JP6075845B2 - Water-in-oil emulsified cosmetic - Google Patents
Water-in-oil emulsified cosmetic Download PDFInfo
- Publication number
- JP6075845B2 JP6075845B2 JP2012238101A JP2012238101A JP6075845B2 JP 6075845 B2 JP6075845 B2 JP 6075845B2 JP 2012238101 A JP2012238101 A JP 2012238101A JP 2012238101 A JP2012238101 A JP 2012238101A JP 6075845 B2 JP6075845 B2 JP 6075845B2
- Authority
- JP
- Japan
- Prior art keywords
- mass
- water
- preferable
- component
- emulsified cosmetic
- 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.)
- Active
Links
- 239000002537 cosmetic Substances 0.000 title claims description 51
- 239000000843 powder Substances 0.000 claims description 66
- 239000001023 inorganic pigment Substances 0.000 claims description 49
- 239000002245 particle Substances 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 38
- 229920000642 polymer Polymers 0.000 claims description 38
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 36
- 229920001296 polysiloxane Polymers 0.000 claims description 28
- 239000011787 zinc oxide Substances 0.000 claims description 20
- 238000002834 transmittance Methods 0.000 claims description 12
- 239000000049 pigment Substances 0.000 claims description 10
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000003921 oil Substances 0.000 description 41
- -1 polysiloxane unit Polymers 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 235000014692 zinc oxide Nutrition 0.000 description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 18
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 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 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 239000010419 fine particle Substances 0.000 description 8
- 239000002736 nonionic surfactant Substances 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 4
- 239000005871 repellent Substances 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003256 environmental substance Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000002940 repellent Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001256 steam distillation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000007762 w/o emulsion Substances 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- 239000004909 Moisturizer Substances 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 229940073609 bismuth oxychloride Drugs 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229940105847 calamine Drugs 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 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 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000010696 ester oil Substances 0.000 description 2
- FCDZZFLRLVQGEH-UHFFFAOYSA-N ethane-1,2-diol;prop-2-enoic acid Chemical compound OCCO.OC(=O)C=C FCDZZFLRLVQGEH-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 229910052864 hemimorphite Inorganic materials 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000007561 laser diffraction method Methods 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 230000001333 moisturizer Effects 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000790 scattering method Methods 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 230000000475 sunscreen effect Effects 0.000 description 2
- 239000000516 sunscreening agent Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CPYIZQLXMGRKSW-UHFFFAOYSA-N zinc;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+3].[Fe+3].[Zn+2] CPYIZQLXMGRKSW-UHFFFAOYSA-N 0.000 description 2
- DSEKYWAQQVUQTP-XEWMWGOFSA-N (2r,4r,4as,6as,6as,6br,8ar,12ar,14as,14bs)-2-hydroxy-4,4a,6a,6b,8a,11,11,14a-octamethyl-2,4,5,6,6a,7,8,9,10,12,12a,13,14,14b-tetradecahydro-1h-picen-3-one Chemical compound C([C@H]1[C@]2(C)CC[C@@]34C)C(C)(C)CC[C@]1(C)CC[C@]2(C)[C@H]4CC[C@@]1(C)[C@H]3C[C@@H](O)C(=O)[C@@H]1C DSEKYWAQQVUQTP-XEWMWGOFSA-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
- KRQUFUKTQHISJB-YYADALCUSA-N 2-[(E)-N-[2-(4-chlorophenoxy)propoxy]-C-propylcarbonimidoyl]-3-hydroxy-5-(thian-3-yl)cyclohex-2-en-1-one Chemical compound CCC\C(=N/OCC(C)OC1=CC=C(Cl)C=C1)C1=C(O)CC(CC1=O)C1CCCSC1 KRQUFUKTQHISJB-YYADALCUSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241001237961 Amanita rubescens Species 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000004593 Epoxy Substances 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000004166 Lanolin Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- AUNAPVYQLLNFOI-UHFFFAOYSA-L [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O Chemical compound [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O AUNAPVYQLLNFOI-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- BTHCBXJLLCHNMS-UHFFFAOYSA-N acetyloxysilicon Chemical compound CC(=O)O[Si] BTHCBXJLLCHNMS-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000005257 alkyl acyl group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 229920006318 anionic polymer Polymers 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
- DPSWNBLFKLUQTP-UHFFFAOYSA-N bismuth vanadium Chemical compound [V].[Bi] DPSWNBLFKLUQTP-UHFFFAOYSA-N 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 239000004204 candelilla wax Substances 0.000 description 1
- 235000013868 candelilla wax Nutrition 0.000 description 1
- 229940073532 candelilla wax Drugs 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000035597 cooling sensation Effects 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IUJAMGNYPWYUPM-UHFFFAOYSA-N hentriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC IUJAMGNYPWYUPM-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- RWGFKTVRMDUZSP-UHFFFAOYSA-N isopropyl-benzene Natural products CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 235000019388 lanolin Nutrition 0.000 description 1
- 229940039717 lanolin Drugs 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 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
- 239000002562 thickening agent Substances 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
- 239000008096 xylene Substances 0.000 description 1
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.
従来、化粧料の化粧持ちや使用感を改善するため、フッ素変性シリコーン（例えば、特許文献１）を含有する化粧料や、フッ素変性シリコーンと微粒子酸化亜鉛を組み合わせた化粧料（特許文献２）などが提案されている。 Conventionally, cosmetics containing fluorine-modified silicone (for example, Patent Document 1), cosmetics combining fluorine-modified silicone and fine particle zinc oxide (Patent Document 2), etc. in order to improve the cosmetic durability and feeling of use of cosmetics, etc. Has been proposed.
フッ素変性シリコーンと微粒子酸化亜鉛を組み合わせ、油中水型乳化化粧料とした場合、微粒子酸化亜鉛が凝集しやすいため、肌に塗布した後、パウダーファンデーションを重ねて仕上げると、肌上でむらや粉っぽさが生じ、厚ぼったい仕上がりになってしまうという課題があった。また、パウダーファンデーションの塗布時の初期のひっかかり感や、ごわつき感を生じるという課題も見出した。 When a fluorine-modified silicone and fine-particle zinc oxide are combined to form a water-in-oil emulsion cosmetic, the fine-particle zinc oxide tends to agglomerate. There was a problem that the finish was thick and the finish was thick. In addition, the present inventors also found a problem that an initial catching feeling and a feeling of stickiness at the time of applying the powder foundation were generated.
本発明者らは、無機顔料を特定の割合で内包するポリマー粉体と、特定のフッ素変性シリコーン及び微粒子酸化亜鉛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 present inventors have used a polymer powder encapsulating an inorganic pigment in a specific ratio, a specific fluorine-modified silicone, and a fine particle zinc oxide in combination at a specific ratio, thereby solving the above-described problem in water-in-oil emulsification. We found that cosmetics can be obtained.
本発明は、次の成分（Ａ）、（Ｂ）及び（Ｃ）：
（Ａ）無機顔料を内包するポリマー粉体であって、（ａ）白色無機顔料、（ｂ）赤色無機顔料、及び（ｃ）黄色無機顔料を含み、（ａ）：（ｂ）：（ｃ）の質量割合が７０〜９９：０．１〜１０：０．１〜２０であるポリマー粉体 ０．３〜２５質量％、
（Ｂ）下記一般式（１）及び（２）
The present invention includes the following components (A), (B) and (C):
(A) A polymer powder containing an inorganic pigment, comprising (a) a white inorganic pigment, (b) a red inorganic pigment, and (c) a yellow inorganic pigment, (a): (b): (c) Polymer powder having a mass ratio of 70 to 99: 0.1 to 10: 0.1 to 0.3 to 25% by mass,
(B) The following general formulas (1) and (2)
（式中、Ｒｆは炭素数６の直鎖又は分岐鎖のパーフルオロアルキル基を示し、Ｒ1、Ｒ2及びＲ3は、同一又は異なって、炭素数１〜６の直鎖又は分岐鎖のアルキル基を示し、ｍは２〜６の数を示し、ｎは１〜６の数を示し、ｐは３〜５０の数を示し、ｓは１〜５の数を示し、ｐ及びｓの割合が、０．６６≦ｐ／（ｐ＋ｓ）≦０．９である）
で表されるポリシロキサン単位を有するフッ素変性シリコーン ０．０１〜５０質量％、
（Ｃ）比表面積１０〜１００ｍ2／ｇの微粒子酸化亜鉛 ０．１〜１５質量％
を含有し、成分（Ａ）と成分（Ｂ）の質量割合（Ａ）／（Ｂ）が、０．０３〜１０である油中水型乳化化粧料を提供するものである。
(In the formula, Rf represents a straight-chain or branched perfluoroalkyl group having 6 carbon atoms, and R 1 , R 2 and R 3 are the same or different and each represents a straight-chain or branched chain having 1 to 6 carbon atoms. Represents an alkyl group, m represents a number of 2 to 6, n represents a number of 1 to 6, p represents a number of 3 to 50, s represents a number of 1 to 5, and the ratio of p and s Is 0.66 ≦ p / (p + s) ≦ 0.9)
0.01 to 50% by mass of a fluorine-modified silicone having a polysiloxane unit represented by
(C) Fine particle zinc oxide having a specific surface area of 10 to 100 m 2 / g 0.1 to 15% by mass
And a water-in-oil emulsified cosmetic in which the mass ratio (A) / (B) of the component (A) and the component (B) is 0.03 to 10.
本発明の油中水型乳化化粧料は、肌に塗布後、パウダーファンデーションを塗布した時でも、肌へのむらづきや粉っぽさが抑制され、仕上がりの厚ぼったさを抑え、自然な仕上がりが得られ、塗布時初期のひっかかり感や、肌のごわつき感が抑制されるものである。特に、パウダーファンデーションを塗布する前に用いる化粧下地として好適である。 The water-in-oil emulsified cosmetic of the present invention has a natural finish that suppresses unevenness and powderiness on the skin even when a powder foundation is applied after application to the skin, suppressing the thickness of the finish. In other words, it is possible to suppress a feeling of initial catching at the time of application and a feeling of firmness of the skin. In particular, it is suitable as a makeup base used before applying a powder foundation.
本発明で用いる成分（Ａ）のポリマー粉体は、ポリマーを母材として、その中に白色無機顔料、赤色無機顔料、黄色無機顔料を内包するものである。好ましくは、ポリマー粒子中に、白色無機顔料、赤色無機顔料、黄色無機顔料が分散して存在するものや、ポリマー粒子表面に、白色無機粉体、赤色無機顔料、黄色無機顔料が存在するもの等が挙げられ、特に、ポリマー粒子中に、白色無機粉体、赤色無機顔料、黄色無機顔料が均一に分散しているものが好ましい。 The polymer powder of the component (A) used in the present invention contains a polymer as a base material and encloses a white inorganic pigment, a red inorganic pigment, and a yellow inorganic pigment therein. Preferably, white inorganic pigments, red inorganic pigments, yellow inorganic pigments are dispersed in the polymer particles, or white inorganic powders, red inorganic pigments, yellow inorganic pigments are present on the surface of the polymer particles. In particular, it is preferable that the white inorganic powder, the red inorganic pigment, and the yellow inorganic pigment are uniformly dispersed in the polymer particles.
（ａ）白色無機顔料としては、例えば、酸化アルミニウム、酸化カルシウム、酸化マグネシウム、酸化亜鉛、酸化ジルコニウム、二酸化チタン（ルチル型、アナターゼ型等）等の金属酸化物；酸化亜鉛／二酸化チタン複合酸化物、酸化アルミニウム／酸化マグネシウム複合酸化物、酸化カルシウム／酸化ジルコニウム複合酸化物等の複合金属酸化物；硫酸バリウム等の硫酸塩；炭酸カルシウム等の炭酸塩などが挙げられ、これらの白色無機顔料は、単独又は２種以上を混合して用いることができる。これらのうち、化粧料中における安定性等の観点から、二酸化チタン、酸化アルミニウム、酸化亜鉛、酸化ジルコニウム等の金属酸化物、酸化亜鉛／二酸化チタン複合酸化物が好ましく、二酸化チタンがより好ましい。 (A) Examples of white inorganic pigments include metal oxides such as aluminum oxide, calcium oxide, magnesium oxide, zinc oxide, zirconium oxide, titanium dioxide (rutile type, anatase type, etc.); zinc oxide / titanium dioxide composite oxide Composite metal oxides such as aluminum oxide / magnesium oxide composite oxide, calcium oxide / zirconium oxide composite oxide; sulfates such as barium sulfate; carbonates such as calcium carbonate, and the like. It can use individually or in mixture of 2 or more types. Of these, metal oxides such as titanium dioxide, aluminum oxide, zinc oxide, and zirconium oxide, and zinc oxide / titanium dioxide composite oxide are preferable, and titanium dioxide is more preferable from the viewpoint of stability in cosmetics.
