Chemistry and formulation of para phenylene diamine based hair dye

Presented by: STEFFI THOMAS
Assistant Professor
School of Pharmacy, LNCTU
Bhopal
School of Pharmacy, LNCTU, Bhopal

HAIR DYES
 Hair dye or hair color is a chemical tool which is used
to change the color of a person’s hair
 They are used to change the color of gray hair, a sign of
an older age.
 Now in current trend younger people use hair color as
a trend

HAIR STRUCTURE
 Hair is made of keratin, water and dead cells.
 Each strand of hair is made up of 3 layers:-
1. Cuticle
2. Cortex
3. Medulla

HAIR FOLLICLE
 It surrounds the root of the hair
 It is made up of external root sheath and internal root
sheath
 Sebaceous glands:- responsible for oily secretion called
Sebum
 It prevents hair drying and prevent hair drying and
prevent excessive evaporation of water from the skin

HAIR COLOR
 The color of hair is due to melanin
 It is synthesized by melanocytes scattered in the
matrix of the bulb and passes into cells of the cortex
and medulla
 Dark-colored hair contains mostly true melanin
 Blond and red color hair contains more of sulfur
 Gray hair occurs with progressive decline in tyrosine,
an enzyme necessary for the synthesis of melanin

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 DYES
 Early Egyptians used the first hair color.
 First culture to color hair
 Used:
– Henna- Red hues
– Chamomile- Blonde Hues
– Sage- Brown Hues
 Red hair was popular due to: Queen Elizabeth’s red hair.
Women would: – Apply mixture of black sulfur, alum,
and honey and sit in the sun until the hair has turned a
golden.


Cont…
 Late 1800’s Paraphenylenediamine (PPD) – Chemical
base for hair color
– Mixed with metallic salts for color
-Metallic salts are a combination of copper, lead, silver,
and other metals with a weak acid
 Early 20th Century
- Popular for actresses to color their hair.
- It wasn’t until the middle of the century that a
common woman dying her hair was accepted.

Cont…
 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.

PARAPHENYLENEDIAMINE (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.
 Paraphenylenediamine (PPD) is a chemical substance that
is widely used as a permanent hair dye.
 PPD is used in hair dye because it is a permanent dye that
gives a natural look, and the dyed hair can also be
shampooed or permed without losing its colour.
 It is a white crystalline powder

Cont..
 It is also used in other industrial products such as
- Textile or fur dyes
- Dark colored cosmetics
- Temporary tattoos
- Photographic development

Cont..
 The base PPD is colourless and requires oxygen for it to
become a dye, thus PPD hair dyes are usually packaged
as 2 bottles, one that contains the PPD dye and the
other containing a developer or oxidiser.
 Darker shades of hair dye products contain higher
concentrations of PPD than lighter shades.
 The darker shades of hair dye are often used by people
with naturally dark hair.

Cont..
 Fully oxidized PPD is not a sensitiser, but the intermediate,
partially oxidised form of PPD may cause contact
allergic dermatitis in sensitive individuals. Hair colour
preparations containing PPD or its derivatives carry a
warning on the packaging recommending
a self patch test prior to use of the dye.
 PPD was declared the Contact Allergen of the Year for 2006
by the American Contact Dermatitis Society (ACDS).

IDEAL PROPERTIES OF HAIR DYE
 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.

Composition of Hair dye
 Differ from manufacturer to manufacturer.
 In general, hair dyes include dyes,
– modifiers
– antioxidants
– alkali
– soaps
– ammonia
– wetting agents
– fragrance

Cont..
 A variety of other chemicals used in small amounts
that impart special qualities to hair (such as softening
the texture) or give a desired action to the dye (such as
making it more or less permanent).
 Dye chemicals are usually amino compounds.
 Other chemicals used in hair dyes act as modifiers,
which stabilize the dye pigments or otherwise act to
modify the shade.
 The modifiers may bring out color tones, such as green
or purple, which complement the dye pigment. e.g.
resorcinol

Cont..
 Antioxidants protect the dye from oxidizing with air.
Most commonly used is sodium sulfite.
 Alkali are added to change the pH of the dye formula,
because the dyes work best in a highly alkaline
composition. Ammonium hydroxide is a common
alkali.

