Hair Color Research Update

contents

Hair Color History

1 Scientic Breakthroughs Chemistry through the ages Global Impact How hair color crosses cultures around the world

Old Science vs. New Science

8 Carbonate + Glycinate = Hair Fiber Integrity Superior color results with less damage

The Bigger Picture

13 Free Radical Formation Across Multiple Disciplines Hair colors contribution to understanding these molecular culprits 14 P&G Research Partnerships Cross-discipline connections spur innovation

Hair Color Explored Biology Basics

2 Layer Up Hair composition, cycles, and the effects of color Color Processes Revealed Temporary to permanent color possibilities 10 Factors In Fading Color Mechanical to environmental causes investigated 10 Shine and Color Human perception of light reection 12 Conditioning Breakthrough Modied aminosilicones

Whats Next?
14 Pigmentation Breakthroughs Biochemical inuence on hair pigmentation 15 Summary

Chemistry At-a-Glance
4 Oxidative Dye Formulas The components of conventional oxidative colorants How Coloring Alters Biology The effect of coloring on the f-layer Free Radical Formation EDDS Addresses the HO* Radical Consequences of hair colorant dened

13 Hair Color Safety Government and research institute ndings

Hair Color History

Beyond its biological function of keeping the head protected and warm, hairs true value lies in its ability to make a highly personal, visual statement about oneself. Throughout history, hair color has dened cultures, social status, professions, age and self-image; so when humans discovered ways to change hair color, it signied a major step in self-expression. This self expression, however, has always been inuenced by innovative science.

Scientic Breakthroughs

The rst major breakthrough in hair coloring history came in 1863, when chemist Dr. August Wilhelm von Hofmann reported the dye properties of para-phenylenediamine (PPD). His discovery led to the birth of the synthetic hair dye industry, and PPD still dominates the eld today. Hofmann was also known for his studies of organic derivatives of ammonia and for discovering the rst unsaturated alcohol and several organic dyes.1 On the heels of Hofmanns discovery, in 1867 London chemist E.H. Thiellay and Parisian hairdresser Leon Hugot demonstrated the advantages of hydrogen peroxide as a better chemical way to lighten hair than alkaline solutions. Their discovery soon became widely recognized, and oxidizing products remain the basis of bleaching preparations today. After the mid 1920s, oxidation dyes were greatly improved and the fashionable use of hair coloring boomed.2

The introduction of salon and then home hair dyes during the same period brought about a revolutionary change worldwide and an explosion of hair color options. Clairols founder, Lawrence M. Gelb, introduced hair color to salons more than 70 years ago when he discovered a European preparation and brought it to the U.S. When Clairol launched its rst salon colors in 1931, millions of women began using them. Instant Clairol Oil Shampoo Tint soon changed the look of Americans.3 In 1950, Clairol introduced Miss Clairol Hair Color Bath, the rst real breakthrough that lightened hair without the harshness and complicated handling of bleach. For the rst time, hair could be lightened, tinted, conditioned and shampooed in only one step instead of ve, in only 20 minutes. Within six months of this watershed discovery, hair coloring mania soared. The number of women going to the salon for permanent hair coloring increased

by more than 500 percent.4 Soon after, with the abundance of safe, inexpensive, easy-to-use products, home hair dying quickly grew in popularity. Fast forward to 2007, where the next hair color breakthrough is currently unfolding, the rst in over 50 years. Advances in understanding the molecular structure of hair have allowed scientists to develop improved technologies that minimize the amount of damage in the coloring process, and even create specialized products that restore health and brilliance to colored hair. The new chemistry of hair color is here, making hair color easier, quicker, and more eective than ever.

Hair Color: Research Update 1

Global Impact Today, millions of women color their hair spanning every age, race, nationality and religion. According to recent surveys, at least 88 percent of all women feel their hair has an eect on their self condence.5 Around the globe, the primary reason women color their hair is to look and feel better about themselves, feeling strongly that the products they use are fundamental in achieving this goal.6 With so many women taking such pride and care in their hair, the market is poised for a new scientic breakthrough. Todays woman demands quick, ecient product results that easily t into her hectic lifestyle, and hair color is certainly no exception. Today, hair color manufacturers have sophisticated research and development divisions that develop a broad range of advanced salon and home hair coloring products, addressing the complex needs of their consumers. These advances can only be understood by starting with hair basics.