（ｂ）赤色無機顔料としては、例えば、ベンガラ、酸化鉄／酸化チタン焼結物、カドミウムレッド、モリブデンレッド等が挙げられ、ベンガラが好ましい。
（ｃ）黄色無機顔料としては、例えば、黄酸化鉄、酸化セリウム、ビスマスバナジウムイエロー、黄鉛、カドミウムイエロー等が挙げられ、黄酸化鉄が好ましい。
(B) Examples of red inorganic pigments include Bengala, iron oxide / titanium oxide sintered product, cadmium red, and molybdenum red. Bengala is preferable.
Examples of (c) yellow inorganic pigments include yellow iron oxide, cerium oxide, bismuth vanadium yellow, yellow lead, and cadmium yellow, and yellow iron oxide is preferable.
（ａ）白色無機顔料、（ｂ）赤色無機顔料、及び（ｃ）黄色無機顔料の平均粒径は、それぞれ０．０１〜０．５μｍであるのが、ポリマー粉体中に均一に分散させる点から好ましい。 The average particle size of (a) white inorganic pigment, (b) red inorganic pigment, and (c) yellow inorganic pigment is 0.01 to 0.5 μm, respectively, and is uniformly dispersed in the polymer powder. To preferred.
（ａ）白色無機粉体、（ｂ）赤色無機顔料、（ｃ）黄色無機顔料のポリマー粉体中の質量割合は、光の短波長側をカットして、毛穴・色ムラを目立たないようにさせる観点から、（ａ）：（ｂ）：（ｃ）＝７０〜９９：０．１〜１０：０．１〜２０であり、７０〜９７：１〜１０：２〜２０が好ましく、８０〜９７：１〜５：２〜１５がより好ましく、９０〜９７：１〜３：２〜７が更に好ましい。 The mass ratio of (a) white inorganic powder, (b) red inorganic pigment, and (c) yellow inorganic pigment in the polymer powder is such that the short wavelength side of the light is cut so that pores and color unevenness are not noticeable. (A) :( b) :( c) = 70 to 99: 0.1 to 10: 0.1 to 20, 70 to 97: 1 to 10: 2 to 20 is preferable, and 80 to 97: 1 to 5: 2-15 are more preferable, and 90 to 97: 1 to 3: 2 to 7 are still more preferable.
無機顔料には、例えば、撥水性を付与するシリコーン処理、撥水・撥油性を付与するフッ素処理等の表面処理が施されていることが好ましい。シリコーン処理が施された無機顔料は、一般的な有機溶媒中への分散性に優れ、フッ素処理が施された無機顔料は、フッ素系溶媒中への分散性に優れている。 The inorganic pigment is preferably subjected to a surface treatment such as a silicone treatment for imparting water repellency and a fluorine treatment for imparting water and oil repellency. An inorganic pigment subjected to silicone treatment is excellent in dispersibility in a general organic solvent, and an inorganic pigment subjected to fluorine treatment is excellent in dispersibility in a fluorine-based solvent.
ポリマー粉体中における無機顔料の含有量は、粉体の光透過性と光散乱性のバランス面から、合計で５〜４０質量％であるのが好ましく、１０〜２０質量％であるのがより好ましい。
なお、無機顔料としては、前記（ａ）、（ｂ）及び（ｃ）以外に、黒色無機顔料（黒酸化鉄等）や、セラミック顔料（陶磁器顔料）などを含有することができる。
The content of the inorganic pigment in the polymer powder is preferably 5 to 40% by mass in total, more preferably 10 to 20% by mass, from the balance of light transmittance and light scattering of the powder. preferable.
In addition to (a), (b) and (c), the inorganic pigment can contain a black inorganic pigment (black iron oxide or the like), a ceramic pigment (ceramic pigment), or the like.
一方、母材となる前記ポリマー粉体として用いられるポリマーとしては、化粧料に通常用いられるものであれば特に限定されるものではなく、例えば、ポリメチルメタクリレート等の（メタ）アクリル系樹脂、ナイロン、ポリエステル、ポリエチレン、ポリスチレン、ポリウレタン、シリコーン樹脂、セルロース等が挙げられる。なかでも、（メタ）アクリル系樹脂、セルロースが好ましく、（メタ）アクリル系樹脂がより好ましい。
また、重合体が透明又は半透明であり、その製造が容易であって、粒子強度及び耐溶剤性に優れるものが好ましく、架橋ポリマーが好ましく、ラウリル（メタ）アクリレート−エチレングリコールジ（メタ）アクリレートコポリマーがさらに好ましい。
On the other hand, the polymer used as the polymer powder as the base material is not particularly limited as long as it is usually used in cosmetics. For example, (meth) acrylic resins such as polymethyl methacrylate, nylon , Polyester, polyethylene, polystyrene, polyurethane, silicone resin, cellulose and the like. Especially, (meth) acrylic-type resin and a cellulose are preferable and (meth) acrylic-type resin is more preferable.
In addition, the polymer is transparent or translucent, and its production is easy, and those having excellent particle strength and solvent resistance are preferred, a crosslinked polymer is preferred, and lauryl (meth) acrylate-ethylene glycol di (meth) acrylate is preferred. More preferred are copolymers.
ポリマーに無機顔料を内包させる方法は、用いられるポリマーの種類により適宜選択することができる。例えば、ポリマーの種類がナイロン樹脂の場合、パラフィン等と環状ラクタムとを混合して、加熱、溶解させ、得られた混合物に、所望量の無機顔料（成分（ａ）、（ｂ）、（ｃ）を含む）の粉末を添加する。これを、かき混ぜながら、重合促進剤、例えば、三塩化リン等を添加してアルカリ重合を行ない、粒子を得る。更に該粒子を濾別し、得られた粒子を、有機溶剤、例えば、イソプロピルアルコール、ベンゼン等又は水で洗浄し、次いで、乾燥する方法等が挙げられる。 The method of encapsulating the inorganic pigment in the polymer can be appropriately selected depending on the type of polymer used. For example, when the type of polymer is nylon resin, paraffin or the like and cyclic lactam are mixed and heated and dissolved, and the resulting mixture is mixed with a desired amount of inorganic pigment (components (a), (b), (c )) Is added. While stirring this, a polymerization accelerator such as phosphorus trichloride is added to perform alkali polymerization to obtain particles. Further, the particles are separated by filtration, and the obtained particles are washed with an organic solvent such as isopropyl alcohol, benzene, or water, and then dried.
また、例えば、ポリマーの種類がシリコーン樹脂の場合、アンモニア、アミン等の水溶液と無機顔料（成分（ａ）、（ｂ）、（ｃ）を含む）の粉末とを混合し、得られた混合物に加水分解性シラン、アルコキシシラン、アセトキシシラン等を混合してアルコキシシラン等を加水分解する。次いで、アルコキシシラン等の加水分解物と、アルコキシシラン等の加水分解物又は加水分解されていないアルコキシシラン等との縮合反応を行ない、粒子を得る。更に該粒子を濾別し、得られた粒子を水洗して乾燥する方法等が挙げられる。 Also, for example, when the type of polymer is a silicone resin, an aqueous solution of ammonia, amine or the like and an inorganic pigment (including components (a), (b), and (c)) powder are mixed, and the resulting mixture is mixed. Hydrolyzable silane, alkoxysilane, acetoxysilane or the like is mixed to hydrolyze alkoxysilane or the like. Next, a condensation reaction between a hydrolyzate such as alkoxysilane and a hydrolyzate such as alkoxysilane or an unhydrolyzed alkoxysilane is performed to obtain particles. Further, there may be mentioned a method of filtering the particles, washing the obtained particles with water and drying.
さらに、例えば、ポリマーの種類が、（メタ）アクリル系樹脂の場合、モノマーとして（メタ）アクリル酸エステル、重合開始剤としてのラウロイルパーオキサイドを混合して溶解し、得られた混合物に、所望量の無機顔料（成分（ａ）、（ｂ）、（ｃ）を含む）を添加して分散させる。得られた分散液をポリビニルアルコール水溶液に添加して分散させ、撹拌しながら加熱して重合（懸濁重合）を行ない、粒子を得る。該粒子を濾別し、得られた粒子を水洗して乾燥する方法等が挙げられる。 Furthermore, for example, when the polymer type is a (meth) acrylic resin, (meth) acrylic acid ester as a monomer and lauroyl peroxide as a polymerization initiator are mixed and dissolved, and the desired amount is added to the resulting mixture. The inorganic pigment (including components (a), (b) and (c)) is added and dispersed. The obtained dispersion is added to and dispersed in an aqueous polyvinyl alcohol solution and heated with stirring to perform polymerization (suspension polymerization) to obtain particles. Examples include a method of filtering the particles, washing the obtained particles with water and drying.
また、ポリマー粒子内における無機顔料の分散状態は、高分散状態であることが好ましく、分散状態をコントロールする方法としては、ホモジナイザー、高圧ホモジナイザー、超音波分散機、アトライターミル、ボールミル等の機械を用いる分散方法；低分子界面活性剤〔例えば、アニオン界面活性剤（ラウリル硫酸ナトリウム、ポリオキシエチレンラウリルエーテル硫酸ナトリウム等）、カチオン界面活性剤、非イオン界面活性剤等〕、高分子分散剤〔例えば、デンプン、ポリビニルアルコール、カルボキシメチルセルロース、メチルポリシロキサン等〕などを用いる分散方法等が挙げられる。 Further, the dispersion state of the inorganic pigment in the polymer particles is preferably a high dispersion state, and as a method for controlling the dispersion state, a machine such as a homogenizer, a high-pressure homogenizer, an ultrasonic disperser, an attritor mill, or a ball mill is used. Dispersion method used: low molecular surfactant (for example, anionic surfactant (sodium lauryl sulfate, polyoxyethylene lauryl ether sodium sulfate, etc.), cationic surfactant, nonionic surfactant, etc.), polymer dispersant [for example , Starch, polyvinyl alcohol, carboxymethylcellulose, methylpolysiloxane, etc.] and the like.
成分（Ａ）のポリマー粉体の平均粒径は、毛穴等の皮溝部や皮丘部に対して均一な付着性を発現することにより、肌へのむらづき、仕上がりの厚ぼったさを抑制し、自然な仕上がりを与え、塗布時の初期のひっかかり感を軽減する点から、１μｍ以上が好ましく、３μｍ以上がより好ましい。また、ポリマー粒子の平均粒径の上限値は、使用時の粉っぽさを抑える観点から、３０μｍ以下が好ましく、１５μｍ以下がより好ましい。
本発明において、成分（Ａ）の平均粒径は、エタノールを溶媒とし、レーザー回折式粒度分布測定器を用いて測定された体積基準平均粒径をいう。なお、ポリマー粉体中の顔料の粒子径は、電子顕微鏡観察により測定しても良い。
The average particle size of the polymer powder of component (A) suppresses unevenness to the skin and the thickness of the finish by expressing uniform adhesion to the skin groove part and skin hill part such as pores. From the viewpoint of giving a natural finish and reducing the initial catching feeling during coating, the thickness is preferably 1 μm or more, more preferably 3 μm or more. In addition, the upper limit of the average particle size of the polymer particles is preferably 30 μm or less, more preferably 15 μm or less, from the viewpoint of suppressing powderiness during use.
