JP2016160218A - Water-in-oil type emulsion cosmetic - Google Patents
Water-in-oil type emulsion cosmetic Download PDFInfo
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- JP2016160218A JP2016160218A JP2015040305A JP2015040305A JP2016160218A JP 2016160218 A JP2016160218 A JP 2016160218A JP 2015040305 A JP2015040305 A JP 2015040305A JP 2015040305 A JP2015040305 A JP 2015040305A JP 2016160218 A JP2016160218 A JP 2016160218A
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- 239000002537 cosmetic Substances 0.000 title claims abstract description 51
- 239000000839 emulsion Substances 0.000 title abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 47
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 18
- -1 perfluoroalkyl silane Chemical compound 0.000 claims abstract description 17
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 15
- 229920002050 silicone resin Polymers 0.000 claims abstract description 14
- 239000011787 zinc oxide Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- BPCXHCSZMTWUBW-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F BPCXHCSZMTWUBW-UHFFFAOYSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000007762 w/o emulsion Substances 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 125000005395 methacrylic acid group Chemical group 0.000 claims 1
- 238000004381 surface treatment Methods 0.000 claims 1
- 239000010419 fine particle Substances 0.000 abstract description 6
- 238000003892 spreading Methods 0.000 abstract description 6
- 229910000077 silane Inorganic materials 0.000 abstract description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 14
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 14
- 239000004205 dimethyl polysiloxane Substances 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- 230000002087 whitening effect Effects 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000006071 cream Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 229920002379 silicone rubber Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 230000037393 skin firmness Effects 0.000 description 2
- 230000000475 sunscreen effect Effects 0.000 description 2
- 239000000516 sunscreening agent Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- UUJLHYCIMQOUKC-UHFFFAOYSA-N trimethyl-[oxo(trimethylsilylperoxy)silyl]peroxysilane Chemical compound C[Si](C)(C)OO[Si](=O)OO[Si](C)(C)C UUJLHYCIMQOUKC-UHFFFAOYSA-N 0.000 description 2
- GYDYJUYZBRGMCC-INIZCTEOSA-N (2s)-2-amino-6-(dodecanoylamino)hexanoic acid Chemical compound CCCCCCCCCCCC(=O)NCCCC[C@H](N)C(O)=O GYDYJUYZBRGMCC-INIZCTEOSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical class O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- OSCJHTSDLYVCQC-UHFFFAOYSA-N 2-ethylhexyl 4-[[4-[4-(tert-butylcarbamoyl)anilino]-6-[4-(2-ethylhexoxycarbonyl)anilino]-1,3,5-triazin-2-yl]amino]benzoate Chemical compound C1=CC(C(=O)OCC(CC)CCCC)=CC=C1NC1=NC(NC=2C=CC(=CC=2)C(=O)NC(C)(C)C)=NC(NC=2C=CC(=CC=2)C(=O)OCC(CC)CCCC)=N1 OSCJHTSDLYVCQC-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical class C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241001237961 Amanita rubescens Species 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- IUMSDRXLFWAGNT-UHFFFAOYSA-N Dodecamethylcyclohexasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 IUMSDRXLFWAGNT-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004909 Moisturizer Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical class CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001166 anti-perspirative effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000003213 antiperspirant Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000001333 moisturizer Effects 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- BOJSDHZZKKYWAS-UHFFFAOYSA-N tetrakis(trimethylsilyl)silane Chemical compound C[Si](C)(C)[Si]([Si](C)(C)C)([Si](C)(C)C)[Si](C)(C)C BOJSDHZZKKYWAS-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- BUBJWNWWARPCBH-UHFFFAOYSA-N tris(trimethylsilyl)methylsilicon Chemical compound C[Si](C)(C)C([Si])([Si](C)(C)C)[Si](C)(C)C BUBJWNWWARPCBH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- Cosmetics (AREA)
Abstract
Description
本発明は、油中水型乳化化粧料に関する。 The present invention relates to a water-in-oil emulsified cosmetic.
微粒子酸化亜鉛を含有した化粧料は、カバー効果や、なめらかな使用感などが得られることが知られている。
例えば、特許文献１には、微粒子酸化亜鉛とシリコーンエラストマー粉体を含有する粉末固型化粧料が、化粧もちに優れ、なめらかでしっとりした感触を有し、肌へのフィット感に優れることが記載されている。特許文献２には、微粒子酸化亜鉛と高分子球状弾性粉体を含有する粉末化粧料が、高いスキンケア効果を有し、なめらかで肌当たりが良いことが記載されている。特許文献３には、微粒子酸化亜鉛と球状弾性樹脂粉体を含有する粉末化粧料が、カバー効果が得られ、自然な仕上りで使用感に優れることが記載されている。
It is known that cosmetics containing particulate zinc oxide can provide a cover effect and a smooth feeling of use.
For example, Patent Document 1 describes that a powder solid cosmetic containing fine zinc oxide and silicone elastomer powder is excellent in makeup, has a smooth and moist feel, and has an excellent fit to the skin. Has been. Patent Document 2 describes that a powder cosmetic containing fine-particle zinc oxide and a polymer spherical elastic powder has a high skin care effect, and is smooth and has good skin contact. Patent Document 3 describes that a powder cosmetic containing fine zinc oxide and spherical elastic resin powder has a cover effect and is excellent in use feeling with a natural finish.
近年では、更なるカバー効果や使用感の向上が求められているが、本発明者らは、微粒子酸化亜鉛を含有する化粧料では、塗布時にダマができやすく、ざらつきやすく、塗布初期にひっかかり感を生じやすい、という課題を見出した。 In recent years, there has been a demand for further improvement of the cover effect and the feeling of use. The problem that it is easy to produce was discovered.
本発明者らは、微粒子酸化亜鉛に、パーフルオロアルキルシランで表面処理した特定粒子径の球状有機樹脂粉体と、２５℃で固体のフッ素変性シリコーン樹脂又はアクリル−シリコーン系グラフト共重合体を、特定の割合で組み合わせて用いることにより、上記課題を解決した油中水型乳化化粧料が得られることを見出した。 The inventors of the present invention include a spherical organic resin powder having a specific particle diameter that is surface-treated with perfluoroalkylsilane, and a fluorine-modified silicone resin or an acrylic-silicone graft copolymer that is solid at 25 ° C. It discovered that the water-in-oil type emulsified cosmetic which solved the said subject was obtained by using combining in a specific ratio.
本発明は、次の成分（Ａ）、（Ｂ）及び（Ｃ）：
（Ａ）パーフルオロアルキルシランで表面処理した、粒子径０．０１μｍ以上１．０μｍ以下の球状有機樹脂粉体 ０．１〜２０質量％、
（Ｂ）比表面積１０〜１００ｍ2／ｇの微粒子酸化亜鉛 ０．０１〜４０質量％、
（Ｃ）２５℃で固体のフッ素変性シリコーン樹脂又はアクリル−シリコーン系グラフト共重合体 ０．０１〜１０質量％
を含有し、成分（Ｃ）に対する成分（Ａ）の質量割合（Ａ）／（Ｃ）が、０．０３〜５０である油中水型乳化化粧料に関する。
The present invention includes the following components (A), (B) and (C):
(A) 0.1-20% by mass of a spherical organic resin powder having a particle size of 0.01 μm or more and 1.0 μm or less, which is surface-treated with perfluoroalkylsilane,
(B) 0.01 to 40% by mass of fine zinc oxide having a specific surface area of 10 to 100 m 2 / g,
(C) Fluorine-modified silicone resin or acrylic-silicone graft copolymer solid at 25 ° C. 0.01 to 10% by mass
It is related with the water-in-oil type emulsion cosmetics whose mass ratio (A) / (C) of the component (A) with respect to a component (C) is 0.03-50.
本発明の油中水型乳化化粧料は、パウダーファンデーションをスポンジで重ね付け使用したときの塗布初期のひっかかり感が少なく、塗布中ののびに優れ、塗布直後の白浮きが抑制されるとともに、肌のハリ感が得られ、肌荒れの目立ちを抑制することができる。 The water-in-oil emulsified cosmetic of the present invention has little initial feeling of application when the powder foundation is overlapped with a sponge, is excellent in spreading during application, suppresses whitening immediately after application, A firm feeling can be obtained, and the conspicuousness of rough skin can be suppressed.
