JPH0534328B2 - - Google Patents
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- Publication number
- JPH0534328B2 JPH0534328B2 JP2038064A JP3806490A JPH0534328B2 JP H0534328 B2 JPH0534328 B2 JP H0534328B2 JP 2038064 A JP2038064 A JP 2038064A JP 3806490 A JP3806490 A JP 3806490A JP H0534328 B2 JPH0534328 B2 JP H0534328B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon atoms
- alkyl group
- formula
- hair
- group
- 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
- 125000004432 carbon atom Chemical group C* 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 38
- 239000000118 hair dye Substances 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 150000003839 salts Chemical class 0.000 claims description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 19
- XIWMTQIUUWJNRP-UHFFFAOYSA-N amidol Chemical compound NC1=CC=C(O)C(N)=C1 XIWMTQIUUWJNRP-UHFFFAOYSA-N 0.000 claims description 17
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000000982 direct dye Substances 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- 150000004780 naphthols Chemical class 0.000 claims description 3
- 229910006069 SO3H Inorganic materials 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 210000004209 hair Anatomy 0.000 description 36
- 241000283707 Capra Species 0.000 description 23
- 235000013350 formula milk Nutrition 0.000 description 16
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 13
- 235000019646 color tone Nutrition 0.000 description 10
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 8
- 239000000975 dye Substances 0.000 description 8
- 238000004043 dyeing Methods 0.000 description 8
- 229940018564 m-phenylenediamine Drugs 0.000 description 8
- 229960001755 resorcinol Drugs 0.000 description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 6
- OBCSAIDCZQSFQH-UHFFFAOYSA-N 2-methyl-1,4-phenylenediamine Chemical compound CC1=CC(N)=CC=C1N OBCSAIDCZQSFQH-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 5
- -1 hydrogen peroxide Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- VPMMJSPGZSFEAH-UHFFFAOYSA-N 2,4-diaminophenol;hydrochloride Chemical compound [Cl-].NC1=CC=C(O)C([NH3+])=C1 VPMMJSPGZSFEAH-UHFFFAOYSA-N 0.000 description 3
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 3
- 229910000071 diazene Inorganic materials 0.000 description 3
- 239000012458 free base Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000008213 purified water Substances 0.000 description 3
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LPMBTLLQQJBUOO-KTKRTIGZSA-N (z)-n,n-bis(2-hydroxyethyl)octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)N(CCO)CCO LPMBTLLQQJBUOO-KTKRTIGZSA-N 0.000 description 2
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 241000872198 Serjania polyphylla Species 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- ZZTCCAPMZLDHFM-UHFFFAOYSA-N ammonium thioglycolate Chemical compound [NH4+].[O-]C(=O)CS ZZTCCAPMZLDHFM-UHFFFAOYSA-N 0.000 description 2
- 229940075861 ammonium thioglycolate Drugs 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 229940055577 oleyl alcohol Drugs 0.000 description 2
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 235000020610 powder formula Nutrition 0.000 description 2
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- ZBTRTXLGWIKSMO-UHFFFAOYSA-N (4-aminophenyl)sulfamic acid Chemical compound NC1=CC=C(NS(O)(=O)=O)C=C1 ZBTRTXLGWIKSMO-UHFFFAOYSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- OQWWMUWGSBRNMA-UHFFFAOYSA-N 1-(2,4-diaminophenoxy)ethanol Chemical compound CC(O)OC1=CC=C(N)C=C1N OQWWMUWGSBRNMA-UHFFFAOYSA-N 0.000 description 1
- PCAXITAPTVOLGL-UHFFFAOYSA-N 2,3-diaminophenol Chemical compound NC1=CC=CC(O)=C1N PCAXITAPTVOLGL-UHFFFAOYSA-N 0.000 description 1
- 229940113489 2,4-diaminophenoxyethanol Drugs 0.000 description 1
- HQCHAOKWWKLXQH-UHFFFAOYSA-N 2,6-Dichloro-para-phenylenediamine Chemical compound NC1=CC(Cl)=C(N)C(Cl)=C1 HQCHAOKWWKLXQH-UHFFFAOYSA-N 0.000 description 1
