JP3243401B2 - Hair dye composition - Google Patents
Hair dye compositionInfo
- Publication number
- JP3243401B2 JP3243401B2 JP28573495A JP28573495A JP3243401B2 JP 3243401 B2 JP3243401 B2 JP 3243401B2 JP 28573495 A JP28573495 A JP 28573495A JP 28573495 A JP28573495 A JP 28573495A JP 3243401 B2 JP3243401 B2 JP 3243401B2
- Authority
- JP
- Japan
- Prior art keywords
- hair
- water
- dyeing
- weight
- hair dye
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims description 25
- 239000000118 hair dye Substances 0.000 title claims description 24
- 229920000642 polymer Polymers 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000980 acid dye Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000002506 iron compounds Chemical class 0.000 claims description 5
- 229920003169 water-soluble polymer Polymers 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000004043 dyeing Methods 0.000 description 28
- 210000004209 hair Anatomy 0.000 description 21
- -1 p-phenylenediamine compound Chemical class 0.000 description 14
- 239000007787 solid Substances 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 6
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 6
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 6
- 241000283707 Capra Species 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- VFKZECOCJCGZQK-UHFFFAOYSA-M 3-hydroxypropyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCO VFKZECOCJCGZQK-UHFFFAOYSA-M 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- ULBOONPTGYVECK-UHFFFAOYSA-N 5-(dimethylamino)-3-ethyl-2-methylpent-2-enoic acid Chemical compound OC(=O)C(C)=C(CC)CCN(C)C ULBOONPTGYVECK-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920002907 Guar gum Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920006322 acrylamide copolymer Polymers 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- HSAAILPTFCIOSG-UHFFFAOYSA-N diethyl sulfate 1-ethenylpyrrolidin-2-one Chemical compound C(=C)N1C(CCC1)=O.S(=O)(=O)(OCC)OCC HSAAILPTFCIOSG-UHFFFAOYSA-N 0.000 description 2
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 2
- 229940043264 dodecyl sulfate Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 210000004517 glycocalyx Anatomy 0.000 description 2
- 239000000665 guar gum Substances 0.000 description 2
- 235000010417 guar gum Nutrition 0.000 description 2
- 229960002154 guar gum Drugs 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 2
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- UBVSIAHUTXHQTD-UHFFFAOYSA-N 2-n-(4-bromophenyl)-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(NC=2C=CC(Br)=CC=2)=N1 UBVSIAHUTXHQTD-UHFFFAOYSA-N 0.000 description 1
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- QQILFGKZUJYXGS-UHFFFAOYSA-N Indigo dye Chemical compound C1=CC=C2C(=O)C(C3=C(C4=CC=CC=C4N3)O)=NC2=C1 QQILFGKZUJYXGS-UHFFFAOYSA-N 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- DGOBMKYRQHEFGQ-UHFFFAOYSA-L acid green 5 Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=CC(=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 DGOBMKYRQHEFGQ-UHFFFAOYSA-L 0.000 description 1
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 1
- YJVBLROMQZEFPA-UHFFFAOYSA-L acid red 26 Chemical compound [Na+].[Na+].CC1=CC(C)=CC=C1N=NC1=C(O)C(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=CC=C12 YJVBLROMQZEFPA-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- DBZJJPROPLPMSN-UHFFFAOYSA-N bromoeosin Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(Br)=C(O)C(Br)=C1OC1=C(Br)C(O)=C(Br)C=C21 DBZJJPROPLPMSN-UHFFFAOYSA-N 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- VQHHOXOLUXRQFQ-UHFFFAOYSA-L dipotassium;4,5,6,7-tetrachloro-2',4',5',7'-tetraiodo-3-oxospiro[2-benzofuran-1,9'-xanthene]-3',6'-diolate Chemical compound [K+].[K+].O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C([O-])C(I)=C1OC1=C(I)C([O-])=C(I)C=C21 VQHHOXOLUXRQFQ-UHFFFAOYSA-L 0.000 description 1
