JP6815066B2 - Water-in-oil emulsified cosmetics - Google Patents
Water-in-oil emulsified cosmetics Download PDFInfo
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- JP6815066B2 JP6815066B2 JP2015035406A JP2015035406A JP6815066B2 JP 6815066 B2 JP6815066 B2 JP 6815066B2 JP 2015035406 A JP2015035406 A JP 2015035406A JP 2015035406 A JP2015035406 A JP 2015035406A JP 6815066 B2 JP6815066 B2 JP 6815066B2
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- 239000002537 cosmetic Substances 0.000 title claims description 67
- 239000003921 oil Substances 0.000 claims description 72
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 62
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000011787 zinc oxide Substances 0.000 claims description 31
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 27
- 239000010419 fine particle Substances 0.000 claims description 27
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 27
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 26
- 239000004215 Carbon black (E152) Substances 0.000 claims description 23
- 229930195733 hydrocarbon Natural products 0.000 claims description 23
- 150000002430 hydrocarbons Chemical class 0.000 claims description 23
- 229920001296 polysiloxane Polymers 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 229920006037 cross link polymer Polymers 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229940008099 dimethicone Drugs 0.000 claims description 10
- 125000002252 acyl group Chemical group 0.000 claims description 9
- 229920002545 silicone oil Polymers 0.000 claims description 9
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 7
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 6
- 229960003493 octyltriethoxysilane Drugs 0.000 claims description 6
- 238000004945 emulsification Methods 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 description 38
- 239000000203 mixture Substances 0.000 description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000843 powder Substances 0.000 description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- -1 siloxanes Chemical class 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 239000002736 nonionic surfactant Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- SGVYKUFIHHTIFL-UHFFFAOYSA-N 2-methylnonane Chemical compound CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 4
- 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 4
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 4
- IUMSDRXLFWAGNT-UHFFFAOYSA-N Dodecamethylcyclohexasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 IUMSDRXLFWAGNT-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- NYEZZYQZRQDLEH-UHFFFAOYSA-N 2-ethyl-4,5-dihydro-1,3-oxazole Chemical compound CCC1=NCCO1 NYEZZYQZRQDLEH-UHFFFAOYSA-N 0.000 description 2
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229920006007 hydrogenated polyisobutylene Polymers 0.000 description 2
- 239000004615 ingredient Substances 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
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 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
- VKPSKYDESGTTFR-UHFFFAOYSA-N isododecane Natural products CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 description 2
- 230000005923 long-lasting effect Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 230000000475 sunscreen effect Effects 0.000 description 2
- 239000000516 sunscreening agent Substances 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- GYDYJUYZBRGMCC-INIZCTEOSA-N (2s)-2-amino-6-(dodecanoylamino)hexanoic acid Chemical compound CCCCCCCCCCCC(=O)NCCCC[C@H](N)C(O)=O GYDYJUYZBRGMCC-INIZCTEOSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- 241001237961 Amanita rubescens Species 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004909 Moisturizer Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 125000005055 alkyl alkoxy group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- LMGZGXSXHCMSAA-UHFFFAOYSA-N cyclodecane Chemical compound C1CCCCCCCCC1 LMGZGXSXHCMSAA-UHFFFAOYSA-N 0.000 description 1
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 230000001333 moisturizer Effects 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BOJSDHZZKKYWAS-UHFFFAOYSA-N tetrakis(trimethylsilyl)silane Chemical compound C[Si](C)(C)[Si]([Si](C)(C)C)([Si](C)(C)C)[Si](C)(C)C BOJSDHZZKKYWAS-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- BUBJWNWWARPCBH-UHFFFAOYSA-N tris(trimethylsilyl)methylsilicon Chemical compound C[Si](C)(C)C([Si])([Si](C)(C)C)[Si](C)(C)C BUBJWNWWARPCBH-UHFFFAOYSA-N 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
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- Cosmetics (AREA)
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.
粉体を含有する油中水型乳化化粧料では、肌に塗布したときの仕上がりが良好であることが求められている。
例えば、特許文献１には、架橋型ポリエーテル変性シリコーン、フッ素変性シリコーン油、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粉体を含有する油中水型乳化化粧料が、肌の皮溝・皮丘に均一に付着、つきが良く、肌が荒れて見えるのを防止し、粉感が目立たない、肌を明るく見せることが記載されている。
Water-in-oil emulsified cosmetics containing powder are required to have a good finish when applied to the skin.
For example, in Patent Document 1, water-in-oil emulsified cosmetics containing powders surface-treated with crosslinked polyether-modified silicones, fluorine-modified silicone oils, and tridecafluorooctylriethoxysilane are used for skin grooves. It is described that it adheres evenly to the skin hills, adheres well, prevents the skin from appearing rough, makes the powdery feeling inconspicuous, and makes the skin look bright.
酸化鉄と微粒子酸化亜鉛を含有する油中水型乳化化粧料では、製造時に色ムラが起きやすく、得られた化粧料も色ブレが大きく、品質に劣ることがあった。また、化粧料を肌に塗布した直後の仕上りに劣り、肌がくすんで見えるという課題があった。 Water-in-oil emulsified cosmetics containing iron oxide and fine particle zinc oxide are prone to color unevenness during production, and the obtained cosmetics also have large color blurring and may be inferior in quality. In addition, there is a problem that the finish is inferior immediately after the cosmetic is applied to the skin and the skin looks dull.
本発明者らは、アルキルアルコキシシランで特定量表面処理した微粒子酸化亜鉛と、架橋型ポリエーテル変性シリコーンを組合わせ、さらに、揮発性シリコーン油及び揮発性炭化水素油を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 combine fine zinc oxide having a specific amount of surface-treated with alkylalkoxysilane and crosslinked polyether-modified silicone, and further use a volatile silicone oil and a volatile hydrocarbon oil in combination. We have found that a water-in-oil emulsified cosmetic that solves the problem can be obtained.
本発明は、次の成分（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）及び（Ｅ）：
（Ａ）アルキルアルコキシシランで３〜２０質量％表面処理した、比表面積１０〜１００ｍ2／ｇの微粒子酸化亜鉛 ０．０１〜２０質量％、
（Ｂ）酸化鉄 ０．０１〜１０質量％、
（Ｃ）揮発性シリコーン油 １〜５０質量％、
（Ｄ）揮発性炭化水素油 ０．５〜４０質量％、
（Ｅ）次の一般式（１）
In the present invention, the following components (A), (B), (C), (D) and (E):
(A) Fine particle zinc oxide having a specific surface area of 10 to 100 m 2 / g, surface-treated with 3 to 20% by mass of alkylalkoxysilane, 0.01 to 20% by mass,
(B) Iron oxide 0.01-10% by mass,
(C) Volatile silicone oil 1 to 50% by mass,
(D) Volatile hydrocarbon oil 0.5-40% by mass,
(E) The following general formula (1)
（式中、各Ｒは、メチル基又はフェニル基を示し、各Ｒ'は水素原子、炭素数１〜３０のアルキル基又はアシル基を示し、各Ｒ"は炭素数１〜３０のアルキル基若しくはアシル基、又はケイ素原子１〜３０のシロキサン基を示す。ｄは１〜２０の数を示し、ｅ及びｆは０〜２００の数を示し、ｅ及びｆが同時に０となることはない。ｇは０〜３０の数を示し、ｈは１〜１００の数を示し、ｉは１０〜２０００の数を示し、ｊは１〜１０００の数を示し、ｋは１〜１０００の数を示す）
で表される架橋型ポリエーテル変性シリコーン ０．０１〜２０質量％
を含有する油中水型乳化化粧料に関する。
(In the formula, each R represents a methyl group or a phenyl group, each R'represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an acyl group, and each R "represents an alkyl group having 1 to 30 carbon atoms or an acyl group. It indicates an acyl group or a siloxane group of 1 to 30 silicon atoms. D indicates a number of 1 to 20, e and f indicate a number of 0 to 200, and e and f do not become 0 at the same time. Indicates a number from 0 to 30, h indicates a number from 1 to 100, i indicates a number from 10 to 2000, j indicates a number from 1 to 1000, and k indicates a number from 1 to 1000).
Cross-linked polyether-modified silicone represented by 0.01 to 20% by mass
Concerning water-in-oil emulsified cosmetics containing.
本発明の油中水型乳化化粧料は、製造時に乳化し易く、粉体が均一に分散し、製造直後の外観が均一で色ムラがないものである。また、肌に塗布した後の仕上りは、マット感があり、明るく、しかも、４時間経過後も、肌の仕上がりのマット感及び明るさが持続する。 The water-in-oil emulsified cosmetic of the present invention is easy to emulsify during production, the powder is uniformly dispersed, the appearance immediately after production is uniform, and there is no color unevenness. In addition, the finish after application to the skin has a matte feeling and is bright, and the matte feeling and brightness of the skin finish are maintained even after 4 hours have passed.
