JPH04359913A - New copolymer and cosmetic containing same - Google Patents
New copolymer and cosmetic containing sameInfo
- Publication number
- JPH04359913A JPH04359913A JP13478491A JP13478491A JPH04359913A JP H04359913 A JPH04359913 A JP H04359913A JP 13478491 A JP13478491 A JP 13478491A JP 13478491 A JP13478491 A JP 13478491A JP H04359913 A JPH04359913 A JP H04359913A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- group
- silicone
- formula
- copolymer
- 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.)
- Pending
Links
- 239000002537 cosmetic Substances 0.000 title claims abstract description 26
- 229920001577 copolymer Polymers 0.000 title abstract description 22
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 29
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 9
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 7
- 125000000129 anionic group Chemical group 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 229920006243 acrylic copolymer Polymers 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 14
- -1 acrylic ester Chemical class 0.000 abstract description 13
- 150000003839 salts Chemical class 0.000 abstract description 13
- 125000003277 amino group Chemical group 0.000 abstract description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 abstract description 4
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 abstract description 3
- 229940050176 methyl chloride Drugs 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract 3
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 abstract 2
- 239000006260 foam Substances 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000002453 shampoo Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 5
- 239000003205 fragrance Substances 0.000 description 5
- 239000003915 liquefied petroleum gas Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000008719 thickening Effects 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 239000008213 purified water Substances 0.000 description 4
- 238000001226 reprecipitation Methods 0.000 description 4
- 229920005573 silicon-containing polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- BHDFTVNXJDZMQK-UHFFFAOYSA-N chloromethane;2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound ClC.CN(C)CCOC(=O)C(C)=C BHDFTVNXJDZMQK-UHFFFAOYSA-N 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000012085 test solution Substances 0.000 description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Chemical group 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- PUSKHXMZPOMNTQ-UHFFFAOYSA-N ethyl 2,1,3-benzoselenadiazole-5-carboxylate Chemical compound CCOC(=O)C1=CC=C2N=[Se]=NC2=C1 PUSKHXMZPOMNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000003676 hair preparation Substances 0.000 description 2
- 239000008266 hair spray Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002884 skin cream Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000010913 used oil Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- NMGPHUOPSWFUEB-UHFFFAOYSA-N 2-(butylamino)ethyl 2-methylprop-2-enoate Chemical compound CCCCNCCOC(=O)C(C)=C NMGPHUOPSWFUEB-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- BGRXBNZMPMGLQI-UHFFFAOYSA-N 2-octyldodecyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OCC(CCCCCCCC)CCCCCCCCCC BGRXBNZMPMGLQI-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 241000195940 Bryophyta Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 208000001840 Dandruff Diseases 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- AOMUHOFOVNGZAN-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CCO)CCO AOMUHOFOVNGZAN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- IIYDLZIQFFBPND-UHFFFAOYSA-N bromomethane 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical group CBr.C(C(=C)C)(=O)OCCN(C)C IIYDLZIQFFBPND-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- JLGZTGCSKYLUJS-UHFFFAOYSA-N chloromethane;2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical group ClC.CCN(CC)CCOC(=O)C(C)=C JLGZTGCSKYLUJS-UHFFFAOYSA-N 0.000 description 1
- NZEMTRYQTLSFKK-UHFFFAOYSA-N chloromethane;2-(diethylamino)ethyl prop-2-enoate Chemical group ClC.CCN(CC)CCOC(=O)C=C NZEMTRYQTLSFKK-UHFFFAOYSA-N 0.000 description 1
- WQHCGPGATAYRLN-UHFFFAOYSA-N chloromethane;2-(dimethylamino)ethyl prop-2-enoate Chemical group ClC.CN(C)CCOC(=O)C=C WQHCGPGATAYRLN-UHFFFAOYSA-N 0.000 description 1
- BOYBOCSCIOGQOZ-UHFFFAOYSA-N chloromethane;2-methylprop-2-enoic acid Chemical compound ClC.CC(=C)C(O)=O BOYBOCSCIOGQOZ-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000004193 disodium 5'-ribonucleotide Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- AZDCYKCDXXPQIK-UHFFFAOYSA-N ethenoxymethylbenzene Chemical compound C=COCC1=CC=CC=C1 AZDCYKCDXXPQIK-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- PZWZMVCYWFZOHE-UHFFFAOYSA-N methyl 2-[(1-methoxy-1-oxobutan-2-yl)diazenyl]butanoate Chemical compound COC(=O)C(CC)N=NC(CC)C(=O)OC PZWZMVCYWFZOHE-UHFFFAOYSA-N 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-N methyl sulfate Chemical compound COS(O)(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-N 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 235000011929 mousse Nutrition 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- 229940073665 octyldodecyl myristate Drugs 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229920006268 silicone film Polymers 0.000 description 1
- 239000000264 sodium ferrocyanide Substances 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001567 vinyl ester resin Chemical group 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、優れた潤滑性、増粘性
、泡質改良性等を有する新規なシリコーン／（メタ）ア
クリル系共重合体及びこれを含有する化粧料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel silicone/(meth)acrylic copolymer having excellent lubricity, thickening properties, foam quality improvement properties, etc., and cosmetics containing the same.
【０００２】0002
【従来の技術及び発明が解決しようとする課題】一般に
化粧料には、良好な特性を付与する目的で、種々の重合
体が配合されている。例えばこれらの重合体は化粧料塗
布時の感触を向上させ、化粧料に適度の粘性を付与する
増粘剤、洗浄剤や泡状化粧料の泡質改良剤等として使用
されている。かかる増粘剤、泡質改良剤としては、ポリ
ビニルアルコール、セルロース誘導体、アクリル酸誘導
体、カチオン化セルロース誘導体等が用いられているが
、これらはいずれも単独では感触の面で不充分であり、
塗布・乾燥後のごわつきを生じる等の問題があった。BACKGROUND OF THE INVENTION Cosmetics generally contain various polymers for the purpose of imparting good properties. For example, these polymers are used as thickeners that improve the feel of cosmetics when applied, give appropriate viscosity to cosmetics, detergents, foam quality improvers for foamy cosmetics, and the like. Polyvinyl alcohol, cellulose derivatives, acrylic acid derivatives, cationized cellulose derivatives, etc. have been used as such thickeners and foam quality improvers, but all of these alone are insufficient in terms of feel.
There were problems such as stiffness after application and drying.
【０００３】また、特開平２−２５４１１号公報には、
シリコンとアクリレートを共重合させた被膜形成剤を用
いた化粧料が開示されている。この重合体は、耐水性は
有するが、溶媒としてイソパラフィン等の炭化水素、揮
発性シリコーン等を必要とするため、使用できる剤型に
制限があり、感触的にも充分とはいえなかった。[0003] Also, in Japanese Patent Application Laid-Open No. 2-25411,
Cosmetics using a film-forming agent made by copolymerizing silicone and acrylate have been disclosed. Although this polymer has water resistance, it requires a hydrocarbon such as isoparaffin, volatile silicone, etc. as a solvent, so there are restrictions on the dosage forms that can be used, and it was not satisfactory in terms of feel.