- LQJVOKWHGUAUHK-UHFFFAOYSA-L disodium 5-amino-4-hydroxy-3-phenyldiazenylnaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].OC1=C2C(N)=CC(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=C1N=NC1=CC=CC=C1 LQJVOKWHGUAUHK-UHFFFAOYSA-L 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 235000012732 erythrosine Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- SXQCTESRRZBPHJ-UHFFFAOYSA-M lissamine rhodamine Chemical compound [Na+].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=C(S([O-])(=O)=O)C=C1S([O-])(=O)=O SXQCTESRRZBPHJ-UHFFFAOYSA-M 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JMXROTHPANUTOJ-UHFFFAOYSA-H naphthol green b Chemical compound [Na+].[Na+].[Na+].[Fe+3].C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21.C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21.C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21 JMXROTHPANUTOJ-UHFFFAOYSA-H 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- KXXXUIKPSVVSAW-UHFFFAOYSA-K pyranine Chemical compound [Na+].[Na+].[Na+].C1=C2C(O)=CC(S([O-])(=O)=O)=C(C=C3)C2=C2C3=C(S([O-])(=O)=O)C=C(S([O-])(=O)=O)C2=C1 KXXXUIKPSVVSAW-UHFFFAOYSA-K 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- AZJPTIGZZTZIDR-UHFFFAOYSA-L rose bengal Chemical compound [K+].[K+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 AZJPTIGZZTZIDR-UHFFFAOYSA-L 0.000 description 1
- 210000004761 scalp Anatomy 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- LGZQSRCLLIPAEE-UHFFFAOYSA-M sodium 1-[(4-sulfonaphthalen-1-yl)diazenyl]naphthalen-2-olate Chemical compound [Na+].C1=CC=C2C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C(S([O-])(=O)=O)C2=C1 LGZQSRCLLIPAEE-UHFFFAOYSA-M 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- CGXSFOUXEQBDCJ-UHFFFAOYSA-N sodium;8-hydroxy-5,7-dinitronaphthalene-2-sulfonic acid Chemical compound [Na+].C1=C(S(O)(=O)=O)C=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 CGXSFOUXEQBDCJ-UHFFFAOYSA-N 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- UJMBCXLDXJUMFB-UHFFFAOYSA-K trisodium;5-oxo-1-(4-sulfonatophenyl)-4-[(4-sulfonatophenyl)diazenyl]-4h-pyrazole-3-carboxylate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-UHFFFAOYSA-K 0.000 description 1
Landscapes
- Cosmetics (AREA)
Description
【0001】[0001]
【発明の属する技術分野】本発明は、染着性及び堅牢性
に優れ、更に染毛後の感触が良好な染毛剤組成物に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hair dye composition which is excellent in dyeing property and fastness and has a good feel after hair dyeing.
【0002】[0002]
【従来の技術】従来、頭髪用の染毛剤組成物としては、
p−フェニレンジアミン系化合物などの酸化染料を用
い、酸化還元反応を利用して頭髪の染色を行う酸化染毛
剤と、酸性染料を用い、酸性領域で頭髪の染色を行う酸
性染毛剤とがある。このうち酸性染毛剤は、酸性染料
と、例えばベンジルアルコール、N−メチルピロリドン
などの染毛促進剤と、例えばヒドロキシエチルセルロー
スなどの増粘剤などを配合し、例えばクエン酸などの
酸、又は例えばクエン酸ナトリウムなどのそれらの酸の
塩によってpHを1.5〜4.5に調整したものであ
る。しかしながら、こうした酸性染毛剤は染着性及び堅
牢性が充分でないため、その解決を図る目的で酸性染料
に染毛促進剤を併用する提案が、特開昭61−5321
1号公報や特開昭62−164612号公報などを始め
として、多数なされている。2. Description of the Related Art Conventionally, hair dye compositions for hair have been
An oxidation hair dye that dyes hair using an oxidation-reduction reaction using an oxidation dye such as a p-phenylenediamine compound, and an acid hair dye that dyes hair in an acidic region using an acid dye. is there. Among them, the acid hair dye, an acid dye, for example, benzyl alcohol, a hair dye accelerator such as N-methylpyrrolidone, and a thickener such as hydroxyethyl cellulose, for example, is blended, for example, an acid such as citric acid, or The pH was adjusted to 1.5 to 4.5 with a salt of those acids, such as sodium citrate. However, since such acid hair dyes do not have sufficient dyeing properties and fastness, it has been proposed to use a hair dye accelerator together with an acid dye for the purpose of solving the problems.
