BUSINESS simultaneously bleaches the users' natural hair color and "develops" the oxidative dye in solution as it penetrates the hair shaft. Many dye kits also include conditioning as a third step. Another type of permanent hair dye, mostly used to darken gray hair, depends on a solution of lead acetate that gradually darkens hair by reacting with the sulfur of hair keratin. The Just for Men line from Combe International depends on such a system. According to the Food & Drug Administration, lead acetate is safe to use as "progressive" hair color because controlled human studies show lead is not absorbed into the body from dye use.
FLUSH WITHI COLOR Continuing progress in hair dye chemistry satisfies diverse desires of young and old MARC S. REISCH, C&EN NORTHEAST NEWS BUREAU
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came only in colors most would think of as natural. Blonds, brunettes, and redheads could as readily come out of a bottle as grow naturally from the scalp. But the chemist's art and retail opportunities now make possible choices some would never have considered before—and might never even consider now—such as "cupcake pink" and "electric blue." Such vivid hair dyes can be found at the mall-based teen-oriented retail chain Hot Topics. However, the most recent technical developments in hair dyes don't just benefit teenagers looking to stand out—or fit in. Chemists have also developed more conventional dyes that last up to six weeks. And they have designed conditioners and shampoos to give a "boost" to colors and keep them from fading. These improvements in hair dyeing technology have not only increased color options, durability, and luster, but they also now offer more opportunities to consumers both young and old, and to men as well as women. Hair dyeing is one of the fastest growing segments of the personal care market. Industry consultant Kline & Co. estimates that U.S. retail sales of home dyeing kits grew at double-digit rates during the 1990s and reached $1.6 billion in 2001. Market research firm Euromonitor sets HTTP://WWW.CEN-ONLINE.ORG
the global hair dye market at $7.2 billion. According to Kline Project Manager Carrie Bonner, a recent study of consumer buying habits found that 37% of those surveyed purchased hair dyes over the past year. Survey results show that 42% of U.S. women and 25% of men use dyes, Bonner says. Among different age groups, the largest users of dyes were 16 to 20 years old: 48% purchased hair dyes. The next largest group, she says, are 40 to 49 years old, 45% ofwhom purchased hair dyes. Only 24% of those 60 years or older purchased dyes. What this has to say about the social mores of dye users, the age of users who have hair enough to dye, and the vanity of those who take the plunge is beyond the scope of C&EN's survey of the dyes business. Yet this much is certain: Dyes are in demand. To satisfy consumers, formulators offer three basic types—permanent, semipermanent, and temporary hair colors. Oxidation is king. Depending on whom you talk to, between 60 and 90% of dyes sold are the permanent two-part systems that can last six weeks. The first part is a solution consisting of dyes and dye intermediates in an aqueous ammoniacal solution generally containing soap, detergents, and conditioning agents. The second part is a hydrogen peroxide solution often called the developer. Users mix the two parts just before applying to their hair. This mixture swells the hair, and
OTHER TYPES of hair dyes are semipermanent, which largely depends on direct dyes and last a few washings; and temporary, which mostly depend on basic dyes and wash out after one to three washings. Meyer R. Rosen, president of Interactive Consulting, says French cosmetics maker EOréal has about half of the U.S. dye market; the Clairol unit of Procter & Gamble controls another 40%. Revlon is a much smaller factor, he says, as is Combe, which largely caters to men. According to Rosen, these firms are looking for new inspiration in unusual places. "Many hair dye scientists are reading wool textile dye literature," he says. "That is where many of their ideas come from, because of the similarity between wool and hair." Clairol, for instance, has recognized that the presence of copper in normal tap water can prematurely degrade textile colors as well as hair color "when it complexes in some way with the hair dye," Rosen says. The firm's Nice 'n Easy hair dye will soon include what he calls "a new star compound" from Procter & Gamble's fabric care business that will block copper. However, he says he doesn't know what the proprietary ingredient is. However, category-advancing technology doesn't come from formulators alone. National Starch & Chemical has developed dissolvable starch-based film strips it plans to introduce to the personal care market that are not unlike the Listerine Cool Mint breath strips based on an entirely different biogums technology These films can incorporate from 10 to 4 0 % of an active ingredient, according to John C. Leighton, senior technology director. And they can be adapted to apply temporary or permanent hair dyes. They are, however, two to three years away from commercialization, Leighton says. The water-dissolvable films might be C&EN