Agreement With Why Use Hair Color (Percent of Users Who Agree) 7 UK To feel better about myself To feel more condent To look and feel more attractive To cover my gray To cover root re-growth 77 65 61 57 57 Mexico 82 76 71 66 81 China 71 67 52 51 55 Russia 81 79 84 56 73 USA 69 50 62 57 not asked

Biology Basics
Layer Up Hair is composed of proteins (keratin) embedded in a sulphurrich matrix encased in a sheath of overlapping scales. Hair has two distinct parts: the hair bulb (root), the biologically active part of hair where new hair is formed, and the shaft, the visible yet biologically inert part of hair that is sunk in a follicle beneath the skin. As cells in the base of the follicle are pushed up, they harden

and undergo pigmentation, the basis of hair color.8 Hair is made of three layers: the cuticle, cortex, and medulla. The cuticle consists of tightly packed, overlapping, colorless cells. The cortex contains varying amounts of two natural color pigments that determine a persons hair color. It also supports the physical and mechanical properties of hair, and determines its tensile strength and texture. The medulla is typically a hollow shaft inside the hair. To permanently

History of Hair Color

1200 BC: Some Egyptians use natural dyes to darken hair, such as kohl and henna, while others wear wigs to alter hair color, including Cleopatra. 1500s: Queen Elizabeth I redenes the standard of beauty in the Western World with her red hair and fair skin. Women all over Europe don red wigs to try and emulate the Queen. 1863: Chemist Dr. August Wilhelm von Hofmann reports the dye properties of PPD. His discovery leads to the birth of the synthetic hair dye industry, and PPD still dominates the eld today. 1867: London chemist E.H. Thiellay and Parisian hairdresser Leon Hugot demonstrate the advantages of hydrogen peroxide as a better chemical way to lighten hair than alkaline solutions. 1907: Eugene Schueller creates the rst blonde hair dye technology using PPD in Paris, becoming the first commercially available oxidative/permanent hair color.

2 Hair Color: Research Update

change the color of hair, a coloring product must be able to penetrate the cuticle to deposit or remove color in the cortex.9

densely packed melanin granules full of eumelanin pigment, while gray hair has no pigment at all.10 Hair follicles go through approximately 7-15 melanocyte seeding/replacement cycles in the average gray-free life span of 45 years. The average age of onset of graying for people of Caucasian descent is mid 30s, for people of Asian descent late 30s and for people of African descent mid 40s. By age 50, 50 percent of all people are likely to have 50 percent gray hair. Graying can happen gradually or suddenly, and gray hair may be more resistant to articial color.11 Color Processes Revealed

highlights, bleaching and toning to achieve drastic color changes, and glossing or glazing for more subtle changes. Variation in chemistry allows exibility when it comes to levels of hair dyes.12 Temporary (level 0) dyes or color rinses are acid dyes that do not diuse into the hair or bind rmly. Color coats the surface of the hair shaft but does not penetrate the cuticle, so the dye is easily washed out after the rst shampoo. While color results are limited, the dye may be a good option to test colors or to refresh dyed hair. Semi-permanent (level 1) products use low-molecular-weight ingredients, such as nitroaromatic amines or aromatic dyes, but do not contain ammonia or peroxide. Color is already formed in the bottle. These dyes gently add color molecules to the cuticle layer, but do not bind

tip

medulla

cuticle

root

Hair follicle composition

Natural hair color depends on the amount and distribution of pigment (melanin) in the cortex, which is hereditary. Dark pigment, called eumelanin, is responsible for brown and black color, and phaeomelanin produces blonde and red. Black hair, for example, contains

At home or at a salon, the processes involved in coloring make the palette of possibilities limitless. Todays hair color products can remove (lift) natural hair color, add (deposit) a new color to natural color, or accomplish both processes at the same time. There are also products for adding

1931: The Clariol Company is established. Instant Clairol Oil Shampoo Tint soon changes the look of Americans.

1953: Wella develops the rst permanent cream colorants, offering women a less messy way to color their hair.

1980s: Demi-permanents closely resemble permanent products, but the levels of active ingredients are reduced. This prevents noticeable bleaching and slows down the penetration into the hair so that color is only formed in the outer part of the ber.

2003: Scientists develop a method to reduce damage from the HO* radical, and increase color formation by adding a chelant to hair color products called ethylenediaminedisuccinic acid (EDDS), which prevents copper formation on the hair shaft.

2007: Scientists develop a new bleach engine that signicantly reduces hair ber and f-layer damage and cuts the time it takes to color hair to ten minutes.

Hair Color: Research Update 3

Level 0

Level 1 Pigment deposition across different levels of hair dye

Level 3

rmly to the hair protein. Washing hair opens the cuticle, allowing color to escape. Conditioner smooths and closes the cuticle layer. Level 1 products wash out typically between four and six shampoos. They can make hair the same depth of color as the natural base or darker, but cannot lighten hair. Demi-permanent (level 2) and permanent (level 3) colors involve oxidative chemistry, during which the coloring components are mixed just before they are applied. Permanent dyes are the most important and most widely-sold commercial hair dyes. The primary dierence between level 2 and level 3 products is the alkalizing agent and the concentration of peroxide. Demi-permanent colors wash out in up to 24 shampoos. They can enhance and brighten natural color and blend or cover up grays. However, demi-permanent colors have little or no lightening potential. Since

they use about three percent hydrogen peroxide and a nonammonia alkalizer, the cuticle does not swell as greatly with level 3 dyes, making dye penetration less ecient. Permanent (level 3) colors, comprising 80 percent of the hair coloring market share, are the most versatile and long-lasting and are available in the widest spectrum of shades.13 These can lighten hair by two to three levels, change color in subtle or dramatic ways, and last until hair grows out. They also provide 100 percent gray coverage, even on resistant grays. Re-application is recommended every four to six weeks to avoid noticeable regrowth.