There have been many publications such as Japanese Patent Publication No. 1 and Japanese Patent Application Laid-Open No. 62-164612.
【0003】[0003]
【発明が解決しようとする課題】ところがこのような酸
性染毛剤には、染毛促進剤が多量に配合されているため
に、染毛処理した頭髪がバサつくという問題があった。
そこで本発明は、このような従来の酸性染毛剤の欠点を
改良して、染着性及び堅牢性が優れ、更に染毛後の感触
が良好な新規の染毛剤組成物をを提供することを目的と
した。However, since such an acidic hair dye contains a large amount of a hair dye accelerating agent, there is a problem that the hair treated with the hair dye becomes rough.
Therefore, the present invention improves such disadvantages of the conventional acidic hair dye, and provides a novel hair dye composition having excellent dyeing properties and fastness, and further having a good feel after hair dyeing. It was aimed at.
【0004】[0004]
【課題を解決するための手段】本発明者らは、かかる目
的のために鋭意研究を行った結果、水溶性酸性染料に対
して特定の配合成分を組み合わせて用いることにより、
染着性及び堅牢性が優れ、更に染毛後の感触が良好な染
毛剤組成物が得られることを見出し、本発明を完成する
に至った。Means for Solving the Problems The present inventors have conducted intensive studies for this purpose, and as a result, by using a specific compounding component in combination with a water-soluble acid dye,
The present inventors have found that a hair dye composition having excellent dyeing properties and fastness and a good feel after hair dyeing can be obtained, thereby completing the present invention.
【0005】すなわち本発明は、水溶性酸性染料Aと、
両性ポリマー及びカチオン電荷を有する窒素含有量が固
形分中0.5〜6.0%であるカチオン化ポリマーから
選ばれる一種または二種以上の水溶性ポリマーBと、鉄
化合物Cと、有機溶剤Dと、水Eとを含むことを特徴と
する染毛剤組成物である。That is, the present invention provides a water-soluble acid dye A,
One or more water-soluble polymers B selected from an amphoteric polymer and a cationized polymer having a cationic charge and having a nitrogen content of 0.5 to 6.0% in solids, an iron compound C, and an organic solvent D And water E.
【0006】[0006]
【発明の実施の形態】本発明の組成物において用いられ
る水溶性酸性染料Aは、例えば赤色102号、黄色4
号、黄色5号、赤色201号、赤色227号、だいだい
色205号、褐色201号、赤色502号、赤色503
号、赤色504号、赤色506号、だいだい色402
号、黄色402号、黄色406号、黄色407号、赤色
213号、赤色214号、赤色3号、赤色104号、赤
色105号の (1)、赤色106号、緑色2号、緑色3
号、だいだい色207号、黄色202号の (1)、黄色2
02号の (2)、青色202号、青色202号、青色20
5号、青色2号、黄色203号、青色201号、緑色2
01号、青色1号、赤色230号の (1)、赤色231
号、赤色232号、緑色204号、緑色205号、赤色
401号、黄色403号の(1)、緑色401号、緑色4
02号、黒色401号、紫色401号などが挙げられる
が、通常の化粧品等に使用し得る水溶性酸性染料であれ
ばよく、特に限定されない。DETAILED DESCRIPTION OF THE INVENTION The water-soluble acid dye A used in the composition of the present invention is, for example, Red No. 102, Yellow 4
No. 5, Yellow No. 5, Red No. 201, Red No. 227, Orange No. 205, Brown No. 201, Red No. 502, Red No. 503
No., Red No. 504, Red No. 506, Orange 402
No. 402, Yellow No. 406, Yellow No. 407, Red No. 213, Red No. 214, Red No. 3, Red No. 104, Red No. 105 (1), Red No. 106, Green No. 2, Green No. 3
No., Orange No. 207, Yellow No. 202 (1), Yellow 2
02 (2), Blue 202, Blue 202, Blue 20
No. 5, Blue No. 2, Yellow No. 203, Blue No. 201, Green No. 2
No. 01, Blue No. 1, Red No. 230 (1), Red 231
No., Red No. 232, Green No. 204, Green No. 205, Red No. 401, Yellow No. 403 (1), Green No. 401, Green No. 4
No. 02, black No. 401, purple No. 401, etc., but are not particularly limited as long as they are water-soluble acidic dyes that can be used for ordinary cosmetics and the like.
