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Basics of Cosmetic Chemistry Section 3
Basics of Cosmetic Chemistry Section 3
Oils of Nature
Natural oils, fats and waxes, and the processes that turn these
primary ingredients for cosmetic formulations and surfactants.
1. Cosmetic Elegance
2. Label Name (Marketing)
3. Unique Chemistry
4. Unique Components
Acids
Antioxidants
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Oils of Nature Beginning Cosmetic Chemistry
One could well assume that since natural oils have been around for a long period
of time, that there is nothing additional to discover about their use. This assumption
is incorrect. US Patent Application 20050069516, filed March 31, 2005 discloses a
product for application to the hair, comprising: (i) a first hair conditioning agent,
wherein said first hair conditioning agent penetrates into the core of the hair; (ii)
a second hair conditioning agent, wherein said second hair conditioning agent
penetrates into the cortex region of the hair but does not substantially penetrate
into the core of the hair; and (iii) a third hair conditioning agent, wherein said
third hair conditioning agent remain on the hair surface and does not substantially
penetrate into the cortex of the hair; wherein said product comprises advertising
stating that said first hair conditioning agent, said second hair conditioning agent,
and said third hair conditioning agent condition different regions of the hair. The
patent application goes on to teach that examples of first hair conditioning agents
include, but are not limited to, avocado oil, apricot kernel oil, olive oil, sesame oil,
and coconut oil, Examples of second hair conditioning agents include, but are not
limited to, meadowfoam seed. Examples of third hair conditioning agents include,
but are not limited to sunflower oil, and almond oil.
Many patent applications relate to synergistic effects between formulation ad-
ditives and many natural oils. With the growing interest in green products, one can
reasonably expect that the use of natural oils in formulations will increase.
CH2-OH O CH2-OC(O)-R
| || |
CH-OH + 3 RC-OH ———> CH-OC(O)-R + 3 H2O
| |
CH2OH CH2-O-C(O)-R
Glycerin Fatty Acid Triglyceride Water
Triglycerides are a very important class of raw materials for making fatty deriva-
tives, including surfactants. Saponification is a general term to define the chemical
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Beginning Cosmetic Chemistry Chapter 12
reaction that breaks the ester linkage. When the triglyceride is saponified to make
a surfactant, such as soap, glycerin is liberated. When a wax is saponified, a fatty
alcohol is liberated. Thus, the types of products that can be made using the two
types of materials are quite different functionally. Glycerin, produced as a by-
product of saponification, is water-soluble and fatty-insoluble. The fatty alcohol
produced as a by-product of the saponification of a wax is water-insoluble and
generally fatty-soluble.
Differentiating among triglycerides: Normally, a physical property such
as melting point is used to differentiate among the members of a chemical fam-
ily. Because oils, fats, butters and waxes are complex mixtures of homologues of
similar chemical structures, it is difficult to obtain a true melting point. As the
lower molecular weight fractions melt, they act as solvents to dissolve the higher
molecular weight products. This results in a very wide melting “range” for these
compounds. For this reason, titer point is generally determined on fats, oils, waxes
and butters.
The titer is defined as the re-solidification point of the melted oil, fat, butter or
wax. The procedure is to heat the product to be tested until it is completely liquid,
then to slowly cool with stirring. This process is done until the temperature stays
constant for 30 seconds, or begins to rise. The titer point is the highest temperature
indicated by this rise.1
Fats have a titer point of greater than 40.5°C. Oils have a titer point of less than
40.5°C. Butters have a titer between 20–40.5°C.
Oils are liquid at room temperature. We now use this word to describe any
compound that is a liquid and is insoluble in water. As a result, jojoba is referred
to as an oil, despite the fact it is really a liquid wax. It is therefore very important
to realize that the terms wax and triglyceride define the chemical nature of a com-
pound; the terms oil, butter and fat define a physical property.
Classification: The Cosmetic, Toiletry & Fragrance Association (CTFA) now
requires the genus and species of the plants or insects that produce a given wax,
oil, butter or fat and all products that are derived from the various oils, fats, butters
and waxes. This is due, in part, to the European Union’s use of the Latin names for
ingredient listings. This information helps the formulator understand the source
of the fatty portion of the surfactant.
Triglycerides can be classified according to their carbon chain lengths. For
instance, in Table 12.1 the triglycerides are grouped by carbon chain lengths less
than C-18, equal to C-18, and greater than C-18.
Oil Preparation
The process that allows for the transformation of a plant seed into a clear, low-
odor oil suitable for cosmetic use is a process that we generally take for granted. The
properties of the oil are determined by the plant source and the processing used.
The oils discussed in this article are referred to as “vegetable oils.” This distinc-
tion differentiates them from the “essential oils” that are steamed out of a variety
of plant parts, including flowers, leaves, peels and some seeds. These essential
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Oils of Nature Beginning Cosmetic Chemistry
oils, which often have an attractive aroma, are not triglycerides. Instead, they are
usually “isoprenoids,” which indicates that they come from a different chemical
pathway in plants. Plants store vegetable oils (triglycerides) as energy sources for
seeds when they germinate.
Pressing: Steam works well to extract essential oils like coriander oil, but it does
not work well for triglyceride oils. Triglyceride and wax ester oils can be squeezed
out of seeds using a turning screw that presses the mashed-up seed against a metal
barrel with slits in the side. The oil and some fine particles squeeze out through the
narrow slits. This operation would be called an oil expeller or seed oil press.
The oil from the seed oil press can be filtered and called “virgin” oil, especially
if it isn’t heated up to get more oil out. The oil from the seed oil press can also be
called “crude” oil. Alternatively, oil can be dissolved in solvent, which can then be
evaporated, leaving the extracted oil.
Often, seeds are flaked to increase surface area. The seeds are processed into
thin flakes before pressing or solvent extraction. The flaking improves oil yield by
breaking open the small oil pockets in the seeds. Sometimes the seeds are heated
before flaking so that the proteins in the seed won’t break down the oil or other
things in the seed. The preheating is also called preconditioning. The oil comes out
more easily if it is hot, but excessive heat damages the oil quality.
Sometimes the seeds are crushed and formed into pieces called “collets” that
have lots of holes or openings. This step also is done before solvent extraction so
the oil can flow out more easily. Solvent extracted oil with some solvent still in it
is called the “miscella.”
Crude oil can usually be good enough for chemical uses. In a process called
“winterization,” a well-filtered “virgin” oil can be kept cold to remove any solid
waxes that might crystallize out.
Many cosmetics applications require cold-pressed, virgin oil. On the other hand,
some seeds are too low in oil to economically remove the oil by pressing. In any
case, once you have the crude oil, you can move onto refining.
Refining: Refining is done by filtering the oil through clay or silica (like fine
sand) that can remove color. In an operation called “degumming,” alkali in water
is added to the oil and some ingredients, especially fatty acids and “phospholipids,”
go into the water or settle out or are filtered out. Finally, in an operation called
deodorization, steam can be passed through the oil to remove odor. This step also
breaks down oxygen attached to the oil, which might lower oil quality.
After all of this refining, the oil should be light in color, odorless, and have no
oxygen breakdown products or solid wax. The customer’s requirements for the oil
in terms of color, odor and the like will determine the number of steps needed to
get an acceptable product. Consequently, the amount of useable oil you have left
after refining is often related not only to the amount of crude oil present in the
seed, but is also related to the requirements of color, titer point and properties you
impose for the final oil.
Functionality: The oils that are commonly used in cosmetic products are com-
plex mixtures of different triglycerides, but also contain various other components
that are useful. For example, olive oil can be processed to contain highly desirable
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Beginning Cosmetic Chemistry Chapter 12
CLASS 3 Animal-derived products rich in carbon chain lengths greater than C-18
Number Name Source CAS Number Predominant species
4. Beeswax Cera alba 8006-40-4 C26 wax
5. Shellac Wax Shellac cera 97766-50-2 C30 wax
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Oils of Nature Beginning Cosmetic Chemistry
A very important use for natural oils is food. When this market segment is
removed from considerations, a handful of oils make up the majority of product
consumed for industrial application.
ALL OTHER 6
CASTOR 1
LINSEED 4
TUNG 5
RAPESEED 5
SOYBEAN 9
COCONUT OIL 20
TALL OIL 50
0 10 20 30 40 50 60
Figure 12.2. Relative percentages of selected oils used for non-food purposess
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Oils of Nature Beginning Cosmetic Chemistry
Derivatives
Natural oils are important raw materials for making a variety of downstream
products. These include fatty alcohols, fatty acids, and methyl esters. These inter-
mediates can be fractionated into specific carbon number products (for example
C12 or lauryl alcohol), or not fractionated and remain coco alcohol.
Fatty alcohols, fatty acids, and methyl esters are in turn are reacted with other
materials to become surfactants, See Chapter 11 “Surfactant Science” for more
details on these materials.
Wax esters: Wax esters are defined as esters of long-chained acids that have
been reacted with long-chained alcohols. Other chemicals are called waxes if they
possess tactile properties similar to a true wax. An example is beeswax. Polishes
are a major application area for this class of materials. Wax esters have two fatty
groups. One is contained in the alcohol portion of the molecule, the other is in
the acid group. Esters are synthesized by the reaction of an organic acid with an
organic alcohol (Figure 12.3). Esterification is the reverse of saponification, in
that ester linkages are formed.
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Beginning Cosmetic Chemistry Chapter 12
O O
|| ||
R-C-OH + R’OH ————> RC-OR’ + H2O
Acid Alcohol Ester Water
Methyl esters: Triglycerides may be easily turned into methyl esters by reaction
with methanol and catalyst. Base catalysts are preferred. As the reaction proceeds,
the reaction mixture turns hazy as glycerin is liberated. Once complete, the excess
methanol is distilled off, glycerin is removed from the bottom after it settles, and
the methyl ester is distilled into its fractions.
The methyl ester formed by the reaction, if not distilled, is still referred to by the
oil name (for example methyl cocoate). However once fractionated, the material is
named by carbon distribution. Methyl cocoate is fractionated into methyl laurate,
methyl myristate, and so on. The triglyceride source is lost in the name of the methyl
ester. The names for the common alkyl groups are given in Table 12.4.
Natural Petroleum-Based
Triglycerides Ethylene Alpha-olefin
Methyl Ester
See Chart 5
Ether Ether
Sulfosuccinate Sulfate Phosphate Sulfate Phosphate
Alkyl Ether
Glycosides Fatty Alcohols Ethoxylates Sulfosuccinate
Ether
Esters Carboxylates Ether Carboxylate
Ester
Esters
Sulfates
Ester Phosphates
Sulfates
Amphoterics Phosphobetaine
Sulfobetaine
Complex Esters
Quats Imidazoline
Betaines
Amphoteric
Ester
Betaine
Amido Amine
Amine Oxide Sorbitan Esters Ethoxylated Sorbitan
Esters
Quats
Sulfobetaine Phosphobetaine
Methyl
Alkanomide
Ester
Alcohol
Conclusion
The preparation of useful surfactants in the personal-care market is dependent
upon several factors. These include the process used by the converter of the natural
materials into intermediates, the converter of the intermediates into surfactants, and
the skill of the formulator to make products that deliver a benefit to consumers. The
importance of the selection of the raw material feedstock is also an important factor
in the preparation of products that all is too often is overlooked. The formulator of
products should consider all of these factors in preparing products.
References
1. AJ O’Lenick, D Steinberg, K Klein and LaVay, Oils of Nature, Allured Publishing Corp,
Carol Stream, IL (2007)
2. AJ O’Lenick, Surfactants Chemistry and Properties, Allured Publishing Corp, Carol
Stream, IL 13–15 (1999)
Chapter 13
Understanding Emulsions
A definition of emulsions and their effect on formulations.
A t some point in your career as a formulator, you will need to combine incom-
patible materials into one product. Many methods have been developed for
accomplishing this task, but none has been employed more than emulsions.
Definitions
Various definitions for emulsions have been suggested, some simple, others
quite complex. In this chapter, we will consider an emulsion to be any heteroge-
neous system that has at least one immiscible or barely miscible liquid dispersed in
another liquid in the form of tiny droplets, like an insoluble oil dispersed in water.
For the interested reader, a more rigorous definition can be found in Becher’s
Encyclopedia of Emulsion Technology.1
Emulsions are the most common type of delivery system used for cosmetic
products. They enable a wide variety of ingredients to be quickly and conveniently
delivered to hair and skin. The types of emulsions used for cosmetic products are
typically semisolid materials consisting of an aqueous (hydrophilic) portion and an
oily (hydrophobic) portion. These two portions make up the internal and external
phases of the emulsion. The internal phase is composed of the materials that make
up the tiny dispersed (or emulsified) droplets, while the external phase is made up
of the rest of the materials. Usually, the external phase (also called the continuous
phase) is the more abundant of the two.
O/W and w/o: The most typical emulsion is one in which an oil is dispersed
in water. Understandably, this type is called an oil/water emulsion (o/w). Another
type of simple emulsion is a water/oil emulsion (w/o), in which water is emulsified.
Whether an emulsion is the o/w or w/o type depends on many factors, including
the concentration of each material in the system, the type of emulsifier and the
processing steps used to create the emulsion.
Size: The particles that make up the emulsion’s internal phase are polydisperse
(meaning they have variable sizes), and their average size is often used for emul-
sion classification. For example, if their average diameter is less than 100 Å, it is
referred to as a micellar emulsion. A particle diameter of 100–2000 Å is known as
a microemulsion. Larger particles make up macroemulsions, which are the most
common type used in cosmetic product formulations.
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Understanding Emulsions Beginning Cosmetic Chemistry
Emulsion Components
Because an emulsion is a mixture of incompatible ingredients, one might wonder
how they stay together. In reality, they do not. One of the essential characteristics
of an emulsion is that eventually, given enough time or energy, it will separate into
its original phases. However, cosmetic products are not meant to last forever, and
the true challenge for the cosmetic formulator is designing systems that will remain
stable over the useful life of the product. One way to make this task easier is to have
a good working knowledge about the characteristics of each part of an emulsion
including the oil phase, the aqueous phase and the emulsifier.
Oil phase: This phase is composed of nonpolar compounds that are generally
not compatible with water. These include materials such as fats, oils and waxes
and all of their derivatives, including fatty alcohols and acids, esters, hydrocar-
bons, glycerides and silicones. For cosmetic applications, these materials provide
numerous benefits. On skin, they act as emollients, providing an appealing feel.
They can also soften and improve the skin’s moisture retaining properties because
they leave behind a water repellent film. When used on hair, they provide con-
ditioning to aid in styling and shine to improve the hair’s appearance. While the
components of the oil phase provide many benefits, they are formulated into an
emulsion because, in concentrated form, they can give too much of a good thing
and make hair oily or tacky.
Aqueous phase: This part of an emulsion is made up of water and all the other
hydrophilic materials in the system. These materials can be humectants like glycerin
or propylene glycol, water soluble polymers which thicken or provide conditioning,
preservatives, colorants, electrolytes or feature ingredients such as plant extracts
or hydrolyzed proteins. The aqueous phase has the added benefit of reducing the
greasy feel of the oil phase and reducing the cost of the overall formulation.
Emulsifiers: These compounds make emulsions possible by stabilizing the
dispersion of the internal phase in the continuous phase. They are the surfactants
that reduce the interfacial tension between the two phases. Typical emulsifiers
are molecules that have a hydrophilic portion and a lipophilic portion. They are
classified as either anionic, cationic, nonionic or amphoteric, depending on the
nature of their water soluble head group. Stearic acid is an example of an anionic
emulsifier. It has a long, lipophilic carbon chain (tail) attached to a hydrophilic
carboxylic acid group (head).
When placed in water, emulsifiers have a tendency to align themselves in a
manner that reduces the interaction between their hydrophilic and lipophilic ends.
If enough emulsifier is present, spherical structures called micelles can be formed.
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Beginning Cosmetic Chemistry Chapter 13
Emulsion Structures
While micelles are a common
structure found in emulsions, they
are only one of many possibilities.
The exact structure adopted by
any composition depends upon
the component concentrations,
their solubility characteristics and
the method by which they are pro- Figure 13.1. Emulsion micelle
duced. At higher concentrations, the
internal phase can pack itself into
long, hexagonal columns. At even higher concentrations, lamellar structures, which
are planar sheets of surfactant, are formed. These liquid crystalline structures are
similar to the lipid bilayers common in biological membranes. They are typically
employed in skin products and are said to give more effective results.
Emulsion Stability
As most chemists know, oil and water do not mix. If they are put together in a
container and shaken, the oil may break into smaller particles and disperse for a
few moments. However, when the shaking stops, the dispersed oil particles quickly
combine and separate from the water. When an emulsifier is added to this system,
the oil particles stabilize because they are incorporated into the lipophilic interior
part of the micelles. In this way, the oil particles are shielded from each other and
their coagulation is inhibited, resulting in a stable emulsion.
Although emulsifiers help stabilize the interaction between the oil and water
phases, emulsions are still inherently unstable according to the second law of
thermodynamics; they eventually will separate. The speed at which this occurs or
how complete the separation is depends on the composition of the emulsion. For
instance, a system of mineral oil and water will form a macroemulsion when agitated
that immediately separates upon standing. If a small amount of an emulsifier such
as polysorbate 80 is added, the system may remain stable for a few days. Other
emulsions with different oil phases and emulsifiers can remain stable for years but,
in theory, every emulsion will separate.
Emulsion Destabilization
Investigation into the process of emulsion destabilization has revealed four
primary mechanisms. They are creaming, flocculation, coalescence and inversion.
Although explained separately here, they occur simultaneously in real life emul-
sions (Figure 13.2).
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Understanding Emulsions Beginning Cosmetic Chemistry
Creaming: The droplets in an emulsion have varying densities and are, there-
fore, prone to a destabilizing process known as creaming. In this process, the less
dense particles tend to rise to the top. The resulting emulsion has two sections,
one having more of the internal phase and the other having more of the external
phase. A classic example is unhomogenized milk in which the fatty cream rises to
the top. Creaming represents a less serious stability problem then, because none
of the particles actually combine. It can be reversed by agitation.
Flocculation: During this process, the internal phase droplets form a weak,
reversible association. This process is typically caused by inadequate surface
charge on the micelles, which reduces the repulsive force between them. The two
particles remain distinct, and they do not change in size. This development can be
demonstrated by taking two billiard balls and touching them to each other. While
they are touching, an association is formed. However, it can easily be disrupted
by removing one of the balls. In the same way, flocculation in an emulsion can be
reversed by providing agitation to the system. For this reason, flocculation is also
a less serious threat to emulsion stability.
Coalescence: When two internal phase droplets get close enough, they can
combine to form one larger particle. This process represents a more serious sta-
bility problem because it is irreversible. If enough particles coalesce, the result is
a complete separation of the two phases. A similar phenomenon called “Ostwald
ripening” also happens in emulsions. This process, first described by Wilhelm
Ostwald in 1896, involves the tendency of smaller particles to combine with larger
particles producing even larger particles and less stability. From a thermodynamic
standpoint, molecules at the surface of a particle are energetically less stable than
those packed in the middle. For smaller particles the ratio of surface to internal
molecules is much higher than those of larger particles. Smaller particles will thus
combine with larger ones to reduce the overall energy of the system. This process
can eventually lead to phase separation.
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Beginning Cosmetic Chemistry Chapter 13
The HLB and 3-D HLB systems are not the only ones that are available for
formulators. Because it is known that a material’s ability to emulsify changes with
temperature, the Phase Inversion Temperature (PIT) system was developed. It is
very similar to the HLB except that it rates materials based on the temperature at
which the emulsifier causes o/w emulsions to invert to w/o emulsions. Another, more
sophisticated system is known as the Cohesive Energy Ratio (CER) system. This
system rates materials on the basis of thermodynamic principles. It is particularly
useful for many anionic surfactants.
Conclusion
The usefulness of emulsions for cosmetic products has been demonstrated by
their continued use since the dawn of time. They will undoubtedly be an important
product form for many years to come. While emulsions are an indispensable tool
for formulators, it is unfortunate that more attention is not given to them in the
typical college chemistry curriculum. Perhaps this review will inspire the reader
to learn more about these interesting systems.
References
1. P Becher, Encyclopedia of Emulsion Technology, Vol 3, Marcel Dekker, NY (1996)
2. Cosmetic Bench Reference, Allured Publishing, Carol Stream, IL (1998)
3. Harry’s Cosmeticology 8th edition, CHS Press, New York (2000)
4. P Becher, Emulsions: Theory and Practice, Reinhold Publishing Corp, NY 2 (1965)
5. W Griffin, J Soc Cos Chem 1 311 (1949)
Additional References
1. HW Hibbot, Handbook of Cosmetic Science, Macmillan Company, NY 175 (1963)
2. L Prince, Microemulsions Theory and Practice, Academic Press Inc, NY 1–2 (1977)
3. C Fox, An introduction to multiple emulsions, Cosm Toil 11(101) 101–112 (1986)
4. G Whalley, Surfactant structures and micelles, Happi 8 62–6 (1997)
5. P Becher, Encyclopedia of Emulsion Technology, Marcel Dekker, NY 133 (1983)
6. GM Eccleston, Application of emulsion stability theories to mobile and semisolid o/w
emulsions, Cosm Toil 11(101) 73–6 (1986)
7. MM Rieger, Stability testing of macroemulsions, Cosm & Toil 5(106) 59 (1991)
8. GM Eccleston, Application of emulsion stability theories to mobile and semisolid o/w
emulsions, Cosm Toil 11(101) 135 (1986)
9. C Fox, An introduction to multiple emulsions, Cosm & Toil 11(101) 109-11 (1986)
10. K Gallagher, Microemulsion gels: a formulatorís guide, Happi 2 58–64 (1993)
11. G Dahms, Stabilization and delivery of vitamins and enzymes using multiple
emulsions, J Soc Cosm Chem 47 (4) 278 (1996)
12. A O’Lenick and J Parkinson, Applying the three dimensional HLB system, Cosm Toil
112(11) 59–64 (1997)
13. L Prince, Microemulsions Theory and Practice, Academic Press Inc, NY (1977)
Chapter 14
Silicone Chemistry
Silicones are increasingly important in cosmetic formulations,
and silicone science is an area where many new developments
are being made.
SiO2 + C → Si + CO2
The metamorphosis of quartz into Si metal is the first step in a series of steps
that ultimately provide compounds useful in the personal care market. Figure
14.1 shows the quartz and silicon.
Figure 14.1. Quartz to Silicon. The top left shows SiO,2 which is converted into Si.
© 2005 Thomas O’Lenick Used with permission
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Silicone Chemistry Beginning Cosmetic Chemistry
The term “silicone” is reserved for materials that contain a Si-O-Si linkage.
These materials are well known and are used extensively in the personal care area.
The difficulty is that the term silicone is applied to a wide range of materials rang-
ing in solubility from insoluble in both water and oils, to soluble in water or oil.
To complicate things further, the molecular weight of the polymer will determine
if the resulting product is a wetting agent, a conditioner a gum or a film former.
Silicones are likely the most rewarding class of raw materials to add to a formula-
tion because of the unique attributes these polymers confer and at the same time
one of the most frustrating classes of compounds with which to work because of
the variability of properties available within the class.
Silicone compounds have been known since 1860, but were of little commercial
interest until the 1940s. Over the years, silicone compounds have received growing
acceptance in many personal care applications. In fact it has been said that four of
10 new personal care products introduced in the 1990s have silicone in them.
When the term “silicone is applied to a compound, one thinks of silicone fluids.
While historically silicone fluids are the oldest derivative used in personal care ap-
plications, they are used only sparingly in our industry. The early work with silicone
fluids in our industry has resulted in Silicone Misconceptions, shown in Table 14.2.
While specific product classes that have some of the attributes shown in the table
exist, so do a plethora of materials that are likewise silicone compounds that have
different properties. Understanding the structure/function relationship in selecting
silicones is key to efficient formulations.
Group Opposites
Since water, mineral oil and silicone oil are mutually insoluble, the terms “hy-
drophilic and “hydrophobic” need to be expanded to include silicone compounds.
The following terms have been recommended1;
CH3
CH3
CH3
O1/2
CH3
–O1/2
–O1/2
If the Si atom has anything other than CH3 on it, it is referred to as a “*” com-
pound. It is the Si-H materials that are reacted with vinyl groups in the function-
alization reaction that allows for organofunctional silicone polymers.
CH3
CH3
CH3
H
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Beginning Cosmetic Chemistry Chapter 14
O1/2
H3
Construction Examples
There are three classes of compounds based upon their construction:
CH3—Si–O—(—Si—O–)50—(–Si—O–)10—Si—CH3
R—Si–O—(–Si—O–)10—Si—R
R—Si–O—(—Si—O–)50—(–Si—O–)10—Si—R
It should be clear that each class of compound will have different properties
based upon its construction.
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Silicone Chemistry Beginning Cosmetic Chemistry
The “construction” is the molecular knitting machine that makes the silicone
backbone.
The “Functionalization” is the “Lego Set” of appendages that provide
functionality.
“Construction” without “Functionalization” results in silicone homopolymers
(fluids).
“Functionalization” is not possible without “Construction”.
PEG/PPG Dimethicone
Consider the reaction:
CH3—Si–O—(–Si—O–)a—(O–Si—)b—Si—CH3 + a CH2=CH–CH2O(CH2CH2O)8H m
CH3—Si–O—(–Si—O–)a—(O–Si—)b—Si—CH3
O(CH2CH2O)8H
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Beginning Cosmetic Chemistry Chapter 14
Regardless of the value of “a” and “b” the INCI name is PEG-8-dimethicone.
The question then becomes is PEG-8-Dimethicone water-soluble? The answer
is it depends upon how many “a” and “b” units there are in the molecule (Table
14.4).
3. Derivitization
In instances where the functionalization results in a molecule that has a reactive
group present, subsequent chemistries can be applied to that group. An illustrative
group is the PEG-8-dimethicone
CH3—Si–O—(–Si—O)a—(–Si—O)b—Si—CH3
O–(CH2CH2O)8H
Since the OH group is a carbanol, it can be reacted in many of the same ways
the hydroxyl group in lauryl alcohol ethoxylates can be reacted. These reactions
are called derivitization. Many reactions have been conducted using products of
construction and functionalization as reactants. These are the derivative silicones.
The attached table is an example of products made using this powerful technique.
In fact an entire world of compounds that are analogous to hydrocarbon based
surfactants are available in the world of silicone surfactants. Many of these materials
were patented; some still remain covered by patents.
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Silicone Chemistry Beginning Cosmetic Chemistry
Anionic Compounds
Hydrocarbon Products Silicone Products
Phosphate Esters Silicone Phosphate Esters5,6
Sulfates Silicone Sulfates7
Carboxylates Silicone Carboxylates8,9
Sulfosuccinates Silicone Sulfosuccinates10,11
Cationic Compounds
Hydrocarbon Products Silicone Products
Alkyl Quats Silicone Alkyl Quats12
Amido Quats Silicone Amido Quats13
Imidazoline Quats Silicone Imidazoline Quats14
Amphoteric Compounds
Hydrocarbon Products Silicone Products
Amino Proprionates Silicone Amphoterics15
Betaines Silicone Betaines16
Phosphobetaines Silicone Phosphobetaines17
Nonionic Compounds
Hydrocarbon Products Silicone Products
Alcohol Alkoxylates Dimethicone Copolyol
Alkanolamids Silicone Alkanolamids18
Esters Silicone Esters19,20,21,22
Taurine Derivatives Silicone Taurine23
Isethionates Silicone Isethionates24
Alkyl Glycosides Silicone Glycosides25
CH3—Si–O—(–Si—O)a—(–Si—O)b—Si—CH3
O–(CH2CH2O)8—C(O)–CH2CH2 –COH
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Beginning Cosmetic Chemistry Chapter 14
CH3—Si–O—(–Si—O)a—(–Si—O)b—Si—CH3
O–(CH2CH2O)8—C(O)–CH2CH2 –COH
CH3—Si–O—(–Si—O)a—(–Si—O)b—Si—CH3
O–(CH2CH2O)8—C(O)–CH2CH2 –C(O)O–
CH3(CH2)15—N+—(CH3) 3
This complex has unique properties, in that it reduces irritation of the quat by
more than an order of magnitude.
25% Active Testing
Product Eye Irritation*
Cetyltimonium Chloride 106.0
Cetylsil S 8.3
The Cetylsil S product is low irritation, does not build up and has very low
irritation properties.
References
1. www.siliconespectator.com
2. AJ O’Lenick., J of Surfactants & Detergents, 3 (2) 229 (2000)
3. WC Griffin,, J Soc Cosm Chem, 1, 311 (1949)
4. AJ O’Lenick et al., Cosm & Toil, 111 (10) 37 (1996)
5. AJ O’Lenick et al., Cosm & Toil, 112 (11) 59 (1997)
6. US Patent 5,149,765 to O’Lenick (September 1992)
7. US Patent 4,724,248 to Dexter et al. (February 1988)
8. US Patent 4,960,845 to O’Lenick (October 1990)
9. US Patent 3,560,544 to Haluska (February 1971)
10. US Patent 5,296,625 to O’Lenick (March 1994)
11. US Patent 4,717,498 to Maxon (January 1988)
12. US Patent 4,777,277 to Colas (November 1998)
13. US Patent 5,098,979 to O’Lenick (March 1992)
14. US Patent 5,153,294 to O’Lenick (October 1992)
15. US Patent 5,196,499 to O’Lenick (February 1993)
16. US Patent 5,073,619 to O’Lenick (December 1991)
17. US Patent 4,654,161 to Kollmeier (March 1987)
18. US Patent 5,237,035 to O’Lenick (August 1993)
19. US Patent 5,070,171 to O’Lenick (December 1991)
20. US Patent 5,070,168 to O’Lenick (December 1994)
21. US Patent 4,724,258 issued to Dexter (February 1988)
22. US Patent 6,338,042 to O’Lenick (December 2002)
23. US Patent 5,280,099 to O’Lenick (January 1994)
24. US Patent 5,300,666 to O’Lenick (April 1994)
25. US Patent 5,120,812 to O’Lenick (June 1992)
Chapter 15
Creating Colorful
Cosmetics
An introduction to colorants in the personal care industry.
A dding color to the cosmetic products has many implications. It can be aimed to
hide the sluggish yellowish hue of some bases, or to fulfill the esthetic require-
ments for increased consumer attraction, or, finally, to temporarily color the skin
surface. Indeed, this task is surprisingly complicated and difficult. It is important for
chemists to not only understand the esthetics of color and its impact on consumer
perception, but also to be watchful for problems with color stability/compatibility
in formulations. They must be knowledgeable of the associated regulatory issues,
on a worldwide basis, too.
New chemists are often surprised that colorants are a separate and complex
step in a formulation process. As an introduction to colorants, this chapter will
describe the basic chemistry of these materials, the key regulatory issues associated
with the use of colorants and fundamental factors to consider when formulating.
Unless otherwise noted, specific regulations are based on the US code of Federal
Regulations. Readers are urged to review the CTFA International Color Handbook
for rules for specific regions. Other important norms to be taken into account when
exporting/importing product containing colors are issued by EU and Japan, just to
mention the most significant ones.
Colorants
History: For centuries—in an attempt to imitate the attractive plumage of
many animals—people have used a variety of natural materials, such as coal, chalk,
copper ore, henna, saffron, and other mineral and plant derivatives, to impart color
to the body. Until the 20th century, few limitations were placed on the types of
colorants that could be used in personal-care products or in foods. Such a lack of
legislation proved to be dangerous; many compounds that provided brilliant color
might contain toxic metal complexes. Near the turn of the century, a number of
illnesses and deaths in the United States were attributed to products formulated
with unsafe colorants used in foods.
This tragedy led to the passage of the Food and Drug Act of 1906, which estab-
lished a list of approved color additives. Restrictions for colors used in cosmetics were
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Creating Colorful Cosmetics Beginning Cosmetic Chemistry
added to this legislation in 1938 with the passage of the Food, Drug and Cosmetic
Act, a more comprehensive version of the law. This legislation required that each
individual batch of so-called “coal-tar” colorant must be confirmed as conforming to
the standards set forth in the law to be considered approved or “certified.”3 Despite
efforts to safeguard the public from unsafe colorants, in the early 1950s, several
children fell ill after eating foods that contained high levels of color additives. This
mishap resulted in the Color Additives Amendments of 1960, which allowed the
FDA to set use limitations on colors to ensure that harmful levels would not be
used. It resulted in requirements that color manufacturers provide thorough test
data (“certification”) indicating the safety of their individual batch of colorants. Such
safety concerns in the past 50 years have caused the number of approved colors to
dwindle. In 1959, 116 certifiable colors existed; in 2007, only 36.1,2
Today the debate continues about the safety of specific colorants. Indeed, color
additives are one of the most carefully scrutinized cosmetic ingredients worldwide.
This scrutiny is, in part, because of the chemical reactivity of these colorants, their
impurities, the extended and continuous human exposure through food, cosmetics
and drugs. Strangely enough, for some colorants, the leading international norms
have different views about their safety characteristics, so that quite striking dif-
ferences in purity parameters and acceptance criteria exist in the different part of
the cosmetic planet.3,4
of organic colorant meets or exceeds the FDA standards before it can be sold for
cosmetic, drug or food use. In EU and Japan, specific purity criteria exist, that must
be respected when using the color additives, but no batch certification is required by
specific labs. The CTFA International Color Handbook2 contains a comprehensive
list of the nomenclature of approved colorants in different countries.
• Iron oxides
Iron oxide ores are difficult to purify so their synthetic forms are more eco-
nomically acceptable. Those iron oxides used in cosmetics include the yellow
hydrated iron oxide, as well as brown, red and black iron oxides. Structural
differences among them reside in the combined water amount and in the
crystal shape and size. In black iron oxide, bivalent and trivalent iron atoms
coexist. Providing all the colors of rust, iron oxides are widely used to give all
skin-shades, when blended with titanium dioxide, a very white pigment.
• Carbon blacks
These pigments are black, as the name implies, and are useful in mascara
and eye-liner formulations. Carbon blacks are produced from carbon de-
posits burned onto an iron surface with a natural gas flame or by controlled
calcination of animal bones. Since they need batch certification, they have
been included in the synthetic organic colorant bundle6.
• Chromium oxide greens
Chromium oxide greens consist of anhydrous and hydrated Cr2O3, purified
by acid washings. Their hues are respectively olive-green and blue-green
• Ultramarines
Ultramarine colors are created by melting together sulfur, soda ash, china
clay and charcoal pitch. They are available in pink and blue.
• Bismuth oxychloride: is a white inorganic pearling agent7
• Metallic powders: Aluminum, copper and bronze are used for providing
metallic luster.
Other inorganic pigments include a light violet manganese complex (manga-
nese ammonium pyrophosphate) and the dark-blue ferric and ferric-ammonium
ferrocyanides.
A list of white or off-white powders, like talc, zinc oxide, kaoiln, mica, pyro-
phyllite and the like are also included in the colorant list, but their main use is as
extenders, fillers, skin adhesion, transparency, shine or flow promoters.
Inorganic pigments are not considered to have the same kinds of health risks
associated with the organic colors and, therefore, do not require certification in the
United States. Nevertheless both in the United States as in the EU and Japan1,2,3,4,
their purity criteria, concerning the toxic or allergenic heavy metal impurities have
to met specific set standards. Inorganic colors are not soluble, so their applications
are limited to the make-up category, as the majority of pigments.
Hues
Furthermore, inorganic pigments are not available in the range of hues that
the organics offer and their color tone is a lot less brilliant than that provided by
organic colorants8
See Table 15.2 for a partial list of inorganic pigments and other colorants that
do not require certification.
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Beginning Cosmetic Chemistry Chapter 15
FD&C Blue No. 1 Brilliant blue FCF, Food blue2, allowed in lip/Oral, Eyes,
External, Rinse-off products
D&C Blue No. 4 Alphazurine FG, allowed in External, Rinse-off products
D&C Brown No. 1 Resorcin brown, allowed in External, Rinse-off products
FD&C Green No. 3 Fast green FCF, food green 3, allowed in lip/Oral, External,
Rinse-off products
D&C Green No. 5 Alizarin cyanine green, allowed in lip/Oral, Eyes, External,
Rinse-off products
D&C Orange No. 5 Dibromofluoroescein, allowed in lip/Oral, External,
Rinse-off products, 5% max in lipsticks
D&C Red No. 6 Lithol rubin B, allowed in lip/Oral, External, Rinse-off
products
D&C Red No. 21 Tetrabromofluorescein, allowed in lip/Oral, External,
Rinse-off products
D&C Violet No. 2 Alizurol purple SS, allowed in External, Rinse-off products
Ext. D&C Yellow No. 7 Fluorescein, allowed in External, Rinse-off products
D&C Yellow No. 8 Uranine, allowed in External, Rinse-off products*
Mode of action
Pigments provide color to the products via reflection at their surface of a part
of the incoming light. The reflected color is the component of the light spectrum
that is not absorbed by the pigment surface; black pigment absorbs all the visible
spectrum. Therefore, their pigmenting force and hue in a product depends on their
aggregation state and amount of exposed surface (therefore, on particles dimension).
They are not transparent and provide temporary superficial colors to the skin by
adhesion mechanism provided by the make-up vehicle. Moreover, any chemical
modification of their surface can modify their shade and coloring strength9.
Soluble colorants impart color to solution by absorbing in a precise interval of
wavelengths, while the non absorbed light pass trough and hits the eye. They do
not affect transparency of solutions
Selecting Colorants
Most, but not all, cosmetic products have some type of colorant added, but it
can be difficult for formulating chemists to decide which one to use. Many factors
determine the appropriate colorant choice, including the regulatory status of the
colorant, the physical and chemical properties of the formula, the chemical stability
of the colorant, and, of course, the exact shade of color desired10.
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Creating Colorful Cosmetics Beginning Cosmetic Chemistry
Type of product: This first subdivision concerns the reason for coloring the
finished product. If is intended to impart temporarily color to the skin by adhesion,
product belongs to the make-up field and pigments must be used (soluble colorants
bleed onto the skin). In all other cases, a key factor to consider when selecting a
colorant is the time of permanence of the product onto the skin (rinse-off or leave-
on) and where on the body it will be used (application site). This information will
determine which regulatory class of color may be used.
Regulatory state: In the United States, precise limits exist so that synthetic
organic (certified) products intended to be applied near the eye or onto the lips
and around the oral cavity, must bear clear indications of allowed use in this areas,
that must literally appear (e.g. “approved for the eye area”) in the law1 or use in-
organics. Among the colors allowed in cosmetics (FD&C, D&C, Ext. D&C) the
last category is allowed only on eternal parts of the body, and not to the lips or any
part covered by mucous membrane. Cosmetics (and OTC drugs) that are used in
or around the oral cavity must use FD&C colors or specifically approved D&C
colors, because of the risk of incidental ingestion. Pearls, layered materials that
provide interference phenomena with visible light, may also represent an alterna-
tive way for using colored traces around the eyes. Four inorganic colors not allowed
are silver, henna, lead acetate, chlorophyllin-copper complex and bismuth citrate.
Certified organic colors that are approved in the United States for the eye area
are FD&C Yellow No.5 and its lakes, FD&C Blue No.1 and its lakes, FD&C Red
No.40 and its lakes, D&C Black No.2 and No.3 (for specific eye-area products)
and D&C Green No.5.
The chemist should also be aware that some certifiable colors have specific use
level limits. In general, the inorganic colorants may be used without restriction in
any of these products, but, for instance, ultramarines, chromium oxides and ferric
and ferric-ammonium ferrocyanides cannot be used in the lips area.
Table 15.3. Examples of inorganic colorants and other materials not requiring
certification but only compliance to CFR
*As an example, in Europe, specifications for Iron oxides require compliance with food grade
quality norms.
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Beginning Cosmetic Chemistry Chapter 15
Shades
One of the most basic considerations in color selection is the desired shade
of the product being formulated. Cosmetic products rely on color to promote a
certain image or convey a consumer concept.
In make-up products, such as eye shadow and lipstick, that image may require
that the product’s color to be continually updated to keep pace with the latest
fashion trends. This ongoing evolution of new and different product colors can be
a challenge for the formulator. When the chemist attempts to match the color of
another commercial product, the ingredient statement on that product may provide
a good starting point. But in make-up the color list is comprehensive of pigments
that are present in all shades (by the wording “may contain”. The specific certified
color name must be included in the ingredient statements for products marketed
in the United States for EU, specific purity criteria requirements and allowed body
area of use must be checked in the permitted colorant list of the European law.
Picking an inorganic pigment may be more difficult because the pigment name
(iron oxide, for example) may apply to several shades.. In the case where an ingre-
dient statement is not available or the chemist is not directly matching the color of
another cosmetic product, the formulator must rely on experience to judge which
colorants are most appropriate. A good eye for color and the patience to learn by trial
and error are valuable skills to have when color matching. Color chart collections
like the Pantone® or instruments like colorimeters or spectrophotometers could
be of help for precise matching and for “color communication” among different
company departments.
In all other products, the selection and dosage of colors is a lot easier, as today
the choice of available shades of soluble permitted colors is quite restrict. A mini-
mum of creativity is required to obtain specific hues by blending colorant. Generally
blends require a maximum of three soluble dyes.
Inorganic organic
dull brilliant
polar medium polarity
high concentration diluted on substrate
hard soft
pH stable * pH sensitive
light fast may discolor
high specific gravity low density
hard to micronize easy to micronize
difficult to wet with oils easily wet by oils
may equalize their skin distribution, as the adoption of adequate wetting agents11,
or the use of coated pigments.
References
1. Code of Federal Regulations, 21 CFR 74.
2. CTFA International Color Handbook, 4th ed., The Cosmetic, Toiletry, and Fragrance
Association, Inc., Washington (2007)
3. EU Official Gazette L97/1 (April 4th, 2006)
4. The Comprehensive Licensing Standards of Cosmetics by Categories, YAKUJI NIPPO,
LTD. Australia (1999)
5. T Mitsui, New Cosmetic Science, Elsevier, Amsterdam 370–405 (1997)
6. J Hollenberg, “Meet D&C Black no2: A New, Old Cosmetic Color Additive” Cosm Toil
120(4) 87–90 (2005)
7. Q Peng and M Tellefsen, Bismuth Oxychloride—“A Multifunctional Color Additive,”
Cosm Toil 118(9) 53–62 (2003)
8. E Desmarthon and M Seu-Salerno. “A Co-Precipitation Process for Inventing New
Lakes,” Cosm Toil 121(3) 105–14 (2006)
9. B Brewster, Pigments: Achieving the Effect, Cosm Toil 120 26–34 (2005)
10. Color Formulary Review, Cosm Toil 119 (6) 86–12 (2004)
11. L Rigano et al, A new approach to powder dispersion in Liquid Foundations
Proceedings, IFSCC Conference—Acapulco 239–57 (1997)
12. H Epstein H, Color Quality Control, Cosm Toil 111(3) 21–4 (1996)
13. E Desmarthon, Cream in Powder Form: A New Concept in Make-up, Cosm Toil 122(12)
70–6 (2007)
14. M Graziano and B Adhia, Metallic Pigments in Personal Care Applications, Cosm Toil
121(10) 63–72 (2006)
15. B Brewster, Reflecting on Soft Focus, Cosm Toil 118(9) 16–21 (2003)
16. T Tanaka et al., Development of a New Chiaro-scuro Make-up Product Using Mica
Coated with Titanium Lower Oxides, Proceedings of the X IFSCC Congress—Venezia
261–81 (1994)
17. M Medelnick, Color Variable Pigments, Proceedings of the XXI IFSCC Congress—
Berlin (2000))
Chapter 16
Pigments:
Achieving the Effect
A look at pigments and how they are achieving special effects.
I n the land of pigments, one can quickly arrive at the region of math and physics.
We will avoid that region but still manage to sample a few numbers and take a look
at pigments and how they are achieving special effects, like interference and pearl-
escence. New materials and new technologies are driving these effects. Regulatory
agencies are overseeing them. Market researchers are counting them. Consumers
are demanding them. And cosmetics are more varied because of them.
Let us first clarify that although the terms pigment and colorant are often used
interchangeably, they actually have different meanings, as explained by Sanjoy
Ganguly, industry manager, Cosmetic Americas, Sun Chemicals.
“Colorant truly carries a broader classification,” Ganguly says. “Colorant en-
compasses anything that imparts color to a substrate, including pigments and dyes.
Pigment, however, has a narrower definition and relates to an insoluble organic and
inorganic molecule that is physically and chemically unaffected by its vehicle.”
The Market
In July 2005, The Freedonia Group issued a report1 showing pigment demand
by type for the US cosmetics and toiletries industry (and other industries) in 2004
with projections through 2014. Freedonia breaks pigments into three types:
• Organic. These are complex molecules whose long chemical names are usually
expressed instead as a color, a shade, and the regulatory approval status—such
as D&C Red No. 6. Organic pigments may be water-soluble, oil-soluble, or
insoluble. The insoluble form (a dye precipitated on an insoluble substrate)
is known as a lake, such as D&C Red No. 6 Barium Lake. The carbon blacks
are also organic pigments.
• Inorganic. Inorganic pigments are composed of insoluble metallic compounds,
such as iron oxides, chromium oxides, titanium dioxide, ultramarines, and
ferric ammonium ferrocyanide.
• Special effect. These pigments are intended to achieve interactive visual ef-
fects supplementary to the basic color. They use materials such as synthetic
fluorphlogopite, guanine, bismuth oxychloride, and mica. Some popular effects
are described as pearlescence, interference, and color travel.
159
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Pigments: Achieving the Effect Beginning Cosmetic Chemistry
The Effects
The effects of pigments have been described in numerous publications, and
are summarized here from several sources.2–4
Conventional organic and inorganic pigments are considered absorption pig-
ments because they absorb certain wavelengths of the incident white light. The
phenomenon of color is produced by scattering of the remaining unabsorbed com-
ponent of the formerly white light. For these particles the effect is independent
of geometry.
Metallic pigments consist of tiny flat pieces of aluminum, copper, gold, zinc,
and other metals that reflect light the way a mirror does. Zinc is approved as a
cosmetic colorant only when alloyed with copper. Gold is approved in Europe and
Japan but not in the United States as a cosmetic colorant. For metallic pigments,
the effect depends on the viewing angle.
Interference pigments (including pearlescent pigments) are typically composed
of thin, translucent platelets coated with metal oxides, such as titanium dioxide
and/or iron oxide. White light striking the surface of these pigments is refracted,
reflected and scattered by the layers that make up the pigment. Through a super-
imposition (or interference) of the reflected rays of light, a changing play of color
is created, with the most intense color seen at the angle of reflection. The colors
produced by interference are dependent on the angle of observation and the angle
of illumination.
Phil Linz notes that absorption effects and interference effects can be combined.
For example, absorption colors can be added to a mica-based pigment coated with
TiO2. “If carmine is added and the interference color is red, a red pigment would
result; but if that same system were changed slightly so that the TiO2 layer were
slightly thicker and now gives a blue interference, the combination of the blue
interference and the red carmine mass tone would give a purple pigment,” Linz
said. “The other important parameter in these pigments is particle (lateral) size of
the mica substrate; larger pigments give more sparkly, more transparent effects;
smaller particles give more opacity and more of a silky/satiny effect.”
The Pigments
Let’s look at some interesting pigments mentioned in the Freedonia report. Here
we’ll focus on effects pigments from Eckart Cosmetic Colours LLC (Painesville,
Ohio USA), Engelhard Corporation (Iselin, NJ USA), and the Rona Business Unit
of EMD Chemicals Incorporated (Hawthorne, NY USA). Also mentioned was Sun
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Pigments: Achieving the Effect Beginning Cosmetic Chemistry
SunPURO Launched
Sun Chemical has launched the SunPUROe product line with a series of
synthetic yellow, red, and black iron oxides. The line is said to be universally
compliant. Its colors far exceed existing regulatory specifications in the United
States, Europe, and Japan.
Sun Chemical manufactures these colorants using meticulously controlled
processes to ensure their high purity, low metal content, and small particle
size, according to the company’s Web site.
Other pigment products available from Sun Chemical include SunCRO-
MAe organic and inorganic pigments, SunSHINEe pearlescent pigments
composed of TiO2-coated synthetic fluorphlogopite, and SynMICA functional
filler composed of synthetic mica.
e
SunCROMA and SunPURO are trademarks of Sun Chemical. SunSHINE is a registered
trademark of Sun Chemical.
Visionaire line of metallic pigments comes in nine shades, which are achieved
by the natural color of the metals: a silver shade from aluminum; a cinnamon
shade from copper; and three shades of bronze based on varying the percentages
of copper and zinc in the bronze alloy. The copper and bronze shades are further
processed to yield an additional four shades.
Engelhard borosilicate Reflecks pigment: In March 2005, Engelhard in-
troduced four new colors. Three are in the Reflecksb Colors family. The fourth
is Twinkles of Turquoise, a unique blue-green iridescent pigment in Englehard’s
Reflecks line of iridescent and pearlescent borosilicate-based pigments that re-
portedly takes effect-enhancing pigments to new levels of chroma, color purity,
brightness, transparency, and reflectivity. These pigments are said to be especially
dramatic in transparent formulas such as gels and clear sticks.
Borosilicate, the substrate in these Reflecks pigments, is chemically stable
glass containing essentially calcium borosilicate and sodium borosilicate (Table
16.2). The designated INCI name for this material is calcium sodium borosilicate.
The unique effects of the Reflecks effect pigments are attributed to their cleaner
substrate and their unique morphology.
Ingredient % wt/wt
SiO2 65-72
Al2O3 1-7
CaO 4-11
MgO 0-5
B2O3 0-8
ZnO 0-6
R2O (Na2O + K2O) 9-17
all of the TiO2-coated borosilicate pigment particles have a uniform color, while the
TiO2-coated mica pigment particles consist of a range of colors,” Uzunian wrote.
In addition, mica and borosilicate differ in terms of their reflectance spectra.
Uzunian studied the reflectance spectra for pearl mica pigments at the 0° specu-
lar angle on micas of four different thicknesses (0–600 nm). He found that each
thickness of mica produced a different interference color. Borosilicate pigment
substrates are typically thicker. In a similar study on borosilicates of five different
thicknesses (3000–5000 nm) he found that there is no interference phenomenon
for the light penetrating through the borosilicate substrate.
In summation, borosilicate pigments provide color, luster, and hiding power
that are different from other effect pigments. They are stable in both alkaline and
acidic environments, and in common solvents and aqueous systems. Borosilicate’s
advantages mean that many other companies are using this material. For instance,
EMD Chemicals launched its Ronastarc calcium-aluminum-borosilicate-base Silver
White pigment in 2003. It is described as a sparking pigment, particle size 20-200
µm, with multicolor effect. Other shades (gold, blue, and copper), prepared on the
Ronastar platform, are now available, with more expected soon.
However, Martha Graziano points out that mica-based pearls are likely to be
around a long time. “Borosilicate-based technology does provide a new look, but
the cost is roughly 10 times the cost of mica-based pearls—which realistically can-
not be economical in many formulations,” Graziano said.
EMD Chemicals Timiron Splendid pigments: Now let’s spend a few minutes
with Phil Linz as he describes the multilayer technology5,6 used by EMD Chemi-
cals to make their Timirond Spendid interference pigments, a line of six pigments
launched in 1999. The same technology is used in the company’s Xironae line of
currently six effect pigments launched in 2002.
“The ordinary classic interference pigment is composed of a layer of mica
coated with a layer of TiO2. The color is developed in the same way that color is
developed in an oil slick on water. There’s a thin film of TiO2; some of the light hit-
ting that surface is transmitted, some is refracted, and some is reflected. Because
of this selective reflection, and by determining the thickness of that layer, you can
generate an interference color of green or gold or red or whatever. That’s roughly
the technology of the 1960s.
“In the last five to seven years we learned that if you put another layer of silica
on top of that TiO2 and then you put another layer of TiO2, there are more surfaces
to reflect and there are more chances for the light to be intensified.
“So the classic interference color is OK, and we will sell products with that, but
clearly the newer multilayer pigments will give you much more brilliance, much
more color intensity than a monolayer pigment.
“That was the initial thrust. But then our researchers said, “What if we change
the thickness of the silica layer?’ If light comes in at a shorter angle, it comes out at
a correspondingly shorter angle. Because the reflected light depends on wavelength
and the path length the light is traveling, you’ll get a color at the short angle. But
if light comes in at a wider angle, you’ll also have a reflection at that wider angle
but it will have a much longer path length and the effect will be that it will reflect
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Beginning Cosmetic Chemistry Chapter 16
a different color. That’s what our color travel pigments are about: one pigment
giving multicolored effects. And again, it comes out of the same basic multilayered
technology.
“So basically we’ve gone in two directions with our multilayer pigments. The first
phase was simply making a stronger interference pigment. The second phase was
color travel, where you can create a pigment that looks purple at 1 viewing angle
and green at another. It’s the same technology, but a variation on the theme.
“What’s next? Basically, in all these systems you’re dealing with a substrate that
is coated in some way, usually with a cosmetically acceptable metal oxide. We’ve
prepared materials with various substrates (mica, silica, alumina, and borosilicate);
other substrates may yet find their way into commercial use. And methods of coating,
or even coating materials, may yet be improved, to give more uniform reflection,
therefore higher brilliance.
“Who’s doing it? Look at any list of pigment companies. We’re all doing it!”
References
1. P Prokop, Pigments: Inorganic, Organic & Specialty, The Freedonia Group, Inc.
Cleveland USA (Jul 29, 2005)
2. C Weingrod, Three-Dimensional color, available at http://www.danielsmith.com/learn/
inksmith/200211/ (accessed Aug 10, 2005)
3. G Uzunian, B Aucar and L Song, Borosilicate-based effect pigments, undated article
in Cosmetics & Toiletries Manufacture Worldwide; also available at www.ctmw.com/
articles2004/ctmw%20Engelhard.pdf
4. L-P Sung, ME Nadal, P Stutzman and ME McKnight, Characterization of coating
microstructure using laser scanning confocal microscopy, available at http://slp.nist.
gov/appearance/acs_aug2000.pdf (accessed Aug 1, 2005)
5. P Linz, Formulation approaches to interference pigments, Cosmet Toil 116(2) 61–66
(2001)
6. P Linz and Q Peng, Color-Travel cosmetic pigments: Interference to the max, Cosmet
Toil 118(12) 63–70 (2003)
Chapter 17
Background
The physiological function of hair on humans is insignificant compared to its
psychological significance. Humans place great social value on the color, texture,
shape and appearance of hair. The properties that are prized vary from time to time
and culture to culture, but what remains constant is that people generally want their
hair to be different in some regard than it exists in its natural state. This very basic
desire to alter the appearance of the hair has resulted in the need for many different
procedures and processes for safely altering the hair. Providing the desired color,
tint, texture, straightness, and other cosmetically appealing properties to the hair
while avoiding damaging the hair and causing irritation of safety issues to the hair
is a key challenge to the cosmetic chemist and the topic of this chapter.
During formal education, chemists are taught how to control chemical reac-
tions. In making the transition from academia to the cosmetic industry, chemists
may be surprised to find that reactions are generally undesirable in personal care
products because they may well have negative effects associated with the reaction.
Unwanted reactions in a cosmetic product may interfere with its stability and, even
more important, the wrong reaction could have dangerous side effects on hair and
skin. Most of the procedures and processes carried out by the cosmetic chemist do
not include reactive processes. Wetting, foaming, conditioning, and emulsification
performed on the hair are physical processes caused by selection of the proper
molecule added to the formulation.
Nonetheless, reaction chemistry does play an important role in at least one major
category of personal care products. These products are intentionally designed to
cause reactions that have beneficial effects on hair: relaxers, permanent-waving
products and oxidative hair colors. This chapter introduces this class of reactive
hair care products and their chemistry.
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The Science of Reactive Hair Care Products Beginning Cosmetic Chemistry
A. Permanent Waving
In the interest of fashion, a wide variety of changes are made to hair in its
natural state to provide properties that are of interest. The first to be addressed is
shape. Almost an unlimited amount of curl can be placed into, or removed from
the hair. It is desirable to style hair into attractive configurations and to have it hold
its shape for an extended period of time. Shaping hair (providing it with wave),
has been practiced for centuries in one form or another.1 In the early 1900s, wav-
ing was accomplished by heating hair with cumbersome and dangerous electrical
devices.2 During the past 50 years, cosmetic science has developed increasingly
effective chemical techniques to impart a lasting wave or curl to hair. This process
is known as permanent waving or perming. The adjective “permanent” is a bit of a
misnomer because the wave only affects existing hair at the time of treatment; as
new hair grows out of the scalp, it will grow in its original, unwaved configuration.
Permanent-wave products are available in different forms known as acid, cold or
neutral waves. The technology employed in these products is based primarily on
two types of chemicals: thioglycolates and bisulfites.
Before beginning the discussion of how permanent waves work, it should be
understood by the reader that the science of reactive hair care products is very
involved and that this chapter is meant only as an introduction for the uninitiated
chemist. A number of technical articles describe these processes in detail.3,4,5 To
understand the basics of permanent waving, it is important to realize that hair is
composed of helical protein structures. Protein structures are made up of amino
acids linked in a peptide bond. The sequence of the amino acids is referred to as
primary structure. This structure cannot be modified without destroying the hair.
However, what can be modified is the interaction of sulfur rich amino acids. These
amino acids can bond with each other and form crosslinked protein polymers by
sulfur-sulfur bonds. This reaction results in a structure to the protein that alters
the shape of the hair. The structure of hair showing the sulfur-sulfur interaction is
shown in Table 17.1.
These bonds are responsible for hair’s structure, and they can be disrupted by
certain reducing reactions. (An experienced chemist will note that this explanation
is a simplified version of what is, in reality, a very complex process.)6
As previously noted, the most common reducing agents are thioglycolic acid
derivatives and bisulfite. These chemicals are used more than any others because
they have the best history of efficacy and have been the workhorses of the perma-
nent wave industry since the 1940s. Highly effective permanent-waving solutions
can be formulated by combining these reactive agents with other ingredients to
control pH and viscosity.
The process: The first step in the perming process is to physically rearrange the
original configuration of the hair on curlers or rods. The size of the rod determines
the size of the curl. Before rolling hair onto the plastic rods, thin sheets of tissue
paper, known as “end wraps,” are used to cover the ends of the hair. These end
wraps help the hair hold the proper configuration and protect the fragile ends by
absorbing excess perming solution.
When all the plastic rollers are in place, apply the perming solution and work
into the hair. During this stage of the process, the sulfur–sulfur bonds of the hair
break. The length of time required for this stage depends on a number of factors,
including the strength of the perm solution, the degree to which the hair will be
restructured and the condition of the hair. During this processing step, the hair is
plasticized as the disulfide bonds controlling its original structure are disrupted.
Some types of perming products require the use of heat from a hair dryer to ac-
celerate the reaction.
After a set amount of time, the hair is rinsed with water to stop the reducing
action. Next, a neutralizing solution is added to oxidize the protein residues. This
oxidation step relinks the sulfur-sulfur bonds. However, because the hair has been
stretched and curled on plastic rods, the newly rearranged disulfide bonds hold the
hair in a curled arrangement even after removing the plastic rods.
Achieving a good permanent wave depends on proper control of the reduction
and oxidation reaction kinetics so hair is not under- or over-processed. A detailed
discussion of protein reaction kinetics is beyond the scope of this chapter but
several excellent references are provided for the technically ravenous reader.7 It is
important for the chemist to understand that the perming process causes significant
damage to hair because of the breakage of the bonds and the swelling that ensues.
This swelling action results from exposure to the highly alkaline materials and can
cause significant cross-sectional or lateral damage. Damage can also occur when
treating improperly wrapped hair with a reducing solution.
Permanent wave formulations: In general, perms contain a number of ingredi-
ent classes (Table 17.2).6
These ingredients are formulated into three general types of perms: alkaline,
acid and bisulfite. Alkaline perms, also known as cold waves, use thioglycolic acid
as the active. This name may seem like a misnomer, but the name is derived from
the final pH of the product. Alkaline perms typically have a pH greater than 9.
Borish gives examples of commercial products in each of these categories.8 He also
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The Science of Reactive Hair Care Products Beginning Cosmetic Chemistry
EQUATION 17.1
Because of this salt formation, it is difficult to react the sulfo groups to reform
all of the disulfide bonds, and, therefore, bisulfite perms can leave hair physically
weaker and with a softer, less stable perm. Still, these formulations are popular in
the marketplace because they are less aggressive and can be used at a lower pH.
B. Hair Relaxers
Another process commonly used on the hair is “referred to as relaxing hair”.
“Relaxing” is the name given to the reactive process used to straighten excessively
curly hair. This process is typically used on African hair, which is significantly curlier
than Caucasian or Asian hair. This curliness is the result of the unique structure
of African hair, which is more elliptical and varies more in diameter. These factors
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Beginning Cosmetic Chemistry Chapter 17
produce hair shafts that are extremely twisted or kinked.9 For fashion reasons, or
simply for manageability, some desire to make this type of hair less curly or even to
straighten it. Straightening can be done mechanically by pressing the hair with hot
implements or chemically by breaking the bonds in the hair with reactive products.
The latter method is the topic of this discussion.
Relaxers work in a manner similar to permanent waves: They rely on reactive
chemicals to break amino-acid-based sulfur bonds, thereby allowing the structure
of hair to be rearranged. The process of hair straightening is also known as lanthi-
onization, which refers to the conversion of the amino acid, cystine to the amino
acid, lanthionine.
In very general terms, there are two key differences between relaxing and waving
hair. First, because the relaxing process is intended to straighten hair, it does not
require hair to be wrapped on to rods or curlers. Second, relaxing tends to break
more bonds than perming. Accordingly, the chemistry of relaxers is somewhat dif-
ferent than the thioglycolate/bisulfite waving systems described above. Relaxers
are commonly based on metal hydroxides (such as ammonium hydroxide, sodium
hydroxide, lithium hydroxide or guanadine hydroxide.) These agents react more
aggressively with the hair than the perming solutions. Having said this, we also note
that some mild relaxers are, indeed, based on ammonium thioglycolate.
The procedure for a relaxer treatment is as follows: first, the hair is divided into
sections to simplify application. A thin layer of protective processing cream (typi-
cally petroleum jelly) is then applied to the hairline, ears and ends of the hair. This
hydrophobic layer shields skin from a harsh reaction from the aqueous solution.
The ends of the hair should also be protected from absorbing too much solution
and being over-processed.
After taking precautionary measures, the hair is parted equally and the cream
relaxer is brushed on section by section. The hair is then smoothed with the back of
a comb until achieving the desired straightness. Processing time varies from 10–20
minutes depending on hair type, condition and degree of straightening required.
Care must be taken not to leave the relaxer on too long or considerable hair dam-
age, such as breakage and scalp irritation, may occur. The relaxer cream is then
rinsed off with warm to very warm water. Good rinsing is critical to ensure that
the reactive agents have been completely removed; otherwise, additional damage
to hair and scalp could occur.
Some relaxers do not require a separate oxidation step. However, it is common
to shampoo the hair with a neutralizing shampoo immediately after relaxing. This
shampoo/rinse cycle removes relaxer cream and neutralizes excess alkalinity.10 In
addition, the neutralizing shampoo ameliorates the effects of the highly alkaline
treatment. The result is that the bonds of the hair are locked into their newly
straightened configuration. Most relaxers require an additional conditioning step to
help offset the damage caused by the reactive process. As with perms, the relaxing
process only lasts until new hair growth occurs.
Relaxer formulations: Since the 1950s, the market has seen the introduction
of a variety of formulations. These formulas are primarily based on three key com-
ponents: water-soluble/water-dispersible alkaline agent, oil phase and water phase. 11
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The Science of Reactive Hair Care Products Beginning Cosmetic Chemistry
They all contain materials, such as petrolatum or mineral oil to help protect the
scalp, or fatty alcohols to thicken the product and emulsifiers that are alkali-stable.
The various types differ by the type of alkaline agent employed. Lye relaxers con-
tain between 1.85–2.4% sodium hydroxide, depending on the strength required.
“No Lye” relaxers are formulated with guanadine hydroxide and are significantly
less irritating than the sodium type. Because of its inherent instability, guanadine
hydroxide must be formed in situ by mixing calcium hydroxide with guanadine car-
bonate. These components must be separate until the product is ready to be used.
Some brands claim to be “No Lye” and “No Mix;” these capitalize on the common
use of the term “lye” to apply only to sodium or potassium hydroxide (they are, in
fact, based on lithium hydroxide). Relaxers can also be formulated with different
specialty ingredients such as conditioning agents.
3. Hair Bleaching
Another process that uses reactive chemistry to change the hair is bleaching.
When hair is bleached the natural color is destroyed either partially, resulting in
lighter color hair, or entirely, resulting in blonde hair, devoid of color bodies. The
color bodies that exist in hair are melanin particles embedded in the cortex. The
color observed is dictated by the type, size, shape, distribution and concentration
of particles in the hair. Since, natural pigment exist inside the cortex the color
changing effect of bleaching must occur after penetration both cuticle and cortex.
This penetration causes damage, which does not repair. For this reason frequent
bleaching is a problem. Hydrogen peroxide under alkaline conditions is effective
in bleaching hair. The addition of persulfate dramatically improves the efficient of
hydrogen peroxide on hair.
The color of hair is measured by level shown in Table 17.3. Generally bleaching
will lighten the hair about 2 levels. Very aggressive bleaching will lighten by 4–6
levels, but much more damage is done to the hair in the process.
Level 1 Black
Level 2 Dark brown
Level 3 Medium brown
Level 4 Light brown
Level 5 Lightest brown
Level 6 Dark Blonde
Level 7 Medium blonde
Level 8 Light blonde
Level 9 Very light blonde
Level 10 Lightest blonde
Level 11 Extermely blonde
Level 12 Ultra light blonde
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Beginning Cosmetic Chemistry Chapter 17
is applied to a small patch of skin, the inside of the elbow, for example. Patch test-
ing may need to be done 24 hours before the coloring treatment is to take place.
A small curl of hair should be tested, too, before application to the entire hair to
assess tone of color and timing of contact.
After testing has shown no problems, the actual coloring process can begin.
First, the peroxide and the tint are mixed together in the applicator bottle. The hair
is partitioned and the tint is applied from the scalp to the porous ends. The hair is
left alone for 10–20 minutes while the reaction proceeds. During the last five or 10
minutes, the solution is spread toward the ends to even the color. The hair is then
rinsed and shampooed to remove excess color and halt the reaction.
The degree of color imparted to the hair depends on the concentrations of dye
and peroxide, processing conditions, even the condition of the hair at the time of
application. Also note that these coloring and bleaching processes are inherently
damaging to hair because some of the protein bonds are destroyed by the oxida-
tion/reduction reactions. Hair should not be color-processed for several weeks after
perming to avoid compounding this damage. Likewise, hair should not be colored
before perming as the perm process will physically remove some color, and it could
chemically alter the color.
Permanent hair color formulations: Permanent dye formulations consist
of two components that are separate until the product is ready to be applied. The
first component contains the oxidative dye precursors that are typically aromatic
p-diamines or p-aminophenols, such as p-phenylene diamine. These colorless pre-
cursors react to form dye intermediates, which, in turn, react with dye couplers to
produce color. The dye couplers include such materials as resorcinol, 1-napthol, and
hydroquinone. Formulations may contain five or more dye precursors or couplers,
so many reactions may occur at the same time.
Clarence R. Robbins gives an excellent discussion of oxidation reactions. He
notes the active intermediates react “with resorcinol to form polyindophenols and
trinuclear dyes, with m-diamines to form indamines, with m-aminophenols to form
indamines; and with naphthol and hydroquinone to form indophenols.”13
An alkali is used as part of the dye base to swell the hair and enhance penetra-
tion of the dye precursors. In addition, this portion of the formula may include
solvents, surfactants, thickeners and metal chelating agents. The second formula
component contains hydrogen peroxide and stabilizing agents. The two compo-
nents are mixed together just before use to initiate the reactions that will form the
permanent dyes.
When formulating hair coloring products, regulatory and toxicological consid-
erations are extremely important. These issues are not discussed in detail in this
chapter, but the formulator working in this area should be aware of the safety con-
cerns. The concerns include minor short-term effects, such as contact dermatitis.
Sensitization caused by these reactive products can lead to itching and redness. In
addition, concerns about the long-term systemic effects of these materials persist
because several aromatic diamines test positive as mutagens in the Ames test.11
Therefore, any dye products for hair coloring are scrutinized to ensure they pres-
ent no risk. For example, after the US Food and Drug Administration determined
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Beginning Cosmetic Chemistry Chapter 17
that a product containing the dye 2,4-diamino anisole must include a cancer warn-
ing label, the industry removed this ingredient from formulations.11 This example
shows how the cosmetic industry is responsive to safety issues, not only for reactive
products, but for personal care products in general.
Conclusions
This chapter was intended to introduce some very basic concepts to the cos-
metic chemist about a very complicated group of reactive processes applied to hair.
The processes are complicated not only by the raw materials used, but also the
methods of application and the duration of application. It is our recommendation
that before any of the information is used to begin formulation of the products
discussed in this chapter, the chemist consult various text books and literature with
more extensive information.
The processes that are described here are used in a $2 billion annual market
for the United States and a $7 billion annual market worldwide. Consumers are
likely to demand continued improvement in both ease of use and final results
obtained when the products are used. This allows creative cosmetic chemists the
opportunity to improve products.
References
1. AE Lee, JB Bozza, S Huff and R de la Mettrie, Permanent Waves: An Overview Cosm
& Toil 105 37–66 (1988)
2. W Edman, Current cold wave formulations, Soap Cosm Chem Spec (9) 42 (1979)
3. MG De Navarre, The Chemistry and Manufacture of Cosmetics, Van Nostrand, New
York, 471–481 (1941)
4. ML Garcia, EM Nadgorny, LJ Wolfram, Phsiochemical changes in hair during waving J
Soc Cosm Chem 41 149-151 (1990)
5. J Nothen, V Bollert, G Blankenburg and H Hocker The influence of the osmotic
swelling behavior on the quality of the permanent wave. Proceedings of the 16th
IFSCC International Congress, New York (1990)
6. ET Borish, Hair Waving, Hair and Hair Care, Marcell Dekker, New York191–215 (1997)
7. P Busch et al, Testing Permanent Waves, Cosm & Toil 111(4) 41 (1996)
8. US Patent 3,864,476 Bisulfite Permanent Waving, issued Feb. 4, 1975
9. 10 AN Syed, et al, African-American Hair, Cosm & Toil 110 (10) 39 (1995)
10. A Syed, “Ethnic hair care products.” In Hair and Hair Care, Marcel Dekker, New York
235 (1997)
11. P Obukowho, et al, Hair Curl Relaxers, Cosm & Toil 110(10) 65 (1995)
12. KC Brown, Hair coloring Hair and Hair Care, Marcel Dekker, New York, 192 (1997)
13. CR Robbins, Chemical and Physical Behavior of Human Hair 2nd ed, Springer-Verlag,
176 (1988)