Hair Coloring

Products
CE 457/527
Colloid and Surface Phenomena
Spring 2004

Shushan Munshi
2785-9562

Table of Content
Introduction

Formulation
Permanent & demi-permanent hair color
Semi-permanent hair color
Temporary hair color

4
4
7
8

Coloring Process

10

Packaging

12

Reference

13

Introduction
Hair coloring is currently a globally accepted fashion phenomenon. From the
young generation with playful attitude towards hair coloring to the older generation who
hide their gray hair, hair coloring products have been consumed by both men and women.
To meet the customer demand and to further enhance the product, research has been done
to improve the coloring affects and to minimize the damage to the hair. This report will
focus on the few types of hair coloring products and the coloring process of the hair will
be discussed in a molecular level.
In the market, several different kinds of hair coloring products are available. Hair
coloring can be applied through coloring shampoos or hair dyes. The hair coloring
products can be categorized in several types, which include the permanent, demipermanent, semi-permanent, and temporary. The permanent coloring lasts until the hair
grows out, demi-permanent lasts up to 24 washes, semi-permanent lasts for six to eight
weeks, and temporary lasts for one to three washes. [7]
In general approximately one third of the world market is accounted by Western
Europe, a quarter by North America, and one fifth by Latin America, and 15% by the
Asia-Pacific region. Studies have shown that the permanent hair coloring products make
up the majority of the market worldwide. Often these products will be described as
Level 3 for the use of oxidative or permanent dyes. A lot of the products has been
targeted towards the male market as well has the teenagers. There are demands for
brighter hair color and as well as hiding the gray hair with a lighter color. Either way, the
market is growing as well as the research done in this subject. [7]

Formulation
Permanent & demi-permanent hair color:
Permanent hair coloring product is formulated with two different components of
precursor-coupler base and oxidizing base. The precursor-coupler base consists of
surfactants, alkaline, reducing agent, precursors, couplers, and water (Table 1). The
oxidizing base consists of an oxidizing agent (e.g. peroxide), stabilizer for the peroxide,
and surfactants (Table 2). Since the peroxide is unstable in alkaline solution, the
precursor-coupler base and the oxidizing base have to be formulated separately for
product storage. [2&8]
Surfactants are used to help dissolve the precursors and couplers, to assist in
spreading the dye evenly over the hair, and to thicken the product so it does not drip
easily while applying the product. [2] Alkaline is required to facilitate the oxidation
reaction, and the reducing agent to inhibit oxidation of precursors by air. The surfactant
in the oxidizing base works as a thickener by the surfactants precipitating on dilution
when the two components are mixed together, resulting in a much thicker mixture. [4]

Ingredient
Dodecyl benzene Sulfonate (50%)
Cocodiethanolamide
Neodol 91-2.5
Ammonium hydroxide
Sodium sulfite
p-Phenylenediamine
o-Aminophenol
p-Aminophenol
4-Methyl-5-aminophenol
m-Aminophenol
Water

Weight % of ingredient for desired hair color

Dark brown
Light brown
Red
Black
14.0
14.0
14.0
14.0
9.0
9.0
9.0
9.0
6.0
6.0
6.0
6.0
6.0
6.0
6.0
6.0
0.3
0.3
0.3
0.3
0.4
0.4
0.3
0.4
0.2
0.4
0.4
0.4
0.2
64.0
63.9
63.9
63.9

Table 1:Sample precursor-coupler base ingredients

Ingredient
Hydrogen peroxide (30%)
Dodecyl benzene Sulfonate (50%)
Phosphoric acid
Water

Weight %
50.0
33.0
1.0
16.0

Table 2: Sample Oxidizer base ingredients.

Dyes for permanent coloring are achieved by an oxidation reaction of a dye

precursor followed by a reaction with a dye coupler. Schematic of the reaction of an
oxidation dye is shown in Figure 1.

Figure 1: Schematic of oxidative hair dyeing reaction.

The common oxidation reagents are hydrogen peroxide and ammonium hydroxide, and
the primary intermediates are usually ortha- or para-substituted amino aromatic
compounds. Dye couplers are electron-rich aromatic phenols or amines. Figure 2 and 3
shows some sample dye precursors and dye couplers, respectively. Combination of
different dye precursors and dye couplers gives different coloring affect.

