Hair Dyes and Colorants

Unit 2, Lec No 16
 What is hair dye?
•Hair Dye or Hair Color: is
a chemical tool that is used
to change the color of a
person's hair.
•used mostly to change
gray hair; a sign of an
advanced age.
•Younger people that used
hair dye use it as a fashion
 What is Hair Dyes ?

• Hair Dye or Hair color is a chemical tool which is used to change

the color of person’s hair.
• They are used mostly to change gray hair, a sign of an older age.
• Now in current trend younger people used hair color as a
fashion.
 Hair Structure

• Human hair is mainly made up of Keratin, water and dead cells.

• Each Strand of Hair is made up of three layers;
I. Cuticle
II. Cortex
III. Medulla
• Cuticle is made up of scale-like,
overlapping protein cells which protect
the
cortex
•A healthy hair: when the cuticle lie flat
around the hair shaft.
•A damaged hair is when the cuticle of the
hair is raised.
•Natural black hair
color is due to melanin
clusters of dispersed
within the colorless
keratin-based cortex
of hair.
 history of hair dye
• French researchers have found that
Egyptians, Greek and Romans were using to
dye their hair several thousands years ago
• Since the Greco-Roman period, organic hair
dyes obtained from plants such as henna
have been used, but other unusual formulas
based on lead compounds which generated
lead sulfide (PbS) nanocrystals with a
diameter of only 5 nanometers .
Pharaoh Ramesses II ,reddish-yellow
colour of the mummy's hair had been
brought about by its being dyed with a
dilute henna solution;
They found that the treated hair showed the
presence of galena nanocrystals(under 5 nm). but
these blackening PbS particles are much smaller than
melanin clusters by 4-5 orders of magnitude in
.volume
• In 1907, Eugè ne Schueller, a
young French chemist,
developed an innovative hair-
colour formula. He called his
improved hair dye Auréole.
Schueller formulated and
manufactured his own
products, which he then sold
to Parisian hairdressers.
 Cortex

• It is located peripheral to the medulla and forms the major part of the
shaft.
• It consists of elongated cells, containing pigment granules in dark hair
while air in white hair.
 Cuticle

• It is the outermost layer of the hair and consists of keratinized.

• It is made up of scale-like protein cells which are overlapping.
• Protein cells protect the cortex.
• Natural black hair color is due to the melanin clusters of dispersed within
the colorless keratin-based cortex of hair.
 Medulla

• It is the central part of the shaft and is generally noticeable in thick

hairs.
• It is composed of two or three rows of polyhedral cells containing
pigment granules and air spaces.
 Hair Follicle
• It is surrounding the root of the hair.
• It is made up of an external root sheath and an internal root sheath.
• The external root sheath is downward continuation of the epidermis.
• Near the surface it contains all the epidermal layers.
• The external root sheath contains only stratum Basale.
• The hair follicle is divided into three segments.
• Around each hair follicle are nerve endings called hair root plexuses which
are sensitive to touch.
• They respond if a hair shaft is moved.
1. Infundibulum
2. Isthmus
3. Inferior segment
 Infundibulum

• It extends from the surface opening of the follicle from the surface
opening of the follicle to the level of the opening of its sebaceous
gland.
• The infundibulum's a part of the pilosebasecous canal that is used as a
route for the discharge of sebum.
 Isthmus

• It extends from the infundibulum to the level of insertion of the

arrector pili muscle.
 Inferior segment

• It is in the growing follicle of nearly uniform diameter except at its

base
• The base of the bulb is invaginated by a tuft of vascularized loose
connective tissue called dermal papilla.
• The papilla of the hair contains many blood vessels and provides
nourishment for the growing hair.
• The bulb also contain a ring of cell called the matrix.
• Matrix is the germinal layer, responsible for the growth of the existing
hairs and produce new hairs by cell division when older hairs are
shed.
 Sebaceous(oil) glands

• It is responsible for the oily secretion called sebum.

• Sebum is the mixture of fats, cholesterol, proteins and inorganic salts.
• It prevent hair drying and prevent excessive evaporation of water from
the skin,
 Hair color

• The color of the hair is due to primarily to melanin.