本発明で用いる成分（Ａ）の有機樹脂粉体は、球状のものである。球状とは、真球、略球状、回転楕円体を含み、表面に凹凸がある球状粉体等であっても良い。
球状樹脂粉体としては、通常の化粧料に用いられるものであればいずれでも良く、例えば、ポリアミド樹脂、ナイロン樹脂、ポリエステル樹脂、ポリエチレン樹脂、ポリ四フッ化エチレン樹脂、ポリプロピレン樹脂、ポリスチレン樹脂、ベンゾグアナミン樹脂、ポリメチルベンゾグアナミン樹脂、ポリウレタン樹脂、ビニル樹脂、フッ素樹脂、アクリル樹脂、メラミン樹脂；ジメチルシリコーンを架橋したシリコーンエラストマーやポリメチルシルセスキオキサン等のシリコーン樹脂；アクリル酸ブチル・酢酸ビニル共重合体、スチレン・アクリル酸共重合体、ジビニルベンゼン・スチレン共重合体から選ばれる１種または２種以上の重合体または共重合体のパウダー等の架橋型あるいは非架橋型の有機粉体が挙げられる。
これらのうち、アクリル樹脂粉体が好ましく、アクリル酸エステル、メタクリル酸エステル、アクリル酸アルキレングリコール、メタクリル酸アルキレングリコールから選ばれる１種又は２種以上の重合体がより好ましい。
The organic resin powder of component (A) used in the present invention is spherical. The spherical shape may be a spherical powder or the like including a true sphere, a substantially spherical shape, and a spheroid and having irregularities on the surface.
Any spherical resin powder may be used as long as it is used in ordinary cosmetics. For example, polyamide resin, nylon resin, polyester resin, polyethylene resin, polytetrafluoroethylene resin, polypropylene resin, polystyrene resin, benzoguanamine Resin, Polymethylbenzoguanamine resin, Polyurethane resin, Vinyl resin, Fluorine resin, Acrylic resin, Melamine resin; Silicone elastomer such as silicone elastomer cross-linked with dimethyl silicone and polymethylsilsesquioxane; Butyl acrylate / vinyl acetate copolymer Cross-linked or non-cross-linked organic powders such as one or two or more polymers selected from styrene / acrylic acid copolymers and divinylbenzene / styrene copolymers or copolymer powders.
Among these, acrylic resin powder is preferable, and one or more polymers selected from acrylic acid ester, methacrylic acid ester, alkylene glycol acrylate, and alkylene glycol methacrylate are more preferable.
また、成分（Ａ）の球状有機樹脂粉体は、パーフルオロアルキルシランで表面処理したものである。パーフルオロアルキルシランのうち、下記式で示されるトリデカフルオロオクチルトリエトキシシランで表面処理されたものが好ましい。
Ｆ3Ｃ−(ＣＦ2)5−(ＣＨ2)2−Ｓｉ−(ＯＣＨ2ＣＨ3)3
トリデカフルオロオクチルトリエトキシシランとしては、大東化成工業社より販売されているＦＨＳが好適である。
The spherical organic resin powder of component (A) is a surface treated with perfluoroalkylsilane. Of the perfluoroalkylsilanes, those surface-treated with tridecafluorooctyltriethoxysilane represented by the following formula are preferred.
F 3 C— (CF 2 ) 5 — (CH 2 ) 2 —Si— (OCH 2 CH 3 ) 3
As the tridecafluorooctyltriethoxysilane, FHS sold by Daito Kasei Kogyo Co., Ltd. is suitable.
粉体をトリデカフルオロオクチルトリエトキシシランで表面処理する方法としては、例えば、トリデカフルオロオクチルトリエトキシシランをミキサー内で滴下または添加して粉体と混合した後、熱処理を行い、必要に応じて解砕する方法や、トリデカフルオロオクチルトリエトキシシランを溶解又は分散させた有機溶剤液と粉体とを混合した後、有機溶剤を除去し、乾燥後解砕する方法などが挙げられる。
中でも、トリデカフルオロオクチルトリエトキシシランを有機溶剤に溶解又は分散させ、粉体とミキサー内で混合しながら、ミキサーを減圧下で加温して有機溶剤を除去した後、必要に応じて熱処理及び解砕する製造方法が好ましい。ここで用いる有機溶剤としては、例えばメタノール、エタノール、イソプロピルアルコール、イソブタノール、アセトン、酢酸エチル、酢酸ブチル、メチルエチルケトン、ジクロロメタン、クロロホルムに代表される極性有機溶剤や、ノルマルヘキサン、トルエン、キシレンのような炭化水素系有機溶剤が適当である。
As a method of surface-treating the powder with tridecafluorooctyltriethoxysilane, for example, tridecafluorooctyltriethoxysilane is dropped or added in a mixer and mixed with the powder, followed by heat treatment, and if necessary And a method in which an organic solvent liquid in which tridecafluorooctyltriethoxysilane is dissolved or dispersed and a powder are mixed, the organic solvent is removed, and the mixture is crushed after drying.
Among them, tridecafluorooctyltriethoxysilane is dissolved or dispersed in an organic solvent, and while mixing the powder and the mixer in the mixer, the mixer is heated under reduced pressure to remove the organic solvent. A production method for crushing is preferred. Examples of the organic solvent used here include polar organic solvents such as methanol, ethanol, isopropyl alcohol, isobutanol, acetone, ethyl acetate, butyl acetate, methyl ethyl ketone, dichloromethane, and chloroform, and normal hexane, toluene, and xylene. Hydrocarbon organic solvents are suitable.
パーフルオロアルキルシランの処理量は粉体によって異なるが、塗布初期のひっかかり感が少なく、塗布中、ダマの形成を抑制する点から、パーフルオロアルキルシランで表面処理した球状有機樹脂粉体の質量に対して、０．０５質量％以上が好ましく、０．１質量％以上がより好ましく、０．５質量％以上がさらに好ましく、５０質量％以下が好ましく、２０質量％以下がより好ましく、８質量％以下がさらに好ましい。また、パーフルオロアルキルシランの処理量は、パーフルオロアルキルシランで表面処理した球状有機樹脂粉体の質量に対して、０．０５〜５０質量％であるのが好ましく、０．１〜２０質量％であるのがより好ましく、０．５〜８質量％であるのがさらに好ましい。 The amount of perfluoroalkylsilane treated varies depending on the powder, but it is less likely to be caught in the initial stage of application, and it suppresses the formation of lumps during application. On the other hand, 0.05 mass% or more is preferable, 0.1 mass% or more is more preferable, 0.5 mass% or more is more preferable, 50 mass% or less is preferable, 20 mass% or less is more preferable, and 8 mass%. The following is more preferable. Moreover, it is preferable that the processing amount of perfluoroalkyl silane is 0.05-50 mass% with respect to the mass of the spherical organic resin powder surface-treated with perfluoroalkyl silane, and 0.1-20 mass%. It is more preferable that it is 0.5 to 8% by mass.
成分（Ａ）のパーフルオロアルキルシランで表面処理した球状有機樹脂粉体は、塗布初期のひっかかり感が少なく、塗布中、ダマの形成を抑制する点から、粒子径０．０１μｍ以上１．０μｍ以下であり、０．１〜０．７μｍが好ましく、０．２〜０．５μｍがより好ましい。
また、成分（Ａ）のパーフルオロアルキルシランで表面処理した球状有機樹脂粉体は、塗布初期のひっかかり感が少なく、塗布中、ダマの形成を抑制する点から、平均粒子径０．１〜０．５μｍであるのが好ましく、０．３〜０．４μｍがより好ましい。
なお、本発明において、成分（Ａ）の粒子径は、パーフルオロアルキルシランで表面処理した状態で測定したものを指し、その測定方法は、電子顕微鏡の映像で観察し、測定粒子１００個中の粒子の数を測定され、ヒストグラムを作成して得られる個数基準の粒子径分布である。また、平均粒子径は、個数基準の粒子径のメディアン径（５０％径）分布により求められる。
The spherical organic resin powder surface-treated with the component (A) perfluoroalkylsilane is less likely to get caught at the initial stage of application, and has a particle size of 0.01 μm or more and 1.0 μm or less from the viewpoint of suppressing formation of lumps during application 0.1 to 0.7 μm is preferable, and 0.2 to 0.5 μm is more preferable.
In addition, the spherical organic resin powder surface-treated with the component (A) perfluoroalkylsilane is less likely to be caught in the initial stage of application, and has an average particle diameter of 0.1 to 0 because it suppresses the formation of lumps during application. 0.5 μm is preferable, and 0.3 to 0.4 μm is more preferable.
