HAIR DYE

Hair dye is one of the oldest known beauty preparations, and was used by ancient
cultures in many parts of the world. Records of ancient Egyptians, Greeks,
Hebrews, Persians, Chinese, and early Hindu peoples all mention the use of hair
colorings. Early hair dyes were made from plants, metallic compounds, or a mixture
of the two. Rock alum, quicklime, and wood ash were used for bleaching hair in
Roman times, and herbal preparations included mullein, birch bark, saffron, myrrh,
and turmeric. Henna was known in many parts of the world; it produces a reddish
dye.
Many different plant extracts were used for hair dye in Europe and Asia before the
advent of modern dyes. Indigo, known primarily as a fabric dye, could be combined
with henna to make light brown to black shades of hair dye. An extract of the
flowers of the chamomile plant was long used to lighten hair, and this is still used in
many modern hair preparations. The bark, leaves, or nutshells of many trees were
used for hair dyes. Wood from the brazilwood tree yielded brown hair dyes, and
another hair dye known in antiquity as fustic was derived from a tree similar to the
mulberry. Other dyes were produced from walnut leaves or nut husks, and from the
galls, a species of oak trees. Some of these plant-derived dyes were mixed with
metals such as copper and iron, to produce more lasting or richer shades.
The golden red hair captured by many Renaissance painters was artificially
produced by some women. The Italian recipe was to comb a solution of rock alum,
black sulfur, and honey through the hair and then let the hair dry in sunlight. Other
hair dyes, dating from the sixteenth century, were preparations of lead, quicklime,
and salt, or silver nitrate in rose water. Another early method of coloring hair was to
apply powder. Pure white powder for hair or wigs was the mark of aristocratic dress
in Europe during the seventeenth and eighteenth centuries. White powder was
made of wheat starch or potato starch, sometimes mixed with plaster of paris, flour,
chalk, or burnt alabaster. Similarly colored powders were sometimes used as well.
These were made by adding natural pigments such as burnt sienna or umber to
white powder to make brown, and India ink was sometimes used to make black
powder. In Biblical times, people used powdered gold on their hair. The use of
powdered gold and silver returned briefly as a fad in Europe among the wealthy in
the mid-nineteenth century. Other hair colorants were blocks similar to crayons
made with wax, soap, and pigments. These could be wetted and rubbed on the
hair, or applied with a wet brush.

Preparations such as these were the only hair dyes available until the late
nineteenth century. Hydrogen peroxide was discovered in 1818, but it was not until
1867 that it was exhibited at the Paris Exposition as an effective hair lightener. A
London chemist and a Parisian hairdresser began marketing a 3% hydrogen
peroxide formula at the Exposition as eau de fontaine de jouvence golden (golden
fountain of youth water), and this was the first modern chemical hair colorant.
Advances in chemistry led to the production of more hair dyes in the late nineteenth
century. The first synthetic organic hair dye developed was pyrogallol, a substance
that occurs naturally in walnut shells. Beginning in 1845, pyrogallol was used to dye
hair brown, and it was often used in combination with henna. Socalled amino dyes were developed and marketed in Europe in the 1880s. The
earliest was p-phenylenediamine, patented in Germany by E. Erdmann in 1888 as
a dye for fur, hair, and feathers. To dye hair with p-phenylenediamine and related
dyes, a weak solution of the chemical, mixed with caustic soda, sodium carbonate,
or ammonia, was applied to the hair. Then hydrogen peroxide was applied, which
brought out the color. The amino dyes produced a more natural-looking black than
previous dyes, and could make shades of red and brown as well.
A French hairdresser, Gaston Boudou, first marketed a standardized range of hair
dyes in 1910. Whereas earlier hair colors had been mixed on the spot by hair
dressers, and the colors produced were variable, Boudou's dyes produced a
predictable color. Sold in a range of 18 colors, from black to light blond, these
became very popular both in Europe and in the United States. The amino dyes,
however, caused allergic reactions in a significant portion of users. Researchers in
the United States are credited with creating a modified, less toxic amino-based hair
dye, for standardizing the method of applying the dye, and for establishing strict
specifications for the purity and strength of the raw materials. Further advances in
hair dye chemistry were made by the makers of Clairol. Clairol produced the first
one-step hair dye in 1950. This eliminated the time-consuming
preliminary shampoo and pre-lightening that was the established hair-dying
protocol. With intensive marketing of this easy-to-use product, the percentage of
women in the United States who dyed their hair grew from approximately 8% to
almost
50%
by
1973.

