jefferson, NY 11777
(516) 928-6954
Product Testing Research Suppliers
M/A/R/C, Inc.
7850 North Belt Line Road
Irving, TX 75063
(214) 506-3451
Market Facts, Inc.
3040 West Salt Creek Lane
Arlington Heights, IL 60005
(708) 590-7000
Moskowitz/Jacobs Inc.
14 Madison Ave.
Valhalla, NY 10595
(914) 428-9204
Walker Research
3939 Priority Way South Drive
P.O. Box 80432
Indianapolis, IN 46280-0432
(317) 843-8665
Simulated Test Market Modeling
 The BASES Group
50 E. RiverCenter Boulevard
Suite 1000
Covington, KY 41011
(606) 655-6106
Test Market or In-Store Testing
Market Decisions
8044 Montgomery Road
Cincinnati, OH 45236
(513) 891-8000
Information Resources, Inc. (IRI)
150 N. Clinton
Chicago, IL 60661 1416
(312) 559-2355

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12
International Regulations for Hair Care Products
Richard M. Bednarz and Thomas E. Hamernik
Amway Corporation, Ada, Michigan
I.
Introduction
As is the case for other consumer products, the primary purpose behind the regulatory
control of hair care products is consumer protection. Under the general philosophy of
consumer safety, programs exist that run the gamut from the elaborate, such as the over-
the-counter drug review and the color additives approval processes in the United States,
to the simple, such as the listing of ingredients on product labels, designed to alert the
consumer to potential allergenic materials.
In addition to differing perceptions of and responses to safety risks, different countries
have different philosophical approaches on the level of government involvement
necessary to ensure the safety of products available to its citizens. Some countries want
government to ensure complete product safety. They place relatively little responsibility
on manufacturers. Others, such as the United States, shift more responsibility for product
safety to the manufacturer or seller. For many categories of products, including cosmetics,
the U.S. government has only minimal direct involvement in product safety; i.e., there is
no premarket clearance or registration requirement. A result of this practice is that
products reach the market quickly and efficiently. However, should a product prove to be
unsafe, the manufacturer or distributor is subject to significant liability. Japan, on the
other hand, has traditionally placed more responsibility on the government to ensure
product safety. The product manufacturer is not held

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to the same standard of liability as in the United States. However, this philosophy is
changing in Japan as evidenced by the recent enactment of product liability legislation.
European systems vary between these two philosophies according to country (1).
It is no surprise that these and other differences produce a diversity of regulations
affecting cosmetic products. For the most part, each country has unique regulations to
control products sold in its jurisdiction. The regulations vary from country to country,
requiring variations in products and labels, and there is seemingly little concern for the
impact of these variations on international business (1).
II.
Cosmetics, Drugs, or Both?
Classification as cosmetic or drug has a significant impact on many aspects of a consumer
product. The effects range from ingredient and product claim restrictions to
manufacturing practices compliance and premarket registration requirements. To
understand how a product may be classified as either a cosmetic or a drug, a review of
the statutory definition of each is appropriate. The U.S. Food, Drug and Cosmetic Act
defines cosmetics as:
Articles intended to be rubbed, poured, sprinkled or sprayed on, or introduced into, or otherwise
applied to the human body or any part thereof for cleansing, beautifying, promoting attractiveness,
or altering the appearance.
With minor modifications, the same basic definition is used worldwide. Drugs, on the
other hand, are defined as:
Articles intended for use in the diagnosis, cure, mitigation, treatment, or prevention of disease in
man and articles (other than food) intended to affect the structure or any function of the body of man.
It is quite interesting to review how various jurisdictions around the world categorize
products as drugs, cosmetics, or both through the application of the aforementioned
definitions. In the United States, the deciding factor in whether a product is considered a
cosmetic or a drug is not the product's composition or function, but rather its stated
purpose or claims. A classic example of this is a shampoo that claims, removes dandruff
flaking. This is a cosmetic claim in keeping with the cleansing/beautifying aspect of the
statutory cosmetic definition. Modification of this claim to protects against dandruff
flaking implies disease prevention, which would clearly fall within the statutory definition
of a drug. In practice, products may have both cosmetic and drug claims as well as
cosmetic and drug functions. Thus products such as antidandruff shampoos are
frequently classified into both the cosmetic and drug categories. This situation

 Page 333
evolves directly from the stated purposes of the product. If the product makes both
cosmetic claims (e.g., cleans/beautifies the hair) and drug claims (e.g., prevents dandruff),
it is both a cosmetic and a drug and is subject to the regulatory compliance requirements
of both categories.
In addition to the elements included in the U.S. definition of a cosmetic, the European
Union (EU) has added an important final phrase to their definition of a cosmetic:
A cosmetic product shall mean any substance or preparation intended to be placed in contact with
the various external parts of the human body (epidermis, hair system, nails, lips and external genital
organs) or with the teeth and the mucous membranes of the oral cavity with a view exclusively or
mainly to cleaning them, perfuming them, changing their appearance and/or correcting body odours
and/or protecting them or keeping them in good condition. [Emphasis added.]
While protection is generally considered a drug claim in the United States, because of the
statutory definition it is a cosmetic claim in Europe. Referring to the earlier examples of
claims, both the claim removes dandruff flaking and the claim protects against dandruff
flaking are cosmetic claims in Europe.
In Japan, consumer hair care products are classified as either quasi-drugs or cosmetics.
Like drugs and medical devices, quasi-drugs and cosmetics are subject to regulations
promulgated under the Pharmaceutical Affairs Law. Quasi-drugs are defined in the law as
articles that exert mild actions on the human body. Quasi-drugs also include articles
specifically designated as such by the Minister of Health and Welfare (MHW). Hair care
products designated as quasi-drugs by the Minister include hair dyes, waving agents,
depilatories, hair straighteners, nutrient hair growers, and medicated cosmetics (which
include antidandruff preparations).
Japanese cosmetics are defined in a similar manner as in other countries; i.e., cosmetics
are articles applied to the body for the purpose of cleansing, beautifying, altering
appearance, etc. Japan has expanded upon this common definition by including the
phrase that cosmetics are also articles for keeping the skin and hair healthy. Another
Japanese distinction is the added proviso that the action of the [cosmetic] article on the
human body [should be] mild. Using the earlier examples, the claim removes dandruff
flaking would be a cosmetic claim in Japan, while protects against dandruff flaking would
render a product a quasi-drug due to designation.
As mentioned earlier, the classification of a product as a cosmetic or a drug has far-
reaching implications in many areas of regulatory compliance. This will be discussed in
greater detail in the following section; however, a basic understanding of the U.S. OTC
(over-the-counter) Drug Review process and the history behind quasi-drugs in Japan may
help place things in perspective.

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The U.S. OTC Drug Review process began in 1972 as a Food and Drug Administration
(FDA) response to the large number of new drug applications for OTCs that the agency
was required to assess for safety and efficacy. The agency believed that development of
drug monographs that would provide conditions under which OTC products could be
safely marketed would free the agency from the time-consuming and laborious task of
individual product reviews. The OTC Drug Review process occurs in three phases. In the
first phase, a panel of qualified experts, the advisory review panel, reviews available
published and unpublished (submitted by manufacturers) scientific data on safety and
efficacy of specific categories of drugs (e.g., dandruff products). The purpose of the
panel's review is to establish the active ingredients, concentrations, and labeling
considerations under which the drugs are considered safe and effective for their intended
use. A proposed monograph reporting the panel's findings is published in the Federal
Register. Following FDA review and public commentary on the proposal, the FDA
publishes a tentative final monograph, a proposed rule that sets forth the agency's
assessment of the conditions under which the OTC drug is Generally Recognized As Safe
and Effective (GRAS and GRAE) and not misbranded. Following a second public
comment period, a final monograph is published. The final monograph establishes the
monograph conditions under which a drug can be marketed. The conditions include
allowed active ingredients, labeling requirements, and related criteria, which will be
covered in greater detail in later sections.
The development of the category of quasi-drugs in Japan has a long and interesting
history. The law controlling quasi-drugs began when Western medications were
introduced into Japan and the medications began to supplant traditional Oriental
therapies. To control the new materials, a series of drug and nonproprietary drug
regulations were promulgated during the 1870s and 1880s. The regulations distinguished
between articles with and without therapeutic effect. Products without therapeutic effect
included nutritional beverages, tooth powders, and skin lotions and were exempted from
the regulations until 1900, when the Regulation for Controlling Preparations Exempt from
Nonproprietary Drug Regulations was published. Products regulated under this order
included hair dyes, hair growers, and cosmetics that contained potentially harmful
substances.
Nothing further of substance occurred until the postwar period 50 years later, when many
of the earlier, fragmented laws were combined into a new Pharmaceutical Affairs Law,
which was amended in 1960 to include the quasi-drug category. This change allowed a
broader range of retail merchandisers to be licensed to sell drugs with a mild action as
freely as the merchants could sell cosmetics. The law stipulated that manufacturing of
quasi-drugs would conform to the same manufacturing practices required for therapeutic
drugs, a practice similar to that required for OTC drugs in the United States.

 Page 335

III.
Hair Care ProductsSafety Considerations
Statutory language to assure the safety of cosmetic products is markedly similar among
countries. Commonly, the various statutes have a general safety provision written into
them to assure that cosmetics and drugs introduced into commerce are safe for public use.
For example, the United States Federal Food, Drug and Cosmetic Act at Section 601(a)
states that A cosmetic shall be deemed to be adulteratedif it bears or contains any
poisonous or deleterious substance which may render it injurious to users under labeled
or customary conditions of use. Article 2 of the EU Cosmetics Directive states more
simply that a cosmetic must not cause damage to human health when applied under
normal or foreseeable conditions of use. Japan also has a general safety provision in its
Pharmaceutical Affairs Law for cosmetics and quasi-drugs; safety is assured by the
various regulations (standards, positive lists, etc.) promulgated under the law.
The three jurisdictionsthe United States, the European Union, and Japanvary considerably
in how they enforce compliance with the safety provisions of their laws. The United
States leaves the onus on the manufacturer to substantiate the safety of cosmetic products
that it marketsthere is no requirement for premarket clearance. Of course, if the cosmetic
product is also a drug and if a new drug indication is claimed or a new active ingredient is
used, the product or active may need premarket approval as a New Drug. In the European
Union under the 6th Amendment to the Cosmetics Directive, each marketed product is
required to have an information dossier available for inspection at an appropriate
member-country location. The dossier must include a description of the safety profile for
each product marketed within the European Community. As in the United States, there is
no premarket clearance requirement in the European Union, with the exception of Spain,
Portugal, and Greece, which require product notification (not involving review/approval)
before marketing. Japan also requires that a submission be made for license approval
from the Minister of Health and Welfare prior to distribution of a product.
A.
Safety Considerations in Japan
Regulations in Japan describe several mechanisms for assuring the safety of cosmetics
and quasi-drugs. Foremost among these is a system for licensing which provides
permission to manufacture or import cosmetics and quasi-drugs. The licenses are granted
by the Ministry of Health and Welfare (MHW).
Submission for a license requires assurance of conformance to any of the standards
prescribed for the article and assurance that only materials approved by the ministry have
been used in the formulation. Deviations from the approved materials list, such as the use
of a new material, require the submission of data from preclinical and clinical safety
studies in accordance with specified guidelines. To obtain approval for use of a new raw
material, results from the