Chemistry At-a-Glance
Oxidative Dye Formulas Most oxidative dye formulations contain two or more ingredients that act as dye precursors or couplers,

4 Hair Color: Research Update

essential ingredients common to most permanent dyes. They generally consist of p-diamines and p-aminophenols. Precursors are oxidized to active intermediates when they have penetrated the hair shaft. Intermediates then react with ingredients called color couplers to create washresistant dyes. Couplers modify the color produced by the oxidation of precursor compounds. A conventional oxidative colorant is made up of two components which are mixed together directly before application to the hair. Dye Precursor / Alkalizer / Thickening System This component contains several ingredients, each with dierent functions. They are packaged together because they are completely compatible with each other and must be kept away from the oxidizing agent (hydrogen peroxide). The rst component is an alkalizing agent (usually ammonia and/ or an ammonia substitute such as monoethanolamine [MEA]). This has a number of roles in the hair colorant process: Swelling the hair ber to aid in diusion of the dye precursors Raising the hairs internal pH and ensuring that the overall dye mix has a high pH

Facilitating the formation of the dyes within the hair ber and catalyzing melanin bleaching The second component is a mixture of dye precursors. These are the ingredients that react together within the hair ber, resulting in the formation of color. The third is a surfactant (and optionally polymer) thickening system that provides the solubilization of the rst two components (particularly the dyes) and, when mixed with the H2O2 component (below)

provides the nal viscosity to hold the product on the hair bers without mess and dripping into the eyes, and if applicable, is tailored to work optimally with any application or mixing device supplied with the product.
Hydrogen Peroxide Oxidant It

is essential that this component be kept at a low pH for storage to ensure stability; but it is only at high pH that bleaching and dyeing occurs. This component may also contain polymers or surfactants that thicken when

Common Hair Colorant Ingredients & Their Functions Component Solvent Surfactant Alkali Buffer Function Dye vehicle Foaming, thickening Swell hair, bleaching Stabilize, reproducible Sample Ingredients Water, Propylene glycol, Ethanol, Glycerin Sodium lauryl sulfate, Ceteareth-25, Cocoamide MEA, Oleth-5 Ammonia, Monoethanolamine Disodium phosphate, Citric acid

Dye precursors

Impart color

P-Aminophenol, 1-Naphtol, P-Phenylenediamine, 4-Amino-2-hydroxytoluene Glyceryl stearate, Cetearyl alcohol Polyquaternium, Cetrimonium chloride Hydrogen peroxide

Fatty alcohols Quaternary compounds Peroxide

Emmolients Conditioning Oxidant, bleaching

Hair Color: Research Update 5

mixed with the high pH tint, and/or provide conditioning and rinsing benets when the combined dye mass is rinsed from the hair. Hydrogen peroxide plays the following roles: o A source of oxidizing agent for catalyzing the reaction of dye precursors o Dispersing and solubilizing the hairs natural pigment, melanin, while bleaching the hairs natural pigment and any previous articial colorant present in the hair ber Once these components are mixed and applied to the hair surface, two complementary processes take place: bleaching the hairs natural pigment and other articial pigments present in the hair, and diusion of dye precursors into the hair, followed by coupling reactions that result in the formation of chromophores within the hair ber, which are then too big to diuse out of the hair. The end result achieved results in the balance of these two processes, the mixture of dye precursors, the initial hair color and hair quality. More complex colors may contain several precursors and many couplers, and involve multiple reactions. To create each shade in the hair coloring spectrum, formulators must become artisans, assessing which developers and couplers to combine, how much

of each to use, and the ratio and total concentration of the various intermediates. How Coloring Alters Biology Hair is protected by a covalently bound, mono-molecular layer of unique branched fatty acid 18 methyl eicosanoic acid (18-MEA). 18-MEA, often referred to as the f-layer, is the fatty lipid layer that binds to the surface of the cuticle and acts as the hairs natural conditioning system. Because the f-layer has a natural lubricating mechanism and is water repellent, it gives each hair fiber a built-in conditioning system that reduces damage caused by blow-drying and brushing. 14, 15

