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j. Soc. Cosmet. Chem., 36, 31-37 (January/February 1985) Oxidative dyeing of keratin fibers KEITH C. BROWN, STANLEY POHL, ANNE E. KEZER, and DAVID COHEN, C/alto/Research & Development Laboratories, 2 B/ach/ey Road, Stamford, CT 06922. Received October 31, 1984. Presented at the Annual Meeting of the Society of Cosmetic Chemists, New York, December 6-7, 1984. Synopsis Dye uptake by hair and wool cloth has been measured by a reflectance technique. Using a statistical experimental design, color formation from a single pair of reactants has been used to define and quantify many of the factors that control the process. Although peroxide concentration has little effect, color intensity depends on the concentration of reactants and added surfactants and on the dyeing time. These results can, in some cases, be predicted from the solution kinetics of the coupling reaction where the rate- controlling step is formation of a reactive intermediate from hydrogen peroxide, followed by a series of faster oxidative and coupling steps to give the dye. However, there are significant differences between the dyeouts and solution chemistry reflecting the important role of the substrate on the dyeing process. INTRODUCTION Previous studies on the chemistry of oxidative dyeing of keratin fibers have concentrated largely on the reactions occurring in dye solutions (1-3). While these results appear to correlate with actual fiber dyeouts in most cases, there are significant differences reflecting both chemical and physical effects of the substrate. In addition, the oxidant used for the solution studies, potassium hexacyanoferrate, is not commonly used in dyeing practice. We now report results on dye uptake by hair and wool and on the factors that control the process when hydrogen peroxide is used as oxidant. In particular we have evaluated the amount of color deposited on hair and wool from two oxidative dye couples in use in current hair dye formulations: p-phenylenediamine (PPD)/4- amino-2-hydroxytoluene (AHT) and N, N-bis-(2-hydroxyethyl)-p-phenylenediamine (BHP)/1-naphthol (NAP). This paper describes the variation of dye uptake with factors such as dye and H202 concentration, solution pH, dyeing time and concentrations of ammonia and surfactant in the dye solution and compares the results with those predicted from the kinetics and mechanism of the solution reaction. EXPERIMENTAL All dyeing solution components were commercial materials used without further pu- riffcation. Samples of indo dyes were isolated from coupling reactions using atmospheric 31