• It is synthesized by melanocytes scattered in the matrix of the bulb and
passes into cells of the cortex and medulla.
• Dark-coloured hair contains mostly true melanin.
• Blond and red hair contain more sulfur.
• Grey hair occurs with a progressive decline in tyrosine, an enzyme
necessary for synthesis of melanin.
• White hair results from accumulation of air bubbles in the medullary
shaft.
 Functions of Hair

1. Protective: The primary function of hair is protection.

The hair on the head provide protection from the head injury and
sunrays.
Eyebrows and eyelashes protect the eyes from foreign particles.
Hair in the nostrils protects against inhaling insects and foreign
particles.
2. Cosmetics: Long locks of shiny hairs is a cosmetic requirement, this is the only reason
hairs are shampooed, oiled, groomed, styled and even colored.
 History of hair dye

• French researchers have found that Egyptians, Greek and Romans

were using dyes several thousands years ago.
• Organic hair dyes obtained from plants such as henna have been used,
but other unusual formulas based on lead compounds.
• In the 1661 Eighteen Books of the Secrets of Art & nature, various
methods of coloring hair black,gold,green,red,yellow, and white are
explained.
• Development of synthetic dyes for hair is traced to the 1860s
discovery of the reactivity of para-phenylenediamine(PPD) with air.
 History of hair dye

• Eugene Schueller, the founder of L’ORÉAL, is recognized for creating the

first synthetic hair dye.
• In 1947 the German cosmetics firm Schwarzkopf launched the first home
color product, “Poly Color”.
• Hair dying is now become a multibillion industry which involves the use
of both plant-derived and synthetic dyes.
 Desirable Qualities of a Hair colorant

• It should impart the same color which it indicates on its label.

• It must color the hairs only and not the skin.
• The color that it imparts to the hair must be stable to air, light, water and shampoo.
• It should be easy to apply.
• It should have reasonable stability or shelf life.
• It should not be toxic to the skin or hair and should not impart the natural gloss and
texture of the hair.
• It should not be allergic and a dermatitis sensitizer.
• It should impart color to the hair in a short contact time.
 Types of Hair color

Most common classifications

• Temporary
• Semi-Permanent
• Demi-Permanent:
-Oxidative Deposit-only
• Permanent:
-Deposit
-Oxidative
 Temporary

• These type of hair colors used to color the hair for temporarily.
• The colorants which are used doesn’t penetrate into the hair or surroundings
• Can be easily rinsed off after one shampooing.
• Temporarily hair coloring some time used to apply finely ground metals by means of
a “Puffer Spray”.
• Such metals, which includes brasses, bronzes and aluminum , both untreated and
anodized in various colors, it provides metallic effect when applied to hair, mainly
used for highlighting.
• Powders, setting lotions, crayons are used for temporary color.
• Hair spray is used to prevent the powder ‘brushing-off’ easily.
 Temporary

• Temporary hair coloring may also achieved by using yhe leuco

derivative of a basic dye like crystal violet.
• The various types of products used for temporary coloring of hair
include rinses, lotions, aerosols, crayons, etc.
• In rinses aqueous or hydro alcoholic solutions of simple dye stuffs are
used.
• In lotions dyes in solution with a transparent polymer, such as 3%
polyvinyl pyrolidone in water or aqueous alcohol.
• Crayons are used either directly rubbed on to the wet hair or applied
with the help of hair brush.
 Hair Crayon

• Formula
Triethanolamine 70%

Glycerol monolaurate 5.5%

Gum Tragacanth 2.5%

Stearic acid 13.5%

Beeswax 5%

Carnauba wax 13.5%

Ozokerite 8%

Color 9.5%
 Hair Dye Powder

• Formula
p-Phenylenediamine sulfate 11%
p-Aminophenol q.s
m-Phenylenediamine sulfate 15%
4-Chlororesorcinol 10%
Tetra sodium EDTA 1.50%
Erythorbic acid 3%
Carrageenan and Xanthan gum 11%
Sodium lauryl sulfate 11%
Monohydrate sodium perborate 25%
Sodium Chloride q.s
 Temporary Colour-in-Shampoo

