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J. Cosmet. Sci., 56, 29-46 CTanuary/February 2005) A novel "permanent" acid-type hair color made possible with dye-metal ion complex technology M. OCHIAI, T. KAW ASOE, M. YASUDA, Y. HARADA, T. KIMURA, T. KAMBE, and J. KURITA, Product Development Center (M.O., T. Ka., Y.H., T. Karn.), Basic Research Center (M. Y., T. Ki.), and Institute of Beauty Science U. K.), Shiseido Co., Ltd., 2-2-1 Hayabuchi, Tsuzuki-ku, Yokoharna-shi, 224-8558.fapan. Accepted for publication December 14! 2004. Presented in part at the 22nd Congress of the Internationa( Federation of the Societies of Cosmetic Chemists (IFSCC), Edinburgh, Scotland, September 26, 2002. Synopsis The advantages and disadvantages of oxidative permanent and acid-type semi-permanent hair colors are evident. The former provides a longlasting "permanent" color, while the latter imparts less damage to the hair. We developed a novel acid-type hair color technology that can allow an acid dye and a metal ion ro form a complex inside the hair similar to the oxidative hair color. It is well known that acid dye diffuses into the hair and creates an ionic bond with the positively charged amino acid residues of hair protein. However, the dye can be extracted easily from the hair by daily shampooing due ro the weakness of the bond. In order to strengthen this bond and to prevent the extraction of the dye by shampooing, an aluminum chloride ion was chosen as the metal ion component to form the dye-metal complex. A proper composition of penetration enhancers, benzyl alcohol and ethyl alcohol, was required to allow acid dyes to interact with the aluminum chloride ion after each component penetrates deeply into the hair to form a complex inside the hair. To provide color brightness and a color longevity effect to hair color, glycolic acid was also selected due to the observation that a weak acid with a small molecular weight would enhance those effects. INTRODUCTION Hair coloring products can be categorized into three groups according to dyes (1,2). The first type of hair coloring product is temporary hair color, which is absorbed physically onto the surface of hair. The second type is semi-permanent hair color, whose anionic or cationic character has affinity to hair protein. The third type is oxidative or permanent hair color. In the third type, small dye molecules [e.g., p-phenylenediamine, MW: 108) diffuse into hair and produce a dye complex inside the hair cortex through chemical reactions (3-5 ). Due to its color brightness and color longevity effect, oxidative hair color is most popularly used and has a firm market position in the hair color category in Japan as well as Europe and the United States (6). On the other hand, oxidative hair color damages hair and has an irritating smell (e.g., ammonia odor) because it needs the 29