bers. Repeated coloring can cause this protective surface to completely disappear. As a result, the hair becomes hydrophilic (water loving) instead of hydrophobic (water repellent), and the natural lubricating properties are removed. Hair is more susceptible to damage, feels dry and is hard to detangle. It looks duller and less colorful, and requires more conditioning. Free Radical Formation EDDS Addresses The HO* Radical Most hair color users understand that by its nature, permanent color makes irreversible changes to hair structure. The bleaching and oxidation action chemically alter hair proteins, lipids and pigments. While pigment changes are desirable, the changes to proteins and lipids can cause hair to be more susceptible to damage. Most consumers adapt to these changes by using conditioners to protect hair and limiting hair color application to once every 4-6 weeks. However, what they may not know is that not all the damage done by hair colorants is necessary. There are two key reactive species in current permanent hair color: the perhydroxyl anion (HOO-) and the HO* radical. The HOO- species is the species intentionally put in by manufacturers. While it has some damaging side eects, it is the

Outer -layer (18-MEA) d = 2.5 nm

(Jones et al., J. Invest. Dermatol., 106(3), 1996. 461-464)

O S S

O S

O S

O S

O S

O S

O S

Epicuticle

f-Layer of a hair follicle

During permanent coloring, the combination of hydrogen peroxide, ammonia and high pH removes some of the protective f-layer, causing additional oxidation of the hair surface and some irreversible physiochemical changes in hair

6 Hair Color: Research Update

FT-IR cysteic acid formation in presence vs. absence of copper ions in water

Suppression of Free Radical Formation

The suppression of free radical formation can be visualized microscopically by comparing gas production from a formulation containing no EDDS chelant (0.1% EDTA) vs. one containing EDDS (1% level). Signicantly fewer gas bubbles can be seen being formed in the sample treated with EDDS clearly demonstrating the ability of EDDS to reduce the gas formation signicantly.

120 100
FT-IR cysteic acid units

Copper in tap water No copper in tap water

80 60 40 20 0 0

3 Cycle number

Performance Data for Chelants vs. the Cu/Ca Conditional Formation Constant Ratio16
Gas Formation after 10 min., no EDDS

Chelant (0.05M) Added to Colorant Cream No Copper Control EDDS DTPA EDTA HEDP

Ratio of Cu to Ca Conditional Formation Constant 4 x 1011 4.6 x 107 1.6 x 106 7.7 x 103

SEM Damage Index Score 5.0 6.8 49.8 68.6 61.0

F-IR Cysteic Acid Units 100 110 147 165 163

Gas Formation after 10 min., with EDDS

species that is responsible for the desired changes to hair color. The HO* radical, however, is an undesired by-product of a reaction between H202 and metal ions. It does not contribute to the development of color but does contribute to hair damage. The elimination of this unnecessary free radical can signicantly reduce

hair damage without compromising hair colorant performance. One approach to reducing the free radical is to eliminate the exposure to metal ions. Metal ions come into the hair through exposure to water. Studies show that protein damage, as measured by formation of cysteic acid, is signicantly reduced by elimination

of copper in tap water.

Addressing the HO* Radical

Recently, hair color scientists discovered a way to reduce damage from the HO* radical, blocking its formation with the use of chelants molecules that can coordinate metals through multiple

Hair Color: Research Update 7

binding sites. They added EDDS (ethylenediaminedisuccinic acid), a chelant which is highly selective to copper, to home hair coloring kits. During the coloring process, EDDS binds to the copper, preventing access to the copper by hydrogen peroxide, which results in better
OLD CHEMISTRY
DYE PRECURSORS

color formation and less damage. The preference of the EDDS for copper over calcium makes it superior to traditional chelants, such as EDTA or DTPA, and more ecient at preventing ber damage.

NEW CHEMISTRY
DYE PRECURSORS

A 5-cycle repeat test showed that EDDS prevents more than 95 percent of radical damage. After-care conditioners, which water-proof hair, additionally help prevent damage and copper absorption as color ages. By minimizing free radical damage, advances such as EDDS help hair remain resilient and retain a healthy, lustrous look.17

+
BLEACH ENGINE

+
BLEACH ENGINE

Old Science vs. New Science

Carbonate + Glycinate = Hair Fiber Integrity Exploring the damage caused by current oxidants, it is apparent that an improved option would have numerous benets for preserving hair integrity. Recently, scientists made the rst new advance in home coloring technology in more than 50 years. By altering coloring chemistry, this breakthrough technology takes hair coloring to a new level, achieving excellent color and shine faster and with less damage to hair. Put simply, it addresses both the key consumer benet, good hair color, and the key consumer complaint, hair damage. The technology centers around a new bleach engine, combining ammonium carbonate, hydrogen peroxide and sodium glycinate. The result is a powerful oxidative bleach,