【0007】かかる水溶性酸性染料Aは、組成物全量に
対して0.05〜3.0重量%、好ましくは0.2〜
1.5重量%の範囲で配合される。水溶性酸性染料Aの
配合量が0.05重量%未満では充分な染着性が得られ
ず、また3.0重量%を越えても染着性の向上は見られ
ない。The water-soluble acid dye A is used in an amount of 0.05 to 3.0% by weight, preferably 0.2 to 3.0% by weight based on the total amount of the composition.
It is blended in the range of 1.5% by weight. If the amount of the water-soluble acid dye A is less than 0.05% by weight, sufficient dyeing properties cannot be obtained, and if it exceeds 3.0% by weight, no improvement in dyeing properties is observed.
【0008】本発明の組成物において用いられる水溶性
ポリマーBは、両性ポリマー及びカチオン電荷を有する
窒素含有量が固形分中0.5〜6.0%であるカチオン
化ポリマーから選ばれたものである。そのうち両性ポリ
マーとしては、例えばN−メタクリロイルオキシエチル
−N,N−ジメチルアンモニウム−α−N−メチルカル
ボキシベタイン・メタクリル酸アルキルエステル共重合
体、塩化ジメチルジアリルアンモニウム・アクリルアミ
ド・アクリル酸のターポリマーなどが挙げられる。ここ
で、N−メタクリロイルオキシエチル−N,N−ジメチ
ルアンモニウム−α−N−メチルカルボキシベタイン・
メタクリル酸アルキルエステル共重合体の市販品として
は、ユカフォーマーW(三菱化学社製、固形分30%)
などが挙げられ、塩化ジメチルジアリルアンモニウム・
アクリルアミド・アクリル酸のターポリマーの市販品と
しては、マーコートプラス3330(カルゴン社製、固
形分10%)などが挙げられる。The water-soluble polymer B used in the composition of the present invention is selected from an amphoteric polymer and a cationized polymer having a cationically charged nitrogen content of 0.5 to 6.0% in solids. is there. Among them, examples of the amphoteric polymer include N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine / alkyl methacrylate copolymer and terpolymer of dimethyldiallylammonium chloride / acrylamide / acrylic acid. No. Here, N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine.
Commercially available methacrylic acid alkyl ester copolymers include Yuka Former W (manufactured by Mitsubishi Chemical Corporation, solid content 30%).
And dimethyldiallylammonium chloride.
Commercially available acrylamide / acrylic acid terpolymers include Marcoat Plus 3330 (manufactured by Calgon, solid content 10%).
【0009】またカチオン化ポリマーとしては、例えば
ヒドロキシエチルセルロース・ヒドロキシプロピルトリ
メチルアンモニウムクロリドエーテル、ヒドロキシエチ
ルセルロースジメチルジアリルアンモニウムクロリド共
重合体、グアーガム・塩化ヒドロキシプロピルトリメチ
ルアンモニウムエーテル、塩化ジメチルジアリルアンモ
ニウム・アクリルアミド共重合体、ジエチル硫酸ビニル
ピロリドン・N,N−ジメチルアミノエチルエチルメタ
クリル酸共重合体などが挙げられる。Examples of the cationized polymer include hydroxyethylcellulose / hydroxypropyltrimethylammonium chloride ether, hydroxyethylcellulose dimethyldiallylammonium chloride copolymer, guar gum / hydroxypropyltrimethylammonium chloride ether, dimethyldiallylammonium chloride / acrylamide copolymer, and the like. And vinylpyrrolidone diethyl sulfate / N, N-dimethylaminoethylethyl methacrylic acid copolymer.
