Hair Shampoos and Hair Colorants

Washing hair and scalp is a near-universal practice. As it is part of our hygienic

routine. Why? This is to prevent the accumulation of dirt, product residue, sweat,
unwanted sebum and dead skin on our scalp. Hair Shampoos was developed in 1930’s.
The first shampoo containing synthetic surfactants is introduced as Drene. But it is known
today as Modern Shampoo. It became widely used in laundry markets by the mid-1940s
and appeared in a shampoo format during the 1950s.
Shampoos are probably the most widely used hair products today. Based on
synthetic detergents they are relatively insensitive to water hardness, thus allowing for
efficient rinsing since there are no scum residues.
What are these synthetic detergents?
A synthetic detergent is composed of surfactants they are a cleansing substance
that acts similarly to soap, but is made from chemical compounds instead of fats and lye.
SOAP is produced from animal or plant fat thru the reaction called saponification. This
Detergents since its composed of surfactants they will form micelles that emulsify
hydrophobic substances in water. Shampoo is an effective cleansing agent for hair and
scalp as defined in the early days.
Requirements of a shampoo
1. To remove sebum (the secretion of the sebaceous glands) and atmospheric
pollutants from the hair and scalp.
2. To remove the residues of previously applied hair treatments, e.g. polymeric
constituents from styling lotions and hair sprays.
3. To deliver an optimum level of foam to satisfy the expectation of the user.
4. To leave the hair in a satisfactory condition after rinsing so that it can be
combed easily both in the wet and dry state.
5. To perform as a vehicle for the deposition of beneficial materials onto the
hair and scalp.
6. To be non-toxic and non-irritating to the hair and the scalp.
7. To be non-damaging to the tissues of the eye if inadvertently splashed.

Classification of shampoos
Shampoos are usually classified according to function, e.g.
anti-dandruff- contains antifungal and antimicrobial ingredients zinc pyrithione to
help relieve itching and flaking, buildup, and excess sebum production in your scalp.
Medicated- are used to relieve itching and/or scaling, but they can also treat
bacterial or fungal infections.
 2-in-l shampoo- A 2-in-1 shampoo is a product designed to give the cleaning
benefits of shampoo while also providing some of the conditioning benefits of a
conditioner.
mild baby shampoo- products intended to be used to cleanse the hair of infants
and children under the age of three. LESS IRRITATING.
basic beauty shampoo
premium conditioning shampoo - The conditioning shampoo combines the
excellent cleaning power of mild surfactants with the moisturizing and detangling
properties of a conditioner. Examples are our conditioners like keratin, creamsilk, dove,
etc.
9.2 THE ACTION OF SHAMPOO ON THE HAIR - The original prime purpose of the
shampoo is to cleanse the hair. According to Lawrence and Breuer, who recognized three
basic components of hair soil and this are:
1. Sebum, the oily secretion of the sebaceous glands.
2. Proteinaceous matter arising from the cell debris of the stratum corneum
layers of the scalp, and the protein content of sweat.
3. Atmospheric pollutants and residues from other hair-care products.