In the present invention, the particle diameter of the component (A) refers to that measured in a state of being surface-treated with perfluoroalkylsilane, and the measurement method is observed with an electron microscope image, and in 100 measured particles. This is a particle size distribution based on the number obtained by measuring the number of particles and creating a histogram. Further, the average particle diameter is obtained from a median diameter (50% diameter) distribution of particle diameters based on the number.
また、本発明においては、塗布初期のひっかかり感が少なく、塗布中、ダマの形成を抑制する点から、全ての球状有機樹脂粉体の３０質量％以上が、粒子径０．０１μｍ以上１．０μｍ以下の球状有機樹脂粉体であるのが好ましく、５０質量％以上がより好ましく、
６５質量％以上がさらに好ましく、７５質量％以上がよりさらに好ましい。
In addition, in the present invention, the feeling of catching at the initial stage of coating is small, and from the viewpoint of suppressing the formation of lumps during coating, 30% by mass or more of all spherical organic resin powders have a particle size of 0.01 μm or more and 1.0 μm. It is preferably the following spherical organic resin powder, more preferably 50% by mass or more,
65 mass% or more is further more preferable, and 75 mass% or more is further more preferable.
成分（Ａ）は、１種又は２種以上を用いることができ、塗布初期のひっかかり感が少なく、塗布中、ダマの形成を抑制する点から、含有量は、全組成中に０．１質量％以上であり、０．３質量％以上が好ましく、０．５質量％以上がより好ましく、１質量％以上がさらに好ましく、２０質量％以下であり、１５質量％以下が好ましく、１０質量％以下がより好ましく、８質量％以下がさらに好ましい。また、成分（Ａ）の含有量は、全組成中に０．１〜２０質量％であり、０．３〜１５質量％が好ましく、０．５〜１０質量％がより好ましく、１〜８質量％がさらに好ましい。 Component (A) can be used singly or in combination of two or more, and the content is 0.1 mass in the total composition from the viewpoint that the feeling of catching at the initial stage of coating is small and the formation of lumps is suppressed during coating. % Or more, preferably 0.3% by weight or more, more preferably 0.5% by weight or more, further preferably 1% by weight or more, 20% by weight or less, preferably 15% by weight or less, and 10% by weight or less. Is more preferable, and 8 mass% or less is still more preferable. Moreover, content of a component (A) is 0.1-20 mass% in all the compositions, 0.3-15 mass% is preferable, 0.5-10 mass% is more preferable, 1-8 mass % Is more preferable.
成分（Ｂ）の微粒子酸化亜鉛は、比表面積が１０〜１００ｍ2／ｇのものであり、良好な使用感を得る点から、比表面積が１５〜９５ｍ2／ｇのものが好ましい。 The component (B) fine particle zinc oxide has a specific surface area of 10 to 100 m 2 / g, and a specific surface area of 15 to 95 m 2 / g is preferred from the viewpoint of obtaining a good feeling of use.
成分（Ｂ）の微粒子酸化亜鉛は、そのまま使用することができるが、必要に応じて、例えば、シリコーン処理、脂肪酸処理、ラウロイルリジン処理、レシチン処理、Ｎ−アシルアミノ酸処理、金属石鹸処理、フッ素化合物処理、アルキルシラン処理等の疎水化処理したものを用いることもできる。微粒子酸化亜鉛の分散性を向上させる点から、シリコーン処理したものが好ましく、通常の方法により処理したものを用いることができる。
なお、微粒子酸化亜鉛を疎水化処理した場合、成分（Ｂ）の含有量や比表面積は、疎水化処理した剤を含めての質量や比表面積を意味する。
The fine particle zinc oxide of component (B) can be used as it is, but if necessary, for example, silicone treatment, fatty acid treatment, lauroyllysine treatment, lecithin treatment, N-acylamino acid treatment, metal soap treatment, fluorine compound A hydrophobized treatment such as a treatment or an alkylsilane treatment can also be used. From the viewpoint of improving the dispersibility of the fine particle zinc oxide, those treated with silicone are preferred, and those treated by a usual method can be used.
In addition, when the fine particle zinc oxide is hydrophobized, the content and specific surface area of the component (B) mean the mass and specific surface area including the hydrophobized agent.
成分（Ｂ）は、１種又は２種以上を用いることができ、化粧持ちに優れ、良好な使用感を得る点から、含有量は、全組成中に０．０１質量％以上であり、０．１質量％以上が好ましく、１質量％以上がより好ましく、４０質量％以下であり、２０質量％以下が好ましく、８質量％以下がより好ましい。また、成分（Ｂ）の含有量は、全組成中に０．０１〜４０質量％であり、０．１〜２０質量％が好ましく、１〜８質量％がより好ましい。 Component (B) can be used singly or in combination of two or more, and the content is 0.01% by mass or more in the total composition from the viewpoint of excellent makeup and good usability, and 0 1 mass% or more is preferable, 1 mass% or more is more preferable, 40 mass% or less is preferable, 20 mass% or less is preferable, and 8 mass% or less is more preferable. Moreover, content of a component (B) is 0.01-40 mass% in the whole composition, 0.1-20 mass% is preferable, and 1-8 mass% is more preferable.
本発明において、成分（Ｂ）に対する成分（Ａ）の質量割合（Ａ）／（Ｂ）は、パウダーファンデーションをスポンジで重ね付け使用したときの塗布初期のひっかかり感が少なく、塗布中ののびに優れ、塗布直後の白浮きが抑制されるとともに、肌のハリ感が得られ、肌荒れの目立ちを抑制する点から、０．０５以上が好ましく、０．１以上がより好ましく、０．３以上がさらに好ましく、０．５以上がよりさらに好ましく、２０以下が好ましく、５以下がより好ましく、３以下がさらに好ましく、１以下がよりさらに好ましい。また、成分（Ｂ）に対する成分（Ａ）の質量割合（Ａ）／（Ｂ）は、０．０５〜２０が好ましく、０．１〜５がより好ましく、０．３〜３がさらに好ましく、０．５〜１がよりさらに好ましい。 In the present invention, the mass ratio (A) / (B) of the component (A) to the component (B) is less likely to be caught in the initial stage of application when the powder foundation is overlapped with a sponge and is excellent in spreading during application. From the viewpoint that whitening immediately after application is suppressed, a firm feeling of the skin is obtained, and the conspicuousness of rough skin is suppressed, 0.05 or more is preferable, 0.1 or more is more preferable, and 0.3 or more is further Preferably, 0.5 or more is more preferable, 20 or less is preferable, 5 or less is more preferable, 3 or less is more preferable, and 1 or less is more preferable. Moreover, 0.05-20 are preferable, as for the mass ratio (A) / (B) of the component (A) with respect to a component (B), 0.1-5 are more preferable, 0.3-3 are more preferable, 0 .5 to 1 is even more preferable.
本発明で用いる成分（Ｃ）のうち、２５℃で固体のフッ素変性シリコーン樹脂としては、下記一般式（１）
Ｒ1 gＳｉＯ(4-g)/2 （１）
（式中、Ｒ1は炭素数１〜８の炭化水素基、フェニル基、水酸基又は一般式−Ｒ2−Ｒｆ（Ｒ2は炭素数２〜６の２価のアルキレン基を示し、Ｒｆは炭素数１〜８のパーフルオロアルキル基を示す）であって、水酸基及び一般式−Ｒ2−Ｒｆを必須とする官能基から任意に選ばれ、ｇは平均数で１．０≦ｇ≦１．８である。尚、Ｒ1は、同じであっても、異なっても良い）
で表される構造を有するものが好ましい。
Among the components (C) used in the present invention, the fluorine-modified silicone resin that is solid at 25 ° C. has the following general formula (1):
R 1 g SiO (4-g) / 2 (1)
(In the formula, R 1 represents a hydrocarbon group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, or a general formula —R 2 —Rf (R 2 represents a divalent alkylene group having 2 to 6 carbon atoms, and Rf represents carbon A perfluoroalkyl group having a number of 1 to 8), which is arbitrarily selected from functional groups having a hydroxyl group and the general formula -R 2 -Rf as essential, and g is an average number of 1.0 ≦ g ≦ 1. 8) R 1 may be the same or different.
What has the structure represented by these is preferable.
フッ素変性シリコーン樹脂は、皮膚や粉体に対する付着性の点から、分子内にシラノール基を有し、シラノール基中のＯＨ基の割合が、樹脂質量に対して０．１〜５質量％であるのが好ましく、０．５〜５質量％がより好ましい。 The fluorine-modified silicone resin has a silanol group in the molecule from the viewpoint of adhesion to skin and powder, and the ratio of the OH group in the silanol group is 0.1 to 5% by mass with respect to the resin mass. Of 0.5 to 5% by mass is more preferable.