【０００４】従って、優れた潤滑性、増粘性、泡質改良
剤等を有し、水系基剤に分散可能な新規なポリマー、及
びこれを配合し、塗布した時の感触が良好で、かつ泡状
化粧料や洗浄剤に用いた時、クリーミィな泡質を有する
化粧料が望まれていた。[0004] Therefore, we have developed a new polymer that has excellent lubricity, thickening properties, foam quality improver, etc., and can be dispersed in an aqueous base, and a new polymer that has a good feel when applied and that has good foam properties. There has been a desire for cosmetics that have a creamy foam quality when used in cosmetics and cleansing agents.
【０００５】[0005]
【課題を解決するための手段】かかる実情において、本
発明者らは鋭意研究を行った結果、特定の４級アミノ基
を有する（メタ）アクリル酸エステル系モノマー又は（
メタ）アクリルアミド系モノマーと、シリコーンマクロ
マーを共重合させて得られるシリコーン／（メタ）アク
リル系共重合体が、優れた潤滑性、増粘性、泡質改良性
等を有し、水系溶媒に容易に分散し、さらに、これを配
合した化粧料は、塗布時の感触が非常に良好で、しかも
優れた泡質を有することを見出し、本発明を完成した。[Means for Solving the Problems] Under these circumstances, the present inventors conducted intensive research and found that (meth)acrylic acid ester monomers having a specific quaternary amino group or (
The silicone/(meth)acrylic copolymer obtained by copolymerizing a meth)acrylamide monomer and a silicone macromer has excellent lubricity, thickening properties, foam quality improvement properties, etc., and is easily soluble in aqueous solvents. The present invention was completed based on the discovery that a cosmetic containing the dispersed and blended cosmetic has a very good feel when applied and has excellent foam quality.
【０００６】すなわち、本発明は、（ａ）及び（ｂ）（
ａ）式（１）That is, the present invention provides (a) and (b) (
a) Formula (1)
【０００７】[0007]
【化３】[C3]
【０００８】（式中、Ｒ１は水素原子又はメチル基を示
し、Ｒ２は炭素数２〜３のアルキレン基を示し、Ｒ３、
Ｒ４及びＲ５は同一又は異なってメチル基又はエチル基
を示し、ａは０又は１を示し、Ｘはアニオン性基を示す
）で表される４級アミノ基を有する（メタ）アクリル酸
エステル系モノマー又は（メタ）アクリルアミド系モノ
マー（ｂ）式（２）(In the formula, R1 represents a hydrogen atom or a methyl group, R2 represents an alkylene group having 2 to 3 carbon atoms, R3,
R4 and R5 are the same or different and represent a methyl group or ethyl group, a represents 0 or 1, and X represents an anionic group) A (meth)acrylic acid ester monomer having a quaternary amino group or (meth)acrylamide monomer (b) formula (2)
【０００９】[0009]
【化４】[C4]
【００１０】（式中、Ｙはラジカル重合性基を示し、Ｒ
６、Ｒ７、Ｒ８、Ｒ９及びＲ１０は、同一又は異なって
メチル基、アルコキシル基、置換されていてもよいフェ
ニル基又は置換されていてもよいフェノキシ基を示し、
ｍは１〜１０の整数を示し、ｎは５〜１５０ の整数を
示す）で表されるシリコーンマクロマーをラジカル重合
開始剤の存在下に重合させて得られるシリコーン／（メ
タ）アクリル系共重合体及びこれを含有する化粧料を提
供するものである。(In the formula, Y represents a radically polymerizable group, and R
6, R7, R8, R9 and R10 are the same or different and represent a methyl group, an alkoxyl group, an optionally substituted phenyl group or an optionally substituted phenoxy group,
A silicone/(meth)acrylic copolymer obtained by polymerizing a silicone macromer (m is an integer of 1 to 10, n is an integer of 5 to 150) in the presence of a radical polymerization initiator. and cosmetics containing the same.
【００１１】本発明共重合体の製造に用いられる（ａ）
成分の４級アミノ基を有する（メタ）アクリル酸エステ
ル系モノマー又は（メタ）アクリルアミド系モノマーは
、前記式（１）で表され、式中、Ｘで表されるアニオン
性基としては、無機又は有機のいずれでもよく、例えば
塩素原子、臭素原子等のハロゲン原子、硫酸、メチル硫
酸等の酸残基等が挙げられる。（ａ）成分としては、例
えばＮ，Ｎ−ジメチルアミノエチルメタクリレートメチ
ルクロリド四級塩、Ｎ，Ｎ−ジエチルアミノエチルメタ
クリレートメチルクロリド四級塩、Ｎ，Ｎ−ジメチルア
ミノプロピルメタクリレートメチルクロリド四級塩、Ｎ
，Ｎ−ジエチルアミノプロピルメタクリレートメチルク
ロリド四級塩、Ｎ，Ｎ−ジメチルアミノエチルアクリレ
ートメチルクロリド四級塩、Ｎ，Ｎ−ジエチルアミノエ
チルアクリレートメチルクロリド四級塩、Ｎ，Ｎ−ジメ
チルアミノエチルメタクリレートメチルブロミド四級塩
等が挙げられる。これら（ａ）成分は、単独又は２種以
上を組み合わせて用いることができ、モノマー全体の１
０〜９５重量％（以下、単に「％」で示す）、特に４０
〜８０％用いるのが好ましい。(a) used in the production of the copolymer of the present invention
The component (meth)acrylic acid ester monomer or (meth)acrylamide monomer having a quaternary amino group is represented by the above formula (1), where the anionic group represented by X is inorganic or Any organic material may be used, and examples thereof include halogen atoms such as chlorine atoms and bromine atoms, and acid residues such as sulfuric acid and methyl sulfuric acid. Component (a) includes, for example, N,N-dimethylaminoethyl methacrylate methyl chloride quaternary salt, N,N-diethylaminoethyl methacrylate methyl chloride quaternary salt, N,N-dimethylaminopropyl methacrylate methyl chloride quaternary salt,
, N-diethylaminopropyl methacrylate methyl chloride quaternary salt, N,N-dimethylaminoethyl acrylate methyl chloride quaternary salt, N,N-diethylaminoethyl acrylate methyl chloride quaternary salt, N,N-dimethylaminoethyl methacrylate methyl bromide quaternary salt Examples include grade salt. These (a) components can be used alone or in combination of two or more, and each of these components
0 to 95% by weight (hereinafter simply indicated as "%"), especially 40%
It is preferable to use ~80%.