【0010】ここで、ヒドロキシエチルセルロース・ヒ
ドロキシプロピルトリメチルアンモニウムクロリドエー
テルの市販品としては、レオガードMGP、レオガード
KGP(ライオン社製)などが挙げられ、ヒドロキシエ
チルセルロースジメチルジアリルアンモニウムクロリド
共重合体の市販品としては、セルコートL−200、セ
ルコートH−60(ナショナルスターチ社製)などが挙
げられる。またグアーガム・塩化ヒドロキシプロピルト
リメチルアンモニウムエーテルの市販品としては、ジャ
ガーC−13−S、ジャガーC−15−S(セラニーズ
・シュタイン・ホール社製)などが挙げられ、塩化ジメ
チルジアリルアンモニウム・アクリルアミド共重合体の
市販品としては、マーコート550(カルゴン社製、固
形分8%)などが挙げられる。ジエチル硫酸ビニルピロ
リドン・N,N−ジメチルアミノエチルエチルメタクリ
ル酸共重合体の市販品としては、ガフコート755N
(ISP社製、固形分20%)などが挙げられる。Here, commercially available products of hydroxyethylcellulose / hydroxypropyltrimethylammonium chloride ether include Leogard MGP, Leogard KGP (manufactured by Lion), and commercially available products of hydroxyethylcellulose dimethyldiallylammonium chloride copolymer. And Cellcoat L-200, Cellcoat H-60 (manufactured by National Starch), and the like. Examples of commercially available guar gum and hydroxypropyltrimethylammonium chloride include Jaguar C-13-S and Jaguar C-15-S (manufactured by Celanese Stein Hall Co.), and dimethyldiallylammonium chloride / acrylamide copolymer. As a commercially available product of merging, Marcoat 550 (manufactured by Calgon, solid content 8%) and the like can be mentioned. A commercially available product of vinylpyrrolidone diethyl sulfate / N, N-dimethylaminoethylethyl methacrylic acid copolymer is Guffcoat 755N.
(Made by ISP, solid content: 20%).
【0011】これらの両性ポリマー及びカチオン電荷を
有する窒素含有量が固形分中0.5〜6.0%から選ば
れた水溶性ポリマーBは、固形分として組成物全量に対
して0.01〜1.0重量%、好ましくは0.05〜
0.5重量%の範囲で配合される。配合量が0.01重
量%未満では染毛後の感触に充分な満足が得られず、
1.0重量%を越えても染毛後の感触の向上は得られな
い。The amphoteric polymer and the water-soluble polymer B having a cationically charged nitrogen content of 0.5 to 6.0% in the solid content are contained in an amount of 0.01 to 0.01% based on the total weight of the composition. 1.0% by weight, preferably 0.05 to
It is blended in the range of 0.5% by weight. If the amount is less than 0.01% by weight, the feeling after hair dyeing cannot be sufficiently satisfied,
Even if it exceeds 1.0% by weight, no improvement in the feel after hair dyeing can be obtained.
【0012】本発明の組成物において用いられる鉄化合
物Cは、例えば硫酸第1鉄、塩化第2鉄、クエン酸鉄、
酢酸鉄などが挙げられる。これらの鉄化合物Cは、組成
物全量に対して0.001〜1.0重量%、好ましくは
0.01〜0.5重量%の範囲で配合される。配合量が
0.001重量%未満では充分な染着性が得られず、
1.0重量%を越えても染着性の向上は見られない。The iron compound C used in the composition of the present invention includes, for example, ferrous sulfate, ferric chloride, iron citrate,
Iron acetate and the like. These iron compounds C are added in the range of 0.001 to 1.0% by weight, preferably 0.01 to 0.5% by weight, based on the total amount of the composition. If the amount is less than 0.001% by weight, sufficient dyeing properties cannot be obtained,
Even if it exceeds 1.0% by weight, no improvement in dyeing properties is observed.