RAW MATERIALS
Most commercial hair dye formulas are complex, with dozens of ingredients, and
the formulas differ considerably from manufacturer to manufacturer. In general, hair
dyes include dyes, modifiers, antioxidents, alkalizers, soaps, ammonia, wetting
agents, fragrance, and 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). The dye chemicals
are usually amino compounds, and show up on hair dye ingredient lists with such
names as 4-amino-2-hydroxytoluene and m-Aminophenol. Metal oxides, such as
titanium dioxide and iron oxide, are often used as pigments as well.
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. One
commonly used modifier is resorcinol, though there are many others. Antioxidants
protect the dye from oxidizing with air. Most commonly used is sodium sulfite.
Alkalizers 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 alkalizer.
Beyond these basic chemicals, many different chemicals are used to impart special
qualities to a manufacturer's formula. They may be shampoos, fragrances,
chemicals that make the formula creamy, foamy, or thick, or contribute to the overall
action of the formula.
Hair dyes are usually packaged with a developer, which is in a separate bottle. The
developer is most often based on hydrogen peroxide, with the addition of small
amounts of other chemicals depending on the manufacturer.

Checking ingredients

1 Before a batch of hair dye is made, the ingredients must be certified. That
is, the chemicals must be tested to make sure they are what they are
labeled, and that they are the proper potency. Certification may be done by
the manufacturer in-house. In many cases, the ingredients arrive from a

reputable distributor who has provided a Certificate of Analysis, and this

satisfies the manufacturer's requirements.

Weighing

2 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.

Pre-mixing

3 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 158F(70C) is pumped in. Other ingredients or solvents may also
be added to the pre-mix. The pre-mix is agitated for approximately 20
minutes.

Mixing

4 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.

In a formula in which no pre-mixing is required, after checking and weighing, the in

gredients 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

104F(40C), so that it does not evaporate. Fragrances too are often added at the
end of the mix.

Filling

5 The finished batch of hair dye is then piped or delivered to a tank in the
filling area. A nozzle from this tank lets a measured amount of hair dye into
bottles, moving beneath it on a belt. The filled bottles continue on the belt to
machines, which affix labels and cap them.

Packaging

6 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.

Quality Control
Government regulations control what ingredients may be used in hair dyes, as
many of them are toxic. Industry researchers will have already tested a formula
numerous times in the laboratory before it reaches the manufacturing stage, to
make sure a formula is non-irritating, works well, performs consistently, etc. As part
of the manufacturing process, workers check their chemicals before they go into a
batch, to make sure only the correct chemicals at the correct potency are used.
After the batch is mixed, samples are taken, and these are subjected to a series of
standard tests. Lab technicians make sure that the batch is the required viscosity
and pH balance, and they will also test the dye's action on a swatch of hair. If a hair
dye formula is being made for the first time, or if a formula has been altered,
technicians will also test samples of the dye after the filling stage.

BIBLIOGRAPHY
Balsam, M.S. and Edward Sagarin. Cosmetics Science and Technology. John
Wiley
&
Sons,
1972.