In the present invention, the average particle size of component (A) refers to a volume-based average particle size measured using ethanol as a solvent and a laser diffraction particle size distribution analyzer. The particle diameter of the pigment in the polymer powder may be measured by observation with an electron microscope.
成分（Ａ）のポリマー粉体の形状は、球状、紡錘状、棒状、板状、不定形状などいずれでも良く、光散乱効果と使用感に優れる点から、球状、紡錘状が好ましい。「球状」とは、真球である必要はなく、例えば、真球状のもの；略球状のもの；正反射及び／又は乱反射を抑制する性質を発現する回転楕円体；球状のものの表面に凹凸があるもの等をいう。 The shape of the polymer powder of component (A) may be any of spherical, spindle-shaped, rod-shaped, plate-shaped, and indefinite shape, and spherical and spindle-shaped are preferable from the viewpoint of excellent light scattering effect and feeling of use. The “spherical shape” does not need to be a true sphere, for example, a true sphere; a substantially spherical shape; a spheroid that exhibits a property of suppressing regular reflection and / or irregular reflection; Something.
また、ポリマー粉体は、肌の色むらと肌の凹凸や毛穴を目立たなくさせる効果の点から、全透過率は４０％以上８０％未満であるのが好ましく、５０％以上８０％未満であるのがより好ましく、ヘイズ値は４５以上１００未満が好ましく、６０以上１００未満がより好ましい。
全透過率とヘイズ値の測定は、粉体０．４ｇ、アミノ変性シリコーン（ＳＦ８４１７、東レ・ダウコーニング社製）１．６ｇを良く練り込んだものをガラス板に塗布して、サンプルとし、Ｈａｚｅ−ｍｅｔｅｒ ＨＭ−１５０（村上色彩技術研究所社製）にて行なう。測定には、波長５５０ｎｍをピークとした光、８°視野光を用いる。
The polymer powder preferably has a total transmittance of 40% or more and less than 80%, preferably 50% or more and less than 80%, from the viewpoint of making the skin color unevenness, skin irregularities and pores inconspicuous. More preferably, the haze value is preferably 45 or more and less than 100, and more preferably 60 or more and less than 100.
The total transmittance and haze value are measured by applying 0.4 g of powder and 1.6 g of amino-modified silicone (SF8417, manufactured by Dow Corning Toray) well onto a glass plate to obtain a sample. -Meter HM-150 (manufactured by Murakami Color Research Laboratory). For the measurement, light having a peak at a wavelength of 550 nm and 8 ° field light are used.
ポリマー粉体は、そのままの状態で用いることができるが、更にその表面に、通常用いられている疎水化処理剤で疎水化処理を施して用いることもできる。
疎水化処理剤としては、通常用いられるものであれば特に制限されないが、例えば、ハイドロジェンオルガノポリシロキサン等のシリコーン油、脂肪酸金属塩、アルキルリン酸、アルキルリン酸のアルカリ金属塩又はアミン塩、炭素数８〜２２のＮ−モノ脂肪族アシル塩基性アミノ酸、パーフルオロアルキル基を有するリン酸エステル等が挙げられ、それぞれ単独で又は２種以上を混合して用いることができる。疎水化処理剤のうち、シリコーン油、パーフルオロアルキル基を有するリン酸エステルが好ましい。
The polymer powder can be used as it is, but it can also be used after its surface has been subjected to a hydrophobizing treatment with a commonly used hydrophobizing agent.
The hydrophobizing agent is not particularly limited as long as it is usually used. For example, silicone oil such as hydrogen organopolysiloxane, fatty acid metal salt, alkyl phosphoric acid, alkali metal salt of alkyl phosphoric acid or amine salt, Examples thereof include N-monoaliphatic acyl basic amino acids having 8 to 22 carbon atoms, phosphate esters having a perfluoroalkyl group, and the like, each of which can be used alone or in admixture of two or more. Of the hydrophobizing agents, silicone oil and phosphoric acid ester having a perfluoroalkyl group are preferred.
成分（Ａ）は、１種又は２種以上を用いることができ、肌へのむらづきや粉っぽさを抑制する観点から、含有量は、全組成中に０．３質量％以上であり、好ましくは０．５質量％以上、より好ましくは２質量％以上である。そして、仕上がりが厚ぼったくならず、自然な仕上がりが得られる点から、２５質量％以下であり、好ましくは２０質量％以下であり、より好ましくは１５質量％以下である。また、成分（Ａ）は、全組成中に０．３〜２５質量％含有され、好ましくは０．５〜２０質量％であり、より好ましくは２〜１５質量％含有される。 Component (A) can use 1 type (s) or 2 or more types, and content is 0.3 mass% or more in the whole composition from a viewpoint of suppressing the nonuniformity and powderiness to skin. Preferably it is 0.5 mass% or more, More preferably, it is 2 mass% or more. And it is 25 mass% or less from the point from which a finish does not become thick and a natural finish is obtained, Preferably it is 20 mass% or less, More preferably, it is 15 mass% or less. Moreover, a component (A) is contained in 0.3-25 mass% in the whole composition, Preferably it is 0.5-20 mass%, More preferably, 2-15 mass% is contained.
本発明で用いる成分（Ｂ）のフッ素変性シリコーンは、前記一般式（１）及び（２）で表されるポリシロキサン単位を有するものである。
式中、Ｒ1 、Ｒ2 及びＲ3 で示されるアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等の直鎖アルキル基；イソプロピル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ネオペンチル基、１−エチルプロピル基等の分岐鎖アルキル基；シクロペンチル、シクロヘキシル等の環状アルキル基などが挙げられる。
The fluorine-modified silicone of component (B) used in the present invention has a polysiloxane unit represented by the general formulas (1) and (2).
In the formula, examples of the alkyl group represented by R 1 , R 2 and R 3 include linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group; isopropyl group, sec- Examples thereof include branched alkyl groups such as butyl group, tert-butyl group, neopentyl group and 1-ethylpropyl group; cyclic alkyl groups such as cyclopentyl and cyclohexyl.
また、ｍは２〜６の数を示し、好ましくは２〜５、より好ましくは３である。ｎは１〜６の数を示し、好ましくは１〜４、より好ましくは２である。
ｐは３〜５０の数を示し、好ましくは３〜１０、より好ましくは３〜６である。ｓは１〜５の数を示し、好ましくは１〜３、より好ましくは１である。
Moreover, m shows the number of 2-6, Preferably it is 2-5, More preferably, it is 3. n shows the number of 1-6, Preferably it is 1-4, More preferably, it is 2.
p shows the number of 3-50, Preferably it is 3-10, More preferably, it is 3-6. s shows the number of 1-5, Preferably it is 1-3, More preferably, it is 1.
また、ｐ及びｓの割合、すなわち、一般式（１）で表されるポリシロキサン単位ｐの、一般式（１）及び（２）で表されるポリシロキサン単位の合計ｐ＋ｓに対する変性率は、使用感や化粧持ちに優れ、外観のムラが起こりにくく、化粧料を塗布した後の塗布ムラを起こりにくくする点から、０．６６≦ｐ／（ｐ＋ｓ）≦０．９であり、０．７５≦ｐ／（ｐ＋ｓ）≦０．８３が好ましい。 The ratio of p and s, that is, the modification rate of the polysiloxane unit p represented by the general formula (1) with respect to the total p + s of the polysiloxane units represented by the general formulas (1) and (2) is used. 0.66 ≦ p / (p + s) ≦ 0.9, and 0.75 ≦ from the viewpoint that it is excellent in feeling and makeup, is less likely to cause uneven appearance, and is less likely to cause uneven application after the cosmetic is applied. p / (p + s) ≦ 0.83 is preferable.
成分（Ｂ）のフッ素変性シリコーンは、例えば、特開平６−１８４３１２号公報に記載の方法に従って、製造することができる。
成分（Ｂ）としては、次の一般式（３）で表されるものが好ましい。
The fluorine-modified silicone as component (B) can be produced, for example, according to the method described in JP-A-6-184212.
As the component (B), those represented by the following general formula (3) are preferable.
（式中、ｐ及びｓは、前記と同じ意味を示し、ｑは５の数を示す） (Wherein p and s have the same meaning as described above, and q represents a number of 5)
成分（Ｂ）は、１種又は２種以上を用いることができ、肌へのむらづきや粉っぽさがなく、仕上がりが厚ぼったくならず、自然な仕上がりが得られる点から、含有量は、化粧料全体に対して、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、５０質量％以下であり、３０質量％以下が好ましく、１５質量％以下がより好ましい。また、成分（Ｂ）の含有量は、０．０１〜５０質量％であり、０．１〜３０質量％が好ましく、１〜１５質量％がより好ましい。 Ingredient (B) can be used alone or in combination of two or more, and there is no unevenness or powderiness on the skin, the finish does not become thick, and a natural finish is obtained. 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, 50% by mass or less, preferably 30% by mass or less, and 15% by mass or less with respect to the whole material. Is more preferable. Moreover, content of a component (B) is 0.01-50 mass%, 0.1-30 mass% is preferable and 1-15 mass% is more preferable.
本発明において、成分（Ａ）及び（Ｂ）の質量割合（Ａ）／（Ｂ）は、パウダーファンデーションを重ねて仕上げた際に、肌へのむらづきや粉っぽさがなく、仕上がりが厚ぼったくならず、自然な仕上がりが得られ、塗布時初期のひっかかり感や、肌のごわつき感が抑制される観点から、０．０３以上が好ましく、０．１以上がより好ましく、０．４以上がさらに好ましく、１０以下が好ましく、４以下がより好ましく、３以下がさらに好ましい。また、成分（Ａ）及び（Ｂ）の質量割合（Ａ）／（Ｂ）は、０．０３〜１０であるのが好ましく、０．１〜４がより好ましく、０．４〜３がさらに好ましい。 In the present invention, the mass ratios (A) / (B) of the components (A) and (B) can be used when the finish is thick when the powder foundation is overlaid and there is no unevenness or powderiness on the skin. From the viewpoint of obtaining a natural finish and suppressing the initial squeezing feeling at the time of application and the feeling of firmness of the skin, 0.03 or more is preferable, 0.1 or more is more preferable, and 0.4 or more is more preferable. 10 or less is preferable, 4 or less is more preferable, and 3 or less is more preferable. Further, the mass ratio (A) / (B) of the components (A) and (B) is preferably 0.03 to 10, more preferably 0.1 to 4, and still more preferably 0.4 to 3. .
本発明で用いる成分（Ｃ）の微粒子酸化亜鉛は、比表面積が１０〜１００ｍ2／ｇのものであって、１５〜９５ｍ2／ｇのものが好ましい。このような比表面積の微粒子酸化亜鉛を用いることにより、化粧持ちに優れ、良好な使用感を得ることができる。 Particulate zinc oxide component (C) used in the present invention has a specific surface area be of 10 to 100 m 2 / g, preferably from 15~95m 2 / g. By using the fine particle zinc oxide having such a specific surface area, the cosmetic durability is excellent and a good feeling of use can be obtained.
成分（Ｃ）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、シリコーン、金属セッケン、レシチン、Ｎ−アシルアミノ酸、フッ素化合物等によって、撥水及び／又は撥油処理を行ったものを用いることもできる。化粧崩れを防ぎ、化粧料中の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、メチルハイドロジェンポリシロキサンを用いたシリコーン処理をするのがより好ましい。これらの処理は、通常の方法により行うことができる。 The finely divided zinc oxide of component (C) can be used as it is, but if necessary, it is subjected to water and / or oil repellent treatment with silicone, metal soap, lecithin, N-acylamino acid, fluorine compound or the like. Can also be used. From the standpoint of preventing makeup collapse and improving the dispersibility of the fine zinc oxide in the cosmetic, a silicone-treated one is preferred, and a silicone treatment using methylhydrogenpolysiloxane is more preferred. These processes can be performed by a normal method.