また、フッ素変性シリコーン樹脂は、２５℃で固体のものである。このため、環状シリコーン、ジメチルポリシロキサン等に溶解して使用するのが好ましい。環状シリコーンとしては、オクタメチルシクロテトラシロキサン（Ｄ４）及びデカメチルシクロペンタシロキサン（Ｄ５）から選ばれる１種以上に溶解して用いるのが好ましい。 The fluorine-modified silicone resin is solid at 25 ° C. For this reason, it is preferable to use it by dissolving in cyclic silicone, dimethylpolysiloxane or the like. The cyclic silicone is preferably used by dissolving in one or more selected from octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5).
このようなフッ素変性シリコーン樹脂としては、ＩＮＣＩ名「トリフルオロプロピルジメチル／トリメチルシロキシシリケート（Trifluoropropyldimethyl／Trimethylsiloxysilicate）」である、ＸＳ６６−Ｂ８２２６、ＸＳ６６−Ｃ１１９１、ＸＳ６６−Ｂ８６３６（以上、モメンティブ・パフォーマンス・マテリアルズ社製）等の市販品を用いることができる。 As such a fluorine-modified silicone resin, INCI names “Trifluoropropyldimethyl / Trimethylsiloxysilicate”, XS66-B8226, XS66-C1191, XS66-B8636 (above, Momentive Performance Materials) Commercially available products such as those manufactured by the company) can be used.
また、成分（Ｃ）のうち、アクリル−シリコーン系グラフト共重合体としては、一般式（２） Among the components (C), the acrylic-silicone graft copolymer may be represented by the general formula (2)
（式中、Ｒ11はメチル基又は水素原子を示し、Ｒ12は、１個又は２個のエーテル結合で遮断されていても良い、炭素数１〜１０の２価の飽和炭化水素基を示し、ｋは３〜３００の数を示す。）
で表される分子鎖の型末端にラジカル重合性基を有するジメチルポリシロキサン化合物を含むモノマー(C1)を重合させて得られるアクリル−シリコーン系グラフト共重合体が好ましい。
一般式（２）中、Ｒ12で示される、１個又は２個のエーテル結合で遮断されていても良い、炭素数１〜１０の２価の飽和炭化水素基は、直鎖状又は分岐鎖状のいずれでも良く、炭素数１〜７のものが好ましい。具体的には、-CH2-、-(CH2)3-、-(CH2)6-、-(CH2)8-、-(CH2)10-、-CH2-CH(CH3)-CH2-、-CH2CH2OCH2CH2CH2-、-CH2CH2OCH2CH(CH3)CH2-、-CH2CH2OCH2CH2OCH2CH2CH2- などが挙げられる。
また、ｋは３〜３００の数であり、化粧持続性に優れる点から、５〜１００が好ましい。
(In the formula, R 11 represents a methyl group or a hydrogen atom, and R 12 represents a divalent saturated hydrocarbon group having 1 to 10 carbon atoms which may be blocked by one or two ether bonds. K represents a number of 3 to 300.)
An acrylic-silicone graft copolymer obtained by polymerizing a monomer (C1) containing a dimethylpolysiloxane compound having a radical polymerizable group at the mold end of the molecular chain represented by
In the general formula (2), the divalent saturated hydrocarbon group having 1 to 10 carbon atoms which may be blocked by one or two ether bonds represented by R 12 is linear or branched. Any of these may be used, and those having 1 to 7 carbon atoms are preferred. Specifically, -CH 2 -,-(CH 2 ) 3 -,-(CH 2 ) 6 -,-(CH 2 ) 8 -,-(CH 2 ) 10- , -CH 2 -CH (CH 3 ) -CH 2 -, - CH 2 CH 2 OCH 2 CH 2 CH 2 -, - CH 2 CH 2 OCH 2 CH (CH 3) CH 2 -, - CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 CH 2 -And so on.
Moreover, k is a number of 3-300, and 5-100 are preferable from the point which is excellent in makeup persistence.
一般式（２）で表されるジメチルポリシロキサン化合物としては、以下のものを好適に使用することができる。尚、式中のＭｅはメチル基を示す。 As the dimethylpolysiloxane compound represented by the general formula (2), the following can be suitably used. In the formula, Me represents a methyl group.
アクリル−シリコーン系グラフト共重合体は、このような一般式（２）で表されるジメチルポリシロキサン化合物(C1)を含むモノマーを重合させて得られるものである。ジメチルポリシロキサン化合物(C1)以外に用いられるものマーとしては、アクリレート及び／又はメタクリレートを主体とするラジカル重合性モノマー(C2)が挙げられる。
アクリレート及び／又はメタクリレートを主体とするラジカル重合性モノマーは、ラジカル重合性不飽和結合を分子中に１個有する化合物であり、アクリレート及び／又はメタクリレートを主体とするとは、ラジカル重合性モノマー(C2)において、アクリレート及び／又はメタクリレートの合計量が、ラジカル重合性モノマー全体の５０質量％以上を占めることを意味する。
The acrylic-silicone graft copolymer is obtained by polymerizing a monomer containing the dimethylpolysiloxane compound (C1) represented by the general formula (2). Examples of the monomer other than the dimethylpolysiloxane compound (C1) include a radical polymerizable monomer (C2) mainly composed of acrylate and / or methacrylate.
The radically polymerizable monomer mainly composed of acrylate and / or methacrylate is a compound having one radically polymerizable unsaturated bond in the molecule, and mainly composed of acrylate and / or methacrylate is a radically polymerizable monomer (C2). Means that the total amount of acrylate and / or methacrylate occupies 50% by mass or more of the entire radical polymerizable monomer.
用いるアクリレート及び／又はメタクリレートとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート等のアルキル（メタ）アクリレート；２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート；炭素数１〜１０のパーフルオロアルキル（メタ）アクリレートなどが挙げられる。中でも、メチルメタクリレート、ブチルメタクリレート、２−エチルヘキシルアクリレートが好ましく、メチルメタクリレート、ブチルメタクリレート、２−エチルヘキシルアクリレートを組み合わせたものがより好ましい。
また、アクリレート及び／又はメタクリレート以外のモノマーとしては、スチレン、置換スチレン、酢酸ビニル、（メタ）アクリル酸、無水マレイン酸、マレイン酸エステル、フマル酸エステル、塩化ビニル、塩化ビニリデン、エチレン、プロピレン、ブタジエン、アクリロニトリル、フッ化オレフィン等が挙げられる。
Examples of the acrylate and / or methacrylate used include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate , Hydroxyalkyl (meth) acrylates such as 2-hydroxypropyl (meth) acrylate; perfluoroalkyl (meth) acrylates having 1 to 10 carbon atoms. Among these, methyl methacrylate, butyl methacrylate and 2-ethylhexyl acrylate are preferable, and a combination of methyl methacrylate, butyl methacrylate and 2-ethylhexyl acrylate is more preferable.
As monomers other than acrylate and / or methacrylate, styrene, substituted styrene, vinyl acetate, (meth) acrylic acid, maleic anhydride, maleic acid ester, fumaric acid ester, vinyl chloride, vinylidene chloride, ethylene, propylene, butadiene , Acrylonitrile, fluorinated olefin, and the like.
一般式（２）で表されるジメチルポリシロキサン化合物(C1)を含むモノマーを重合させるには、通常のラジカル重合法に従い、例えば、ラジカル重合開始剤の存在下、溶液重合、乳化重合、懸濁重合、バルク重合等により行うことができる。
得られるアクリル−シリコーン系グラフト共重合体は、重量平均分子量が、３０００〜２０００００であるのが好ましく、５０００〜１０００００がより好ましい。
In order to polymerize the monomer containing the dimethylpolysiloxane compound (C1) represented by the general formula (2), according to a normal radical polymerization method, for example, in the presence of a radical polymerization initiator, solution polymerization, emulsion polymerization, suspension It can be carried out by polymerization, bulk polymerization or the like.
The resulting acrylic-silicone graft copolymer preferably has a weight average molecular weight of 3000 to 200000, more preferably 5000 to 100,000.
アクリル−シリコーン系グラフト共重合体としては、一般式（２）で表されるジメチルポリシロキサン化合物(C1)と、アクリレート及び／又はメタクリレートを主体とするラジカル重合性モノマー(C2)を、ラジカル共重合して得られるものが好ましい。
この場合、一般式（２）で表されるジメチルポリシロキサン化合物(C1)と、アクリレート及び／又はメタクリレートを主体とするラジカル重合性モノマー(C2)の重合比率(C1)／(C2)は、１／１９〜２／１であるのが好ましい。
また、アクリル−シリコーン系グラフト共重合体としては、ＫＰ５４５、ＫＰ５４９、ＫＰ５５０（信越化学工業社製）等の市販品を用いることができる。
As the acrylic-silicone graft copolymer, a dimethylpolysiloxane compound (C1) represented by the general formula (2) and a radical polymerizable monomer (C2) mainly composed of acrylate and / or methacrylate are radically copolymerized. What is obtained is preferable.
In this case, the polymerization ratio (C1) / (C2) of the dimethylpolysiloxane compound (C1) represented by the general formula (2) and the radical polymerizable monomer (C2) mainly composed of acrylate and / or methacrylate is 1 / 19 to 2/1 is preferable.
Commercially available products such as KP545, KP549, and KP550 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as the acrylic-silicone graft copolymer.
成分（Ｃ）としては、フッ素変性シリコーン樹脂がより好ましい。
成分（Ｃ）は、フッ素変性シリコーン樹脂及びアクリル−シリコーン系グラフト共重合体から選ばれる１種又は２種以上を用いることができ、フッ素変性シリコーン樹脂とアクリル−シリコーン系グラフト共重合体を組み合わせて用いることもできる。
成分（Ｃ）の含有量は、カバー力や塗布中ののびに優れ、化粧料を肌に均一に塗布することができ、肌なじみが早い点から、全組成中に０．０１質量％以上であり、０．０５質量％以上が好ましく、０．１質量％以上がより好ましく、１質量％以上がさらに好ましく、２５質量％以下であり、２０質量％以下が好ましく、１５質量％以下がより好ましく、１０質量％以下がさらに好ましい。また、成分（Ｃ）の含有量は、全組成中に、０．０１〜２５質量％であり、０．０５〜２０質量％が好ましく、０．１〜１５質量％がより好ましく、１〜１０質量％がさらに好ましい。
As the component (C), a fluorine-modified silicone resin is more preferable.
As the component (C), one or more selected from fluorine-modified silicone resins and acrylic-silicone graft copolymers can be used, and the fluorine-modified silicone resin and acrylic-silicone graft copolymer are combined. It can also be used.
The content of component (C) is excellent in covering power and spreading during application, can apply cosmetics evenly to the skin, and has a fast skin familiarity. Yes, 0.05 mass% or more is preferable, 0.1 mass% or more is more preferable, 1 mass% or more is more preferable, 25 mass% or less is preferable, 20 mass% or less is preferable, and 15 mass% or less is more preferable. 10 mass% or less is more preferable. Moreover, content of a component (C) is 0.01-25 mass% in the whole composition, 0.05-20 mass% is preferable, 0.1-15 mass% is more preferable, 1-10 More preferred is mass%.
本発明において、成分（Ｃ）に対する成分（Ａ）の質量割合（Ａ）／（Ｃ）は、パウダーファンデーションをスポンジで重ね付け使用したときの塗布初期のひっかかり感が少なく、塗布中ののびに優れ、塗布直後の白浮きが抑制されるとともに、肌のハリ感が得られ、肌荒れの目立ちを抑制する点から、０．０３以上であり、０．０５以上が好ましく、０．１以上がより好ましく、０．３以上がさらに好ましく、５０以下であり、４０以下が好ましく、１５以下がより好ましく、６以下がさらに好ましい。また、成分（Ｃ）に対する成分（Ａ）の質量割合（Ａ）／（Ｃ）は、０．０３〜５０であり、０．０５〜４０が好ましく、０．１〜１５がより好ましく、０．３〜６がさらに好ましい。 In the present invention, the mass ratio (A) / (C) of the component (A) to the component (C) is less likely to be caught in the initial stage of application when the powder foundation is overlapped with a sponge and is excellent in spreading during application. From the point that whitening immediately after application is suppressed, a firmness of the skin is obtained, and roughness of the skin is suppressed, it is 0.03 or more, preferably 0.05 or more, and more preferably 0.1 or more. 0.3 or more is more preferable, 50 or less, 40 or less is preferable, 15 or less is more preferable, and 6 or less is more preferable. Moreover, mass ratio (A) / (C) of the component (A) with respect to a component (C) is 0.03-50, 0.05-40 are preferable, 0.1-15 are more preferable, and 0.1. 3-6 are more preferable.
本発明の油中水型乳化化粧料は、さらに、（Ｄ）揮発性シリコーン油を含有することができ、肌に塗布したときに良好な使用感を与えることができる。揮発性とは、３５〜８７℃の引火点を有するものである。
揮発性シリコーン油としては、例えば、ジメチルポリシロキサン（１．５ｃｓ）、ジメチルポリシロキサン（２ｃｓ）等の直鎖状ジメチルポリシロキサン；トリス（トリメチルシリル）メチルシラン、テトラキス（トリメチルシリル）シラン等の分岐状シロキサン；オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン、ドデカメチルシクロヘキサシロキサン等の環状ジメチルシロキサンなどが挙げられる。
The water-in-oil emulsified cosmetic of the present invention can further contain (D) a volatile silicone oil, and can give a good feeling when used on the skin. Volatile has a flash point of 35-87 ° C.
Examples of the volatile silicone oil include linear dimethylpolysiloxanes such as dimethylpolysiloxane (1.5cs) and dimethylpolysiloxane (2cs); branched siloxanes such as tris (trimethylsilyl) methylsilane and tetrakis (trimethylsilyl) silane; Examples thereof include cyclic dimethylsiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.
成分（Ｄ）は、１種又は２種以上を用いることができ、肌へののびに優れ、肌に塗布後、成分（Ｄ）が肌から揮散した後の肌の使用感に優れる点から、含有量は、全組成中に２質量％以上が好ましく、５質量％以上がより好ましく、１０質量％以上がさらに好ましく、４０質量％以下が好ましく、３０質量％以下がより好ましく、２３質量％以下がさらに好ましい。また、成分（Ｄ）の含有量は、全組成中に、２〜４０質量％が好ましく、５〜３０質量％がより好ましく、１０〜２３質量％がさらに好ましい。 Component (D) can be used singly or in combination of two or more, and is excellent in spreading to the skin, and after being applied to the skin, the component (D) is excellent in the feeling of use after evaporating from the skin. The content is preferably 2% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, and 23% by mass or less in the total composition. Is more preferable. Moreover, 2-40 mass% is preferable in the whole composition, as for content of a component (D), 5-30 mass% is more preferable, and 10-23 mass% is further more preferable.
本発明において、（Ｅ）水の含有量は、使用感や安定性に優れる点から、全組成中に１質量％以上が好ましく、１０質量％以上がより好ましく、２５質量％以上がさらに好ましく、７０質量％以下が好ましく、５５質量％以下がより好ましく、４５質量％以下がさらに好ましい。また、（Ｅ）水の含有量は、全組成中に１〜７０質量％が好ましく、１０〜５５質量％がより好ましく、２５〜４５質量％がさらに好ましい。 In the present invention, the content of (E) water is preferably 1% by mass or more, more preferably 10% by mass or more, and even more preferably 25% by mass or more in the total composition from the viewpoint of excellent usability and stability. 70 mass% or less is preferable, 55 mass% or less is more preferable, and 45 mass% or less is further more preferable. Moreover, 1-70 mass% is preferable in the whole composition, and, as for content of (E) water, 10-55 mass% is more preferable, and 25-45 mass% is further more preferable.
本発明の油中水型乳化化粧料は、前記成分のほか、通常の化粧料に用いられる成分、例えば、成分（Ａ）、（Ｂ）以外の粉体、前記以外の油性成分、界面活性剤、顔料、水溶性及び油溶性ポリマー、エタノール、多価アルコール、防腐剤、酸化防止剤、色素、増粘剤、pH調整剤、香料、紫外線吸収剤、保湿剤、血行促進剤、冷感剤、制汗剤、殺菌剤、皮膚賦活剤、保湿剤などを含有することができる。 The water-in-oil emulsified cosmetic of the present invention includes the components used in ordinary cosmetics in addition to the above components, for example, powders other than components (A) and (B), oily components other than those described above, and surfactants. , Pigments, water-soluble and oil-soluble polymers, ethanol, polyhydric alcohols, preservatives, antioxidants, dyes, thickeners, pH adjusters, fragrances, ultraviolet absorbers, moisturizers, blood circulation promoters, cooling sensitizers, Antiperspirants, bactericides, skin activators, humectants and the like can be included.
本発明の油中水型乳化化粧料は、通常の方法に従って製造することができ、剤型としては、液状、乳液状、ペースト状、クリーム状、ジェル状等の剤型にすることができ、乳液状、クリーム状が好ましい。
また、本発明の油中水型乳化化粧料は、化粧下地、ファンデーション、コンシーラー；ほお紅、アイシャドウ、マスカラ、アイライナー、アイブロウ、オーバーコート剤、口紅等のメイクアップ化粧料；日やけ止め乳液、日焼け止めクリーム等の紫外線防御化粧料などとして適用することができる。なかでも、化粧下地、リキッドファンデーションが好ましい。
本発明の油中水型乳化化粧料は、単品のみの使用においても、リキッドファンデーションやパウダーファンデーション・白粉等の粉体化粧料の重ね付けにおいても使用することができる。
The water-in-oil emulsified cosmetic of the present invention can be produced according to a usual method, and the dosage form can be a liquid, emulsion, paste, cream, gel, etc. An emulsion or cream is preferred.
Further, the water-in-oil emulsified cosmetic of the present invention comprises a makeup base, foundation, concealer; makeup cosmetics such as blusher, eyeshadow, mascara, eyeliner, eyebrow, overcoat agent, lipstick; sunscreen emulsion, It can be applied as UV protection cosmetics such as sunscreen cream. Of these, a makeup base and a liquid foundation are preferable.
The water-in-oil emulsified cosmetic of the present invention can be used in the case of using only a single product, or in the case of overlaying powder cosmetics such as liquid foundation, powder foundation, and white powder.
本発明の油中水型乳化化粧料は、配合安定性、使用性、使用感の点から、２５℃における粘度が２０００〜２０００００mPa・sであるのが好ましく、３０００〜１０００００mPa・sがより好ましく、４０００〜７００００mPa・sがさらに好ましい。
ここで、粘度は、２５℃において、粘度計（東機産業社製、VISCOMETER ＴＶＢ-１０形粘度計、回転数６ｒ／ｍｉｎ，ローターＮｏ．Ｍ３、１ｍｉｎ）で測定する。
上述した実施形態に関し、本発明は、更に以下の組成物を開示する。
The water-in-oil emulsified cosmetic of the present invention preferably has a viscosity at 25 ° C. of 2000 to 200000 mPa · s, more preferably 3000 to 100000 mPa · s, from the viewpoint of blending stability, usability, and feeling of use. 4000 to 70000 mPa · s is more preferable.
Here, the viscosity is measured at 25 ° C. with a viscometer (manufactured by Toki Sangyo Co., Ltd., VISCOMETER TVB-10 type viscometer, rotational speed 6 r / min, rotor No. M3, 1 min).
This invention discloses the following compositions further regarding embodiment mentioned above.
＜１＞次の成分（Ａ）、（Ｂ）及び（Ｃ）：
（Ａ）パーフルオロアルキルシランで表面処理した、粒子径０．０１μｍ以上１．０μｍ以下の球状有機樹脂粉体 ０．１〜２０質量％、
（Ｂ）比表面積１０〜１００ｍ2／ｇの微粒子酸化亜鉛 ０．０１〜４０質量％、
（Ｃ）２５℃で固体のフッ素変性シリコーン樹脂又はアクリル−シリコーン系グラフト共重合体 ０．０１〜１０質量％
を含有し、成分（Ｃ）に対する成分（Ａ）の質量割合（Ａ）／（Ｃ）が、０．０３〜５０である油中水型乳化化粧料。
<1> The following components (A), (B) and (C):
(A) 0.1-20% by mass of a spherical organic resin powder having a particle size of 0.01 μm or more and 1.0 μm or less, which is surface-treated with perfluoroalkylsilane,
(B) 0.01 to 40% by mass of fine zinc oxide having a specific surface area of 10 to 100 m 2 / g,
(C) Fluorine-modified silicone resin or acrylic-silicone graft copolymer solid at 25 ° C. 0.01 to 10% by mass
The water-in-oil type emulsified cosmetics whose mass ratio (A) / (C) of the component (A) with respect to a component (C) is 0.03-50.
＜２＞成分（Ａ）が、好ましくは、球状アクリル樹脂粉体であって、アクリル酸エステル、メタクリル酸エステル、アクリル酸アルキレングリコール、メタクリル酸アルキレングリコールから選ばれる１種又は２種以上の重合体がより好ましい前記＜１＞記載の油中水型乳化化粧料。
＜３＞成分（Ａ）の球状有機樹脂粉体が、好ましくは、トリデカフルオロオクチルトリエトキシシランで表面処理されたものである前記＜１＞又は＜２＞記載の油中水型乳化化粧料。
＜４＞成分（Ａ）において、パーフルオロアルキルシランの処理量が、好ましくは、パーフルオロアルキルシランで表面処理した球状有機樹脂粉体の質量に対して、０．０５質量％以上であって、０．１質量％以上がより好ましく、０．５質量％以上がさらに好ましく、５０質量％以下が好ましく、２０質量％以下がより好ましく、８質量％以下がさらに好ましい前記＜１＞〜＜３＞のいずれか１記載の油中水型乳化化粧料。
<2> Component (A) is preferably a spherical acrylic resin powder, and one or more polymers selected from acrylic acid ester, methacrylic acid ester, alkylene glycol acrylate, and alkylene glycol methacrylate More preferably, the water-in-oil emulsified cosmetic according to <1>.
<3> The water-in-oil emulsion cosmetic according to <1> or <2>, wherein the spherical organic resin powder of component (A) is preferably surface-treated with tridecafluorooctyltriethoxysilane .
<4> In component (A), the treatment amount of perfluoroalkylsilane is preferably 0.05% by mass or more based on the mass of the spherical organic resin powder surface-treated with perfluoroalkylsilane, <1> to <3>, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, more preferably 50% by mass or less, more preferably 20% by mass or less, and even more preferably 8% by mass or less. The water-in-oil emulsified cosmetic according to any one of the above.
＜５＞成分（Ａ）のパーフルオロアルキルシランで表面処理した球状有機樹脂粉体が、好ましくは、粒子径０．１〜０．７μｍであって、０．２〜０．５μｍがより好ましい前記＜１＞〜＜４＞のいずれか１記載の油中水型乳化化粧料。
＜６＞成分（Ａ）のパーフルオロアルキルシランで表面処理した球状有機樹脂粉体が、好ましくは、平均粒子径０．１〜０．５μｍであって、０．３〜０．４μｍがより好ましい前記＜１＞〜＜５＞のいずれか１記載の油中水型乳化化粧料。
＜７＞全ての球状有機樹脂粉体の３０質量％以上が、粒子径０．０１μｍ以上１．０μｍ以下の球状有機樹脂粉体であるのが好ましく、５０質量％以上がより好ましく、６５質量％以上がさらに好ましく、７５質量％以上がよりさらに好ましい前記＜１＞〜＜６＞のいずれか１記載の油中水型乳化化粧料。
＜８＞成分（Ａ）の含有量が、好ましくは、全組成中に０．３質量％以上であって、０．５質量％以上がより好ましく、１質量％以上がさらに好ましく、１５質量％以下が好ましく、１０質量％以下がより好ましく、８質量％以下がさらに好ましい前記＜１＞〜＜７＞のいずれか１記載の油中水型乳化化粧料。
<5> The spherical organic resin powder surface-treated with the perfluoroalkylsilane of component (A) is preferably a particle diameter of 0.1 to 0.7 μm, more preferably 0.2 to 0.5 μm. The water-in-oil emulsified cosmetic according to any one of <1> to <4>.
<6> The spherical organic resin powder surface-treated with the perfluoroalkylsilane of component (A) is preferably an average particle diameter of 0.1 to 0.5 μm, more preferably 0.3 to 0.4 μm. The water-in-oil emulsion cosmetic according to any one of <1> to <5>.
<7> 30% by mass or more of all spherical organic resin powders are preferably spherical organic resin powders having a particle size of 0.01 μm or more and 1.0 μm or less, more preferably 50% by mass or more, and 65% by mass. The water-in-oil emulsified cosmetic according to any one of <1> to <6>, wherein the above is more preferable, and 75% by mass or more is more preferable.
The content of <8> component (A) is preferably 0.3% by mass or more in the total composition, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and 15% by mass. The water-in-oil emulsion cosmetic according to any one of the above items <1> to <7>, preferably 10% by mass or less, more preferably 8% by mass or less.
