Ann. Rep. Tokyo Metr. Inst. P.H., 55, 2004 化粧品に配合される新規頭髪用染料の分析法 Analysis of ew Hair Colorants of Cosmetics ahomi UKI Yoshiaki AKAMURA Ken'ichiro MORI Kiyosi TERASHIMA Toshiro YOKOYAMA and Kouichi IT A rapid and simple analysis by HPLC was developed to determine the suitability of 14 new synthetic hair colorants for cosmetics. The analytical procedure was as follows The samples were diluted with 50% methanol and injected into HPLC The HPLC conditions were as follows HPLC column ODS (4.6 mm i.d. 150 mm), mobile phase 1 Methanol / H2O linear gradient mobile phase 2 0.04% phophoric acid including 0.5% sodium 1-decanesulfonate / Methanol(40:60), photodiode-array 200-800 nm column temperature 40 The 14 new hair colorants were separated for about 30 min and were identified from the absorbant spectra of each peak By using this method new hair colorants used in 15 commercial cosmetics were determined to have good handling quality Keywords HPLC cosmetics hair colorant semipermanent hair dye preparation analysis はじめに 13 1) 13 30 2) 3), 16 25 4). Cosmetic Ingredient Review Expert Panel (CIR) 5) 14 HPLC 方法 1. 試薬 Fig.1 3( AO3 ) HC 3( HR3) HC 4( ) HC 1( ) HC 2( ) 9( ) Huwell Chemicals HC 1( HR1) HC 2( ) Jos. H. Lowenstein & Sons. Inc 2- -6- -4- ( ACP) Aldrich 76( ) 57( ) 16( ) 17( ) 99( ) ( ) 169-0073 3-24-1 Tokyo Metropolitan Institute of Public Health 3-24-1, Hyakunin-cho, Shinjuku-ku, Tokyo 169-0073 Japan
80 Ann. Rep. Tokyo Metr. Inst. P.H., 55, 2004 O 2 SO 3 a O 2 O 2 O 2 H H H H 2 H 2 CH 2 CH H 2 AO1 HR1 HR3 O 2 H HCH 2 CH 2 O 2 OCH 2 CH 2 HCH 2 CH 2 HCH 2 CH 2 O 2 O 2 (CH 2 CH 2 ) 2 Cl H 2 O 2 ACP OCH 3 (CH 3 ) 3 (CH 3 ) 3 H 3 C CH 2 CH 2 CH 2 CH 2 H 2 O 2 H 2 Br O H H (CH 3 ) 3 (CH 3 ) 3 (CH 3 ) 3 Fig.1. Structure of ew Hair Colorants Table1. ICI ame of ew Hair Colorants ICI name Abbreviation Analytical Wavelength (nm) Acid Orange o.3 AO3 360 HC Red o.1 HR1 500 HC Red o.3 HR3 500 HC Orange o.1 435 HC Yellow o.2 440 HC Yellow o.4 420 HC Blue o.2 550 Disperse Black o.9 455 2-amino-6-chloro-4- nitrophenol ACP 320 Basic red o.76 505 Basic Yellow o.57 380 Basic Brown o.16 480 Basic Brown o.17 450 Basic Blue o.99 6 ICI : International omenclature for Cosmetic Ingredients 97 0 % ICI Table1. ( ) ( ) 2. 試料 15 12 16 3. 標準溶液の調製 0.01 g 50 % ml 1,000 g/ml HR1 AO3 HR3 1.0 ml ml 0 g/ml 50 25 g/ml ACP 4. 添加回収試験用試料溶液の調製 g mg ( ) HM-500 1 g ml 5. 試験溶液の調製 ml 0.5 g / (1:1) ml (2,500 rpm )
