WHAT'S THAT STUFF?

March 13,2000 Volume 78, Number 11

Hair Coloring
Ever since Madonna became a star in the
mid-1980s, I—a natural brunette—had a
not-so-secret desire to be a blonde. Over the
years, I made and canceled a few
appointments to have my hair colored. I just
never had the nerve to go through with it
until last summer, when my gray streak had
gotten so big it was no longer a fashion
statement, it was—well—gray hair!

So, I kept that last appointment. I was really

going to take the peroxide plunge. Sitting in
[Photo by Cliff Braverman]
the salon, my hairdresser took what looked
like a pastry brush and saturated my hair with clear whitish goo that looked
like icing for cinnamon buns and told me, "There's no turning back, now."
When I asked, "What's that stuff?" he said he didn't know. "You have the
chemistry degree," he reminded me. A little while later, with ammonia and
other smells in the air, I didn't need a degree to tell me that there was some
serious chemistry going on up there.

Curious, I began looking around and found out that there is some pretty
interesting chemistry involved in coloring hair. Here is what I learned: People
have been changing the color of their hair for millennia, but it wasn't until
1907 that French chemist Eugène Schueller created the first safe commercial
hair coloring. His invention was based on p-phenylenediamine that later
provided the foundation of his company, the French Harmless Hair Dye Co.,
which became L'Oréal .

There are several basic types of hair dyes on the market. There are temporary
hair colors, which are applied in the form of rinses, gels, mousses, and sprays.
They coat the surface of the hair and usually wash out within two or three
shampoos. Semipermanent dyes penetrate into the hair shaft, but not as
deeply as permanent dyes. Although semipermanent dyes do not rinse off
with water, they do fade and wash out of hair after about five to 10
shampoos.

Gradual or progressive dyes—like Grecian Formula 16—surprised me. They

are usually marketed to men and contain lead acetate [Pb(CH3COO)2]. As the
solution is rubbed on the hair, it penetrates the cuticle and the Pb2+ ions react
with sulfur atoms in the proteins to form lead sulfide (PbS), which is a dark
color. The more frequently the solution is applied, the darker the, ahem, lead
head.

The most interesting chemistry to me, however, was the chemistry of

permanent hair dyes—especially those that lighten and color in one process.
These formulations penetrate deeply into the hair shaft and don't wash out.

Before any permanent color can penetrate the hair shaft, the cuticle, or outer
layer, must be opened so that chemicals can get in to the natural pigment
molecules. Under a microscope, the cuticle of human hair looks a lot like
overlapping snake scales. The pigments, which are protein granules, are
stored in the cortex of the hair beneath the scaly cuticle layer.

There are two types of melanin protein found in the hair: eumelanin, which is
responsible for hair shades from black to brown, and phaeomelanin, which is
responsible for red and yellow-ish colors. Absence of pigment, which was
my problem, produces white or gray hair. The melanin type and granule size
determine the color of hair, while the density of distribution of these pigment
granules determines how light or dark the hair is. But enough on natural hair
color.

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. The primary
intermediates are ortho or para diaminobenzenes, aminohydroxybenzenes,
and to a lesser extent dihydroxybenzenes that develop color on oxidation.
The color couplers don't oxidize readily but react with the oxidized primary
intermediates to provide a wider variety of colors. The couplers are phenols,
meta disubstituted phenylenediamines and phenyleneaminophenols, and
various resorcinol (1,3-dihydroxybenzene) derivatives.
As soon as the ammonia dye solution and the hydrogen peroxide solution are
mixed together, they are applied to the hair. The ammonia in the mixture
(less than 1% concentration) causes the hair to swell and the cuticle scales to
separate a little. After this happens, the dye precursors are able to penetrate
the cuticle before they have fully reacted with each other and with the
hydrogen peroxide. This is why even when brown hair coloring is first
applied it looks whitish. This is also why you have to wait a half hour or
more for the color to develop.

Darker shades are obtained by using higher concentrations of intermediates.

Tones can also be adjusted. For example, addition of resorcinol will make a
shade more yellow, while adding 4-amino-2-hydroxytoluene will make the
shade redder. Sometimes dyes are used along with the oxidation dye
intermediates to add vibrancy to the tone that is not otherwise available.
Usually these dyes are used to add intensity to gold or red shades.

I never had a desire to look like Lucille Ball, so I don't think I'm going to go
for red hair, but if I did, the formulation used most likely would contain
2-nitro-p-phenylenediamine. I understand that this orange-red color would be
quite bright and that the narrower absorption spectrum of this dye produces
much purer hair color than the broader visible absorption bands of other dyes.
Sounds intense.

I'm glad I have all these choices and don't have to be gray-haired before I
want to be. Let's hear it for better—and blonder—living through chemistry!

Linda Raber