- MGLZGLAFFOMWPB-UHFFFAOYSA-N 2-chloro-1,4-phenylenediamine Chemical compound NC1=CC=C(N)C(Cl)=C1 MGLZGLAFFOMWPB-UHFFFAOYSA-N 0.000 description 1
- HGUYBLVGLMAUFF-UHFFFAOYSA-N 2-methoxybenzene-1,4-diamine Chemical compound COC1=CC(N)=CC=C1N HGUYBLVGLMAUFF-UHFFFAOYSA-N 0.000 description 1
- YGOFNNAZFZYNIX-UHFFFAOYSA-N 3-N-phenylbenzene-1,2,3-triamine Chemical compound NC=1C(=C(C=CC1)NC1=CC=CC=C1)N YGOFNNAZFZYNIX-UHFFFAOYSA-N 0.000 description 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 1
- RAUWPNXIALNKQM-UHFFFAOYSA-N 4-nitro-1,2-phenylenediamine Chemical compound NC1=CC=C([N+]([O-])=O)C=C1N RAUWPNXIALNKQM-UHFFFAOYSA-N 0.000 description 1
- 201000004569 Blindness Diseases 0.000 description 1
- 241001070941 Castanea Species 0.000 description 1
- 235000014036 Castanea Nutrition 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- BZORFPDSXLZWJF-UHFFFAOYSA-N N,N-dimethyl-1,4-phenylenediamine Chemical compound CN(C)C1=CC=C(N)C=C1 BZORFPDSXLZWJF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- SMVRDGHCVNAOIN-UHFFFAOYSA-L disodium;1-dodecoxydodecane;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC SMVRDGHCVNAOIN-UHFFFAOYSA-L 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000003700 hair damage Effects 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Cosmetics (AREA)
Description
〔産業上の利用分野〕
本発明は、空気酸化型１剤式染毛剤組成物、更
に詳細には、人体の毛髪を黒褐色の自然な色調に
染色することができ、毛髪に対する染着性、日光
堅牢性および耐洗濯性にすぐれ、毛髪の損傷も少
なく、かつ使用の簡便な空気酸化（自動酸化）型
１剤式染毛剤組成物に関する。
〔従来の技術及び発明が解決しようとする課題〕
従来、白髪染として汎用されているのは、ｐ−
フエニレンジアミンを主体とした酸化染料（プレ
カーサーという）を過酸化水素等の酸化剤で酸化
し、ついでレゾルシン等のカツプラー類とカツプ
リング反応を行うことによつて発色して毛髪を染
色する方法であり、この方法により染色性、色
調、日光堅ろう性、洗濯堅ろう性が比較的良好な
染毛が行なわれている。
しかし、この染毛剤においてもいくつかの欠点
が存する。酸化染料を用いた染毛剤は通常酸化反
応を行うため、酸化剤の併用が不可欠であり、過
酸化水素を始め、過ホウ酸塩、過炭酸塩等の過酸
化物が使用される。このため市販の染毛剤は使用
時に水を加え過酸化無機塩類を分解反応させる粉
末１剤式と、酸化染料を含有する１剤と過酸化水
素を含有する２剤とを使用時に混合して用いる２
剤式とがある。
このどちらの場合にも混合のための専用の器具
と、均一に混合しなければならないという面倒な
操作が必要であるとともに、この操作は染毛直前
に実施し、またすみやかに染毛を完了しなければ
ならないという時間的な制約がある。さらに発色
用の過酸化物はどれも皮膚、特に粘膜や眼に対し
強い刺激を与え、誤つて眼に入つた場合には失明
などの重い傷害を残すおそれがある。
このため、斯かる酸化剤を用いずに空気によつ
て自然に酸化発色する酸化染料を含有し、かつ染
着性、日光堅ろう性、洗濯堅ろう性、摩擦堅ろう
性および色調等に対する要求を十分に満足する染
毛剤組成物が検討されてきている。
通常染毛剤に用いられる酸化染料の中で、それ
自身単独で空気酸化により徐々に発色するものに
は、ｐ−フエニレンジアミンまたはその塩（以
下、その塩類が知られているものはすべて塩類を
も含む）、トルエン−２，５−ジアミン、ｐ−ア
ミノフエノール、ｏ−アミノフエノール、ｐ−メ
チルアミノフエノール、２，４−ジアミノフエノ
ール、ピロガロール、カテコール、ヒドロキノ
ン、レゾルシンなど多数知られているが、これら
の中で２，４−ジアミノフエノールはそのレドツ
クス電位が他に比べて極めて低く、アルカリ性溶
液中では数分で発色する。他の酸化染料では比較
的レドツクス電位の低いｐ−アミノフエノールで
も発色に数時間を必要とする。
そこで、この２，４−ジアミノフエノールを用
いた空気酸化型染毛剤の開発が試みられている
が、この染料は単独で用いた場合、色調が赤紫〜
赤褐色であり、白髪染の色調としては不自然であ
る。
また、特開昭53−72836号公報には２，４−ジ
アミノフエノールとCo、Fe、Mn、Cu、Cr塩と
の組合せにより毛髪上に褐色〜黒色調を与えるこ
とが開示されているが、この方法は発色に用いら
れる金属イオンにより、後日、パーマネントウエ
ーブ処理に悪影響を与える。
さらにヨーロツパ特許第74243号明細書には２，
４−ジアミノフエノールと２−メトキシ−ｐ−フ
エニレンジアミンとの組合せにより黒色色調を生
ずると示されているが、この方法によつても染色
強度はさほど高くはなく、色調も不自然な赤味が
強いものとなる。
特開昭62−126114号公報には２，４−ジアミノ
フエノールと１，５−ジヒドロキシナフタレンと
の組合せにより、黒褐色に毛髪を染色すると開示
されているが、この方法では１，５−ジヒドロキ
シナフタレンの毛髪への浸透性が低いため、通常
の放置時間（10〜60分）の後、すすぎの操作によ
つてほとんど流されてしまい、わずかに２，４−
ジアミノフエノールを単独で用いた場合と同一の
色調が残つただけであつた。
このように、これまでに２，４−ジアミノフエ
ノールを用いた空気酸化型１剤式染毛剤組成物に
おいては自然な黒系の色調に毛髪を染色するもの
は得られていない。
〔課題を解決するための手段〕
斯かる実状において本発明者は、２，４−ジア
ミノフエノールの反応性について鋭意検討した結
果、２，４−ジアミノフエノールは、プレカーサ
ー（ｐ−ジアミン類、ｐ−アミノフエノール類）
の共存下で、プレカーサーの空気酸化を促進す
る、すなわち、２，４−ジアミノフエノールの存
在により、プレカーサーの酸化体であるキノンジ
イミン（モノイミン）の生成が促進されることを
発見し、従来酸化剤なしでは極めて発色の遅かつ
たｐ−ジアミン類も２，４−ジアミノフエノール
若しくはその塩と組合わせることにより、空気酸
化が促進され、キノンジイミン／２，４−ジアミ
ノフエノールカツプリング生成物による良好な黒
系の色調が得られることを見出した。
また、更にキノンジイミンとカツプリング反応
を起こす特定のｍ−ジアミン類、フエノール類、
ナフトール類を添加すれば、良好な黒〜黒緑色の
色調が得られることを見出した。また更に、直接
染料を添加することにより、極めて高彩度で自然
な多彩な色調が得られることを見出し、本発明を
完成した。
すなわち、本発明における第１の発明は次の成
分（a′）及び(b)
(a′) 一般式（′）
〔式中、R1′は水素原子、炭素数１〜８のアル
キル基、炭素数１〜８のヒドロキシアルキル
基、