本発明に用いる成分（Ａ）は、アルキルアルコキシシランで３〜２０質量％表面処理した、比表面積１０〜１００ｍ2／ｇの微粒子酸化亜鉛である。
成分（Ａ）の微粒子酸化亜鉛は、比表面積１０〜１００ｍ2／ｇのものであって、比表面積１５〜６０ｍ2／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。成分（Ａ）の比表面積は、ＢＥＴ法により測定される。また、化粧持ちに優れ、良好な使用感を得る点から、平均粒子径は、５〜４０ｎｍであるのが好ましく、１０〜３０ｎｍがより好ましい。
The component (A) used in the present invention is fine particle zinc oxide having a specific surface area of 10 to 100 m 2 / g, which has been surface-treated with alkylalkoxysilane in an amount of 3 to 20% by mass.
Particulate zinc oxide component (A), there is a specific surface area of 10 to 100 m 2 / g, as a specific surface area of 15 to 60 2 / g are preferred. By using the fine particle zinc oxide having such a specific surface area, it is possible to obtain excellent long-lasting makeup and a good feeling of use. The specific surface area of the component (A) is measured by the BET method. In addition, the average particle size is preferably 5 to 40 nm, more preferably 10 to 30 nm, from the viewpoint of excellent long-lasting makeup and obtaining a good feeling of use.
成分（Ａ）の微粒子酸化亜鉛は、アルキルアルコキシシランで表面処理したものである。アルキルアルコキシシランとしては、炭素数６〜２０の分岐又は直鎖のアルキル基を有するものが好ましく、オクチルトリエトキシシラン、オクチルトリメトキシシラン等がより好ましく、オクチルトリエトキシシランがさらに好ましい。
なお、微粒子酸化亜鉛をアルキルアルコキシシランで処理した場合、成分（Ａ）の含有量や比表面積は、アルキルアルコキシシランで処理した剤を含めての質量や比表面積を意味する。
The fine particle zinc oxide of the component (A) is surface-treated with an alkylalkoxysilane. As the alkylalkoxysilane, those having a branched or linear alkyl group having 6 to 20 carbon atoms are preferable, octyltriethoxysilane, octyltrimethoxysilane and the like are more preferable, and octyltriethoxysilane is further preferable.
When the fine particle zinc oxide is treated with alkylalkoxysilane, the content and specific surface area of the component (A) mean the mass and specific surface area including the agent treated with alkylalkoxysilane.
アルキルアルコキシシランを用いた表面処理の方法は、制限されないが、例えば、ヘンシェルミキサー、スーパーミキサー等の高速攪拌機を用いてアルキルアルコキシシランと微粒子酸化亜鉛とを混合する等の乾式処理方法や、アルキルアルコキシシランを微粒子酸化亜鉛のスラリー中に添加し、攪拌・混合する等の湿式処理方法等を用いることができる。 The surface treatment method using alkylalkoxysilane is not limited, but for example, a dry treatment method such as mixing alkylalkoxysilane and fine particle zinc oxide using a high-speed stirrer such as a Henschel mixer or a super mixer, or alkylalkoxy. A wet treatment method such as adding silane to a slurry of fine particle zinc oxide, stirring and mixing can be used.
アルキルアルコキシシランの処理量は、アルキルアルコキシシランで表面処理した微粒子酸化亜鉛全質量中のアルキルアルコキシシランの質量割合が、３〜２０質量％であり、４〜１０質量％であるのが好ましい。
この割合で、アルキルアルコキシシランで表面処理した微粒子酸化亜鉛を用いることにより、油中水型乳化化粧料の製造時に乳化し易く、粉体を均一に分散させることができる。
The amount of the alkylalkoxysilane treated is such that the mass ratio of the alkylalkoxysilane to the total mass of the fine particle zinc oxide surface-treated with the alkylalkoxysilane is 3 to 20% by mass, preferably 4 to 10% by mass.
By using fine particle zinc oxide surface-treated with alkylalkoxysilane at this ratio, it is easy to emulsify during the production of water-in-oil emulsified cosmetics, and the powder can be uniformly dispersed.
成分（Ａ）の微粒子酸化亜鉛は、１種又は２種以上を用いることができ、化粧持ちに優れ、良好な使用感を得る点から、含有量は、全組成中に０．０１質量％以上であり、０．１質量％以上が好ましく、２質量％以上がより好ましく、４質量％以上がさらに好ましく、２０質量％以下であり、１７質量％以下が好ましく、１３質量％以下がより好ましい。また、成分（Ａ）の含有量は、全組成中に０．０１〜２０質量％であり、０．１〜１７質量％が好ましく、２〜１３質量％がより好ましく、４〜１３質量％がさらに好ましい。 As the fine particle zinc oxide of the component (A), one kind or two or more kinds can be used, and the content is 0.01% by mass or more in the total composition from the viewpoint of excellent cosmetic retention and good usability. It is preferably 0.1% by mass or more, more preferably 2% by mass or more, further preferably 4% by mass or more, 20% by mass or less, preferably 17% by mass or less, and more preferably 13% by mass or less. The content of the component (A) is 0.01 to 20% by mass, preferably 0.1 to 17% by mass, more preferably 2 to 13% by mass, and 4 to 13% by mass in the total composition. More preferred.
成分（Ｂ）の酸化鉄としては、通常の化粧料に用いられるものであればいずれでも良く、例えば、ベンガラ、黄酸化鉄、黒酸化鉄を用いることができ、これらを含む複合粉体等であっても良く、酸化チタンを酸化鉄で被覆した粉体でも良い。
成分（Ｂ）の酸化鉄は、疎水化処理したものを用いることができ、撥水性及び撥油性が十分に発現し、感触や流動性が良好になるので好ましい。
疎水化処理としては、通常の化粧料用粉体に施されている処理であれば制限されず、シリコーン処理、脂肪酸処理、ラウロイルリジン処理、レシチン処理、Ｎ−アシルアミノ酸処理、金属石鹸処理、アルキルアルコキシシラン処理、フッ素化合物処理等が挙げられる。これらのうち、シリコーン処理、アルキルアルコキシシシラン処理、トリデカフルオロオクチルトリエトキシシラン処理したものが好ましい。
なお、酸化鉄を疎水化処理した場合、成分（Ｂ）の含有量は、疎水化処理した剤を含めての質量を意味する。
As the iron oxide of the component (B), any iron oxide used in ordinary cosmetics may be used. For example, red iron oxide, yellow iron oxide, and black iron oxide can be used, and a composite powder containing these can be used. It may be present, or it may be a powder obtained by coating titanium oxide with iron oxide.
As the iron oxide of the component (B), a hydrophobized iron oxide can be used, which is preferable because it sufficiently exhibits water repellency and oil repellency and improves the feel and fluidity.
The hydrophobization treatment is not limited as long as it is a treatment applied to ordinary cosmetic powders, and is not limited to silicone treatment, fatty acid treatment, lauroyl lysine treatment, lecithin treatment, N-acylamino acid treatment, metal soap treatment, and alkyl. Examples thereof include alkoxysilane treatment and fluorine compound treatment. Of these, those treated with silicone, alkylalkoxysisilane, and tridecafluorooctylliethoxysilane are preferable.
When iron oxide is hydrophobized, the content of the component (B) means the mass including the hydrophobized agent.
成分（Ｂ）の酸化鉄は、１種又は２種以上を用いることができ、製造時の色ムラを抑制し、塗布後の肌の仕上りに明るさを与える点から、含有量は、全組成中に０．０１質量％以上であり、０．０２質量％以上が好ましく、０．０３質量％以上がより好ましく、１０質量％以下であり、４質量％以下が好ましく、１質量％以下がより好ましい。また、成分（Ｂ）の含有量は、全組成中に０．０１〜１０質量％であり、０．０２〜４質量％が好ましく、０．０３〜１質量％がより好ましい。 As the iron oxide of the component (B), one type or two or more types can be used, and the content is the total composition from the viewpoint of suppressing color unevenness during production and giving brightness to the finish of the skin after application. It is 0.01% by mass or more, preferably 0.02% by mass or more, more preferably 0.03% by mass or more, more preferably 10% by mass or less, preferably 4% by mass or less, and more preferably 1% by mass or less. preferable. The content of the component (B) is 0.01 to 10% by mass, preferably 0.02 to 4% by mass, and more preferably 0.03 to 1% by mass in the total composition.
成分（Ｃ）の揮発性シリコーン油において、揮発性とは、３５〜８７℃の引火点を有するものである。
成分（Ｃ）の揮発性シリコーン油としては、例えば、ジメチルポリシロキサン（１ｃｓ）、ジメチルポリシロキサン（１．５ｃｓ）、ジメチルポリシロキサン（２ｃｓ）等の直鎖状ジメチルポリシロキサン；トリス（トリメチルシリル）メチルシラン、テトラキス（トリメチルシリル）シラン等の分岐状シロキサン；オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン、ドデカメチルシクロヘキサシロキサン等の環状ジメチルシロキサンなどが挙げられる。
これらのうち、油中水型乳化化粧料を肌に塗布した後、成分（Ｃ）が揮発した後の使用感が良好で、塗布後の肌の仕上りのマット感に優れる点から、ジメチルポリシロキサン（１ｃｓ）、ジメチルポリシロキサン（１．５ｃｓ）、ジメチルポリシロキサン（２ｃｓ）等の直鎖状ジメチルポリシロキサン；オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン、ドデカメチルシクロヘキサシロキサン等の環状ジメチルシロキサンが好ましく、ジメチルポリシロキサン（１ｃｓ）、ジメチルポリシロキサン（２ｃｓ）、デカメチルシクロペンタシロキサンがより好ましい。
In the volatile silicone oil of the component (C), the volatility is one having a flash point of 35 to 87 ° C.