+
NH3
ammonia

+
H2O2
hydrogen peroxide

+
H2O2
hydrogen peroxide

(NH4 )2CO3
ammonium carbonate

C2H5NO2
amino acid sodium glycinate

pH 10-11
2030 Minutes

pH 9.0
10 Minutes

COLOR FORMATION

+ +

COLOR FORMATION

+ +

BLEACH MELANIN & LIGHTEN HAIR

BLEACH MELANIN & LIGHTEN HAIR

FIBER DAMAGE

REDUCED FIBER DAMAGE

HOOperhydroxyl anion

HO*
hydroxyl radical

f-layer removal and signicant ber damage, which aect surface feel hydroxyl radical is damaging without a radical scavenger harsh higher pH

HCO4peroxymonocarbonate

reduces f-layer and hair ber damage, leading to improved hair feel inactivated radical scavenger protects carbonate ber integrity radical gentle lower pH

CO3-*

8 Hair Color: Research Update

% f-Layer Retention After One Treatment

100 90 Force to Break (gmf)

Tensile Strength
treated with ammonium carbonate technology

TOF SIMS analysis of 18 MEA

1 cycle % f-layer on hair retained

80 70 60 50 40 30 20

New Chemistry Blonde

34.6

New Chemistry Brown

47.3

Old Chemistry Blonde

0.0

10 0 Untreated Hair No Scavenger Added Sodium Glycinate

Old Chemistry Brown

2.5

which delivers improved lightening performance with signicantly reduced levels of volatile ammonia for a much more beautiful, less chemical, in-use experience. The key bleaching species, the peroxymonocarbonate ion, is formed in situ from the reaction of ammonium carbonate and hydrogen peroxide, and is more selective toward melanin than keratin.
O O

New Chemistry Benets

Left: Hair shaft damages with new chemistry (10 min), Right: Hair shaft damages with current technology (30 min) Left: Baseline 50% gray, Middle: Ten minutes with new chemistry, Right: Ten minutes with current technology

+
C -O OH

HOOH
-O

C O OH

Peroxymonocarbonate ion

The carbonate accelerates bleaching and allows color formation and bleaching to occur at 9.0 pH compared to 10.0 11.0 pH, making it less damaging, with ten times fewer basic OH- ions and ten times fewer damaging perhydroxyl anions. Sodium

glycinate acts as a radical scavenger, removing any carbonate radicals being formed, thus minimizing damage to hair. Together, these elements produce faster, more targeted bleaching and faster color formation with improved hair condition during and after coloring. Technical and consumer

tests demonstrate a high shine with excellent color and gray coverage in ten minutes (compared to the standard 30 minutes), less damage to the f-layer and cuticle, and improved odor.

Hair Color: Research Update 9

Hair Color Explored

Factors in Fading Color Dyes are formulated to give hair long-lasting and richly hued colors, but several factors from mechanical to environmental can accelerate color changes and fading: Poor initial color application. When color has not been given enough time to penetrate the hair shaft, color molecules are not as tightly bound in the cortex, allowing them to be washed away. Most of noticeable fading appears after the rst two washes, indicating that the color molecules settled on the outside of the hair shaft and had not penetrated deeply enough to be retained through washes. Cuticle damage. The cuticle is the primary protection for the hair cortex where the majority of color molecules are housed. If friction or excessive chemical treatments damage the cuticle and strip away its protective fatty layer, the exposed cortex will chip away, and color molecules will escape during shampooing. Protection of the cuticle with shampoos and conditioners that contain frictionreducing silicones helps reduce this type of color loss.

Water exposure. Fading due to water exposure is often related to a damaged cuticle. When the cuticle is overly compromised, water can more easily enter the cortex and some of the color molecules can be pulled out and washed away. Shampoos do not strip color. In fact, data shows that water alone is responsible for the majority of color lost during shampooing.18 Conditioning shampoos and conditioners with cationic surfactants and waterproong amino silicones can help combat the eects of water exposure.

radiation penetrates the hair and breaks down color molecules. The process happens with both natural and articial pigments in the cortex and is the reason people develop highlights after spending long periods of time in the sun. UV protectants are added to some shampoos and styling products to help prevent hair color fade due to sunlight, although their ecacy is debated. Wearing a hat is the best protection against UV damage. Some shades fade more quickly than others. Red shades tend to fade the fastest because they have relatively small molecule size, which can diuse from the hair and wash away more quickly than other shades.20 UV exposure also breaks down the red tone more easily, while pure browns and blacks resist fading because their color molecules tend to be larger. Blonde shades have little color, so fading is less of a concern. Shine and Color

Scientists measure shine intensity and chroma saturation in hair color development

UV exposure. UV light is known to fade color in many substrates such as wood, cloth and paint. Hair is no dierent.19 UV