[Industrial Field of Application] The present invention relates to an air-oxidized one-component hair dye composition, more specifically, it is capable of dyeing human hair to a natural dark brown tone, and has a property of dyeing the hair, This invention relates to an air oxidation (auto-oxidation) one-component hair dye composition that has excellent sunlight fastness and washing resistance, causes less hair damage, and is easy to use. [Prior art and problems to be solved by the invention] Conventionally, p-
This is a method of dyeing hair by oxidizing an oxidation dye (called a precursor) mainly composed of phenylenediamine with an oxidizing agent such as hydrogen peroxide, and then performing a coupling reaction with a coupler such as resorcinol. By this method, hair dyeing with relatively good dyeability, color tone, sunlight fastness, and washing fastness is achieved. However, this hair dye also has some drawbacks. Since hair dyes using oxidative dyes usually undergo an oxidation reaction, the combined use of an oxidizing agent is essential, and peroxides such as hydrogen peroxide, perborates, and percarbonates are used. For this reason, commercially available hair dyes include one powder formula in which water is added and the inorganic peroxide salts undergo a decomposition reaction, and the other is a powder formula in which water is added and a two-part formula containing hydrogen peroxide is mixed at the time of use. use 2
There is a drug formula. In both cases, special equipment for mixing and a tedious operation to ensure uniform mixing are required, and this operation must be carried out immediately before dyeing the hair to ensure that the hair dyeing is completed promptly. There are time constraints that require it. Furthermore, all coloring peroxides are highly irritating to the skin, especially to the mucous membranes and eyes, and if they accidentally come into contact with the eyes, there is a risk of serious damage such as blindness. Therefore, it contains an oxidation dye that naturally oxidizes and develops color in the air without using such an oxidizing agent, and satisfies the requirements for dyeability, sunlight fastness, washing fastness, friction fastness, color tone, etc. Satisfactory hair dye compositions have been investigated. Among the oxidation dyes commonly used in hair dyes, those that gradually develop color by themselves by air oxidation include p-phenylenediamine or its salts (hereinafter, all known salts are salts). ), toluene-2,5-diamine, p-aminophenol, o-aminophenol, p-methylaminophenol, 2,4-diaminophenol, pyrogallol, catechol, hydroquinone, and resorcinol. Among these, 2,4-diaminophenol has an extremely low redox potential compared to others and develops color in a few minutes in an alkaline solution. Among other oxidative dyes, even p-aminophenol, which has a relatively low redox potential, requires several hours for color development. Therefore, attempts have been made to develop an air oxidation type hair dye using this 2,4-diaminophenol, but when this dye is used alone, the color tone ranges from reddish-purple to purple.
It is reddish brown, which is an unnatural tone for gray hair dye. Furthermore, JP-A-53-72836 discloses that a combination of 2,4-diaminophenol and Co, Fe, Mn, Cu, and Cr salts imparts a brown to black tone to the hair. This method has an adverse effect on subsequent permanent wave processing due to the metal ions used for color development. Furthermore, European Patent No. 74243 specifies 2,
It has been shown that a combination of 4-diaminophenol and 2-methoxy-p-phenylenediamine produces a black tone, but even with this method, the dyeing strength is not very high and the color tone is an unnatural reddish. becomes strong. JP-A-62-126114 discloses that hair is dyed dark brown by a combination of 2,4-diaminophenol and 1,5-dihydroxynaphthalene; however, in this method, 1,5-dihydroxynaphthalene is Due to its low penetration into the hair, most of the 2,4-