【００１２】（ｂ）成分のシリコーンマクロマーは前記
式（２）で表され、式中、Ｙで示されるラジカル重合性
基としては、例えばビニル基、（メタ）アクリロイル基
、ビニルベンジル基、スチリル基、（メタ）アクリルア
ミド基、ビニルエーテル基、ビニルエステル基などが挙
げられる。これらシリコーンマクロマーの具体例として
は、ポリジメチルシロキシプロピル（メタ）アクリル酸
エステル、ポリジメチルシロキシプロピルビニルベンジ
ルエーテル、ポリメチルフェニルシロキシペンテン、ポ
リジメチルシロキシプロピル（メタ）アクリルアミド、
ポリジメチルシロキシプロピル酸ビニルベンジレート、
ポリメチルフェニルシロキシエトキシエチレン等が挙げ
られ、これらのうち特にポリジメチルシロキシプロピル
（メタ）アクリル酸エステル、ポリジメチルシロキシプ
ロピル（メタ）アクリルアミド等が好ましい。これら（
ｂ）成分は、単独又は２種以上を組み合わせて用いるこ
とができ、モノマー全体の５〜９０％、特に２０〜６０
％用いるのが好ましい。The silicone macromer of component (b) is represented by the above formula (2), and in the formula, the radically polymerizable group represented by Y includes, for example, a vinyl group, a (meth)acryloyl group, a vinylbenzyl group, and a styryl group. , (meth)acrylamide group, vinyl ether group, vinyl ester group, etc. Specific examples of these silicone macromers include polydimethylsiloxypropyl (meth)acrylate, polydimethylsiloxypropyl vinylbenzyl ether, polymethylphenylsiloxypentene, polydimethylsiloxypropyl (meth)acrylamide,
Polydimethylsiloxypropylic acid vinyl benzylate,
Examples include polymethylphenylsiloxyethoxyethylene, and among these, polydimethylsiloxypropyl (meth)acrylate, polydimethylsiloxypropyl (meth)acrylamide, and the like are particularly preferred. these(
Component b) can be used alone or in combination of two or more, and accounts for 5 to 90% of the total monomers, especially 20 to 60% of the total monomers.
It is preferable to use %.
【００１３】本発明のシリコーン／（メタ）アクリル系
共重合体は、上記（ａ）成分及び（ｂ）成分を組み合わ
せ、ラジカル重合開始剤の存在下、バルク重合法、溶液
重合法、懸濁重合法、乳化重合法等の公知の重合法によ
り重合させることにより製造される。この時、上記２種
のモノマー以外のモノマーを本発明の効果を損なわない
範囲で共重合させることもできる。これらのうち、特に
溶液重合法により製造するのが有利である。溶液重合法
で用いる溶媒としては極性有機溶剤が好ましく、水混和
性有機溶剤を水と混合して用いることもできる。かかる
有機溶剤としては、例えばメタノール、エタノール、プ
ロパノール等の炭素数１〜３の脂肪族アルコール；アセ
トン、メチルエチルケトン等のケトン類及び酢酸エチル
等のエステル類などが挙げられ、これらのうち、特にメ
タノール、エタノール、アセトン又はこれらと水との混
合液が好ましい。これら有機溶剤は、単独又は２種以上
を組み合わせて用いることができる。The silicone/(meth)acrylic copolymer of the present invention can be prepared by combining the above components (a) and (b), and performing bulk polymerization, solution polymerization, or suspension polymerization in the presence of a radical polymerization initiator. It is produced by polymerization using a known polymerization method such as a polymerization method or an emulsion polymerization method. At this time, monomers other than the above two types of monomers may be copolymerized within a range that does not impair the effects of the present invention. Among these, it is particularly advantageous to produce by solution polymerization. The solvent used in the solution polymerization method is preferably a polar organic solvent, and a water-miscible organic solvent can also be used in combination with water. Examples of such organic solvents include aliphatic alcohols having 1 to 3 carbon atoms such as methanol, ethanol, and propanol; ketones such as acetone and methyl ethyl ketone; and esters such as ethyl acetate. Among these, methanol, Ethanol, acetone, or a mixture of these and water is preferred. These organic solvents can be used alone or in combination of two or more.
【００１４】ラジカル重合開始剤としては、例えば２，
２’−アゾビスイソブチロニトリル、２，２’−アゾビ
ス（２，４−ジメチルバレロニトリル）、２，２’−ア
ゾビス（４−メトキシ−２，４−ジメチルバレロニトリ
ル）、ジメチル−２，２’−アゾビスブチレート、２，
２’−アゾビス（２−メチルブチロニトリル）、１，１
’−アゾビス（１−シクロヘキサンカルボニトリル）等
のアゾ化合物が好適である。また、ｔ−ブチルペルオク
トアート、ジクミルペルオキシド、ジ−ｔ−ブチルペル
オキシド、ジベンゾイルオキシド等の有機過酸化物を使
用することもできる。これら重合開始剤は、モノマー混
合物に対して０．００１ 〜２．０ モル％、特に０．
０１〜１．０ モル％用いるのが好ましい。Examples of radical polymerization initiators include 2,
2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2, 2'-azobisbutyrate, 2,
2'-azobis(2-methylbutyronitrile), 1,1
Azo compounds such as '-azobis(1-cyclohexanecarbonitrile) are preferred. Moreover, organic peroxides such as t-butyl peroctoate, dicumyl peroxide, di-t-butyl peroxide, and dibenzoyl oxide can also be used. These polymerization initiators are contained in an amount of 0.001 to 2.0 mol%, especially 0.001 to 2.0 mol%, based on the monomer mixture.
It is preferable to use 01 to 1.0 mol%.
【００１５】重合は、通常３０〜１００ ℃、好ましく
は５０〜８０℃で１〜１０時間行われ、使用するラジカ
ル重合開始剤、モノマー溶剤の種類などにより適宜選定
される。また、重合は、窒素等の不活性ガス雰囲気下で
行うのが好ましい。[0015] Polymerization is usually carried out at 30 to 100°C, preferably 50 to 80°C, for 1 to 10 hours, and is appropriately selected depending on the type of radical polymerization initiator and monomer solvent used. Further, the polymerization is preferably carried out under an inert gas atmosphere such as nitrogen.
【００１６】重合後、反応液から再沈殿、溶剤留去など
、公知の方法により共重合体を単離することができる。
また、得られた共重合体は、再沈殿を繰り返したり、膜
分離、クロマトグラフ法、抽出法などにより、未反応の
モノマー等を除去して精製することができる。After the polymerization, the copolymer can be isolated from the reaction solution by known methods such as reprecipitation and solvent distillation. Further, the obtained copolymer can be purified by repeating reprecipitation, removing unreacted monomers, etc. by membrane separation, chromatography, extraction, etc.
【００１７】このようにして得られる本発明のシリコー
ン／（メタ）アクリル系共重合体は、表面摩擦が非常に
小さいため、各種の化粧料に配合して、優れた感触、潤
滑性等を付与することができる。また、優れた増粘性を
有するため、各種クリーム状、ゲル状等の形態の化粧料
に増粘剤として、また泡状化粧料、洗浄剤の泡質改良剤
として配合することもできる。[0017] The silicone/(meth)acrylic copolymer of the present invention thus obtained has very low surface friction, so it can be incorporated into various cosmetics to impart excellent feel, lubricity, etc. can do. Furthermore, since it has excellent thickening properties, it can be incorporated into various cream-like, gel-like, and other forms of cosmetics as a thickener, and as a foam quality improver for foamy cosmetics and detergents.
