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 grey hair, a sign of an older age.
•Now in current trend younger people used hair color as a fashion.

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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.
•The first safe Commercial hair color was created in 1909 by French
Chemist Eugene schuller, using the chemical Paraphenylenediamine (PPD).
•Eugene Schueller, the founder of L’ORÉAL, is recognized for creating the
first synthetic hair dye.
•Hair dying is now become a multibillion industry which involves the use
of both plant-derived and synthetic dyes.

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Hair color
• The natural color of hair depends on the ratio and quantities of two
proteins (melanins), eumelanin and phaeomelanin.
•These are synthesized by melanocytes scattered in the matrix of the bulb
and passes into cells of the cortex and medulla.
• Eumelanin is responsible for brown to black hair shades while
phaeomelanin is responsible for golden blond, ginger and red color.
• The absence of either type of melanin produces white / grey hair i.e.,
•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.

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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.

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Types of Hair color
Most common classifications
Depending upon the deposition of various Dyes for suitable time
limit, the dyes are classified into four categories. They are :
1)Temporary
2)Semi-Permanent
3)Demi-Permanent:
– Oxidative Deposit-only
4)Permanent: –

– Non-Oxidative
– Deposit / Oxidative

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Temporary
•These type of hair colors used to color the hair for
temporarily.
•The pigment molecules are large and cannot penetrate the
cuticle layer. Instead, the color particles remain adsorbed
(closely adherent) to the hair shaft and are easily removed
with a single 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. 8 WWW.DULOMIX.COM

•Powders, setting lotions, crayons are used for temporary color.
•Hair spray is used to prevent the powder ‘brushing-off’ easily.
•Temporary hair coloring may also achieved by using the 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.

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Hair Crayon
➢ Formula

Triethanolamine 70%
Glycerolmonolaurate 5.5%
Gum Tragacanth 2.5%
Stearic acid 13.5%
Beeswax 5%
Carnauba wax 13.5%
Ozokerite 8%
Color 9.5%

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Semi-Permanent Colorants
•Also known as, Oxidation Tints / Penetrating Tints / Peroxide Tints /
Synthetic Organic Tints / Para-dyes / “Tints”
•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 Nitrophenylene diamines
either Nitroaminophenes or either Aminoanthraquinones or Aniline
Derivative Tints from Para-Phenylediamines.
• Darker dyes have more p-phenylenediamine

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Shampoo Hair colorant(Semi-permanent)
➢ 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
Deionized water Up to 100

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Demi-Permanent (Oxidative Deposit-Only)
• Process falls between the semi-permanent and permanent dye process.
• Uses a catalyst such as a 10% mild peroxide developer with a non-
ammonia alkali to swell the cuticle, allow dye molecules to penetrate into
the cortex and deposit color inside the hair shaft.
• A neutral or slightly acid after-rinse is used to stop the alkaline swelling
reaction, allow the cuticle to close, and trap the color molecules
inside.
• The mild chemical reaction does not lighten the melanin and hardly
changes the hair structure.

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• Chemicals of Concern : Uses mostly aniline
derivative dyes.
• The alkali (high pH) used to swell the cuticle
is from either Mono- ethanolamine (MEA) or
amino methyl propanol (AMP).

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Permanent Hair color
•Most Popular hair dye products.
•Consists of two parts-(i) Dye intermediate
(ii) Oxidizing 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 reaction with modifiers.

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•The primary intermediate would be an aromatic compound with least
electrons 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.

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Most permanent hair dyes use a two-step process, which first removes the
original color of the hair and then deposits a new color.
Mechanism of hair dyeing “Oxidative/Lift Deposit”
• An alkaline reaction(most often ammonia ) causes the cuticle to swell,
allowing hydrogen peroxide and dye to enter.
• The hydrogen peroxide “oxidizes” (diffuses) the melanin, and “lifts”
(lightens) the color.
• The hydrogen peroxide also causes the dye to “develop” and “deposit”
color.
• A neutral or slightly acid after-rinse stops the alkaline reaction, allows the
cuticle to close, and traps the color molecules inside.

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Base for Oxidation Hair Dye
➢ Formula

Isopropanol 7.5
Oleic acid 22
Coconut di-ethanolamine 10
Ammonium(0.880) 6.6
Deionized water q.s. to 100

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Permanent: Non-Oxidative
(Natural permanent dye)
✓ People have been coloring their hairs for thousands

of year using plant and minerals. Some of these
natural agents contain pigments e.g.: Henna, black
walnut shells (Vegetable Tints) and other contain
natural bleaching agents like vinegar.

✓ Natural pigments generally works by coating the hair
shaft with color but they aren’t more gentle than
modern formulations.

✓ Problems with Vegetable Tints: Henna – can trigger asthma and other
allergic reactions

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Metallic Dyes:
– Contain metallic salts from lead acetate, lead, copper, cobalt, silver
nitrate
– Not used professionally .toys ,furs
Compound Dyes:
– Mix of vegetative tints and metallic dyes
– Not used professionally
Problems with Metallic Dyes
• Can cause headaches, scalp irritation, facial swelling, contact dermatitis,
lead poisoning, and hair breakage, toxic,.
• Bottles of metallic dyes can explode

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Paraphenylene Diamine
(PPD)
Paraphenylene diamine,
or
1,4-diaminobenzene,
or
1,4-phenylenediamine

• PPD is the most common constituent of hair dye formulations.
PPD is commonly used in Africa, Middle East and Indian
subcontinent.

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PPD
• This is a derivative of aniline, aromatic amine,
& 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.
uses
• PPD is a precursor to aramid plastics and fibers (PPD crystals)
such as Kevlar.
• dyeing furs
• Photochemical measurements
• azo-dye manufacturing 22 WWW.DULOMIX.COM

• as a hair dye
• mixed with ‘Henna’ to color the 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 .

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Toxicity of PPD
• 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

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

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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.

Other manifestations
• It is commonly the direct cause of death in children and adults with PPD
poisoning. Cardiac toxicity is mainly caused by the direct toxic effect of PPD
on the heart, rhabdomyolysis of the cardiac muscle causing severe damage
and hyperkalemia

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Management
Hair dye ingestion is a medical emergency.
• Emergency measures should include gastric lavage. Patients should be
monitored for respiratory distress and endotracheal intubation has to be
performed early if laryngeal edema develops.
• Metabolic acidosis has to be corrected. Early intervention with half normal
saline and soda bicarbonate infusion has been shown to be beneficial in
Rhabdomyolysis.
• Antihistamines and steroids are commonly used because of the possibility
of a hypersensitivity reaction to PPD.
• Alkaline diuresis using isotonic saline, sodium bicarbonate and diuretics is
used in the management of myoglobinuria

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REFERENCES

➢ Cosmeceuticals by Y. Madhusudan Rao
➢ Cosmetics by Poucher.
➢ Cosmetics by Sagarin
➢ Cosmetics: Formulation Manufacture and Quality Control by P.P. Sharma

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THANK YOU

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