＜９＞成分（Ｂ）の微粒子酸化亜鉛が、好ましくは、比表面積１５〜９５ｍ2／ｇのものである前記＜１＞〜＜８＞のいずれか１記載の油中水型乳化化粧料。
＜１０＞成分（Ｂ）の微粒子酸化亜鉛が、好ましくは、疎水化処理したものであって、シリコーン処理したものがより好ましい前記＜１＞〜＜９＞のいずれか１記載の油中水型乳化化粧料。
＜１１＞成分（Ｂ）の含有量が、好ましくは、全組成中に０．１質量％以上であって、１質量％以上がより好ましく、２０質量％以下が好ましく、８質量％以下がより好ましい前記＜１＞〜＜１０＞のいずれか１記載の油中水型乳化化粧料。
＜１２＞成分（Ｂ）に対する成分（Ａ）の質量割合（Ａ）／（Ｂ）が、好ましくは、０．０５以上であって、０．１以上がより好ましく、０．３以上がさらに好ましく、０．５以上がよりさらに好ましく、２０以下が好ましく、５以下がより好ましく、３以下がさらに好ましく、１以下がよりさらに好ましい前記＜１＞〜＜１１＞のいずれか１記載の油中水型乳化化粧料。
<9> The water-in-oil emulsified cosmetic according to any one of <1> to <8>, wherein the particulate zinc oxide of component (B) is preferably one having a specific surface area of 15 to 95 m 2 / g.
<10> The water-in-oil type according to any one of <1> to <9>, wherein the particulate zinc oxide of the component (B) is preferably hydrophobized and more preferably siliconized Emulsified cosmetic.
The content of the <11> component (B) is preferably 0.1% by mass or more, more preferably 1% by mass or more, preferably 20% by mass or less, and more preferably 8% by mass or less in the total composition. The water-in-oil emulsified cosmetic according to any one of the above <1> to <10>.
<12> The mass ratio (A) / (B) of the component (A) to the component (B) is preferably 0.05 or more, more preferably 0.1 or more, and further preferably 0.3 or more. 0.5 or more is more preferable, 20 or less is preferable, 5 or less is more preferable, 3 or less is more preferable, 1 or less is still more preferable 1 or less The water-in-oil any one of said <1>-<11> Type emulsified cosmetic.
＜１３＞成分（Ｃ）の２５℃で固体のフッ素変性シリコーン樹脂が、好ましくは、下記一般式（１）
Ｒ1 gＳｉＯ(4-g)/2 （１）
（式中、Ｒ1は炭素数１〜８の炭化水素基、フェニル基、水酸基又は一般式−Ｒ2−Ｒｆ（Ｒ2は炭素数２〜６の２価のアルキレン基を示し、Ｒｆは炭素数１〜８のパーフルオロアルキル基を示す）であって、水酸基及び一般式−Ｒ2−Ｒｆを必須とする官能基から任意に選ばれ、ｇは平均数で１．０≦ｇ≦１．８である。尚、複数のＲ1は、同じであっても、異なっても良い）
で表される構造を有するものであって、トリフルオロプロピルジメチル／トリメチルシロキシシリケート（Trifluoropropyldimethyl／Trimethylsiloxysilicate）がより好ましい前記＜１＞〜＜１２＞のいずれか１記載の油中水型乳化化粧料。
＜１４＞成分（Ｃ）のアクリル−シリコーン系グラフト共重合体が、好ましくは、一般式（２）
<13> The fluorine-modified silicone resin that is solid at 25 ° C. of the component (C) is preferably the following general formula (1)
R 1 g SiO (4-g) / 2 (1)
(In the formula, R 1 represents a hydrocarbon group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, or a general formula —R 2 —Rf (R 2 represents a divalent alkylene group having 2 to 6 carbon atoms, and Rf represents carbon A perfluoroalkyl group having a number of 1 to 8), which is arbitrarily selected from functional groups having a hydroxyl group and the general formula -R 2 -Rf as essential, and g is an average number of 1.0 ≦ g ≦ 1. 8) The plurality of R 1 may be the same or different.
The water-in-oil emulsified cosmetic according to any one of the above items <1> to <12>, which has a structure represented by formula (II), and is more preferably trifluoropropyldimethyl / trimethylsiloxysilicate.
<14> The acryl-silicone graft copolymer of component (C) is preferably represented by the general formula (2)
（式中、Ｒ11はメチル基又は水素原子を示し、Ｒ12は、１個又は２個のエーテル結合で遮断されていても良い、炭素数１〜１０の２価の飽和炭化水素基を示し、ｋは３〜３００の数を示す。尚、複数のＲ11、Ｒ12は、同じであっても、異なっても良い）
で表される分子鎖の型末端にラジカル重合性基を有するジメチルポリシロキサン化合物を含むモノマー(C1)を重合させて得られるアクリル−シリコーン系グラフト共重合体であって、一般式（２）で表されるジメチルポリシロキサン化合物(C1)と、アクリレート及び／又はメタクリレートを主体とするラジカル重合性モノマー(C2)を、ラジカル共重合して得られるものがより好ましい前記＜１＞〜＜１２＞のいずれか１記載の油中水型乳化化粧料。
＜１５＞成分（Ｃ）の含有量が、好ましくは、全組成中に０．０５質量％以上であって、０．１質量％以上がより好ましく、１質量％以上がさらに好ましく、２０質量％以下が好ましく、１５質量％以下がより好ましく、１０質量％以下がさらに好ましい前記＜１＞〜＜１４＞のいずれか１記載の油中水型乳化化粧料。
(In the formula, R 11 represents a methyl group or a hydrogen atom, and R 12 represents a divalent saturated hydrocarbon group having 1 to 10 carbon atoms which may be blocked by one or two ether bonds. , K represents a number from 3 to 300. The plurality of R 11 and R 12 may be the same or different.
An acrylic-silicone graft copolymer obtained by polymerizing a monomer (C1) containing a dimethylpolysiloxane compound having a radically polymerizable group at the mold end of the molecular chain represented by formula (2): Of the above <1> to <12>, those obtained by radical copolymerization of the dimethylpolysiloxane compound (C1) and a radical polymerizable monomer (C2) mainly composed of acrylate and / or methacrylate are more preferable. The water-in-oil emulsion cosmetic according to any one of the above.
The content of <15> component (C) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 1% by mass or more, and 20% by mass in the total composition. The water-in-oil emulsified cosmetic according to any one of <1> to <14>, wherein the following is preferable, 15% by mass or less is more preferable, and 10% by mass or less is more preferable.
＜１６＞成分（Ｃ）に対する成分（Ａ）の質量割合（Ａ）／（Ｃ）が、好ましくは、０．０５以上であって、０．１以上がより好ましく、０．３以上がさらに好ましく、４０以下が好ましく、１５以下がより好ましく、６以下がさらに好ましい前記＜１＞〜＜１５＞のいずれか１記載の油中水型乳化化粧料。
＜１７＞さらに、（Ｄ）揮発性シリコーン油を含有することができ、好ましくは、直鎖状ジメチルポリシロキサン、分岐状シロキサン、環状ジメチルシロキサンを含有する前記＜１＞〜＜１５＞のいずれか１記載の油中水型乳化化粧料。
＜１８＞成分（Ｄ）の含有量が、好ましくは、全組成中に２質量％以上であって、５質量％以上がより好ましく、１０質量％以上がさらに好ましく、４０質量％以下が好ましく、３０質量％以下がより好ましく、２３質量％以下がさらに好ましい前記＜１７＞記載の油中水型乳化化粧料。
<16> The mass ratio (A) / (C) of the component (A) to the component (C) is preferably 0.05 or more, more preferably 0.1 or more, and further preferably 0.3 or more. 40 or less, more preferably 15 or less, and even more preferably 6 or less, the water-in-oil emulsified cosmetic according to any one of <1> to <15>.
<17> Further, (D) any one of the above <1> to <15>, which may contain volatile silicone oil, and preferably contains linear dimethylpolysiloxane, branched siloxane, and cyclic dimethylsiloxane. 1. A water-in-oil emulsified cosmetic according to 1.
The content of <18> component (D) is preferably 2% by mass or more in the total composition, more preferably 5% by mass or more, further preferably 10% by mass or more, and preferably 40% by mass or less, 30 mass% or less is more preferable, and 23 mass% or less is further more preferable, The water-in-oil type emulsion cosmetic as described in said <17>.
＜１９＞（Ｅ）水の含有量が、好ましくは、全組成中に１質量％以上であって、１０質量％以上がより好ましく、２５質量％以上がさらに好ましく、７０質量％以下が好ましく、５５質量％以下がより好ましく、４５質量％以下がさらに好ましい前記＜１＞〜＜１８＞のいずれか１記載の油中水型乳化化粧料。
＜２０＞２５℃における粘度が、好ましくは、２０００〜２０００００mPa・sであって、３０００〜１０００００mPa・sがより好ましく、４０００〜７００００mPa・sがさらに好ましい前記＜１＞〜＜１９＞のいずれか１記載の油中水型乳化化粧料。
<19> (E) The content of water is preferably 1% by mass or more in the total composition, more preferably 10% by mass or more, further preferably 25% by mass or more, and preferably 70% by mass or less, The water-in-oil emulsified cosmetic according to any one of <1> to <18>, wherein 55% by mass or less is more preferable, and 45% by mass or less is more preferable.
<20> The viscosity at 25 ° C. is preferably 2000 to 200000 mPa · s, more preferably 3000 to 100000 mPa · s, and further preferably 4000 to 70000 mPa · s, and any one of the above <1> to <19> The water-in-oil emulsified cosmetic described.
実施例１〜９及び比較例１〜３
表１に示す組成の油中水型乳化化粧料（ファンデーション）を製造し、塗布初期のひっかかり感のなさ、塗布直後の肌の白浮きのなさ、塗布直後の肌の荒れの目立たなさ及び塗布直後の肌のハリを評価した。結果を表１に併せて示す。
Examples 1-9 and Comparative Examples 1-3
Manufactures water-in-oil emulsified cosmetics (foundations) having the composition shown in Table 1, with no initial catching feeling, no whitening of skin immediately after application, no noticeable rough skin immediately after application, and immediately after application The skin firmness was evaluated. The results are also shown in Table 1.
（製法）
粉体相成分を混合粉砕し、別途混合した油相成分に添加してディスパーで分散した。その後、水相成分を添加し、ディスパーで分散後、ホモミキサーで撹拌することにより、油中水型乳化化粧料を得た。
(Manufacturing method)
The powder phase component was mixed and ground, added to the separately mixed oil phase component, and dispersed with a disper. Then, the water phase component was added, dispersed with a disper, and then stirred with a homomixer to obtain a water-in-oil emulsified cosmetic.
（評価方法）
専門評価者１０名が、各油中水型乳化化粧料を肌に塗布したとき、塗布初期のひっかかり感のなさ、塗布直後の肌の白浮きのなさ、塗布直後の肌の荒れの目立たなさ及び塗布直後の肌のハリを、以下の基準で官能評価した。なお、表中の評価結果は、専門評価者１０名の合計点で示した。
(Evaluation method)
When 10 expert evaluators applied each water-in-oil type emulsified cosmetic to the skin, there was no feeling of catching at the initial stage of application, no whitening of the skin immediately after application, no noticeable roughness of the skin immediately after application, and The firmness of the skin immediately after application was sensory evaluated according to the following criteria. In addition, the evaluation result in a table | surface was shown by the total score of 10 expert evaluators.
（１）塗布初期のひっかかり感のなさ：
５；塗布初期のひっかかり感を感じない。
４；塗布初期のひっかかり感をほとんど感じない。
３；塗布初期のひっかかり感を少し感じる。
２；塗布初期のひっかかり感を感じる。
１；塗布初期のひっかかり感をかなり感じる。
(1) No initial catching feeling:
5: Feels not caught in the initial stage of application.
4; Almost no initial catching feeling.
3; A slight feeling of catching at the initial stage of application is felt.
2; Feeling a catch at the initial stage of application.
1; A feeling of catching at the initial stage of application is considerably felt.
（２）塗布直後の白浮きのなさ：
５；肌の白浮きが目立たない。
４；肌の白浮きがほとんど目立たない。
３；肌の白浮きが少し目立つ。
２；肌の白浮きが目立つ。
１；肌の白浮きが非常に目立つ。
(2) No whitening immediately after application:
5; Skin whitening is not noticeable.
4: The whitening of the skin is hardly noticeable.
3; Whitening of the skin is a little noticeable.
2; Whitening of the skin is conspicuous.
1: Whitening of the skin is very noticeable.
（３）塗布直後の肌の荒れの目立たなさ：
５；肌の荒れが目立たない。
４；肌の荒れがほとんど目立たない。
３；肌の荒れが少し目立つ。
２；肌の荒れが目立つ。
１；肌の荒れが非常に目立つ。
(3) Inconspicuous rough skin immediately after application:
5; Rough skin is not noticeable.
4; rough skin is hardly noticeable.
3; Rough skin is a little noticeable.
2; rough skin is conspicuous.
1: The rough skin is very conspicuous.
（４）塗布直後の肌のハリ：
５；頬に非常にハリがあるように見える。
４；頬にハリがあるように見える。
３；頬に少しハリがあるように見える。
２；頬にあまりハリがなく見える。
１；頬にハリがなく見える。
(4) Skin firmness immediately after application:
5; The cheeks look very firm.
4; The cheeks appear to be firm.
3; It seems that there is a little elasticity on the cheek.
2; The cheeks appear not to be very firm.
1; There is no elasticity on the cheek.
Claims (7)
（Ａ）パーフルオロアルキルシランで表面処理した、粒子径０．０１μｍ以上１．０μｍ以下の球状有機樹脂粉体 ０．１〜２０質量％、
（Ｂ）比表面積１０〜１００ｍ2／ｇの微粒子酸化亜鉛 ０．０１〜４０質量％、
（Ｃ）２５℃で固体のフッ素変性シリコーン樹脂又はアクリル−シリコーン系グラフト共重合体 ０．０１〜１０質量％
を含有し、成分（Ｃ）に対する成分（Ａ）の質量割合（Ａ）／（Ｃ）が、０．０３〜５０である油中水型乳化化粧料。 The following components (A), (B) and (C):
(A) 0.1-20% by mass of a spherical organic resin powder having a particle size of 0.01 μm or more and 1.0 μm or less, which is surface-treated with perfluoroalkylsilane,
(B) 0.01 to 40% by mass of fine zinc oxide having a specific surface area of 10 to 100 m 2 / g,
(C) Fluorine-modified silicone resin or acrylic-silicone graft copolymer solid at 25 ° C. 0.01 to 10% by mass
The water-in-oil type emulsified cosmetics whose mass ratio (A) / (C) of the component (A) with respect to a component (C) is 0.03-50.
Ｒ1 gＳｉＯ(4-g)/2 （１）
（式中、Ｒ1は炭素数１〜８の炭化水素基、フェニル基、水酸基又は一般式−Ｒ2−Ｒｆ（Ｒ2は炭素数２〜６の２価のアルキレン基を示し、Ｒｆは炭素数１〜８のパーフルオロアルキル基を示す）であって、水酸基及び一般式−Ｒ2−Ｒｆを必須とする官能基から任意に選ばれ、ｇは平均数で１．０≦ｇ≦１．８である）
で表される構造を有する、２５℃で固体のフッ素変性シリコーン樹脂である請求項１〜５のいずれか１項記載の油中水型乳化化粧料。 Component (C) is represented by the following general formula (1)
R 1 g SiO (4-g) / 2 (1)
(In the formula, R 1 represents a hydrocarbon group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, or a general formula —R 2 —Rf (R 2 represents a divalent alkylene group having 2 to 6 carbon atoms, and Rf represents carbon A perfluoroalkyl group having a number of 1 to 8), which is arbitrarily selected from functional groups having a hydroxyl group and the general formula -R 2 -Rf as essential, and g is an average number of 1.0 ≦ g ≦ 1. 8)
The water-in-oil emulsified cosmetic according to any one of claims 1 to 5, which is a fluorine-modified silicone resin solid at 25 ° C having a structure represented by:
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| JP2014101311A (en) * | 2012-11-20 | 2014-06-05 | Kao Corp | Water-in-oil type emulsion cosmetic |
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| WO2019111831A1 (en) * | 2017-12-04 | 2019-06-13 | 花王株式会社 | Water-in-oil type emulsion cosmetic |
| JP2019099576A (en) * | 2017-12-04 | 2019-06-24 | 花王株式会社 | Water-in-oil type emulsion cosmetic |
| CN111432793A (en) * | 2017-12-04 | 2020-07-17 | 花王株式会社 | Water-in-oil type emulsion cosmetic |
| JP7272783B2 (en) | 2017-12-04 | 2023-05-12 | 花王株式会社 | Water-in-oil emulsified cosmetic |
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