【0013】本発明の組成物において用いられる有機溶
剤Dは、例えばN−メチルピロリドン、N−エチルピロ
リドン等のN−アルキルピロリドン、例えばエチレンカ
ーボネート、プロピレンカーボネート等の低級アルキレ
ンカーボネート及び、例えばベンジルアルコール、β−
フェニルアルコール等の芳香族アルコールから選ばれる
ものである。これらの有機溶剤は、組成物全量に対して
3〜40重量%、好ましくは5〜20重量%配合され
る。また、これに加えて助溶剤として、低級脂肪族アル
コール、多価アルコール、セロソルブ類などの溶剤を配
合することもできる。有機溶剤の配合量が3重量%未満
では充分な染着性が得られず、また40重量%を越える
とそれ以上の染着性の向上が見られないばかりか、染毛
後の感触が低下する。The organic solvent D used in the composition of the present invention is, for example, N-alkylpyrrolidone such as N-methylpyrrolidone or N-ethylpyrrolidone, for example, lower alkylene carbonate such as ethylene carbonate or propylene carbonate, and benzyl alcohol, for example. β-
It is selected from aromatic alcohols such as phenyl alcohol. These organic solvents are blended in an amount of 3 to 40% by weight, preferably 5 to 20% by weight based on the total amount of the composition. In addition, solvents such as lower aliphatic alcohols, polyhydric alcohols, and cellosolves can be added as co-solvents. If the amount of the organic solvent is less than 3% by weight, sufficient dyeing properties cannot be obtained, and if it exceeds 40% by weight, further improvement in dyeing properties cannot be seen, and the feeling after hair dyeing is reduced. I do.
【0014】更に、本発明の組成物は、そのpHが好ま
しくは2〜5、より好ましくは2〜4の範囲に入るよう
に調整される。pHが2より小さいと頭髪又は頭皮を傷
める恐れがあり、またpHが5より大きいと染着性が低
下する。かかるpHの調整は、例えば乳酸、酒石酸、ク
エン酸等の有機酸、及び例えばリン酸、塩酸等の無機酸
を用いることができる。Further, the composition of the present invention is adjusted so that its pH preferably falls within the range of 2 to 5, more preferably 2 to 4. If the pH is lower than 2, the hair or the scalp may be damaged, and if the pH is higher than 5, the dyeing property is reduced. For such pH adjustment, for example, organic acids such as lactic acid, tartaric acid, and citric acid, and inorganic acids such as phosphoric acid and hydrochloric acid can be used.
【0015】本発明においては、上記の成分のほかに、
通常の化粧料や染毛料に用いられる、例えば防腐剤、キ
レート剤、可溶化剤、安定化剤、増粘剤、感触向上剤、
香料、噴射剤等の配合成分を、本発明の効果を損なわな
い範囲で適宜配合することができる。In the present invention, in addition to the above components,
Used in ordinary cosmetics and hair dyes, for example, preservatives, chelating agents, solubilizers, stabilizers, thickeners, feel improvers,
Blending components such as fragrances and propellants can be appropriately blended within a range that does not impair the effects of the present invention.
【0016】本発明の染毛剤組成物は、液状、乳液状、
クリーム状、ペースト状、ゼリー状、又はエアゾールフ
ォーム状などの剤型をもつ染毛剤とすることができる。The hair dye composition of the present invention may be a liquid, an emulsion,
It can be a hair dye having a dosage form such as cream, paste, jelly, or aerosol foam.
【0017】かかる本発明の染毛剤組成物を使用して染
毛施術する場合、頭髪に組成物を塗布したのち、30〜
50℃に加温して染毛することが好ましい。In the case of performing hair dyeing treatment using the hair dye composition of the present invention, after applying the composition to the hair, 30 to 30 hours is applied.
It is preferable to heat the hair to 50 ° C. to dye the hair.
【0018】[0018]
【実施例】以下、実施例によって本発明を更に具体的に
説明するが、本発明はこれらの例によって何等限定され
るものではない。EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto.