TYPES OF HAIR COLOR
 Temporary hair color
 Semi permanent hair color
 Permanent hair color
 Natural permanent dye

1.Temporary hair color
 Temporary hair color is available in various product forms
including rinses, shampoos, gels, sprays, foams.
 This type of hair color is typically used to give brighter, more
vibrant shades or colors such as orange or red, that may be
difficult to achieve with semi-permanent and permanent hair
color.
 While temporary hair color products hold a lesser market than
semi- permanent and permanent agents, they have value in that
they can be easily and quickly removed without bleaching or
application of a different coloring product.
 These colorants do not penetrate into cortex or medulla.
 As such the dye is easily removed with shampoo so known as
temporary hair color

 HAIR CRAYON
INGREDIENTS QUANTITY
Triethanolamine 70%
Glycerol monolaureate 5.5%
Gum tragacanth 2.5%
Stearic acid 13.5%
Bees wax 5%
Carnauba wax 13.5%
Ozokerite 8%
Color q.s.

 TEMPORARY COLOR-IN-SHAMPOO
Water 50.10%
Polyquaternium-10 1.50%
Methyl paraben 0.15%
Propylene glycol 2%
Disodium cocamido
propionate
15%
Lauramide DEA 2%
PEG-5 Hydrogenated tallow
amine
4%
Color 1%

2. Semi permanent hair color
 Differ form color shampoo with respect to time
 Give stronger & more permanent coloration to hair
 Some colors are removed in 4-8 shampooings.
 Dyes used are: Nitrophenylenediamine,
Nitroaminopheols, Aminoanthraquinones.
 Mixture is prepared before preparing color shades.
 Should be studied on white wool or hair.
 Semi hair color has no Ammonia.

 CREAM HAIR COLORANT
Basic dye Less than 1%
Cetyl trimethylammonium
chloride-30
4%
Oleth-20 0.2
Cetostearyl alcohol 3%
Glyceryl stearate/PEG-100
stearate
3%
Triethanolamine To adjust pH upto 8
Preservative q.s.
Perfume q.s.
Deionised water Upto 100%

3. Permanent color
 All "permanent" hair color products and lighteners contain both
a developer, or oxidizing agent, and an alkalizing ingredient as
part of their ammonia or an ammonia substitute.
 The purpose of this is to:
– raise the cuticle of the hair fiber so the tint can penetrate,
– facilitate the formation of tints within the hair fiber,
– bring about the lightening action of peroxide.
 When the tint (color) containing the alkalizing ingredient is
combined with the developer (usually hydrogen peroxide), the
peroxide becomes alkaline and diffuses through the hair fiber,
entering the cortex, where the melanin is located.
 The lightening occurs when the alkaline peroxide breaks up the
melanin and replaces it with new color.

Cont..
 Ammonia is the alkaline chemical that open the
cuticle and allows the hair color to penetrate the
Cortex of the hair.
 It also acts as a catalyst when the permanent hair color
comes together with the peroxide.
 Peroxide is used as a developer or oxidizing agent.
 The developer removes pre-existing color.

Cont..
 Peroxide breaks chemical bonds in hair, releasing
sulfur, which accounts for the characteristic odor of
hair color.
 As the melanin is decolorized, a new permanent color
is bounded to the hair cortex.
 Various types of alcohols and conditioners may also be
present in hair dye.
 The conditioners close the cuticle after coloring to seal
in and protect the new color.

Cont..
 Permanent hair-coloring products consist of two
components that are packaged separately and mixed
together immediately before application.
- One package contains a solution of hydrogen peroxide
(usually 6%) in water or a lotion base.
- The other package usually contains an ammonia
solution of dye intermediates and preformed dyes—
called couplers.

 BASE FOR OXIDATION HAIR DYE
Isopropanol 7.5%
Oleic acid 22%
Coconut diethanolamide 10%
Ammonium (0.880) 6.6
Deionised water q.s. to 100

4.NATURAL PERMANENT DYE
 Now a days, plant materials are used e.g. henna leaves
 Infusions, decoctions of plant materials are used.
 The paste of powder of henna leaves prepared in hot
water
 After cooling it is applied with stiff brush & allow to
dry.
 Henna contains lawsone (2- hydroxy- 1,4-
napthaquinone)

Cont..
 Advantages of henna:
-Non-toxic
-Non sensitizing to skin
-But laborious work to prepare henna paste
- Following composition is generally used nowadays:
Powdered henna- 89%
Pyrogallic acid -6%
CuSO4 -5%
 Concentration of pyrogallic acid responsible for color

Cont..
 Disadvantages of Henna:-
-Henna can trigger asthma and other allergic reaction
-Application is laborius and messy as it can stain the
fingers and nails

Dye intermediates in semi-permanent
hair dyes
 Shades Name of dye intermediate
Yellow- 4 - nitro- m- phenylene diamine
Orange- 2 - amino- 4- nitrophenol
Red - 4 - (2- hydroxy ethyl) amino- 3- nitrophenol
Violet- 1 – 4 - diamino-5- nitro- anthraquinone