• Formula
Water 50.10%
Polyquaternium-10 1.50%
Methyl Paraben 0.15%
Propylene Glycol 2%
Disodium Cocamido Propionate 15%
Lauramide DEA 2%
Citric acid 0.70%
Lauramide Oxide 5.55%
PEG-5 hydrogenated tallow amine 4%
Colorant 1%
 Semi-Permanent Colorants

• Most of them are basic dye stuffs, whose cationic character gives them
a natural affinity for the hair.
• Metallized dye stuffs in combination with nitro derivatives of aromatic
diamines or aminophenols.
• Shampoo is the most commonly used base.
• Performance of colorants can be enhanced by the inclusion of
solvents.
• Semi-permanent dyes contain mainly either Nirtophenylene diamines
either Nitroaminophenes or either Aminoanthraquinones.
 Liquid Hair Color (Semi-Permanent)

• Formula
Basic dye <1
Cetyl trimethyl ammonium chloride-30% 3
Oleth-20 0.5
Hydroxy propylmethyl cellulose 0.8
Triethanolamine Up to ph 8
Preservative q.s.
Perfume q.s.
Benzyl alcohol 3
Deionised water Up to 100
 Cream Hair Colourant(Semi-Permanent)

• Formula
Basic dyes <1
Cetyl trimethylammonium chloride-30% 4
Oleth-20 0.2
Cetosteryl alcohol 3
Glyceryl sterate/PEG-100 sterate 3
Triethanolamine Up to ph 8
Preservative q.s
Perfume q.s
Deionised water Up to 100
Shampoo Hair colourant(Semi-permaent)

• Formula
Metallized dyes <2
Ammonium lauryl sulfate-30% 10
Oleth-20 0.5
Hydroxy propyl methyl cellulose 0.5
Citric acid 0.3
Preservative q.s
Perfume q.s
Benzyl alcohol 2
PPG-2 butyl ether 2
Deionised water Up to 100
 Permanent Hair color

• Most Popular hair dye products.

• The dyes are formed during the dyeing process and are not present, as such in the solution
before application.
• Consists of two parts-(i) Dye intermediate
(ii) Oxiding agent
• Dye intermediates are blends of primary intermediates and coupling agents or modifier, in a
suitable base.
• During the dying of hair, the intermediate solutions and the oxidizing solutions are mixed
and
applied to the hair.
• The primary intermediates are gradually oxidized and then undergo coupling reacetion with
modifiers.
2.Permanent hair colors:
• are the most popular hair dye
products
• Permanent hair-coloring dyes consist
of three components. They are:
• Primary intermediates & Couplers(the
color)
• Oxidants (Hydrogen peroxide )
• An alkali usually ammonia
• The primary intermediates form color
on oxidation.
• The modern permanent dyes consists of
solutions of paraphenylenediamine (PPD),
or similar “para” compounds.
• Couplers will react with the oxidized
products of the primary intermediates and
form dyes which are then applied to hair.
• Hydrogen peroxide is a major factor
in permanent hair coloring techniques
• Hydrogen peroxide
diffuses the melanin,
and lightens the
natural color of hair

□ Ammonia causes
cuticle to swell and
separate

□ Both agents called the

developer
Dye
molecules
Permanent Hair color

• The primary intermediate hould be an aromatic compound with least

electrone donating groups in the 1,2 or 1,4 positions.
• The most effective combination are either two amino groups or one
amino groups or one amino and one hydroxyl group attached to
benzene or toluene ring.
Permanent Hair color

• Oxidation then takes place to form quinonimine e.g.,

 Skin and eye manifestations
• . Nowadays, it is well
known that PPD cause
skin irritation, kerato-
conjunctivitis,
conjunctival swelling and
eczema of the eyelids.
Allergic reactions
causing dermatitis,
urticaria and asthma
have also been reported
 Respiratory system and upper
airway manifestations
• One of the most severe
clinical manifestations
and the main cause of
death in PPD poisoning is
upper airway
obstruction (angio-
edema) manifesting
with a hard swollen
protruding tongue and
edematous bull neck.
• required tracheostomy
for upper airway
obstruction
Permanent Hair color