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used to put color streaks in hair or color a whole head of hair. But the films are versatile, he says, and could, for instance, be used as dissolving cleansing cloths to replace disposable nonwoven cleansing cloths now on the market. Or the films could be used to dispense conditioners, styling fixatives, and skin care ingredients such as vitamins, antioxidants, or blemish cover-ups. Dye suppliers say interest in hair dyeing is growing so rapidly that they expect other consumer products companies to get into the act. One says he wouldn't be surprised if Unilever enters the hair dyes business and takes on giants EOréal and Clairol. Hair dye ingredient suppliers know that "the technology for permanent hair coloring is 100 years old," says Glenn Gutkowski, senior technical account manager for LCW, a unit of the flavor, fragrance, and colorants firm Sensient Technologies. "I wouldn't expect the development of many new oxidative intermediates. Most of what I see is changing delivery systems and market changes." Color-enhancing shampoos and conditioners are a growing business, Gutkowski says. The company's line ofArianor basic dyes can be included in shampoos and conditioners to help prevent color washout of previously dyed hair. Consumers can also use these products to gradually add to and build upon a color they like, he says. For the youth market, L C W also sells a line of semipermanent dyes that "lend themselves to bright pure colors such as yellow, red, green, and purple," Gutkow-
ski says. "Some will even fluoresce under black light. Other dyes we supply don't have an impact on hair color, but they will fluoresce under a black light." These dyes, as well as others the company sells, are all "certified" dyes, which means they are FDA approved and don't require the "patch test" label the FDA requires of other hair dyes. That label warns consumers of potential allergic reactions. Charles A. Steele, a chemist with Keystone Aniline, a dye distributor, says, "The colors most people grow up with on their heads are in greatest demand." But "teenage girls and the clubbing set want wild and wacky colors. And the wilder, the better." Keystone can supply permanent dyes to cover the gray for most people and temporary dyes for those who play on the wild side. Like LCW, it can help customers formulate dye systems, and for "the more established companies that do their own formulations, we can arrange synthesis of dyes they isolate and specify" Dye systems based on acid or basic dye technology were originally developed for textiles. And it is the "bright visual effects from textiles that most interest cosmetic chemists today," Steele says. Many textile
TO DYE FOR A scientist at Ondeo Nalco prepares an experimental polymer for personal care. chemists have joined hair care companies and are experimenting to see if they can translate "the bright vivid effects from clothing" to hair dyes. "I expect more diversity in the way people dye their hair," Steele says. Some of the
hair-color methods are quite surprising. One notable new product from hair care products companyTish & Snookys Manic Panic is a styling gel for streaking, tipping, or adding splashes of color to hair including sterling silver and metallic blues and reds. For more traditional color systems, Keystone is offering an alternative to pphenylenediamine (PPD), the widely used primary intermediate in oxidative hair dyes. People who are allergic to the ingredient can develop dermatitis. This known sensitizer is no longer widely used in Europe, Steele says, and has largely been replaced by toluene-2,5-diamine sulfate (TDS). This alternative to PPD develops brown shades that are slightly redder and warmer than P P D It can be substituted for PPD, Steele says, but does require some reformulation work. "We encourage people to use TDS because the industry perception is that it is less of a sensitizer than PPD." The TDS that Keystone supplies is manufactured byjames Robinson, aU.K.