Dye intermediates in permanent
hair dyes
 Oxidation bases:
– p- phenylene diamine
– p- toluenediamine
– p- amino diphenylamine
– p- aminophenol
– p- diamino anisole
– o- phenylene diamine
– o- aminophenol

MANUFACTURING PROCESS
 Checking ingredients
 Weighing
 Pre-mixing
 Mixing
 Filling

Cont..
 Checking ingredients
• Before a batch of hair dye is made, the ingredients
must be certified.
• Certification may be done by the manufacturer in-
house.
• In many cases, the ingredients arrive from a
reputable vendor who has provided a CoA (Certificate
of Analysis) and this satisfies the manufacturer's
requirements

Cont..
 Weighing
• Next a worker weighs out the ingredients for the
batch.
• For some ingredients, only a small amount is
necessary in the batch.
• But if a very large batch is being made, and several
ingredients are needed in large amounts, these may be
piped in from storage tanks.

Cont..
 Pre-mixing
• In some hair dye formulas, the dye chemicals are pre-
mixed in hot water.
• The dye chemicals are dumped in a tank, and water
which has been already heated to 158°F(70°C) is
pumped in.
• Other ingredients or solvents may also be added to
the pre-mix.
• The pre-mix is agitated for approximately 20 minutes

Cont..
 Mixing
• The pre-mix is then added to a larger tank,
containing the other ingredients of the hair dye.
• In a small batch, the tanks used may hold about
1,600 lbs (725 kg), and they are portable.
• A worker wheels the pre-mix tank to the second mix
tank and pours the ingredients in.
• For a very large batch, the tanks may hold 10 times as
much as the portable tanks, and in this case they are
connected by pipes.

Cont..
• In a formula in which no pre-mixing is required, after
checking and weighing, the ingredients go directly to the
mixing step.
• The ingredients are simply mixed in the tank until the
proper consistency is reached.
• If a heated pre-mix is used, the second mix solution must
be allowed to cool.
• The ingredients that follow the pre-mix may be additional
solvents, surfactants, and alkalizers.
• If the formula includes alcohol, it is no added until the
mix reaches 40°C, so that it does not evaporate.
• Fragrances too are often added at the end of the mix.

Cont..
 Packaging
• From the filling area, the bottles are taken to the
packaging line.
• At the packaging line, the hair dye bottle is put in a box,
together with any other elements such as a bottle of
developer or special finishing shampoo, instruction sheet,
and gloves and cap, or any other tools provided for the
consumer.
• After the package is complete, it is put in a shipping
carton.
• The full cartons are then taken to the warehouse to await
distribution.

EVALUATION
 CONSISTENCY:-It should not be too viscous,
otherwise application will become difficult, the
consistency should be minimum so that after
application it will not drain off
 SPREADABILITY:-Hair dye should be easily
spreadable so that it can be applied evenly
 COLOR UNIFORMITY:-The color of hair dye and
hair color should be uniform, color shade should
remain same and give desired color after application
 pH:-Should be neutral

Cont..
 Sensitization test (effect on skin & eye)/Allergy test-
Behind the ear, using a cotton bud, apply a small quantity
of unmixed colorant product sufficient to cover an area of
1-2 cm2 (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 duration any sort of abnormal reaction such
as itching, redness or swelling in or around the test area,
Do not apply the product.

 Effect on hair (Half head test):-Comparative
assessment of two hair care products (shampoo,
conditioner, hairspray, gel, mousse, etc.) is performed.
For e.g. What does the foam of shampoo feel like?
Which conditioner treatment results in softer hair and
easy combing? Which product gives more volume?
Procedure- trained hairdresser part the hair of the test
subject in the middle, apply two products, each to one-
half of the hair and assess the cosmetic acceptance as
well as major product properties such as foam
consistency, spraying rate, spray pattern, residue on
hair or comb, spreadability and much more.

 Test for developer
• pH (2 to 4)
• Assay for H2O2 (max. 12 m/m)
• Residue on evaporation (max. 0.2 m/v) – % by
mass = m/V x 100

ADVERSE EFFECTS
 Hair dye or hair coloring involves the use of Chemicals
that are capable of removing, replacing or covering up
pigments naturally found inside the hair shaft.
 Use of these Chemicals can result in a range of adverse
effects including temporary skin irritation or allergy,
hair breakage, skin discoloration etc.

THANKS

Chemistry and formulation of para phenylene diamine based hair dye

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Chemistry and formulation of para phenylene diamine based hair dye