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j. Cosmet. Sci., 56, 121-134 (March/April 2005) Reaction characteristics of a tooth-bleaching agent containing H 2 02 and NaF: In vitro study of crystal structure change in treated hydroxyapatite and chemical states of incorporated fluorine Y. TANIZA WA, Analytical Research Center, Lion Corporation, 13-12, Hirai 7 -chome, Edogawa-ku, Tokyo, 13 2-00 3 5 Japan. Accepted for publication February 16, 2005. Synopsis This in vitro study was performed to elucidate the reaction mechanism of sodium fluoride (NaF), which is added to tooth-bleaching agents to lessen the adverse effect of hydrogen peroxide (H2O2) on teeth. Both hydroxyapatite (HAP) and dihydrated dicalcium phosphate (DCPD), model substances for dental hard tissues, dissolved easily in a simple H2O2 solution. In the H2O2/NaF solutions, however, fluorine com­ pounds that could not be identified by X-ray diffraction (XRD) due to the smallness of the products were formed on the surface of the HAP. X-ray photoelectron spectroscopy (XPS) studies demonstrated that fluoridated hydroxyapatite (FHAP) was formed on HAP, and that calcium fluoride (CaF2) formation was accelerated by increasing the concentrations of fluorine and H2O2 along with the partial dissolution of HAP. In H2O)NaF solution, DCPD also transformed easily to FHAP and CaF2 , which are favorable to the remineralization process on the tooth surface. Thus, the mechanism of NaF was elucidated, and its use together with H2O2 for tooth bleaching was proved to be effective. Methodologically, the XPS two­ dimensional plot made it possible for the first time to directly estimate the ratio of FHAP and CaF2 in the reaction products, in contrast to the conventional wet-analytical method, which is simply based on the difference in solubility of the two components. INTRODUCTION White teeth are preferable from a cosmetic point of view, and tooth whitening is of interest to dentists and their patients. Toothpastes remove external discoloration, which is localized mainly in the pellicle on the surface of teeth, commonly through the polishing effect of abrasives ( 1-3 ). In our previous work ( 4), attention was directed to the mechanism of pellicle formation. Internal discoloration, however, is a result of defects in the tooth development process, and is also acquired through the use of medicines like tetracycline. Those kinds of discolorations cannot be removed by toothpaste, and there­ fore dental bleaching has been used to reach this objective. The development of bleach­ ing agents and their formulation have been important goals for oral care researchers and dental product manufacturers. To attain these goals, an understanding of the reaction characteristics between the tooth surface and the bleaching agents is required. 121