Figure 2: Example of dye precursors.

Figure 3: Example of dye couplers.

Studies have been done to control the primary intermediates. Several allergic
dermatitis and nefrotoxic effect has been reported due to aminophenols and 1,4benzenediamine, and some dye intermediates are toxic compounds and carcinogenic.

However additions of cationic surfactants of tetradecyltrimethylammonium bromide

(TTAB) or haxadecyltrimethylammonium bromide (CTAB) allows the separation of
these haza rdous intermediates. [3]
Demi-permanent hair coloring is similar to the permanent hair coloring in terms
of oxidative dyes but resembles the lasting properties of a semi-permanent hair color.
The amount of peroxide is less and therefore offers less damage to the hair.
Semi-permanent hair color:
Semi-permanent hair coloring products does not require any peroxide or mixing.
The formulation consists of solvents, surfactants, amide, fragrance, and acid or alkali
(Table 3). The solvents most commonly used are water and glycols or glycol derivatives,
and the purpose of the acid or alkali is to adjust the pH.
Weight % of ingredient for desired hair color
Ingredient
Light brown
Dark brown
Red-auburn
Cocodiethanolamide
10.0
10.0
10.0
Sodium dodecyl benze ne sulfonate (52%)
4.0
4.0
4.0
Neodol 91-2.5
6.0
6.0
6.0
Sodium lauryl sulfate
2.5
2.5
2.5
2-nitro-p-phenylenediamine
0.4
0.4
0.4
HC Red No. 3
0.2
0.2
HC Yellow No. 2
0.2
0.2
0.2
HC Blue No. 2
0.1
Water
76.7
76.6
76.9
Table 3: Sample semi-permanent hair coloring product ingredients * .

The types of dyes used are neutral aromatic amine, nitro aromatic amine, or
anthraquinone derivatives. Some examples of semi-permanent dyes are shown in Figure
4. The dyes can be classified as mono-, di-, or trinuclear (ring) dyes. Studies have
shown that small mononuclear hair dyes has a higher rate of rinsing out. Larger dyes are
*

The colors are achieved when applied to naturally light blonde hair.

able to reach more hindered position in the hair shaft and therefore the hair color lasts
longer. [2]

Figure 4: Example of semi-permanent dyes. [2]

Temporary hair color:

Temporary coloring formulation is achieved by a mixture of color additives,
surfactant, and acid or alkaline (Table 4). These products are available in the forms of
rinses, gels, mousses, and sprays.

Figure 5: Example of cationic basic dyes used in temporary hair coloring products. [2]

Cationic basic dyes are often used in the formulations. Figure 5 shows some
sample cationic basic dyes. Several different kinds of dyes are used for one formulation
to achieve the desired hair color.

Ingredient
Nonoxynol-9
Hydroxyethylcellulose (HHR)
Cetylrimmonium chloride
Neodol 91-2.5
Citric acid trihydrate
Trisodium phosphate
Direct black 51
Acid violet 43
Direct red 80
Acid orange 24
External D&C Violet 2
D&C Red 33
FD&C Yellow 6
D&C Yellow 10
Water

Weight % of ingredient for desired hair color

Brown
Red
White
1.0
1.0
1.0
0.7
0.7
0.7
0.6
0.6
0.6
0.5
0.5
0.5
0.5
0.5
0.3
0.05
0.01
0.04
0.03
0.03
0.05
0.04
0.02
0.03
0.01
0.005
0.005
96.54
96.79
96.65

Table 4: Sample temporary hair coloring product ingredient.* [2]

The colors are achieved when applied to naturally light blonde hair.