成分（Ｃ）は、１種又は２種以上を用いることができ、化粧の持続性に優れ、肌へのむらづきや粉っぽさがなく、仕上がりが厚ぼったくならず、自然な仕上がりが得られる点から、含有量は、化粧料全体に対し、０．１質量％以上であり、０．５質量％以上が好ましく、１質量％以上がより好ましく、１５質量％以下であり、１０質量％以下が好ましく、６質量％以下がより好ましい。また、成分（Ｃ）の含有量は、化粧料全体に対して、０．１〜１５質量％であり、０．５〜１０質量％が好ましく、１〜６質量％がより好ましい。 Component (C) can be used singly or in combination of two or more, has excellent makeup persistence, has no unevenness or powderiness on the skin, does not make the finish thick, and obtains a natural finish Therefore, the content is 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, 15% by mass or less, and 10% by mass or less, based on the entire cosmetic. Preferably, 6 mass% or less is more preferable. Moreover, content of a component (C) is 0.1-15 mass% with respect to the whole cosmetics, 0.5-10 mass% is preferable, and 1-6 mass% is more preferable.
本発明において、成分（Ｂ）及び（Ｃ）の質量割合（Ｂ）／（Ｃ）は、自然な仕上がりが得られ、塗布時初期のひっかかり感や、肌のごわつき感が抑制される観点から、０．０５以上が好ましく、０．５以上がより好ましく、１以上がさらに好ましく、３０以下が好ましく、２０以下がより好ましく、１５以下がさらに好ましい。また、成分（Ｂ）及び（Ｃ）の質量割合（Ｂ）／（Ｃ）は、０．０５〜３０であるのが好ましく、０．５〜２０がより好ましく、１〜１５がさらに好ましい。 In the present invention, the mass ratio (B) / (C) of the components (B) and (C) provides a natural finish, and from the viewpoint of suppressing the initial catching feeling at the time of application and the firmness of the skin, 0.05 or more is preferable, 0.5 or more is more preferable, 1 or more is more preferable, 30 or less is preferable, 20 or less is more preferable, and 15 or less is more preferable. Moreover, it is preferable that mass ratio (B) / (C) of component (B) and (C) is 0.05-30, 0.5-20 are more preferable, 1-15 are still more preferable.
本発明の油中水型乳化化粧料は、更に（Ｄ）トリデカフルオロオクチルエトキシシランで表面処理された粉体を含有することができる。
成分（Ｄ）の粉体は、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である。
Ｆ3Ｃ−(ＣＦ2)5−(ＣＨ2)2−Ｓｉ−(ＯＣＨ2ＣＨ3)3
粉体を表面処理するフッ素化合物のうちでも、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した粉体を用いることにより、肌のむらづきを抑制し、自然な仕上がりを得ることができる。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、大東化成工業株式会社より販売されているＦＨＳが好適である。
The water-in-oil emulsified cosmetic of the present invention can further contain (D) a powder surface-treated with tridecafluorooctylethoxysilane.
The powder of component (D) is surface-treated with tridecafluorooctyltriethoxysilane represented by the following formula.
F 3 C— (CF 2 ) 5 — (CH 2 ) 2 —Si— (OCH 2 CH 3 ) 3
Among the fluorine compounds that surface-treat the powder, by using the powder surface-treated with tridecafluorooctyltriethoxysilane, it is possible to suppress uneven skin and obtain a natural finish. As the tridecafluorooctyltriethoxysilane, FHS sold by Daito Kasei Kogyo Co., Ltd. is suitable.
処理される粉体としては、通常の化粧料に用いられる体質顔料、着色顔料であれば特に制限されず、例えば、ケイ酸、無水ケイ酸、ケイ酸マグネシウム、タルク、セリサイト、マイカ、カオリン、ベンガラ、クレー、ベントナイト、チタン被膜雲母、オキシ塩化ビスマス、酸化ジルコニウム、酸化マグネシウム、酸化チタン、酸化亜鉛、酸化アルミニウム、硫酸カルシウム、硫酸バリウム、硫酸マグネシウム、炭酸カルシウム、炭酸マグネシウム、酸化鉄、群青、酸化クロム、水酸化クロム、カラミン及びカーボンブラック、これらの複合体等の無機粉体；ポリアミド、ポリエステル、ポリプロピレン、ポリスチレン、ポリウレタン、ビニル樹脂、尿素樹脂、フェノール樹脂、フッ素樹脂、ケイ素樹脂、アクリル樹脂、メラミン樹脂、エポキシ樹脂、ポリカーボネート樹脂、ジビニルベンゼン・スチレン共重合体、シルクパウダー、セルロース、長鎖アルキルリン酸金属塩、Ｎ−モノ長鎖アルキルアシル塩基性アミノ酸、これらの複合体等の有機粉体；さらに、上記無機粉体と有機粉体との複合粉体などが挙げられる。 The powder to be treated is not particularly limited as long as it is an extender pigment or a color pigment used in ordinary cosmetics, for example, silicic acid, silicic anhydride, magnesium silicate, talc, sericite, mica, kaolin, Bengala, clay, bentonite, titanium coated mica, bismuth oxychloride, zirconium oxide, magnesium oxide, titanium oxide, zinc oxide, aluminum oxide, calcium sulfate, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, iron oxide, ultramarine, oxidation Inorganic powders such as chromium, chromium hydroxide, calamine and carbon black, and composites thereof; polyamide, polyester, polypropylene, polystyrene, polyurethane, vinyl resin, urea resin, phenol resin, fluorine resin, silicon resin, acrylic resin, melamine Resin, Epoxy Organic powders such as resins, polycarbonate resins, divinylbenzene / styrene copolymers, silk powder, cellulose, long-chain alkyl phosphate metal salts, N-mono long-chain alkyl acyl basic amino acids, and complexes thereof; A composite powder of inorganic powder and organic powder can be used.
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, chloroform, and normal hexane, toluene, xylene, and the like. Hydrocarbon organic solvents are suitable.
トリデカフルオロオクチルトリエトキシシランの処理量は粉体によって異なるが、成分（Ｄ）の粉体質量に対して、０．０５質量％以上が好ましく、０．１質量％以上がより好ましく、５０質量％以下が好ましく、２０質量％以下がより好ましい。また、０．０５〜５０質量％であるのが好ましく、０．１〜２０質量％処理されるのがより好ましい。この処理量であれば、撥水性及び撥油性が十分に発現し、感触や流動性も良好であるので好ましい。 The treatment amount of tridecafluorooctyltriethoxysilane varies depending on the powder, but is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and 50% by mass with respect to the mass of the powder of the component (D). % Or less is preferable, and 20% by mass or less is more preferable. Moreover, it is preferable that it is 0.05-50 mass%, and it is more preferable to process 0.1-20 mass%. This treatment amount is preferable because water repellency and oil repellency are sufficiently exhibited, and feel and fluidity are good.
成分（Ｄ）は、塗布時の粉っぽさと仕上がりの点から、平均粒径が０．０１〜２０μｍであるのが好ましく、０．０１〜１０μｍであるのがより好ましい。
なお、本発明において、成分（Ｄ）の粒径は、電子顕微鏡観察、レーザー回折／散乱法による粒度分布測定機によって、測定される。具体的には、レーザー回折／散乱法の場合、エタノールを分散媒として、レーザー回折散乱式粒度分布測定器（例えば、堀場製作所製、ＬＡ−９２０）で測定する。
Component (D) preferably has an average particle size of 0.01 to 20 μm, more preferably 0.01 to 10 μm, from the standpoint of powderiness and finish at the time of application.
In the present invention, the particle size of the component (D) is measured with an electron microscope observation and a particle size distribution measuring device by a laser diffraction / scattering method. Specifically, in the case of the laser diffraction / scattering method, measurement is performed with a laser diffraction / scattering particle size distribution analyzer (for example, LA-920, manufactured by Horiba, Ltd.) using ethanol as a dispersion medium.
成分（Ｄ）は、１種又は２種以上を用いることができ、化粧の持続性に優れる点から、含有量は、全組成中に０．１質量％以上が好ましく、より好ましくは０．５質量％以上、さらに好ましくは１質量％以上であり、３０質量％以下が好ましく、２５質量％以下がより好ましく、２０質量％以下が更に好ましい。また、成分（Ｄ）は、全組成中に０．１〜３０質量％含有されるのが好ましく、０．５〜２５質量％がより好ましく、１〜２０質量％含有されるのがさらに好ましい。 Component (D) can be used singly or in combination of two or more, and the content is preferably 0.1% by mass or more, more preferably 0.5% in the total composition from the viewpoint of excellent makeup durability. % By mass or more, more preferably 1% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less. Moreover, it is preferable that 0.1-30 mass% of components (D) are contained in the whole composition, 0.5-25 mass% is more preferable, and it is further more preferable that 1-20 mass% is contained.
成分（Ｄ）に含まれる着色顔料の含有量は、パウダーファンデーションを重ねて仕上げた際の肌へのむらづきや粉っぽさがなく、仕上がりが厚ぼったくならず、自然な仕上がりが得られる点から、全組成中に５質量％以下であるのが好ましく、４質量％以下がより好ましい。
ここで、着色顔料とは、白色、又は有色の顔料であれば特に制限されず、例えば、クレー、ベントナイト、チタン被膜雲母、オキシ塩化ビスマス、酸化ジルコニウム、酸化マグネシウム、酸化チタン、酸化亜鉛、酸化アルミニウム、硫酸カルシウム、硫酸バリウム、硫酸マグネシウム、炭酸カルシウム、炭酸マグネシウム、酸化鉄、群青、酸化クロム、水酸化クロム、カラミン及びカーボンブラック、これらの複合体等の無機顔料が挙げられる。
The content of the color pigment contained in the component (D) is not uneven or powdery on the skin when the powder foundation is overlaid, the finish does not become thick, and a natural finish is obtained. The total composition is preferably 5% by mass or less, more preferably 4% by mass or less.
Here, the colored pigment is not particularly limited as long as it is a white or colored pigment. For example, clay, bentonite, titanium-coated mica, bismuth oxychloride, zirconium oxide, magnesium oxide, titanium oxide, zinc oxide, aluminum oxide Inorganic pigments such as calcium sulfate, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, iron oxide, ultramarine, chromium oxide, chromium hydroxide, calamine and carbon black, and composites thereof.
本発明に用いられる水の含有量は、使用感、保存安定性の点から、全組成中に、１０質量％以上が好ましく、１５質量％以上がより好ましく、６０質量％以下が好ましく、５０質量％以下がより好ましい。また、水は全組成中に、１０〜６０質量％含有されるのが好ましく、１５〜５０質量％がより好ましい。 The content of water used in the present invention is preferably 10% by mass or more, more preferably 15% by mass or more, and preferably 60% by mass or less, and 50% by mass in the total composition from the viewpoint of usability and storage stability. % Or less is more preferable. Moreover, it is preferable to contain 10-60 mass% of water in the whole composition, and 15-50 mass% is more preferable.
また、本発明に用いられる油剤は、２０℃で液状のものが挙げられ、固体状、ペースト状の油剤を用いる場合には、一度別の油剤や溶媒に溶解してから用いることが好ましい。
本発明で用いる油剤としては、シリコーン油、炭化水素油、高級脂肪酸、高級アルコール、エステル油（油脂を含む）、エーテル油、鉱油等が挙げられ、使用感の観点から、シリコーン油、炭化水素油、エステル油がより好ましく、シリコーン油がさらに好ましい。なかでも、ジメチルポリシロキサン、シクロポリシロキサンがよりさらに好ましい。
これら油剤は、１種又は２種以上用いることができる。
また、本発明に用いられる油剤の含有量は、全組成中に、１０質量％以上が好ましく、２０質量％以上がより好ましく、５０質量％以下が好ましく、４０質量％以下がより好ましい。また、油剤は、全組成中に、１０〜５０質量％含有するのが好ましく、２０〜４０質量％がより好ましい。
In addition, the oil used in the present invention may be liquid at 20 ° C. When a solid or paste oil is used, it is preferably used after being dissolved in another oil or solvent.
Examples of the oil used in the present invention include silicone oils, hydrocarbon oils, higher fatty acids, higher alcohols, ester oils (including fats and oils), ether oils, mineral oils, etc. Ester oil is more preferable, and silicone oil is more preferable. Of these, dimethylpolysiloxane and cyclopolysiloxane are more preferable.
These oil agents can be used alone or in combination of two or more.