【００１８】本発明の化粧料は、前記シリコーン／（メ
タ）アクリル系共重合体を配合し、通常の方法に従って
製造することができ、例えばヘアースプレー、セットフ
ォーム、セットローション、ジェル、シャンプー、皮膚
洗浄剤、リンス、マニキュア、マスカラ、スキンクリー
ム等として、水溶液、水性アルコール溶液、乳濁液、ク
リーム、ゲル等の剤形で適用することができる。The cosmetic of the present invention can be produced by blending the silicone/(meth)acrylic copolymer according to a conventional method, such as hair spray, setting foam, setting lotion, gel, shampoo, skin care, etc. It can be applied as a cleanser, rinse, nail polish, mascara, skin cream, etc. in the form of an aqueous solution, hydroalcoholic solution, emulsion, cream, gel, etc.
【００１９】本発明に用いられるシリコーン／（メタ）
アクリル系共重合体は、それ自体被膜形成能を有するが
、さらに通常の被膜形成性ポリマーと併用することによ
って当該ポリマーの被膜形成能を損うことなく、形成さ
れた被膜に良好な平滑性を付与する性能を有する。ここ
で、通常の被膜形成性ポリマーとしては、ポリビニルピ
ロリドン系ポリマー、両性アクリル系ポリマー、塩基性
アクリル系ポリマー等が挙げられる。ここでポリビニル
ピロリドン系ポリマーとしては、ポリビニルピロリドン
〔市販品として、ルビスコール Ｋ１２、１７、３０
、６０、８０、９０（以上、バスフ社）や、ＰＶＰ
Ｋ１５、３０、６０、９０（以上、ガフ社）等がある〕
、ポリビニルピロリドン／酢酸ビニル共重合体〔市販品
として、ルビスコール ＶＡ２８、３７、５５、６４
、７３（以上、バスフ社）や、ＰＶＰ／ＶＡ Ｅ−７
３５、Ｅ−６３５、Ｅ−５３５、Ｅ−３３５（以上、ガ
フ社）等がある〕、ポリビニルピロリドン／酢酸ビニル
／プロピオン酸ビニル三元共重合体〔市販品として、ル
ビスコール ＶＡＰ３４３（バスフ社）等がある〕、
ポリビニルピロリドン／アルキルアミノアクリレート共
重合体〔市販品として、ルビフレックス（バスフ社）、
コポリマー ８４５、９３７、９５８（以上、ガフ社
）等がある〕、ポリビニルピロリドン／アクリレート／
（メタ）アクリル酸共重合体〔市販品として、ルビフレ
ックス ＶＢＭ３５（バスフ社）等がある〕、ポリビ
ニルピロリドン／アルキルアミノアクリレート／ビニル
カプロラクタム共重合体〔市販品として、コポリマー
ＶＣ−７１３（ガフ社）等がある〕等が挙げられる。
また、両性アクリル系ポリマーとしては、ジアルキルア
ミノエチル（メタ）アクリレート／（メタ）アクリル酸
アルキルエステル共重合体〔市販品として、ユカフォー
マーＭ−７５、ＳＭ（三菱油化（株）等がある〕、アク
リル酸ヒドロキシプロピル／メタクリル酸ブチルアミノ
エチル／アクリル酸オクチルアミド共重合体〔市販品と
して、アムフォーマー ２８−４９１０ （ナショナ
ルスターチ社）等がある〕等が挙げられる。また塩基性
アクリル系ポリマーとしては、アクリルアミド・アクリ
ルエステル系四元共重合体〔市販品として、ポリマー
ＲＰ−７７Ｓ（花王（株））等がある〕等が挙げられ
る。Silicone/(meth) used in the present invention
The acrylic copolymer itself has film-forming ability, but when used in combination with a normal film-forming polymer, it can impart good smoothness to the formed film without impairing the film-forming ability of the polymer. It has the ability to confer. Here, typical film-forming polymers include polyvinylpyrrolidone polymers, amphoteric acrylic polymers, basic acrylic polymers, and the like. Here, as the polyvinylpyrrolidone polymer, polyvinylpyrrolidone [commercially available products include Rubiscoll K12, 17, 30
, 60, 80, 90 (and above, Basuf Corporation), and PVP
There are K15, 30, 60, 90 (all manufactured by Gaff), etc.)
, polyvinylpyrrolidone/vinyl acetate copolymer [commercially available products include Rubiscol VA28, 37, 55, 64
, 73 (Basuf Corporation), PVP/VA E-7
35, E-635, E-535, E-335 (all manufactured by Gough Co., Ltd.)], polyvinylpyrrolidone/vinyl acetate/vinyl propionate terpolymer [commercially available products include Rubiscoll VAP343 (Busf Co., Ltd.)] etc.],
Polyvinylpyrrolidone/alkylaminoacrylate copolymer (commercially available products include Rubiflex (Basuf),
Polyvinylpyrrolidone/acrylate/
(Meth)acrylic acid copolymer [commercially available products include Rubiflex VBM35 (Basuf Co., Ltd.)], polyvinylpyrrolidone/alkylaminoacrylate/vinylcaprolactam copolymer [commercially available products include copolymer
VC-713 (Gaff), etc.). Examples of amphoteric acrylic polymers include dialkylaminoethyl (meth)acrylate/(meth)acrylic acid alkyl ester copolymer [commercially available products include Yukaformer M-75 and SM (Mitsubishi Yuka Co., Ltd.)], Hydroxypropyl acrylate/butylaminoethyl methacrylate/octyl acrylate copolymer (commercially available products include Amformer 28-4910 (National Starch Co.)), etc. Basic acrylic polymers include: Acrylamide/acrylic ester quaternary copolymer [as a commercially available product, polymer
Examples include RP-77S (Kao Corporation).
【００２０】上記の被膜形成性ポリマーを併用する場合
、当該被膜形成性ポリマー１０重量部に対し、前記のシ
リコーン／（メタ）アクリル系共重合体を１〜５重量部
の割合で配合するのが好ましい。When the above film-forming polymer is used in combination, the silicone/(meth)acrylic copolymer is preferably blended in an amount of 1 to 5 parts by weight per 10 parts by weight of the film-forming polymer. preferable.
【００２１】かくして得られた本発明化粧料は、ヘアス
プレー、ヘアセットジェル、スタイリングムース等とし
て好適であり、毛髪に適度のセット保持力と良好な平滑
性を付与することができる。The thus obtained cosmetic composition of the present invention is suitable as a hair spray, a hair setting gel, a styling mousse, etc., and is capable of imparting an appropriate setting holding power and good smoothness to the hair.
【００２２】これらのうち、噴射剤を用いる毛髪化粧料
においては、原液中に本発明のシリコーン／（メタ）ア
クリル系共重合体を０．０１〜１５％、好ましくは０．
１ 〜６％；エタノール等の低級アルコール類、ポリオ
ール類、水などの溶剤を５０〜９９．８％；炭化水素類
、エステル油類、シリコーン及びその誘導体、天然油脂
などの油剤を０．１ 〜２０％配合するのが好ましく、
上記の如く従来用いられている他の被膜形成性ポリマー
を組み合わせて使用することもできる。また、必要に応
じて高級アルコール類、ミリスチン酸オクチルドデシル
、グリセリン、ポリエチレングリコール、ポリオキシエ
チレンヘキサデシルエーテル等の感触向上剤を０．５
〜３．０ ％、ポリオキシエチレンステアリルエーテル
等のカチオン性高分子などの被膜形成助剤を０．１ 〜
３．０ ％併用することもできる。なお、噴射剤として
は、ＬＰＧ １００％、フロンガス １００％、ＬＰＧ
／フロンガス混合ガス、ジメチルエーテル １００％、
ＬＰＧ／ジメチルエーテル混合ガスなどの液化ガス；二
酸化炭素、窒素などの圧縮ガスなどを１種又は２種以上
組み合わせて用いることができる。Among these, in hair cosmetics using a propellant, the silicone/(meth)acrylic copolymer of the present invention is contained in the stock solution in an amount of 0.01 to 15%, preferably 0.01 to 15%.