Only the same color tone remained as when diaminophenol was used alone. As described above, no air-oxidized one-component hair dye composition using 2,4-diaminophenol that dyes hair to a natural black tone has been obtained so far. [Means for Solving the Problems] Under such circumstances, the present inventors have conducted intensive studies on the reactivity of 2,4-diaminophenol, and have found that 2,4-diaminophenol is a precursor (p-diamines, p- aminophenols)
In other words, the presence of 2,4-diaminophenol promoted the production of quinone diimine (monoimine), an oxidant of the precursor, in the presence of 2,4-diaminophenol. By combining p-diamines, which are extremely slow in color development, with 2,4-diaminophenol or its salt, air oxidation is promoted, resulting in a good black color due to the quinone diimine/2,4-diaminophenol coupling product. It was found that a color tone of . In addition, specific m-diamines and phenols that cause a coupling reaction with quinone diimine,
It has been found that a good black to black-green color tone can be obtained by adding naphthols. Furthermore, the present invention was completed based on the discovery that by adding a direct dye, extremely high chroma and a wide variety of natural color tones can be obtained. That is, the first invention of the present invention has the following components (a') and (b) (a') general formula (') [In the formula, R 1 ' is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms,
【式】また
は−SO3Hを示し、R2′は水素原子、炭素数１
〜８のアルキル基または炭素数１〜８のヒドロ
キシアルキル基を示し、R3、R4は同一かまた
は異なつて、水素原子、炭素数１〜４のアルキ
ル基、炭素数２〜４のアルコキシ基、ハロゲン
原子、−COOH、−COOR5（R5は炭素数１〜４
のアルキル基）、−CONH2または−SO3Hを示
す。但し、R3とR4がともに水素原子の場合に
おいて、R1′およびR2′がともに水素原子、炭素
数１〜８のアルキル基および炭素数１〜８のヒ
ドロキシアルキル基から選ばれる基となること
はない〕
で表わされるｐ−ジアミン誘導体若しくはその
塩の中より選ばれる１種または２種以上のｐ−
ジアミン類
(b) ２，４−ジアミノフエノール若しくはその塩
を含有し、かつ（a′）成分と(b)成分のモル比が
100：１〜１：５であることを特徴とする空気酸
化型１剤式染毛剤組成物を提供するものである。
更に第２の発明は次の成分(a)、(b)及び(c)
(a) 一般式（）
〔式中、R1は水素原子、炭素数１〜８のアル
キル基、炭素数１〜８のヒドロキシアルキル
基、[Formula] or -SO 3 H, R 2 ' is a hydrogen atom, carbon number 1
-8 alkyl group or C1-8 hydroxyalkyl group, R 3 and R 4 are the same or different, hydrogen atom, C1-4 alkyl group, C2-4 alkoxy group , halogen atom, -COOH, -COOR 5 (R 5 has 1 to 4 carbon atoms
), -CONH2 or -SO3H . However, in the case where R 3 and R 4 are both hydrogen atoms, R 1 ′ and R 2 ′ are both hydrogen atoms, a group selected from a C 1-8 alkyl group, and a C 1-8 hydroxyalkyl group. One or more p-diamine derivatives or salts thereof represented by
Diamines (b) Contains 2,4-diaminophenol or its salt, and the molar ratio of component (a') and component (b) is
The present invention provides an air oxidation type one-part hair dye composition characterized by a ratio of 100:1 to 1:5. Furthermore, the second invention comprises the following components (a), (b) and (c) (a) general formula () [In the formula, R 1 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms,
【式】または−
SO3Hを示し、R2は水素原子、炭素数１〜８の
アルキル基または炭素数１〜８のヒドロキシア
ルキル基を示し、R3、R4は同一かまたは異な
つて、水素原子、炭素数１〜４のアルキル基、
炭素数２〜４のアルコキシ基、ハロゲン原子、
−COOH、−COOR5（R5は炭素数１〜４のアル
キル基）、−CONH2または−SO3Hを示す〕
で表わされるｐ−ジアミン誘導体若しくはその
塩の中より選ばれる１種または２種以上のｐ−
ジアミン類
(b) ２，４−ジアミノフエノール若しくはその塩
(c) 次の(i)、(ii)及び(iii)の化合物の中より選ばれ
る
１種又は２種以上
(i) 一般式（）
〔式中、ＸはＮまたはCHを示し、R6、R7、
R8、R9は同一かまたは異なつて、水素原子、
炭素数１〜８のアルキル基または炭素数１〜
８のヒドロキシアルキル基を示し、R10は炭
素数１〜４のアルキル基、炭素数１〜４のア
ルコキシ基、−Ｏ（CH2）oOH（ここでｎは１〜
４の数）、ハロゲン原子、−COOH、−
COOR11（R11は炭素数１〜４のアルキル基）、
−CONH2または−SO3Hを示す〕
で表わされるｍ−ジアミン誘導体若しくはそ
の塩
(ii) フエノール類
(iii) ナフトール類
を含有し、かつ(a)成分と(b)成分のモル比が100：
１〜１：５であることを特徴とする空気酸化型１
剤式染毛組成物を提供するものである。
また更に第３の発明は(d)成分として直接染料を
添加してなる空気酸化型１剤式染毛剤組成物を提
供するものである。
本発明における(a)成分のｐ−ジアミン類または
その塩は前記一般式（）またはその塩で表され
るものであるが、具体的には、ｐ−フエニレンジ
アミン、トルエン−２，５−ジアミン、２−クロ
ロ−ｐ−フエニレンジアミン、ジアミノジフエニ
ルアミン、Ｎ−フエニル−ｐ−フエニレンジアミ
ン、Ｎ，Ｎ−ジメチル−ｐ−フエニレンジアミ
ン、Ｎ，Ｎ−（ビスヒドロキシエチル）−ｐ−フエ
ニレンジアミン、２，６−ジクロロ−ｐ−フエニ
レンジアミン、ｐ−アミノフエニルスルフアミン
酸またはそれらの塩などが挙げられる。
本発明における(c)成分のうち(i)のｍ−ジアミン
類またはその塩は前記一般式（）またはその塩
で表わされるものであるが、その好ましい具体例
としては、ｍ−フエニレンジアミン、２，４−ジ
アミノトルエン、２，４−ジアミノフエノキシエ
タノール、２，６−ジアミノピリジン等またはそ
れらの塩などが挙げられる。
また、(c)成分のうち(ii)のフエノール類として
は、次の一般式（）
〔式中、R12、R13、R15、R16は同一かまた異な