Moreover, 10 mass% or more is preferable in the whole composition, as for content of the oil agent used for this invention, 20 mass% or more is more preferable, 50 mass% or less is preferable, and 40 mass% or less is more preferable. Moreover, it is preferable to contain 10-50 mass% of oil agents in the whole composition, and 20-40 mass% is more preferable.
また、本発明に用いられる界面活性剤は、アニオン界面活性剤、カチオン界面活性剤、両性界面活性剤、非イオン界面活性剤が挙げられる。中でも、非イオン界面活性剤が好ましく、ポリエーテル変性シリコーンがより好ましい。成分（Ａ）、（Ｂ）、（Ｃ）を安定に乳化させる観点から、ＨＬＢ値が１以上、７以下が好ましく、ＨＬＢ値が２以上、６以下がより好ましい。
界面活性剤の含有量は、全組成中に０．１質量％以上が好ましく、０．２質量％以上がより好ましく、８質量％以下が好ましく、６質量％以下がより好ましい。また、界面活性剤は、全組成中に０．１〜８質量％含有するのが好ましく、０．２〜６質量％がより好ましい。
Examples of the surfactant used in the present invention include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. Among these, nonionic surfactants are preferable, and polyether-modified silicones are more preferable. From the viewpoint of stably emulsifying the components (A), (B), and (C), the HLB value is preferably 1 or more and 7 or less, and the HLB value is more preferably 2 or more and 6 or less.
The content of the surfactant is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, preferably 8% by mass or less, and more preferably 6% by mass or less in the total composition. Moreover, it is preferable to contain 0.1-8 mass% of surfactant in the whole composition, and 0.2-6 mass% is more preferable.
ここで、ＨＬＢ（親水性−親油性のバランス〈Hydrophilic-Lypophilic Balance〉）は、界面活性剤の全分子量に占める親水基部分の分子量を示すものであり、非イオン界面活性剤については、グリフィン（Griffin）の式により求められるものである。
２種以上の非イオン界面活性剤から構成される混合界面活性剤のＨＬＢは、次のようにして求められる。混合界面活性剤のＨＬＢは、各非イオン界面活性剤のＨＬＢ値をその配合比率に基づいて相加算平均したものである。
Here, HLB (hydrophilic-lipophilic balance <Hydrophilic-Lypophilic Balance>) indicates the molecular weight of the hydrophilic group portion in the total molecular weight of the surfactant. For nonionic surfactants, Griffin ( Griffin).
The HLB of the mixed surfactant composed of two or more kinds of nonionic surfactants is obtained as follows. The HLB of the mixed surfactant is obtained by averaging the HLB values of the nonionic surfactants based on the blending ratio.
混合ＨＬＢ＝Σ（ＨＬＢｘ×Ｗｘ）／ΣＷｘ
ＨＬＢｘは、非イオン界面活性剤ＸのＨＬＢ値を示す。
Ｗｘは、ＨＬＢｘの値を有する非イオン界面活性剤Ｘの重量（ｇ）を示す。
Mixed HLB = Σ (HLBx × Wx) / ΣWx
HLBx indicates the HLB value of the nonionic surfactant X.
Wx indicates the weight (g) of the nonionic surfactant X having a value of HLBx.
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、ワセリン、ラノリン、セレシン、マイクロクリスタリンワックス、カルナバロウ、キャンデリラロウ等の固形油分；水溶性及び油溶性ポリマー；前記成分以外の粉体；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 is a component used in ordinary cosmetics in addition to the above components, for example, solid oils such as petrolatum, lanolin, ceresin, microcrystalline wax, carnauba wax, candelilla wax; And oil-soluble polymers; powders other than the above components; ethanol, polyhydric alcohols, preservatives, antioxidants, dyes, thickeners, pH adjusters, fragrances, ultraviolet absorbers, moisturizers, blood circulation promoters, cooling sensations Agents, antiperspirants, bactericides, skin activators, moisturizers and the like.
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重ねて仕上げた際の肌へのむらづきや粉っぽさがなく、仕上がりが厚ぼったくならず、自然な仕上がりが得られる点から、成分（Ａ）〜（Ｄ）以外の粉体を１０質量％以下含むことが好ましい。より好ましくは５質量％以下、さらに好ましくは１質量％以下含むことができる。 The water-in-oil emulsified cosmetic composition of the present invention has no unevenness or powderiness on the skin when the powder foundation is overlaid, and the finish does not become thick and a natural finish is obtained. It is preferable to contain 10 mass% or less of powders other than A) to (D). More preferably, it is 5 mass% or less, More preferably, it can contain 1 mass% or less.
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る。剤型としては、液状、乳液状、クリーム状、ジェル状が挙げられ、乳液状が好ましい。
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；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より好ましく、化粧下地がさらに好ましい。
The water-in-oil emulsified cosmetic of the present invention can be produced according to a usual method. Examples of the dosage form include liquid, emulsion, cream, and gel, and emulsion is preferred.
In addition, the water-in-oil emulsified cosmetic of the present invention comprises a makeup base, foundation; makeup cosmetics such as blusher, eye shadow, mascara, eyeliner, eyebrow, overcoat agent, lipstick, etc .; sunscreen emulsion, sunscreen It can be applied as UV protection cosmetics such as cream. Among these, a makeup base and a liquid foundation are more preferable, and a makeup base is more preferable.
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５００〜２０万mPa・sであるのが好ましく、１０００〜１０万mPa・sがより好ましく、２０００〜５万mPa・sであるのが更に好ましい。ここで、粘度はＢ型粘度計で測定したものである。
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 500 to 200,000 mPa · s, preferably 1,000 to 100,000 mPa · s, from the viewpoint of blending stability, usability, and feeling of use. Is more preferable, and it is still more preferable that it is 2000-50,000 mPa * s. Here, the viscosity is measured with a B-type viscometer.
This invention discloses the following compositions further regarding embodiment mentioned above.
＜１＞次の成分（Ａ）、（Ｂ）及び（Ｃ）：
（Ａ）無機顔料を内包するポリマー粉体であって、（ａ）白色無機顔料、（ｂ）赤色無機顔料、及び（ｃ）黄色無機顔料を含み、（ａ）：（ｂ）：（ｃ）の質量割合が７０〜９９：０．１〜１０：０．１〜２０であるポリマー粉体 ０．３〜２５質量％、
（Ｂ）下記一般式（１）及び（２）
<1> The following components (A), (B) and (C):
(A) A polymer powder containing an inorganic pigment, comprising (a) a white inorganic pigment, (b) a red inorganic pigment, and (c) a yellow inorganic pigment, (a): (b): (c) Polymer powder having a mass ratio of 70 to 99: 0.1 to 10: 0.1 to 0.3 to 25% by mass,
(B) The following general formulas (1) and (2)
（式中、Ｒｆは炭素数６の直鎖又は分岐鎖のパーフルオロアルキル基を示し、Ｒ1、Ｒ2及びＲ3は、同一又は異なって、炭素数１〜６の直鎖又は分岐鎖のアルキル基を示し、ｍは２〜６の数を示し、ｎは１〜６の数を示し、ｐは３〜５０の数を示し、ｓは１〜５の数を示し、ｐ及びｓの割合が、０．６６≦ｐ／（ｐ＋ｓ）≦０．９である）
で表されるポリシロキサン単位を有するフッ素変性シリコーン ０．０１〜５０質量％、
（Ｃ）比表面積１０〜１００ｍ2／ｇの微粒子酸化亜鉛 ０．１〜１５質量％
を含有し、成分（Ａ）と成分（Ｂ）の質量割合（Ａ）／（Ｂ）が、０．０３〜１０であって、０．１〜４が好ましく、０．４〜３がより好ましい油中水型乳化化粧料。
(In the formula, Rf represents a straight-chain or branched perfluoroalkyl group having 6 carbon atoms, and R 1 , R 2 and R 3 are the same or different and each represents a straight-chain or branched chain having 1 to 6 carbon atoms. Represents an alkyl group, m represents a number of 2 to 6, n represents a number of 1 to 6, p represents a number of 3 to 50, s represents a number of 1 to 5, and the ratio of p and s Is 0.66 ≦ p / (p + s) ≦ 0.9)
0.01 to 50% by mass of a fluorine-modified silicone having a polysiloxane unit represented by
(C) Fine particle zinc oxide having a specific surface area of 10 to 100 m 2 / g 0.1 to 15% by mass
The mass ratio (A) / (B) of the component (A) and the component (B) is 0.03 to 10, preferably 0.1 to 4, and more preferably 0.4 to 3. Water-in-oil emulsified cosmetic.
＜２＞成分（Ａ）において、（ａ）白色無機粉体、（ｂ）赤色無機顔料、（ｃ）黄色無機顔料のポリマー粉体中の質量割合は、（ａ）：（ｂ）：（ｃ）＝７０〜９９：０．１〜１０：０．１〜２０であり、７０〜９７：１〜１０：２〜２０が好ましく、８０〜９７：１〜５：２〜１５がより好ましく、９０〜９７：１〜３：２〜７が更に好ましい前記＜１＞記載の油中水型乳化化粧料。
＜３＞成分（Ａ）において、母材となるポリマーが、（メタ）アクリル系樹脂、セルロースであって、（メタ）アクリル系樹脂が好ましく、ラウリル（メタ）アクリレート−エチレングリコールジ（メタ）アクリレートコポリマーがより好ましい前記＜１＞又は＜２＞記載の油中水型乳化化粧料。
<2> In the component (A), the mass ratio of (a) white inorganic powder, (b) red inorganic pigment, and (c) yellow inorganic pigment in the polymer powder is (a) :( b) :( c ) = 70-99: 0.1-10: 0.1-20, preferably 70-97: 1-10: 2-20, more preferably 80-97: 1-5: 2-15, 90 -97: 1-3: 2-7 are more preferable, The water-in-oil type emulsion cosmetic as described in said <1>.
<3> In component (A), the polymer used as a base material is a (meth) acrylic resin or cellulose, and a (meth) acrylic resin is preferable, and lauryl (meth) acrylate-ethylene glycol di (meth) acrylate The water-in-oil emulsion cosmetic according to <1> or <2>, wherein a copolymer is more preferable.
＜４＞成分（Ａ）の平均粒径が１〜３０μｍであって、３〜１５μｍが好ましい前記＜１＞〜＜３＞のいずれか１記載の油中水型乳化化粧料。
＜５＞成分（Ａ）が、全透過率４０％以上８０％未満であって、５０％以上８０％未満が好ましく、ヘイズ値４５以上１００未満であって、６０以上１００未満が好ましい前記＜１＞〜＜４＞のいずれか１記載の油中水型乳化化粧料。
<4> The water-in-oil emulsion cosmetic according to any one of <1> to <3>, wherein the average particle size of the component (A) is 1 to 30 μm, and preferably 3 to 15 μm.
<5> The component (A) has a total transmittance of 40% or more and less than 80%, preferably 50% or more and less than 80%, a haze value of 45 or more and less than 100, and preferably 60 or more and less than 100 <1. The water-in-oil emulsified cosmetic according to any one of> to <4>.
＜６＞成分（Ａ）の含有量が、全組成中に０．３〜２５質量％であって、０．５〜２０質量％が好ましく、２〜１５質量％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＞成分（Ｂ）の含有量が、全組成中に０．０１〜５０質量％であって、０．１〜３０質量％が好ましく、１〜１５質量％がより好ましい前記＜１＞〜＜６＞のいずれか１記載の油中水型乳化化粧料。
<6> The content of the component (A) is 0.3 to 25% by mass in the entire composition, preferably 0.5 to 20% by mass, and more preferably 2 to 15% by mass. <5> The water-in-oil emulsified cosmetic according to any one of <5>.
<7> The content of the component (B) is 0.01 to 50% by mass in the total composition, preferably 0.1 to 30% by mass, and more preferably 1 to 15% by mass. The water-in-oil emulsified cosmetic according to any one of <6>.