1 to 6%; 50 to 99.8% of lower alcohols such as ethanol, polyols, and solvents such as water; 0.1 to 99.8% of solvents such as hydrocarbons, ester oils, silicones and their derivatives, and natural oils and fats. It is preferable to mix 20%,
As mentioned above, other conventionally used film-forming polymers can also be used in combination. In addition, if necessary, feel improvers such as higher alcohols, octyldodecyl myristate, glycerin, polyethylene glycol, polyoxyethylene hexadecyl ether, etc.
~3.0%, and 0.1~3.0% film forming aid such as cationic polymer such as polyoxyethylene stearyl ether.
It can also be used in combination at 3.0%. In addition, as a propellant, LPG 100%, CFC gas 100%, LPG
/ Freon gas mixed gas, dimethyl ether 100%,
Liquefied gas such as LPG/dimethyl ether mixed gas; compressed gas such as carbon dioxide, nitrogen, etc. can be used alone or in combination of two or more.
【００２３】また、ヘアセットジェルなどのゲル状毛髪
化粧料においては、シリコーン／アクリル系共重合体を
０．５ 〜１０．０％、好ましくは１．０ 〜３．０
％；上記の被膜形成性ポリマー ０．５〜１０％；ポリ
アクリル酸、ヒドロキシエチルセルロース等の水溶性高
分子を増粘剤として０．５ 〜２．０ ％配合するのが
好ましく、これに精製水及び所望により低級アルコール
を加えた溶剤を用いるのが好ましい。また、従来汎用さ
れている水溶性高分子と併用することができ、感触を向
上させることができる。[0023] Furthermore, in gel-like hair cosmetics such as hair setting gels, the silicone/acrylic copolymer is contained in an amount of 0.5 to 10.0%, preferably 1.0 to 3.0%.
%; 0.5 to 10% of the above film-forming polymer; 0.5 to 2.0% of a water-soluble polymer such as polyacrylic acid or hydroxyethyl cellulose is preferably blended as a thickener, and purified water It is preferable to use a solvent to which a lower alcohol is added if desired. Furthermore, it can be used in combination with conventionally widely used water-soluble polymers, and the feel can be improved.
【００２４】その他、シャンプー、皮膚洗浄剤、リンス
等の化粧料には、本発明のシリコーン／アクリル系共重
合体を０．１ 〜５．０ ％、特に０．５ 〜２．０
％配合するのが好ましい。[0024] In addition, cosmetics such as shampoos, skin cleansers, conditioners, etc. contain the silicone/acrylic copolymer of the present invention in an amount of 0.1 to 5.0%, particularly 0.5 to 2.0%.
% is preferable.
【００２５】また、マスカラ、マニキュア、スキンクリ
ーム等においては、本発明のシリコーン／アクリル系共
重合体を０．００１ 〜１０．０％配合するのが好まし
い。[0025] Furthermore, in mascara, nail polish, skin cream, etc., the silicone/acrylic copolymer of the present invention is preferably blended in an amount of 0.001 to 10.0%.
【００２６】なお、本発明の化粧料には、通常用いられ
ている防腐剤、紫外線吸収剤、金属イオン封鎖剤、抗フ
ケ剤等の薬効剤や、色素、香料などを目的に応じて適宜
添加することもできる。[0026] The cosmetics of the present invention may optionally contain commonly used medicinal agents such as preservatives, ultraviolet absorbers, sequestering agents, anti-dandruff agents, pigments, fragrances, etc. You can also.
【００２７】[0027]
【発明の効果】本発明のシリコーン／（メタ）アクリル
系共重合体は、優れた被膜形成能を有し、シリコーンマ
クロマーを含有しているため、塗布面上に薄いシリコー
ンの被膜を形成する。この結果、従来の共重合体では得
られなかった潤滑性を得ることができ、塗布時の感触が
非常に良好である。このため、従来ゴワつき等を抑える
ために化粧料に配合されていた油剤等の量を減少させる
ことができ、これにより塗布後のベタつきを低減するこ
ともできる。さらに、増粘効果を示すことから、これを
増粘剤として化粧料に配合することにより、化粧料をな
がれにくくしたり、成形したときに崩れにくくすること
もできる。さらに、泡状化粧料、洗浄剤においては、泡
をクリーミィーにする優れた泡質改良性を付与すること
ができる。また、本発明のシリコーン／（メタ）アクリ
ル系共重合体を含有する化粧料は、常湿のみならず、高
湿度下においても優れた感触を有し、しかも洗浄により
容易に洗い落とすことができるものである。[Effects of the Invention] The silicone/(meth)acrylic copolymer of the present invention has excellent film-forming ability, and since it contains silicone macromer, it forms a thin silicone film on the coated surface. As a result, it is possible to obtain lubricity that cannot be obtained with conventional copolymers, and the feel during application is very good. For this reason, it is possible to reduce the amount of oils and the like that have been conventionally incorporated into cosmetics to suppress stiffness, and thereby it is also possible to reduce stickiness after application. Furthermore, since it exhibits a thickening effect, it can be added to cosmetics as a thickener to make the cosmetics difficult to run or crumble when molded. Furthermore, in foam cosmetics and detergents, it can impart excellent foam quality improvement properties that make the foam creamy. In addition, the cosmetic containing the silicone/(meth)acrylic copolymer of the present invention has an excellent feel not only under normal humidity but also under high humidity, and can be easily washed off. It is.
【００２８】[0028]
【実施例】次に、実施例を挙げて、本発明を更に詳細に
説明するが、本発明はこれら実施例に限定されるもので
はない。
実施例１
還流冷却器、滴下ロート、温度計、窒素ガス導入管及び
攪拌装置を取り付けた四つ口フラスコに窒素ガスを導入
した後、フラスコを加熱昇温して、１時間窒素置換を行
った。一方、滴下ロート（滴下ロートＡと称する）に２
，２’−アゾビスイソブチロニトリル（ＡＩＢＮ）１重
量部及びイソプロピルアルコール１０重量部を入れ、も
う一方の滴下ロート（滴下ロートＢと称する）にポリジ
メチルシロキシプロピルメタクリル酸エステル（式（２
）中、ｎ＝１４０ ）５０重量部、Ｎ，Ｎ−ジメチルア
ミノエチルメタクリレートメチルクロリド四級塩５０重
量部及びイソプロピルアルコール １００重量部を入れ
た。フラスコを６０℃に保った状態で、滴下ロートＡの
内容物及び滴下ロートＢの内容物を４時間かけて滴下し
、重合した。重合後、酢酸エチルで２回再沈精製し、８
０℃、２０ｍｍＨｇで１２時間真空乾燥した。得られた
共重合体は、白色の固体であり、ＮＭＲによる組成比は
、ジメチルシロキサン：Ｎ，Ｎ−ジメチルアミノエチル
メタクリレートメチルクロリド四級塩＝４８：５２、Ｇ
ＰＣによるポリスチレン換算重量平均分子量は約１２５
０００であった。EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 After introducing nitrogen gas into a four-necked flask equipped with a reflux condenser, dropping funnel, thermometer, nitrogen gas introduction tube, and stirring device, the flask was heated to raise its temperature and nitrogen substitution was performed for 1 hour. . On the other hand, in the dropping funnel (referred to as dropping funnel A),
, 1 part by weight of 2'-azobisisobutyronitrile (AIBN) and 10 parts by weight of isopropyl alcohol were added to the other dropping funnel (referred to as dropping funnel B), and polydimethylsiloxypropyl methacrylate (formula (2)
), 50 parts by weight of N,N-dimethylaminoethyl methacrylate methyl chloride quaternary salt and 100 parts by weight of isopropyl alcohol were added. While keeping the flask at 60° C., the contents of dropping funnel A and dropping funnel B were added dropwise over 4 hours to polymerize. After polymerization, it was purified by reprecipitation twice with ethyl acetate, and 8
It was vacuum dried at 0° C. and 20 mmHg for 12 hours. The obtained copolymer is a white solid, and the composition ratio according to NMR is dimethylsiloxane:N,N-dimethylaminoethyl methacrylate methyl chloride quaternary salt = 48:52, G
Polystyrene equivalent weight average molecular weight by PC is approximately 125
It was 000.
【００２９】実施例２
還流冷却器、滴下ロート、温度計、窒素ガス導入管及び
攪拌装置を取り付けた四つ口フラスコに窒素ガスを導入
した後、フラスコを加熱昇温して、１時間窒素置換を行
った。一方、滴下ロート（滴下ロートＡと称する）に２
，２’−アゾビスイソブチロニトリル（ＡＩＢＮ）５重
量部及びイソプロピルアルコール１０重量部を入れ、も
う一方の滴下ロート（滴下ロートＢと称する）にポリジ
メチルシロキシプロピルメタクリル酸エステル（式（２
）中、ｎ＝１４０ ）２０重量部、Ｎ，Ｎ−ジメチルア
ミノエチルメタクリレートメチルクロリド四級塩８０重
量部及びイソプロピルアルコール １００重量部を入れ
た。フラスコを６０℃に保った状態で、滴下ロートＡの
内容物及び滴下ロートＢの内容物を４時間かけて滴下し
、重合した。重合後、酢酸エチルで２回再沈精製し、８
０℃、２０ｍｍＨｇで１２時間真空乾燥した。得られた
共重合体は、白色の固体であり、ＮＭＲによる組成比は
、ジメチルシロキサン：Ｎ，Ｎ−ジメチルアミノエチル
メタクリレートメチルクロリド四級塩＝２２：７８、Ｇ
ＰＣによるポリスチレン換算重量平均分子量は約８３０
００であった。Example 2 After introducing nitrogen gas into a four-necked flask equipped with a reflux condenser, dropping funnel, thermometer, nitrogen gas introduction tube, and stirring device, the flask was heated to raise its temperature and replaced with nitrogen for 1 hour. I did it. On the other hand, in the dropping funnel (referred to as dropping funnel A),
, 5 parts by weight of 2'-azobisisobutyronitrile (AIBN) and 10 parts by weight of isopropyl alcohol were added to the other dropping funnel (referred to as dropping funnel B), and polydimethylsiloxypropyl methacrylate (formula (2)
), 20 parts by weight of n=140), 80 parts by weight of N,N-dimethylaminoethyl methacrylate methyl chloride quaternary salt, and 100 parts by weight of isopropyl alcohol were added. While keeping the flask at 60° C., the contents of dropping funnel A and dropping funnel B were added dropwise over 4 hours to polymerize. After polymerization, it was purified by reprecipitation twice with ethyl acetate, and 8
It was vacuum dried at 0° C. and 20 mmHg for 12 hours. The obtained copolymer is a white solid, and the composition ratio according to NMR is dimethylsiloxane:N,N-dimethylaminoethyl methacrylate methyl chloride quaternary salt = 22:78, G
Polystyrene equivalent weight average molecular weight by PC is approximately 830
It was 00.
【００３０】試験例１
本発明のシリコーン／アクリル系共重合体及び市販のジ
メチルシリコーンについて、これらを市販の整髪剤用被
膜形成樹脂であるポリビニルピロリドンに添加した場合
の、すべり及び高湿度下でのセットの崩れ難さを専門パ
ネラー１０名により感触評価した。結果を表１に示す。
（試料）
本発明共重合体Ａ：ポリシロキシルプロピルメタクリル
酸エステル（式（２）中、ｎ＝１４０ ）／トリメチル
アミノエチルメタクリレート＝５０／５０（％）本発明
共重合体Ｂ：ポリシロキシルプロピルメタクリル酸エス
テル（式（２）中、ｎ＝１４０ ）／トリメチルアミノ
エチルメタクリレート＝２０／８０（％）市販ジメチル
シリコーン：ＫＴ−５（東芝シリコーン（株）製）
（試験溶液）各試料０．６ ％及びポリビニルピロリド
ン２．０ ％のエタノール溶液を調製した。
（試験方法）
（１） すべり
長さ１８ｃｍ、重さ１０ｇの毛束を水でぬらし、タオル
ドライした後、試験溶液 ０．２ｇを塗布し、自然乾燥
させた。この毛束について、下記の基準で専門パネラー
１０名により感触評価した。
（２） セット保持力
長さ１８ｃｍ、重さ １．５ｇの毛束を水でぬらし、タ
オルドライした後、試験溶液を塗布し、直径２ｃｍのロ
ッドに巻いて自然乾燥させた。乾燥後、カールのついた
毛髪からロッドをはずした。これを恒湿箱（２０℃、９
８％ＲＨ）に３０分間つるし、カールの伸びを観察し、
セット保持力を下記の基準で評価した。
◎：たいへん良い
○：良い
△：普通
×：悪いTest Example 1 Regarding the silicone/acrylic copolymer of the present invention and commercially available dimethyl silicone, when these were added to polyvinylpyrrolidone, which is a commercially available film-forming resin for hair styling products, the effects of slippage and under high humidity were The difficulty of the set falling apart was evaluated by 10 expert panelists. The results are shown in Table 1. (Sample) Copolymer of the present invention A: Polysiloxylpropyl methacrylate (in formula (2), n = 140)/trimethylaminoethyl methacrylate = 50/50 (%) Copolymer of the present invention B: Polysiloxyl Propyl methacrylate ester (in formula (2), n=140)/trimethylaminoethyl methacrylate = 20/80 (%) Commercially available dimethyl silicone: KT-5 (manufactured by Toshiba Silicone Corporation) (Test solution) Each sample 0. Ethanol solutions of 6% and 2.0% polyvinylpyrrolidone were prepared. (Test method) (1) A hair bundle with a sliding length of 18 cm and a weight of 10 g was wetted with water, towel-dried, and then 0.2 g of the test solution was applied and air-dried. The feel of this hair bundle was evaluated by 10 expert panelists according to the following criteria. (2) Set holding power A hair bundle with a length of 18 cm and a weight of 1.5 g was wetted with water, towel-dried, then the test solution was applied, and the hair was wrapped around a rod with a diameter of 2 cm and air-dried. After drying, the rod was removed from the curled hair. Store this in a constant humidity box (20℃, 9
8% RH) for 30 minutes, observe the curl growth,
The set retention force was evaluated based on the following criteria. ◎: Very good ○: Good △: Average ×: Bad
【００３１】[0031]
【表１】[Table 1]
【００３２】実施例３ ミスト：下記成
分を混合して、ミストを製造した。
（成分）
（％
） 本発明共重合体Ａ（試験例１と同じ）
０．６ 両性ポリマー
（ユカフォーマーＭ７５：ダイヤケムコ社製）
５．０ 非イオン性界面活性剤
（グリセルイソステアレート）
０．５ エタノール
適量 香料
微量
計
１００．０本発明のミス
トは、従来使用されていた油剤を使用することなく、ポ
リマーのごわつきをおさえ、感触の良好なカール保持性
に優れたものであった。Example 3 Mist: A mist was prepared by mixing the following components. (component)
(%
) Invention copolymer A (same as Test Example 1)
0.6 Ampholytic polymer (Yukaformer M75: manufactured by Diachemco)
5.0 Nonionic surfactant (glycer isostearate)
0.5 ethanol
Appropriate amount fragrance
Very small amount
total
100.0 The mist of the present invention suppressed the stiffness of the polymer without using conventionally used oil agents, and had excellent curl retention with a good feel.
【００３３】実施例４ トリートメント
フォーム：下記成分を混合して、トリートメントフォー
ムを製造した。
（成分）
（％
） 本発明共重合体Ａ（試験例と同じ）
３．０ 非イオン性界面活性
剤
（ソフタノール９０；日本触媒製）
１．０ 香料
微量 精製水
適量 液化石油ガス
１０．０ 計
１００．０本発明の
トリートメントフォームは従来使用していた油剤を添加
することなく、毛髪に優れた平滑性としっとり感を与え
、これまで問題となっていた油剤のべたつき、手うつり
感のない、自然な感触を与えるものであった。Example 4 Treatment foam: A treatment foam was produced by mixing the following ingredients. (component)
(%
) Invention copolymer A (same as test example)
3.0 Nonionic surfactant (Softanol 90; manufactured by Nippon Shokubai)
1.0 Fragrance
Trace amount purified water
Appropriate amount liquefied petroleum gas
10.0 total
100.0 The treatment foam of the present invention provides excellent smoothness and moisturizing to the hair without adding conventionally used oils, and eliminates the stickiness and sticky feeling of oils, which have been problems in the past. It gave a natural feel.
【００３４】実施例５ シャンプー剤：
下記成分を混合して、毛髪用シャンプーを製造した。
（成分）
（％
） ラウリルポリオキシエチレン硫酸エステル ト
リエタノールアミン塩（４０％水溶液）
３２．０ ラウロイルジエタノールアミド
４．０
ポリエチレングリコール
１．０ 本発明共重合
体Ａ（試験例１と同じ）
１．０ 精製水
適量 香料
微量 計
１００．０本発明のシャンプーはクリーミィ
な泡質を有し、洗浄後の毛髪の感触も良好であった。Example 5 Shampoo:
A hair shampoo was prepared by mixing the following ingredients. (component)
(%
) Lauryl polyoxyethylene sulfate triethanolamine salt (40% aqueous solution)
32.0 Lauroyl diethanolamide 4.0
polyethylene glycol
1.0 Copolymer A of the present invention (same as Test Example 1)
1.0 Purified water
Appropriate amount fragrance
Trace amount meter
100.0 The shampoo of the present invention had creamy foam quality and the hair felt good after washing.
【００３５】実施例６ セットフォーム
剤：下記成分を混合して、セットフォーム剤を製造した
。
（成分）
（％
） 本発明共重合体Ａ（試験例１と同じ）
１．０ 両性ポリマー
（ユカフォーマーＭ７５：ダイヤケムコ社製）
１．０ 非イオン性界面活性剤
（ソフタノール９０：日本触媒製）
１．０ 香料
微量 精製水
適量 液化石油ガス
１０．０
計
１００．０Example 6 Setting foam agent: A setting foam agent was prepared by mixing the following components. (component)
(%
) Invention copolymer A (same as Test Example 1)
1.0 Ampholytic polymer (Yukaformer M75: manufactured by Diachemco)
1.0 Nonionic surfactant (Softanol 90: Nippon Shokubai)
1.0 Fragrance
Trace amount purified water
Appropriate amount liquefied petroleum gas
10.0
total
100.0
【００３６】
試験例２
実施例６及び市販のヘアフォームＡ（両性ポリマー（ユ
カフォーマー）、ジメチルシリコーン及びポリエーテル
シリコーンを使用）について、感触による性能評価を行
った。結果を表２に示す。
（評価方法）実験用人頭モデル（ウィッグ）２組の毛髪
を水でぬらした後、実施例６及び市販のヘアフォームを
それぞれ２ｇ塗布し、直径２ｃｍのロッドに巻いて自然
乾燥させた。乾燥後、毛髪からロッドをはずし、すべり
、ごわつき感、セット力を専門パネラー１０名により評
価した。この後、これを恒湿箱（２０℃、９８％ＲＨ）
に３０分間放置し、セットのくずれを観察した。さらに
、このウィッグをシャンプーで洗浄し、洗い落ちやすさ
を評価した。
◎：たいへん良い
○：良い
△：普通
×：悪い[0036]
Test Example 2 The performance of Example 6 and commercially available hair foam A (using an amphoteric polymer (Yukaformer), dimethyl silicone, and polyether silicone) was evaluated by touch. The results are shown in Table 2. (Evaluation method) After wetting the hair of two sets of experimental human head models (wigs) with water, 2 g of each of Example 6 and commercially available hair foam was applied, and the hair foam was wound around a rod with a diameter of 2 cm and air-dried. After drying, the rod was removed from the hair, and 10 expert panelists evaluated slippage, stiffness, and setting power. After that, store it in a constant humidity box (20℃, 98%RH)
The set was left for 30 minutes, and the set was observed for deterioration. Furthermore, this wig was washed with shampoo and the ease with which it was washed off was evaluated. ◎: Very good ○: Good △: Average ×: Bad
【００３７】[0037]
【表２】[Table 2]
Claims (2)
素数２〜３のアルキレン基を示し、Ｒ３、Ｒ４及びＲ５
は同一又は異なってメチル基又はエチル基を示し、ａは
０又は１を示し、Ｘはアニオン性基を示す）で表される
４級アミノ基を有する（メタ）アクリル酸エステル系モ
ノマー又は（メタ）アクリルアミド系モノマー （ｂ）式（２） 【化２】 （式中、Ｙはラジカル重合性基を示し、Ｒ６、Ｒ７、Ｒ
８、Ｒ９及びＲ１０は、同一又は異なってメチル基、ア
ルコキシル基、置換されていてもよいフェニル基又は置
換されていてもよいフェノキシ基を示し、ｍは１〜１０
の整数を示し、ｎは５〜１５０ の整数を示す）で表さ
れるシリコーンマクロマーをラジカル重合開始剤の存在
下に重合させて得られるシリコーン／（メタ）アクリル
系共重合体。Claim 1: (a) and (b) (a) Formula (1) [Formula 1] (wherein, R1 represents a hydrogen atom or a methyl group, R2 represents an alkylene group having 2 to 3 carbon atoms, R3, R4 and R5
are the same or different and represent a methyl group or an ethyl group, a represents 0 or 1, and X represents an anionic group. ) Acrylamide monomer (b) Formula (2) [Formula 2] (In the formula, Y represents a radically polymerizable group, R6, R7, R
8, R9 and R10 are the same or different and represent a methyl group, an alkoxyl group, an optionally substituted phenyl group, or an optionally substituted phenoxy group, and m is 1 to 10.
, n is an integer from 5 to 150) in the presence of a radical polymerization initiator.
アクリル系共重合体を含有する化粧料。[Claim 2] The silicone/(meth) according to Claim 1.
A cosmetic containing an acrylic copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13478491A JPH04359913A (en) | 1991-06-06 | 1991-06-06 | New copolymer and cosmetic containing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13478491A JPH04359913A (en) | 1991-06-06 | 1991-06-06 | New copolymer and cosmetic containing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04359913A true JPH04359913A (en) | 1992-12-14 |
Family
ID=15136476
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13478491A Pending JPH04359913A (en) | 1991-06-06 | 1991-06-06 | New copolymer and cosmetic containing same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04359913A (en) |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5480634A (en) * | 1989-07-12 | 1996-01-02 | Mitsubishi Chemical Corporation | Hair-care products containing copolymers formed from unsaturated hydrophilic monomers and unsaturated monomers having a polysiloxane group |
| WO1996021417A1 (en) * | 1995-01-09 | 1996-07-18 | The Procter & Gamble Company | Aqueous hair setting composition containing silicone grafted copolymer |
| US5618524A (en) * | 1989-08-07 | 1997-04-08 | The Procter & Gamble Company | Hair conditioning and styling compositions |
| US5653969A (en) * | 1996-03-21 | 1997-08-05 | The Procter & Gamble Company | Low residue hair care compositions |
| US5653968A (en) * | 1996-03-21 | 1997-08-05 | The Proctor & Gamble Company | Rinse-off hair care compositions |
| US5658557A (en) * | 1989-08-07 | 1997-08-19 | The Procter & Gamble Company | Hair care compositions comprising silicone-containing copolymers |
| US5665337A (en) * | 1996-03-21 | 1997-09-09 | The Procter & Gamble Company | Low residue hair care compositions using grafted copolymers |
| US5667771A (en) * | 1996-03-21 | 1997-09-16 | The Procter & Gamble Company | Rinse-off hair care compositions using grafted copolymers |
| US5804173A (en) * | 1996-09-04 | 1998-09-08 | The Procter & Gamble Company | Personal care compositions |
| US5830447A (en) * | 1996-09-04 | 1998-11-03 | The Procter & Gamble Company | Personal care compositions |
| US5863527A (en) * | 1996-09-04 | 1999-01-26 | The Proctor & Gamble Company | Personal care compositions |
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| US5929173A (en) * | 1997-05-12 | 1999-07-27 | The Procter & Gamble Company | Toughened grafted polymers |
| US6074628A (en) * | 1997-04-25 | 2000-06-13 | Procter & Gamble | Hairspray compositions containing silicon block copolymers |
| US6106820A (en) * | 1997-05-12 | 2000-08-22 | Procter & Gamble Company | Cosmetic compositions |
| US6113883A (en) * | 1997-04-25 | 2000-09-05 | The Procter & Gamble Company | Hair styling compositions comprising silicone-containing copolymers |
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-
1991
- 1991-06-06 JP JP13478491A patent/JPH04359913A/en active Pending
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| US5480634A (en) * | 1989-07-12 | 1996-01-02 | Mitsubishi Chemical Corporation | Hair-care products containing copolymers formed from unsaturated hydrophilic monomers and unsaturated monomers having a polysiloxane group |
| US5618524A (en) * | 1989-08-07 | 1997-04-08 | The Procter & Gamble Company | Hair conditioning and styling compositions |
| US5658557A (en) * | 1989-08-07 | 1997-08-19 | The Procter & Gamble Company | Hair care compositions comprising silicone-containing copolymers |
| US5997853A (en) * | 1989-08-07 | 1999-12-07 | The Procter & Gamble | Hair conditioning and styling compositions |
| US5911979A (en) * | 1995-01-09 | 1999-06-15 | The Procter & Gamble Company | Aqueous hair setting composition containing silicone grafted copolymer |
| WO1996021417A1 (en) * | 1995-01-09 | 1996-07-18 | The Procter & Gamble Company | Aqueous hair setting composition containing silicone grafted copolymer |
| US5653969A (en) * | 1996-03-21 | 1997-08-05 | The Procter & Gamble Company | Low residue hair care compositions |
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| US5804173A (en) * | 1996-09-04 | 1998-09-08 | The Procter & Gamble Company | Personal care compositions |
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| US6074628A (en) * | 1997-04-25 | 2000-06-13 | Procter & Gamble | Hairspray compositions containing silicon block copolymers |
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| US6106820A (en) * | 1997-05-12 | 2000-08-22 | Procter & Gamble Company | Cosmetic compositions |
| US6165457A (en) * | 1997-05-12 | 2000-12-26 | The Procter & Gamble Company | Personal care compositions containing toughened grafted polymers |
| US5929173A (en) * | 1997-05-12 | 1999-07-27 | The Procter & Gamble Company | Toughened grafted polymers |
| JP2006298860A (en) * | 2005-04-22 | 2006-11-02 | Osaka Organic Chem Ind Ltd | Base for cationic cosmetic |
| JP2006347918A (en) * | 2005-06-14 | 2006-12-28 | Osaka Organic Chem Ind Ltd | Cationic cosmetic |
| JP2013227312A (en) * | 2012-03-30 | 2013-11-07 | Kose Corp | Hair cosmetic |
| JP2013227310A (en) * | 2012-03-30 | 2013-11-07 | Kose Corp | Hair cosmetic |
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| JP2013227311A (en) * | 2012-03-30 | 2013-11-07 | Kose Corp | Hair cosmetic |
| CN104203209A (en) * | 2012-03-30 | 2014-12-10 | 株式会社高丝 | Hair cosmetic |
| KR20150002619A (en) * | 2012-03-30 | 2015-01-07 | 코세 코퍼레이션 | Hair cosmetic |
| US20150050231A1 (en) * | 2012-03-30 | 2015-02-19 | Kose Corporation | Hair cosmetic |
| US9364421B2 (en) | 2012-03-30 | 2016-06-14 | Kose Corporation | Hair cosmetic |
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