つて水素原子、炭素数１〜５のアルキル基、炭素
数１〜５のヒドロキシアルキル基、炭素数１〜５
のアルコキシ基、炭素数１〜５のカルボキシアル
キル基、炭素数１〜５の１〜３級アミノアルキル
基、−COOH、−COOR17（R17は炭素数１〜４のア
ルキル基）、[Formula] or -SO 3 H, R 2 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydroxyalkyl group having 1 to 8 carbon atoms, and R 3 and R 4 are the same or different, hydrogen atom, alkyl group having 1 to 4 carbon atoms,
Alkoxy group having 2 to 4 carbon atoms, halogen atom,
-COOH, -COOR 5 (R 5 is an alkyl group having 1 to 4 carbon atoms), -CONH 2 or -SO 3 H] One or two selected from p-diamine derivatives or salts thereof represented by More than species p-
Diamines (b) 2,4-diaminophenol or its salt (c) One or more compounds selected from the following compounds (i), (ii) and (iii) (i) General formula () [In the formula, X represents N or CH, R 6 , R 7 ,
R 8 and R 9 are the same or different, hydrogen atoms,
Alkyl group having 1 to 8 carbon atoms or 1 to 8 carbon atoms
8 hydroxyalkyl group, R 10 is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, -O(CH 2 ) o OH (where n is 1 to 4
4), halogen atom, -COOH, -
COOR 11 (R 11 is an alkyl group having 1 to 4 carbon atoms),
-CONH 2 or -SO 3 H] m-diamine derivative or its salt containing (ii) phenols (iii) naphthols, and the molar ratio of component (a) to component (b) is 100 :
Air oxidation type 1 characterized by a ratio of 1 to 1:5
A chemical hair dye composition is provided. A third aspect of the present invention provides an air-oxidized one-part hair dye composition comprising a direct dye as component (d). The p-diamines or salts thereof as component (a) in the present invention are represented by the general formula () or salts thereof, and specifically, p-phenylenediamine, toluene-2,5- Diamine, 2-chloro-p-phenylenediamine, diaminodiphenylamine, N-phenyl-p-phenylenediamine, N,N-dimethyl-p-phenylenediamine, N,N-(bishydroxyethyl)-p -phenylenediamine, 2,6-dichloro-p-phenylenediamine, p-aminophenylsulfamic acid or salts thereof. Of the components (c) in the present invention, (i) m-diamines or salts thereof are represented by the general formula () or salts thereof, and preferred specific examples include m-phenylenediamine, Examples include 2,4-diaminotoluene, 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, and salts thereof. In addition, among the components (c), the phenols (ii) are expressed by the following general formula () [In the formula, R 12 , R 13 , R 15 , and R 16 are the same or different, and are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms, and a hydroxyalkyl group having 1 to 5 carbon atoms.
alkoxy group, carboxyalkyl group having 1 to 5 carbon atoms, primary to tertiary aminoalkyl group having 1 to 5 carbon atoms, -COOH, -COOR 17 (R 17 is an alkyl group having 1 to 4 carbon atoms),
本発明の染毛剤組成物は毛髪に対する染着性、
日光堅ろう性、耐洗濯性に優れ、使用も簡便なも
のであり、さらにはこれを用いて白髪を染色すれ
ば、自然な毛髪の黒を基調とした色調を短時間で
得ることが可能である。また、直接染料を加える
ことにより、より染色性の高い多彩な色調を得る
ことが可能となる。
〔実施例〕
実施例 １
下記の第１表に示す組成の染毛剤組成物を調製
した。
The hair dye composition of the present invention has a property of dyeing hair,
It has excellent sunlight fastness and washing resistance, and is easy to use.Furthermore, by using it to dye gray hair, it is possible to obtain the natural black-based tone of hair in a short time. . Furthermore, by adding a direct dye, it is possible to obtain a variety of color tones with higher dyeability. [Examples] Example 1 A hair dye composition having the composition shown in Table 1 below was prepared.
【表】
上記の各組成物をヤギ毛に塗布し、それぞれ10
分間室温で放置後、水洗して、さらにシヤンプー
とリンスを行なつたところ、比較品１の組成物で
はヤギ毛は全く染色されなかつた。
また、比較品２、本発明品１および本発明品２
により処理したヤギ毛についてそれぞれ反射吸収
スペクトルを測定した（第１図）。比較品２では、
λ＝450〜500nｍに反射吸収極大を示し、不自然
な赤みが認められる。一方、本発明品１では、ト
ルエン−２，５−ジアミンと２，４−ジアミノフ
エノールのカツプリング生成物に伴う、栗色がか
つた黒系の色調が得られる。また、本発明品では
トルエン−２，５−ジアミンとｍ−フエニレンジ
アミンとのカツプリング生成物による青み（λ＝
600〜650nｍ）がさらに上乗せされ、自然な黒緑
色となる。
実施例 ２
実施例１の本発明品２中のトルエン−２，５−
ジアミンをｐ−フエニレンジアミンに置き換えて
染毛剤組成物を調製した。これを本発明品３とす
る。この組成物をヤギ毛に塗布し、10分間室温放
置後、洗浄したところ、ヤギ毛は自然な黒緑色に