Human perception of color depends on the ability of our eyes and brains to detect and interpret the reection of light on objects. When light shines on hair, part of it penetrates and is absorbed by the dye molecules, and part is reected back. Hairs shine band, which is

10 Hair Color: Research Update

Fact vs. Fiction: Hair Dye Revealed

Myth: Coloring is the main cause of hair damage. Fact: While coloring can be damaging, heat and mechanical damage also play a signicant role. Myth: All hair colors use the same dyes. Fact: Many hair colors use the same ingredients, but in unique combinations, with varying levels and amounts, to create very different colors. Some ingredients are patented, so they are only used by the original manufacturer. The developers and couplers can react together to form many different dye molecules, each with a different color. Myth: Low ammonia is better for your hair. Fact: All combinations of ammonia as well as MEA, another alkali, can damage hair because of their high pH level. The damage, a function of peroxide, occurs from the chemicals formed when the mixed peroxide and alkali come in contact with the hair. The primary benet of low ammonia is less odor. Myth: Dyed blonde shades cause more hair damage than brown, red or black shades. Fact: The majority of hair shades have similar hair damage proles. Hair damage is caused by the amount of peroxide and alkali, like ammonia, in the dye. Most shades use the same amount and concentration of peroxide and have similar alkali levels. Myth: Anti-dandruff shampoos cause color to fade faster. Fact: Successive washing of color-treated hair shows a pyrithione zinc shampoo, the most effective dandruff treatment to date, to be no different than a cosmetic shampoo, or even regular tap water. Myth: Swimming pool water can turn hair green. Fact: Exposure of blonde hair, particularly chemically bleached or damaged hair, to high concentrations of copper in tap water or swimming pools can result in green hair. The best treatment is avoidance; using a bathing cap while keeping hair healthy and hydrophobic with an aminosilicone-based conditioner. Severe discoloration may be reversed by a professional stylist, in some cases.

Hair Color: Research Update 11

typically around the crown of the head, shows how well the bers reect light from the surface. The chroma band, which lies adjacent to the lighter shine band, is responsible for how successfully color information is revealed from within hair. The stronger the chroma band, the more intense the color will appear. Hair chroma is the colorfulness of hair compared to white. Chroma saturation, or color intensity, measures how much color the hair contains. The more saturated a color, the more sensation comes from the light of a single wavelength. Further, damage to the cuticle can diminish hairs ability to reect light, making it appear dull. When developing colors, hair dye formulators seek to mimic hairs natural shine by developing dye mixtures that penetrate the cuticle in order to maintain color intensity over time, without fading or washing out, but that also help maintain the overall health of hair for maximum shine. Additionally, daily use of shampoos and conditioners containing silicone based ingredients will enhance and refresh hair shine.21 Conditioning Breakthrough To overcome challenges inherent to the coloring process, scientists have developed a breakthrough technology in the form of a modied silicone that

deposits well on colored hair. Normal silicones are hydrophobic. They attach well to non-colored hydrophobic hair but not to colored hydrophilic hair, making them wash away easily. The modied aminosilicones are more hydrophilic and hence attach much better to colored hair. This durable lm protects hair from further damage and color fading, preserves color vibrance and shine, and allows hair to regain some of its natural protective water repellence. Technical testing of a conditioner with the modied silicone showed signicantly less fading as a result of washing and exposure to ultraviolet light and reduced damage compared to standard conditioners. The modied silicone functions as part of a patented conditioning gel network base; a releasing active (dialkylquat), and a silicone resin that interact with aminosilicone to provide additional longer-lasting performance to conditioners. The key durable active ingredients are amodimethicone, a conditioning agent; dicetyldimonium chloride, a silicone-releasing and conditioning agent; and trimethylsiloxysilicate, a durability aid. Researchers have also developed a daily maintenance conditioner for colored hair containing a special ingredient, amidopropyl dimethylamine glutamate (BAPDMA),

12 Hair Color: Research Update

New Conditioner Technology

Durable conditioner advances allow for mimicking the hydrophobic layer of virgin hair

of testing and usage by millions of people worldwide. Extensive studies have concluded that hair colorants are safe when used as directed and pose no health risk to pregnant women, unborn babies or infants. The comprehensive scientic research portfolio includes studies from the American Cancer Society, Johns Hopkins University School of Public Health, and Cancer Research UK.22 A major review of studies published in the Journal of the American Medical Association in 2005 concluded that there was no increased risk of cancer from the use of hair dyes,23 which conrmed the results of prior major reviews of more than 70 studies in 1993 by the International Agency for Research on Cancer, a group of the World Health Organization, and 83 studies between 1993 and 2003 by Johns Hopkins University School of Public Health, reviewed by the U.S. Cosmetic Ingredient Review Panel.24 25 In a more recent 2006 update, the U.S. CIR again concluded that the available epidemiology studies are insucient to conclude there is a casual relationship between hair dye use and cancer (www.cir-safety.org).
Sensitivity Testing