• Permanent dye systems are able to dye hair a lighter shade than the
original.
• Peroxide and ammonia, present in excess to controlled oxidation of
intermediates and simultaneously bleach hair.
• These dyes are capable of confusing the difference in color between
individual hair.
• Very effective on mixed colored white hair and black hair.
• They cause some hair damage.
 Base for Oxidation Hair Dye

• Formula

Isopropanol 7.5

Oleic acid 22

Coconut diethanolamide 10

Ammonium(0.880) 6.6

Deionised water q.s. to 100

 Base for Oxidation Dye

• Formula
PPG-2-methyl ether 1.8
Oleic acid 4
Coconut diethanolamide 11
Sodium lauryl ether sulfate,27% 36
Salt q.s.
Ammonium(0.880) 2
Deionisd water q.s. to 100
 Paraphenylene Diamine
((PPD
paraphenylenediamine,
or
1,4-diaminobenzene,
or 1,4-
phenylenediamine
 PPD
• This derivative of aniline,
aromatic amine, is a
colourless solid when
pure but are partially
oxidized and appear
yellowish.
• Some misinformation has
led to PPD being
described as a black
mineral from the bank of
the River Nile. This
gave PPD an undeserved
distinction as being
natural. (PPD crystals)
Black stone dye
 uses
• PPD is a precursor
to aramid Kevlar (p-aramid fibre)
dyeings
plastics and
fibers such as
Kevlar.
• dyeing furs
• Photochemical

measurements
• azo-dye
• as a hair dye
• mixed with ‘Henna’ to
color palms of hands and
soles of feet and to dye
hair a dark red shade .
• it was also used to kill
wild animals when added
to food .
 Toxicity of PPD
• First case of PPD poisoning was reported in
a hairdresser in 1924 following exposure
due to PPD dye handling.
• PPD is readily absorbed on dermal contact.
Six children in a series of 31 Sudanese
children with PPD poisoning were reported
not to have ingested hair dye. An Arab
lady developed acute life threatening
pulmonary edema after she had painted
one hand with a henna mixture.
• PPD poisoning commonly by ingestion
• PPD is metabolized by
cytochrome P450 oxidase to
form a reactive metabolite
Bondrawski’s base ,a
compound reported to cause
anaphylaxis as well as being
strongly mutagenic and highly
toxic
• Excreted by kidneys
 Natural Permanent Dye

Vegetable Tints:
• Made up From plant materials and henna which gives
Brownish-chestnut shade.
• Henna is obtained by grinding leaves and stems

of Lawsonia alba known as Egyptien privet.

Problem:
• Henna can trigger asthma and other allergic
reactions.
• Application is laborius and messy Cause staining of
Fingers and nails
 Evalution Parameter of Hair Dye

• Consistency- It should not too viscous, otherwise application will

become difficult, the consistency should be minimum so that
after application it will not drain off.
• Spreadabillity- Hair dye should be easily spreadable so it can easily
apply evenly.
• Color Uniformity- The color of hair dye and hair color should be
uniform, color shade should be remains same and gives desired color
after application.
• pH- pH should be netural.
 Evalution Parameter of Hair Dye

Allergy test:
• Remove earrings. Behind the ear and using a cotton bud, apply a small quantity
of unmixed colorant product sufficient to cover an area of 1-2cm² (e.g. the size of
a small coin).
• Re-apply two or three times allowing it to dry between each application.
Carefully
reseal the colorant container and keep it for the application 48 hours later.
• Leave for 48 hours without washing, covering or touching.
• If during this period you notice any abnormal reactions, such as itching, redness
or swelling in or around the test area, Do Not Apply The Product.
 References

• Google
• Cosmetics and Toiletries Industry by Williams and Schmitt.
• Cosmetics by Poucher.
• Cosmetics by Sagarin
• Cosmetics: Formulation Manufacture and Quality Control by P.P.
Sharma
Thank You