Examples of the volatile silicone oil of the component (C) include linear dimethylpolysiloxanes such as dimethylpolysiloxane (1cs), dimethylpolysiloxane (1.5cs), and dimethylpolysiloxane (2cs); tris (trimethylsilyl) methylsilane. , Branched siloxanes such as tetrakis (trimethylsilyl) silane; cyclic dimethylsiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.
Of these, after applying the water-in-oil emulsified cosmetic to the skin, the feeling of use after the component (C) has volatilized is good, and the finish of the skin after application is excellent in matteness. Therefore, dimethylpolysiloxane Linear dimethylpolysiloxane such as (1cs), dimethylpolysiloxane (1.5cs), dimethylpolysiloxane (2cs); cyclic dimethylsiloxane such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane Is preferable, and dimethylpolysiloxane (1cs), dimethylpolysiloxane (2cs), and decamethylcyclopentasiloxane are more preferable.
成分（Ｃ）の揮発性シリコーン油は、１種又は２種以上を用いることができ、塗布後の肌の仕上りのマット感に優れる点から、含有量は、全組成中に１質量％以上であり、５質量％以上が好ましく、１０質量％以上がより好ましく、５０質量％以下であり、３５質量％以下が好ましく、２２質量％以下がより好ましい。また、成分（Ｃ）の含有量は、全組成中に１〜５０質量％であり、５〜３５質量％が好ましく、１０〜２２質量％がより好ましい。 As the volatile silicone oil of the component (C), one type or two or more types can be used, and the content is 1% by mass or more in the total composition from the viewpoint of excellent matte feeling of the skin finish after application. Yes, 5% by mass or more is preferable, 10% by mass or more is more preferable, 50% by mass or less, 35% by mass or less is preferable, and 22% by mass or less is more preferable. The content of the component (C) is 1 to 50% by mass, preferably 5 to 35% by mass, and more preferably 10 to 22% by mass in the total composition.
成分（Ｄ）は、揮発性の炭化水素油である。揮発性とは、３５〜８７℃の引火点を有するものである。
成分（Ｄ）の揮発性炭化水素油としては、例えば、ｎ−デカン、ｎ−ウンデカン、ｎ−ドデカン等のパラフィン系炭化水素油；イソデカン、イソドデカン、水添ポリイソブテン等のイソパラフィン系炭化水素油；シクロデカン、シクロドデカン等の環状パラフィン炭化水素油が挙げられる。これらのうち、炭素数８〜１６の炭化水素油が好ましく、炭素数１０〜１６の炭化水素油がより好ましく、炭素数１２の炭化水素油がさらに好ましい。なかでも、イソパラフィン系炭化水素油が好ましく、イソドデカン、炭素数１２の水添ポリイソブテンがより好ましい。市販品としては、マルカゾールＲ（丸善石油化学社製）、パールリーム３（日油社製）等が挙げられる。
Component (D) is a volatile hydrocarbon oil. Volatile means having a flash point of 35 to 87 ° C.
Examples of the volatile hydrocarbon oil of the component (D) include paraffinic hydrocarbon oils such as n-decane, n-undecane, and n-dodecane; isoparaffinic hydrocarbon oils such as isodecane, isododecane, and hydrogenated polyisobutene; cyclodecane. , Cyclododecane and other cyclic paraffin hydrocarbon oils. Of these, a hydrocarbon oil having 8 to 16 carbon atoms is preferable, a hydrocarbon oil having 10 to 16 carbon atoms is more preferable, and a hydrocarbon oil having 12 carbon atoms is further preferable. Of these, isoparaffinic hydrocarbon oil is preferable, and isododecane and hydrogenated polyisobutene having 12 carbon atoms are more preferable. Examples of commercially available products include Marcazole R (manufactured by Maruzen Petrochemical Co., Ltd.) and Pearl Dream 3 (manufactured by NOF Corporation).
成分（Ｄ）の揮発性炭化水素油は、１種又は２種以上を用いることができ、塗布後の肌の仕上りのマット感に優れ、成分（Ａ）を油中水型乳化化粧料中に安定に分散させ、ビーカー内壁に付着することを抑制する点から、含有量は、全組成中に０．５質量％以上であり、１質量％以上が好ましく、４質量％以上がより好ましく、４０質量％以下であり、２５質量％以下が好ましく、１６質量％以下がより好ましい。また、成分（Ｄ）の含有量は、全組成中に０．５〜４０質量％であり、１〜２５質量％が好ましく、４〜１６質量％がより好ましい。 As the volatile hydrocarbon oil of the component (D), one type or two or more types can be used, and the matte feeling of the skin finish after application is excellent, and the component (A) is added to the water-in-oil emulsified cosmetic. The content is 0.5% by mass or more, preferably 1% by mass or more, more preferably 4% by mass or more, and more preferably 40% by mass or more in the total composition from the viewpoint of stably dispersing and suppressing adhesion to the inner wall of the beaker. It is 5% by mass or less, preferably 25% by mass or less, and more preferably 16% by mass or less. The content of the component (D) is 0.5 to 40% by mass, preferably 1 to 25% by mass, and more preferably 4 to 16% by mass in the total composition.
本発明において、成分（Ｃ）及び（Ｄ）の質量割合（Ｃ）／（Ｄ）は、製造時に乳化し易く、粉体が均一に分散し、製造直後の外観が均一で色ムラがなく、肌に塗布した後の仕上りは、マット感があり、明るく、しかも、時間が経過しても、肌の仕上がりのマット感及び明るさが持続する点から、０．２以上が好ましく、０．４以上がより好ましく、０．７以上がさらに好ましく、４０以下が好ましく、１０以下がより好ましく、５以下がさらに好ましい。また、成分（Ｃ）及び（Ｄ）の質量割合（Ｃ）／（Ｄ）は、０．２〜４０が好ましく、０．４〜１０がより好ましく、０．７〜５がさらに好ましい。 In the present invention, the mass ratios (C) / (D) of the components (C) and (D) are easily emulsified during production, the powder is uniformly dispersed, the appearance immediately after production is uniform, and there is no color unevenness. The finish after application to the skin is matte and bright, and 0.2 or more is preferable, and 0.4 or more is preferable because the matte feeling and brightness of the skin finish are maintained over time. The above is more preferable, 0.7 or more is further preferable, 40 or less is preferable, 10 or less is more preferable, and 5 or less is further preferable. The mass ratio (C) / (D) of the components (C) and (D) is preferably 0.2 to 40, more preferably 0.4 to 10, and even more preferably 0.7 to 5.
本発明で用いる成分（Ｅ）の架橋型ポリエーテル変性シリコーンは、前記一般式（１）で表されるものである。
式中、Ｒ"は、炭素数１〜１５のアルキル基が好ましい。また、ｇは０〜１５の数、ｈは１〜４０の数、ｉは１０〜２００の数、ｊは１〜５０の数、ｋは１〜５０の数が好ましい。尚、複数のＲ、Ｒ’、Ｒ”、ｄ、ｅ、ｆ、ｇ、ｈ、ｉ、ｊ、ｋは、同じであっても、異なっても良い。
The crosslinked polyether-modified silicone of the component (E) used in the present invention is represented by the general formula (1).
In the formula, R "is preferably an alkyl group having 1 to 15 carbon atoms. In addition, g is a number of 0 to 15, h is a number of 1 to 40, i is a number of 10 to 200, and j is a number of 1 to 50. The number and k are preferably 1 to 50. A plurality of R, R', R ", d, e, f, g, h, i, j and k may be the same or different. good.
成分（Ｅ）の架橋型ポリエーテル変性シリコーンは、例えば、特開平4-272932号公報に記載の方法により製造することができる。
また、成分（Ｅ）の架橋型ポリエーテル変性シリコーンは、揮発性炭化水素油に希釈又は分散されたものが好ましく、揮発性炭化水素油としては、ポリイソブテンがより好ましい。
The crosslinked polyether-modified silicone of the component (E) can be produced, for example, by the method described in JP-A-4-272932.
Further, the crosslinked polyether-modified silicone of the component (E) is preferably diluted or dispersed in a volatile hydrocarbon oil, and the volatile hydrocarbon oil is more preferably polyisobutene.
成分（Ｅ）としては、ジメチコン（ＰＥＧ−１０／１５）クロスポリマー、（ＰＥＧ−１５／ラウリルジメチコン）クロスポリマー、（ＰＥＧ−１０／ラウリルジメチコン）クロスポリマーが好ましい。
また、成分（Ｅ）としては、例えば、ＫＳＧ−２１０、ＫＳＧ−２４０（ジメチコン／（ＰＥＧ−１０／１５））クロスポリマー）；ＫＳＧ−３１０、ＫＳＧ−３２０、ＫＳＧ−３３０（（ＰＥＧ−１５／ラウリルジメチコン）クロスポリマー）；ＫＳＧ−３４０（（ＰＥＧ−１０／ラウリルジメチコン）クロスポリマー及び（ＰＥＧ−１５／ラウリルジメチコン）クロスポリマー）（以上、信越化学工業社製）等の市販品を用いることができる。
As the component (E), dimethicone (PEG-10 / 15) crosspolymer, (PEG-15 / lauryldimethicone) crosspolymer, and (PEG-10 / lauryldimethicone) crosspolymer are preferable.