 Page 336
following studies must be submitted: acute oral toxicity, primary skin irritation, repeat-
insult skin irritation, sensitization, phototoxicity, photosensitization (required for UV-
absorbing materials), eye irritation, mutagenicity, and human patch-test studies. For
products containing the new material, the submission must include results of acute oral
toxicity (required if the new material has an LD50 of 2 g/kg or less), eye irritation (or
where the new ingredient used in the formula has no irritant effect per se, the test may be
omitted provided that the product has a low potential to contact the eye), and human
patch tests for products that are not rinsed off after use. Additional studies are required
for materials considered hazardous, such as preservatives, antibacterial agents,
antioxidants, sequestering agents, UV-absorbing materials, and coal-tar colors. The
Ministry believes that these materials represent potentially more hazardous exposure
situations; and, therefore, they require data submitted from subchronic, chronic, and
reproductive studies as well as from absorption, distribution, metabolism, and excretion
studies.
Data from preclinical animal studies can be developed outside of Japan provided the
studies are demonstrated to be reliable, such as assurance that the studies were conducted
in conformance to Good Laboratory Practices requirements. Similarly, the use of human
patch test studies conducted outside Japan is acceptable as long as their reliability is
recognized. However, MHW cautions that (a) appropriate tests employing controls which
utilize products marketed in Japan are required, and (b) for products applied to the face
or mucous membranes, patch testing conducted in Japan, or other Japanese experience is
required.
For submissions for licensing of quasi-drugs, data developed outside of Japan may be
acceptable if their reliability is recognized. However, data collected in Japan are
considered essential for indications and effects which may vary among races, such as skin
effects related to melanin and light, and effects of permanent waving agents and dyes on
the hair.
B.
Safety Considerations in the United States
Although the United States has no premarket clearance requirements for cosmetics,
substantiation of safety prior to market is inherent in the general safety provision
prohibiting the introduction of an adulterated product into interstate commerce as
discussed earlier. Indeed, the Code of Federal Regulations at 21 CFR 740.10 states:
Each ingredient used in a cosmetic product and each finished cosmetic product shall be adequately
substantiated for safety prior to marketing. Any such ingredient or product whose safety is not
adequately substantiated prior to marketing is misbranded unless it contains the following
 conspicuous statement on the principal display panel: Warningthe safety of this product has not been
determined.

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Obviously, carrying such a statement would be devastating to any product. It follows,
therefore, that companies invariably conduct appropriate safety evaluations of products
and ingredients before they introduce them into interstate commerce.
Enforcement of the general safety provision for cosmetics occurs through FDA's
inspection authority. In following up on a consumer product experience complaint, FDA
inspectors may request review of the safety information on a product. In addition, FDA
conducts surveillance of products in the marketplace, evaluates composition, and/or
conducts analyses to determine whether products contain any substances believed to be
harmful.
Coal-tar hair dyes have a specific exemption from the general safety provision of the
Food, Drug and Cosmetic Act, as amended. Section 601(a) states:
That [the] provision shall not apply to coal-tar hair dye, the label of which bears the following
legend conspicuously displayed thereon: CautionThis product contains ingredients which may cause
skin irritation on certain individuals and a preliminary test according to accompanying directions
should first be made. This product must not be used for dye in the eyelashes or eyebrows; to do so
may cause blindness, and the labeling of which bears adequate directions for such preliminary
testing.
Hair care products that, because of their claims, are considered drugs as well as cosmetics
must comply with requirements laid down in the appropriate monograph for OTC drug
products developed by the FDA. These monographs specify approved active ingredients
and their use levels, claims and indications, directions-for-use statements, and warnings.
Hair care products that fall into the OTC category include antidandruff preparations such
as rinses and shampoos.
A Final Monograph for Dandruff, Seborrheic Dermatitis, and Psoriasis Drug Products for
Over-the-Counter Human Use was published at 21 CFR Part 358 on December 4, 1991.
The monograph establishes conditions under which OTC antidandruff, psoriasis, and
seborrheic dermatitis products are generally recognized as safe, effective, and not
misbranded. Listed in Part 358 are acceptable active ingredients and their ranges,
combinations of ingredients, indications, directions-for-use statements, and warnings.
Essentially, this monograph establishes a blueprint for labeling an OTC antidandruff,
psoriasis, or seborrheic dermatitis product using approved active ingredients at prescribed
concentrations. Since most antidandruff shampoos and rinses are cosmetics, their labeling
must also comply with ingredient disclosure statements required for cosmetics.
C.
Safety Considerations in the European Union
The Sixth Amendment to the Cosmetics Directive (76/768/EEC) was approved by the
Council of Ministers of the European Union on June 14, 1993. Article 2 of that Directive
states:

 Page 338
A cosmetic product put on the market within the Community must not cause damage to human health
when applied under normal or reasonably foreseeable conditions of use, taking account, in
particular, of the product's presentation, its labeling, any instructions for its use and disposal as
well as any other indication or information provided by the manufacturer or his authorized agent.
In addition, Article 7a of the directive specifies requirements for maintaining a filei.e., a
dossieron each cosmetic product manufactured or imported into the Community. The
dossier can be maintained at any indicated single company or company agent location
within the Community, and it is to be written in a national language of the country where
it is being maintained. Alternatively, the dossier may be written in any EU member state's
language provided that it is understood by the designated competent authority of the
country examining the dossier where the dossier is maintained. A safety assessment of the
finished product and formulation must be included as a section in the dossier. The
assessment must consider the general toxicological profile of the ingredient, its chemical
structure and its level of exposure and would generally be supplemented with data on
product experience, route(s) of exposure, etc., as prepared by a qualified safety assessor.
The data for the safety assessment are to be collected using GLPs as required under
Directive 87/18/EEC.
The recently adopted Sixth Amendment of the Cosmetics Directive has other implications
for the safety assessment of cosmetic products and ingredients. The amendment prohibits
animal testing of cosmetic ingredients after January 1, 1998, mandating that relevant and
reliable alternatives to animal testing be adopted by January 1, 1997. The EU Commission
is to consult with the Scientific Committee on Cosmetology to determine whether
satisfactory progress has been made in the validation of alternative methods to assure
consumer safety. Should no valid alternatives be available at the effective date of
adoption, the commission must submit a report on progress, and draft measures to
postpone the date of implementation for a period of at least 2 years.
The manufacturers of many noncosmetic consumer products, including home care
products, are now subject to the Dangerous Substances Directive (67/548/EEC) and the
Dangerous Preparations Directive (88/379/EEC). These directives have major effects on
product labeling owing to the requirement for the use of warning statements and symbols
on these products. The warning symbols apply to products classified as potentially
harmful to humans or the environment. The symbols selected are quite prominenta large
X, T, or C for certain safety hazards, and a dead fish and defoliated tree for certain
environmental hazards. At present, cosmetic products are specifically exempted from the
directives; however, there has been discussion of cosmetics being covered under the
directives in the future.

 Page 339

IV.
Ingredient Considerations
Ingredients are the tools with which the cosmetic chemist works and are thus of primary
importance. While the availability of ingredients is broad (over 8000 cosmetic ingredients
are in use throughout the world), the actual choice is somewhat limited due to product
classification (cosmetic versus drug) and other regulatory restrictions. The regulatory
restrictions, vary widely from country to country. We will again examine the three major
markets of the United States, Europe, and Japan.
The United States is the least restrictive of the three markets. With the following two
exceptions and the general safety requirement discussed earlier, all cosmetic ingredients
are available for use by the cosmetic chemist. The code of Federal Regulations, Title 21,
Part 700, identifies a few ingredients specifically restricted or prohibited for use in
cosmetics; e.g., restrictions on the promotion of eggs in shampoos and prohibition of the
use of vinyl chloride, bithionol, chloroform, methylene chloride, and mercury-containing
preservatives except in eye-area products. The CFR further specifies allowed color
additives, a listing that interestingly is one of the most restrictive in the world. The
traditional coal-tar dyes, now including all organic pigments, require batch testing and
certification by the FDA prior to their use in cosmetics. Certified batches of colors employ
FD&C, D&C, and Ext. D&C nomenclature to differentiate these lots from non-certified
material. Only certified organic colors specified for cosmetic use are permitted. This
requirement is particularly important to keep in mind for products imported into the
United States, for even these externally sourced color additives are required to be certified
by the FDA prior to use in products intended to be sold in the United States. Another
entire group of color additives such as talc, iron oxides, carmine, ultramarines, henna, etc.
are exempt from certification testing. However, they still must conform to specifications
found in 21 CFR Part 73.
OTC drugs in the United States have an additional area of ingredient restriction beyond
the two areas mentioned above for cosmetic products. The individual monographs will
specify the allowed active ingredients and their use restrictions for each type of OTC
drug. Of most importance to the hair care chemist is the Final Monograph for Drug
Products for the Control of Dandruff, Seborrheic Dermatitis, and Psoriasis discussed
earlier. The monograph restricts the allowed active ingredients to coal tar, zinc pyrithione,
salicylic acid, selenium sulfide, and sulfur. Reference Title 21 of CFR, Part 358 for details
of use restrictions and other considerations.
In the European Union, while most ingredients are able to be freely utilized by the
cosmetic chemist, there are regulatory restrictions.
Annex II of the EU Cosmetics Directive (76/768/EEC) contains a listing of 412 ingredients
specifically prohibited for use in cosmetic products. Annex III, Parts 1 and 2, of the same
directive identifies an additional 64 ingredients

 Page 340
whose use in cosmetic products is subject to specified restrictions, often concentration
limitations and/or label warnings. As many of these restricted ingredients are of
significance in hair care products (particularly for hair waving/straightening/depilatory
compounds, coloring agents for hair dyes, and antidandruff actives), the cosmetic chemist
should become familiar with these ingredients and their restrictions.
Annex IV provides a listing of coloring agents allowed for use in cosmetic products, their
allowed field(s) of application, and any limitations or requirements for their use. Those
color additives identified by an E number are required to meet the specifications and
purity criteria for food colors found in Annex III of the 1962 Directive concerning
foodstuffs and coloring matters. It should be noted that hair dyes are specifically excluded
from Annex IV of the cosmetics directive. While some hair dyes are specifically
prohibited for use in cosmetic products based on their listing in Annex II, and others are
subject to restrictions as identified in Annex III, any other oxidative hair dye may be used
provided its safety can be generally defended as required in the directive.
Annex VI lists the preservatives that are allowed, either permanently or provisionally,
together with maximum concentrations and any limitations, requirements, and label
warnings.
Annex VII identifies UV filters that may be contained in cosmetic sunscreen products.
These UV filters are restricted only for use in skin protection. UV filters added to other
cosmetic products solely for the purpose of protecting the product itself against UV
radiation are not restricted by Annex VII. This exception extends to hair care products
containing UV filters designed to protect the hair against color fading or other effects of
UV radiation.
The EU Commission has stated an interest in extending the EU's positive-list approach to
cosmetic ingredients utilized as coloring agents for hair dying. In anticipation of future
proposed legislation in this area, the cosmetic industry associations throughout Europe are
in the process of preparing a listing of oxidative hair dye colors which would form the
basis of such a proposal.
Japan's approach to cosmetic ingredients is unique in that all ingredients must be
preapproved by the ministry of health for each product category. The primary sources for
the identity of ingredients currently approved are:
Japanese Cosmetic Ingredient Dictionary (JCID)
Japanese Standards of Cosmetic Ingredients (JSCI II and Supplements I and II)
Comprehensive Licensing Standards of Cosmetics by Category (CLS Parts IVI)
Japanese Standards of Quasi-Drug Ingredients, 2nd Edition
Japanese Cosmetic Ingredients Codex and Supplement (JCIC)
Should a manufacturer or importer wish to use an ingredient not currently approved, the
licensing application for a product containing the new ingredient