Left: Virgin hair, Middle: Hair colored and treated with new conditioner technology, Right: Hair colored without new conditioner

engineered specically to rebuild the layer. By rebuilding the layer, hair can return to its hydrophobic nature. One side of the BAPDMA molecule attaches to the damaged part of hair. The other side mimics the layer, acting as a patch for the damaged areas, and prepares hair for the deposition of silicones. Applied daily, the conditioner provides intensive care for even the most damaged hair, with high levels of conditioning, moisturizing and protective ingredients that smooth and align hair bers for shine and softness. Hair Color Safety Hair color products are strictly regulated by government groups in Europe, North America and Japan, and have been proven safe throughout more than a century

hair dyes can cause allergic reactions in a few individuals. Allergic reactions to hair coloring are very rare, estimated at approximately one in every one million applications, and they mainly occur with very dark hair-coloring shades. However, manufacturers recommend testing the products 48 hours before each salon or home color treatment to determine skin sensitivity, which can change over time. Most hair-coloring packages provide instructions on sensitivity testing, which generally advise users to test a small amount of the product on their forearm prior to full application. Some suggest applying a thin lm of petroleum jelly around their hairline, but primarily as a safeguard against staining of facial skin rather than as a sensitivity precaution. All hair-coloring products warn against using hair dye on facial hair, such as eyebrows.26

The Bigger Picture

Free Radical Formation Across Multiple Disciplines

Like other products in common use, such as certain foods or drugs,

Free radicals have long been known to damage proteins, oils and other important chemical compounds. Free radicals have been implicated in accelerating aging but also play an important role in degradation

Hair Color: Research Update 13

of building materials (such as polymers and paints) and degradation of foods. Free radicals are damaging because they attack and damage DNA, proteins (collagen, elastin, keratin) and moisture barrier lipids. The primary method for ghting free radicals is the use of antioxidants, which slow down the process of aging and the decomposition of cells. Currently the vast majority of anti-aging and UV protection products on the market contain some form of antioxidants. Lifestyle experts from dieticians to personal trainers are toting antioxidant secrets to success. By addressing free radical formation in hair color, researchers are able to further their general knowledge base for other disciplines, promoting overall health benets to consumers. P&G Research Partnerships P&G science innovation has been a foundation for company growth and development from the beginning. P&Gs expertise in leveraging cross-discipline connections has allowed a continuous network of people, facilities, technologies and consumers in dierent regions to create one product from lessons learned from making another. P&Gs laundry care division helped contribute to the discovery of this new chemistry through its own upstream bleach chemistry research

being conducted to help manage radical formation on clothing bers, which exemplies this continual process of shared ideas and information throughout the company. Additionally, P&G consistently enlists the collaboration of independent institutes to broaden the scope of research, which in this case include the Textile Research Institute (Princeton, US), DWI (German Wool Research Institute), CSMA (Centre for Surface and Materials Analysis, UK).

Melanogenic Zone DP Hair bulb matrix

Dermal sheath

Hair follicle with melanin granules

Courtesy of Dr. Desmond J. Tobin, University of Bradford, UK

Whats Next?
Pigmentation Breakthroughs New understandings in genetics and biology and the role of DNA in dictating the color, condition and health of hair are taking hair-coloring technology into a whole new realm. By utilizing new technologies, scientists have access to powerful new tools to explore ways to improve hair health and appearance. For example, research presented at the 2007 Intercontinental Meeting of Hair Research Societies addressed how biochemicals can signicantly inuence hair pigmentation. Researchers from Britain and the US studied melanocytes, cells which are responsible for pigment, in hair follicles for the presence of certain hormone receptors that may

aect follicle growth and coloration. They found that the hormones may respond dierently within these and other hair follicle cells, including broblasts (responsible for cell structure), depending on their interaction with biochemicals. When the researchers stimulated the melanocytes with hormone proteins, the reaction induced an increased production of melanin and cell growth. The proteins also stimulated expression and activity of tyrosinase (an important amino acid to melanin production), evoking a conclusion that biochemicals may aect specic cellular functions when exposed to melanocytes.27 These, and other advances in technology and genetics, promise to improve hair coloring and care in the years ahead, providing women and men in all parts of the world with the tools they need to maintain beautiful, healthy hair.

14 Hair Color: Research Update

Summary New discoveries in hair biology and coloring chemistry have led to signicant advances in hair coloring products and possibilities, reducing the trade-os in hair health. Researchers have developed new hair coloring technologies that optimize color intensity, minimize the amount of damage in the coloring process, speed processing time, and improve the appearance and health of colored hair. Increased understanding of how hair biology changes during coloring has also allowed formulators to create better tools such as postcoloring conditioners that help improve hair health at a microscopic level to achieve brilliant, long-lasting color and shine. New research will continue to push the envelope of what is possible in hair color. Moving forward, researchers will continue to build from current breakthroughs, consistently oering new benets in home hair color. Consumers will not only benet from milestones like speed processing time and color intensity, but will be able to indulge in an overall better inuse experience.