The components (E) include, for example, KSG-210, KSG-240 (dimethicone / (PEG-10 / 15)) crosspolymer); KSG-310, KSG-320, KSG-330 ((PEG-15 /)). Lauryl dimethicone) crosspolymer); KSG-340 ((PEG-10 / lauryldimethicone) crosspolymer and (PEG-15 / lauryldimethicone) crosspolymer) (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and the like can be used. it can.
成分（Ｅ）の架橋型ポリエーテル変性シリコーンは、１種又は２種以上を用いることができ、油中水型乳化化粧料を肌に塗布した後、成分（Ｃ）、（Ｄ）が揮発し、成分（Ａ）、（Ｂ）が肌表面に残留したとき、肌へ密着し、仕上りのマット感、明るさに優れ、塗布後時間が経過しても、マット感、明るさが持続する点から、含有量は、全組成中に０．０１質量％以上であり、０．０５質量％以上が好ましく、０．１質量％以上がより好ましく、２０質量％以下であり、１０質量％以下が好ましく、２質量％以下がより好ましい。また、成分（Ｅ）の含有量は、全組成中に０．０１〜２０質量％であり、０．０５〜１０質量％が好ましく、０．１〜２質量％がより好ましい。 As the crosslinked polyether-modified silicone of the component (E), one type or two or more types can be used, and the components (C) and (D) volatilize after the water-in-oil emulsified cosmetic is applied to the skin. When the components (A) and (B) remain on the skin surface, they adhere to the skin and have an excellent matte feeling and brightness of the finish, and the matte feeling and brightness are maintained even after a lapse of time after application. Therefore, the content is 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, 20% by mass or less, and 10% by mass or less in the total composition. Preferably, it is 2% by mass or less, more preferably. The content of the component (E) is 0.01 to 20% by mass, preferably 0.05 to 10% by mass, and more preferably 0.1 to 2% by mass in the total composition.
本発明において、成分（Ａ）及び（Ｅ）の質量割合（Ａ）／（Ｅ）は、製造時に乳化し易く、粉体が均一に分散し、製造直後の外観が均一で色ムラがなく、肌に塗布した後の仕上りは、マット感があり、明るく、しかも、時間が経過しても、肌の仕上がりのマット感及び明るさが持続する点から、０．５以上が好ましく、１以上がより好ましく、２以上がさらに好ましく、３以上がよりさらに好ましく、４００以下が好ましく、２００以下がより好ましく、１００以下がさらに好ましく、６０以下がよりさらに好ましい。また、成分（Ａ）及び（Ｅ）の質量割合（Ａ）／（Ｅ）は、０．５〜４００が好ましく、１〜２００がより好ましく、２〜１００がさらに好ましく、３〜６０がよりさらに好ましい。 In the present invention, the mass ratios (A) / (E) of the components (A) and (E) are easily emulsified during production, the powder is uniformly dispersed, the appearance immediately after production is uniform, and there is no color unevenness. The finish after application to the skin has a matte feeling and is bright, and from the viewpoint that the matte feeling and brightness of the skin finish persists over time, 0.5 or more is preferable, and 1 or more is preferable. More preferably, 2 or more is further preferable, 3 or more is further preferable, 400 or less is preferable, 200 or less is more preferable, 100 or less is further preferable, and 60 or less is further preferable. The mass ratios (A) / (E) of the components (A) and (E) are preferably 0.5 to 400, more preferably 1 to 200, further preferably 2 to 100, and even more preferably 3 to 60. preferable.
本発明の油中水型乳化化粧料は、さらに、（Ｆ）パラメトキシケイ皮酸オクチルを含有することができ、紫外線吸収剤として含有することができる。
成分（Ｆ）のパラメトキシケイ皮酸オクチルの含有量は、製造直後の外観の均一性を維持する点から、全組成中に０．１質量％以上が好ましく、１質量％以上がより好ましく、２質量％以上が更に好ましく、１５質量％以下が好ましく、１２質量％以下がより好ましく、８質量％以下が更に好ましい。また、成分（Ｆ）の含有量は、全組成中に０．１〜１５質量％が好ましく、１〜１２質量％がより好ましく、２〜８質量％が更に好ましい。
The water-in-oil emulsified cosmetic of the present invention can further contain (F) octyl paramethoxycinnamate and can be contained as an ultraviolet absorber.
The content of octyl paramethoxycinnamate of the component (F) is preferably 0.1% by mass or more, more preferably 1% by mass or more in the entire composition from the viewpoint of maintaining the uniformity of appearance immediately after production. 2% by mass or more is further preferable, 15% by mass or less is preferable, 12% by mass or less is more preferable, and 8% by mass or less is further preferable. The content of the component (F) is preferably 0.1 to 15% by mass, more preferably 1 to 12% by mass, and even more preferably 2 to 8% by mass in the total composition.
本発明の油中水型乳化化粧料は、界面活性剤が用いられ、かかる界面活性剤としては、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（Ｃ）、（Ｄ）、（Ｆ）を安定に乳化させる観点から、ＨＬＢ値が１以上、７以下であるのが好ましく、ＨＬＢ値が２以上、６以下がより好ましい。 A surfactant is used in the water-in-oil emulsified cosmetic of the present invention, and examples of such a surfactant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. Of these, nonionic surfactants are preferred, and polyether-modified silicones are more preferred. From the viewpoint of stably emulsifying the components (C), (D), and (F), 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.
ここで、ＨＬＢ（親水性−親油性のバランス〈Hydrophilic-Lipophilic 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-Lipophilic Balance>) indicates the molecular weight of the hydrophilic group portion in the total molecular weight of the surfactant, and for nonionic surfactants, Griffin ( It is obtained by the formula of Griffin).
The HLB of a mixed surfactant composed of two or more types of nonionic surfactants is obtained as follows. The HLB of the mixed surfactant is the HLB value of each nonionic surfactant averaged by phase addition 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の質量（ｇ）を示す。
Mixed HLB = Σ (HLBx × Wx) / ΣWx
HLBx indicates the HLB value of the nonionic surfactant X.
Wx indicates the mass (g) of the nonionic surfactant X having a value of HLBx.
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、６質量％以下が好ましく、３質量％以下がより好ましい。また、界面活性剤の含有量は、全組成中に０．１〜６質量％が好ましく、０．２〜３質量％がより好ましい。 The content of the surfactant in the total composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, preferably 6% by mass or less, and more preferably 3% by mass or less. The content of the surfactant is preferably 0.1 to 6% by mass, more preferably 0.2 to 3% by mass in the total composition.
本発明において、水の含有量は、安定な油中水型乳化化粧料を得る点から、全組成中に５〜７０質量％であるのが好ましく、１５〜６０質量％がより好ましく、２０〜４８質量％が更に好ましい。 In the present invention, the water content is preferably 5 to 70% by mass, more preferably 15 to 60% by mass, and 20 to 20% by mass in the total composition from the viewpoint of obtaining a stable water-in-oil emulsified cosmetic. 48% by mass is more preferable.
また、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、前記以外の油性成分、前記以外の粉体、界面活性剤、香料、保湿剤、美容成分、薬効成分、紫外線吸収剤、増粘剤、殺菌剤、ｐＨ調整剤、酸化防止剤、防腐剤等を含有することができる。 In addition to the above components, the water-in-oil emulsified cosmetic of the present invention includes components used in ordinary cosmetics, such as oily components other than the above, powders other than the above, surfactants, fragrances, and moisturizers. , Beauty ingredient, medicinal ingredient, ultraviolet absorber, thickener, bactericide, pH adjuster, antioxidant, preservative and the like can be contained.
本発明の油中水型乳化化粧料は、通常の方法により製造することができ、剤型としては、液状、乳液状、ペースト状、クリーム状、ジェル状等の剤型にすることができ、乳液状、クリーム状が好ましい。
また、本発明の油中水型乳化化粧料は、化粧下地、ファンデーション、コンシーラー；ほお紅、アイシャドウ、マスカラ、アイライナー、アイブロウ、オーバーコート剤、口紅等のメイクアップ化粧料；日やけ止め乳液、日焼け止めクリーム等の紫外線防御化粧料などとして適用することができる。なかでも、化粧下地、リキッドファンデーションがより好ましい。
The water-in-oil emulsified cosmetic of the present invention can be produced by a usual method, and the dosage form can be liquid, emulsion, paste, cream, gel or the like. Emulsified or creamy is preferable.
The water-in-oil emulsified cosmetic of the present invention is a makeup base, foundation, concealer; make-up cosmetics such as blusher, eye shadow, mascara, eyeliner, eyebrow, overcoat agent, lipstick; sunscreen emulsion, It can be applied as an ultraviolet protective cosmetic such as a sunscreen cream. Of these, makeup bases and liquid foundations are more preferable.
＜１＞次の成分（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）及び（Ｅ）：
（Ａ）アルキルアルコキシシランで３〜２０質量％表面処理した、比表面積１０〜１００ｍ2／ｇの微粒子酸化亜鉛 ０．０１〜２０質量％、
（Ｂ）酸化鉄 ０．０１〜１０質量％、
（Ｃ）揮発性シリコーン油 １〜５０質量％、
（Ｄ）揮発性炭化水素油 ０．５〜４０質量％、
（Ｅ）次の一般式（１）
<1> The following components (A), (B), (C), (D) and (E):
(A) Fine particle zinc oxide having a specific surface area of 10 to 100 m 2 / g, surface-treated with 3 to 20% by mass of alkylalkoxysilane, 0.01 to 20% by mass,
(B) Iron oxide 0.01-10% by mass,
(C) Volatile silicone oil 1 to 50% by mass,
(D) Volatile hydrocarbon oil 0.5-40% by mass,
(E) The following general formula (1)
（式中、各Ｒは、メチル基又はフェニル基を示し、各Ｒ'は水素原子、炭素数１〜３０のアルキル基又はアシル基を示し、各Ｒ"は炭素数１〜３０のアルキル基若しくはアシル基、又はケイ素原子１〜３０のシロキサン基を示す。ｄは１〜２０の数を示し、ｅ及びｆは０〜２００の数を示し、ｅ及びｆが同時に０となることはない。ｇは０〜３０の数を示し、ｈは１〜１００の数を示し、ｉは１０〜２０００の数を示し、ｊは１〜１０００の数を示し、ｋは１〜１０００の数を示す）
で表される架橋型ポリエーテル変性シリコーン ０．０１〜２０質量％
を含有する油中水型乳化化粧料。
(In the formula, each R represents a methyl group or a phenyl group, each R'represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an acyl group, and each R "represents an alkyl group having 1 to 30 carbon atoms or an acyl group. It indicates an acyl group or a siloxane group of 1 to 30 silicon atoms. D indicates a number of 1 to 20, e and f indicate a number of 0 to 200, and e and f do not become 0 at the same time. Indicates a number from 0 to 30, h indicates a number from 1 to 100, i indicates a number from 10 to 2000, j indicates a number from 1 to 1000, and k indicates a number from 1 to 1000).
Cross-linked polyether-modified silicone represented by 0.01 to 20% by mass
Water-in-oil emulsified cosmetic containing.
＜２＞成分（Ａ）の微粒子酸化亜鉛が、好ましくは、比表面積１５〜６０ｍ2／ｇのものである前記＜１＞記載の油中水型乳化化粧料。
＜３＞成分（Ａ）の微粒子酸化亜鉛が、好ましくは、平均粒子径５〜４０ｎｍであって、平均粒子径１０〜３０ｎｍ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。
＜４＞成分（Ａ）の微粒子酸化亜鉛が、好ましくは、炭素数６〜２０の分岐又は直鎖のアルキル基を有するアルキルアルコキシシランで表面処理したものであって、オクチルトリエトキシシラン、オクチルトリメトキシシランがより好ましく、オクチルトリエトキシシランで表面処理したものがさらに好ましい前記＜１＞〜＜３＞のいずれか１記載の油中水型乳化化粧料。
＜５＞成分（Ａ）において、アルキルアルコキシシランの処理量が、好ましくは、微粒子酸化亜鉛の質量の４〜１０質量％である前記＜１＞〜＜４＞のいずれか１記載の油中水型乳化化粧料。
＜６＞成分（Ａ）の含有量が、好ましくは、全組成中に０．１質量％以上であって、２質量％以上がより好ましく、４質量％以上がさらに好ましく、１７質量％以下が好ましく、１３質量％以下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。
<2> The water-in-oil emulsified cosmetic according to <1> above, wherein the fine particle zinc oxide of the component (A) preferably has a specific surface area of 15 to 60 m 2 / g.
<3> The water-in-oil emulsification according to <1> or <2>, wherein the fine particle zinc oxide of the component (A) preferably has an average particle diameter of 5 to 40 nm, and more preferably an average particle diameter of 10 to 30 nm. Cosmetics.
<4> The fine particle zinc oxide of the component (A) is preferably surface-treated with an alkylalkoxysilane having a branched or linear alkyl group having 6 to 20 carbon atoms, and is octylliethoxysilane or octylly. The water-in-oil emulsified cosmetic according to any one of <1> to <3>, wherein methoxysilane is more preferable, and those surface-treated with octylliethoxysilane are more preferable.
<5> The water in oil according to any one of <1> to <4>, wherein the amount of the alkylalkoxysilane treated in the component (A) is preferably 4 to 10% by mass based on the mass of the fine particle zinc oxide. Mold emulsified cosmetics.
<6> The content of the component (A) is preferably 0.1% by mass or more, more preferably 2% by mass or more, further preferably 4% by mass or more, and 17% by mass or less in the total composition. The water-in-oil emulsified cosmetic according to any one of <1> to <5>, preferably 13% by mass or less.
＜７＞成分（Ｂ）の酸化鉄が、好ましくは、ベンガラ、黄酸化鉄、黒酸化鉄、これらを含む複合粉体、酸化チタンを酸化鉄で被覆した粉体である前記＜１＞〜＜６＞のいずれか１記載の油中水型乳化化粧料。
＜８＞成分（Ｂ）の酸化鉄が、好ましくは、疎水化処理したものであって、シリコーン処理、アルキルアルコキシシシラン処理、トリデカフルオロオクチルトリエトキシシラン処理したもの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）の含有量が、好ましくは、全組成中に０．０２質量％以上であって、０．０３質量％以上がより好ましく、４質量％以下が好ましく、１質量％以下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。
<7> The iron oxide of the component (B) is preferably red iron oxide, yellow iron oxide, black iron oxide, a composite powder containing these, and a powder obtained by coating titanium oxide with iron oxide. 6> The water-in-oil emulsified cosmetic according to any one of.
<8> The iron oxide of the component (B) is preferably hydrophobized, and more preferably treated with a silicone treatment, an alkylalkoxysisilane treatment, or a tridecafluorooctylliethoxysilane treatment. ~ The water-in-oil emulsified cosmetic according to any one of <7>.
<9> The content of the component (B) is preferably 0.02% by mass or more, more preferably 0.03% by mass or more, preferably 4% by mass or less, and 1% by mass or less in the total composition. The water-in-oil emulsified cosmetic according to any one of <1> to <8>, which is more preferable.
＜１０＞成分（Ｃ）の揮発性シリコーン油が、好ましくは、ジメチルポリシロキサン（１ｃｓ）、ジメチルポリシロキサン（１．５ｃｓ）、ジメチルポリシロキサン（２ｃｓ）、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン、ドデカメチルシクロヘキサシロキサンであって、ジメチルポリシロキサン（１ｃｓ）、ジメチルポリシロキサン（２ｃｓ）、デカメチルシクロペンタシロキサンがより好ましい前記＜１＞〜＜９＞のいずれか１記載の油中水型乳化化粧料。
＜１１＞成分（Ｃ）の含有量が、好ましくは、全組成中に５質量％以上であって、１０質量％以上がより好ましく、３５質量％以下が好ましく、２２質量％以下がより好ましい前記＜１＞〜＜１０＞のいずれか１記載の油中水型乳化化粧料。
<10> The volatile silicone oil of the component (C) is preferably dimethylpolysiloxane (1cs), dimethylpolysiloxane (1.5cs), dimethylpolysiloxane (2cs), octamethylcyclotetrasiloxane, decamethylcyclopenta. The water in oil according to any one of <1> to <9>, wherein siloxane, dodecamethylcyclohexasiloxane, dimethylpolysiloxane (1cs), dimethylpolysiloxane (2cs), and decamethylcyclopentasiloxane are more preferable. Mold emulsified cosmetics.
<11> The content of the component (C) is preferably 5% by mass or more, more preferably 10% by mass or more, preferably 35% by mass or less, and more preferably 22% by mass or less in the total composition. The water-in-oil emulsified cosmetic according to any one of <1> to <10>.
＜１２＞成分（Ｄ）の揮発性の炭化水素油が、好ましくは、パラフィン系炭化水素油、イソパラフィン系炭化水素油、環状パラフィン炭化水素油であって、炭素数８〜１６の炭化水素油がより好ましく、炭素数１０〜１６の炭化水素油がさらに好ましく、炭素数１２の炭化水素油がよりさらに好ましい前記＜１＞〜＜１１＞のいずれか１記載の油中水型乳化化粧料。
＜１３＞成分（Ｄ）の含有量が、好ましくは、全組成中に１質量％以上であって、４質量％以上がより好ましく、２５質量％以下が好ましく、１６質量％以下がより好ましい前記＜１＞〜＜１２＞のいずれか１記載の油中水型乳化化粧料。
＜１４＞成分（Ｃ）及び（Ｄ）の質量割合（Ｃ）／（Ｄ）が、好ましくは、０．２以上であって、０．４以上がより好ましく、０．７以上がさらに好ましく、４０以下が好ましく、１０以下がより好ましく、５以下がさらに好ましい前記＜１＞〜＜１３＞のいずれか１記載の油中水型乳化化粧料。
<12> The volatile hydrocarbon oil of the component (D) is preferably a paraffinic hydrocarbon oil, an isoparaffinic hydrocarbon oil, or a cyclic paraffin hydrocarbon oil, and a hydrocarbon oil having 8 to 16 carbon atoms is preferable. The water-in-oil emulsified cosmetic according to any one of <1> to <11>, wherein a hydrocarbon oil having 10 to 16 carbon atoms is more preferable, and a hydrocarbon oil having 12 carbon atoms is even more preferable.
<13> The content of the component (D) is preferably 1% by mass or more, more preferably 4% by mass or more, preferably 25% by mass or less, and more preferably 16% by mass or less in the total composition. The water-in-oil emulsified cosmetic according to any one of <1> to <12>.
<14> The mass ratio (C) / (D) of the components (C) and (D) is preferably 0.2 or more, more preferably 0.4 or more, still more preferably 0.7 or more. The water-in-oil emulsified cosmetic according to any one of <1> to <13>, wherein 40 or less is preferable, 10 or less is more preferable, and 5 or less is further preferable.
＜１５＞成分（Ｅ）の架橋型ポリエーテル変性シリコーンが、好ましくは、ジメチコン（ＰＥＧ−１０／１５）クロスポリマー、（ＰＥＧ−１５／ラウリルジメチコン）クロスポリマー、（ＰＥＧ−１０／ラウリルジメチコン）クロスポリマーであって、（ＰＥＧ−１５／ラウリルジメチコン）クロスポリマー、（ＰＥＧ−１０／ラウリルジメチコン）クロスポリマーがより好ましい前記＜１＞〜＜１４＞のいずれか１記載の油中水型乳化化粧料。
＜１６＞成分（Ｅ）の含有量が、好ましくは、全組成中に０．０５質量％以上であって、０．１質量％以上がより好ましく、１０質量％以下が好ましく、２質量％以下がより好ましい前記＜１＞〜＜１５＞のいずれか１記載の油中水型乳化化粧料。
＜１７＞成分（Ａ）及び（Ｅ）の質量割合（Ａ）／（Ｅ）が、好ましくは、０．５以上であって、１以上がより好ましく、２以上がさらに好ましく、３以上がよりさらに好ましく、４００以下が好ましく、２００以下がより好ましく、１００以下がさらに好ましく、６０以下がよりさらに好ましい前記＜１＞〜＜１６＞のいずれか１記載の油中水型乳化化粧料。
<15> The crosslinked polyether-modified silicone of component (E) is preferably a dimethicone (PEG-10 / 15) crosspolymer, (PEG-15 / lauryl dimethicone) crosspolymer, (PEG-10 / lauryl dimethicone) cloth. The water-in-oil emulsified cosmetic according to any one of <1> to <14>, wherein the polymer is a (PEG-15 / lauryl dimethicone) cross polymer and a (PEG-10 / lauryl dimethicone) cross polymer. ..
<16> The content of the component (E) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, preferably 10% by mass or less, and 2% by mass or less in the total composition. The water-in-oil emulsified cosmetic according to any one of <1> to <15>, which is more preferable.
<17> The mass ratio (A) / (E) of the components (A) and (E) is preferably 0.5 or more, more preferably 1 or more, further preferably 2 or more, and more preferably 3 or more. The water-in-oil emulsified cosmetic according to any one of <1> to <16>, further preferably 400 or less, more preferably 200 or less, further preferably 100 or less, and even more preferably 60 or less.
＜１８＞さらに、（Ｆ）パラメトキシケイ皮酸オクチルを含有することができる前記＜１＞〜＜１７＞のいずれか１記載の油中水型乳化化粧料。
＜１９＞成分（Ｆ）のパラメトキシケイ皮酸オクチルの含有量が、好ましくは、全組成中に０．１質量％以上であって、１質量％以上がより好ましく、２質量％以上が更に好ましく、１５質量％以下が好ましく、１２質量％以下がより好ましく、８質量％以下がさらに好ましい前記＜１＞〜＜１８＞のいずれか１記載の油中水型乳化化粧料。
＜２０＞水の含有量が、好ましくは、全組成中に５〜７０質量％であって、１５〜６０質量％がより好ましく、２０〜４８質量％がさらに好ましい前記＜１＞〜＜１９＞のいずれか１記載の油中水型乳化化粧料。
<18> The water-in-oil emulsified cosmetic according to any one of <1> to <17>, which can further contain (F) octyl paramethoxycinnamate.
<19> The content of octyl paramethoxycinnamate in the component (F) is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further 2% by mass or more in the total composition. The water-in-oil emulsified cosmetic according to any one of <1> to <18>, preferably 15% by mass or less, more preferably 12% by mass or less, still more preferably 8% by mass or less.
<20> The content of water is preferably 5 to 70% by mass, more preferably 15 to 60% by mass, still more preferably 20 to 48% by mass in the total composition of the above <1> to <19>. The water-in-oil emulsified cosmetic according to any one of.
製造例１（オクチルシリル化微粒子酸化亜鉛の製造１）
微粒子酸化亜鉛９５質量％とオクチルトリエトキシシラン５質量％、トルエンからなるスラリーを作成し、ビーズミル（シンマルエンタープライゼス社製、ダイノミル）を用いて粉砕・解砕を行った。次いで、トルエンを減圧下に加熱留去した後、送風気流型乾燥機を用いて１５０℃にて４時間加熱処理し、オクチルシリル化微粒子酸化亜鉛を得た。
Production Example 1 (Production of octylsilylated fine particle zinc oxide 1)
A slurry composed of fine particles of zinc oxide (95% by mass), octyltriethoxysilane (5% by mass), and toluene was prepared, and pulverized and crushed using a bead mill (Dynomill manufactured by Simmal Enterprises). Then, after heating and distilling off toluene under reduced pressure, heat treatment was performed at 150 ° C. for 4 hours using a blower airflow type dryer to obtain octylsilylated fine particle zinc oxide.
製造例２（オクチルシリル化微粒子酸化亜鉛の製造２）
微粒子酸化亜鉛９３質量％とオクチルトリエトキシシラン７質量％、トルエンからなるスラリーを作成し、ビーズミル（シンマルエンタープライゼス社製、ダイノミル）を用いて粉砕・解砕を行った。次いで、トルエンを減圧下に加熱留去した後、送風気流型乾燥機を用いて１５０℃にて４時間加熱処理し、オクチルシリル化微粒子酸化亜鉛を得た。
Production Example 2 (Production of octylsilylated fine particle zinc oxide 2)
A slurry composed of 93% by mass of fine-grained zinc oxide, 7% by mass of octyltriethoxysilane, and toluene was prepared, and pulverized and crushed using a bead mill (Dynomill manufactured by Simmal Enterprises). Then, after heating and distilling off toluene under reduced pressure, heat treatment was performed at 150 ° C. for 4 hours using a blower airflow type dryer to obtain octylsilylated fine particle zinc oxide.
製造例３（オクチルシリル化微粒子酸化亜鉛の製造３）
微粒子酸化亜鉛９８質量％とオクチルトリエトキシシラン２質量％と、トルエンからなるスラリーを作成し、ビーズミル（シンマルエンタープライゼス社製、ダイノミル）を用いて粉砕・解砕を行った。次いで、トルエンを減圧下に加熱留去した後、送風気流型乾燥機を用いて１５０℃にて４時間加熱処理し、オクチルシリル化微粒子酸化亜鉛を得た。
Production Example 3 (Production of octylsilylated fine particle zinc oxide 3)
A slurry composed of 98% by mass of fine-grained zinc oxide, 2% by mass of octyltriethoxysilane, and toluene was prepared, and pulverized and crushed using a bead mill (Dynomill manufactured by Simmal Enterprises). Then, after heating and distilling off toluene under reduced pressure, heat treatment was performed at 150 ° C. for 4 hours using a blower airflow type dryer to obtain octylsilylated fine particle zinc oxide.
製造例４（シリコーン処理微粒子酸化亜鉛の製造）
微粒子酸化亜鉛９５質量％とメチルハイドロジェンポリシロキサン（ＫＦ−９９Ｐ、信越化学工業社製）５質量％と、イソプロピルアルコールからなるスラリーを作成し、よく攪拌・粉砕した後、イソプロピルアルコールを減圧下に加熱留去し、空気中１５０℃で４時間加熱処理を行い、シリコーン処理微粒子酸化亜鉛を得た。
Production Example 4 (Production of Silicone-treated Fine Particle Zinc Oxide)
A slurry consisting of 95% by mass of fine particle zinc oxide, 5% by mass of methylhydrogenpolysiloxane (KF-99P, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and isopropyl alcohol was prepared, stirred and pulverized well, and then the isopropyl alcohol was reduced under reduced pressure. The mixture was evaporated by heating and heat-treated in air at 150 ° C. for 4 hours to obtain silicone-treated fine particle zinc oxide.
製造例５（酸化鉄被覆酸化チタンの製造）
（１）ルチル型酸化チタン凝集粒子の製造：
１６０ｇ／Ｌの炭酸ナトリウム溶液中に洗浄メタチタン酸を硫酸で溶解した硫酸チタニル溶液を、液温が１０℃を超えないようにゆっくりと滴下し、ｐＨが１０．０になった時、硫酸チタニルの滴下を止めた。この中和で得られたオルソチタン酸の白色沈殿をろ過し、十分洗浄した。
次に、１０℃以下に冷却しながら濃塩酸中に洗浄したオルソチタン酸ケーキを添加し、オルソチタン酸が完全に溶解するまで撹拌した。このオルソチタン酸の塩酸溶解液を、ＴｉＯ２濃度８０ｇ／Ｌ、塩酸濃度１００ｇ／Ｌに調整し、撹拌しながら加温して５５℃に液温を合わせ、２０時間撹拌して加水分解を行った。得られたルチル型酸化チタンを中和・洗浄・乾燥し、ルチル型酸化チタン粒子を得た。
得られた粒子を透過型電子顕微鏡で観察したところ、辺の大きさが０．０６〜０．１２μｍ、厚さが０．０２〜０．０６μｍの扇状ルチル型酸化チタン粒子が凝集した、平均粒子径０．３μｍの球状ルチル型酸化チタン凝集粒子であり、摩擦感テスターによる平均摩擦係数は０．５４であった。
（２）ベンガラ被覆酸化チタンの製造：
苛性ソーダ水溶液を加温（３０〜３５℃）溶解し、（１）で得られたルチル型酸化チタン凝集粒子１００ｋｇを分散させ、硫酸第二鉄液（４１．５％）１９．０ｋｇを含む水溶液を添加・撹拌し、９０℃、２時間反応させる。得られた複合化物を水洗・中和し、乾燥させる。粉砕後、７００℃、３時間電気炉で焼成させた後、ふるいをかけ、ベンガラ３質量％被覆酸化チタンを得た。
得られたベンガラ３質量％被覆酸化チタンは、平均粒子径０．３μｍ、比表面積１９ｍ２／ｇであった。
Production Example 5 (Production of Iron Oxide Coated Titanium Oxide)
(1) Production of rutile-type titanium oxide agglomerated particles:
A solution of titanyl sulfate in which washed metatitanic acid is dissolved in sulfuric acid in a solution of sodium carbonate of 160 g / L is slowly added dropwise so that the liquid temperature does not exceed 10 ° C., and when the pH reaches 10.0, the titanyl sulfate is added. The dripping was stopped. The white precipitate of orthotitanic acid obtained by this neutralization was filtered and washed thoroughly.
Next, the orthotitanic acid cake washed in concentrated hydrochloric acid was added while cooling to 10 ° C. or lower, and the mixture was stirred until the orthotitanic acid was completely dissolved. This hydrochloric acid solution of orthotitanic acid was adjusted to a TiO2 concentration of 80 g / L and a hydrochloric acid concentration of 100 g / L, heated with stirring to adjust the liquid temperature to 55 ° C., and stirred for 20 hours for hydrolysis. .. The obtained rutile-type titanium oxide was neutralized, washed, and dried to obtain rutile-type titanium oxide particles.
When the obtained particles were observed with a transmission electron microscope, average particles in which fan-shaped rutile-type titanium oxide particles having a side size of 0.06 to 0.12 μm and a thickness of 0.02 to 0.06 μm were aggregated. It was a spherical rutile-type titanium oxide agglomerated particle having a diameter of 0.3 μm, and the average friction coefficient by a friction tester was 0.54.
(2) Manufacture of red iron oxide coated titanium oxide:
An aqueous solution of caustic soda is dissolved by heating (30 to 35 ° C.), 100 kg of rutile-type titanium oxide agglomerated particles obtained in (1) is dispersed, and an aqueous solution containing 19.0 kg of ferric sulfate solution (41.5%) is prepared. Add and stir, and react at 90 ° C. for 2 hours. The obtained composite is washed with water, neutralized, and dried. After pulverization, the mixture was calcined in an electric furnace at 700 ° C. for 3 hours and then sieved to obtain titanium oxide coated with 3% by mass of Bengala.
The obtained titanium oxide coated with 3% by mass of Bengala had an average particle diameter of 0.3 μm and a specific surface area of 19 m2 / g.
製造例６（フッ素変性シリコーンの製造）
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 2L four-necked flask equipped with a thermometer and a cooling tube, add 800 g (2.2 mol) of FA-6 (manufactured by Unimattech) and 175.78 g (4.4 mol) of granular NaOH (manufactured by Wako Pure Chemical Industries, Ltd.). It was. The temperature inside the flask was adjusted to 60 ° C. by heating while stirring at 200 rpm with a 12 cm crescent stirring blade manufactured by Teflon (registered trademark) under a nitrogen atmosphere. 398.73 g (3.3 mol) of allyl bromide (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise thereto over 2 hours. After completion of the dropping, the mixture was stirred at 70 ° C. for 1 hour and at 80 ° C. for 1 hour. Then, 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 for layer separation. The upper aqueous layer was extracted, 800 g of ion-exchanged water was further added, and the mixture was stirred, allowed to stand, and the aqueous layer was removed again. 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, add 52.89 g (111 mmol) of hydrogen polysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) represented by the following formula, and under a nitrogen atmosphere, 8 cm crescent moon manufactured by Teflon (registered trademark). The mixture was stirred with a blade at 200 rpm, 2% by mass chloroplatinic acid hexahydrate / 0.66 g of isopropyl alcohol 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 the dropping, the mixture was stirred at 110 ° C. for 2 hours. Then, the temperature was lowered to 70 ° C. 25.07 g of 0.1% NaOH solution was added, and the mixture was stirred for 2 hours. The mixture was dehydrated at 60 ° C./5 KPa, and after the dehydration was completed, 2.51 g of Carborafine 3 (manufactured by Japan Enviro Chemicals, Inc.) was added and stirred for 2 hours. The filtrate was filtered through a 0.1 μm PTFE membrane filter, and the filtrate was steam distilled using 62.5 g of water at 100 ° C. to obtain 206.3 g of the target compound (Compound B1) (yield 89%).
製造例７（ポリ（Ｎ−プロピオニルエチレンイミン）変性シリコーンの製造）
２−エチル−２−オキサゾリン１２．９ｇ（０．１３モル）と酢酸エチル２７．７ｇとを混合し、混合液をモレキュラーシーブ（ゼオラムＡ−４、東ソー社製）２．０ｇで、２８℃１５時間脱水を行った。
また、側鎖一級アミノプロピル変性ポリジメチルシロキサン（ＫＦ−８０１５、信越シリコーン社製、重量平均分子量１０００００、アミン当量２００００）１００ｇと酢酸エチル２０３ｇとを混合し、混合液をモレキュラーシーブ１５．２ｇで、２８℃１５時間脱水を行った。
上記の脱水２−エチル−２−オキサゾリンの酢酸エチル溶液に硫酸ジエチル０．７７ｇ（０．００５モル）を加え、窒素雰囲気下８時間、８０℃で加熱還流し、末端反応性ポリ（Ｎ−プロピオニルエチレンイミン）を合成した。ＧＰＣにより測定した数平均分子量は２７００であった。
この末端反応性ポリ（Ｎ−プロピオニルエチレンイミン）溶液を、上記の脱水した側鎖一級アミノプロピル変性ポリジメチルシロキサン溶液を一括して加え、１０時間、８０℃で加熱還流した。
反応混合物を減圧濃縮し、Ｎ−プロピオニルエチレンイミン−ジメチルシロキサン共重合体を白色ゴム状固体（１０８ｇ）として得た。最終生成物におけるオルガノポリシロキサンセグメントの質量比は０．８７、最終生成物の重量平均分子量は１１５０００であった。
Production Example 7 (Production of poly (N-propionylethyleneimine) -modified silicone)
12.9 g (0.13 mol) of 2-ethyl-2-oxazoline and 27.7 g of ethyl acetate are mixed, and the mixed solution is 2.0 g of molecular sieve (Zeolam A-4, manufactured by Tosoh Corporation) at 28 ° C. 15 Time dehydration was performed.
Further, 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (KF-8015, manufactured by Shin-Etsu Silicone Co., Ltd., weight average molecular weight 100,000, amine equivalent 20000) and 203 g of ethyl acetate were mixed, and the mixed solution was prepared with 15.2 g of molecular sieve. Dehydration was performed at 28 ° C. for 15 hours.
0.77 g (0.005 mol) of diethyl sulfate was added to the above-mentioned ethyl acetate solution of dehydrated 2-ethyl-2-oxazoline, and the mixture was heated under reflux at 80 ° C. for 8 hours under a nitrogen atmosphere to undergo terminal-reactive poly (N-propionyl). Ethylimine) was synthesized. The number average molecular weight measured by GPC was 2700.
This terminally reactive poly (N-propionylethyleneimine) solution was collectively added with the above-mentioned dehydrated side chain primary aminopropyl-modified polydimethylsiloxane solution, and the mixture was heated under reflux at 80 ° C. for 10 hours.
The reaction mixture was concentrated under reduced pressure to give an N-propionylethyleneimine-dimethylsiloxane copolymer as a white rubbery solid (108 g). The mass ratio of the organopolysiloxane segment in the final product was 0.87, and the weight average molecular weight of the final product was 115,000.
実施例１〜１２及び比較例１〜４
表１に示す組成の油中水型乳化化粧料（ファンデーション）を製造し、製造中時の乳化のし易さ、製造直後の外観、ビーカーの内壁への付着状態、塗布直後の肌の仕上がりのマット感及び仕上がりの明るさ、塗布４時間経過後の肌の仕上がりのマット感及び仕上がりの明るさを評価した。結果を表１に併せて示す。
Examples 1-12 and Comparative Examples 1-4
A water-in-oil emulsified cosmetic (foundation) having the composition shown in Table 1 is manufactured, and the ease of emulsification during manufacturing, the appearance immediately after manufacturing, the state of adhesion to the inner wall of the beaker, and the finish of the skin immediately after application The matte feeling and the finished brightness, the matte feeling and the finished brightness of the skin after 4 hours of application were evaluated. The results are also shown in Table 1.
（製造方法）
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。
(Production method)
The powder phase components were mixed and pulverized, added to the separately mixed oil phase components, and dispersed with a disper. Then, the aqueous 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）
（１）製造時の乳化のし易さ：
専門評価者が、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後、水相成分を添加するとき、分散時の製造の容易性を、以下の３段階で評価した。
Ａ；水相成分を油相成分中に容易に乳化させることができる。
Ｂ；水相成分を油相成分中に乳化させるのに時間がかかる。
Ｃ；水相成分を油相成分中に乳化させることが難しい。
(Evaluation method)
(1) Ease of emulsification during manufacturing:
When a professional evaluator mixes and pulverizes the powder phase component, adds it to the separately mixed oil phase component, disperses it with a disper, and then adds the aqueous phase component, the ease of production at the time of dispersion is described in the following 3 Evaluated in stages.
A: The aqueous phase component can be easily emulsified in the oil phase component.
B: It takes time to emulsify the aqueous phase component into the oil phase component.
C: It is difficult to emulsify the aqueous phase component into the oil phase component.
（２）製造直後の外観：
専門評価者が、前記製造方法で製造した化粧料をビーカーに入れ、直後の化粧料の液面の外観を、以下の３段階で評価した。
Ａ；化粧料の表面が均一で色ムラがない。
Ｂ；化粧料の表面に１，２か所色筋が現れる。
Ｃ；化粧料の表面にマーブル上の色模様が現れる。
(2) Appearance immediately after manufacture:
A professional evaluator put the cosmetics produced by the above-mentioned production method into a beaker, and evaluated the appearance of the liquid surface of the cosmetics immediately after that in the following three stages.
A: The surface of the cosmetic is uniform and there is no color unevenness.
B; Color streaks appear in one or two places on the surface of the cosmetic.
C: A color pattern on the marble appears on the surface of the cosmetic.
（３）ビーカーの内壁への付着状態：
専門評価者が、前記製造方法で製造した化粧料をビーカーに入れ、１２時間静置後、ビーカー内の化粧料を別の容器に移した後、ビーカー内に残った化粧料の内壁への付着状態を、以下の３段階で評価した。
Ａ；化粧料が内壁に均一に付着している。
Ｂ；化粧料の凝集物が不均一に付着している。
Ｃ；化粧料の凝集物が不均一に付着し、ビーカーの底には化粧料の凝集物が沈降している。
(3) Adhesion to the inner wall of the beaker:
A professional evaluator puts the cosmetics manufactured by the above manufacturing method in a beaker, allows them to stand for 12 hours, transfers the cosmetics in the beaker to another container, and then adheres the cosmetics remaining in the beaker to the inner wall. The condition was evaluated in the following three stages.
A: The cosmetics are evenly attached to the inner wall.
B: Agglomerates of cosmetics are non-uniformly attached.
C: Cosmetic agglomerates adhere unevenly, and cosmetic agglomerates settle on the bottom of the beaker.
（４）肌の仕上がりのマット感及び仕上がりの明るさ：
専門評価者５名が、各油中水型乳化化粧料を肌に塗布したとき、塗布直後の肌の仕上がりのマット感及び仕上がりの明るさ、塗布４時間経過後の肌の仕上がりのマット感及び仕上がりの明るさを、以下の基準で官能評価した。結果は、５名の合計点で示した。
(4) Matte feeling and brightness of the finish of the skin:
When 5 expert evaluators applied each water-in-oil emulsified cosmetic to the skin, the matte feeling and brightness of the skin finish immediately after application, the matte feeling of the skin finish 4 hours after application, and The brightness of the finished product was sensorimetrically evaluated according to the following criteria. The results are shown by the total score of 5 people.
（４−１）塗布直後の肌の仕上がりのマット感：
５；肌にマット感がある。
４；肌にややマット感がある。
３；どちらとも言えない。
２；肌にあまりマット感がない。
１；肌にマットがない。
(4-1) Matte feeling of skin finish immediately after application:
5; The skin has a matte feel.
4; The skin has a slightly matte feel.
3; I can't say either.
2; The skin does not feel very matte.
1; There is no mat on the skin.
（４−２）塗布直後の肌の仕上がりの明るさ：
５；肌が顕著に明るく見える。
４；肌が明るく見える。
３；肌がやや明るく見える。
２；肌があまり明るく見えない。
１；肌が明るく見えない。
(4-2) Brightness of skin finish immediately after application:
5; The skin looks significantly brighter.
4; The skin looks bright.
3; The skin looks a little bright.
2; The skin does not look very bright.
1; The skin does not look bright.
（４−３）塗布４時間経過後の肌の仕上がりのマット感：
５；肌にマット感がある。
４；肌にややマット感がある。
３；どちらとも言えない。
２；肌にあまりマット感がない。
１；肌にマットがない。
(4-3) Matte feeling of skin finish 4 hours after application:
5; The skin has a matte feel.
4; The skin has a slightly matte feel.
3; I can't say either.
2; The skin does not feel very matte.
1; There is no mat on the skin.
（４−４）塗布４時間経過後の肌の仕上がりの明るさ：
５；肌が顕著に明るく見える。
４；肌が明るく見える。
３；肌がやや明るく見える。
２；肌があまり明るく見えない。
１；肌が明るく見えない。
(4-4) Brightness of skin finish 4 hours after application:
5; The skin looks significantly brighter.
4; The skin looks bright.
3; The skin looks a little bright.
2; The skin does not look very bright.
1; The skin does not look bright.
実施例１３（下地化粧料）
実施例１〜１２と同様にして、表２に示す組成の下地化粧料を製造した。
得られた下地化粧料は、製造時に乳化し易く、粉体が均一に分散し、製造直後の外観が均一で色ムラがなく、また、肌に塗布した後の仕上りは、マット感があり、明るく、しかも、４時間経過後も、その仕上がりが持続する。
Example 13 (base cosmetic)
The base cosmetics having the compositions shown in Table 2 were produced in the same manner as in Examples 1 to 12.
The obtained base cosmetic is easily emulsified during manufacturing, the powder is uniformly dispersed, the appearance immediately after manufacturing is uniform and there is no color unevenness, and the finish after application to the skin has a matte feeling. It is bright and the finish lasts even after 4 hours.
実施例１４（リキッドファンデーション）
実施例１〜１２と同様にして、表３に示す組成のリキッドファンデーションを製造した。
得られたリキッドファンデーションは、製造時に乳化し易く、粉体が均一に分散し、製造直後の外観が均一で色ムラがなく、また、肌に塗布した後の仕上りは、マット感があり、明るく、しかも、４時間経過後も、その仕上がりが持続する。
Example 14 (Liquid Foundation)
A liquid foundation having the composition shown in Table 3 was produced in the same manner as in Examples 1 to 12.
The obtained liquid foundation is easy to emulsify during manufacturing, the powder is evenly dispersed, the appearance immediately after manufacturing is uniform and there is no color unevenness, and the finish after application to the skin is matte and bright. Moreover, the finish is maintained even after 4 hours have passed.
Claims (3)
（Ａ）アルキルアルコキシシランで３〜２０質量％表面処理した、比表面積１０〜１００ｍ2／ｇの微粒子酸化亜鉛 ０．０１〜２０質量％、
（Ｂ）酸化鉄 ０．０１〜１０質量％、
（Ｃ）揮発性シリコーン油 １〜５０質量％、
（Ｄ）揮発性炭化水素油 ０．５〜４０質量％、
（Ｅ）次の一般式（１）
で表される架橋型ポリエーテル変性シリコーン ０．０１〜２０質量％、
を含有し、成分（Ｃ）及び（Ｄ）の質量割合（Ｃ）／（Ｄ）が、０．２〜１０であり、
成分（Ａ）及び（Ｅ）の質量割合（Ａ）／（Ｅ）が、２〜６０である油中水型乳化化粧料。 The following components (A), (B), (C), (D) and (E):
(A) Fine particle zinc oxide having a specific surface area of 10 to 100 m 2 / g, surface-treated with 3 to 20% by mass of alkylalkoxysilane, 0.01 to 20% by mass,
(B) Iron oxide 0.01-10% by mass,
(C) Volatile silicone oil 1 to 50% by mass,
(D) Volatile hydrocarbon oil 0.5-40% by mass,
(E) The following general formula (1)
Cross-linked polyether-modified silicone represented by 0.01 to 20% by mass,
Containing the mass ratio of the component (C) and (D) (C) / ( D) is, Ri 0.2-10 der,
A water-in-oil emulsified cosmetic having a mass ratio (A) / (E) of the components (A) and (E) of 2 to 60 .
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