 Page 341
must include detailed information on the ingredient's origin, physical and chemical
properties/specifications, and detailed safety substantiation.
Japan's Ministry of Health and Welfare has also published a listing of coal-tar colors
permitted for use in cosmetics and quasi-drugs. The 95 color additives in this list are
further identified by area of allowed usage, either all cosmetic applications or restricted to
non-mucous-membrane use. Non-coal-tar colors, analogous to the U.S. FDA's
noncertifiable colors, are not separately regulated in Japan, but rather are reviewed as any
other cosmetic ingredient during the licensing process. As previously mentioned, the
oxidative hair dyes are quasi-drugs in Japan. A listing of both active and inactive
ingredients permitted for use in hair dyes can be found in Volume 1 of the Japanese
Standards of Quasi-Drug Ingredients.
Finally, a small listing of ingredients whose use in cosmetic products is restricted is
identified in the Ministry of Health and Welfare Notification No. 321, and a listing of
prohibited cosmetic ingredients is found in PAB/ERD-2 Notification No. 100.
V.
Labeling Considerations
The product label is one aspect of a cosmetic that is very closely scrutinized by regulatory
authorities. The basic labeling requirements common to all cosmetic products represent
only the beginning of a complex assortment of regulatory information that a manufacturer
is required to present to the consumer on the product label. While it is not within the
scope of this chapter to identify all of the details of labeling regulations, the major
labeling requirements will be summarized here to sensitize the cosmetic chemist to their
importance.
Basic to all cosmetic product regulations is the requirement to label a product with: (a) a
statement of product identity, (b) a net quantity of contents statement, and (c) the identity
of the manufacturer, importer, or distributor. These items are self-explanatory in concept,
but exhibit significant differences in implementation. For example, with the exception of
the United States, all countries recognize the metric system as the basis of the net quantity
of contents declaration. The United States has traditionally required the use of the U.S.
weights and measures (inch-pound) system for consumer products. In a series of
legislative actions promulgated as a result of the Metric Conversion Act of 1975, the Fair
Packaging and Labeling Act (FPLA) has been recently amended to require the use of both
the customary inch-pound system and the metric system, referred to as the International
System of Units (SI). As of this writing, the FDA has only proposed rules that would
bring FDA-regulated products into compliance with this change to the FPLA, an action
that has been finalized for most other consumer product areas under a final Federal Trade
Commission ruling of January 12, 1994.
Another example that illustrates the complexity of regulation related to this

 Page 342
seemingly simple requirement for net contents declarations is international non-
conformity in units of measurements. In the United States, viscous products are labeled in
terms of weighte.g., ounces/grams. The European system requires the same viscous
products to be labeled in volume measurese.g., milliliters. In Japan, the requirements are
more definitive. Products with a viscosity greater than 10,000 centipoise are defined as
solids and are labeled in terms of weight. Those of lesser viscosity are deemed liquids and
labeled in volume measures. The measurement units mandated for aerosol products are
also not uniform. While the United States and Japan require aerosol contents to be
disclosed in weight measure, the EU requires the same products to be declared in volume
measure.
The requirement for ingredient labeling of cosmetic products is of primary importance to
the cosmetic industry. Regulations pertaining to this issue are either in effect or in the
process of promulgation in many major markets of the world. The U.S. cosmetic chemist
is familiar with the FDA requirement for cosmetic ingredient label declarations based
most commonly on the use of the Cosmetic, Toiletry, and Fragrance Association (CTFA)
nomenclature. Effective November 1, 1994, Australia requires ingredient declarations also
based on CTFA nomenclature. Similarly, Canada's Health Protection Branch has proposed
cosmetic ingredient declaration regulations based on CTFA nomenclature; however,
bilingual declarations in both French and English may ultimately be required as this
regulation is finalized.
Modifications to this theme continue. In the Sixth Amendment to the EU Cosmetics
Directive, enacted in 1993, the EU Commission has also required ingredient declarations.
CTFA, working in concert with the European cosmetic association COLIPA, has modified
the Cosmetic Ingredient Dictionary to include new materials found in European products
and to meet some unique requirements of European regulation or custom. Examples are
colorant designation by use of Color Index number in addition to the U.S. CFR
designation, the use of Latin genus and species for botanicals rather than the common
U.S. name, and the use of the European Pharmacopoeia name for certain trivial names
commonly used in the English language, such as water, wax, oil. The fifth edition of the
CTFA dictionary has subsequently been reissued as the International Cosmetic Ingredient
Dictionary (INCI).
Similar ingredient declaration requirements have been enacted recently in Mexico and
Brazil, again based on INCI nomenclature, but requiring that ingredients be translated into
Spanish and Portuguese, respectively. (The CTFA has recently rendered a translation of
the dictionary into Spanish, and a French translation is under development.) It's enough
to make an international marketer cryso close, yet so incompatible.
Other countries take a different approach to ingredient labeling. Japan, for example,
requires only specified ingredients to be identified on the label. These

 Page 343
ingredients are ones that are suspected of causing skin allergic reactions. There are about
100 such ingredients identified on the so-called gray list; the list includes preservatives
and all coal-tar colorants. Taiwan R.O.C., while requiring ingredient labeling, in practice
gives the manufacturer/importer the choice of full ingredient labeling or labeling, at
minimum, the three major ingredients. Not surprisingly, many companies choose the
latter.
The value of partial disclosure of cosmetic ingredients was recently refuted by Heinz J.
Eiermann, former FDA Director, Division of Colors and Cosmetics. To label only those
ingredients known or suspected to cause irritation or allergic reaction would probably be
worse than no disclosure at all, because it could mislead consumers into believing that
they should only be concerned about the listed ingredients, and that the ingredients which
are not declared on the label are safe (2). In looking at worldwide cosmetic ingredient
labeling requirements, it would appear that many, but not all, regulatory authorities agree
with Mr. Eiermann.
The expiration dating of cosmetic and OTC/quasi-drugs is another labeling requirement
of interest to the cosmetic chemist. In the United States, cosmetics are not required to be
expiry dated. OTC drugs require expiry dating unless their labeling does not display
dosage limitations and they are stable for at least three years as supported by appropriate
stability data. OTC hair care products would generally not have dosage limitations and
would, therefore, be exempt from expiry labeling provided they are stable for at least 3
years.
In the European Union, cosmetics require expiration dating only if their documented shelf
life is less than 30 months. Japan has a similar exemption from cosmetic expiration dating;
however, it is based on a shelf life of 3 years. Japanese quasi-drugs share this cosmetic
exemption, with the exception of 13 product types containing specified ingredients. It
should be noted that quasi-drug product types requiring expiry dating include some items
of interest to the hair care chemist, including p-phenylenediamine and other oxidizing
dyes, peroxide compounds, and thioglycolic acid and its salts.
There are numerous other labeling requirements, many of which are country-specific,
product-specific, or ingredient-specific. It is recommended that the cosmetic chemist
work closely with a regulatory affairs analyst to determine how this myriad of regulations
affects the product(s) being developed. The regulatory affairs analyst will research the
cosmetic and drug regulations that apply and will be able to guide the chemist on the most
appropriate choice of ingredients, allowed claims platform, and labeling requirements.
This analysis should optimally be performed toward the start of the project to avoid
discovering a fatal flaw too late, such as an improper preservative being used, the actives
combination chosen for the product being disallowed, or a desired marketing claim being
forbidden.

 Page 344

VI.
Packaging Regulations
A.
Standard Sizing
There are regulations in some jurisdictions (e.g., Japan, Latin America, and the European
Union) that require standard size packaging. Canada also has standard sizing regulations
in place; however, as of this writing is in the process of revising their legislation to delete
this requirement for most product categories. Canadian authorities are not enforcing the
existing regulations in the interim.
The situation in the European Union will be used as an example of typical standard sizing
regulations. Directive 80/232/EEC describes nominal quantities and capacities permitted
for certain packaged products, including many cosmetics and hair care products. The
directive is commonly referred to as the Standard Ranges Directive. It is one of several
promulgated to achieve harmony among the various member countries for the purpose of
facilitating consumer price comparisons. The directive covers packages, including aerosol
packages, with nominal fill capacities of from 5 g or 5 ml to 10 kg or 10 L. Packages
destined solely for professional use, or those for sale in duty-free shops, and certain
alcohol-containing products are excluded from the requirements.
Hair care product packages (except dyes) covered by the directive are those containing
lacquers, shampoos, rinses, strengtheners, brilliantines, and hair creams (except alcohol-
containing hair lotions are excluded). Container capacities allowed in the directive are for
25, 50, 75, 100, 125, 150, 200, 250, 300, 400, 500, 750, 1000, and 2000 sizes, labeled in
grams for products sold in solid and powder forms and in milliliters for products sold as
liquids or pastes. Hair lotions containing alcohol at 70% or less by volume, and
fragranced at less than 3% by volume, can have, in addition to the container capacities
listed above, 15-, 30-, and 40-ml capacities, but a 2000-ml capacity is not allowed. Annex
IV of the directive specifies volume capacities for products sold in metal and aerosol
containers. The reader should refer to the directive directly or may contact any of several
trade associations that can advise on specifics for products of interest. In addition, the
reader is referred to the Aerosols Directive (75/324/EEC) for safety standards for the
filling and labeling of aerosol dispensers.
B.
The e Mark
European products that satisfy the minimum fill requirements specified under the so-
called Liquids (75/106/EEC) and Solids (75/211/EEC) Directives and that conform to the
Standard Ranges Directive (80/232/EEC) may use a special e mark, actually a reverse
epsilon, on the label. Products that do not bear the e mark may be required to undergo
metrological controls at border entry points to evaluate them for compliance with the
directives. Although it is not compulsory to mark packages with the e symbol, when used,
it is a gen-

 Page 345
eral recognition of a package's conformance to the directives and therefore acts as a
passport for product movement into and within the European Union.
C.
Deceptive Packaging and Slack-Fill
Although a variety of deceptive packaging practices and codes exist, it is rare to uncover
regulations specific to the subject of deceptive packaging. For example, in the United
States, Section 602(d) of the U.S. Food, Drug, and Cosmetic Act, as amended, states that
a cosmetic is considered to be misbranded if its container is made, formed, or filled so as
to be misleading. However, the U.S. FDA has not promulgated regulations that expand on
this statement. Instead, the most common method used to enforce the law and to protect
the consumer from being deceived by packaging which is underfilled or constructed so
that it appears to contain more than its net quantity of contents statement indicates, is
through prosecution under fair trade practices laws.
One country, Australia, had been an exception to this lack of specificity. Prior to 1988,
deceptive packaging was defined and enforced under specific Deceptive Packaging
Regulations. The regulations were repealed in 1988 and replaced with a self-regulatory
agreement entitled the Deceptive Practices in Packaging Code of Practice which applies to
both imported and Australian-produced goods. The code is aimed at providing the
consumer with some degree of certainty that the apparent size of a package reasonably
indicates the amount of product contained therein. Several years of consideration of
controls by state governments, industry, and consumer organizations culminated in the
code and provided the basis for application of uniform standards throughout the country.
Packaging meeting the requirements of the code is not considered deceptive by state and
territorial authorities.
An agreement similar to the Australian Code of Practices also exists in California. In
1988, officials from the Office of the California Attorney General, the California
Department of Food and Agriculture, and the California Association of Weights and
Measures Officials adopted California's Slack-Fill Enforcement Guidelines. The
guidelines are intended to apply only to cosmetics, toiletries, fragrances, and OTC drugs.
The philosophy embodied in the guidelines is that a container is misleading if (a) it does
not allow the consumer to fully view its contents, and (b) the container is nonfunctionally
slack-filled.
Slack fill is defined as the difference between the actual capacity of a container and the
volume of product contained therein. Nonfunctional slack fill is the empty space in a
package that is filled to less than its capacity for reasons other than (a) protection of the
contents, or (b) the requirements of the machines used to fill the package. The guidelines
apply to outer containers or exterior packaging rather than to the fill of an immediate
product container which is covered by California's Slack-Fill Law.
Three of the 12 package-related guidelines apply to hair care products.