Sebum, is the primary cause of hair soil. Sebaceous glands cover the vast majority of
your body. face and scalp contain the highest concentration of glands. While smooth
surfaces typically have fewer glands. Areas that has no glands at all are the palm of our
hands, lips, and sole of feet.
How does Sebum produce?
The sebaceous glands produce sebum through holocrine secretion (HOLOCRINE
GLAND CELLS ACCUMULATE A SECRETORY PRODUCT AND EVENTUALLY THE
ENTIRE CELL RUPTURES TO RELEASE THE PRODUCT, REPLACED CELL BY
OTHER EPITHELIAL CELL THRU CELL DIVISION), a process of programmed cell
death. Specialized cells, called sebocytes, dissolve and release sebum into the
sebaceous glands. Sebum travels through the follicular duct that connects the sebaceous
gland to the hair follicle. The growing hair pulls the sebum up and onto the surface of the
skin.
Breuer also established, that the rate of sebum spreading is greater when hair is dried
using electric hair drier compared to allowing the hair to dry at room temp.
9.2.1 The process of soil removal
We have three types:
Similarities of the three is they must be wetted, so that surface tension of the water is
reduced by the shampoo surfactant ,thus, allowing full contact with the soil's surface.
soluble soil is then removed in the aqueous medium. However, the removal of Oily soil or
sebum is removed by a process known as 'roll-up' the displacement of the soil by the
detergent solution (Surfactant molecule: hydrophilic “head” attracts water, and lipophilic
“tail” attracts oil which creates a push-pull process that causes the oils dirt and deposits
to roll up into little balls that can be lifted off in the water and rinsed from the hair). While,
Insoluble particulate soils tend to be removed by electrostatic repulsion between the soil
and the hair fibre assisted by repulsion between the surfactant molecules adsorbed onto
the hair fibre and those dissolved onto the soil.
Another cleaning mechanism is according to Chan:
-the detergent micelles make contact with the lipid surface for a finite time during which
they take up an increment of lipid.
- This is assimilated to form lipid-detergent co-micelles which detach and 'float away'
- This rectangular diagrammatic micelle represents hydrocarbon domain created by the
non-polar regions of the detergent molecules; the small circles represent the polar heads
of these molecules.
FOAMING OF SHAMPOO
• The 'signal' to which the user responds when applying a shampoo is how quickly
it builds up lather and how copious that lather is (LATHER: a frothy white mass of bubbles
produced by the surfactants or simply lather is BUBBLES). This tends to colour the user's
later impressions of the other performance characteristics of the shampoo.
• There are Three well-defined stages appear to be involved in foaming: the rapidity
with which the foam is formed; the peak volume of the foam; and the consistency of the
lather. So, a shampoo is being judged as creamy if it has a high consistency of foam.
- Ross and miles technique which involves the use of a tap funnel. shampoo solution
is transferred to a tap-funnel ---- from the tap funnel it will run in a standard time
into a large measuring cylinder which is then contains with a set volume of the
solution. The result of the stream of solution from the funnel impacting on the liquid
in the cylinder is to generate a foam. SO, FROM THAT the volume of the foam can
be read directly.
- Heart and Degeorge which uses the in-vitro laboratory techniques. The principle
of the method is that a high-consistency foam will take considerably longer to flow
out via the stem (broad) of a powder funnel than a foam which is thin and dubbed
as non-creamy.
- An ideal laboratory method for predicting the foaming power of shampoos is thru
practical shampooing process. Lather production in practical shampooing is not
thru these methods which is by cascading water, mechanical stirring or gas
injection. It is in fact achieved by a process of compressing and shearing hair when
it is saturated with shampoo solution. So, by compressing and shearing the
foaming power of shampoos or the consistency of foam is now then quantified.
Shampoo ingredients
A shampoo is basically a solution of a detergent modified by additives to render it easier
to apply and to safeguard against deterioration of the hair condition after the shampoo
has been rinsed away. DETERGENTS made from long molecules that contain a head
and tail. These molecules are called surfactants (foaming agent).
1. Main detergents- These are classified according to the way in which they ionize.
o ANIONIC- The molecule of an anionic-active synthetic detergent is a long carbon
chain to which a sulfo group (―SO3) is attached, forming the negatively charged (anionic)
part.
• Alkyl Sulfates, Alkyl ether sulfates- The manufacturing process for alkyl
ether sulfates is similar to that for alkyl sulfates, but an ethoxylated fatty
alcohol is used. The carbon chain length affects the solubility, foaming,
detergency, viscosity and mildness of the product.
• Sulfosuccinates- Produce good foaming and detergent properties.
• Isothionates, taurides and sarcosinates.
o NONIONICS- materials here are not major ingredients. However, they act as CO-
SURFACTANTS (they are combined w/ surfactants to enrich the properties of primary
surfactant), RHEOLOGY MODIFIERS (to increase viscosity), and SOLUBILIZERS for
insoluble components such as fragrance oils.
o AMPHOTERICS- These are defined as having both anionic and cationic charges
in the hydrophilic head. The negative group is usually carboxylic and the positive group
amino. ALKALINE SOLN- anionic predominates, ACIDIC SOLN- cationic predominates.
The isoelectric point lies between the two extremes at a position where the two charges
are equal. The molecule at this point is called a zwitterion, and does not behave as a
surfactant. HOWEVER, if we raise or low the ph it will allows the molecule to regain its
surfactant properties. AMPHO when combined to anionic there is enhancement to foam
and viscosity. There is also a synergistic effect on mildness.
• Imidazoline derivatives- found in baby or other mild shampoo since it has
a very low irritation potential.
o CATIONICS- incompatible with anionics (due to difference of charges) and are
unlikely to be used in shampoo systems. The use of these detergents is limited by their
poor ability to cleanse and foam.
2. Foam boosters and stabilizers
3. Opacifiers
4. Hydrotopes
5. Viscosity modifiers, including hydrocolloids and electrolytes
6. Special additives for hair condition Special additives for scalp health, including
antidandruff additives
• Thickeners, pearlizers (responsible for creamy appearance, pearlized effect
created by glycol distearate) and opacifiers (uses latex opacifiers to obtain
flat opaque appearance), preservatives (most commonly used is the
parabens), pH modifiers (isoionoic point for the hair fibre lies between pH
5.6 and 6.2, It is advisable to balance the pH of the formulation to within this
range. So to balance we use CITRIC ACID to prevent our scalp to strip
natural oil therefore reduce frizzy and dry hair and also to keep the cuticle
sealed to close the gate for opportunistic pathogens)
7. Functional additives- promote good condition of the hair. Hair in good condition is easy
to comb both in wet and dry state.
• Antidandruff agents- There are Three agents associated with the treatment
of dandruff (dandruff manifests itself as the detachment of flakes of scalp
skin). Zinc pyrithione the first scientifically based organic therapeutic agent.
And piroctone olamine which is almost the same in structure with ZPT the
difference is that PO has the presence of pyridine ring.
8. Sequestering agents- Another important shampoo ingredient that does not participate
in cleansing is the sequestering agent. The function of sequestering agents is to
chelate magnesium and calcium ions preventing the formation of insoluble soaps,
known as 'scum.