染まつた。
実施例 ３
実施例１の本発明品２中のｍ−フエニレンジア
ミンを２，４−ジアミノトルエンに置き換えて染
毛剤組成物を調製した。これを本発明品４とす
る。この組成物をヤギ毛に塗布し、10分間室温放
置後、洗浄したところ、ヤギ毛は自然な黒緑色に
染まつた。
実施例 ４
実施例１の本発明品２中のｍ−フエニレンジア
ミンを２，６−ジアミノピリジンに置き換えて染
毛剤組成物を調製した。これを本発明品５とす
る。この組成物をヤギ毛に塗布し、10分間室温放
置後、洗浄したところ、ヤギ毛は自然な黒緑色に
染まつた。
実施例 ５
実施例１の本発明品２中のｍ−フエニレンジア
ミン（0.25重量％）をレゾルシン（0.5重量％）
に置き換えて染毛剤組成物を調製した。これを本
発明品６とする。この組成物をヤギ毛に塗布し、
10分間室温放置後、洗浄したところ、ヤギ毛は自
然な黒色に染まつた。
実施例 ６
実施例１の本発明品２中のｍ−フエニレンジア
ミン（0.25重量％）をα−ナフトール（0.3重量
％）とレゾルシン（0.3重量％）の混合物に換え
て染毛剤組成物を調製した。これを本発明品７と
する。この組成物をヤギ毛に塗布し、10分間室温
放置後、洗浄したところ、ヤギ毛は自然な黒色に
染まつた。
実施例 ７
実施例１の本発明品２中に、さらにステイール
ブルー〔Steel Blue；ウイリアムズ（Williams）
社製〕を加えて染毛剤組成物を調製した。これを
本発明品８とする。この組成物をヤギ毛に塗布
し、10分間室温放置後、洗浄したところ、ヤギ毛
は青味がかかつた黒色に染まつた。
実施例 ８
下記組成の染毛剤組成物を調製した。
（重量％）
オレイン酸 5.00
オレイン酸ジエタノールアミド 4.00
オレイルアルコール 1.00
ポリオキシエチレンオクチルドデシルエーテル
5.00
エタノール 7.50
プロピレングリコール 5.00
50％チオグリコール酸アンモニウム 0.25
トルエン−２，５−ジアミン（フリーベース）
1.25
レゾルシン 0.20
マダーレツド〔Madder Red；ウイリアムズ
（Williams）社製〕 0.20
ｍ−フエニレンジアミン 0.03
２，４−ジアミノフエノール塩酸塩 0.90
28％アンモニア水 PH９調整量
精製水 バランス量
これを本発明品９とする。この組成物をヤギ毛
に塗布し、10分間室温放置後、洗浄したことろ、
ヤギ毛は自然な栗色に染まつた。
実施例 ９
下記組成の染毛剤組成物を調製した。
（重量％）
オレイン酸 5.00
オレイン酸ジエタノールアミド 4.00
オレイルアルコール 1.00
ポリオキシエチレンオクチルドデシルエーテル
5.00
エタノール 7.50
プロピレングリコール 5.00
50％チオグリコール酸アンモニウム 0.25
トルエン−２，５−ジアミン（フリーベース）
1.00
ｍ−アミノフエノール 0.40
レゾルシン 0.20
ｍ−フエニレンジアミン 0.03
２，４−ジアミノフエノール塩酸塩 0.90
ｐ−ニトロ−ｏ−フエニレンジアミン 0.10
28％アンモニア水 PH９調整量
精製水 バランス量
これを本発明品１０とする。この組成物をヤギ
毛に塗布し、10分間室温放置後、洗浄したとこ
ろ、ヤギ毛はわずかに栗色がかつた黒色に染まつ
た。
実施例 10
下記組成の染毛剤組成物を調製した。
（重量％）
ラウリルエーテル硫酸ナトリウム 2.50
ヒドロキシエチルセルロース（高粘度品） 0.50
アスコルビン酸 0.20
トルエン−２，５−ジアミン（フリーベース）
1.00
レゾルシン 0.20
ｍ−フエニレンジアミン 0.03
２，４−ジアミノフエノール塩酸塩 0.90
ステイールブルー〔Steel Blue；ウイリアムズ
（Williams）社製〕 0.05
リン酸 PH5.0調整量
精製水 バランス量
これを本発明品１１とする。この組成物をヤギ
毛に塗布し、10分間室温放置後洗浄した。この操
作を１日１回ずつ１週間繰り返したところ、ヤギ
毛は自然な黒色に染まつた。[Table] Each of the above compositions was applied to goat hair, and 10% of each composition was applied to goat hair.
After being left at room temperature for a minute, it was washed with water, and then shampooed and rinsed. As a result, the goat hair was not dyed at all with the composition of Comparative Product 1. In addition, comparative product 2, inventive product 1, and inventive product 2
The reflection and absorption spectra of each of the goat hairs treated with the above method were measured (Fig. 1). In comparison product 2,
The reflection and absorption maximum is observed at λ=450 to 500 nm, and an unnatural reddish tinge is observed. On the other hand, in the product 1 of the present invention, a maroon-black color tone is obtained due to the coupling product of toluene-2,5-diamine and 2,4-diaminophenol. In addition, the product of the present invention has a blue tint (λ=
600 to 650 nm) is further added to give a natural black-green color. Example 2 Toluene-2,5- in the invention product 2 of Example 1
A hair dye composition was prepared by replacing the diamine with p-phenylenediamine. This is referred to as Invention Product 3. When this composition was applied to goat hair, left at room temperature for 10 minutes, and then washed, the goat hair was dyed a natural black-green color. Example 3 A hair dye composition was prepared by replacing m-phenylenediamine in product 2 of the present invention in Example 1 with 2,4-diaminotoluene. This will be referred to as Invention Product 4. When this composition was applied to goat hair, left at room temperature for 10 minutes, and then washed, the goat hair was dyed a natural black-green color. Example 4 A hair dye composition was prepared by replacing m-phenylenediamine in product 2 of the present invention in Example 1 with 2,6-diaminopyridine. This is referred to as Invention Product 5. When this composition was applied to goat hair, left at room temperature for 10 minutes, and then washed, the goat hair was dyed a natural black-green color. Example 5 The m-phenylenediamine (0.25% by weight) in the invention product 2 of Example 1 was mixed with resorcinol (0.5% by weight).