【0019】水溶性酸性染料として黒色401号、紫色
401号、及びだいだい色205号を、また、両性ポリ
マーとして、マーコートプラス3330(カルゴン社
製、固形分:10%)、ユカフォーマーW(三菱化学社
製、固形分:30%)、カチオン電荷を有する窒素含有
量が固形分中0.5〜6.0%であるカチオン化ポリマ
ーとして、マーコート550(カルゴン社製、固形分:
8%、N含有量:5.8%)、マーコート100(同社
製、固形分:40%、N含有量:9.0%)、及びレオ
ガードMGP(ライオン社製、固形分:100%、N含
有量:1.8%)を用い、鉄化合物として塩化第2鉄
を、また有機溶剤としてベンジルアルコールをエタノー
ルと組み合わせて用いたほか、増粘剤としてヒドロキシ
エチルセルロースを、pH調整剤としてクエン酸を、そ
して安定化剤としてポリオキシエチレン(10E.O.)ノニ
ルフェニルエーテルを用いて、表1の配合に従って実施
例及び比較例の染毛剤組成物a〜jを調製した。そし
て、これらの染毛剤組成物について、次のようにして染
着性試験、堅牢性試験、及び感触官能性試験を行った。As water-soluble acid dyes, black 401, purple 401, and orange 205 are used. As amphoteric polymers, Marcoat Plus 3330 (manufactured by Calgon Co., solid content: 10%), Yuka Former W (Mitsubishi Chemical Corporation) As a cationized polymer having a cationic charge and having a nitrogen content of 0.5 to 6.0% in the solid content, Mercoat 550 (manufactured by Calgon Corporation, solid content: 30%).
8%, N content: 5.8%), Mercoat 100 (manufactured by the company, solid content: 40%, N content: 9.0%), and Leogard MGP (manufactured by Lion Corporation, solid content: 100%, N Ferric chloride as an iron compound, benzyl alcohol in combination with ethanol as an organic solvent, hydroxyethyl cellulose as a thickener, and citric acid as a pH adjuster. Using polyoxyethylene (10E.O.) nonylphenyl ether as a stabilizer, hair dye compositions a to j of Examples and Comparative Examples were prepared in accordance with the formulations shown in Table 1. Then, a dyeing test, a fastness test, and a touch sensory test were performed on these hair dye compositions as follows.
【0020】染着性試験 長さ10cm、重さ約2gの山羊毛束を、3重量%ポリオ
キシエチレン(2EO)ラウリル硫酸ナトリウム水溶液
2mlで洗浄し、更に温水で充分にすすぎ流した。その
後、余分な水分を拭き取り、染毛剤組成物2gを均一に
塗付したのち、40℃の恒温槽中に15分間放置した。
その後、室温(25℃)で5分間保持し、温水で充分に
すすいだ。そして乾燥したのち、以下の基準により、染
着性を評価した。 ◎ 均一且つ濃く染着し、山羊毛束の白色が目立たない。 ○ 均一に染着し、山羊毛束の白色が目立たない。 △ 染着がやや不均一で、山羊毛束の白色がやや目立つ。 × 染着が不均一で、山羊毛束の白色が目立つ。 Dyeing test A goat wool bundle having a length of 10 cm and a weight of about 2 g was washed with 2 ml of a 3% by weight aqueous solution of sodium polyoxyethylene (2EO) lauryl sulfate and rinsed thoroughly with warm water. Thereafter, excess water was wiped off, 2 g of the hair dye composition was uniformly applied, and then left in a thermostat at 40 ° C. for 15 minutes.
Thereafter, the mixture was kept at room temperature (25 ° C.) for 5 minutes and rinsed sufficiently with warm water. After drying, the dyeability was evaluated according to the following criteria. ◎ Uniformly and deeply dyed, the white color of the goat hair bundle is inconspicuous. ○ Uniform dyeing, the white color of the goat bundle is not noticeable. △ The dyeing is slightly uneven, and the white color of the goat wool bundle is somewhat noticeable. × Dyeing is uneven and the white color of the goat bundle is conspicuous.
【0021】堅牢性試験 染着性試験によって染着した毛束を、染着後24時間放
置したのち3重量%ポリオキシエチレン(2EO)ラウ
リル硫酸ナトリウム水溶液50ml中に15分間浸漬し
た。そして更に1.5重量%の塩化セチルトリメチルア
ンモニウム水溶液50ml中に浸漬する。こうしてこの塩
化セチルトリメチルアンモニウム水溶液への色落ちの程
度を、以下の基準により評価した。 ◎ 洗液への色落ちがあまりない。 ○ 洗液への色落ちが少しある。 △ 洗液への色落ちがかなりある。 × 洗液への色落ちがある。 Fastness test The hair bundle dyed by the dyeing test was left for 24 hours after dyeing and then immersed in 50 ml of a 3% by weight aqueous solution of sodium polyoxyethylene (2EO) lauryl sulfate for 15 minutes. Then, it is further immersed in 50 ml of a 1.5% by weight aqueous solution of cetyltrimethylammonium chloride. Thus, the degree of discoloration of the cetyltrimethylammonium chloride aqueous solution was evaluated according to the following criteria. ◎ There is not much discoloration to the washing liquid. ○ There is a little discoloration to the washing liquid. △ There is considerable discoloration to the washing liquid. × Discoloration to the washing liquid.