9.6 Manufacture and Preparation of Shampoos

Shampoo preparation is uncomplicated and straightforward compared to other personal
care product. Different factors affect the development of shampoos. It is important to note
that excipients have a direct effect on the preparation as it dictates what the final outcome
may look like and perform. Long-term stability and microbial integrity is ensured by
manufacturers in order to prolong the availability of the preparation.
Regulatory compliance is an important factor as it addresses consumer safety and
acceptability. Stability tests help monitor shampoo preparation conditions. This is needed
in order to produce quality products that can be shipped to the market. Shampoo
manufacturing also has problems. Despite precautions employed by manufacturers, they
still face problems when manufacturing or preparing shampoos. Excipients often help fix
mixing problems.Shampoo preparation is a process which employs excipients and
techniques in order to achieve the desired product.
Shampoo Preparation
In shampoo preparation, the manufacturing process is rather simple. However, there are
cases wherein certain factors may affect the shampoo preparation process.
Straightforward cases wherein the ingredients are inert towards each other. These cases
only need consistency adjusters. In order to achieve the desired consistency N-alkyl
betaine is often added. Solubility problem cases are much more common. These
problems often occur when the ingredients aren’t mixed well or when manufacturers face
mixing problems. Electrolyte adjusters aid in solubility problems. Materials such as NaCl
often help in these types of problems. Solution aided by heat can also help in shampoo
manufacturing. Citric acid balances the shampoo’s pH. The addition of citric acid aids in
balancing the shamppo’s pH level which is in the range of 5.6 to 6.2
Shampoo Formulations
Frequent wash formula shampoo is for daily use. This shampoo formulation is often used
daily, with lower active ingredient concentrations and higher surfactant levels - these
shampoos are gentle to the hair which help sebum levels to be balanced in order not to
damage the hair. Ex. Palmolive, Sunsilk
Conditioning shampoo makes hair lustrous and soft. This shampoo claims to do two
things - conditioning and wash; they have grown in popularity in recent years. These
formulations contain silicone and polyquaterniums that enables the formulation’s desired
effect, however, manufacturers are implored to make sure that silicone levels are
balanced and can be diminished when washing. Ex. Creamsilk
Premium shampoos balance, thicken, and add volume to hair. In recent years these type
of formulations have exhibited growth in popularity due to their claims. These shampoos
have mild surfactant levels and utilize excipients such as panthenol and wheat proteins.
Ex Tresemme
Anti Dandruff shampoos have zinc pyrithione. Anti Dandruff shampoos are
straightforward, with the aid of an active ingredient like zinc pyrithione it alleviates
dandruff problems which stem from scalp irritation to eczema to seborrheic dermatitis. In
recent advancements pyroctone olamine which has a pyridine ring is utilized in order to
produce clear anti dandruff shampoos, used as an antimicrobial agent; also Triclosan can
be employed as an ingredient for antimicrobial purposes however its anti dandruff activity
has yet to be observed. Ex. Head and Shoulders
Baby shampoos should be gentle to babies when applied. This formulation has intricate
requirements as it is used in babies. Nonionic detergents like polysorbate 20 are often
employed together with PEG 600 distearate in which controls the preparation’s viscosity.
Ex. Johnsons…….. under the age of 3
10 Hair colorants
Hair colorants are ancient. These hair products date back to thousands of years ago. Hair
dye formulations have advanced in techniques. Over the years these techniques in
improving formulations have been centered around longer wear before fading of color.
Due to this shift, products with gentler formulations and newer thickening systems have
risen in the market. Hair is diverse around the world, from light blonde to dark blacks.
Dopaquinone initiates pheomelanin and eumelanin formation. Pheomelanin and
eumelanin are both pigments that enable us to have color in our hair. Pheomelanin is for
reds and yellows while Eumelanin is for dark browns and blacks. Dopaquinone initiates
pheomelanin formation when it reacts with cysteine, on the other hand, an intramolecular
reaction causes dopaquinone to produce eumelanin. Hair is diverse around the world,
from light blonde to dark blacks.
Pheomelanin and Eumelanin when combined produces different hair color variations.
This is in fact dependent on the amount of the pigments present and the size of
distribution of the pigment granules in the hair fiber.
Factors affecting Dye Performance and Absorption of Dyes
Hair dye affects the cuticle and the cortex. The cuticle is a crystalline protein structure
with overlapping layer structure in the hair. On the other hand, the cortex is a gelatinous
material in the hair. The cuticle regulates dye absorption. With this in mind the cuticle
absorbs product through diffusion which is then absorbed into the hair fiber. In diffusion,
the smaller the particle the faster it is absorbed opposite to larger molecules.
Damaged fiber absorbs larger molecules faster. With the hair fiber damaged, large
molecule absorption is fastened which affects the hair making it more porous. This
declines the cuticle’s resistance towards absorption. Alkaline pH and urea’s role in hair
dye performance. Manufacturers have to note that the usage of alkaline pH and urea in
a product permits the potential of diffusion. Right after washing, the hair returns to its
normal pH and state.
Hair colorant excipients affect dye absorption. Thickeners, pH, surfactants have direct
effects on the finished product. These excipients determine the partition coefficient of the
hair dye between the hair dye and the carrier. Glycol derivatives and alcohol can solubilize
ingredients. This aims to lessen the impact or the hair dyes performance.
Major Categories
There are different categories of hair dye which differ from pH levels, thickeners, and
amount of dye. These variables are important as they directly affect the performance of
the product.
So… the major categories are:
• Temporary
• Semi Permanent (direct dyes)
• Gradual colorants (auto-oxidative and metallic dyes)
• Natural dyes
• Demi Permanent (oxidation dyes)
• Permanent (oxidation dyes)
The feel of the hair when the dye is applied and the wearing properties greatly influences
how dyes are formulated.
Temporary Dyes
Based on acid dyes
Damaged hair and heat affect dye longevity. Leave-in dye technique. The hair is not
rinsed after application.
Semi Permanent Dyes
Used for forty years already.
Offers dark colors without hydrogen peroxide. Which results in zero hair melanin
bleaching, they wash out regularly, and apply mild highlighting to the hair.
These products wash out gradually, so there is no problem with roots or retouching. They
are easy to use, and do not require mixing. Hence they are a good entry product. Finally,
they are easy to fragrance, because there is no Ammonia. This method uses compounds
that are already coloured. i.e. no chemistry occurs to form the dye compounds in the hair,
as in oxidation dye products. Which allows the dye to wash out gradually with time.
Delivery systems are optimized to produce a good product. The excipient parameters are
employed in order to make sure that the shampoo preparation is highly optimized when
it comes to its partition coefficient.
Semi Permanent dyes weren’t popular until recently. The lack of good violet and blue
colors impacted its popularity. Semi permanent dyes not only diffuse into, but out of, the
hair. With this process it allows the person’s percentage coefficient to have balanced
levels. Thus, when formulating,one generally uses dyes with a wide range of molecular
sizes. This is necessary to obtain the full color palette and to compensate for the fact that
permeability and substantivity of the dyes differ for the porous tips of the hair and
undamaged root end.
PERMANENT SYSTEMS: DYES

Formulation
Fine-tuning- Colour, Intensity, Brightness
Reactive species for the couplers are the conjugate bases,
p-phenylenediimines and uncharged p-benzoquinone monoimine
The rate of break down of H ₂O ₂ increases with pH.
Facts
p-Phenylenediamines with resorcinol
α-Naphtol
There is some Background colour formation by p-phenylenediamine

Novel approaches
Formation of Indo dyes
L'oreal patented the use of an iodide catalyst
Clairol developed a method that did not require H2O2

Oxidation dye product enhancements

Alkyl phenol ethoxylates
Polymeric thickeners
Pohl et al suggest the use of polyacrylate thickeners
a. Dye-containing component & Peroxide component + Alkalizing agent

Oxidation dyes: minimizing fading on the hair

“permanent” colour on the hair
OFF-shade fading
Blue indo dye formed from m-phenylenediamine cyclized to form a red phenazine
Prevent degradation of red dyes

Gradual colorants
Application of heavy metals
Solutions of lead/bismuth salts
Roman empire

Auto-oxidative dyes
Reasons why they have not been utilized
1. Difficulty in manufacture & Handling of the most useful dyes
2. Inability to "fine-tune" the shades

NATURAL DYES
Clairol invention- Melanin, Cupric ion + 5,6-dihydroxyindole (1% or less)
Ferricyanide-mediated oxidation of DOPA- combined with oxidation dye
precursors
Plant pigments- logwood, chamomile, henna