Today, hair dyes are widely used, either to cover up grey hairs, or simply by those
wanting to change their natural hair colour. The chemistry behind how they change
the colour of hair can actually get pretty complicated, but this graphic tries to boil it
down to the key classes of chemicals involved, and an overview of the process that
produces the dye molecules.
Before talking about the chemistry of hair dyes, its worth giving a mention to the
molecules that cause our hair to be coloured in the first place. These are pigments
called melanins, of which there are two types: eumelanin, and pheomelanin.
Eumelanin causes shades ranging from brown to black, whilst pheomelanin gives
colours in the range of blond to red. Darker hair, therefore, contains more

eumelanin; generally, eumelanin is often the more abundant of the two types,
though red hair contains primarily pheomelanin. Differing hair colours are merely
the consequence of different balances in concentrations of these two pigments,
and blond hair is often a result of a low concentration of melanin in general.
There are a number of ways of dyeing hair, but well be examining permanent
(oxidative) dyes. These dyes are based on an observation made over 150 years
ago, that a chemical called paraphenylenediamine (PPD) produces brown shades
when exposed to oxidising agents. Today, PPD is still one of the primary chemicals
used in hair dyes as a primary intermediate, and, despite a number of online claims
to the contrary, its use in these dyes is not banned in any country, though its levels
are regulated. Its ubiquity, along with that of similar related compounds, is due to
the fact that even in the 150 years since the discovery of its potential, weve still yet
to find any better alternative for permanent hair dyeing. The PPD derivative 2,5diaminotoluene or p-aminophenols are also sometimes used as alternative primary
intermediates.
Primary intermediates only produce dye molecules when exposed to an oxidising
agent. For this reason, hydrogen peroxide is included in almost all hair dyes.
Hydrogen peroxide is a strong oxidising agent, and can oxidise the natural melanin
pigments in hair, removing some of the conjugated double bonds that lead to their
colour, and making their molecules colourless. More commonly, of course, we refer
to this as bleaching the hair. The peroxide also oxidises the primary intermediate
molecules, producing a reactive species which can then go on an react and form
the dye molecules.
Of course, just being able to dye hair a dark brown colour wouldnt be all that much
use if dark brown isnt the colour youre after. For this reason, other compounds are
also added into the hair dye mixture. Known as couplers or coupling agents, whilst
these compounds are not coloured themselves, they can react with molecules of
the primary intermediates to produce a range of different coloured dyes. Hair dyes
will typically include a range of different couplers in varying concentrations in order
to achieve the exact shade required, so its rarely the case of it being one particular
dye that causes the hair colour, but a mixture. The couplers are broadly grouped
into three categories: blue couplers, red couplers, and green couplers.
The reactions which produce the dyes are carried out at an alkaline pH, and in
many cases this is provided by the presence of ammonia in the formulation. The

ammonia causes the cuticles of the hair to swell, which then allows the dye
molecules to pass into the hair and induce permanent colouring. This process can,
however, damage the hair, particularly if you frequently dye it. For this reason,
many companies have produced ammonia-free hair dyes, using substitutes such
as ethanolamine. This is a milder agent, but also doesnt cause the cuticle to swell
as much as ammonia, meaning it has a few aesthetic drawbacks: it often washes
out after a certain time period, unlike permanent colourings which merely grow out,
and isnt as effective at lightening hair.
If youre a regular user of permanent hair dyes, you might be wondering if there are
any health concerns surrounding them. Some components in hair dyes have been
categorised as sensitisers that is, that after an initial exposure, a repeat
exposure could lead to an allergic reaction. This is the reason that some hair dyes
recommend performing an allergy test 48 hours before applying the formulation to
the hair, in order to guard against severe allergic reactions. Whilst life-endangering
reactions are rare, they are not unheard of only this month, a woman
experienced potentially deadly anaphylaxis, and another woman died in 2011 after
a similar reaction.
Cancer risk from some of the chemicals in hair dyes has also been debated. Whilst
studies have yet to establish a strong link, some studies looking at people who use
hair dyes regularly at work discovered a correlation with a minor increase in rates of
bladder cancer. As a result, they recommend that gloves are always used when
applying the dyes. Studies on those who merely dye their own hair at home found
no relation between development of bladder cancer and use of the dyes, though
future studies may help to clarify whether this also poses a minor risk. If you do use
hair dyes, gloves should be used, and the formulation shouldnt be left on the hair
for longer than the recommended time period.