【0022】感触官能性試験 染着性試験と同様な操作で施術した日本人黒髪の毛束
の、温水で洗い流したときの柔らかさ及び指通りの良さ
と、乾燥後の毛髪の艶及びなめらかさとについて、専門
のパネラーが、以下の基準により評価した。 ◎ 非常になめらかで、指通り・艶共によい。 ○ なめらかで、指通り・艶共によい。 △ ややきしみがあり、指通り・艶共にやや悪い。 × きしみがあり、ざらつきがある。 Tactile sensation test The softness of hair bundles of Japanese black hair treated in the same manner as in the dyeing test and the goodness of fingers when rinsed with warm water, and the gloss and smoothness of the hair after drying. And expert panelists evaluated according to the following criteria. ◎ It is very smooth and has good finger and gloss. ○ Smooth, good finger and gloss. △ There is a slight squeak, and both fingering and gloss are slightly poor. × There are squeaks and roughness.
【0023】[0023]
【表1】 [Table 1]
【0024】[0024]
【発明の効果】本発明の染毛剤組成物は、染着性及び堅
牢性に優れ、更に染毛後の感触が良好であるという効果
を有する。Industrial Applicability The hair dye composition of the present invention is excellent in dyeing properties and fastness, and has an effect that the feeling after hair dyeing is good.
Claims (1)
カチオン電荷を有する窒素含有量が固形分中0.5〜
6.0%であるカチオン化ポリマーから選ばれる一種ま
たは二種以上の水溶性ポリマーBと、鉄化合物である塩
化第2鉄Cと、有機溶剤Dと、水Eとを含み、かつ、上
記水溶性ポリマーBの配合量が組成物全量に対して0.
01〜1.0重量%であることを特徴とする染毛剤組成
物。1. A water-soluble acid dye A having an amphoteric polymer and a cationically charged nitrogen content of 0.5 to 0.5
One or more water-soluble polymers B selected from 6.0% of a cationized polymer, and a salt being an iron compound
Of ferric C, seen containing an organic solvent D, and the water E, and, on
The amount of the water-soluble polymer B is 0.1% based on the total amount of the composition.
A hair dye composition, which is contained in an amount of from 0.01 to 1.0% by weight .
Priority Applications (1)
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JP28573495A JP3243401B2 (en) | 1995-11-02 | 1995-11-02 | Hair dye composition |
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Application Number | Priority Date | Filing Date | Title |
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JP28573495A JP3243401B2 (en) | 1995-11-02 | 1995-11-02 | Hair dye composition |
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Publication Number | Publication Date |
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JPH09124450A JPH09124450A (en) | 1997-05-13 |
JP3243401B2 true JP3243401B2 (en) | 2002-01-07 |
Family
ID=17695357
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2000355527A (en) * | 1999-06-10 | 2000-12-26 | Kanebo Ltd | Application of hair dye |
JP4686283B2 (en) * | 2005-07-12 | 2011-05-25 | ホーユー株式会社 | Hair dye composition |
JP5483841B2 (en) * | 2008-08-01 | 2014-05-07 | 三菱鉛筆株式会社 | Hair dye composition and hair dye composition applicator using the same |
FR2990852A1 (en) * | 2012-05-24 | 2013-11-29 | Oreal | ANIONIC DYE OR ANONIUM DYE AGAINST AMMONIUM OR PHOSPHONIUM ION, DYE COMPOSITION COMPRISING SAME, AND PROCESS FOR COLORING KERATINIC FIBERS FROM THESE DYES |
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1995
- 1995-11-02 JP JP28573495A patent/JP3243401B2/en not_active Expired - Fee Related
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JPH09124450A (en) | 1997-05-13 |
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