-based hair dye maker and division of Yule Catto Group. Keystone also distributes James Robinson dyes in the U.S. Skin sensitivity issues are an ongoing concern for hair dye makers, says Chao Zheng, research director forJos. H. Lowenstein Sons, which manufactures coal-tarderived hair dyes both in Brooklyn, N.Y., and at plants in China. "Everyone is searching for brighter, longer lasting, and safer dyes," he says. Inspiration for new dye design comes not only from the leather and fur industry, but from the photography industry, too. "When oxidative dyes penetrate hair, they form large molecules that lock onto the hair," Zheng explains. "If we change the structure of the molecule, we can affect the nature of the large molecules and make them more stable in hair." One thing Zheng would like to be able to do is to incorporate an ultraviolet light absorber into the two-part hair dye system. But he has not found any that work. "If we could incorporate a light protector in the hair dye portion instead of the conditioner after-treatment, we could deliver more benefits to the consumer." Many of Lowenstein's customers are outside the U.S. and formulate hair dyes that are one-tenth the cost U.S. customers pay and do not include a separate conditioner treatment,
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as do most U.S. retail permanent dye kits. Ciba Specialty Chemicals does supply a UVprotector that works in a two-part hair dye system, according to Colleen Rocafort, personal care technical services director. The company's Cibafast H is a benzotriazole UV absorber that protects against light-induced fading. Revlon uses patented proprietary technology incorporating it in their ColorStay product line. The absorber is added during the oxidative dye step. The firm has other UV protectants that might be useful for hair treatments. Vittoria Signori, a senior technical service representative at BASF, says her firm's Uvinul benzophenone 3 and benzophenone 4 can also protect hair from color fading in after-dye conditioning treatments. And the company's polyquaternium 44, with a branched structure and low cationic charge, not only conditions but can, in some cases, help thicken a hair-coloring system so it doesn't drip down a person's face. Cibais also a supplier ofpolyquaternium conditioners sold under the Salcare name as well as a line of direct dyes sold under the Vibracolor name. Those dyes combine with oxidative dyes in EOréal's Féria dye kits to provide "intense, vibrant red, yellow, and orange highlights," Rocafort says. TO HELP FORMULATORS put together gentler formulas, Rocafort says Ciba also supplies polymers that allow less use ofperoxide and surfactants and better dispersion of color to the hair. Clairol's Hydrience color line uses Ciba's Salcare liquid dispersion acrylic polymers, while Revlon's color line uses Ciba's acrylate copolymer gels to thicken the color developer. Ondeo Nalco has leveraged its watersoluble polymer expertise in water treatment to develop alineforpersonal and hair care. Pat Marek, performance products business manager, says Merquat 100, a cationic homopolymer, was first used in water treatment. "We found that the molecule also had hair conditioning properties, so we optimized itforhair treatment," he says. The company's polyquaternium 22 series is often found in dye formulations to improve dye coverage, condition hair damaged by the coloring process, and make hair easier to comb. Rohm and Haas is also selling polymers to hair dye formulators. Much of its expertise was first developed in making thickeners for paints and coatings. According to Charles E.Jones, personal care technical services manager, the company's Aculyn acrylic rheology modifiers "act primarily as thickeners and secondarily as flow HTTP ://WWW.C E N - O N L I N E . ORG
control agents" in two-part dye systems. Silicones offer hair dye formulations conditioning properties. But standard dimethicones, used in other hair care formulations, tend to interfere with the dyeing process, explains Robert Ruckle, global manager for consumer care at Crompton's OSi unit. But Silsoft A-483 is a high-molecular-weight organic dimethicone hybrid polymer that conditions during the coloring process. Another variant, Silsoft A-454, is a color-retaining conditioning agent that can
be added to conditioning shampoos to increase the durability of dyed hair. A-454 lessens the tendency of cleansing surfactants to washout hair dye, Ruckle explains. "The use of hair color is exploding," Ciba's Rocafort says. "It's grown at doubledigit rates over the pastfiveyears." And as she and others in the industry see it, that growth—advanced by gentler, more durable, and more colorful formulations— is likely to continue. "Olderpeople want to cover the gray," she says, "and younger people want fashionable and trendy colors." •
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