＜８＞成分（Ｃ）の含有量が、全組成中に０．１〜１５質量％であって、０．５〜１０質量％が好ましく、１〜６質量％がより好ましい前記＜１＞〜＜７＞のいずれか１記載の油中水型乳化化粧料。
＜９＞成分（Ｂ）及び（Ｃ）の質量割合（Ｂ）／（Ｃ）が、０．０５〜３０であって、０．５〜２０が好ましく、１〜１５がより好ましい前記＜１＞〜＜８＞のいずれか１記載の油中水型乳化化粧料。
<8> The content of the component (C) is 0.1 to 15% by mass in the entire composition, preferably 0.5 to 10% by mass, and more preferably 1 to 6% by mass. The water-in-oil emulsified cosmetic according to any one of <7>.
<9> The mass ratio (B) / (C) of the components (B) and (C) is 0.05 to 30, preferably 0.5 to 20, and more preferably 1 to 15 <1>. The water-in-oil emulsified cosmetic according to any one of to <8>.
＜１０＞さらに、（Ｄ）トリデカフルオロオクチルエトキシシランで表面処理した粉体を含有する前記＜１＞〜＜９＞のいずれか１記載の油中水型乳化化粧料。
＜１１＞成分（Ｄ）の含有量が、全組成中に０．１〜３０質量％であって、０．５〜２５質量％が好ましく、１〜２０質量％がより好ましい前記＜１０＞記載の油中水型乳化化粧料。
＜１２＞成分（Ｄ）に含まれる着色顔料の含有量が、全組成中に５質量％以下であって、４質量％以下が好ましい前記＜１０＞又は＜１１＞記載の油中水型乳化化粧料。
<10> The water-in-oil emulsified cosmetic according to any one of <1> to <9>, further comprising (D) a powder surface-treated with tridecafluorooctylethoxysilane.
The content of <11> component (D) is 0.1 to 30% by mass in the total composition, preferably 0.5 to 25% by mass, and more preferably 1 to 20% by mass. Water-in-oil emulsified cosmetic.
<12> The water-in-oil emulsification according to <10> or <11>, wherein the content of the color pigment contained in the component (D) is 5% by mass or less and preferably 4% by mass or less in the total composition. Cosmetics.
製造例１（ポリマー粉体の製造）
１３００mL容のビーカーに、ラウリルメタクリレート ５６ｇ、エチレングリコールジメタクリレート １９ｇ及びラウロイルパーオキシド １．５ｇを仕込み、溶液を得た。また、平均粒径０．２５μｍの酸化チタン（ＣＲ−５０、石原産業社製）、平均粒径０．３８μｍのベンガラ（ベンガラ七宝、森下ベンガラ社製）、平均粒径０．０７×０．７μｍ（針状のため）の黄酸化鉄（イエローＬＬＸＬＯ、チタン工業社製）を、表１に示す割合で混合し、メチルハイドロジェンポリシロキサンを用いて撥水処理（無機粉体に対して２％）した。次に、得られた溶液と、撥水処理した無機顔料とを、表１に示す内包率になるよう混合し、分散させて、分散液を得た。この分散液に１質量％ポリビニルアルコール（ゴーセノールＧＨ−１７、日本合成化学工業社製）水溶液７５０ｇを添加し、超音波分散機を用いて分散した（時間と強度で粒径がコントロールできる）。得られた分散液を１０００mL容のセパラブルフラスコに仕込み、その後、該セパラブルフラスコ内の気相を窒素置換した。次いで、前記分散液を１５０r/minで撹拌しながら、７５℃で８時間、窒素雰囲気下に維持して、重合を行なった。重合終了後、得られた産物を濾過して固体を回収し、水で洗浄し、次いで、減圧乾燥して、表１に示す平均粒径の無機顔料含有ポリマー粉体１２０ｇを得た。
得られたポリマー粉体について、透過率及びヘイズ値を測定した。結果を表１に併せて示す。
Production Example 1 (Production of polymer powder)
In a 1300 mL beaker, 56 g of lauryl methacrylate, 19 g of ethylene glycol dimethacrylate and 1.5 g of lauroyl peroxide were charged to obtain a solution. In addition, titanium oxide with an average particle size of 0.25 μm (CR-50, manufactured by Ishihara Sangyo Co., Ltd.), Bengala with an average particle size of 0.38 μm (Bengara Cloisonne, manufactured by Morishita Bengala), average particle size of 0.07 × 0.7 μm Yellow iron oxide (for needle shape) (Yellow LLXLO, manufactured by Titanium Industry Co., Ltd.) was mixed in the ratio shown in Table 1, and water repellent treatment using methylhydrogenpolysiloxane (2% with respect to inorganic powder) )did. Next, the obtained solution and the water-repellent-treated inorganic pigment were mixed and dispersed so as to have the inclusion rate shown in Table 1 to obtain a dispersion. To this dispersion was added 750 g of a 1% by weight polyvinyl alcohol (GOHSENOL GH-17, manufactured by Nippon Synthetic Chemical Industry) aqueous solution and dispersed using an ultrasonic disperser (the particle size can be controlled by time and strength). The obtained dispersion was charged into a 1000 mL separable flask, and then the gas phase in the separable flask was purged with nitrogen. Next, while stirring the dispersion at 150 r / min, polymerization was carried out at 75 ° C. for 8 hours under a nitrogen atmosphere. After the polymerization was completed, the obtained product was filtered to collect a solid, washed with water, and then dried under reduced pressure to obtain 120 g of an inorganic pigment-containing polymer powder having an average particle size shown in Table 1.
About the obtained polymer powder, the transmittance | permeability and the haze value were measured. The results are also shown in Table 1.
（測定方法）
各粉体の全透過率及びヘイズ値は、Ｈａｚｅ−ｍｅｔｅｒ ＨＭ−１５０（村上色彩技術研究所社製）を用いて測定した。測定には、波長５５０ｎｍをピークとした光を用いた。
試料の調製は以下のように行った。粉体を０．４ｇ秤取り、これをアミノ変性シリコーン（ＳＦ８４１７、東レ・ダウコーニング社）１．６ｇに練り込み、ガラス板へ塗布する。練り込みはフーバーマーラー（混錬機：YOSHIMITSU社製、フーバーマーラー）を用いて１００回転で行い、１回かきとりを入れた後、更に１００回転で練り込んだ。またガラス板への塗布は、０．０２５mmのコーター（YOSHIMITSU社製、コーター）を用いて行った。
(Measuring method)
The total transmittance and haze value of each powder were measured using Haze-meter HM-150 (Murakami Color Research Laboratory Co., Ltd.). For the measurement, light having a peak at a wavelength of 550 nm was used.
The sample was prepared as follows. 0.4 g of the powder is weighed and kneaded into 1.6 g of amino-modified silicone (SF8417, Toray Dow Corning) and applied to a glass plate. The kneading was performed at 100 revolutions using a Hoover Marler (kneader: YOSHIMITSU, Hoover Marler), after scraping once, and further kneading at 100 revolutions. The glass plate was coated using a 0.025 mm coater (manufactured by YOSHIMITSU, coater).
なお、ヘイズ値（Ｈ）は拡散透過率（Ｔｄ）を全透過率（Ｔｔ）で割った値に１００を掛けることで算出されるが、本発明（実施例）に記載するヘイズ値（Ｈ）は各サンプルの厚さによる測定誤差をなくすため、各サンプルが１５μｍのときの値に換算した値（Ｈ15）である。換算式は以下のとおりである。サンプルの厚さは、透過率、ヘイズ値測定後、膜厚計（YOSHIMITSU社製）を用いて測定する。 The haze value (H) is calculated by multiplying the value obtained by dividing the diffuse transmittance (Td) by the total transmittance (Tt) by 100, and the haze value (H) described in the present invention (Example). Is a value (H15) converted to a value when each sample is 15 μm in order to eliminate measurement errors due to the thickness of each sample. The conversion formula is as follows. The thickness of the sample is measured using a film thickness meter (manufactured by YOSHIMITSU) after measuring the transmittance and haze value.
式中、Ttは全透過率、Tdは拡散透過率、Ｌは膜厚である。膜厚は測定後の塗布膜を膜厚計で測定した値を用いる。 In the formula, Tt is the total transmittance, Td is the diffuse transmittance, and L is the film thickness. For the film thickness, a value obtained by measuring the coating film after measurement with a film thickness meter is used.
製造例２
（ａ）平均粒径０．２５μｍの酸化チタン（ＣＲ−５０、石原産業社製）、（ｂ）平均粒径０．３８μｍのベンガラ（ベンガラ七宝、森下ベンガラ社製）、（ｃ）平均粒径０．０７×０．７μｍ（針状のため）の黄酸化鉄（イエローＬＬＸＬＯ、チタン工業社製）を、（ａ）：（ｂ）：（ｃ）＝９５：１：４の割合で混合し、メチルハイドロジェンポリシロキサンを用いて撥水処理（無機粉体に対して２％）した。次に、得られた分散液２０質量部とビスコース８０質量部を粗混合し、無機顔料混合ビスコースを得た。その後、アニオン性高分子であるポリアクリル酸ソーダの水溶液に混ぜて混合し、１０分かけて８０℃に昇温し、さらに３０分間、８０℃にて混合し、凝固粒子を得た。次いで、この凝固粒子をガラスフィルターにてろ別し、０．５質量％塩酸にて中和し、さらに過剰の水とメタノールで洗浄した後、減圧下で乾燥させ、無機顔料内包着色球状セルロース粉体を得た。得られた粒子を、走査型電子顕微鏡を用いて解析した結果、その形状は略球状であり、平均粒径が１０μｍであった。
Production Example 2
(A) Titanium oxide with an average particle size of 0.25 μm (CR-50, manufactured by Ishihara Sangyo Co., Ltd.), (b) Bengala with an average particle size of 0.38 μm (Bengara Cloisonne, manufactured by Morishita Bengala), (c) Average particle size 0.07 × 0.7 μm (for needle shape) yellow iron oxide (Yellow LLXLO, manufactured by Titanium Industry Co., Ltd.) was mixed at a ratio of (a) :( b) :( c) = 95: 1: 4. Water repellent treatment (2% with respect to the inorganic powder) was performed using methyl hydrogen polysiloxane. Next, 20 parts by mass of the obtained dispersion and 80 parts by mass of viscose were roughly mixed to obtain an inorganic pigment mixed viscose. Thereafter, the mixture was mixed with an aqueous solution of polyacrylic acid soda that is an anionic polymer, heated to 80 ° C. over 10 minutes, and further mixed at 80 ° C. for 30 minutes to obtain solidified particles. Next, the coagulated particles are filtered off with a glass filter, neutralized with 0.5% by mass hydrochloric acid, further washed with excess water and methanol, dried under reduced pressure, and colored spherical cellulose powder containing an inorganic pigment. Got. As a result of analyzing the obtained particles using a scanning electron microscope, the shape was substantially spherical, and the average particle size was 10 μm.
製造例３（化合物Ｂ１の合成）
Ｃ6Ｆ13−ＣＨ2ＣＨ2−Ｏ−ＣＨ2ＣＨ＝ＣＨ2 の合成：
温度計、冷却管を備えた２Ｌの四つ口フラスコに、FA-6 （ユニマッテク社製）８００ｇ（２．２mol）と粒状ＮａＯＨ（和光純薬社製）１７５．７８ｇ（４．４mol）を加えた。窒素雰囲気下で、テフロン（登録商標）製１２cm三日月攪拌翼にて２００rpmにて攪拌しながら、加熱し、フラスコ内温度を６０℃とした。そこへ臭化アリル（和光純薬社製）３９８．７３ｇ（３．３mol）を２時間かけて滴下した。滴下終了後７０℃で１時間、８０℃で１時間撹拌した。その後１３０℃に昇温し、過剰の臭化アリルを除去した。６０℃まで冷却後、イオン交換水８００ｇを入れ、３０分間攪拌、その後静置して分層させた。上層の水層を抜き出し、さらにイオン交換水８００ｇを入れ、再度攪拌、静置、水層除去を行った。６０℃／５KPaにて脱水し、１００℃／２KPaにて蒸留し、留分として、Ｃ6Ｆ13−ＣＨ2ＣＨ2−Ｏ−ＣＨ2ＣＨ＝ＣＨ2 ７７４．９ｇを得た（収率８８％）。
Synthesis of C 6 F 13 -CH 2 CH 2 -O-CH 2 CH = CH 2:
To a 2 L four-necked flask equipped with a thermometer and a cooling tube, 800 g (2.2 mol) of FA-6 (Unimatec) and 175.78 g (4.4 mol) of granular NaOH (Wako Pure Chemical Industries) were added. It was. While stirring at 200 rpm with a 12 cm crescent stirring blade made of Teflon (registered trademark) in a nitrogen atmosphere, the temperature in the flask was adjusted to 60 ° C. Thereto, 398.73 g (3.3 mol) of allyl bromide (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 70 ° C. for 1 hour and at 80 ° C. for 1 hour. Thereafter, the temperature was raised to 130 ° C. to remove excess allyl bromide. After cooling to 60 ° C., 800 g of ion-exchanged water was added, stirred for 30 minutes, and then allowed to stand to separate the layers. The upper aqueous layer was extracted, and 800 g of ion-exchanged water was further added, followed by stirring, standing still, and removal of the aqueous layer. Dried at 60 ℃ / 5KPa, 100 ℃ / distilled at 2 KPa, as a fraction, to obtain a C 6 F 13 -CH 2 CH 2 -O-CH 2 CH = CH 2 774.9g ( yield: 88 %).