55, 2004 81 Table 2. Linear Gradient Condition of Mobile Phase1 Time(min) A(%) B(%) 0 0 0 0 0 20 0 0 30 0 0 30.1 0 0 A:35%Methanol B:80%Methanol Retention time (min) 50 40 30 20 AO3 HR1 HR3 6.HPLC 条件 ( ) TSKgel-ODS80TM 4.6 mm i.d. 150 mm ( ) ) 35 % 80 % Table 2. 0.5 % 1- (SDeS) 0.04 % (40 60) 40 1 ml/min 200 800 nm L 結果および考察 1. 分析条件の検討 1) リニアグラジエント条件 HR1 AO3 HR3 TSKgel-ODS80TM 40 1 ml/min Fig.2 (30:70) HR3 30 HR1 AO3 30 50 % AO3 HR1 30 35 % 20 80 % 30 2) 単一条件 ACP 0.04 % (4:6) 0.04 % (4:6) 0.5 % (SHS) (SOS) (SDeS Fig. 3 SDeS Retention time (min) Fig.2. Effect of Methanol Concentration in Methanol/H 2 O SolutionSystem on Retention Time of ew Hair Colorants 30 25 20 15 5 0 0 30% 35% 40% 50% Gradient condition Concentration of methanol (%) ACP 0% 0.5%SHS 0.5%SOS 0.5%SDeS Counter ion Fig.3. Effect of Counter Ions in 0.04% Phosphoric Acid/ Methanol (40:60) on Retention Time of ew Hair Colorants 1) 2) Fig.4 Fig.5-1 5-2 25 200 g/ml R=0.9996 (n=5) cv 1.3 % AO3 358nm ACP 320nm 382nm (Table 1) 0 g/ml AO3 ACP
82 Ann. Rep. Tokyo Metr. Inst. P.H., 55, 2004 0.13 0.1 Abs 0.05 0.08 0.06 0.04 Abs 0.02 1 9 2 3 4 5 11 0.0 20.0 30.0 (min) Fig.4. Chromatogram of ew Hair Colorants 1:HR3, 2:, 3:, 4:, 5:, 6:HR1, 7:, 8:AO3, 9:ACP, :, 11:, 12:, 13:, 14: A:Mobile Phase 1;Me/H2O gradient system (Table 2) B:Mobile Phase 2;0.04% phosphoric acid, 0.5% sodium 1- decanesulfonate/methanol (40:60) Detection:254nm AO3 6 7 8 12 13 HR1 HR3 0200 400 600 800 200 400 600 (nm) 800 Fig.5-1. Spectrums Wavelength of ew [nm] Hair Colorants (1) ACP 0200 400 600 800 200 400 600 (nm) 800 Fig.5-2. Spectrums Wavelength of ew [nm] Hair Colorats (2) 14 A B Table 3. Recoveries of ew Hair Colorant Cosmetics Added hair Recovery Coefficient colorant rate (%) of Variation Shampoo HR3 97.4 2.2 95.6 3.3 95.3 2.2 95.4 0.6 95.4 0.9 HR1 98.3 3.3 1.7 1.4 AO3 1.7 3.3 ACP 99.7 0.6 0.4 2.3 1.0 2.7 98.5 1.9 99.2 1.1 0.1 2.2 Hair rinse HR3 99.1 1.4 0.3 2.0 0.0 1.5 98.1 1.2 99.9 1.8 HR1 99.1 2.1 0.1 2.7 AO3 96.0 2.9 ACP 0.4 2.9 0.5 1.1 99.9 2.0 3.0 1.8 0.1 1.5 1.3 1.0 added : 0.1%, n=5 2 g/ml HR1 5 g/ml g/ml 25 g/ml 2. 前処理法の検討 0.1 % 1 ml ml 0.5 g HPLC 3. 添加回収試験 0.5 3.0 % 5) 0.1
55, 2004 83 Cosmetics Shampoo Hair rinse Hair coloring preparation Table 4. Analytical Results of ew Hair Colorants Extracted from Commercial Cosmetics Country of origin Indication Result 1 Japan,,, 2 Japan,,,, HY5, HR3, 3 Malaysia hennna,,,,,, 1 Japan, HR3,,,,, HR3,,,, 2 Japan,,,, HY5,,,,,, HR3,, 3 Japan hennna,,,,, 4 Spain hennna,, 5 Malaysia hennna,,,,,,,, 1 Japan hennna,, 2 Japan hennna,, 3 Japan hennna,,,, 4 Malaysia hennna,,,,,,, 1) 5 Malaysia hennna,,,,,,, 1) 6 Malaysia hennna,,,,,,,, 7 Brazil hennna HR1,, HR1,, 1), 1), 1) 1) Un-indicated hair colorant was detected. Table 3 95.3 1.7 % 0.6 3.3 % 96.0 3.0 % 1.2 2.9 % 4. 市販化粧品の分析 15 Table 4 15 11 6) まとめ HPLC 14 25 200 g/ml 30 2 25 g/ml 1.3 % 文献 1) 12 29 331. 2) FRAGRACE JOURAL, 1, 13-14, 2003. 3) FRAGRACE JOURAL, 5, 13, 2003. 4), http://www.jhcia.org/haircolor/coloring/index.html 5) FRAGRACE JOURAL, 8, 16-27, 2001. 6) Le Coz, C-J., Kuhne, S., and Engel, F. : COTACT DERMATITIS, 49, 3, 2003.