Hair Color: Research Update 15

references
1 Bouillon C, Wilkinson J. The Science of Hair Care (Second Edition). CRC Press, 2005; 252-253. Bouillon C, Wilkinson J. The Science of Hair Care (Second Edition). CRC Press, 2005; 252-253. Draelos ZD. Hair Care An Illustrated Dermatologic Handbook. UK, Taylor & Francis, 2005; 85. Data on le, P&G Beauty Data on le, P&G Beauty Data on le, P&G Beauty Data on le, P&G Beauty Robbins C. Chemical and Physical Behavior of Human Hair, 4th ed. Springer-Verlag NY, 2002; 4. Draelos ZD. Hair Care An Illustrated Dermatologic Handbook. UK, Taylor & Francis, 2005; 95. 20 Bouillon C, Wilkinson J. The Science of Hair Care (Second Edition). CRC press, Boca Raton, 2005, 435. 21 Draelos ZD. Hair Care An Illustrated Dermatologic Handbook. UK, Taylor & Francis 2005, 40. 22 The European Cosmetic Toiletry & Perfumery Association Ltd. (COLPA), London. Statement, Aug. 16, 2005. 23 Takkouche B, Etminan M, Montes-Martinez A. Personal Use of Hair Dyes and Risk of Cancer: A Meta-analysis. JAMA 2005, 293: 2516-2525. 24 International Agency for Research on Cancer (IARC). Occupational exposures of hairdressers and barbers and personal use of hair colourants, some hair dyes, cosmetic colourants, industrial dyestuffs and aromatic amines. IARC Monographs on the evalutation of carcionogenic risks to humans 1993; Vol 57: 43 118. 25 Helzlsouer K, Rollison D, Pinney S. Association between hair dye use and health outcomes: Review of the literature published since 1992. Unpublished data submitted by Clairol, Inc. to the US CIR, 2003. 26 Draelos ZD. Hair Care An Illustrated Dermatologic Handbook. UK, Taylor & Francis 2005, 113-114. 27 Kauser S, Slominski A, Wei T, Tobin D. Modulation of the Human Hair Follicle Pigmentary Unit by CorticotropinReleasing Hormone and Urocortin Peptides. Presented at the 2007 Intercontinental Meeting of Hair Research Societies. 2 17 Boswell et al, The Procter & Gamble Company. Composition suitable for the treatment of hair comprising chelants and methods for reducing oxidative hair damage. US Patent 7186275. Sep. 22, 2003. 18 Schwartz J. A Practical Guide to the Occurrence and Treatment of Dandruff and Seborrheic Dermatitis. Presented at the 62nd annual meeting of the American Academy of Dermatology, Washington DC, Feb. 6-11, 2004. 19 Bouillon C, Wilkinson J. The Science of Hair Care, (Second Edition). CRC press, Boca Raton, 2005, 247. 3

4 5 6 7 8

10 Olsen E. Disorders of Hair Growth. McGraw Hill, NY, 1194; 54. 11 Slominsk A, Wortsman J, Przemyslaw MP, Schallreuter K, Paus R, Tobin D. Hair Follicle Pigmentation, Journal of Investigative Dermatology (2005) 124, 1321. 12 Gray J. The World of Hair Colour. Thomson Learning, London, 2005; 62-89. 13 Draelos ZD. Hair Care An Illustrated Dermatologic Handbook. UK, Taylor & Francis, 2005, 94. 14 Carr MC, Holt LA, Drennan J. Using electron microscopy and X-ray microanalysis to study wool morphology and composition. Text Res J 1986, 56: 669-673. 15 Marsh J, Gummer C, Dahlgren M. Novel Permanent Hair Coloring Systems Delivering Color with Reduced Fiber Damage, Journal of Cosmetic Science, Vol. 58, No. 1, January / February, 2007. 16 Negri AP, Cornell HJ, Rivett DE. A model for the surface of keratin bres. Text Res J 1993, 63: 109-115.
16 Hair Color: Research Update

AN ADDITIONAL TOOL
The Hair Color: Research Update CD holds a PowerPoint presentation of the charts and illustrations in this toolkit. Feel free to use the images. Please credit P&G Beauty.

CONTACT INFORMATION
To talk with a P&G scientist or to learn more about ongoing research in the Beauty Science division, visit pgbeautyscience.com, or contact: Dianna Kenneally P&G Beauty Science 513-626-3508 Heather Cunningham P&G Beauty Science 513-626-2606