温度計を備えた３００mLの四つ口フラスコに、下式で表されるハイドロジェンポリシロキサン（信越化学社製）５２．８９ｇ（１１１mmol）を加え、窒素雰囲気下、テフロン（登録商標）製８cm三日月翼にて２００rpmで攪拌し、２質量％塩化白金酸６水和物／イソプロピルアルコール０．６６ｇを加え、１１０℃に昇温した。 To a 300 mL four-necked flask equipped with a thermometer, 52.89 g (111 mmol) of hydrogen polysiloxane (Shin-Etsu Chemical Co., Ltd.) represented by the following formula was added, and Teflon (registered trademark) 8 cm crescent moon was added under a nitrogen atmosphere. The mixture was stirred with a blade at 200 rpm, 2% by mass of chloroplatinic acid hexahydrate / isopropyl alcohol 0.66 g was added, and the temperature was raised to 110 ° C.
Ｃ6Ｆ13−ＣＨ2ＣＨ2−Ｏ−ＣＨ2ＣＨ＝ＣＨ2 １９７．１１ｇ（４８８mmol）を２時間で滴下した。滴下終了後、１１０℃で２時間撹拌した。その後、７０℃まで下げた。０．１％ＮａＯＨ溶液２５．０７ｇを加え、２時間攪拌した。６０℃／５KPaにて脱水し、脱水終了後、同温度にてカルボラフィン３（日本エンバイロケミカルズ社製）２．５１ｇを加え、２時間攪拌した。０．１μm PTFEメンブランフィルターにてろ過し、ろ液を１００℃／５KPa、水６２．５ｇを用いて水蒸気蒸留し、目的化合物（化合物Ｂ１）２０６．３ｇを得た（収率８９％）。 C 6 F 13 —CH 2 CH 2 —O—CH 2 CH═CH 2 197.11 g (488 mmol) was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 110 ° C. for 2 hours. Thereafter, the temperature was lowered to 70 ° C. 25.07 g of 0.1% NaOH solution was added and stirred for 2 hours. After dehydration at 60 ° C./5 KPa, 2.51 g of carborane 3 (manufactured by Nippon Environmental Chemicals) was added at the same temperature, and the mixture was stirred for 2 hours. The mixture was filtered through a 0.1 μm PTFE membrane filter, and the filtrate was subjected to steam distillation using 100 ° C./5 KPa and 62.5 g of water to obtain 206.3 g of the target compound (Compound B1) (yield 89%).
製造例４（化合物Ｂ２の合成）
製造例２と同様にして、Ｃ6Ｆ13−ＣＨ2ＣＨ2−Ｏ−ＣＨ2ＣＨ＝ＣＨ2 を合成した。
温度計を備えた３００mLの四つ口フラスコに、下式で表されるハイドロジェンポリシロキサン（信越化学社製）２１．２９ｇ（５１mmol）を加え、窒素雰囲気下、テフロン（登録商標）製８cm三日月翼にて２００rpmで攪拌し、２質量％塩化白金酸６水和物／イソプロピルアルコール０．２６ｇを加え、１１０℃に昇温した。
In the same manner as in Production Example 2, C 6 F 13 —CH 2 CH 2 —O—CH 2 CH═CH 2 was synthesized.
21.29 g (51 mmol) of hydrogen polysiloxane (Shin-Etsu Chemical Co., Ltd.) represented by the following formula was added to a 300 mL four-necked flask equipped with a thermometer, and Teflon (registered trademark) 8 cm crescent moon was added under a nitrogen atmosphere. The mixture was stirred with a blade at 200 rpm, 2 mass% chloroplatinic acid hexahydrate / isopropyl alcohol 0.26 g was added, and the temperature was raised to 110 ° C.
Ｃ6Ｆ13−ＣＨ2ＣＨ2−Ｏ−ＣＨ2ＣＨ＝ＣＨ2 ７８．７１ｇ（１９５mmol）を２時間で滴下した。滴下終了後、１１０℃で２時間撹拌した。その後、７０℃まで下げた。０．１％ＮａＯＨ溶液１０．０３ｇを加え、２時間攪拌した。６０℃／５KPaにて脱水し、脱水終了後、同温度にてカルボラフィン３（日本エンバイロケミカルズ社製）１．００ｇを加え、２時間攪拌した。０．１μm PTFEメンブランフィルターにてろ過し、ろ液を１００℃／５KPa、水２５ｇを用いて水蒸気蒸留し、目的化合物（化合物Ｂ２）７８．９ｇを得た（収率８５％）。 C 6 F 13 —CH 2 CH 2 —O—CH 2 CH═CH 2 78.71 g (195 mmol) was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 110 ° C. for 2 hours. Thereafter, the temperature was lowered to 70 ° C. 0.13 NaOH solution 10.03g was added and it stirred for 2 hours. After dehydration at 60 ° C./5 KPa, after completion of the dehydration, 1.00 g of carborane 3 (manufactured by Nippon Environmental Chemicals) was added at the same temperature and stirred for 2 hours. The mixture was filtered through a 0.1 μm PTFE membrane filter, and the filtrate was subjected to steam distillation using 100 ° C./5 KPa and 25 g of water to obtain 78.9 g of the target compound (Compound B2) (yield 85%).
製造例５（化合物Ｂ３の合成）
製造例２と同様にして、Ｃ6Ｆ13−ＣＨ2ＣＨ2−Ｏ−ＣＨ2ＣＨ＝ＣＨ2 を合成した。
温度計を備えた３００mLの四つ口フラスコに、下式で表されるハイドロジェンポリシロキサン（信越化学社製）１７．６１ｇ（３３mmol）を加え、窒素雰囲気下、テフロン（登録商標）製８cm三日月翼にて２００rpmで攪拌し、２質量％塩化白金酸６水和物／イソプロピルアルコール０．２７ｇを加え、１１０℃に昇温した。
In the same manner as in Production Example 2, C 6 F 13 —CH 2 CH 2 —O—CH 2 CH═CH 2 was synthesized.
To a 300 mL four-necked flask equipped with a thermometer, 17.61 g (33 mmol) of hydrogen polysiloxane (Shin-Etsu Chemical Co., Ltd.) represented by the following formula was added, and Teflon (registered trademark) 8 cm crescent moon was added under a nitrogen atmosphere. The mixture was stirred with a blade at 200 rpm, 2 mass% chloroplatinic acid hexahydrate / isopropyl alcohol 0.27 g was added, and the temperature was raised to 110 ° C.
Ｃ6Ｆ13−ＣＨ2ＣＨ2−Ｏ−ＣＨ2ＣＨ＝ＣＨ2 ８２．３９ｇ（２０６mmol）を２時間で滴下した。滴下終了後、１１０℃で２時間撹拌した。その後、７０℃まで下げた。０．１％ＮａＯＨ溶液１０．０３ｇを加え、２時間攪拌した。６０℃／５KPaにて脱水し、脱水終了後、同温度にてカルボラフィン３（日本エンバイロケミカルズ社製）１．００ｇを加え、２時間攪拌した。０．１μm PTFEメンブランフィルターにてろ過し、ろ液を１００℃／５KPa、水２５ｇを用いて水蒸気蒸留し、目的化合物（化合物Ｂ３）７５．８ｇを得た（収率８２％）。 C 6 F 13 —CH 2 CH 2 —O—CH 2 CH═CH 2 82.39 g (206 mmol) was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 110 ° C. for 2 hours. Thereafter, the temperature was lowered to 70 ° C. 0.13 NaOH solution 10.03g was added and it stirred for 2 hours. After dehydration at 60 ° C./5 KPa, after completion of the dehydration, 1.00 g of carborane 3 (manufactured by Nippon Environmental Chemicals) was added at the same temperature and stirred for 2 hours. The mixture was filtered through a 0.1 μm PTFE membrane filter, and the filtrate was subjected to steam distillation using 100 ° C./5 KPa and 25 g of water to obtain 75.8 g of the target compound (Compound B3) (yield 82%).
製造例６（化合物Ｂ４の合成）
冷却管及び磁気攪拌子を備えた１００mLの二つ口フラスコに、窒素雰囲気下、メチル水素ポリシロキサン（ＭＤ2ＤH 2Ｍ）（東芝シリコーン社製）を１９．０ｇ（４４．１mmol）、Ｃ8Ｆ17−ＣＨ2ＣＨ2−Ｏ−ＣＨ2ＣＨ＝ＣＨ2 ５３．３ｇ（１０５．８mmol）を仕込んだ。次に、フラスコ内の温度を８０℃に昇温したのち、塩化白金酸の２％イソプロピルアルコール溶液１７４．５μLを加え、６０℃で５時間攪拌した。反応混合物を室温まで冷却した後、ヘキサン５０mL及び活性炭２．２ｇを加え、室温で１時間攪拌した。その後、活性炭を濾別し、溶媒を留去した。未反応の化合物を減圧留去し、目的化合物（化合物Ｂ５）４９．４ｇを無色透明の油状物として得た（収率７８％）。 In a 100 mL two-necked flask equipped with a condenser and a magnetic stirrer, 19.0 g (44.1 mmol) of methyl hydrogen polysiloxane (MD 2 DH 2 M) (manufactured by Toshiba Silicone) under a nitrogen atmosphere, C 8 F 17 —CH 2 CH 2 —O—CH 2 CH═CH 2 53.3 g (105.8 mmol) was charged. Next, after raising the temperature in the flask to 80 ° C., 174.5 μL of a 2% isopropyl alcohol solution of chloroplatinic acid was added and stirred at 60 ° C. for 5 hours. The reaction mixture was cooled to room temperature, 50 mL of hexane and 2.2 g of activated carbon were added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the activated carbon was filtered off and the solvent was distilled off. Unreacted compound was distilled off under reduced pressure to obtain 49.4 g of the objective compound (Compound B5) as a colorless and transparent oil (yield 78%).
実施例１〜１４及び比較例１〜６
表２及び表３に示す組成の油中水型乳化化粧料を製造し、得られた油中水型乳化化粧料塗布後、パウダーファンデーションを重ねて仕上げた際の肌へのむらづきのなさ、粉っぽさのなさ、仕上がりの厚ぼったさのなさ、自然な仕上がり、塗布時初期のひっかかり感のなさ及びごわつき感のなさを評価した。結果を表２及び表３に併せて示す。
Examples 1-14 and Comparative Examples 1-6
After producing water-in-oil emulsified cosmetics having the compositions shown in Tables 2 and 3 and applying the obtained water-in-oil emulsified cosmetics, the powder foundation is not uneven, and powder is not uneven. Evaluation was made on the lack of sharpness, the lack of thick finish, the natural finish, the lack of initial catching and the lack of stiffness when applied. The results are shown in Tables 2 and 3.