A hair dye composition was prepared by substituting . This will be referred to as Invention Product 6. Apply this composition to goat hair,
After leaving it at room temperature for 10 minutes and washing it, the goat hair was dyed a natural black color. Example 6 A hair dye composition was prepared by replacing m-phenylenediamine (0.25% by weight) in product 2 of the present invention in Example 1 with a mixture of α-naphthol (0.3% by weight) and resorcinol (0.3% by weight). Prepared. This is referred to as Invention Product 7. When this composition was applied to goat hair, left at room temperature for 10 minutes, and then washed, the goat hair was dyed a natural black color. Example 7 Inventive product 2 of Example 1 further contained Steel Blue (Williams).
A hair dye composition was prepared. This is referred to as Invention Product 8. When this composition was applied to goat hair, left at room temperature for 10 minutes, and then washed, the goat hair was dyed black with a bluish tint. Example 8 A hair dye composition having the following composition was prepared. (Weight%) Oleic acid 5.00 Oleic acid diethanolamide 4.00 Oleyl alcohol 1.00 Polyoxyethylene octyl dodecyl ether
5.00 Ethanol 7.50 Propylene Glycol 5.00 50% Ammonium Thioglycolate 0.25 Toluene-2,5-diamine (free base)
1.25 Resorcinol 0.20 Madder Red (manufactured by Williams) 0.20 m-phenylenediamine 0.03 2,4-diaminophenol hydrochloride 0.90 28% ammonia water PH9 adjusted amount Purified water Balance amount This is the product of the present invention 9 . This composition was applied to goat hair, left at room temperature for 10 minutes, and then washed.
The goat hair was dyed a natural chestnut color. Example 9 A hair dye composition having the following composition was prepared. (Weight%) Oleic acid 5.00 Oleic acid diethanolamide 4.00 Oleyl alcohol 1.00 Polyoxyethylene octyl dodecyl ether
5.00 Ethanol 7.50 Propylene Glycol 5.00 50% Ammonium Thioglycolate 0.25 Toluene-2,5-diamine (free base)
1.00 m-aminophenol 0.40 Resorcin 0.20 m-phenylenediamine 0.03 2,4-diaminophenol hydrochloride 0.90 p-nitro-o-phenylenediamine 0.10 28% ammonia water PH9 adjusted amount Purified water Balance amount This is the product of the present invention 10 shall be. When this composition was applied to goat hair, left at room temperature for 10 minutes, and then washed, the goat hair was stained black with a slight maroon color. Example 10 A hair dye composition having the following composition was prepared. (Weight%) Sodium lauryl ether sulfate 2.50 Hydroxyethyl cellulose (high viscosity product) 0.50 Ascorbic acid 0.20 Toluene-2,5-diamine (free base)
1.00 Resorcinol 0.20 m-phenylenediamine 0.03 2,4-diaminophenol hydrochloride 0.90 Steel Blue (manufactured by Williams) 0.05 Phosphoric acid PH5.0 adjusted amount Purified water Balance amount This is the product of the present invention 11 shall be. This composition was applied to goat hair, left at room temperature for 10 minutes, and then washed. When this operation was repeated once a day for a week, the goat hair was dyed a natural black color.
第１図は実施例１にて染毛剤で処理したヤギ毛
の反射吸収スペクトルを示す図面である。
FIG. 1 is a drawing showing the reflection and absorption spectrum of goat hair treated with a hair dye in Example 1.
Claims (1)
キル基、炭素数１〜８のヒドロキシアルキル
基、 【式】【式】または− SO3Hを示し、R2′は水素原子、炭素数１〜８
のアルキル基または炭素数１〜８のヒドロキシ
アルキル基を示し、R3、R4は同一かまたは異
なつて、水素原子、炭素数１〜４のアルキル
基、炭素数２〜４のアルコキシ基、ハロゲン原
子、−COOH、−COOR5（R5は炭素数１〜４の
アルキル基）、−CONH2または−SO3Hを示す。
但し、R3とR4がともに水素原子の場合におい
て、R1′およびR2′がともに水素原子、炭素数１
〜８のアルキル基および炭素数１〜８のヒドロ
キシアルキル基から選ばれる基となることはな
い〕 で表わされるｐ−ジアミン誘導体若しくはその
塩の中より選ばれる１種又は２種以上のｐ−ジ
アミン類 (b) ２，４−ジアミノフエノール若しくはその塩
を含有し、かつ（a′）成分と(b)成分のモル比が
100：１〜１：５であることを特徴とする空気
酸化型１剤式染毛剤組成物。 ２ 次の成分(a)、(b)及び(c) (a) 一般式（） 〔式中、R1は水素原子、炭素数１〜８のアル
キル基、炭素数１〜８のヒドロキシアルキル
基、 【式】【式】または− SO3Hを示し、R2は水素原子、炭素数１〜８の
アルキル基または炭素数１〜８のヒドロキシア
ルキル基を示し、R3、R4は同一かまたは異な
つて、水素原子、炭素数１〜４のアルキル基、
炭素数２〜４のアルコキシ基、ハロゲン原子、
−COOH、−COOR5（R5は炭素数１〜４のアル
キル基）、−CONH2または−SO3Hを示す〕 で表わされるｐ−ジアミン誘導体若しくはその
塩の中より選ばれる１種または２種以上のｐ−
ジアミン類 (b) ２，４−ジアミノフエノール若しくはその塩 (c) 次の(i)、(ii)及び(iii)の化合物の中より選ばれ
る
１種又は２種以上 (i) 一般式（） 〔式中、ＸはＮまたはCHを示し、R6、R7、
R8、R9は同一かまたは異なつて、水素原子、
炭素数１〜８のアルキル基または炭素数１〜
８のヒドロキシアルキル基を示し、R10は炭
素数１〜４のアルキル基、炭素数１〜４のア
ルコキシ基、−Ｏ（CH2）oOH（ここでｎは１〜
４の数）、ハロゲン原子、−COOH、−
COOR11（R11は炭素数１〜４のアルキル基）、
−CONH2または−SO3Hを示す〕 で表わされるｍ−ジアミン誘導体若しくはそ
の塩 (ii) フエノール類 (iii) ナフトール類 を含有し、かつ(a)成分と(b)成分のモル比が100：
１〜１：５であることを特徴とする空気酸化型１
剤式染毛剤組成物。 ３ 更に(d)成分として直接染料を添加してなる請
求項１または２記載の空気酸化型１剤式染毛剤組
成物。[Claims] First-order components (a') and (b) (a') General formula (') [In the formula, R 1 ' represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms, [Formula] [Formula] or -SO 3 H, and R 2 ' represents a hydrogen atom , carbon number 1-8
represents an alkyl group or a hydroxyalkyl group having 1 to 8 carbon atoms, and R 3 and R 4 are the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 2 to 4 carbon atoms, a halogen It represents an atom, -COOH, -COOR5 ( R5 is an alkyl group having 1 to 4 carbon atoms), -CONH2 or -SO3H .
However, when R 3 and R 4 are both hydrogen atoms, R 1 ′ and R 2 ′ are both hydrogen atoms and have 1 carbon number.
-8 alkyl groups and C1-8 hydroxyalkyl groups] One or more p-diamines selected from p-diamine derivatives or salts thereof represented by Class (b) Contains 2,4-diaminophenol or its salt, and the molar ratio of component (a') to component (b) is
An air oxidation type one-component hair dye composition characterized in that the ratio is 100:1 to 1:5. 2 The following components (a), (b) and (c) (a) General formula () [In the formula, R 1 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms, [Formula] [Formula], or -SO 3 H, and R 2 represents a hydrogen atom, a carbon It represents an alkyl group having 1 to 8 carbon atoms or a hydroxyalkyl group having 1 to 8 carbon atoms, and R 3 and R 4 are the same or different, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
Alkoxy group having 2 to 4 carbon atoms, halogen atom,
-COOH, -COOR 5 (R 5 is an alkyl group having 1 to 4 carbon atoms), -CONH 2 or -SO 3 H] One or two selected from p-diamine derivatives or salts thereof represented by More than species p-
Diamines (b) 2,4-diaminophenol or its salt (c) One or more compounds selected from the following compounds (i), (ii) and (iii) (i) General formula () [In the formula, X represents N or CH, R 6 , R 7 ,
R 8 and R 9 are the same or different, hydrogen atoms,
Alkyl group having 1 to 8 carbon atoms or 1 to 8 carbon atoms
8 hydroxyalkyl group, R 10 is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, -O(CH 2 ) o OH (where n is 1 to 4
4), halogen atom, -COOH, -
COOR 11 (R 11 is an alkyl group having 1 to 4 carbon atoms),
-CONH 2 or -SO 3 H] m-diamine derivative or its salt containing (ii) phenols (iii) naphthols, and the molar ratio of component (a) to component (b) is 100 :
Air oxidation type 1 characterized by a ratio of 1 to 1:5
Formula hair dye composition. 3. The air-oxidized one-component hair dye composition according to claim 1 or 2, further comprising a direct dye as component (d).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3806490A JPH0386813A (en) | 1989-02-20 | 1990-02-19 | Air oxidation type hair dyeing agent composition of one-agent type |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4007889 | 1989-02-20 | ||
| JP1-40078 | 1989-02-20 | ||
| JP1-153501 | 1989-06-15 | ||
| JP15350189 | 1989-06-15 | ||
| JP3806490A JPH0386813A (en) | 1989-02-20 | 1990-02-19 | Air oxidation type hair dyeing agent composition of one-agent type |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0386813A JPH0386813A (en) | 1991-04-11 |
| JPH0534328B2 true JPH0534328B2 (en) | 1993-05-21 |
Family
ID=27289686
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3806490A Granted JPH0386813A (en) | 1989-02-20 | 1990-02-19 | Air oxidation type hair dyeing agent composition of one-agent type |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0386813A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9237993B2 (en) | 2014-01-24 | 2016-01-19 | Combe Incorporated | Gradual haircolor compositions and methods of using the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6028807A (en) * | 1983-07-27 | 1985-02-14 | Mitsubishi Rayon Co Ltd | Manufacture of module by using porous hollow yarn membrane |
| JPS62126114A (en) * | 1985-11-26 | 1987-06-08 | Kindai Kagaku Kk | Hair dye |
| JPH0253715A (en) * | 1988-08-18 | 1990-02-22 | Hoyu Co Ltd | Autoxidation one-pack hair-dye |
-
1990
- 1990-02-19 JP JP3806490A patent/JPH0386813A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6028807A (en) * | 1983-07-27 | 1985-02-14 | Mitsubishi Rayon Co Ltd | Manufacture of module by using porous hollow yarn membrane |
| JPS62126114A (en) * | 1985-11-26 | 1987-06-08 | Kindai Kagaku Kk | Hair dye |
| JPH0253715A (en) * | 1988-08-18 | 1990-02-22 | Hoyu Co Ltd | Autoxidation one-pack hair-dye |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0386813A (en) | 1991-04-11 |
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