 Page 346
Guideline 1 states that a reasonable relationship must exist between inner and outer
containers. Guideline 7 states that for product kits containing multiple components (such
as a permanent waving kit or a hair coloring kit), the size and actual quantity of the
product are less important than proper disclosure of the purpose of the kits, provided
there is proper disclosure of the net contents and the number of uses, treatments, or
applications a consumer can reasonably expect. Guideline 11 states that an immediate
product container will not be regarded as slack-filled if it contains head space necessary
to facilitate mixing, adding, or shaking of liquids or powders by the consumer. Additional
guidelines cover decorative, sample and presentation packaging, small packages, and
pilfering issues.
In addition to these guidelines, the reader should not that the federal Food and Drug
Administration has established regulations (21 CFR 701) which state that the declaration
of net quantity of contents shall not include any term qualifying a unit of weight or mass,
measure, or count that tends to exaggerate the amount of the cosmetic contained in the
packagee.g., giant pint or full quart. A similar regulation exists for drugs.
VII.
Product Registration/Licensing
Your technical product development is complete. Product-use characteristics and efficacy
meet all company expectations. Your product's ingredients meet all regulatory criteria, as
does its packaging. The product is stable, microbiologically sound, and tested for safety.
The label meets all labeling requirements. You are ready to go to market. Not true!
In many, if not most, markets, the product must first be registered. The registration
procedure varies tremendously by market and product type. This section will provide an
overview on the registration/licensing requirements for the three jurisdictionsthe United
States, the European Union, and Japan.
The purpose of registration and licensing is to provide the opportunity for a country's
regulatory authorities to review a product for safety and regulatory compliance prior to
introduction to the market. Some of the more common aspects of this process are
registration of the manufacturing establishment, notification of the product's formula and
related information, and reporting of adverse reactions.
As a general rule in the United States, these processes are voluntary for cosmetics and
mandatory for OTC drugs. The reader is directed to 21 CFR Parts 710, 720, and 730 for
the codification of the voluntary program that has been adopted for cosmetic
establishment registration, ingredient filing, and adverse experience notification. A
recurring word throughout these references is requested, reflecting the voluntary nature
of cosmetic product registration in the United States. The reader is cautioned, however,
not to be lulled into a false sense of security. The FDA has recently been under increasing
political pressure to exert more control over the cosmetics industry. the response of the
in-

 Page 347
dustry to comply with voluntary registrations, a practice championed by the CTFA, has
been a major factor in keeping increasing regulations in this area to a minimum. All
companies are strongly urged to continue and strengthen the trend toward full compliance
to FDA's registration/filing request.
Exactly what is involved? Cosmetic product establishment registration simply requires the
submission of a completed form FD-2511 to the FDA in Washington. The FDA, in turn,
will validate the form and return it with a permanent registration number.
Cosmetic product ingredient filing again requires completion of a form, FDA 2512. This
form requires the name and address of the person designated on the product label and the
manufacturer/packer, the brand name(s) of the cosmetic, the cosmetic category(ies), and
the ingredients in descending order of predominance. Provisions are made for
confidentiality of statements where this is requested/justified. It should be filed within 60
days of commercial distribution of the product. In concert with a program developed by
the CTFA, the FDA now accepts electronic data submission for cosmetic product
ingredient filing.
Reportable (adverse) cosmetic experiences, i.e., injuries, are filed annually via forms FD-
2704 and FD-2706. Separate forms FD-2704 are to be filed for each cosmetic product that
had a reportable experience(s). Form FD-2706 summarizes reportable experiences by
product category. Recently, FDA published a proposal for public comment on whether
the adverse experience portion of the voluntary program (Part 730) should be eliminated
or reduced in scope. FDA noted that its 20-year baseline of adverse reaction rates may be
sufficient to make additional reporting unnecessary. Likely, Part 730 will be modified or
eliminated in the near future.
U.S. manufacturers of OTC drugs are required to register annually with the FDA as a
drug establishment and to file a listing of all drug products, accompanied by a copy of the
label and a quantitative listing of all active ingredients. Changes to listed drugs must be
reported to the FDA every June and December, or alternately when the change occurs. As
with cosmetic products, the qualitative disclosure of inactive ingredients in OTC drugs is
voluntary but recommended. The reader is referred to 21 CFR Part 207 for additional
detail on drug establishment registration and drug listing.
Routine reporting of adverse drug experiences to the FDA is not required. Rather, current
Good Manufacturing Practices found at 21 CFR Part 211.198 requires the maintenance of
a written record of each complaint in a file that remains available for inspection.
In addition to the FDA registration/listing requirements, products utilizing specially
denatured ethanol (e.g., hair sprays) must be registered with the Bureau of Alcohol,
Tobacco and Firearms. Form ATF F5150.19 is used for this purpose, and requires, among
other things, the disclosure of the product's quantitative formula.

 Page 348
The European Union has less formalized requirements for registration/listing. When the
Sixth Amendment to the Cosmetic Directive is fully implemented in 1997, manufacturers
and importers will be required to notify the competent authorities of the member states of
the place of manufacture or initial import of cosmetic products before the products are
placed on the market.
While there are no formal cosmetic product ingredient filing requirements, the Sixth
Amendment requires the establishment of an inventory of cosmetic ingredients. This
inventory will be prepared by the EU Commission with the assistance of the member
states and their national cosmetic trade associations. It will include the ingredient name,
function(s), appropriate restrictions, and label warnings. It is important to note that this
inventory will not constitute a positive listing of allowed cosmetic ingredients. The
commission is to be notified of the use of any new cosmetic ingredients; the commission
will then periodically update the inventory.
The only cosmetic ingredients that require premarket approval are color additives,
preservatives, and ultraviolet filters not found in Annexes IV, VI, and VII, respectively,
the so-called positive lists. Article 8a of the directive details the procedure for obtaining
approval for these specific new chemical usages.
Additional detailed cosmetic product information is required to be maintained within
company files as part of the information dossiers referenced earlier in the discussion on
product safety (see Article 7a of the directive). This information includes:
Qualitative/quantitative composition
Raw material and finished product specifications
Manufacturing process
Safety assessment
Identity and qualifications of safety assessor
Adverse-experience data
Efficacy data
Several of the EU member states have additional individual requirements for
registration/notification. It is expected that most of these requirements will be eliminated
upon adoption into national legislation of the Sixth Amendment to the EU Cosmetic
Directive. For this reason, these individual Member State requirements are only
referenced in summary below:
 Requires registration of ethanol-containing products with the
Ministry of Finance
Italy
Requires notification of cosmetic ingredients, a precursor to
the community-wide inventory required by the Sixth
Amendment
Requires notification of cosmetic products to the Directorate
Portugal
General of Health

(table continued on next page)

 Page 349
(table continued from previous page)
Requires detailed notification of cosmetic products to the
Spain
Ministry of Health
Requires maintenance of a cosmetic dossier, the precursor to the
France
information file required by the Sixth Amendment
Requires notification of cosmetic products to the National
Greece
Organization of Drugs

Japan has the most stringent registration/licensing requirements of the three jurisdictions
examined. Prior to first manufacture (or import) of cosmetic or quasi-drug products, a
company must obtain a license, or kyoka, from the Ministry of Health and Welfare for
each manufacturing site (or business office). The application for this license is presented
to the prefectural government, which performs an examination of applicant's building and
facilities as well as the qualifications of the key personnel. The prefectural governor
presents his recommendation to the ministry, which issues a certificate of license, or
shonin, following their review of the application. This certificate must be renewed every
3 years.
The license to manufacture/import also requires the submission of detailed product
information for the cosmetic products involved. This includes:
Category of cosmetic
Trade name
Quantitative formula
Raw-material specifications and standards
Manufacturing process
Usage and dosage
As raw-material quality is a primary concern of the ministry, conformance to prescribed
raw-material standards is closely examined during the application process. Any of a
variety of recognized ingredient standards may be referenced on the application. Lacking
conformance to one of these standards, the applicant must attach separate sheets detailing
the specifications (standards), in prescribed format, that the ingredient will meet.
Some quasi-drug product categories also have standards applicable to the finished
product itself. For example, permanent waving agents have a standard which lists
specification ranges for pH, total alkalinity, quantities of reducing and oxidizing agents,
and other characteristics.
Table 1 exemplifies the degree of standardization that MHW has adopted in some
instances.
Approval of materials not previously used in cosmetics requires the submission of
detailed technical and safety information. The earlier discussion under Hair Care
ProductsSafety Considerations provides details of the safety testing requirements for such
submissions. Products containing new ingredients are subject to a formal safety
monitoring period during which all adverse ex-

Table 1 Summary of Standards for Permanent Waving Agents
(1) Dual-step (2) Dual- (3) Dual-step (4) Single-step (5) Dual-step permanent (6)
cold step cold tepid cold waving agents with the first col
permanent permanent permanent permanent agent containing thioglycolic stra
Properties waving agents waving waving agents waving agents acid or its salt (consisting of age
containing agents containing containing components mixed at use, con
thioglycolic containing thioglycolic thioglycolic generating exothermal thio
acid or its salt cysteine acid or its salt acid or its salt reaction) aci
First agent
pH 4.59.6 8.09.5 4.59.3 9.49.6 4.59.4
Alkali (amount
of 0.1 N
<7 ml <12 ml <5 ml 3.5-<4.6 ml <7 ml
hydrochloric
acid consumed)
Concentration
of reducing
substance
7.011.0 (%) for mixture of
(thioglycolic 2.07.0 (%) 1.05.0 (%) 3.03.3 (%) Sam
first agents [1] and [2]
acid) after
boiling under
acidic condition
Concentration
of reducing
substance
<4.0% <4.0% <0.5% 3.24.0%
(dithioglycolic
acid) after
reduction

(table continued on next page)

(table continued from previous page)
(3) Dual-step (6
(2) Dual- (4) Single- (5) Dual-step permanent
tepid co
(1) Dual-step cold step cold step cold waving agents with the first
permanent st
permanent waving permanent permanent agent containing thioglycolic
waving agents ag
Properties agents containing waving waving agents acid or its salt (consisting of
containing co
thioglycolic acid agents containing components mixed at use,
thioglycolic th
or its salt containing thioglycolic generating exothermal
acid or its ac
cysteine acid or its saltreaction)
salt sa
Reducing
substances other
than those after
boiling under < 0.6 ml < 0.6 ml < 0.6 ml < 0.8 ml
acidic condition
(0.1N iodine
solution)
Concentration
3.07.5 (%)
of cysteine
Concentration
< 0.65%
of cystine
Temp. rise onmixing: V
Other
1420°C 4
Second agent
Sodium bromate,
Potassium
bromate, Sodium
Types of perborate: Same as inSame as in S
second agent Oxidation activity (1) (1) (1
per does per
person: < 3.5; pH:
4.09.0
Hydrogen
peroxide:
Concentration: <
2.5%; Oxidization
Same as in
activity per dose Same as in (1)
(1)
per person: 0.83.0;
pH: 2.54.5
By heat generation: 1st
Operating Room
Room temp. < 60°C Room temp. agent: 3040°C; 2nd agent: R
temperature temp.
room temp.

 Page 352
periences must be reported to the ministry. This period is generally 1 year for materials
with a history of prior use in other jurisdictions, and 2 years for ingredients new to the
cosmetic industry.
The Pharmaceutical Affairs Law, Article 62-2, provides further guidance for monitoring
adverse experience for all cosmetics. Serious reactions, new studies identifying previously
unrecognized hazards, as well as a high frequency of skin disorders, are examples of
adverse experiences that are required to be notified to the ministry.
MHW introduced the Comprehensive Licensing System of Cosmetics by Category (CLS)
in July 1986. CLS is designed to simplify the licensing procedure. Rather than granting a
license to an individual product, the applicant applies for a license for a category of
cosmetic productse.g., shampoos or hair rinses. Each category of cosmetics has
prescribed tables of allowed ingredients and monographs (standards) for each ingredient.
Only products whose category is listed in the CLS can qualify for a CLS notification.
Additionally, only those ingredients allowed in that CLS category may be used for that
product type. The ingredients must also conform to JCIC specifications. The advantage to
CLS is that this notification process results in immediate approval for manufacture rather
than waiting for license review/approval, which can typically take 3 to 6 months for
cosmetics, and 6 to 9 months for quasi-drugs.
Following the success and acceptance of CLS for cosmetics, MHW is now actively
working toward extending this concept to quasi-drugs.
VIII.
Concluding Remarks
A discussion of international regulations, even as they apply to a narrowly defined
category such as hair care products, readily shows that complex, nonuniform, and
burdensome systems have developed in the various jurisdictions. One can quickly
recognize that there would be wholesale advantages should the current patchwork quilt of
government regulations be simplified and harmonized. The advantages would be
manifested in many ways: (a) formula, package, and labeling would be consistent; (b)
production would benefit from economy of scale in producing the same formula in the
same package for a larger number of markets; and (c) there would be fewer regulatory
delays in processing registrations, notifications, etc.
Efforts are being made to harmonize international regulations. Obviously, one of the main
precepts of the European Union is harmonization to facilitate cross-border trade. This
harmonization includes regulations across the European continent, as the impact of the
European Union is reflected even in non-EU country regulations. In addition, the various
trade associations have become increasingly international in scope, meeting regularly in
support of global harmonization of cosmetic regulations. The recent series of Mutual
Under-

 Page 353
standing conferences sponsored by the cosmetic trade associations of the United States,
the European Union, and Japan is a prime example. Certainly, we have seen great strides
toward harmonization as exemplified by the increasing use of uniform cosmetic
ingredient nomenclature based on the International Cosmetic Ingredient Dictionary
(INCI). Also, it is common practice for trade associations to share ingredient safety
information to help ensure the common listing of restricted ingredients, such as
antimicrobial agents and color additives, around the world. Nonetheless, there is still a
long way to go. The ideal situation would be one where, except for necessary language
differences, a worldwide marketer could label its products with consistent and uniform
language and symbols to distribute to as many markets as practicable. Legislators and
industry should jointly strive to adopt only those regulations that truly protect and inform
the consumer and eliminate and avoid those that serve unrelated political purposes.
References
1. Ricks HT. Mutual Understanding in Changing Times. Fourth International Conference
on Cosmetic Regulation, Tokyo, 1993.
2. Eiermann HJ. Cosmet Toiletries 1992; 107:5763.
Bibliography
Code of Federal Regulations, Title 21, (U.S. Government Printing Office, Washington,
D.C., updated yearly).
Council Directive (76/768/EEC), as amended, Office for Official Publications of the EU,
Luxembourg, Delegation of the Commission of the European Union to the United States,
Washington, D.C., and Comité de Liaison des Associations Européennes de l'Industrie de
la Parfumerie, des Produits Cosmétiques et de Toilette (COLPIA), Brussels.
CTFA Labeling Manual (5th edition) The Cosmetic, Toiletry, and Fragrance Association,
Inc., Washington, D.C., 1990.
Federal Food, Drug and Cosmetic Act, U.S. Government Printing Office, Washington,
D.C. (updated yearly).
Guide to Quasi-Drug and Cosmetic Regulations in Japan Yakuji Nippo, Ltd., Tokyo,
1992.
International Color Handbook (2nd edition) The Cosmetic, Toiletry, and Fragrance
Association, Inc., Washington, D.C., 1992.
International Cosmetic Ingredient Dictionary (5th edition) The Cosmetic, Toiletry, and
Fragrance Association, Inc., Washington, D.C., 1993.
International Resource Manual (3rd edition) The Cosmetic, Toiletry, and Fragrance
Association, Inc., Washington, D.C., 1991.
The Japanese Cosmetics Ingredients Codex Yakuji Nippo, Ltd., Tokyo, 1993.
Supplement to the Japanese Cosmetics Ingredients Codex Yakuji Nippo, Ltd., Tokyo,
1993.

 Page 355

Index
A
Absorption of alcohol by hair, 20
Absorption of waving agents by hair, 169
Accelerated stability testing, 98
Acclaim Salon Waves, 177
Acid salon waves, 177
Acids, effect on -keratin structure of hair, 20
Acrylate polymers in permanent waves, 176
Actuators for hair sprays, 157-158
Additives in mousses, 125-126
Adverse reaction reporting in the U.S., 346
Aerosol
foam mousses, 118-135
hair spray formulations, 157-161
hair sprays, fragrance for, 225
styling aids, 138-146
valves for mousses, 126
Airspray Foamer for mousses, 126
Alcohol absorption into hair, 20
Alcohol in mousses, 122
Alkaline waves (permanent), 176-177
Alkyl amines, 69, 70
Alkyl imidazolines, 69, 74
Allergic dermatitis and hair coloring, 213
Alpha-amino acids, 76
-helix, 2, 10
-keratin, 1-3, 7, 8, 10, 13, 167
-keratin protein in permanent waving, 167
American Society for Testing and Materials (ASTM), 261
Amido amines, 70
Amine oxides, 71
Amines in permanent waving, 175
Aminifunctional silicone in durable conditioner, 93-94
Amino acid analysis of wool, 9
Amino acid changes during perming, 173-174
Amino acids, 76
Aminofunctional silicone in durable conditioner, 93-94
Aminofunctional silicones, 78

 Page 356
Aminophenols in hair coloring, 198
Ammonia in permanent waving, 174
Ammonium persulfate in bleaching, 196
Ammonium thioglycolate, 166
Amodimethicone, 78
Antidandruff products
Anti-oxidants in hair coloring, 199
Anti-soiling of hair, 59
Anti-static agents, 68, 80
Anti-yellowing conditioner, 95-96
Appliances, heated-damage, 67
Attitude measurements in consumer testing, 316-318
B
Back-combing and effect on cuticle, 4
Bending stiffness of hair, 288-289
-keratin, 2
x-ray diffraction, 23
Biodegradability evaluation, conditioners, 99
Biosynthesis of eumelanin, 193-194
Biosynthesis of pheomelanins, 195
Bismuth salts in hair color, 209
Bisulfite waves, mechanism, 168-169
Bisulfite in waving, 168-171, 178
Bisulfite waving formulations, 178
Bleach booster. See Persulfates in hair bleaching
Bleached hair, waving of, 171
Bleaching hair, 196-198
with peroxides, 196
with persulfates, 196
Blow-dry lotion prototype, 111
Body of hair, definition, 285
Bodifying mousse prototype, 129
Body and stiffness, 288-292
Boulder's corrosion test method, 143-144
Bound water, 18
Brazilin in hair color, 211
Bromate neutralizer, 174
Buffers in permanent waves, 174
Build-up of resin on hair, 134
Bureau of Alcohol, Tobacco and Firearms (BATF), 347
C
California Air Resources Board (CARB), 120, 135-136
Can corrosion inhibitors, selection of, 144-145
Can corrosion rating system, 141
CARB. See California Air Resources Board
Carbomers (Carbopol), 57
Carbomers in styling aids, 114
Carbopol (carbomer), 57
Carrageenan gums, 113, 114
Cationic
conditioning agents, 69
dyes in hair color, 212
 polymers, 74
polymers as conditioners in perms, 176
polymers for conditioning, 69
surfactants, 69
Cell membrane complex, 5
Celquat (polyquaternium-4), 75
Ceramide, 81
Certified dyes in hair coloring, 205-206
Chamomile, 84
Chemical relaxers
desired characteristics, 242
lye relaxers, 242-243
maintenance products for, 250-257
manufacturing considerations, 242
neutralizing shampoo, 245-246
stability requirements, 242
Chemical relaxing of ethnic (excessively curly) hair, 240-246
chemistry of lanthionization, 240-241
conditioning relaxers, 240
guanidine hydroxide, 241
irritation during process, 241, 243
lanthionization, 240-241
no base relaxers, 240
no lye relaxers, 240
permanent waving, 246-250
procedure followed, 242
texturizing relaxers, 240
Chemistry of oxidation dyes, 7-10-12
Chitin, 76
Chitosan (PCA), 76
Chlorine hair damage, 67
Cleansing of ethnic or excessively curly hair, 251-252
Clear conditioner formulations, 87-88
CMC (critical micelle concentration), 73
COA. See Certificate of Analysis
Coal tar exemption from FD&C Act, 342
Cocotrimonium collagen hydrolysate, 77

 Page 357
COLIPA (European cosmetic association), 342
Color loss from hair straightening, 203
Color loss from permanent waving, 203
Color rinses, 207
Colors for conditioners, 85
Combability of hair, evaluation of, 265-267
Comb with conditioner, 96
Combing ease with conditioners, 97
Combing force measurements, 97
Combing of hair, evaluation of, 265-267
Concept aided consumer testing, 315
Concept and use testing, 315-316
Conditioner(s)
anti-yellowing effect, 95-96
biodegradability evaluation, 99
clear, 87-88
colors for, 85
containing a cationic polymer, 90
deep treatment, 87
with durable performance, 93-94
excessively curly (ethnic) hair, 252-253
finishing products, 256-257
formulation of, 85-96
formulations - pearlescent, 89-90
gray hair, 95-96
and hair bleaching, 197-198
 with lathering action, 96-97
performance evaluation, 97-98
for permanent wave neutralizers, 176
for permanent waving, 175
preservation of, 85
preshampoo, 94
safety evaluation, 98-99
stability testing, 98
with style retention properties, 92-93.
with volatile silicones, 90-92
Conditioning
by glycerin in permanent waves, 176
comb, 96
mechanism, 68-69
mousse with sunscreen, 95
toners, 85
with plant and herbal extracts, 84
Conditioning agent(s), 65, 69
definition, 68
in hair dyes, 202
lipids, 80
Conical cells in -keratin, 20
Constant sum rating methods in consumer testing, 319-320
Consumer
evaluation of hair products, 303-330
research, effect of time, 307
research techniques for hair product evaluation, 303-330
 wants in hair color, 212-213
Consumer vs. laboratory testing, 303-304
Consumer testing
attitude measurements, 316-318
legal claims substantiation, 311-312
measurement and scaling, 316-323
monadic, 313
product integrity, 310-311
sequential monadic, 314-315
Consumer tests
concept aided, 315
guide formula developers, 308
one-on-one interviews, 312
triads, 312
Control of corrosion in aerosols, 138-146
Copolymers as conditioning agents, 79
Corrosion
aerosol styling aids, 138-146.
inhibitors, selection of, 144-146
Cortex of hair, 3, 5, 17, 66
Cortical cells, 6, 20
Cosmetic Directive of the EEC, 338
Cosmetic Preservatives Encyclopedia, 85
Cosmetics and drugs, U.S., 332-334
Cosmetic, Toiletry, and Fragrance Association (CTFA), 342
Council of American Survey Research Organizations (CASRO), 313, 324-330
Couplers in hair coloring, 198
Creme rinse formulations, 86-87
Crevice cell corrosion tester, 142
Critical micelle concentration (CMC), 73
Crodacels, 76
Crodosone W, 78-79
Cross-linking reagents, 11
Crystalline character of fibers, 23-24
CTFA. See Cosmetic, Toiletry, and Fragrance Association
CTFA Cosmetic Ingredient Dictionary, 342

 Page 358
CTFA International Cosmetic Ingredient Dictionary, 79
Curl activator prototypes, 113, 117
Curl activators for permed hair, 116-117, 251
Curl bounce, measurement of, 288-289
Curl droop measurements, 281
Curling iron, 106
Curl retention testing for styling products, 131-132
Cuticle, 3, 20, 66
Cyclic silicones, 81
Cysteic acid, 11
formation during perming, 173-174
from neutralizing permanent waves, 11
Cystine, 1, 16
reducing agents, 167
as a waving agent, 169
Corrosion
inhibitors, 144-146
temperature effects, 141-142
testing measures and procedures, 142-144
vapor phase, 140
D
Damage evaluation by liquid retention, 275
Damage from
free radicals, 173
hair bleaching, 197
oxidative dyes, 202-203
 permanent waving, 177
Damage to excessively curly hair, 252-253
Damage to hair, 106
Damage to lipids during perming, 174
Deceptive packaging, regulations, 245-246
DDMAO (didecylmethylamine oxide), 71
Deep conditioners, 73
Deep treatment conditioner, 87
Definition of cosmetic, 332
Definition of drug, U.S., 332
Demographics and consumer research, 304
Denatured alcohol, regulation of, 347
Den Beste, curl evaluation method, 279
Design Freedom Salon Wave, 177
Detangling agents, 71
Detangling of hair, evaluation of, 265
Detergency evaluation, 264
Development of conditioner formulations, 85-96
DHI. See 5,6-dihydroxyindole
Didecylmethylamine oxide, 71
5,6-Dihydroxyindole (DHI) in hair color, 210
3,4-Dihydroxyphenylalanine (DOPA) in hair color, 193, 210-211
Dimethicone 56, 78
Dimethicone copolyol 56-57
Dimethyl aminoethylmethacrylate (DMAEMA), 79
Diquaternary salts, 73-74
Direct judgment rating methods in consumer testing, 318-320
Disulfide bond breakdown, 23
Disulfide bonds in keratin, 8, 15
Disulfide linkages, 167
Dithioglycolate (DTG) in permanent waves, 177
Dithioglycolic acid, 169-170
Dithiothreitol as hair reducing agent, 171
DMAEMA, 79
DOPA. See 3,4-Dihydroxyphenylalanine
Dryer processing of acid waves, 177
DTG. See Dithioglycolate
Durable conditioner with aminofunctional silicone, 93-94
Durable conditioning agents, 78
Dye(s)
intermediates in hair coloring, 202
oxidation in hair dyeing, 198-204
selection for semipermanent hair colors, 205-206
selection for temporary hair colors, 208
E
EDTA in hair dyes, 199
Effect of acids on -keratin structure of hair, 20
Effect of chemical treatment on tensile properties of hair, 271-274
Effect of light on hair tensile properties, 271
Electrical conductivity, 14
E mark on European cosmetic product labels, 342-343
Emulsifiers for conditioners, 82
Encyclopedia of Conditioning Rinse Ingredients, 82

 Page 359
Encyclopedia of Polymers and Thickeners for Cosmetics, 82
Environmental concerns, conditioners, 99
Enzyme assisted hair coloring, 210
Epicuticle, 5
Epinephrine in hair dyes, 210
Ethanolamines in permanent waving, 175
Ethnic hair products, 235-259
conditioning, 81
history of, 235
market size, 235
Ethoxylated amines, 69, 71
Ethoxylated quaternaries, 72
Ethylenediaminetetraacetic acid (EDTA) derivatives in hair dyes, 199
Eumelanin, biosynthesis, 193-194
Eumelanins, 193-194
European regulations and hair sprays, 148
European Union (EU) definition of cosmetic, 333
European Union labeling regulations, 341-342
European Union regulations concerning cosmetic ingredients, 339-340
European Union standard sizing regulations, 342
Evaluation of fragrances, procedures for, 226, 228-229
Evaluation of hair
body, 285-292
bulk and resiliency, 285-287
care products by instrumental methods, 261-302
condition, 264-277
 feel, 267-269
frictional forces on, 267-269
luster/shine, 269-270
manageability, 277-292
mousse foam properties, 128-129
shampoo performance, 263-264
static, 283-285
swelling, 274-275
texture, 271
waving agents on tensile properties, 272-274
Even Heat Exothermic Salon Wave, 177
Excessively curly hair
characteristics of, 236-238
[Excessively curly hair]
combing characteristics, 237-238
creme hair dressing, 256
cuticle characteristics of, 236-237
description, 236-238
ellipticity of, 236-237
finishing products for, 257-257
moisture content, 237
oil moisturizing lotion, 256
oil sheen spray, 257
pomade formulations, 256
sebaceous glands, 237
setting products, 255-256
tensile properties, 237
Exocuticle, 5
Exothermic permanent waves, 178
Experimental design for prototype formula development, 97
Expiration dating of cosmetic products, 333
Extract of
brazilwood (brazilin) in hair color, 211
logwood (hematoxylin) in hair color, 211
netgall in hair color, 211
F
Fabric softeners - relation to hair conditioning, 74
Factors influencing consumer test design, 303-307
Faraday cage to evaluate static on hair, 284
Fashion (s)
grunge look and styling aids, 118
in hair styling, 106
and styling products, 116
Fats and fatty esters, 80
Fatty acid composition of natural fats and oils, 70
Fatty protein hydrolysates, 77
Feels So Lively Salon Perm, 177
Fiber entanglement, role of cuticle, 20
Fiber moisture level, 18
Fiber(s)
fiber-fiber friction evaluation of hair, 268
stress-strain curve, 21-24
sulfhydryl disulfide interchange, 22, 26
Filming corrosion inhibitors, 144-146
Finishing products for styling hair, 146-161
Firm hold styling mousse prototype, 130

 Page 360
Fixation in permanent waving. See Neutralization
Fixative polymers used in hair sprays, 154
Flone conditioning mousse by L'Oréal, 119
Foam character in mousses, 122
Foam stability and character in mousses, 122
Foam stiffness measurement for mousses, 131
Foaming conditioner, 96-97
Focus group testing, 312-313
for styling products, 131-132
Follicle, 2
Formaldehyde, 58
Formalin (formaldehyde), 58
Formula development, guidance via consumer tests, 308
Formulation
ideas, source of, 86
of mousses, 120-130
of permanent waves, 175-179
of semi-permanent hair colors, 206-207
Formulations for ethnic permanent waves, 248-250
FPLA. See U.S. Fair Packaging and Labeling Act
Fragmentation of consumer preferences, 304-305
Fragrance
for aerosol hair sprays, 225
basenote, 222
brief. See Profile
certificate of analysis for, 233
 components, 223
for conditioners, 225
creation of, 218
description of typical example, 234
evaluation of, 221-222, 226, 228-229
for hair care products, 217-234
for hair dyes, 225
influence on consumer, 218
influence on perceptions of performance, 218
ingredients of, 223
midnote, 222
MSDS (Material Safety Data Sheet) 231-232
natural vs. synthetic, 223-224
for non-aerosol hair sprays, 225
[Fragrance]
oils, production, 218
for permanent waves, 225-226
profile, 219
prototype for hair care line, 227
for pump hair sprays, 225
regulatory considerations, 229, 231-234
role of, 218
safety, 223
stability testing in products, 229
topnote, 222
Fragrance and memory, 218
Fragrance solubilizers for permanent waves, 176
Free radicals during permanent waving, 173
Free water, 18
Freehold mousse by L'Oréal, 119, 121
Friction evaluation on hair, 267-269
Fundamentals of corrosion, 139-140
Fungicidal action, 72
Future prospects for hair coloring, 214
G
Gafquat (polyquaternium-11), 79
Gafquat 734 (Polyquaternium-11), 79
Gallic acid in hair color, 211
Galvanic corrosion, 139
Gel form of hair coloring, 203
Generally Recognized as Effective (GRAE), 334
Generally Recognized as Safe (GRAS), 334
Germicidal agents, 72
Germicidal quats, 72
Glass transition temperature (Tg), 106-107
Glaze prototype, 115
Globular protein in hair matrix, 17
Glossary of styling aids terms, 105, 162-163.
Glycerin in permanent waves, 176
Glycerin(e), 82
Glyceryl ester of thioglycolic acid (GMT), mechanism of, 171
Glyceryl monothioglycolate (GMT)172
GMT (glyceryl monothioglycolate), 172
Goniophotomer for measuring hair luster/shine, 269-270
Good manufacturing practices (GMPS), 347
Gray list of Japanese cosmetic ingredients, 343
Grooming, damage from, 66

 Page 361
Grunge look. See Fashion
Guar gums, 113, 114
Guar hydroxy propyltrimonium chloride, 76
Guidelines for consumer product testing (CASRO), 310, 323-329
Guidelines for static measuring tests, 285
Guidelines for testing hair product performance, 293-294
Gray hair, 95-96, 195
color for, 208
shampoos, 224
H
Habits and practices in consumer research, 304, 306-307
Hair
body evaluation of, 285-292
bulk as measure of body, 288
changes caused by permanent waving, 171-174
conditioners, function, 4
curvature, measurement of, 278-279
follicle, 16
luster, evaluation of, 269-270
manageability, definition, 277
physical properties of, 13-32
reducing agents, 167
Hair bleaching with lasers, 214
Hair bleaching, use of a toner, 196
Hair care products, safety considerations, 335-338
Hair color, 191-215
 and aging, 195
bleaching, 196-198
changes caused by permanent waving, 171-174
conical cells, 20
consumer considerations, 212-213
cuticle, 3, 20, 66
enzymes, 210
following hair straightening, 203
following permanent wave, 203
for graying hair, 195, 208
gel type, 199
hair color, exemption from safety provisions of FD&C Act, 337
highlighting, 204-205
liquid type, 199
melanin-based, 210-211
[Hair color]
men's, 203
miscellaneous colorants, 211-212
natural colorants, 211
natural human hair, 192, 195
oxidant choice, 198-199
oxidation dyeing, 198-204
safety issues, 213-214
semi-permanent, 204-207
temporary, 207-209
very light shades, 203
Hair damage by
 bleaching, 68
chemical agents, 67-68
free radicals, 173
hair color, 67-68
heat, 276-277
permanent waves, 68, 171-174
repair with conditioners, 68
Hair damage evaluated by
alkaline solubility, 275-276
evaluated by moisture regain, 276-277
tensile properties, 270-274
Hair dyes
anti-oxidants, 199
consistency and viscosity, 199
damage from, 202-203
future prospects, 214
packaging considerations, 200
primary intermediates, 198
sensitization potential, 213
use of couplers, 198
Hair resin build-up with mousse, 134
Hair setting and styling, 105-110
Hair spray(s), 141-161
actuator selection, 157-158
additive selection, 150-151
aerosol 80% VOC prototype, 159.
Asia-Pacific considerations, 148-149
 definition, 146
desired characteristics, 147
55% VOC prototypes, 160
formulation development, 147-149
formulations, VOC considerations, 149
history of, 146, 147
marketing and positioning, 150
neutralization considerations, 151
packaging, 156-158

 Page 362
[Hair spray(s)]
plasticizer choice, 151-152.
propellant selection, 155-156
prototype formulation for Europe, 149
prototype formulations, 157-161
regulatory issues, 147-148
type and consumer preferences, 304-305
resin, neutralizer selection, 151-152
resin solids level choice, 153
valve selection, 156-157
Hair sprays, fragrance development for, 225
Hair stiffness, 15
evaluation of, 288-292
texture, 106
waving (permanent), 166-190
Hair swelling
due to permanent waves, 172
measurement of, 274--277
with water, 15
Hair type and consumer preferences, 304-305
Hair type and consumer research, 304-305
Hair waving, 166-190
Hair and wool, tensile properties compared, 270-272
Heat damage to hair, evaluation, 276-277
Heat processing of permanent waves, 177
Heat styling, damage from, 67
Heat-Activated Whisper Wave, 178
Heats On Self-Heat Foam Conditioner by Helene Curtis, 119
Helene Curtis mousses, 119
Helene Curtis Professional Salon Waves, 177
Helical ropes in -keratin, 20
Hematoxylin in hair color, 211
Henna for hair color, 211
Herbal extracts as conditioners, 84
High-humidity curl retention testing for styling products, 131-132
Highlighting hair via semi-permanent color, 204-205
History of
mousses, 119-120
polymers in hair care, 147
product performance evaluation, 261-262
Home perm, 174
Hookean region of hair's stress-strain curve, 21-24, 270-273, 292
Hydrides as hair reducing agents, 167
Hydrogen bond breaking of -keratin, 21
Hydrogen bonds, 18
Hydrogen peroxide in hair coloring, 198-199
Hydrophobic interaction, 10, 17
Hydroxyethylcellulose (HEC), 113, 114
Hydroxyethylcellulose (Natrosol), 57
2-Hydroxy-1,4-naphthoquinone (lawsone) in hair color, 211
Hydroxypropylmethylcullulose (Methocel), 57, 113-114
I
IFRA (International Fragrance Association), 223
Image analysis for evaluation of hair luster/shine, 271
Imidazolidinyl urea, 58
In-market decision tests, 308-310
INCI. See International Cosmetic Ingredient Dictionary
Indo dyes in hair coloring, 201-202
Influence of packaging on performance perceptions, 306
Ingredient considerations in regulations, 339-341
Ingredient labeling in the EEC (European Economic Community), 342
Ingredient labeling in the U.S., 342
Innovative Products Clause of CARB VOC regulations, 160-161
Instron combing test, 97
Instron tensile testing of combing force, 265-267
Instrumental evaluation of hair combability, 265-267
Instrumental testing methods, 261-302
Interfibril interactions, 106, 108
International considerations in hair spray formulation, 147-148
International Cosmetic Ingredient Dictionary (INCI), 342
International Federation of Societies of Cosmetic Chemists (IFSCC), 263
International Fragrance Association (IFRA), 223
International ingredient labeling for cosmetics, 342

 Page 363
Interval scales in consumer testing, 317
Irritation in permanent waving, 175
Isoelectric point of cuticle, 69
Isopropyl myristate, 80
Isotherm, keratin-water, 18-19
Issues that can be addressed via consumer testing, 307-308
J
Japanese
Comprehensive Licensing System of Cosmetics, 112-22
cosmetic ingredient labeling requirements, 342-343
definitions of cosmetics and drugs, 333
Ministry of Health and Welfare (MHW), 333
registration/licensing requirements, 349-351
regulations concerning cosmetic ingredients 340-341
Jet Foamer for mousses, 126
K
Karaya gum, 113, 114
Keratin, 1, 3, 13 See also -keratin
Keratin and hair follicle, 15-16
Keratin fibers, conical cells, 20
Keratinization, 2
Keratin-water isotherm, 18-19
Keratin-water system, 13-17
Kinetics of permanent waving, 168-169, 171
Kirby method of evaluating permanent waving, 278-279
L
La Forme mousse by Helene Curtis, 119
Labeling considerations for hair care products, 341-343
Laminates for ethnic hair, 254
Langmuir sorption isotherm, 18-19
Lanthionization, 240-241
mechanism of, 241
Laser augmented hair coloring, 214
Laser bleaching of hair, 214
Last Word mousse by Helene Curtis, 119
Lathering conditioner, 96-97
Latherometer for evaluation of foam, 263
Lawsone in hair color, 211
Lead acetate in hair color, 209
Leave-on creme rinse, 87
Legal claims, consumer testing for, 311-312
Life style and styling products, 116
Lipid conditioning agents, 80
Lipid substitutes, 81
Lipids, effect on during perming, 174
Liquid retention as measure of hair swelling, 275
Liquid water, 18
Localized water, 18
L'Oréal mousse, 119
Luxuriance Salon Wave, 177
M
Macrofibrils, 172
Maintenance products for permed ethnic hair, 250-257
blow drying lotions, 253-254
conditioners, 252-253
curl activator formulations, 251
laminates, 254
moisturizing spray, 250-251
Manageability of hair, definition, 277
Manufacturing considerations for
chemical relaxers 242
semipermanent hair colors, 206
Market decision tests, 308-310
Marketing considerations for hair sprays, 150
Marketing and fragrance development, 221
Material Safety Data Sheet (MSDS) for typical fragrance, 231-232
Matrix
in hair structure, 5-6
of keratin microfibrils, 15
proteins, 15, 16
Matrix Salon Waves, 177
McCutcheon's Emulsifiers and Detergents, 83
MEA (monoethanolamine) in permanent waving, 175
Measurable product characteristics by
consumer studies, 306
measurement and scaling in consumer
testing, 316-323
Measurement of shine on hair, 269-270
Mechanism of
 conditioning, 68-69
hair bleaching, 197
hair waving, 169-171
setting products' performance, 106

 Page 364
Medulla, 3, 7
Melanin, 7
decolorization in hair dyeing, 202
granules, 7
pigments, 192, 195, 210-221
Melanocytes, 7
Melanogenesis, 193-194
Men's hair color, 209
Mercaptans in permanent waving, 166-167
Mercaptide ion in permanent waving, 177-178
Mercapto ethanol, 8
Metal salts in hair color, 209
Metal sulfides in hair color, 209
Methylcellulose 57
Methylchloroisothiazolinone, 58
Methylisothiazolinone, 58
Methyl paraben, 58
Micelles 57, 73
Microbiological testing of mousses, 134
Microfibrils, 5-7, 10, 15, 17
Mildness claims for permanent waving, 175
Mixed disulfides in permanent waving, 168
Model of -keratin structure, 15-16
Moisture content of fiber (hair), 18
Moisture regain as measure of hair condition, 276-277
Monadic product tests, 313
Monoethanolamine (MEA) in permanent waving, 175
Morphology of hair, 66
Morphology of keratin, 3
Mousse(s) 118-135
additives for, 125-126
evaluation methods, 127-135
formulations, ingredients and function, 120-126
history of, 119-120
non-aerosol, 126
packaging, 126
polymers and resins used, 124
propellants for, 122-123
prototype formulations, 123, 127-130
stability testing, 134-135
theory of product performance, 120-121
use of alcohol, 122
with sunscreen, 95
Moving boundary mechanism of perming, 170
MSDS (Material Safety Data Sheet) for typical fragrance, 231-232
N
N-(3-chloroallyl)hexaminium chloride (Quaternium 15), 58
Natrosol (hydroxyethyl cellulose), 57
Natural hair color pigments, 192-194
Natural oils, composition, 70
Natural vs. synthetic fragrance, 223-224
Negroid hair, damage, 67
Neutralization of hair spray resins 151-152
Neutralization of permanent waves, effect on hair, 172-173
Neutralizer
bromate, 174
peroxide, 174
Neutralizing solution for ethnic hair perms, 250
Nitrogen blanketing in hair dyes, 199
NMR (nuclear magnetic resonance), 18-19
Nominal scales in consumer testing, 317
Nonaerosol
foam mousses, 126-127, 130
hair spray,80% VOC prototype, 158
hair sprays, fragrance development for, 225
styling mousse prototype, 130
Non-crystalline keratin, 15
Non-ionic self-emulsifying bases, 83
Non-thio reducing agents, 167
Nuclear magnetic resonance (NMR), 18
Nucleic acids, 77
O
Odor in permanent waving, 175
Ogilvie Heat-Activated Whisper Wave, 179
Ogilvie Home Permanent Waves, 178
Opticurl Salon Waves, 177
Ordinal scales in consumer testing, 317
Osmotic shock by permanent waving, 172
Osmotic swelling during perming process, 173
OTC Drugs, U.S., 333-334
OTC Monographs, 337
Overprocessing in permanent waving, 169
Oxidants in hair coloring, 198-199
Oxidation dye(s)
damage from, 202-203

 Page 365
[Oxidation dye(s)]
dyes, chemistry of, 200-202
formulation procedure, 200-214
formulation components, 200
Oxidation dyeing of hair, 198-204
Oxygen and corrosion, 140
Ozone
effects of mousse on, 136
personal care products, 136
regulation of, 136
P
Packaging
for mousses, 126
influence on consumer perceptions, 306
of hair dyes, 7-10
regulations for hair care products, 344-346
Paired comparison consumer tests, 314-315
Panthenol, 81-82
Pantothenic acid, 82
Para-hydroxybenzoates, See also Paraben(s), 58
Paraben(s), 58
Paracept. See Paraben(s)
Parity performance, consumer tests for, 309-310
Passivating corrosion inhibitors, 144-146
Patch testing for hair dyes, 213
Patent, Pert Plus, 57
PEI (polyethyleneimines), 94
Penetration of waving agents, 169
Perborates in hair coloring, 203
Permanent wave(s)
alkaline, 176-177
effect of rinsing, 172
evaluation via method of Kirby, 278-279
formulation of, 174-178
home use, 6-9
mechanism, 11
neutralizer, 174
opacifiers for, 176
regulations in Japan, 350-351
Permanent waving
bleached or tinted hair, 171
conditioners, 176
effect on amino acid content of hair, 173-174
effect on hair, 171-174
[Permanent waving]
effect on tensile properties of hair, 272-274
ethnic hair, 246-250
chemistry of, 247
post-processing treatments, 248
procedure for, 247-248
factors affecting performance, 174-178
history of, 166-167
irritation, 175
 kinetics and mechanisms, 169-171
odor, 171-172
of hair, 166-190
thermodynamics of, 167-168
Peroxide neutralizer, 174
Persulfates in hair bleaching, 196
pH
and hair damage in permanent waving, 177-178
effect on permanent wave performance, 178
of neutralizers in permanent waving, 175
of permanent waves, 174
Phenylenediamines in hair coloring, 198
Pheomelanin, 7
Pheomelanins, 7, 192-195
Phosphines as hair reducing agents, 167
Phosphoglycerides, 81
Physical properties of hair, 13-32
Planning consumer testing, 303-307
Plant derived proteins, 77
Plant extracts as conditioners, 84
Plasticization of keratin, 2, 14
Plasticizers for
hair sprays, 151-152
styling resins, 109
Polydimethylsiloxanes, 81
Polyethyleneimines in pre-shampoo conditioner, 94
Polyhydric phenols in hair color, 209
Polymer JR (polyquaternium-10), 75
Polymeric conditioning agents, general considerations, 80
Polymeric dyes for hair color, 212
Polysaccharides, 75
Polyvinylpyrrolidone (PVP), 109
Pomades, 117-118
Potassium persulfate in bleaching, 196

 Page 366
PPG-9 Diethylmonium chloride
Pre-market clearance for cosmetic products, 335
Polymers
for history of in hair products, 147
for mousses, 124-125
for polymers for conditioning, 69, 74
Polypeptide chains in hair, 15
Polyquaternium-4, 75
Polyquaternium-10, 75
Polyquaternium-24, 76
Polyquaternium-29, 76
Pre-shampoo conditioner, 94
Precisely Right Home Perm, 177
Preservation of conditioners, 85
Preservation of shampoos, 58
Primary intermediates in hair coloring, 198
Procedure for perming excessively curly hair, 247-248
Pro-vitamin B5, 81-82
Processed hair, permanent waving of, 171
Product characteristics influence performance perception, 305
Product claims and consumer testing, 311-312
Product development process - conditioners, 85-96
Product form and consumer preferences, 305
Product integrity, consumer testing for, 310-311
Product performance evaluation, definition of, 262
Product registration and licensing, 346-352
Professional salon wave, 174
Profile of fragrance (brief), 219
Progressive hair color, men, 209
Propellant
choice for hair sprays, 155-156
for mousses, 122-123
Propyl paraben, 58
Proteins, 76
plant derived, 77
Prototype
anhydrous aerosol hair spray formulation, 157
deep penetrating conditioners for ethnic hair, 253
[Prototype]
ethnic permanent wave formulations, 248-250
formulation development, 96-97
formulation evaluation, conditioners, 97-98
fragrance for hair care line, 227
hair spray formulation for Europe, 149.
lye relaxers, 242-243
mousse formulations, 123, 127-130
neutralizing shampoos, 245-246
no-lye relaxers, 244-245
pressing cremes/lotions, 239-240
styling product formulations, 110-118
Pseudo-first-order kinetics for hair waving, 171
Pseudomonas, 58
Pump hair spray(s)
 formulations, 158-160
fragrance for, 225
prototype,<80% VOC, 158
PVM/MA decadiene cross polymers, 114
PVP (polyvinylpyrrolidone), 109
Pyrrolidone carboxylic acid (PCA), 76
Q
Qualitative consumer testing, 303-304
Quantitative consumer testing, 303-306
Quantum Salon Waves, 177
Quasi-drugs in Japan, 333-334
Quaternaries
mechanism of action, 73
structure-function relationship, 72
Quaternary ammonium conditioners for perms, 176
Quaternary ammonium salts, 69, 71-73
Quaternium 15, 58
Quaternium-80, 78-79
Quaternized cellulose polymers, 76
Quaternized polymers for mousses, 124-125
Quaternized proteins, 77
Quatrisoft LM-200 (polyquaternium-24), 76
R
Radial compression as measure of hair bulk or body, 287-288
Ranking methods in consumer testing, 318
Rating methods in consumer testing, 318
Ratio scales in consumer testing, 318

 Page 367
Reduced VOC (55%) aerosol hair spray formula, 160
Reduced VOC aerosol hair spray prototypes, 159-160
Reduced VOC (55%) non-aerosol hair spray formula, 160
Reducing agents, 167
Reduction of disulfide bonds, 11
Registration of cosmetic products in the U.S., 346-347
Registration regulations in the European Union, 347-348
Regulation of hair sprays for VOC's 136-138
Regulation of VOC's by state, 137
Regulations on deceptive packaging and slack-fill, 345-346
Regulatory considerations for fragrances, 229, 231-234
Regulatory issues
for hair care products, 331-354
for hair color, 213-21
for hair sprays, 147-148
Relaxation of ethnic hair. See Chemical relaxing
Relaxation procedure for excessively curly hair, 242
Removal of oxidative dyes, 202
Repair of hair damage, 277
Research Institute for Fragrance Materials (RIFM), 223
Resiliency of hair, measurement of, 286-288
Resin(s)
buildup with mousses, 134
designed for reduced VOC hair sprays, 137-138
levels for hair sprays, 153
levels for styling products, 153
 for mousses, 124
plasticizers, 109
selection for hair sprays, 153-155
Resourcinols in hair dyes, 201
Rheological characteristics of styling products, 107, 108
RIFM (Research Institute for Fragrance Materials) 223
Rinse-off creme rinse, 86
Rosemary, 84
Ross-Miles foam evaluation procedure, 263-264
S
S-Carboxy methyl kerateine A (SCMKA), 9
S-Carboxy methyl kerateine B (SCMKB), 9
Safety considerations for permanent waves, 179
Safety evaluation, conditioners, 98-99
Safety of bromates, 174
Safety of hair care products
in European Union, 335, 337-338
in Japan, 335-336
in the U.S., 336-337
Safety of hair dyes, 213-214
Sage, 84
Salon evaluation of conditioners, 98
Salon perm, 175
Salts
effect on -keratin structure of hair, 20-21
inorganic as thickeners, 57
organic as thickeners, 57
Scale structure of cuticle, 3
Scales used in consumer testing, 317-318
Sculpting lotion prototype, 113
SDMAO (stearyldimethylamine oxide), 71
SEB. See Self-emulsifying bases
Sebum accumulation, 40, 41, 59
Self-emulsifying bases (SEB) 83
Self-emulsifying wax sunscreens in conditioners, 84
Self-timing in permanent waving, 168, 175
Semi-permanent hair color, 204-207
drawbacks, 207
formulation, 206-207
Sensitization potential of hair dyes, 213
Sequential-monadic consumer tests, 313-314
Sequestering agents in hair dyes, 199
Set retention, 280-283
Setting lotion prototype, 111
Setting products for ethnic hair, 255-256
Setting or styling aids, 105-110
Shampoo
for detangling for Afro-American hair, 252
for excessively curly (ethnic) hair, 251-252
fatigue, 40, 59

 Page 368
[Shampoo]
foam evaluation, 263-264
for neutralizing after chemical relaxation, 245-246
Shaping spray prototype, 112
Shelf-life of cosmetic products, regulations on, 342-343
Shine evaluation on hair, 269-270
Shine products, 117
Silicones, 69, 75, 77-78
aminofunctional, 78
cyclic, 81
volatile, 81
Simulated test market consumer testing, 315-316
Slack-fill, packaging regulations, 345-346
Society of Cosmetic Chemists (SCC), 261
Sodium borate in permanent waves, 175
Sodium sulfite in hair dyes, 199
Sodium thioglycolate, effect on hair, 172
Solid oxidants in hair coloring, 203
Solvent sorption into hair, 17-21
Soy proteins, 77
Sphingolipids, 81
Split ends, 4
Spray gel prototype, 115
Springiness of hair, measure of body, 278-279
Spritz, pump prototype formulation, 161
Stability evaluation, conditioners, 98
Stability testing of mousses, 134-135
Standard sizing for cosmetic products, 344
Starch derivatives, 75
Static and combing, 283-285
Static reduction, 80
Stearalkonium chloride, 71
Steartrimonium chloride, 77
Steartrimonium hydrolyzed animal protein, 77
Stearyldimethylamine oxide, 71
Stiffness of hair
measurement of, 288-292
source of, 15
Stop action processing in permanent waving, 175
Straightening of ethnic (curly) hair, 239-250
chemical relaxing, 240-246
pressing cremes/lotions, 239-240
[Straightening of ethnic (curly) hair]
pressing, 239-240
Stress cracking in aerosols, 139-140, 142
Stress-strain curve
of fibers, 21-24
hair properties, 21-24
for hair tensile properties, 271
Stretching stiffness, evaluation of, 291-292
Structure of hair follicle, 15-16
Style arrangement of hair, 277
Style retention, 278-279
Styling aid(s)
appliances, damage from, 67
and fixative products, 105-165
glaze prototype, 115
mousse prototypes, 127, 129
polymers, 109
product prototype formulations, 110-118
proteins, 109
PVP, PVP/VA, PVP/dimethylaminoethyl methacrylate, 109
set retention measurements, 280-283
with shine prototype, 128
spritz prototype, 161
techniques, 106, 107
Styling aid(s), products, 105-165
effect of humidity, moisture, 110
and fashion trends, 116
future needs, 161
mechanism of action, 106
old vs. new, 116
Subjective evaluation of hair treated with mousse, 132-132
Sulfhydril disulfide interchange, 8, 11
Sulfhydryl disulfide interchange with supercontraction, 26-27
Sulfhydryl groups, 8
Sulfitolysis, 11
Sulfur-sulfur cross-links in permanent waving, 167
Sunlight damage to hair, 67
Sunscreens in hair products, 84
Supercontraction, 25-27
via salt effects, 21, 25-27
Superoxide in hair waving, 173
Surface chemistry, 73
Surface conductivity of keratin fibers, 14

 Page 369
Surfactant(s), 69
choice in mousses, 123-124
in hair coloring, 199
selection for temporary hair colors, 208
Swelling
of -keratin cortex, 17
of hair, 17
Synthetic polymers, 75
T
Tackiness in styling products, 109
Tallowdimonium propyltrimonium dichloride, 74
Teltech Technical Knowledge Service, 86
Temperature, effect on permanent wave performance, 178
Temperature effects during semi-permanent hair coloring, 207
Temperature effects on hair, reversible, 23
Temperature and sulfhydryl-disulfide interchange, 24-27
Temporary hair coloring, 207-209
Tensile properties of hair, evaluation of, 271-274
Tensile tester for combing force evaluation, 265-267
Tensile testing apparatus, 272-273
Testing, simulated test markets, 305-306
Testing measures and procedures, 142-144
Test markets, 316
Test methods for corrosion, 142-144
Test methods for performance evaluation, 293-294
Texture of hair, 106
Tg (glass transition temperature) of a polymer, 106-107
TGA (thioglycolic acid), 172
Theory of corrosion and its control 138-146
Therma Vantage Salon Waves, 177
Thermodynamics of permanent waving, 172
Thickeners for conditioners, 82
Thickening agent, 57
Thioglycolate, 166-170
Thioglycolic acid, 8, 166-167
ammonium salt of, 166
derivatives, 166-167
glyceryl ester of, 166
Thiolate anion concentration, in permanent waving, 178
Thiolate anion in hair waving, 170
Time, influence on consumer test results, 307
Toner in hair coloring, 203
Toners in hair bleaching, 196
Torsional braid analyzer, 291-292
Torsional pendulum, 290
Torsional stiffness of hair, 290-292
Toxicology of hair dyes, 213-214
Tricetylmonium chloride, 81
Triglycerides, 80
Tryptophan, 8
Two-step hair coloring, 203
Tyrosine, 7
 in hair color, 193, 210
U
Urea peroxide in hair coloring, 198-199
U.S. Fair Packaging and Labeling Act (FPLA), 341-342
U.S. Food and Drug Administration (FDA), 334
U.S. Food Drug and Cosmetic Act, 332
U.S. Over-the-Counter (OTC) Drug Review, 333-334
US regulations concerning cosmetic ingredients, 339
UV-absorbing compounds, 84
V
Valence styling mousse L'Oréal, 119
Valves for hair sprays, 156-157
Vapor phase corrosion inhibitors, 144-146
Vapor tap valves, 157
Vinyl pyrrolidone, 75
Viscosity control in hair dyes, 199
Viscosity modifiers, shampoos, 57
VOC reduction
in hair sprays, 136-138
for mousses, 135-136
VOC regulations
Innovative Products Clause, 160-161
for mousses, 120
by state, 137
Volatile silicones, 90-92
Volume of hair as measure of body, 285-286, 288
Voluntary registration in the U.S., 346-347
W
Walker, C.J., 239