（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）
各油中水型乳化化粧料を塗布した後にパウダーファンデーション（エスト パウダーメイクアップ アクティブオーラ）を重ねて仕上げたとき、肌へのむらづきのなさ、粉っぽさのなさ、仕上がりの厚ぼったさのなさ、自然な仕上がり、パウダーファンデーションの塗布時初期のひっかかり感のなさ、肌のごわつき感を評価した。なお、表中の評価結果は、専門評価者１０人が下記の５段階で官能評価し、１０人の合計点で示した。
(Evaluation method)
When each water-in-oil emulsified cosmetic is applied and then the powder foundation (Esto Powder Makeup Active Aura) is overlaid, the skin is not uneven, not powdery, and has a thick finish. It was evaluated for its smoothness, natural finish, lack of initial catch when applying powder foundation, and firmness of the skin. In addition, the evaluation result in a table | surface was sensory-evaluated by 10 expert evaluators in the following five steps, and was shown by the total score of 10 people.
（１）肌へのむらづきのなさ：
５；肌へのむらづきが非常にない。
４；肌へのむらづきがない。
３；どちらとも言えない。
２；肌へのむらづきがややある。
１；肌へのむらづきがある。
(1) No unevenness on the skin:
5; There is very little unevenness on the skin.
4; There is no unevenness on the skin.
3; I can't say either.
2; There is some unevenness on the skin.
1; There is unevenness on the skin.
（２）粉っぽさのなさ：
５；粉っぽさが非常にない。
４；粉っぽさがない。
３；どちらとも言えない。
２；粉っぽさがややある。
１；粉っぽさがある。
(2) No powderiness:
5; There is not very powdery.
4; There is no powderiness.
3; I can't say either.
2; Slightly powdery.
1; It is powdery.
（３）仕上がりの厚ぼったさのなさ：
５；厚ぼったさが非常にない。
４；厚ぼったさがない。
３；どちらとも言えない。
２；厚ぼったさがややある。
１；厚ぼったさがある。
(3) The finish is not thick:
5; There is not very thick.
4;
3; I can't say either.
2; Slightly thick.
1; It is thick.
（４）自然な仕上がり：
５；仕上がりが非常に自然である。
４；仕上がりが自然である。
３；どちらとも言えない。
２；仕上がりがあまり自然でない。
１；仕上がりが自然でない。
(4) Natural finish:
5; The finish is very natural.
4; The finish is natural.
3; I can't say either.
2; The finish is not so natural.
1: The finish is not natural.
（５）塗布時初期のひっかかり感：
５；ひっかかり感が非常にない。
４；ひっかかり感がない。
３；どちらとも言えない。
２；ひっかかり感がややある。
１；ひっかかり感がある。
(5) Initial catch feeling during application:
5; There is very little catching feeling.
4; There is no catching feeling.
3; I can't say either.
2; There is a slight feeling of catching.
1; There is a feeling of catching.
（６）ごわつき感のなさ：
５；ごわつき感が非常にない。
４；ごわつき感がない。
３；どちらとも言えない。
２；ごわつき感がややある。
１；ごわつき感がある。
(6) No sense of stiffness:
5: There is no very stiff feeling.
4; There is no sense of stiffness.
3; I can't say either.
2; There is a slight feeling of stickiness.
1;
実施例１５（リキッドファンデーション）
（成分）
（質量％）
（１）フッ素変性シリコーン（化合物Ｂ１；製造例２） ４．５
（２）ジメチルポリシロキサン・ポリオキシアルキレン共重合体
（SH3775M、東レ・ダウコーニング社製） ３．０
（３）デカメチルシクロペンタシロキサン（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製、シリコーン ＴＳＦ４０５） １１．０
（４）ジメチルポリシロキサン
（信越化学工業社製、ＫＦ−９６Ｌ−２ｃｓ） １５．５
（５）パラメトキシケイ皮酸−２−エチルヘキシル ２．０
（６）エタノール ９．８
（７）硫酸マグネシウム ０．３
（８）精製水 残量
（９）トリデカフルオロオクチルトリエトキシシラン5質量％処理酸化チタン ７．５
（１０）トリデカフルオロオクチルトリエトキシシラン5質量％処理ベンガラ ０．４
（１１）トリデカフルオロオクチルトリエトキシシラン5質量％処理黄酸化鉄 ２．０
（１２）トリデカフルオロオクチルトリエトキシシラン5質量％処理黒酸化鉄 ０．１
（１３）トリデカフルオロオクチルトリエトキシシラン3質量％処理タルク ５．０
（１４）粉体８（a:b:c=95:1:4,含有量20％、平均粒径10μｍ） ３．０
（１５）シリコーン処理微粒子酸化亜鉛（テイカ社製、MZ-500）＊１ ３．０
合計 １００
＊１：メチルハイドロジェンポリシロキサンで２質量％処理したもの
Example 15 (Liquid Foundation)
(component)
(mass%)
(1) Fluorine-modified silicone (Compound B1; Production Example 2) 4.5
(2) Dimethylpolysiloxane / polyoxyalkylene copolymer (SH3775M, manufactured by Toray Dow Corning) 3.0
(3) Decamethylcyclopentasiloxane (Momentive Performance Materials Japan GK, Silicone TSF405) 11.0
(4) Dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., KF-96L-2cs) 15.5
(5) Paramethoxycinnamic acid-2-ethylhexyl 2.0
(6) Ethanol 9.8
(7) Magnesium sulfate 0.3
(8) Purified water Remaining amount (9) Tridecafluorooctyltriethoxysilane 5% by mass Treated titanium oxide 7.5
(10) Tridecafluorooctyltriethoxysilane 5% by mass treated bengara 0.4
(11) Tridecafluorooctyltriethoxysilane 5% by mass treated yellow iron oxide 2.0
(12) Tridecafluorooctyltriethoxysilane 5% by mass Black iron oxide 0.1
(13) Tridecafluorooctyltriethoxysilane 3% by mass treated talc 5.0
(14) Powder 8 (a: b: c = 95: 1: 4, content 20%, average particle size 10 μm) 3.0
(15) Silicone-treated fine particle zinc oxide (Taika Co., Ltd., MZ-500) * 1 3.0
Total 100
* 1: 2% by mass treated with methyl hydrogen polysiloxane
（製法）
実施例１〜１４と同様にして、リキッドファンデーション（油中水型乳化化粧料）を製造した。
得られたリキッドファンデーションは、肌へのむらづきや粉っぽさがなく、仕上がりが厚ぼったくならず、自然な仕上がりが得られ、塗布時初期のひっかかり感や、肌のごわつき感が抑制されたものであった。
(Manufacturing method)
A liquid foundation (water-in-oil emulsified cosmetic) was produced in the same manner as in Examples 1-14.
The resulting liquid foundation has no unevenness or powderiness on the skin, and the finish does not become thicker, resulting in a natural finish, which suppresses the initial squeezing feeling and firmness of the skin when applied. there were.
Claims (7)
（Ａ）無機顔料を内包するポリマー粉体であって、（ａ）白色無機顔料、（ｂ）赤色無機顔料、及び（ｃ）黄色無機顔料を含み、（ａ）：（ｂ）：（ｃ）の質量割合が７０〜９９：０．１〜１０：０．１〜２０であるポリマー粉体 ０．５〜２０質量％、
（Ｂ）下記一般式（３）
で表されるフッ素変性シリコーン １〜１５質量％、
（Ｃ）比表面積１０〜１００ｍ2／ｇの微粒子酸化亜鉛 ０．５〜１０質量％
を含有し、成分（Ａ）と成分（Ｂ）の質量割合（Ａ）／（Ｂ）が、０．１〜４である油中水型乳化化粧料。 The following components (A), (B) and (C):
(A) A polymer powder containing an inorganic pigment, comprising (a) a white inorganic pigment, (b) a red inorganic pigment, and (c) a yellow inorganic pigment, (a): (b): (c) The polymer powder has a mass ratio of 70 to 99: 0.1 to 10: 0.1 to 0.5 to 20 % by mass,
(B) The following general formula (3)
1 to 15 % by mass of fluorine-modified silicone represented by
(C) Fine zinc oxide having a specific surface area of 10 to 100 m 2 / g 0.5 to 10 % by mass
A water-in-oil emulsified cosmetic comprising a component (A) and a component (B) having a mass ratio (A) / (B) of 0.1 to 4 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012238101A JP6075845B2 (en) | 2012-10-29 | 2012-10-29 | Water-in-oil emulsified cosmetic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012238101A JP6075845B2 (en) | 2012-10-29 | 2012-10-29 | Water-in-oil emulsified cosmetic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2014088335A JP2014088335A (en) | 2014-05-15 |
| JP6075845B2 true JP6075845B2 (en) | 2017-02-08 |
Family
ID=50790586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012238101A Active JP6075845B2 (en) | 2012-10-29 | 2012-10-29 | Water-in-oil emulsified cosmetic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6075845B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014193654A1 (en) * | 2013-05-31 | 2014-12-04 | 3M Innovative Properties Company | Fluoroalkyl silicones |
| JP6309858B2 (en) * | 2014-08-07 | 2018-04-11 | 花王株式会社 | Powder cosmetics |
| JP6875086B2 (en) * | 2016-08-31 | 2021-05-19 | 花王株式会社 | Cosmetics |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2720134B2 (en) * | 1992-12-15 | 1998-02-25 | 花王株式会社 | Fluorine-modified silicone, method for producing the same, and cosmetic containing the same |
| JP3073877B2 (en) * | 1994-04-04 | 2000-08-07 | 花王株式会社 | Cosmetics |
| JP4789409B2 (en) * | 2003-11-07 | 2011-10-12 | ロレアル | Makeup cosmetics containing colored inorganic pigment inclusion particles and inorganic pigment |
| JP4931568B2 (en) * | 2006-12-11 | 2012-05-16 | ポーラ化成工業株式会社 | Cosmetics containing surface-treated powder |
| JP4931576B2 (en) * | 2006-12-28 | 2012-05-16 | 花王株式会社 | Polymer powder and cosmetic containing the same |
| JP5165304B2 (en) * | 2007-08-02 | 2013-03-21 | 花王株式会社 | Cosmetics |
| JP5727768B2 (en) * | 2010-12-03 | 2015-06-03 | 花王株式会社 | Emulsified cosmetics |
-
2012
- 2012-10-29 JP JP2012238101A patent/JP6075845B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014088335A (en) | 2014-05-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4249717B2 (en) | Cosmetic composition comprising concave particles | |
| JP5630993B2 (en) | Cosmetics | |
| KR20070121033A (en) | Surface-coated powder and cosmetic preparation containing the same | |
| TW200934526A (en) | Method of improving skin appearance using treated macroscopic particles | |
| JP6214387B2 (en) | Water-in-oil emulsified cosmetic | |
| JP2012521962A (en) | Particle composition comprising fusiform particles for cosmetic use | |
| JP6209442B2 (en) | Water-in-oil emulsified cosmetic | |
| JP2739253B2 (en) | Cosmetics | |
| JP6130203B2 (en) | Skin cosmetics | |
| JP4931576B2 (en) | Polymer powder and cosmetic containing the same | |
| JP3669898B2 (en) | Spherical resin particles, method for producing the same, and external preparation | |
| JP5344398B2 (en) | Resin particles, method for producing composite particles, and cosmetics | |
| JP6075845B2 (en) | Water-in-oil emulsified cosmetic | |
| JP7272783B2 (en) | Water-in-oil emulsified cosmetic | |
| JP5930775B2 (en) | Cosmetics | |
| JP5679500B2 (en) | Cosmetics | |
| JP5930776B2 (en) | Cosmetics | |
| JP2006213651A (en) | Solid powder cosmetic | |
| JP2004124045A (en) | Composite polymer particle and its production method | |
| JP3742612B2 (en) | Cosmetics | |
| JP4328103B2 (en) | Cosmetics | |
| JP2004323473A (en) | Cosmetic | |
| JP2017095438A (en) | Water-in-oil emulsion type cosmetic | |
| JP4777872B2 (en) | Cosmetics | |
| JP2011213670A (en) | Water-based solid cosmetic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150929 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20160729 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160802 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20160929 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20161130 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20170104 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170106 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 6075845 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |