WO2023199644A1 - Dispersion and cosmetic containing same - Google Patents
Dispersion and cosmetic containing same Download PDFInfo
- Publication number
- WO2023199644A1 WO2023199644A1 PCT/JP2023/008315 JP2023008315W WO2023199644A1 WO 2023199644 A1 WO2023199644 A1 WO 2023199644A1 JP 2023008315 W JP2023008315 W JP 2023008315W WO 2023199644 A1 WO2023199644 A1 WO 2023199644A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- inorganic oxide
- oxide particles
- dispersion
- dispersion liquid
- Prior art date
Links
- 239000006185 dispersion Substances 0.000 title claims abstract description 110
- 239000002537 cosmetic Substances 0.000 title claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 128
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 116
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 41
- 239000002270 dispersing agent Substances 0.000 claims abstract description 41
- 239000000194 fatty acid Substances 0.000 claims abstract description 41
- 229930195729 fatty acid Natural products 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 35
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 34
- 239000011248 coating agent Substances 0.000 claims abstract description 33
- 238000000576 coating method Methods 0.000 claims abstract description 33
- 239000003921 oil Substances 0.000 claims abstract description 20
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 13
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 13
- 239000010696 ester oil Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 48
- 125000005480 straight-chain fatty acid group Chemical group 0.000 claims description 27
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- 239000011787 zinc oxide Substances 0.000 claims description 10
- WQEPLUUGTLDZJY-UHFFFAOYSA-N pentadecanoic acid Chemical compound CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 9
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 7
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 claims description 6
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 6
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-UHFFFAOYSA-N 0.000 claims description 6
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims description 6
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 claims description 6
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 claims description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 3
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 3
- 239000005639 Lauric acid Substances 0.000 claims description 3
- 235000021314 Palmitic acid Nutrition 0.000 claims description 3
- 229960002446 octanoic acid Drugs 0.000 claims description 3
- 229940005605 valeric acid Drugs 0.000 claims description 3
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 2
- 150000004668 long chain fatty acids Chemical class 0.000 abstract 1
- 238000002834 transmittance Methods 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 14
- -1 glycerin fatty acid ester Chemical class 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229920002545 silicone oil Polymers 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- 239000012756 surface treatment agent Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- LEEDMQGKBNGPDN-UHFFFAOYSA-N 2-methylnonadecane Chemical compound CCCCCCCCCCCCCCCCCC(C)C LEEDMQGKBNGPDN-UHFFFAOYSA-N 0.000 description 3
- SGVYKUFIHHTIFL-UHFFFAOYSA-N 2-methylnonane Chemical compound CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N dodecahydrosqualene Natural products CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 229940057995 liquid paraffin Drugs 0.000 description 3
- 235000019271 petrolatum Nutrition 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 2
- BANXPJUEBPWEOT-UHFFFAOYSA-N 2-methyl-Pentadecane Chemical compound CCCCCCCCCCCCCC(C)C BANXPJUEBPWEOT-UHFFFAOYSA-N 0.000 description 2
- HIQIXEFWDLTDED-UHFFFAOYSA-N 4-hydroxy-1-piperidin-4-ylpyrrolidin-2-one Chemical compound O=C1CC(O)CN1C1CCNCC1 HIQIXEFWDLTDED-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 239000004264 Petrolatum Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002260 anti-inflammatory agent Substances 0.000 description 2
- 229940121363 anti-inflammatory agent Drugs 0.000 description 2
- 230000001166 anti-perspirative effect Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000003213 antiperspirant Substances 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- XJNUECKWDBNFJV-UHFFFAOYSA-N hexadecyl 2-ethylhexanoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(CC)CCCC XJNUECKWDBNFJV-UHFFFAOYSA-N 0.000 description 2
- 239000003906 humectant Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- CJBFZKZYIPBBTO-UHFFFAOYSA-N isotetradecane Natural products CCCCCCCCCCCC(C)C CJBFZKZYIPBBTO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000004812 organic fluorine compounds Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229940066842 petrolatum Drugs 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- YYGNTYWPHWGJRM-UHFFFAOYSA-N (6E,10E,14E,18E)-2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaene Chemical compound CC(C)=CCCC(C)=CCCC(C)=CCCC=C(C)CCC=C(C)CCC=C(C)C YYGNTYWPHWGJRM-UHFFFAOYSA-N 0.000 description 1
- WAYINTBTZWQNSN-UHFFFAOYSA-N 11-methyldodecyl 3,5,5-trimethylhexanoate Chemical compound CC(C)CCCCCCCCCCOC(=O)CC(C)CC(C)(C)C WAYINTBTZWQNSN-UHFFFAOYSA-N 0.000 description 1
- YICVJSOYNBZJAK-UHFFFAOYSA-N 14-methylpentadecyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OCCCCCCCCCCCCCC(C)C YICVJSOYNBZJAK-UHFFFAOYSA-N 0.000 description 1
- 229940043268 2,2,4,4,6,8,8-heptamethylnonane Drugs 0.000 description 1
- DGSZGZSCHSQXFV-UHFFFAOYSA-N 2,3-bis(2-ethylhexanoyloxy)propyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OCC(OC(=O)C(CC)CCCC)COC(=O)C(CC)CCCC DGSZGZSCHSQXFV-UHFFFAOYSA-N 0.000 description 1
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- NFIHXTUNNGIYRF-UHFFFAOYSA-N 2-decanoyloxypropyl decanoate Chemical compound CCCCCCCCCC(=O)OCC(C)OC(=O)CCCCCCCCC NFIHXTUNNGIYRF-UHFFFAOYSA-N 0.000 description 1
- LCVHZNSIAYNAGX-UHFFFAOYSA-N 2-ethylhexyl 3,5,5-trimethylhexanoate Chemical compound CCCCC(CC)COC(=O)CC(C)CC(C)(C)C LCVHZNSIAYNAGX-UHFFFAOYSA-N 0.000 description 1
- XMMODWGMKHUZQW-UHFFFAOYSA-N 2-hydroxy-16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCC(O)C(O)=O XMMODWGMKHUZQW-UHFFFAOYSA-N 0.000 description 1
- RPGJJWLCCOPDAZ-UHFFFAOYSA-N 2-hydroxybehenic acid Chemical compound CCCCCCCCCCCCCCCCCCCCC(O)C(O)=O RPGJJWLCCOPDAZ-UHFFFAOYSA-N 0.000 description 1
- YDZIJQXINJLRLL-UHFFFAOYSA-N 2-hydroxydodecanoic acid Chemical compound CCCCCCCCCCC(O)C(O)=O YDZIJQXINJLRLL-UHFFFAOYSA-N 0.000 description 1
- JGHSBPIZNUXPLA-UHFFFAOYSA-N 2-hydroxyhexadecanoic acid Chemical compound CCCCCCCCCCCCCCC(O)C(O)=O JGHSBPIZNUXPLA-UHFFFAOYSA-N 0.000 description 1
- JYZJYKOZGGEXSX-UHFFFAOYSA-N 2-hydroxymyristic acid Chemical compound CCCCCCCCCCCCC(O)C(O)=O JYZJYKOZGGEXSX-UHFFFAOYSA-N 0.000 description 1
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 description 1
- BGRXBNZMPMGLQI-UHFFFAOYSA-N 2-octyldodecyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OCC(CCCCCCCC)CCCCCCCCCC BGRXBNZMPMGLQI-UHFFFAOYSA-N 0.000 description 1
- UIVPNOBLHXUKDX-UHFFFAOYSA-N 3,5,5-trimethylhexyl 3,5,5-trimethylhexanoate Chemical compound CC(C)(C)CC(C)CCOC(=O)CC(C)CC(C)(C)C UIVPNOBLHXUKDX-UHFFFAOYSA-N 0.000 description 1
- FVKRIDSRWFEQME-UHFFFAOYSA-N 3-methylbutyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCC(C)C FVKRIDSRWFEQME-UHFFFAOYSA-N 0.000 description 1
- BRORPGSJXSLXKN-UHFFFAOYSA-N 6-methylheptyl 3,5,5-trimethylhexanoate Chemical compound CC(C)CCCCCOC(=O)CC(C)CC(C)(C)C BRORPGSJXSLXKN-UHFFFAOYSA-N 0.000 description 1
- KGKQNDQDVZQTAG-UHFFFAOYSA-N 8-methylnonyl 2,2-dimethylpropanoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)(C)C KGKQNDQDVZQTAG-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- RDOFJDLLWVCMRU-UHFFFAOYSA-N Diisobutyl adipate Chemical compound CC(C)COC(=O)CCCCC(=O)OCC(C)C RDOFJDLLWVCMRU-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- CMBYOWLFQAFZCP-UHFFFAOYSA-N Hexyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCCCCC CMBYOWLFQAFZCP-UHFFFAOYSA-N 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- OQILCOQZDHPEAZ-UHFFFAOYSA-N Palmitinsaeure-octylester Natural products CCCCCCCCCCCCCCCC(=O)OCCCCCCCC OQILCOQZDHPEAZ-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004163 Spermaceti wax Substances 0.000 description 1
- BHEOSNUKNHRBNM-UHFFFAOYSA-N Tetramethylsqualene Natural products CC(=C)C(C)CCC(=C)C(C)CCC(C)=CCCC=C(C)CCC(C)C(=C)CCC(C)C(C)=C BHEOSNUKNHRBNM-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
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- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- 238000000151 deposition Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 229940031769 diisobutyl adipate Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- GTXKNKBIKHPHOP-UHFFFAOYSA-N ethyl 7-methyloctanoate Chemical compound CCOC(=O)CCCCCC(C)C GTXKNKBIKHPHOP-UHFFFAOYSA-N 0.000 description 1
- 229940100549 ethylhexyl isononanoate Drugs 0.000 description 1
- GJQLBGWSDGMZKM-UHFFFAOYSA-N ethylhexyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC(CC)CCCCC GJQLBGWSDGMZKM-UHFFFAOYSA-N 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- IUJAMGNYPWYUPM-UHFFFAOYSA-N hentriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC IUJAMGNYPWYUPM-UHFFFAOYSA-N 0.000 description 1
- HGJAQCVKJLUCKW-UHFFFAOYSA-N hexyl 2-ethylhexanoate Chemical compound CCCCCCOC(=O)C(CC)CCCC HGJAQCVKJLUCKW-UHFFFAOYSA-N 0.000 description 1
- 229940100463 hexyl laurate Drugs 0.000 description 1
- 229920006007 hydrogenated polyisobutylene Polymers 0.000 description 1
- 229940078565 isoamyl laurate Drugs 0.000 description 1
- 229940078568 isocetyl myristate Drugs 0.000 description 1
- VKPSKYDESGTTFR-UHFFFAOYSA-N isododecane Natural products CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 description 1
- 229940100554 isononyl isononanoate Drugs 0.000 description 1
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- XUGNVMKQXJXZCD-UHFFFAOYSA-N isopropyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC(C)C XUGNVMKQXJXZCD-UHFFFAOYSA-N 0.000 description 1
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- NEOZOXKVMDBOSG-UHFFFAOYSA-N propan-2-yl 16-methylheptadecanoate Chemical compound CC(C)CCCCCCCCCCCCCCC(=O)OC(C)C NEOZOXKVMDBOSG-UHFFFAOYSA-N 0.000 description 1
- 229940116422 propylene glycol dicaprate Drugs 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/27—Zinc; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/29—Titanium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/31—Hydrocarbons
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/85—Polyesters
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/04—Compounds of zinc
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
Definitions
- the present invention relates to a dispersion containing inorganic oxide particles and a cosmetic containing the same.
- inorganic oxide particles such as titanium oxide and zinc oxide have been contained in cosmetics such as sunscreens (hereinafter simply referred to as cosmetics) because they have an ultraviolet shielding effect.
- a dispersion liquid in which inorganic oxide particles are dispersed at a high concentration is manufactured and the dispersion liquid is used.
- Patent Document 1 discloses a dispersion containing a hydrophobized fine particle metal oxide, a glycerin fatty acid ester and/or a polyglycerin fatty acid ester, a hydroxy fatty acid condensate, a modified silicone, and a hydrocarbon oil.
- this dispersion liquid has high dispersion stability in hydrocarbon oil and can provide a cosmetic that is extremely stable over time.
- Patent Document 2 discloses a dispersion containing a particulate metal oxide surface-treated with trialkoxyalkylsilane, polyhydroxystearic acid, and a non-silicone oil agent. According to Patent Document 2, it is described that this dispersion liquid has excellent dispersibility and stability over time.
- the dispersion described in Patent Document 1 contains as many as three types of dispersants as essential components, it is required to reduce the types of dispersants to be blended. Further, in the example of Patent Document 1, a large amount of cyclic silicone, which is silicone oil, is blended as a solvent in addition to polyisobutene and liquid paraffin, which are hydrocarbon oils. Furthermore, in the dispersion described in Patent Document 2, a silicone coating is formed on the surface of the inorganic oxide particles. In recent years, the characteristics required for dispersions have become more complex and diverse, and as a result, surface treatment agents for inorganic oxide particles, dispersants, and solvents for dispersion liquids are also required to be silicone-free. There is.
- the present invention has been made in view of the above circumstances, and aims to provide a dispersion liquid with good dispersibility using a silicone-free surface treatment agent, dispersant, and solvent, and a cosmetic containing the same. purpose.
- the present inventors discovered that the above-mentioned problems can be solved with a dispersion containing inorganic oxide particles subjected to a specific surface treatment, a specific dispersant, and a specific solvent, and have developed the present invention. completed.
- aspects of the present invention relate to the following dispersions and cosmetics containing inorganic oxide particles subjected to a specific surface treatment, a specific dispersant, and a specific solvent.
- a dispersion containing inorganic oxide particles, a dispersant, and a solvent The inorganic oxide particles have a coating derived from a straight chain fatty acid on the surface thereof, Containing a polyhydroxy fatty acid as the dispersant,
- the solvent contains an oil agent selected from the group consisting of hydrocarbon oils and ester oils.
- dispersion liquid The inorganic oxide particles contain particles selected from the group consisting of titanium oxide and zinc oxide. The dispersion according to [1].
- the inorganic oxide particles further include a coating derived from aluminum hydroxide on the surface thereof. The dispersion according to [1].
- the straight chain fatty acid is stearic acid, margaric acid, valeric acid, caproic acid, enanthic acid, undecanoic acid, lauric acid, tridecylic acid, nonadecylic acid, arachic acid, pentadecylic acid, capric acid, palmitic acid, myristic acid. , nonanoic acid, and caprylic acid,
- the dispersion according to any one of [1] to [3].
- the dispersant contains polyhydroxystearic acid as the polyhydroxy fatty acid.
- the dispersion liquid according to any one of [1] to [4].
- [6] Further contains water, The water content is 0% by mass or more and 10% by mass or less based on the total amount of the dispersion.
- [7] Used in cosmetics The dispersion according to any one of [1] to [6].
- a dispersion liquid according to an embodiment of the present invention is a dispersion liquid containing inorganic oxide particles, a dispersant, and a solvent, wherein the inorganic oxide particles have a coating derived from a straight chain fatty acid on the surface thereof.
- the dispersant contains a polyhydroxy fatty acid
- the solvent contains an oil selected from the group consisting of hydrocarbon oils and ester oils.
- the silicone content of each of the above components is preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0% by mass.
- the dispersibility of the inorganic oxide particles is preferably evaluated based on the transmittance of a dispersion obtained by the method described below. Specifically, the transmittance of the dispersion liquid is determined by coating the dispersion liquid of one embodiment of the present invention on a quartz glass substrate to a wet film thickness of 6 ⁇ m, and drying the resulting dry film.
- the dispersion liquid of this embodiment may contain other components other than the inorganic oxide particles, the dispersant, and the solvent as long as the desired effect can be obtained.
- essential or optional components that may be included in the dispersion liquid of this embodiment will be explained.
- Inorganic oxide particles provide cosmetics with an ultraviolet shielding effect.
- the inorganic oxide particles are provided with a coating derived from straight chain fatty acids on their surfaces.
- inorganic oxide particles include fine particle inorganic oxides such as titanium oxide, zinc oxide, cerium oxide, and bismuth oxide, which have ultraviolet shielding ability, as well as silicic anhydride (silicon oxide), aluminum oxide, which is commonly used in cosmetics.
- examples include fine particle inorganic oxides such as iron oxide, and composites thereof.
- the inorganic oxide particles preferably contain particles selected from the group consisting of titanium oxide and zinc oxide.
- Titanium oxide has a high ability to shield ultraviolet rays in the UVB region (wavelengths of 290 nm to 320 nm), making it possible to increase the SPF (Sun Protection Factor) value of cosmetics containing titanium oxide.
- Zinc oxide has a high ability to shield ultraviolet rays in the UVA region (wavelengths of 320 nm to 400 nm), making it possible to increase the PA (Protection grade of UVA) value of cosmetics containing zinc oxide.
- the upper limit of the particle size of the inorganic oxide particles is not particularly limited, but is preferably 100 nm or less, more preferably 80 nm or less, even more preferably 50 nm or less, and 30 nm or less. This is particularly preferred. By being 100 nm or less, the transmittance (transparency) of the dispersion liquid and manufactured cosmetics can also be made high.
- the lower limit of the particle size of the inorganic oxide particles is not particularly limited, but is preferably 5 nm or more. When the diameter is 5 nm or more, aggregation of inorganic oxide particles is suppressed, and the dispersion stability of dispersions and cosmetics is improved.
- the particle size of the inorganic oxide particles can be determined by, for example, dispersing the powder to primary particles, and then measuring the particle size of a predetermined number of randomly selected particles (for example, 200 particles) using an electron microscope. It can be determined by calculating the average of
- the dispersion liquid of this embodiment is produced by containing inorganic oxide particles having a coating derived from a straight chain fatty acid on the surface, a specific dispersant described below, and a solvent described below.
- the dispersibility of inorganic oxide particles in cosmetics is effectively improved.
- An embodiment in which a film derived from a straight chain fatty acid is provided on the surface of an inorganic oxide particle includes, for example, a film formed by a straight chain fatty acid bonding to the surface of the inorganic oxide particle through hydrogen bonding or the like.
- a group derived from a straight chain fatty acid is bonded to the surface of the inorganic oxide particle through a covalent bond or the like to form a film.
- the said film may be formed on the whole surface of an inorganic oxide particle, and may be formed in a part of the surface of an inorganic oxide particle, the former aspect is preferable.
- the coating adheres well to the complex shapes of the inorganic oxide particles, and has good coverage even with a coating thickness of about 0.5 nm.
- Inorganic oxide particles whose surfaces are provided with a coating derived from such a specific compound can be obtained by surface-treating inorganic oxide particles with a straight chain fatty acid.
- Straight chain fatty acids include stearic acid, margaric acid, valeric acid, caproic acid, enanthic acid, undecanoic acid, lauric acid, tridecylic acid, nonadecylic acid, arachidic acid, pentadecylic acid, capric acid, palmitic acid, myristic acid, and nonanoic acid. , and at least one selected from the group consisting of caprylic acid. Among these, stearic acid is more preferred.
- higher fatty acids such as aluminum hydroxide, wax, higher fatty acid triglycerides, higher fatty acids, higher fatty acid polyvalent metal salts, and higher aliphatic sulfates polyvalent metal salts are present on the surface of the inorganic oxide particles.
- higher alcohols or derivatives thereof perfluorinated or partially fluorinated higher fatty acids, and organic fluorine compounds such as higher alcohols.
- the inorganic oxide particles when the surface of inorganic oxide particles is treated with aluminum hydroxide together with linear fatty acids, the inorganic oxide particles have a coating derived from linear fatty acids and aluminum hydroxide on the surface. can get.
- the inorganic oxide particles will be explained in more detail below.
- Inorganic oxide particles on the surface of which a coating derived from a straight chain fatty acid is formed can be obtained, for example, by subjecting inorganic oxide particles to the following surface treatment using a straight chain fatty acid.
- a method for forming a film derived from straight chain fatty acids on the surface for example, while adjusting the pH of the inorganic oxide particles serving as a base material in an aqueous system, forming a metal salt of a straight chain fatty acid on the surface of the inorganic oxide particles.
- Examples include a method in which inorganic oxide particles and a straight chain fatty acid are stirred and mixed in an organic solvent, and a heat treatment is performed after distilling off the organic solvent.
- the inorganic oxide particles may be produced by the method described above, or, for example, commercially available inorganic oxide particles surface-treated with a straight chain fatty acid may be obtained.
- examples of such surface-treated commercially available inorganic oxide particles include MZ-505T manufactured by Tayka Corporation and ST-455FA manufactured by Titan Industries.
- the dispersion liquid of this embodiment contains inorganic oxide particles having a coating derived from the above-mentioned linear fatty acid and aluminum hydroxide on the surface, a specific dispersing agent described below, and a solvent described below. , the dispersibility of the inorganic oxide particles in the dispersion liquid and the cosmetics produced is effectively improved.
- An embodiment in which the surface of the inorganic oxide particles is provided with a film derived from a straight chain fatty acid and aluminum hydroxide includes, for example, a film in which a straight chain fatty acid and aluminum hydroxide are bonded to the surface of the inorganic oxide particles through hydrogen bonds or the like.
- a film may be formed by bonding groups derived from linear fatty acids and aluminum hydroxide to the surface of the inorganic oxide particles through covalent bonds or the like. It may also be an aspect in which In addition, although the said film may be formed on the whole surface of an inorganic oxide particle, and may be formed in a part of the surface of an inorganic oxide particle, the former aspect is preferable. Further, as a coating, a coating derived from the above two types of compounds may be formed directly on the surface of the inorganic oxide particles, or a coating derived from one of the above two types of compounds. An inner coating may be formed directly on the surface of the inorganic oxide particle, and an outer coating derived from the other compound may be formed on the surface of the inner coating.
- the coating adheres well to the complex shapes of the inorganic oxide particles, and has good coverage even with a coating thickness of about 0.5 nm.
- the inorganic oxide particles preferably contain particles selected from the group consisting of titanium oxide and zinc oxide, and more preferably contain titanium oxide.
- Inorganic oxide particles whose surfaces are coated with a coating derived from such a specific compound can be obtained by surface-treating inorganic oxide particles with a linear fatty acid and aluminum hydroxide.
- higher fatty acids such as wax, higher fatty acid triglycerides, higher fatty acids, higher fatty acid polyvalent metal salts, and higher fatty acid polyvalent metal salts of higher aliphatic sulfates are present.
- higher alcohols or derivatives thereof, perfluorinated or partially fluorinated higher fatty acids, and organic fluorine compounds such as higher alcohols.
- Inorganic oxide particles with a coating derived from a straight chain fatty acid and aluminum hydroxide formed on the surface can be obtained by, for example, subjecting the inorganic oxide particles to the following surface treatment using a straight chain fatty acid and aluminum hydroxide. It will be done.
- a method for forming a film derived from straight chain fatty acids on the surface for example, while adjusting the pH of the inorganic oxide particles serving as a base material in an aqueous system, forming a metal salt of a straight chain fatty acid on the surface of the inorganic oxide particles. Examples include a method in which inorganic oxide particles and a straight chain fatty acid are stirred and mixed in an organic solvent, and a heat treatment is performed after distilling off the organic solvent.
- inorganic oxide particles are dispersed in an aqueous system, a water-soluble salt of aluminum hydroxide is dissolved therein, and the inorganic oxide is added while adjusting the pH.
- examples include a method of depositing aluminum hydroxide on the surface of particles.
- the inorganic oxide particles may be produced by the method described above, or, for example, commercially available inorganic oxide particles surface-treated with a linear fatty acid and aluminum hydroxide may be obtained.
- Commercially available inorganic oxide particles with such surface treatment include ST-450SA, ST-455, STV-455, ST-457SA, ST-485SA15 manufactured by Titan Kogyo Co., Ltd., and STR-100C manufactured by Sakai Chemical Industry Co., Ltd. -LF, Teika's MT-01, MT-100TV, MT-100Z, etc.
- the lower limit of the ratio of the mass of the coating derived from the specific compound to the total mass of the inorganic oxide particles having the coating derived from the specific compound on the surface may be 1% by mass or more.
- the content is preferably 3% by mass or more.
- the upper limit of the mass ratio (e.g., coverage) of the coating derived from the specific compound to the total mass of the inorganic oxide particles having the coating derived from the specific compound on the surface may be 30% by mass or less. It is preferably 20% by mass or less, more preferably 15% by mass or less.
- the upper limit of the mass ratio (e.g., coverage) of the film derived from a specific compound is 30% by mass or less, the mass of the inorganic oxide particles themselves contained in the dispersion can be increased, making it more effective. UV shielding effect can be obtained.
- the lower limit of the content of inorganic oxide particles whose surfaces are coated with a film derived from the specific compound described above is preferably 20% by mass or more, more preferably 30% by mass or more based on the total amount of the dispersion.
- the upper limit of the content of inorganic oxide particles having a coating derived from the above-mentioned specific compound on the surface is preferably 80% by mass or less, more preferably 75% by mass or less, and 70% by mass or less based on the total amount of the dispersion.
- the dispersion stability of the inorganic oxide particles in the dispersion and cosmetics is improved.
- the dispersant disperses the inorganic oxide particles in the dispersion liquid.
- the dispersion liquid of this embodiment contains polyhydroxy fatty acid as a dispersant.
- the dispersion liquid of this embodiment contains the above-described specific inorganic oxide particles and the above-mentioned specific dispersant, so that even if the dispersion liquid is mainly composed of hydrocarbon oil or ester oil as a solvent, The dispersibility of the inorganic oxide particles in the dispersion liquid and the cosmetics produced is effectively improved.
- Polyhydroxy fatty acids are self-condensates of hydroxy fatty acids having 12 or more and 24 or less carbon atoms.
- the hydroxy fatty acid having 12 or more and 24 or less carbon atoms include hydroxylauric acid, hydroxymyristic acid, hydroxypentadecyl acid, hydroxypalmitic acid, hydroxystearic acid, hydroxyisostearic acid, and hydroxybehenic acid.
- hydroxystearic acid is preferred from the viewpoint of improving the dispersibility of inorganic oxide particles.
- the average degree of polymerization of the polyhydroxy fatty acid is preferably 3 or more and 10 or less, more preferably 4 or more and 8 or less.
- RICOS PHF-30-C manufactured by Ito Oil Co., Ltd.
- Saracos HS-6C manufactured by Nisshin Oilio Co., Ltd.
- One type of dispersant may be used alone, or two or more types may be used in combination as necessary.
- the content of the dispersant is preferably determined depending on the content of the above-mentioned inorganic oxide particles in the dispersion.
- the content of the dispersant is preferably determined depending on the content of the above-mentioned inorganic oxide particles in the dispersion.
- the lower limit of the content of the dispersant is preferably 0.5% by mass or more, more preferably 1% by mass or more, based on the content of the inorganic oxide particles, More preferably, the content is 1.5% by mass or more.
- the upper limit of the content ratio of the dispersant is preferably 40% by mass or less, more preferably 35% by mass or less, and 30% by mass or less with respect to the content of the inorganic oxide particles. is even more preferable.
- the content of the dispersant exceeds 40% by mass, the viscosity of the dispersion liquid tends to increase relatively, and the dispersibility and transparency tend to decrease relatively.
- the content of the dispersant is 40% by mass or less, such an increase in viscosity and a decrease in dispersibility and transparency can be effectively suppressed.
- the transmittance (transparency) of the dispersion liquid can be improved. can be made higher.
- solvent is a dispersion of a dispersion.
- an oil agent selected from the group consisting of hydrocarbon oils and ester oils is used.
- hydrocarbon oils examples include isobutene, hydrogenated polyisobutene, decane, isodecane, dodecane, isododecane, tetradecane, isotetradecane, hexadecane, isohexadecane, light isoparaffin, squalene, squalane, liquid paraffin, liquid isoparaffin, light liquid isoparaffin, and heavy Examples include liquid isoparaffin, ⁇ -olefin oligomer, liquid paraffin, cycloparaffin, petrolatum (petrolatum), paraffin wax, beeswax, candelilla wax, cotton wax, ceresin wax, carnauba wax, spermaceti wax, montan wax, microcrystalline wax, Japanese wax, etc. It will be done.
- the number of carbon atoms in the hydrocarbon oil is preferably 4 or more and 40 or less, more preferably 10 or more and 30 or less.
- ester oils include isononyl isononanoate, isotridecyl isononanoate, ethylhexyl isononanoate, isodecyl neopentanoate, isoamyl laurate, hexyl laurate, isopropyl myristate, diisobutyl adipate, isodecyl isononanoate, ethyl isononanoate, isopropyl isostearate.
- One type of solvent may be used alone, or two or more types may be used in combination as necessary.
- the lower limit of the content of the solvent is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and 30% by mass, based on the total amount of the dispersion. % or more is particularly preferable.
- the upper limit of the content of the solvent is preferably 60% by mass or less, and more preferably 57% by mass or less, based on the total amount of the dispersion.
- the dispersion liquid of this embodiment is mainly composed of the above-mentioned hydrocarbon oil or ester oil, and it is preferable that the content of silicone oil is small. Specifically, the content of silicone oil is preferably 5% by mass or less, more preferably 0% by mass, based on the total amount of the dispersion.
- the dispersion liquid of this embodiment can contain various components used in ordinary cosmetics as other components.
- Other ingredients include, for example, water, surfactants, ultraviolet absorbers, waxes, antiperspirants, preservatives/sterilizers, fragrances, salts, antioxidants, pH adjusters, chelating agents, cooling agents, and anti-inflammatory agents.
- Other additives such as whitening agents, thickeners, humectants, and alcohol may also be included.
- the content of water is preferably 0% by mass or more and 10% by mass or less, and 0.01% by mass or more and 5% by mass or less based on the total amount of the dispersion liquid. It is more preferable. Furthermore, depending on the manufacturing conditions of the inorganic oxide particles mentioned above, a certain amount of water may be included. Even such inorganic oxide particles containing water may be used without adjusting the water content, or may be used with the water content increased or decreased.
- the water content is preferably 0% by mass or more and 8% by mass or less, and preferably 0.01% by mass or more and 4% by mass or less based on the total amount of the dispersion liquid. More preferred.
- the method for producing the dispersion liquid of one embodiment of the present invention is not particularly limited, and conventionally known methods can be used. For example, a method of mixing each component using a media stirring mill, a disper, an ultrasonic disperser, a high-speed mixer, etc. can be mentioned.
- the cosmetic according to one embodiment of the present invention can be manufactured using the above-mentioned dispersion.
- the cosmetic contains silicone oil, water, organic solvent, surfactant, ultraviolet absorber, wavelength converter, wax, antiperspirant, preservative/sterilizer, fragrance, salt, antioxidant, and pH adjustment in the dispersion liquid. It can be manufactured by adding and mixing additives such as a chelating agent, a cooling agent, an anti-inflammatory agent, a whitening agent, a thickener, a humectant, alcohol, and other additives.
- the inorganic oxide particles, dispersant, and solvent listed in Table 1 below were mixed in the amounts listed in Table 2 below to prepare the inorganic oxide particles, dispersant, and solvent of Examples 1A to 1C, 2A to 2C, and Comparative Examples 1A to 1C, and 2A to 2C.
- a dispersion was prepared. Specifically, first, the inorganic oxide particles listed in Table 1 below are heated or stored under 90% humidity to increase or decrease the moisture content, thereby forming inorganic oxide particles with low moisture content, We prepared grades with normal moisture content (without moisture adjustment) and high moisture content.
- the dispersion liquid is applied to a quartz glass substrate to a wet thickness of 6 ⁇ m using bar coater #3, and dried at 50° C. to 120° C. for 5 minutes to 30 minutes, depending on the type of solvent. A dry film was formed. Then, the dried film was irradiated with light with a wavelength of 400 nm to 750 nm using UV-3600i Plus manufactured by Shimadzu Corporation, and the integrated value (area) of the transmitted light intensity (transmittance) in the wavelength range of 400 nm to 750 nm was determined. Ta. When the transmittance was 100% in the entire wavelength range, the maximum integrated value was 35,000, so the obtained integrated value was divided by 35,000 and converted into a percentage. The results are shown in Table 2.
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Abstract
Provided are a dispersion having good dispersibility and a cosmetic containing the same, said dispersion containing a surface preparation agent, a dispersant, and a solvent, all including no silicone. In the present invention, a dispersion is used that contains inorganic oxide particles, a dispersant, and a solvent, said inorganic oxide particles having, on the surfaces thereof, a coating derived from long chain fatty acid, said dispersion containing polyhydroxy fatty acid as the dispersant and containing, as the solvent, an oil solution selected from the group consisting of hydrocarbon oil and ester oil.
Description
本発明は、無機酸化物粒子を含有する分散液、及びこれを含む化粧料に関する。
The present invention relates to a dispersion containing inorganic oxide particles and a cosmetic containing the same.
従来より、酸化チタンや酸化亜鉛等の無機酸化物粒子は紫外線遮蔽効果を有することから、日焼け止めサンスクリーン等の化粧料（以下、単に化粧料と表記する。）に含有されている。
Conventionally, inorganic oxide particles such as titanium oxide and zinc oxide have been contained in cosmetics such as sunscreens (hereinafter simply referred to as cosmetics) because they have an ultraviolet shielding effect.
このような化粧料の製造の際には、高濃度の無機酸化物粒子が分散された分散液を製造して、その分散液を使用することが行われる。このような分散液を予め製造することで、化粧料の製造の際に取り扱い性や利便性を向上させることができる。
When manufacturing such cosmetics, a dispersion liquid in which inorganic oxide particles are dispersed at a high concentration is manufactured and the dispersion liquid is used. By producing such a dispersion liquid in advance, handling and convenience can be improved during the production of cosmetics.
例えば、特許文献１には、疎水化処理された微粒子金属酸化物、グリセリン脂肪酸エステル及び／又はポリグリセリン脂肪酸エステル、ヒドロキシ脂肪酸縮合物、変性シリコーン、及び炭化水素油を含む分散液が開示されている。特許文献１によれば、この分散液は炭化水素油中での分散安定性が高く、経時的に極めて安定な化粧料を提供することができることが記載されている。
For example, Patent Document 1 discloses a dispersion containing a hydrophobized fine particle metal oxide, a glycerin fatty acid ester and/or a polyglycerin fatty acid ester, a hydroxy fatty acid condensate, a modified silicone, and a hydrocarbon oil. . According to Patent Document 1, it is described that this dispersion liquid has high dispersion stability in hydrocarbon oil and can provide a cosmetic that is extremely stable over time.
また、特許文献２には、トリアルコキシアルキルシランで表面処理された微粒子金属酸化物、ポリヒドロキシステアリン酸、及び非シリコーン系油剤を含む分散液が開示されている。特許文献２によれば、この分散液は分散性や経時での安定性に優れることが記載されている。
Further, Patent Document 2 discloses a dispersion containing a particulate metal oxide surface-treated with trialkoxyalkylsilane, polyhydroxystearic acid, and a non-silicone oil agent. According to Patent Document 2, it is described that this dispersion liquid has excellent dispersibility and stability over time.
しかし、特許文献１に記載された分散液では３種類もの分散剤を必須成分としているため、配合する分散剤の種類を少なくすることが求められている。また、特許文献１の実施例では、溶剤として、炭化水素油であるポリイソブテンや流動パラフィン以外に、シリコーン油である環状シリコーンが多量に配合されている。さらに、特許文献２に記載された分散液では無機酸化物粒子の表面にシリコーン被膜が形成されている。近年では、分散液に求められる要求特性が複雑多様化しているため、分散液の配合成分として、無機酸化物粒子の表面処理剤、分散剤、及び溶剤にもシリコーンフリーであることが求められている。
However, since the dispersion described in Patent Document 1 contains as many as three types of dispersants as essential components, it is required to reduce the types of dispersants to be blended. Further, in the example of Patent Document 1, a large amount of cyclic silicone, which is silicone oil, is blended as a solvent in addition to polyisobutene and liquid paraffin, which are hydrocarbon oils. Furthermore, in the dispersion described in Patent Document 2, a silicone coating is formed on the surface of the inorganic oxide particles. In recent years, the characteristics required for dispersions have become more complex and diverse, and as a result, surface treatment agents for inorganic oxide particles, dispersants, and solvents for dispersion liquids are also required to be silicone-free. There is.
本発明は、以上の状況に鑑みてなされたものであり、シリコーンフリーの表面処理剤、分散剤、及び溶剤を用いた分散性が良好な分散液、及びこれを含む化粧料を提供することを目的とする。
The present invention has been made in view of the above circumstances, and aims to provide a dispersion liquid with good dispersibility using a silicone-free surface treatment agent, dispersant, and solvent, and a cosmetic containing the same. purpose.
本発明者らは、特定の表面処理が施された無機酸化物粒子と、特定の分散剤と、特定の溶剤を含有する分散液であれば、上記の課題を解決できることを見出し、本発明を完成した。
The present inventors discovered that the above-mentioned problems can be solved with a dispersion containing inorganic oxide particles subjected to a specific surface treatment, a specific dispersant, and a specific solvent, and have developed the present invention. completed.
本発明の態様は、特定の表面処理が施された無機酸化物粒子と、特定の分散剤と、特定の溶剤とを含有する以下の分散液、及び化粧料に関する。
Aspects of the present invention relate to the following dispersions and cosmetics containing inorganic oxide particles subjected to a specific surface treatment, a specific dispersant, and a specific solvent.
［１］ 無機酸化物粒子と、分散剤と、溶剤と、を含有する分散液であって、
前記無機酸化物粒子は、その表面に直鎖脂肪酸に由来する被膜を備え、
前記分散剤として、ポリヒドロキシ脂肪酸を含有し、
前記溶剤として、炭化水素油、及びエステル油からなる群より選ばれる油剤を含有する、
分散液。
［２］ 前記無機酸化物粒子として、酸化チタン、及び酸化亜鉛からなる群より選ばれる粒子を含有する、
［１］に記載の分散液。
［３］ 前記無機酸化物粒子が、その表面にさらに水酸化アルミニウムに由来する被膜を備える、
［１］に記載の分散液。
［４］ 前記直鎖脂肪酸が、ステアリン酸、マルガリン酸、吉草酸、カプロン酸、エナント酸、ウンデカン酸、ラウリン酸、トリデシル酸、ノナデシル酸、アラキン酸、ペンタデシル酸、カプリン酸、パルミチン酸、ミリスチン酸、ノナン酸、及びカプリル酸からなる群より選択される少なくとも１種である、
［１］～［３］のいずれか１つに記載の分散液。
［５］ 前記分散剤が、前記ポリヒドロキシ脂肪酸としてポリヒドロキシステアリン酸を含有する、
［１］～［４］のいずれか１つに記載の分散液。
［６］ さらに水を含み、
前記水の含有量が、分散液の全量に対して０質量％以上１０質量％以下である、
［１］～［５］のいずれか１つに記載の分散液。
［７］ 化粧料に用いられる、
［１］～［６］のいずれか１つに記載の分散液。
［８］ ［１］～［７］のいずれか１つに記載の分散液を含有する、
化粧料。 [1] A dispersion containing inorganic oxide particles, a dispersant, and a solvent,
The inorganic oxide particles have a coating derived from a straight chain fatty acid on the surface thereof,
Containing a polyhydroxy fatty acid as the dispersant,
The solvent contains an oil agent selected from the group consisting of hydrocarbon oils and ester oils.
dispersion liquid.
[2] The inorganic oxide particles contain particles selected from the group consisting of titanium oxide and zinc oxide.
The dispersion according to [1].
[3] The inorganic oxide particles further include a coating derived from aluminum hydroxide on the surface thereof.
The dispersion according to [1].
[4] The straight chain fatty acid is stearic acid, margaric acid, valeric acid, caproic acid, enanthic acid, undecanoic acid, lauric acid, tridecylic acid, nonadecylic acid, arachic acid, pentadecylic acid, capric acid, palmitic acid, myristic acid. , nonanoic acid, and caprylic acid,
The dispersion according to any one of [1] to [3].
[5] The dispersant contains polyhydroxystearic acid as the polyhydroxy fatty acid.
The dispersion liquid according to any one of [1] to [4].
[6] Further contains water,
The water content is 0% by mass or more and 10% by mass or less based on the total amount of the dispersion.
The dispersion according to any one of [1] to [5].
[7] Used in cosmetics,
The dispersion according to any one of [1] to [6].
[8] Contains the dispersion according to any one of [1] to [7],
Cosmetics.
前記無機酸化物粒子は、その表面に直鎖脂肪酸に由来する被膜を備え、
前記分散剤として、ポリヒドロキシ脂肪酸を含有し、
前記溶剤として、炭化水素油、及びエステル油からなる群より選ばれる油剤を含有する、
分散液。
［２］ 前記無機酸化物粒子として、酸化チタン、及び酸化亜鉛からなる群より選ばれる粒子を含有する、
［１］に記載の分散液。
［３］ 前記無機酸化物粒子が、その表面にさらに水酸化アルミニウムに由来する被膜を備える、
［１］に記載の分散液。
［４］ 前記直鎖脂肪酸が、ステアリン酸、マルガリン酸、吉草酸、カプロン酸、エナント酸、ウンデカン酸、ラウリン酸、トリデシル酸、ノナデシル酸、アラキン酸、ペンタデシル酸、カプリン酸、パルミチン酸、ミリスチン酸、ノナン酸、及びカプリル酸からなる群より選択される少なくとも１種である、
［１］～［３］のいずれか１つに記載の分散液。
［５］ 前記分散剤が、前記ポリヒドロキシ脂肪酸としてポリヒドロキシステアリン酸を含有する、
［１］～［４］のいずれか１つに記載の分散液。
［６］ さらに水を含み、
前記水の含有量が、分散液の全量に対して０質量％以上１０質量％以下である、
［１］～［５］のいずれか１つに記載の分散液。
［７］ 化粧料に用いられる、
［１］～［６］のいずれか１つに記載の分散液。
［８］ ［１］～［７］のいずれか１つに記載の分散液を含有する、
化粧料。 [1] A dispersion containing inorganic oxide particles, a dispersant, and a solvent,
The inorganic oxide particles have a coating derived from a straight chain fatty acid on the surface thereof,
Containing a polyhydroxy fatty acid as the dispersant,
The solvent contains an oil agent selected from the group consisting of hydrocarbon oils and ester oils.
dispersion liquid.
[2] The inorganic oxide particles contain particles selected from the group consisting of titanium oxide and zinc oxide.
The dispersion according to [1].
[3] The inorganic oxide particles further include a coating derived from aluminum hydroxide on the surface thereof.
The dispersion according to [1].
[4] The straight chain fatty acid is stearic acid, margaric acid, valeric acid, caproic acid, enanthic acid, undecanoic acid, lauric acid, tridecylic acid, nonadecylic acid, arachic acid, pentadecylic acid, capric acid, palmitic acid, myristic acid. , nonanoic acid, and caprylic acid,
The dispersion according to any one of [1] to [3].
[5] The dispersant contains polyhydroxystearic acid as the polyhydroxy fatty acid.
The dispersion liquid according to any one of [1] to [4].
[6] Further contains water,
The water content is 0% by mass or more and 10% by mass or less based on the total amount of the dispersion.
The dispersion according to any one of [1] to [5].
[7] Used in cosmetics,
The dispersion according to any one of [1] to [6].
[8] Contains the dispersion according to any one of [1] to [7],
Cosmetics.
本発明によれば、シリコーンフリーの表面処理剤、分散剤、及び溶剤を用いた分散性が良好な分散液、及びこれを含む化粧料を提供することができる。
According to the present invention, it is possible to provide a dispersion liquid with good dispersibility using a silicone-free surface treatment agent, dispersant, and solvent, and a cosmetic containing the same.
＜分散液＞
本発明の一実施形態の分散液は、無機酸化物粒子と、分散剤と、溶剤と、を含有する分散液であって、上記無機酸化物粒子は、その表面に直鎖脂肪酸に由来する被膜を備え、上記分散剤として、ポリヒドロキシ脂肪酸を含有し、上記溶剤として、炭化水素油、及びエステル油からなる群より選ばれる油剤を含有する。
かかるシリコーンフリーの表面処理剤、分散剤、及び溶剤を用いることで、無機酸化物粒子の分散性（分散安定性）を向上させることができる。
なお、本明細書において、「フリーである」とは、表面処理剤、分散剤、及び溶剤のいずれの成分についても、シリコーンを少量だけ含んでいてもよく、好ましくはシリコーンを含まないことを意味する。上記各成分のシリコーン含有量は、３質量％以下であることが好ましく、１質量％以下であることがより好ましく、０質量％であることがさらに好ましい。
なお、無機酸化物粒子の分散性は、以下に説明する方法で得られた分散液の透過率をもとに評価することが好ましい。具体的には、分散液の透過率は、本発明の一実施形態の分散液を、石英ガラス基材にＷＥＴ膜厚６μｍになるように塗布及び乾燥し、得られた乾燥膜に、分光光度計を用いて波長４００ｎｍから７５０ｎｍまでの光を照射して、上記波長領域の透過光強度（透過率）の積算値を求め、該積算値を、上記波長領域で透過率が１００％に相当する積算値で割り、パーセント表示に換算することにより求められる。透過率は、６０％以上７０％未満であることが好ましく、７０％以上８０％未満であることがより好ましく、８０％以上であることがさらに好ましい。
また、本実施形態の分散液は、所望する効果が得られる限りにおいて、無機酸化物粒子、分散剤、及び溶剤以外の他の成分を含んでいてもよい。以下、本実施形態の分散液が含み得る、必須、又は任意の成分について説明する。 <Dispersion>
A dispersion liquid according to an embodiment of the present invention is a dispersion liquid containing inorganic oxide particles, a dispersant, and a solvent, wherein the inorganic oxide particles have a coating derived from a straight chain fatty acid on the surface thereof. The dispersant contains a polyhydroxy fatty acid, and the solvent contains an oil selected from the group consisting of hydrocarbon oils and ester oils.
By using such a silicone-free surface treatment agent, dispersant, and solvent, the dispersibility (dispersion stability) of inorganic oxide particles can be improved.
In this specification, "free" means that any of the components of the surface treatment agent, dispersant, and solvent may contain only a small amount of silicone, and preferably does not contain silicone. do. The silicone content of each of the above components is preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0% by mass.
Note that the dispersibility of the inorganic oxide particles is preferably evaluated based on the transmittance of a dispersion obtained by the method described below. Specifically, the transmittance of the dispersion liquid is determined by coating the dispersion liquid of one embodiment of the present invention on a quartz glass substrate to a wet film thickness of 6 μm, and drying the resulting dry film. Using a meter, irradiate light with wavelengths from 400 nm to 750 nm to determine the integrated value of transmitted light intensity (transmittance) in the above wavelength range, and calculate the integrated value as the value corresponding to 100% transmittance in the above wavelength range. It is obtained by dividing by the integrated value and converting it to a percentage. The transmittance is preferably 60% or more and less than 70%, more preferably 70% or more and less than 80%, and even more preferably 80% or more.
Moreover, the dispersion liquid of this embodiment may contain other components other than the inorganic oxide particles, the dispersant, and the solvent as long as the desired effect can be obtained. Hereinafter, essential or optional components that may be included in the dispersion liquid of this embodiment will be explained.
本発明の一実施形態の分散液は、無機酸化物粒子と、分散剤と、溶剤と、を含有する分散液であって、上記無機酸化物粒子は、その表面に直鎖脂肪酸に由来する被膜を備え、上記分散剤として、ポリヒドロキシ脂肪酸を含有し、上記溶剤として、炭化水素油、及びエステル油からなる群より選ばれる油剤を含有する。
かかるシリコーンフリーの表面処理剤、分散剤、及び溶剤を用いることで、無機酸化物粒子の分散性（分散安定性）を向上させることができる。
なお、本明細書において、「フリーである」とは、表面処理剤、分散剤、及び溶剤のいずれの成分についても、シリコーンを少量だけ含んでいてもよく、好ましくはシリコーンを含まないことを意味する。上記各成分のシリコーン含有量は、３質量％以下であることが好ましく、１質量％以下であることがより好ましく、０質量％であることがさらに好ましい。
なお、無機酸化物粒子の分散性は、以下に説明する方法で得られた分散液の透過率をもとに評価することが好ましい。具体的には、分散液の透過率は、本発明の一実施形態の分散液を、石英ガラス基材にＷＥＴ膜厚６μｍになるように塗布及び乾燥し、得られた乾燥膜に、分光光度計を用いて波長４００ｎｍから７５０ｎｍまでの光を照射して、上記波長領域の透過光強度（透過率）の積算値を求め、該積算値を、上記波長領域で透過率が１００％に相当する積算値で割り、パーセント表示に換算することにより求められる。透過率は、６０％以上７０％未満であることが好ましく、７０％以上８０％未満であることがより好ましく、８０％以上であることがさらに好ましい。
また、本実施形態の分散液は、所望する効果が得られる限りにおいて、無機酸化物粒子、分散剤、及び溶剤以外の他の成分を含んでいてもよい。以下、本実施形態の分散液が含み得る、必須、又は任意の成分について説明する。 <Dispersion>
A dispersion liquid according to an embodiment of the present invention is a dispersion liquid containing inorganic oxide particles, a dispersant, and a solvent, wherein the inorganic oxide particles have a coating derived from a straight chain fatty acid on the surface thereof. The dispersant contains a polyhydroxy fatty acid, and the solvent contains an oil selected from the group consisting of hydrocarbon oils and ester oils.
By using such a silicone-free surface treatment agent, dispersant, and solvent, the dispersibility (dispersion stability) of inorganic oxide particles can be improved.
In this specification, "free" means that any of the components of the surface treatment agent, dispersant, and solvent may contain only a small amount of silicone, and preferably does not contain silicone. do. The silicone content of each of the above components is preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0% by mass.
Note that the dispersibility of the inorganic oxide particles is preferably evaluated based on the transmittance of a dispersion obtained by the method described below. Specifically, the transmittance of the dispersion liquid is determined by coating the dispersion liquid of one embodiment of the present invention on a quartz glass substrate to a wet film thickness of 6 μm, and drying the resulting dry film. Using a meter, irradiate light with wavelengths from 400 nm to 750 nm to determine the integrated value of transmitted light intensity (transmittance) in the above wavelength range, and calculate the integrated value as the value corresponding to 100% transmittance in the above wavelength range. It is obtained by dividing by the integrated value and converting it to a percentage. The transmittance is preferably 60% or more and less than 70%, more preferably 70% or more and less than 80%, and even more preferably 80% or more.
Moreover, the dispersion liquid of this embodiment may contain other components other than the inorganic oxide particles, the dispersant, and the solvent as long as the desired effect can be obtained. Hereinafter, essential or optional components that may be included in the dispersion liquid of this embodiment will be explained.
［無機酸化物粒子］
無機酸化物粒子は、化粧料に紫外線遮蔽効果を付与する。この無機酸化物粒子は、その表面には、直鎖脂肪酸に由来する被膜を備える。 [Inorganic oxide particles]
Inorganic oxide particles provide cosmetics with an ultraviolet shielding effect. The inorganic oxide particles are provided with a coating derived from straight chain fatty acids on their surfaces.
無機酸化物粒子は、化粧料に紫外線遮蔽効果を付与する。この無機酸化物粒子は、その表面には、直鎖脂肪酸に由来する被膜を備える。 [Inorganic oxide particles]
Inorganic oxide particles provide cosmetics with an ultraviolet shielding effect. The inorganic oxide particles are provided with a coating derived from straight chain fatty acids on their surfaces.
無機酸化物粒子としては、紫外線遮蔽能を有する酸化チタン、酸化亜鉛、酸化セリウム、酸化ビスマス等の微粒子無機酸化物や、一般的に化粧品に用いられる無水ケイ酸（ケイ素酸化物）、酸化アルミニウム、酸化鉄等の微粒子無機酸化物、及びこれらの複合体等が挙げられる。
Examples of inorganic oxide particles include fine particle inorganic oxides such as titanium oxide, zinc oxide, cerium oxide, and bismuth oxide, which have ultraviolet shielding ability, as well as silicic anhydride (silicon oxide), aluminum oxide, which is commonly used in cosmetics. Examples include fine particle inorganic oxides such as iron oxide, and composites thereof.
無機酸化物粒子としては、酸化チタン、及び酸化亜鉛からなる群より選ばれる粒子を含有することが好ましい。酸化チタンは、紫外線領域のＵＶＢ領域（波長２９０ｎｍ～３２０ｎｍ）での紫外線遮蔽能が高く、酸化チタンを含有する化粧料のＳＰＦ（Ｓｕｎ Ｐｒｏｔｅｃｔｉｏｎ Ｆａｃｔｏｒ）値を高めることが可能となる。酸化亜鉛は、紫外線領域のＵＶＡ領域（波長３２０ｎｍ～４００ｎｍ）での紫外線遮蔽能が高く、酸化亜鉛を含有する化粧料のＰＡ（Ｐｒｏｔｅｃｔｉｏｎ ｇｒａｄｅ ｏｆ ＵＶＡ）値を高めることが可能となる。
The inorganic oxide particles preferably contain particles selected from the group consisting of titanium oxide and zinc oxide. Titanium oxide has a high ability to shield ultraviolet rays in the UVB region (wavelengths of 290 nm to 320 nm), making it possible to increase the SPF (Sun Protection Factor) value of cosmetics containing titanium oxide. Zinc oxide has a high ability to shield ultraviolet rays in the UVA region (wavelengths of 320 nm to 400 nm), making it possible to increase the PA (Protection grade of UVA) value of cosmetics containing zinc oxide.
無機酸化物粒子の粒子径の上限は、特に限定されるものではないが、１００ｎｍ以下であることが好ましく、８０ｎｍ以下であることがより好ましく、５０ｎｍ以下であることがさらに好ましく、３０ｎｍ以下であることが特に好ましい。１００ｎｍ以下であることで、分散液や製造される化粧料の透過率（透明度）も高いものとすることが可能となる。
The upper limit of the particle size of the inorganic oxide particles is not particularly limited, but is preferably 100 nm or less, more preferably 80 nm or less, even more preferably 50 nm or less, and 30 nm or less. This is particularly preferred. By being 100 nm or less, the transmittance (transparency) of the dispersion liquid and manufactured cosmetics can also be made high.
無機酸化物粒子の粒子径の下限は、特に限定されるものではないが、５ｎｍ以上であることが好ましい。５ｎｍ以上であることで、無機酸化物粒子同士の凝集が抑制されて、分散液や化粧料の分散安定性が向上する。
The lower limit of the particle size of the inorganic oxide particles is not particularly limited, but is preferably 5 nm or more. When the diameter is 5 nm or more, aggregation of inorganic oxide particles is suppressed, and the dispersion stability of dispersions and cosmetics is improved.
なお、無機酸化物粒子の粒子径は、例えば、粉体を一次粒子まで分散後、電子顕微鏡でランダムに選択した所定数（例えば２００個）の粒子の粒子径を測定し、その１次粒子径の平均を算出することにより求めることができる。
The particle size of the inorganic oxide particles can be determined by, for example, dispersing the powder to primary particles, and then measuring the particle size of a predetermined number of randomly selected particles (for example, 200 particles) using an electron microscope. It can be determined by calculating the average of
（表面に直鎖脂肪酸に由来する被膜を備える無機酸化物粒子）
本実施形態の分散液は、表面に直鎖脂肪酸に由来する被膜を備える無機酸化物粒子と、後述する特定の分散剤と、後述する溶剤と、を含有することにより、分散液及び製造される化粧料中での無機酸化物粒子の分散性が効果的に向上する。
無機酸化物粒子の表面に、直鎖脂肪酸に由来する被膜を備える態様としては、例えば、無機酸化物粒子の表面に、直鎖脂肪酸が、水素結合等により結合することにより被膜を形成している態様であってもよいし、無機酸化物粒子の表面に、直鎖脂肪酸に由来する基が、共有結合等により結合することにより被膜を形成している態様であってもよい。なお、上記被膜は、無機酸化物粒子の表面全体に形成されていてもよいし、無機酸化物粒子の表面の一部に形成されていてもよいが、前者の態様が好ましい。
被膜は、無機酸化物粒子の複雑な形状にも付き回りがよく、０．５ｎｍ程度の被膜であっても被覆性がよい。
このような特定の化合物に由来する被膜を表面に備える無機酸化物粒子は、無機酸化物粒子を、直鎖脂肪酸で表面処理することにより得られる。 (Inorganic oxide particles with a coating derived from straight chain fatty acids on the surface)
The dispersion liquid of this embodiment is produced by containing inorganic oxide particles having a coating derived from a straight chain fatty acid on the surface, a specific dispersant described below, and a solvent described below. The dispersibility of inorganic oxide particles in cosmetics is effectively improved.
An embodiment in which a film derived from a straight chain fatty acid is provided on the surface of an inorganic oxide particle includes, for example, a film formed by a straight chain fatty acid bonding to the surface of the inorganic oxide particle through hydrogen bonding or the like. Alternatively, it may be an embodiment in which a group derived from a straight chain fatty acid is bonded to the surface of the inorganic oxide particle through a covalent bond or the like to form a film. In addition, although the said film may be formed on the whole surface of an inorganic oxide particle, and may be formed in a part of the surface of an inorganic oxide particle, the former aspect is preferable.
The coating adheres well to the complex shapes of the inorganic oxide particles, and has good coverage even with a coating thickness of about 0.5 nm.
Inorganic oxide particles whose surfaces are provided with a coating derived from such a specific compound can be obtained by surface-treating inorganic oxide particles with a straight chain fatty acid.
本実施形態の分散液は、表面に直鎖脂肪酸に由来する被膜を備える無機酸化物粒子と、後述する特定の分散剤と、後述する溶剤と、を含有することにより、分散液及び製造される化粧料中での無機酸化物粒子の分散性が効果的に向上する。
無機酸化物粒子の表面に、直鎖脂肪酸に由来する被膜を備える態様としては、例えば、無機酸化物粒子の表面に、直鎖脂肪酸が、水素結合等により結合することにより被膜を形成している態様であってもよいし、無機酸化物粒子の表面に、直鎖脂肪酸に由来する基が、共有結合等により結合することにより被膜を形成している態様であってもよい。なお、上記被膜は、無機酸化物粒子の表面全体に形成されていてもよいし、無機酸化物粒子の表面の一部に形成されていてもよいが、前者の態様が好ましい。
被膜は、無機酸化物粒子の複雑な形状にも付き回りがよく、０．５ｎｍ程度の被膜であっても被覆性がよい。
このような特定の化合物に由来する被膜を表面に備える無機酸化物粒子は、無機酸化物粒子を、直鎖脂肪酸で表面処理することにより得られる。 (Inorganic oxide particles with a coating derived from straight chain fatty acids on the surface)
The dispersion liquid of this embodiment is produced by containing inorganic oxide particles having a coating derived from a straight chain fatty acid on the surface, a specific dispersant described below, and a solvent described below. The dispersibility of inorganic oxide particles in cosmetics is effectively improved.
An embodiment in which a film derived from a straight chain fatty acid is provided on the surface of an inorganic oxide particle includes, for example, a film formed by a straight chain fatty acid bonding to the surface of the inorganic oxide particle through hydrogen bonding or the like. Alternatively, it may be an embodiment in which a group derived from a straight chain fatty acid is bonded to the surface of the inorganic oxide particle through a covalent bond or the like to form a film. In addition, although the said film may be formed on the whole surface of an inorganic oxide particle, and may be formed in a part of the surface of an inorganic oxide particle, the former aspect is preferable.
The coating adheres well to the complex shapes of the inorganic oxide particles, and has good coverage even with a coating thickness of about 0.5 nm.
Inorganic oxide particles whose surfaces are provided with a coating derived from such a specific compound can be obtained by surface-treating inorganic oxide particles with a straight chain fatty acid.
直鎖脂肪酸としては、ステアリン酸、マルガリン酸、吉草酸、カプロン酸、エナント酸、ウンデカン酸、ラウリン酸、トリデシル酸、ノナデシル酸、アラキン酸、ペンタデシル酸、カプリン酸、パルミチン酸、ミリスチン酸、ノナン酸、及びカプリル酸からなる群より選択される少なくとも１種が好ましい。これらの中では、ステアリン酸がより好ましい。
Straight chain fatty acids include stearic acid, margaric acid, valeric acid, caproic acid, enanthic acid, undecanoic acid, lauric acid, tridecylic acid, nonadecylic acid, arachidic acid, pentadecylic acid, capric acid, palmitic acid, myristic acid, and nonanoic acid. , and at least one selected from the group consisting of caprylic acid. Among these, stearic acid is more preferred.
なお、無機酸化物粒子の表面には、直鎖脂肪酸とともに、水酸化アルミニウム、ロウ、高級脂肪酸トリグリセライド、高級脂肪酸、高級脂肪酸多価金属塩、高級脂肪族硫酸化物の多価金属塩等の高級脂肪酸、高級アルコール又はそれらの誘導体、パーフロロ化又は部分フッ素化した高級脂肪酸及び高級アルコール等の有機フッ素化合物等を用いて表面処理を行ってもよい。
これらのうち、無機酸化物粒子の表面に、直鎖脂肪酸とともに、水酸化アルミニウムを用いて表面処理を行った場合、表面に直鎖脂肪酸及び水酸化アルミニウムに由来する被膜を備える無機酸化物粒子が得られる。該無機酸化物粒子については、後述するように、さらに詳細に説明する。 In addition, on the surface of the inorganic oxide particles, higher fatty acids such as aluminum hydroxide, wax, higher fatty acid triglycerides, higher fatty acids, higher fatty acid polyvalent metal salts, and higher aliphatic sulfates polyvalent metal salts are present on the surface of the inorganic oxide particles. , higher alcohols or derivatives thereof, perfluorinated or partially fluorinated higher fatty acids, and organic fluorine compounds such as higher alcohols.
Among these, when the surface of inorganic oxide particles is treated with aluminum hydroxide together with linear fatty acids, the inorganic oxide particles have a coating derived from linear fatty acids and aluminum hydroxide on the surface. can get. The inorganic oxide particles will be explained in more detail below.
これらのうち、無機酸化物粒子の表面に、直鎖脂肪酸とともに、水酸化アルミニウムを用いて表面処理を行った場合、表面に直鎖脂肪酸及び水酸化アルミニウムに由来する被膜を備える無機酸化物粒子が得られる。該無機酸化物粒子については、後述するように、さらに詳細に説明する。 In addition, on the surface of the inorganic oxide particles, higher fatty acids such as aluminum hydroxide, wax, higher fatty acid triglycerides, higher fatty acids, higher fatty acid polyvalent metal salts, and higher aliphatic sulfates polyvalent metal salts are present on the surface of the inorganic oxide particles. , higher alcohols or derivatives thereof, perfluorinated or partially fluorinated higher fatty acids, and organic fluorine compounds such as higher alcohols.
Among these, when the surface of inorganic oxide particles is treated with aluminum hydroxide together with linear fatty acids, the inorganic oxide particles have a coating derived from linear fatty acids and aluminum hydroxide on the surface. can get. The inorganic oxide particles will be explained in more detail below.
表面に直鎖脂肪酸に由来する被膜が形成された無機酸化物粒子は例えば、無機酸化物粒子を、直鎖脂肪酸を用いて、以下の表面処理を行うことにより得られる。
表面に直鎖脂肪酸に由来する被膜を形成する方法としては、例えば、基材となる無機酸化物粒子に水系でｐＨ調整を行いつつ、無機酸化物粒子の表面に直鎖脂肪酸の金属塩を形成させることによって行う方法や、有機溶剤中に無機酸化物粒子と直鎖脂肪酸とを撹拌混合し、有機溶媒を留去した後に熱処理する方法が挙げられる。 Inorganic oxide particles on the surface of which a coating derived from a straight chain fatty acid is formed can be obtained, for example, by subjecting inorganic oxide particles to the following surface treatment using a straight chain fatty acid.
As a method for forming a film derived from straight chain fatty acids on the surface, for example, while adjusting the pH of the inorganic oxide particles serving as a base material in an aqueous system, forming a metal salt of a straight chain fatty acid on the surface of the inorganic oxide particles. Examples include a method in which inorganic oxide particles and a straight chain fatty acid are stirred and mixed in an organic solvent, and a heat treatment is performed after distilling off the organic solvent.
表面に直鎖脂肪酸に由来する被膜を形成する方法としては、例えば、基材となる無機酸化物粒子に水系でｐＨ調整を行いつつ、無機酸化物粒子の表面に直鎖脂肪酸の金属塩を形成させることによって行う方法や、有機溶剤中に無機酸化物粒子と直鎖脂肪酸とを撹拌混合し、有機溶媒を留去した後に熱処理する方法が挙げられる。 Inorganic oxide particles on the surface of which a coating derived from a straight chain fatty acid is formed can be obtained, for example, by subjecting inorganic oxide particles to the following surface treatment using a straight chain fatty acid.
As a method for forming a film derived from straight chain fatty acids on the surface, for example, while adjusting the pH of the inorganic oxide particles serving as a base material in an aqueous system, forming a metal salt of a straight chain fatty acid on the surface of the inorganic oxide particles. Examples include a method in which inorganic oxide particles and a straight chain fatty acid are stirred and mixed in an organic solvent, and a heat treatment is performed after distilling off the organic solvent.
無機酸化物粒子は、上記の方法で製造してもよいし、例えば、直鎖脂肪酸によって表面処理された市販の無機酸化物粒子を入手してもよい。このような表面処理された市販の無機酸化物粒子としては、テイカ社製のＭＺ－５０５Ｔ、チタン工業製のＳＴ－４５５ＦＡ等が挙げられる。
The inorganic oxide particles may be produced by the method described above, or, for example, commercially available inorganic oxide particles surface-treated with a straight chain fatty acid may be obtained. Examples of such surface-treated commercially available inorganic oxide particles include MZ-505T manufactured by Tayka Corporation and ST-455FA manufactured by Titan Industries.
（表面に直鎖脂肪酸及び水酸化アルミニウムに由来する被膜を備える無機酸化物粒子）
本実施形態の分散液は、表面に前述の直鎖脂肪酸、及び水酸化アルミニウムに由来する被膜を備える無機酸化物粒子と、後述する特定の分散剤と、後述する溶剤と、を含有することにより、分散液及び製造される化粧料中での無機酸化物粒子の分散性が効果的に向上する。
無機酸化物粒子の表面に、直鎖脂肪酸及び水酸化アルミニウムに由来する被膜を備える態様としては、例えば、無機酸化物粒子の表面に、直鎖脂肪酸及び水酸化アルミニウムが、水素結合等により結合することにより被膜を形成している態様であってもよいし、無機酸化物粒子の表面に、直鎖脂肪酸及び水酸化アルミニウムに由来する基が、共有結合等により結合することにより被膜を形成している態様であってもよい。なお、上記被膜は、無機酸化物粒子の表面全体に形成されていてもよいし、無機酸化物粒子の表面の一部に形成されていてもよいが、前者の態様が好ましい。
また、被膜としては、上記２種の化合物に由来する被膜が、いずれも無機酸化物粒子の表面に直接的に形成されていてもよいし、上記２種の化合物のうち、一方の化合物に由来する内側被膜が、無機酸化物粒子の表面に直接的に形成され、他方の化合物に由来する外側被膜が、上記内側被膜の表面に形成されていてもよい。
被膜は、無機酸化物粒子の複雑な形状にも付き回りがよく、０．５ｎｍ程度の被膜であっても被覆性がよい。
本実施形態の分散液において、無機酸化物粒子としては、酸化チタン、及び酸化亜鉛からなる群より選ばれる粒子を含有することが好ましく、酸化チタンを含有することがより好ましい。
このような特定の化合物に由来する被膜を表面に備える無機酸化物粒子は、無機酸化物粒子を、直鎖脂肪酸及び水酸化アルミニウムで表面処理することにより得られる。 (Inorganic oxide particles with a coating derived from linear fatty acids and aluminum hydroxide on the surface)
The dispersion liquid of this embodiment contains inorganic oxide particles having a coating derived from the above-mentioned linear fatty acid and aluminum hydroxide on the surface, a specific dispersing agent described below, and a solvent described below. , the dispersibility of the inorganic oxide particles in the dispersion liquid and the cosmetics produced is effectively improved.
An embodiment in which the surface of the inorganic oxide particles is provided with a film derived from a straight chain fatty acid and aluminum hydroxide includes, for example, a film in which a straight chain fatty acid and aluminum hydroxide are bonded to the surface of the inorganic oxide particles through hydrogen bonds or the like. Alternatively, a film may be formed by bonding groups derived from linear fatty acids and aluminum hydroxide to the surface of the inorganic oxide particles through covalent bonds or the like. It may also be an aspect in which In addition, although the said film may be formed on the whole surface of an inorganic oxide particle, and may be formed in a part of the surface of an inorganic oxide particle, the former aspect is preferable.
Further, as a coating, a coating derived from the above two types of compounds may be formed directly on the surface of the inorganic oxide particles, or a coating derived from one of the above two types of compounds. An inner coating may be formed directly on the surface of the inorganic oxide particle, and an outer coating derived from the other compound may be formed on the surface of the inner coating.
The coating adheres well to the complex shapes of the inorganic oxide particles, and has good coverage even with a coating thickness of about 0.5 nm.
In the dispersion of the present embodiment, the inorganic oxide particles preferably contain particles selected from the group consisting of titanium oxide and zinc oxide, and more preferably contain titanium oxide.
Inorganic oxide particles whose surfaces are coated with a coating derived from such a specific compound can be obtained by surface-treating inorganic oxide particles with a linear fatty acid and aluminum hydroxide.
本実施形態の分散液は、表面に前述の直鎖脂肪酸、及び水酸化アルミニウムに由来する被膜を備える無機酸化物粒子と、後述する特定の分散剤と、後述する溶剤と、を含有することにより、分散液及び製造される化粧料中での無機酸化物粒子の分散性が効果的に向上する。
無機酸化物粒子の表面に、直鎖脂肪酸及び水酸化アルミニウムに由来する被膜を備える態様としては、例えば、無機酸化物粒子の表面に、直鎖脂肪酸及び水酸化アルミニウムが、水素結合等により結合することにより被膜を形成している態様であってもよいし、無機酸化物粒子の表面に、直鎖脂肪酸及び水酸化アルミニウムに由来する基が、共有結合等により結合することにより被膜を形成している態様であってもよい。なお、上記被膜は、無機酸化物粒子の表面全体に形成されていてもよいし、無機酸化物粒子の表面の一部に形成されていてもよいが、前者の態様が好ましい。
また、被膜としては、上記２種の化合物に由来する被膜が、いずれも無機酸化物粒子の表面に直接的に形成されていてもよいし、上記２種の化合物のうち、一方の化合物に由来する内側被膜が、無機酸化物粒子の表面に直接的に形成され、他方の化合物に由来する外側被膜が、上記内側被膜の表面に形成されていてもよい。
被膜は、無機酸化物粒子の複雑な形状にも付き回りがよく、０．５ｎｍ程度の被膜であっても被覆性がよい。
本実施形態の分散液において、無機酸化物粒子としては、酸化チタン、及び酸化亜鉛からなる群より選ばれる粒子を含有することが好ましく、酸化チタンを含有することがより好ましい。
このような特定の化合物に由来する被膜を表面に備える無機酸化物粒子は、無機酸化物粒子を、直鎖脂肪酸及び水酸化アルミニウムで表面処理することにより得られる。 (Inorganic oxide particles with a coating derived from linear fatty acids and aluminum hydroxide on the surface)
The dispersion liquid of this embodiment contains inorganic oxide particles having a coating derived from the above-mentioned linear fatty acid and aluminum hydroxide on the surface, a specific dispersing agent described below, and a solvent described below. , the dispersibility of the inorganic oxide particles in the dispersion liquid and the cosmetics produced is effectively improved.
An embodiment in which the surface of the inorganic oxide particles is provided with a film derived from a straight chain fatty acid and aluminum hydroxide includes, for example, a film in which a straight chain fatty acid and aluminum hydroxide are bonded to the surface of the inorganic oxide particles through hydrogen bonds or the like. Alternatively, a film may be formed by bonding groups derived from linear fatty acids and aluminum hydroxide to the surface of the inorganic oxide particles through covalent bonds or the like. It may also be an aspect in which In addition, although the said film may be formed on the whole surface of an inorganic oxide particle, and may be formed in a part of the surface of an inorganic oxide particle, the former aspect is preferable.
Further, as a coating, a coating derived from the above two types of compounds may be formed directly on the surface of the inorganic oxide particles, or a coating derived from one of the above two types of compounds. An inner coating may be formed directly on the surface of the inorganic oxide particle, and an outer coating derived from the other compound may be formed on the surface of the inner coating.
The coating adheres well to the complex shapes of the inorganic oxide particles, and has good coverage even with a coating thickness of about 0.5 nm.
In the dispersion of the present embodiment, the inorganic oxide particles preferably contain particles selected from the group consisting of titanium oxide and zinc oxide, and more preferably contain titanium oxide.
Inorganic oxide particles whose surfaces are coated with a coating derived from such a specific compound can be obtained by surface-treating inorganic oxide particles with a linear fatty acid and aluminum hydroxide.
なお、無機酸化物粒子の表面には、直鎖脂肪酸及び水酸化アルミニウムとともに、ロウ、高級脂肪酸トリグリセライド、高級脂肪酸、高級脂肪酸多価金属塩、高級脂肪族硫酸化物の多価金属塩等の高級脂肪酸、高級アルコール又はそれらの誘導体、パーフロロ化又は部分フッ素化した高級脂肪酸及び高級アルコール等の有機フッ素化合物等を用いて表面処理を行ってもよい。
In addition, on the surface of the inorganic oxide particles, in addition to linear fatty acids and aluminum hydroxide, higher fatty acids such as wax, higher fatty acid triglycerides, higher fatty acids, higher fatty acid polyvalent metal salts, and higher fatty acid polyvalent metal salts of higher aliphatic sulfates are present. , higher alcohols or derivatives thereof, perfluorinated or partially fluorinated higher fatty acids, and organic fluorine compounds such as higher alcohols.
表面に直鎖脂肪酸及び水酸化アルミニウムに由来する被膜が形成された無機酸化物粒子は例えば、無機酸化物粒子を、直鎖脂肪酸及び水酸化アルミニウムを用いて、以下の表面処理を行うことにより得られる。
表面に直鎖脂肪酸に由来する被膜を形成する方法としては、例えば、基材となる無機酸化物粒子に水系でｐＨ調整を行いつつ、無機酸化物粒子の表面に直鎖脂肪酸の金属塩を形成させることによって行う方法や、有機溶剤中に無機酸化物粒子と直鎖脂肪酸とを撹拌混合し、有機溶媒を留去した後に熱処理する方法が挙げられる。
表面に水酸化アルミニウムに由来する被膜を形成する方法としては、例えば、無機酸化物粒子を水系で分散させておき、そこへ水酸化アルミニウムの水溶性塩を溶解させ、ｐＨ調整を行いつつ無機酸化物粒子の表面に水酸化アルミニウムを沈着させる方法等が挙げられる。 Inorganic oxide particles with a coating derived from a straight chain fatty acid and aluminum hydroxide formed on the surface can be obtained by, for example, subjecting the inorganic oxide particles to the following surface treatment using a straight chain fatty acid and aluminum hydroxide. It will be done.
As a method for forming a film derived from straight chain fatty acids on the surface, for example, while adjusting the pH of the inorganic oxide particles serving as a base material in an aqueous system, forming a metal salt of a straight chain fatty acid on the surface of the inorganic oxide particles. Examples include a method in which inorganic oxide particles and a straight chain fatty acid are stirred and mixed in an organic solvent, and a heat treatment is performed after distilling off the organic solvent.
As a method for forming a film derived from aluminum hydroxide on the surface, for example, inorganic oxide particles are dispersed in an aqueous system, a water-soluble salt of aluminum hydroxide is dissolved therein, and the inorganic oxide is added while adjusting the pH. Examples include a method of depositing aluminum hydroxide on the surface of particles.
表面に直鎖脂肪酸に由来する被膜を形成する方法としては、例えば、基材となる無機酸化物粒子に水系でｐＨ調整を行いつつ、無機酸化物粒子の表面に直鎖脂肪酸の金属塩を形成させることによって行う方法や、有機溶剤中に無機酸化物粒子と直鎖脂肪酸とを撹拌混合し、有機溶媒を留去した後に熱処理する方法が挙げられる。
表面に水酸化アルミニウムに由来する被膜を形成する方法としては、例えば、無機酸化物粒子を水系で分散させておき、そこへ水酸化アルミニウムの水溶性塩を溶解させ、ｐＨ調整を行いつつ無機酸化物粒子の表面に水酸化アルミニウムを沈着させる方法等が挙げられる。 Inorganic oxide particles with a coating derived from a straight chain fatty acid and aluminum hydroxide formed on the surface can be obtained by, for example, subjecting the inorganic oxide particles to the following surface treatment using a straight chain fatty acid and aluminum hydroxide. It will be done.
As a method for forming a film derived from straight chain fatty acids on the surface, for example, while adjusting the pH of the inorganic oxide particles serving as a base material in an aqueous system, forming a metal salt of a straight chain fatty acid on the surface of the inorganic oxide particles. Examples include a method in which inorganic oxide particles and a straight chain fatty acid are stirred and mixed in an organic solvent, and a heat treatment is performed after distilling off the organic solvent.
As a method for forming a film derived from aluminum hydroxide on the surface, for example, inorganic oxide particles are dispersed in an aqueous system, a water-soluble salt of aluminum hydroxide is dissolved therein, and the inorganic oxide is added while adjusting the pH. Examples include a method of depositing aluminum hydroxide on the surface of particles.
無機酸化物粒子は、上記の方法で製造してもよいし、例えば、直鎖脂肪酸及び水酸化アルミニウムによって表面処理された市販の無機酸化物粒子を入手してもよい。このような表面処理された市販の無機酸化物粒子としては、チタン工業社製のＳＴ－４５０ＳＡ、ＳＴ－４５５、ＳＴＶ－４５５、ＳＴ－４５７ＳＡ、ＳＴ－４８５ＳＡ１５、堺化学工業社製のＳＴＲ－１００Ｃ－ＬＦ、テイカ社製のＭＴ－０１、ＭＴ－１００ＴＶ、ＭＴ－１００Ｚ等が挙げられる。
The inorganic oxide particles may be produced by the method described above, or, for example, commercially available inorganic oxide particles surface-treated with a linear fatty acid and aluminum hydroxide may be obtained. Commercially available inorganic oxide particles with such surface treatment include ST-450SA, ST-455, STV-455, ST-457SA, ST-485SA15 manufactured by Titan Kogyo Co., Ltd., and STR-100C manufactured by Sakai Chemical Industry Co., Ltd. -LF, Teika's MT-01, MT-100TV, MT-100Z, etc.
前述した特定の化合物に由来する被膜を表面に備える無機酸化物粒子の全質量に対する特定の化合物に由来する被膜の質量の割合（例えば、被覆率）の下限は、１質量％以上であることが好ましく、３質量％以上であることが好ましい。特定の化合物に由来する被膜の質量の割合（例えば、被覆率）の下限が１質量％以上である場合、無機酸化物粒子の分散性を向上させることができる。前述した特定の化合物に由来する被膜を表面に備える無機酸化物粒子の全質量に対する特定の化合物に由来する被膜の質量の割合（例えば、被覆率）の上限は、３０質量％以下であることが好ましく、２０質量％以下であることがより好ましく、１５質量％以下であることがさらに好ましい。特定の化合物に由来する被膜の質量の割合（例えば、被覆率）の上限が３０質量％以下である場合、分散液中に含有する無機酸化物粒子自体の質量を多くすることができ、より効果的に紫外線遮蔽効果が得られるようになる。
The lower limit of the ratio of the mass of the coating derived from the specific compound to the total mass of the inorganic oxide particles having the coating derived from the specific compound on the surface (e.g., coverage rate) may be 1% by mass or more. The content is preferably 3% by mass or more. When the lower limit of the mass ratio (for example, coverage) of the coating derived from the specific compound is 1% by mass or more, the dispersibility of the inorganic oxide particles can be improved. The upper limit of the mass ratio (e.g., coverage) of the coating derived from the specific compound to the total mass of the inorganic oxide particles having the coating derived from the specific compound on the surface may be 30% by mass or less. It is preferably 20% by mass or less, more preferably 15% by mass or less. If the upper limit of the mass ratio (e.g., coverage) of the film derived from a specific compound is 30% by mass or less, the mass of the inorganic oxide particles themselves contained in the dispersion can be increased, making it more effective. UV shielding effect can be obtained.
前述した特定の化合物に由来する被膜を表面に備える無機酸化物粒子の含有量の下限は、分散液全量中２０質量％以上であることが好ましく、３０質量％以上であることがより好ましい。無機酸化物粒子の含有量の下限が２０質量％以上である場合、高濃度の分散液とすることが可能となり、化粧料を製造する際の分散液の量も減らすことが可能となって取り扱い性が向上する。前述した特定の化合物に由来する被膜を表面に備える無機酸化物粒子の含有量の上限は、分散液全量中８０質量％以下であることが好ましく、７５質量％以下であることがより好ましく、７０質量％以下であることがさらに好ましい。無機酸化物粒子の含有量の上限が分散液全量中８０質量％以下である場合、分散液や化粧料中での無機酸化物粒子の分散安定性が向上する。
The lower limit of the content of inorganic oxide particles whose surfaces are coated with a film derived from the specific compound described above is preferably 20% by mass or more, more preferably 30% by mass or more based on the total amount of the dispersion. When the lower limit of the content of inorganic oxide particles is 20% by mass or more, it becomes possible to make a highly concentrated dispersion, and the amount of dispersion when manufacturing cosmetics can also be reduced, making it easier to handle. Improves sex. The upper limit of the content of inorganic oxide particles having a coating derived from the above-mentioned specific compound on the surface is preferably 80% by mass or less, more preferably 75% by mass or less, and 70% by mass or less based on the total amount of the dispersion. It is more preferable that it is less than % by mass. When the upper limit of the content of the inorganic oxide particles is 80% by mass or less based on the total amount of the dispersion, the dispersion stability of the inorganic oxide particles in the dispersion and cosmetics is improved.
［分散剤］
分散剤は、分散液中の無機酸化物粒子を分散する。本実施形態の分散液は、分散剤として、ポリヒドロキシ脂肪酸を含有する。本実施形態の分散液は、前述した特定の無機酸化物粒子と、上記特定の分散剤と、を含有することにより、溶剤として炭化水素油又はエステル油を主体とする分散液であっても、分散液及び製造される化粧料中での無機酸化物粒子の分散性が効果的に向上する。 [Dispersant]
The dispersant disperses the inorganic oxide particles in the dispersion liquid. The dispersion liquid of this embodiment contains polyhydroxy fatty acid as a dispersant. The dispersion liquid of this embodiment contains the above-described specific inorganic oxide particles and the above-mentioned specific dispersant, so that even if the dispersion liquid is mainly composed of hydrocarbon oil or ester oil as a solvent, The dispersibility of the inorganic oxide particles in the dispersion liquid and the cosmetics produced is effectively improved.
分散剤は、分散液中の無機酸化物粒子を分散する。本実施形態の分散液は、分散剤として、ポリヒドロキシ脂肪酸を含有する。本実施形態の分散液は、前述した特定の無機酸化物粒子と、上記特定の分散剤と、を含有することにより、溶剤として炭化水素油又はエステル油を主体とする分散液であっても、分散液及び製造される化粧料中での無機酸化物粒子の分散性が効果的に向上する。 [Dispersant]
The dispersant disperses the inorganic oxide particles in the dispersion liquid. The dispersion liquid of this embodiment contains polyhydroxy fatty acid as a dispersant. The dispersion liquid of this embodiment contains the above-described specific inorganic oxide particles and the above-mentioned specific dispersant, so that even if the dispersion liquid is mainly composed of hydrocarbon oil or ester oil as a solvent, The dispersibility of the inorganic oxide particles in the dispersion liquid and the cosmetics produced is effectively improved.
（ポリヒドロキシ脂肪酸）
ポリヒドロキシ脂肪酸は、炭素原子数が１２以上２４以下のヒドロキシ脂肪酸の自己縮合物である。炭素原子数が１２以上２４以下のヒドロキシ脂肪酸としては、例えば、ヒドロキシラウリン酸、ヒドロキシミリスチン酸、ヒドロキシペンタデシル酸、ヒドロキシパルミチン酸、ヒドロキシステアリン酸、ヒドロキシイソステアリン酸、ヒドロキシベヘン酸が挙げられる。これらの中では、無機酸化物粒子の分散性向上の観点から、ヒドロキシステアリン酸が好ましい。
ポリヒドロキシ脂肪酸の平均重合度としては、３以上１０以下が好ましく、４以上８以下がさらに好ましい。
これらの市販品としては、ポリヒドロキシステアリン酸では、ＲＩＣＯＳ ＰＨＦ－３０－Ｃ（伊藤製油社製）、サラコスＨＳ-６Ｃ（日清オイリオ社製）等が挙げられる。 (Polyhydroxy fatty acid)
Polyhydroxy fatty acids are self-condensates of hydroxy fatty acids having 12 or more and 24 or less carbon atoms. Examples of the hydroxy fatty acid having 12 or more and 24 or less carbon atoms include hydroxylauric acid, hydroxymyristic acid, hydroxypentadecyl acid, hydroxypalmitic acid, hydroxystearic acid, hydroxyisostearic acid, and hydroxybehenic acid. Among these, hydroxystearic acid is preferred from the viewpoint of improving the dispersibility of inorganic oxide particles.
The average degree of polymerization of the polyhydroxy fatty acid is preferably 3 or more and 10 or less, more preferably 4 or more and 8 or less.
These commercially available products include RICOS PHF-30-C (manufactured by Ito Oil Co., Ltd.) and Saracos HS-6C (manufactured by Nisshin Oilio Co., Ltd.) for polyhydroxystearic acid.
ポリヒドロキシ脂肪酸は、炭素原子数が１２以上２４以下のヒドロキシ脂肪酸の自己縮合物である。炭素原子数が１２以上２４以下のヒドロキシ脂肪酸としては、例えば、ヒドロキシラウリン酸、ヒドロキシミリスチン酸、ヒドロキシペンタデシル酸、ヒドロキシパルミチン酸、ヒドロキシステアリン酸、ヒドロキシイソステアリン酸、ヒドロキシベヘン酸が挙げられる。これらの中では、無機酸化物粒子の分散性向上の観点から、ヒドロキシステアリン酸が好ましい。
ポリヒドロキシ脂肪酸の平均重合度としては、３以上１０以下が好ましく、４以上８以下がさらに好ましい。
これらの市販品としては、ポリヒドロキシステアリン酸では、ＲＩＣＯＳ ＰＨＦ－３０－Ｃ（伊藤製油社製）、サラコスＨＳ-６Ｃ（日清オイリオ社製）等が挙げられる。 (Polyhydroxy fatty acid)
Polyhydroxy fatty acids are self-condensates of hydroxy fatty acids having 12 or more and 24 or less carbon atoms. Examples of the hydroxy fatty acid having 12 or more and 24 or less carbon atoms include hydroxylauric acid, hydroxymyristic acid, hydroxypentadecyl acid, hydroxypalmitic acid, hydroxystearic acid, hydroxyisostearic acid, and hydroxybehenic acid. Among these, hydroxystearic acid is preferred from the viewpoint of improving the dispersibility of inorganic oxide particles.
The average degree of polymerization of the polyhydroxy fatty acid is preferably 3 or more and 10 or less, more preferably 4 or more and 8 or less.
These commercially available products include RICOS PHF-30-C (manufactured by Ito Oil Co., Ltd.) and Saracos HS-6C (manufactured by Nisshin Oilio Co., Ltd.) for polyhydroxystearic acid.
分散剤は、１種を単独で用いてもよく、必要に応じて２種以上を併用してもよい。
One type of dispersant may be used alone, or two or more types may be used in combination as necessary.
分散剤の含有量は、分散液中の前述した無機酸化物粒子の含有量に応じて決定することが好ましい。表面に特定の化合物を備える無機酸化物粒子と、分散剤と、の適切な含有量比を制御することで、無機酸化物粒子と分散剤との相溶性をより効果的に向上させることが可能となり、無機酸化物粒子の分散性が向上して分散液や製造される化粧料の透過率（透明度）も高いものとすることができる。
The content of the dispersant is preferably determined depending on the content of the above-mentioned inorganic oxide particles in the dispersion. By controlling the appropriate content ratio of the inorganic oxide particles with a specific compound on the surface and the dispersant, it is possible to more effectively improve the compatibility between the inorganic oxide particles and the dispersant. Therefore, the dispersibility of the inorganic oxide particles is improved, and the transmittance (transparency) of the dispersion liquid and the manufactured cosmetic can also be made high.
具体的には、分散剤の含有量の割合の下限は、無機酸化物粒子の含有量に対して、０．５質量％以上であることが好ましく、１質量％以上であることがより好ましく、１．５質量％以上であることがさらに好ましい。分散剤の含有量の下限が０．５質量％以上であることで、無機酸化物粒子の分散性をより向上させることができる。分散剤の含有量の割合の上限は、無機酸化物粒子の含有量に対して、４０質量％以下であることが好ましく、３５質量％以下であることがより好ましく、３０質量％以下であることがさらに好ましい。分散剤の含有量の割合が４０質量％を超えると、分散液の粘度が相対的に上昇する傾向や、分散性及び透明性が相対的に低下する傾向がある。分散剤の含有量が４０質量％以下であることで、このような粘度の上昇や分散性及び透明性の低下を効果的に抑制することができる。
Specifically, the lower limit of the content of the dispersant is preferably 0.5% by mass or more, more preferably 1% by mass or more, based on the content of the inorganic oxide particles, More preferably, the content is 1.5% by mass or more. By setting the lower limit of the content of the dispersant to 0.5% by mass or more, the dispersibility of the inorganic oxide particles can be further improved. The upper limit of the content ratio of the dispersant is preferably 40% by mass or less, more preferably 35% by mass or less, and 30% by mass or less with respect to the content of the inorganic oxide particles. is even more preferable. When the content of the dispersant exceeds 40% by mass, the viscosity of the dispersion liquid tends to increase relatively, and the dispersibility and transparency tend to decrease relatively. When the content of the dispersant is 40% by mass or less, such an increase in viscosity and a decrease in dispersibility and transparency can be effectively suppressed.
また、無機酸化物粒子の含有量に対する分散剤の含有量の割合は２質量％以上２０質量％以下、好ましくは３質量％以上１５質量％以下であることにより、分散液の透過率（透明度）をより高いものとすることができる。
In addition, by setting the content of the dispersant to the content of the inorganic oxide particles to be 2% by mass or more and 20% by mass or less, preferably 3% by mass or more and 15% by mass or less, the transmittance (transparency) of the dispersion liquid can be improved. can be made higher.
［溶剤］
溶剤は、分散液の分散体である。溶剤としては、炭化水素油、及びエステル油からなる群より選ばれる油剤が用いられる。 [solvent]
A solvent is a dispersion of a dispersion. As the solvent, an oil agent selected from the group consisting of hydrocarbon oils and ester oils is used.
溶剤は、分散液の分散体である。溶剤としては、炭化水素油、及びエステル油からなる群より選ばれる油剤が用いられる。 [solvent]
A solvent is a dispersion of a dispersion. As the solvent, an oil agent selected from the group consisting of hydrocarbon oils and ester oils is used.
炭化水素油としては、例えば、イソブテン、水添ポリイソブテン、デカン、イソデカン、ドデカン、イソドデカン、テトラデカン、イソテトラデカン、ヘキサデカン、イソヘキサデカン、軽質イソパラフィン、スクワレン、スクワラン、流動パラフィン、流動イソパラフィン、軽質流動イソパラフィン、重質流動イソパラフィン、α－オレフィンオリゴマー、流動パラフィン、シクロパラフィン、ワセリン（ペトロラタム）、パラフィンワックス、ミツロウ、キャンデリラロウ、綿ロウ、セレシンワックス、カルナウバロウ、鯨ロウ、モンタンロウ、マイクロクリスタリンワックス、モクロウ等が挙げられる。
炭化水素油の炭素原子数は、４以上４０以下が好ましく、１０以上３０以下がより好ましい。 Examples of hydrocarbon oils include isobutene, hydrogenated polyisobutene, decane, isodecane, dodecane, isododecane, tetradecane, isotetradecane, hexadecane, isohexadecane, light isoparaffin, squalene, squalane, liquid paraffin, liquid isoparaffin, light liquid isoparaffin, and heavy Examples include liquid isoparaffin, α-olefin oligomer, liquid paraffin, cycloparaffin, petrolatum (petrolatum), paraffin wax, beeswax, candelilla wax, cotton wax, ceresin wax, carnauba wax, spermaceti wax, montan wax, microcrystalline wax, Japanese wax, etc. It will be done.
The number of carbon atoms in the hydrocarbon oil is preferably 4 or more and 40 or less, more preferably 10 or more and 30 or less.
炭化水素油の炭素原子数は、４以上４０以下が好ましく、１０以上３０以下がより好ましい。 Examples of hydrocarbon oils include isobutene, hydrogenated polyisobutene, decane, isodecane, dodecane, isododecane, tetradecane, isotetradecane, hexadecane, isohexadecane, light isoparaffin, squalene, squalane, liquid paraffin, liquid isoparaffin, light liquid isoparaffin, and heavy Examples include liquid isoparaffin, α-olefin oligomer, liquid paraffin, cycloparaffin, petrolatum (petrolatum), paraffin wax, beeswax, candelilla wax, cotton wax, ceresin wax, carnauba wax, spermaceti wax, montan wax, microcrystalline wax, Japanese wax, etc. It will be done.
The number of carbon atoms in the hydrocarbon oil is preferably 4 or more and 40 or less, more preferably 10 or more and 30 or less.
エステル油としては、例えば、イソノナン酸イソノニル、イソノナン酸イソトリデシル、イソノナン酸エチルヘキシル、ネオペンタン酸イソデシル、ラウリン酸イソアミル、ラウリン酸ヘキシル、ミリスチン酸イソプロピル、アジピン酸ジイソブチル、イソノナン酸イソデシル、イソノナン酸エチル、イソステアリン酸イソプロピル、エチルヘキサン酸ヘキシル、エチルヘキサン酸セチル、トリエチルヘキサノイン、トリ（カプリル酸／カプリン酸）グリセリル、パルミチン酸イソプロピル、ミリスチン酸イソプロピル、パルミチン酸エチルヘキシル、エチルヘキサン酸セチル、ミリスチン酸イソセチル、ミリスチン酸オクチルドデシル、ジカプリン酸プロピレングリコール等が挙げられる。
Examples of ester oils include isononyl isononanoate, isotridecyl isononanoate, ethylhexyl isononanoate, isodecyl neopentanoate, isoamyl laurate, hexyl laurate, isopropyl myristate, diisobutyl adipate, isodecyl isononanoate, ethyl isononanoate, isopropyl isostearate. , hexyl ethylhexanoate, cetyl ethylhexanoate, triethylhexanoin, tri(caprylic/capric)glyceride, isopropyl palmitate, isopropyl myristate, ethylhexyl palmitate, cetyl ethylhexanoate, isocetyl myristate, octyldodecyl myristate , propylene glycol dicaprate, and the like.
溶剤は、１種を単独で用いてもよく、必要に応じて２種以上を併用してもよい。
One type of solvent may be used alone, or two or more types may be used in combination as necessary.
溶剤の含有量の下限は、分散液の全量に対して、５質量％以上であることが好ましく、１０質量％以上であることがより好ましく、２０質量％以上であることがさらに好ましく、３０質量％以上であることが特に好ましい。溶剤の含有量の上限は、分散液の全量に対して、６０質量％以下であることが好ましく５７質量％以下であることがより好ましい。
The lower limit of the content of the solvent is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and 30% by mass, based on the total amount of the dispersion. % or more is particularly preferable. The upper limit of the content of the solvent is preferably 60% by mass or less, and more preferably 57% by mass or less, based on the total amount of the dispersion.
溶剤としては、前述した炭化水素油、エステル油以外に、例えば、シリコーン油、高級脂肪酸油、高級アルコール等の油剤を含有させることもできる。ただし、本実施形態の分散液では、前述した炭化水素油又はエステル油を主体とするものであり、シリコーン油の含有量は少ない方が好ましい。具体的には、シリコ－ン油の含有量は、分散液の全量に対して５質量％以下であることが好ましく、０質量％であることがさらに好ましい。
As a solvent, in addition to the above-mentioned hydrocarbon oil and ester oil, oil agents such as silicone oil, higher fatty acid oil, and higher alcohol can also be included. However, the dispersion liquid of this embodiment is mainly composed of the above-mentioned hydrocarbon oil or ester oil, and it is preferable that the content of silicone oil is small. Specifically, the content of silicone oil is preferably 5% by mass or less, more preferably 0% by mass, based on the total amount of the dispersion.
［その他の成分］
本実施形態の分散液は、その他の成分として、通常の化粧料に使用される種々の成分を配合することができる。その他の成分としては、例えば、水、界面活性剤、紫外線吸収剤、ワックス、制汗剤、防腐剤・殺菌剤、香料、塩類、酸化防止剤、ｐＨ調整剤、キレート剤、清涼剤、抗炎症剤、美白剤、増粘剤、保湿剤、アルコール等のその他の添加剤を含んでよい。 [Other ingredients]
The dispersion liquid of this embodiment can contain various components used in ordinary cosmetics as other components. Other ingredients include, for example, water, surfactants, ultraviolet absorbers, waxes, antiperspirants, preservatives/sterilizers, fragrances, salts, antioxidants, pH adjusters, chelating agents, cooling agents, and anti-inflammatory agents. Other additives such as whitening agents, thickeners, humectants, and alcohol may also be included.
本実施形態の分散液は、その他の成分として、通常の化粧料に使用される種々の成分を配合することができる。その他の成分としては、例えば、水、界面活性剤、紫外線吸収剤、ワックス、制汗剤、防腐剤・殺菌剤、香料、塩類、酸化防止剤、ｐＨ調整剤、キレート剤、清涼剤、抗炎症剤、美白剤、増粘剤、保湿剤、アルコール等のその他の添加剤を含んでよい。 [Other ingredients]
The dispersion liquid of this embodiment can contain various components used in ordinary cosmetics as other components. Other ingredients include, for example, water, surfactants, ultraviolet absorbers, waxes, antiperspirants, preservatives/sterilizers, fragrances, salts, antioxidants, pH adjusters, chelating agents, cooling agents, and anti-inflammatory agents. Other additives such as whitening agents, thickeners, humectants, and alcohol may also be included.
分散液に水を配合する場合には、水の含有量は、分散液の全量に対して０質量％以上１０質量％以下であることが好ましく、０．０１質量％以上５質量％以下であることがより好ましい。
また、前述した無機酸化物粒子の製造条件等により、水が若干量含まれる場合がある。このような水分を含む無機酸化物粒子であっても、水分量を調整することなく使用してもよいし、水分量を増減させて使用してもよい。このような態様の分散液において、水の含有量は、分散液の全量に対して０質量％以上８質量％以下であることが好ましく、０．０１質量％以上４質量％以下であることがより好ましい。 When water is added to the dispersion liquid, the content of water is preferably 0% by mass or more and 10% by mass or less, and 0.01% by mass or more and 5% by mass or less based on the total amount of the dispersion liquid. It is more preferable.
Furthermore, depending on the manufacturing conditions of the inorganic oxide particles mentioned above, a certain amount of water may be included. Even such inorganic oxide particles containing water may be used without adjusting the water content, or may be used with the water content increased or decreased. In the dispersion liquid of such an embodiment, the water content is preferably 0% by mass or more and 8% by mass or less, and preferably 0.01% by mass or more and 4% by mass or less based on the total amount of the dispersion liquid. More preferred.
また、前述した無機酸化物粒子の製造条件等により、水が若干量含まれる場合がある。このような水分を含む無機酸化物粒子であっても、水分量を調整することなく使用してもよいし、水分量を増減させて使用してもよい。このような態様の分散液において、水の含有量は、分散液の全量に対して０質量％以上８質量％以下であることが好ましく、０．０１質量％以上４質量％以下であることがより好ましい。 When water is added to the dispersion liquid, the content of water is preferably 0% by mass or more and 10% by mass or less, and 0.01% by mass or more and 5% by mass or less based on the total amount of the dispersion liquid. It is more preferable.
Furthermore, depending on the manufacturing conditions of the inorganic oxide particles mentioned above, a certain amount of water may be included. Even such inorganic oxide particles containing water may be used without adjusting the water content, or may be used with the water content increased or decreased. In the dispersion liquid of such an embodiment, the water content is preferably 0% by mass or more and 8% by mass or less, and preferably 0.01% by mass or more and 4% by mass or less based on the total amount of the dispersion liquid. More preferred.
＜分散液の製造方法＞
本発明の一実施形態の分散液の製造方法は、特に限定されるものではなく、従来公知の方法を用いることができる。例えば、各成分を媒体撹拌ミル、ディスパー、超音波分散機、高速ミキサー等で混合する方法を挙げることができる。 <Method for producing dispersion>
The method for producing the dispersion liquid of one embodiment of the present invention is not particularly limited, and conventionally known methods can be used. For example, a method of mixing each component using a media stirring mill, a disper, an ultrasonic disperser, a high-speed mixer, etc. can be mentioned.
本発明の一実施形態の分散液の製造方法は、特に限定されるものではなく、従来公知の方法を用いることができる。例えば、各成分を媒体撹拌ミル、ディスパー、超音波分散機、高速ミキサー等で混合する方法を挙げることができる。 <Method for producing dispersion>
The method for producing the dispersion liquid of one embodiment of the present invention is not particularly limited, and conventionally known methods can be used. For example, a method of mixing each component using a media stirring mill, a disper, an ultrasonic disperser, a high-speed mixer, etc. can be mentioned.
＜化粧料＞
本発明の一実施形態の化粧料は、前述した分散液を使用して製造することができる。該化粧料は、分散液にシリコーン油、水、有機溶剤、界面活性剤、紫外線吸収剤、波長変換剤、ワックス、制汗剤、防腐剤・殺菌剤、香料、塩類、酸化防止剤、ｐＨ調整剤、キレート剤、清涼剤、抗炎症剤、美白剤、増粘剤、保湿剤、アルコールその他の添加剤を加えて混合することで製造することができる。 <Cosmetics>
The cosmetic according to one embodiment of the present invention can be manufactured using the above-mentioned dispersion. The cosmetic contains silicone oil, water, organic solvent, surfactant, ultraviolet absorber, wavelength converter, wax, antiperspirant, preservative/sterilizer, fragrance, salt, antioxidant, and pH adjustment in the dispersion liquid. It can be manufactured by adding and mixing additives such as a chelating agent, a cooling agent, an anti-inflammatory agent, a whitening agent, a thickener, a humectant, alcohol, and other additives.
本発明の一実施形態の化粧料は、前述した分散液を使用して製造することができる。該化粧料は、分散液にシリコーン油、水、有機溶剤、界面活性剤、紫外線吸収剤、波長変換剤、ワックス、制汗剤、防腐剤・殺菌剤、香料、塩類、酸化防止剤、ｐＨ調整剤、キレート剤、清涼剤、抗炎症剤、美白剤、増粘剤、保湿剤、アルコールその他の添加剤を加えて混合することで製造することができる。 <Cosmetics>
The cosmetic according to one embodiment of the present invention can be manufactured using the above-mentioned dispersion. The cosmetic contains silicone oil, water, organic solvent, surfactant, ultraviolet absorber, wavelength converter, wax, antiperspirant, preservative/sterilizer, fragrance, salt, antioxidant, and pH adjustment in the dispersion liquid. It can be manufactured by adding and mixing additives such as a chelating agent, a cooling agent, an anti-inflammatory agent, a whitening agent, a thickener, a humectant, alcohol, and other additives.
以下、実施例及び比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されない。
Hereinafter, the present invention will be explained more specifically based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.
［実施例１Ａ～１Ｃ、２Ａ～２Ｃ及び比較例１Ａ～１Ｃ、２Ａ～２Ｃ］
＜分散液の調製＞
下記表１にそれぞれ記載の無機酸化物粒子、分散剤、溶剤を下記表２に記載の含有量で混合して、実施例１Ａ～１Ｃ、２Ａ～２Ｃ及び比較例１Ａ～１Ｃ、２Ａ～２Ｃの分散液を調製した。
具体的には、まず、下記表１に記載の無機酸化物粒子を加温し、又は９０％湿度下で保管して、水分量を増減させることにより、無機酸化物粒子として、低水分量、通常水分量（水分調整していないもの）、高水分量のグレードを準備した。これら水分量が異なる３つのグレードを、表２の「粉体水分量」の項目に記載した（各無機酸化物粒子において、左欄、中央欄、右欄の数値が、それぞれ、低水分グレード、通常水分グレード、高水分グレードの水分量を示す。）。そして、ペイントシェイカーを用いて、ジルコニアビーズにて、前述の無機酸化物粒子、分散剤、溶剤を分散させて分散液を調製した。なお、表２の各成分の含有量の単位は質量％である。また、表２の「スラリー水分量」の項目に記載された数値は、得られた分散液の水分量（理論値）を示す。 [Examples 1A to 1C, 2A to 2C and Comparative Examples 1A to 1C, 2A to 2C]
<Preparation of dispersion>
The inorganic oxide particles, dispersant, and solvent listed in Table 1 below were mixed in the amounts listed in Table 2 below to prepare the inorganic oxide particles, dispersant, and solvent of Examples 1A to 1C, 2A to 2C, and Comparative Examples 1A to 1C, and 2A to 2C. A dispersion was prepared.
Specifically, first, the inorganic oxide particles listed in Table 1 below are heated or stored under 90% humidity to increase or decrease the moisture content, thereby forming inorganic oxide particles with low moisture content, We prepared grades with normal moisture content (without moisture adjustment) and high moisture content. These three grades with different moisture contents are listed in the "powder moisture content" section of Table 2 (for each inorganic oxide particle, the values in the left column, center column, and right column are respectively low moisture grade, Indicates the moisture content of normal moisture grade and high moisture grade.) Then, using a paint shaker, the above-mentioned inorganic oxide particles, dispersant, and solvent were dispersed using zirconia beads to prepare a dispersion liquid. Note that the unit of content of each component in Table 2 is mass %. Moreover, the numerical value described in the item "slurry water content" in Table 2 indicates the water content (theoretical value) of the obtained dispersion liquid.
＜分散液の調製＞
下記表１にそれぞれ記載の無機酸化物粒子、分散剤、溶剤を下記表２に記載の含有量で混合して、実施例１Ａ～１Ｃ、２Ａ～２Ｃ及び比較例１Ａ～１Ｃ、２Ａ～２Ｃの分散液を調製した。
具体的には、まず、下記表１に記載の無機酸化物粒子を加温し、又は９０％湿度下で保管して、水分量を増減させることにより、無機酸化物粒子として、低水分量、通常水分量（水分調整していないもの）、高水分量のグレードを準備した。これら水分量が異なる３つのグレードを、表２の「粉体水分量」の項目に記載した（各無機酸化物粒子において、左欄、中央欄、右欄の数値が、それぞれ、低水分グレード、通常水分グレード、高水分グレードの水分量を示す。）。そして、ペイントシェイカーを用いて、ジルコニアビーズにて、前述の無機酸化物粒子、分散剤、溶剤を分散させて分散液を調製した。なお、表２の各成分の含有量の単位は質量％である。また、表２の「スラリー水分量」の項目に記載された数値は、得られた分散液の水分量（理論値）を示す。 [Examples 1A to 1C, 2A to 2C and Comparative Examples 1A to 1C, 2A to 2C]
<Preparation of dispersion>
The inorganic oxide particles, dispersant, and solvent listed in Table 1 below were mixed in the amounts listed in Table 2 below to prepare the inorganic oxide particles, dispersant, and solvent of Examples 1A to 1C, 2A to 2C, and Comparative Examples 1A to 1C, and 2A to 2C. A dispersion was prepared.
Specifically, first, the inorganic oxide particles listed in Table 1 below are heated or stored under 90% humidity to increase or decrease the moisture content, thereby forming inorganic oxide particles with low moisture content, We prepared grades with normal moisture content (without moisture adjustment) and high moisture content. These three grades with different moisture contents are listed in the "powder moisture content" section of Table 2 (for each inorganic oxide particle, the values in the left column, center column, and right column are respectively low moisture grade, Indicates the moisture content of normal moisture grade and high moisture grade.) Then, using a paint shaker, the above-mentioned inorganic oxide particles, dispersant, and solvent were dispersed using zirconia beads to prepare a dispersion liquid. Note that the unit of content of each component in Table 2 is mass %. Moreover, the numerical value described in the item "slurry water content" in Table 2 indicates the water content (theoretical value) of the obtained dispersion liquid.
＜評価＞
［分散性］
実施例及び比較例の分散液について分散性を確認した。具体的には、ペイントシェイカーにて調製された分散液について、下記［透明性］の評価試験で求められた透過率を、下記の評価基準にて評価した。評価結果を表２に示す。
（評価基準）
５：透過率が８０％以上
４：透過率が７０％以上８０％未満
３：透過率が６０％以上７０％未満
２：透過率が５０％以上６０％未満
１：透過率が５０％未満
×：ゲル化したか、又は粘度が高くなり流動性を失っていた。 <Evaluation>
[Dispersibility]
The dispersibility of the dispersions of Examples and Comparative Examples was confirmed. Specifically, for the dispersion prepared in a paint shaker, the transmittance determined in the following [transparency] evaluation test was evaluated using the following evaluation criteria. The evaluation results are shown in Table 2.
(Evaluation criteria)
5: Transmittance is 80% or more 4: Transmittance is 70% or more and less than 80% 3: Transmittance is 60% or more and less than 70% 2: Transmittance is 50% or more and less than 60% 1: Transmittance is less than 50% × : It gelatinized or the viscosity increased and fluidity was lost.
［分散性］
実施例及び比較例の分散液について分散性を確認した。具体的には、ペイントシェイカーにて調製された分散液について、下記［透明性］の評価試験で求められた透過率を、下記の評価基準にて評価した。評価結果を表２に示す。
（評価基準）
５：透過率が８０％以上
４：透過率が７０％以上８０％未満
３：透過率が６０％以上７０％未満
２：透過率が５０％以上６０％未満
１：透過率が５０％未満
×：ゲル化したか、又は粘度が高くなり流動性を失っていた。 <Evaluation>
[Dispersibility]
The dispersibility of the dispersions of Examples and Comparative Examples was confirmed. Specifically, for the dispersion prepared in a paint shaker, the transmittance determined in the following [transparency] evaluation test was evaluated using the following evaluation criteria. The evaluation results are shown in Table 2.
(Evaluation criteria)
5: Transmittance is 80% or more 4: Transmittance is 70% or more and less than 80% 3: Transmittance is 60% or more and less than 70% 2: Transmittance is 50% or more and less than 60% 1: Transmittance is less than 50% × : It gelatinized or the viscosity increased and fluidity was lost.
［希釈安定性］
実施例１Ａ～１Ｃ及び比較例１Ａ～１Ｃの分散液を、各々用いた溶剤にて、無機酸化物粒子が５質量％になるように希釈し、実施例２Ａ～２Ｃ及び比較例２Ａ～２Ｃの分散液を、各々用いた溶剤にて、無機酸化物粒子が２０質量％になるように希釈し、希釈液の状態を目視にて確認し、下記の評価基準にて評価した。評価結果を表２に示す。
（評価基準）
〇：無機酸化物粒子の沈降は発生しなかった。
△：無機酸化物粒子の沈降は発生したが、実用上問題の無いレベルであった。
×：無機酸化物粒子の沈降が発生し、溶剤と分離した。 [Dilution stability]
The dispersions of Examples 1A to 1C and Comparative Examples 1A to 1C were diluted with the respective solvents so that the inorganic oxide particles were 5% by mass, and the dispersions of Examples 2A to 2C and Comparative Examples 2A to 2C were The dispersion liquid was diluted with the respective solvents used so that the inorganic oxide particles contained 20% by mass, and the state of the diluted liquid was visually confirmed and evaluated based on the following evaluation criteria. The evaluation results are shown in Table 2.
(Evaluation criteria)
○: Sedimentation of inorganic oxide particles did not occur.
Δ: Sedimentation of inorganic oxide particles occurred, but at a level that caused no practical problems.
×: Sedimentation of inorganic oxide particles occurred and separated from the solvent.
実施例１Ａ～１Ｃ及び比較例１Ａ～１Ｃの分散液を、各々用いた溶剤にて、無機酸化物粒子が５質量％になるように希釈し、実施例２Ａ～２Ｃ及び比較例２Ａ～２Ｃの分散液を、各々用いた溶剤にて、無機酸化物粒子が２０質量％になるように希釈し、希釈液の状態を目視にて確認し、下記の評価基準にて評価した。評価結果を表２に示す。
（評価基準）
〇：無機酸化物粒子の沈降は発生しなかった。
△：無機酸化物粒子の沈降は発生したが、実用上問題の無いレベルであった。
×：無機酸化物粒子の沈降が発生し、溶剤と分離した。 [Dilution stability]
The dispersions of Examples 1A to 1C and Comparative Examples 1A to 1C were diluted with the respective solvents so that the inorganic oxide particles were 5% by mass, and the dispersions of Examples 2A to 2C and Comparative Examples 2A to 2C were The dispersion liquid was diluted with the respective solvents used so that the inorganic oxide particles contained 20% by mass, and the state of the diluted liquid was visually confirmed and evaluated based on the following evaluation criteria. The evaluation results are shown in Table 2.
(Evaluation criteria)
○: Sedimentation of inorganic oxide particles did not occur.
Δ: Sedimentation of inorganic oxide particles occurred, but at a level that caused no practical problems.
×: Sedimentation of inorganic oxide particles occurred and separated from the solvent.
［透明性］
実施例及び比較例の分散液について透明性を確認した。具体的には、分散液を石英ガラス基材にＷＥＴ厚６μｍになるようにバーコーター＃３にて塗布し、溶剤の種類に応じて、５０℃～１２０℃、５分～３０分間乾燥することで乾燥膜を形成した。そしてその乾燥膜について島津製作所社製 ＵＶ－３６００ｉ Ｐｌｕｓを用いて波長４００ｎｍから７５０ｎｍまでの光を照射して、波長４００ｎｍから７５０ｎｍの範囲の透過光強度（透過率）の積算値（面積）を求めた。上記波長の全領域で透過率が１００％になると、積算値が最大で３５０００となるので、得られた積算値を３５０００で割り、パーセント表示に換算した。結果を表２に示す。 [transparency]
The transparency of the dispersions of Examples and Comparative Examples was confirmed. Specifically, the dispersion liquid is applied to a quartz glass substrate to a wet thickness of 6 μm using bar coater #3, and dried at 50° C. to 120° C. for 5 minutes to 30 minutes, depending on the type of solvent. A dry film was formed. Then, the dried film was irradiated with light with a wavelength of 400 nm to 750 nm using UV-3600i Plus manufactured by Shimadzu Corporation, and the integrated value (area) of the transmitted light intensity (transmittance) in the wavelength range of 400 nm to 750 nm was determined. Ta. When the transmittance was 100% in the entire wavelength range, the maximum integrated value was 35,000, so the obtained integrated value was divided by 35,000 and converted into a percentage. The results are shown in Table 2.
実施例及び比較例の分散液について透明性を確認した。具体的には、分散液を石英ガラス基材にＷＥＴ厚６μｍになるようにバーコーター＃３にて塗布し、溶剤の種類に応じて、５０℃～１２０℃、５分～３０分間乾燥することで乾燥膜を形成した。そしてその乾燥膜について島津製作所社製 ＵＶ－３６００ｉ Ｐｌｕｓを用いて波長４００ｎｍから７５０ｎｍまでの光を照射して、波長４００ｎｍから７５０ｎｍの範囲の透過光強度（透過率）の積算値（面積）を求めた。上記波長の全領域で透過率が１００％になると、積算値が最大で３５０００となるので、得られた積算値を３５０００で割り、パーセント表示に換算した。結果を表２に示す。 [transparency]
The transparency of the dispersions of Examples and Comparative Examples was confirmed. Specifically, the dispersion liquid is applied to a quartz glass substrate to a wet thickness of 6 μm using bar coater #3, and dried at 50° C. to 120° C. for 5 minutes to 30 minutes, depending on the type of solvent. A dry film was formed. Then, the dried film was irradiated with light with a wavelength of 400 nm to 750 nm using UV-3600i Plus manufactured by Shimadzu Corporation, and the integrated value (area) of the transmitted light intensity (transmittance) in the wavelength range of 400 nm to 750 nm was determined. Ta. When the transmittance was 100% in the entire wavelength range, the maximum integrated value was 35,000, so the obtained integrated value was divided by 35,000 and converted into a percentage. The results are shown in Table 2.
［粘度］
実施例及び比較例の分散液について粘性を確認した。具体的には、Ｂ型粘度計を用いて、回転数６０ｒｐｍ（２５℃）における粘度（ｍＰａ・ｓ）を求めた。結果を表２に示す。 [viscosity]
The viscosity of the dispersions of Examples and Comparative Examples was confirmed. Specifically, the viscosity (mPa·s) at a rotational speed of 60 rpm (25° C.) was determined using a B-type viscometer. The results are shown in Table 2.
実施例及び比較例の分散液について粘性を確認した。具体的には、Ｂ型粘度計を用いて、回転数６０ｒｐｍ（２５℃）における粘度（ｍＰａ・ｓ）を求めた。結果を表２に示す。 [viscosity]
The viscosity of the dispersions of Examples and Comparative Examples was confirmed. Specifically, the viscosity (mPa·s) at a rotational speed of 60 rpm (25° C.) was determined using a B-type viscometer. The results are shown in Table 2.
［ゲル化］
実施例及び比較例の分散液を４０℃にて１週間保管後に該分散液のゲル化の有無を目視にて確認し、下記の評価基準にて評価した。評価結果を表２に示す。
（評価基準）
〇：ゲル化しなかった。
×：ゲル化した。 [Gelification]
After the dispersions of Examples and Comparative Examples were stored at 40° C. for one week, the presence or absence of gelation of the dispersions was visually confirmed and evaluated using the following evaluation criteria. The evaluation results are shown in Table 2.
(Evaluation criteria)
○: No gelation occurred.
×: Gelled.
実施例及び比較例の分散液を４０℃にて１週間保管後に該分散液のゲル化の有無を目視にて確認し、下記の評価基準にて評価した。評価結果を表２に示す。
（評価基準）
〇：ゲル化しなかった。
×：ゲル化した。 [Gelification]
After the dispersions of Examples and Comparative Examples were stored at 40° C. for one week, the presence or absence of gelation of the dispersions was visually confirmed and evaluated using the following evaluation criteria. The evaluation results are shown in Table 2.
(Evaluation criteria)
○: No gelation occurred.
×: Gelled.
表２の結果から、直鎖脂肪酸で表面処理された酸化チタン粒子Ａ１と、分散剤であるポリヒドロキシ脂肪酸Ｂ１を配合した実施例１Ａ～１Ｃの分散液は、分岐鎖を有する脂肪酸で表面処理された酸化チタン粒子Ａ３と、ポリヒドロキシ脂肪酸Ｂ１を配合した比較例１Ａ～１Ｃの分散液と比較して、透明性に優れるとともに、水分量に影響されずに、粘度が安定であることが分かる。
表２の結果から、直鎖脂肪酸で表面処理された酸化亜鉛粒子Ａ２と、ポリヒドロキシ脂肪酸Ｂ１を配合した実施例２Ａ～２Ｃの分散液は、分岐鎖を有する脂肪酸で表面処理された酸化亜鉛粒子Ａ４と、ポリヒドロキシ脂肪酸Ｂ１を配合した比較例２Ａ～２Ｃの分散液と比較して、水分量に影響されずに、安定で経時でゲル化しないことが分かる。 From the results in Table 2, it can be seen that the dispersions of Examples 1A to 1C containing titanium oxide particles A1 surface-treated with a straight-chain fatty acid and polyhydroxy fatty acid B1 as a dispersant were surface-treated with a branched-chain fatty acid. Compared to the dispersions of Comparative Examples 1A to 1C in which titanium oxide particles A3 and polyhydroxy fatty acid B1 were blended, it can be seen that the dispersions have excellent transparency and stable viscosity without being affected by the water content.
From the results in Table 2, it can be seen that the dispersions of Examples 2A to 2C in which zinc oxide particles A2 surface-treated with a straight chain fatty acid and polyhydroxy fatty acid B1 were mixed with zinc oxide particles surface-treated with a branched fatty acid In comparison with the dispersions of Comparative Examples 2A to 2C containing A4 and polyhydroxy fatty acid B1, it can be seen that the dispersions are stable and do not gel over time without being affected by the water content.
表２の結果から、直鎖脂肪酸で表面処理された酸化亜鉛粒子Ａ２と、ポリヒドロキシ脂肪酸Ｂ１を配合した実施例２Ａ～２Ｃの分散液は、分岐鎖を有する脂肪酸で表面処理された酸化亜鉛粒子Ａ４と、ポリヒドロキシ脂肪酸Ｂ１を配合した比較例２Ａ～２Ｃの分散液と比較して、水分量に影響されずに、安定で経時でゲル化しないことが分かる。 From the results in Table 2, it can be seen that the dispersions of Examples 1A to 1C containing titanium oxide particles A1 surface-treated with a straight-chain fatty acid and polyhydroxy fatty acid B1 as a dispersant were surface-treated with a branched-chain fatty acid. Compared to the dispersions of Comparative Examples 1A to 1C in which titanium oxide particles A3 and polyhydroxy fatty acid B1 were blended, it can be seen that the dispersions have excellent transparency and stable viscosity without being affected by the water content.
From the results in Table 2, it can be seen that the dispersions of Examples 2A to 2C in which zinc oxide particles A2 surface-treated with a straight chain fatty acid and polyhydroxy fatty acid B1 were mixed with zinc oxide particles surface-treated with a branched fatty acid In comparison with the dispersions of Comparative Examples 2A to 2C containing A4 and polyhydroxy fatty acid B1, it can be seen that the dispersions are stable and do not gel over time without being affected by the water content.
Claims (8)
- 無機酸化物粒子と、分散剤と、溶剤と、を含有する分散液であって、
前記無機酸化物粒子は、その表面に直鎖脂肪酸に由来する被膜を備え、
前記分散剤として、ポリヒドロキシ脂肪酸を含有し、
前記溶剤として、炭化水素油、及びエステル油からなる群より選ばれる油剤を含有する、
分散液。 A dispersion liquid containing inorganic oxide particles, a dispersant, and a solvent,
The inorganic oxide particles have a coating derived from a straight chain fatty acid on the surface thereof,
Containing a polyhydroxy fatty acid as the dispersant,
The solvent contains an oil agent selected from the group consisting of hydrocarbon oils and ester oils.
dispersion liquid. - 前記無機酸化物粒子として、酸化チタン、及び酸化亜鉛からなる群より選ばれる粒子を含有する、
請求項１に記載の分散液。 The inorganic oxide particles include particles selected from the group consisting of titanium oxide and zinc oxide.
The dispersion according to claim 1. - 前記無機酸化物粒子が、その表面にさらに水酸化アルミニウムに由来する被膜を備える、
請求項１に記載の分散液。 The inorganic oxide particles further include a coating derived from aluminum hydroxide on the surface thereof.
The dispersion according to claim 1. - 前記直鎖脂肪酸が、ステアリン酸、マルガリン酸、吉草酸、カプロン酸、エナント酸、ウンデカン酸、ラウリン酸、トリデシル酸、ノナデシル酸、アラキン酸、ペンタデシル酸、カプリン酸、パルミチン酸、ミリスチン酸、ノナン酸、及びカプリル酸からなる群より選択される少なくとも１種である、
請求項１又は２に記載の分散液。 The straight chain fatty acids include stearic acid, margaric acid, valeric acid, caproic acid, enanthic acid, undecanoic acid, lauric acid, tridecylic acid, nonadecylic acid, arachidic acid, pentadecylic acid, capric acid, palmitic acid, myristic acid, and nonanoic acid. , and at least one selected from the group consisting of caprylic acid,
The dispersion liquid according to claim 1 or 2. - 前記分散剤が、前記ポリヒドロキシ脂肪酸としてポリヒドロキシステアリン酸を含有する、
請求項１又は２に記載の分散液。 The dispersant contains polyhydroxystearic acid as the polyhydroxy fatty acid.
The dispersion liquid according to claim 1 or 2. - さらに水を含み、
前記水の含有量が、分散液の全量に対して０質量％以上１０質量％以下である、
請求項１又は２に記載の分散液。 It also contains water,
The water content is 0% by mass or more and 10% by mass or less based on the total amount of the dispersion.
The dispersion liquid according to claim 1 or 2. - 化粧料に用いられる、
請求項１又は２に記載の分散液。 used in cosmetics,
The dispersion liquid according to claim 1 or 2. - 請求項１又は２に記載の分散液を含有する、
化粧料。 Containing the dispersion liquid according to claim 1 or 2,
Cosmetics.
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| JP2006001886A (en) * | 2004-06-18 | 2006-01-05 | Nikko Chemical Co Ltd | Oil dispersion containing surface-hydrophobicized metal oxide |
| JP2014097943A (en) * | 2012-11-14 | 2014-05-29 | Pola Chem Ind Inc | Skin care composition having high ultraviolet absorption effect |
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| WO2016080270A1 (en) * | 2014-11-17 | 2016-05-26 | 阪本薬品工業株式会社 | Powder dispersant, powder-dispersed composition containing same, and cosmetic |
| JP2016222594A (en) * | 2015-05-29 | 2016-12-28 | テイカ株式会社 | Oily dispersion body and cosmetic using the same |
| JP2018104401A (en) * | 2016-12-22 | 2018-07-05 | 大東化成工業株式会社 | Oily dispersion and cosmetic containing oily dispersion |
| WO2022092097A1 (en) * | 2020-10-27 | 2022-05-05 | 株式会社コーセー | Water-in-oil emulsion cosmetic |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006001886A (en) * | 2004-06-18 | 2006-01-05 | Nikko Chemical Co Ltd | Oil dispersion containing surface-hydrophobicized metal oxide |
| JP2015522046A (en) * | 2012-07-13 | 2015-08-03 | ロレアル | Cosmetic composition containing shielding composite particles |
| JP2014097943A (en) * | 2012-11-14 | 2014-05-29 | Pola Chem Ind Inc | Skin care composition having high ultraviolet absorption effect |
| WO2016080270A1 (en) * | 2014-11-17 | 2016-05-26 | 阪本薬品工業株式会社 | Powder dispersant, powder-dispersed composition containing same, and cosmetic |
| JP2016222594A (en) * | 2015-05-29 | 2016-12-28 | テイカ株式会社 | Oily dispersion body and cosmetic using the same |
| JP2018104401A (en) * | 2016-12-22 | 2018-07-05 | 大東化成工業株式会社 | Oily dispersion and cosmetic containing oily dispersion |
| WO2022092097A1 (en) * | 2020-10-27 | 2022-05-05 | 株式会社コーセー | Water-in-oil emulsion cosmetic |
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