Coloring process
Human hair is primarily proteinaceous and contains a large percentage of
oxidizable groups. The external layer of the hair, called the cuticula contains a large
portion of amorphous keratin, a hair fiber. This undamaged cuticula that contains a few
polar groups, is strongly hydrophobic, and contains negatively charge ionic groups. [1]
The reaction step of the dye with the hair fibers can be summarized in the following four
phases:
1. Diffusion through solution
2. Adsorption or interaction at the fiber surface
3. Diffusion or transport into the fibers
4. Reaction at internal sites in the fibers.
The diffusion of dyes into the fibers can be assumed as diffusion into a cylinder from a
solution of limited volume or from an Infinite Bath. Both approximations give an
accurate diffusion coefficient. However, the temperature, molecular size of the dye,
cross- linking density of the fibers, fiber swelling, and exposure time plays a critical role
in color deposition. [2]
In the presence of an oxidative dye (permanent hair coloring), the hair goes
through an oxidative degradation of disulfide bonds to polar sulfonic acid groups. [1]
Studies on this issue have been done and the mechanisms proposed are a sulfur-sulfur
fission process, and a carbon-sulfur fission process. [2] As the hair is exposed to an
oxidative dye, the hair is damaged due to the irreversible process of degradation of
disulfide bonds.

10

In semi-permanent hair coloring, the dyes are small enough to enter the hair shaft
and can easily leave the hair shaft as the hair is washed (Figure 6). The color of the hair
is a result of the diffusion of dyes into the hair shaft.

Figure 6: Semi-permanent dyes are small enough to enter and exit the hair shaft. As the hair is being
washed, the dye leaves the hair shaft as the hair returns to its original color. [7]

The cationic dyes used in temporary coloring are too large of a molecule to enter
the hair shaft. Instead, the molecules stick onto the hair shaft as a result of the net
negative charge on the hair surface (Figure 7). Since the temporary dyes stick to the
surface of the hair, it is easily removed by one to three washes. However, if the hair has
been chemically treated (e.g. permanent hair coloring) prior to the application of the
temporary dye, the hair becomes more porous and allows the dye to penetrate into the
hair shaft, resulting in the hair color to last longer.

Figure 7: Schematic of the cationic basic dye attracted to the surface of the hair shaft. After a few
wash, the dye will leave the hair surface. [7]

11

Packaging
Prior to distributing the hair coloring products out in the market, the product has
to be properly packaged. The packaging is required to contain a proper label of the
product and should adhere to the FD&C regulations. The label has to advertise the
product with an attractive picture of the hair after treatment. Since the products will be
mass produced and shipped to various locations, the package has to be able to protect the
product while being transported and at the same time has to be cost efficient. [9]
A sample packaging requirements by Bristol-Myers Squibb Company specifies
the exact requirement for hair color product packaging. The package itself can be a
container (e.g. bottle, plastic, recycled paperboard, solid bleached sulphate (SBS)
paperboard). The labels have to be pressure sensitive, contain high gloss paper range of
50 to 80 pounds paper, an accurate picture of the hair shade, and should be placed on the
outer face of each container. [9]

12

Reference:
1. Frster, Th.; Schwuger, M. J. Correlation between adsorption and the effects of
surfactants and polymers on hair Progress in Colloid & Polymer Science 1990,
83, 104-109
2. Robbins, Clarence R.; Chemical and Physical Behavior of Human Hair, 3 rd Edition;
Springer-Verlag New York, Inc.; 1994
3. Lin, C.-E.; Chen, Y.-T. Migration behavior and separation of benzenediamines,
aminophenols and benzenediols by capillary zone electrophoresis Journal of
Chromatography A 2000, 871(1-2), 357-366
4. Bolduc, C.; Shapiro, J. Hair Care Products: Waving, Straightening,
Conditioning, and Coloring Clinics in Dermatology 2001, 19, 431-436
5. http://www.hairsite.com/color/color-technical.htm
6. Herman, S. To dye for Global Cosmetic Industry 2000, 167(4), 46-47
7. Rough, H.; Drake, D.; Robinson, J. Hair colourants dyeing for a change
Speciality Chemicals Magazine 2002, November Issue, 18-19
8. Brown, K. C. Hair coloring products The chemistry and manufacture of
cosmetics, 3rd ed.; Allured Publishing Corp 2000, 397-354
9. Periera, J. J.; Slavin, K. A.; Venneri, N. D.; Container with label for hair dye
United States Patent 6,106,917 2000; Bristol-Myers Squibb Company (New York,
NY)
10. R&D Activities at Kao; Brochure of Kao Corporation 2003

13