JP5869296B2 - Water-in-oil emulsion composition - Google Patents
Water-in-oil emulsion composition Download PDFInfo
- Publication number
- JP5869296B2 JP5869296B2 JP2011234490A JP2011234490A JP5869296B2 JP 5869296 B2 JP5869296 B2 JP 5869296B2 JP 2011234490 A JP2011234490 A JP 2011234490A JP 2011234490 A JP2011234490 A JP 2011234490A JP 5869296 B2 JP5869296 B2 JP 5869296B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- oil
- oil emulsion
- emulsion composition
- phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000203 mixture Substances 0.000 title claims description 101
- 239000007762 w/o emulsion Substances 0.000 title claims description 45
- -1 L-ascorbic acid trisodium palmitate trisodium Chemical compound 0.000 claims description 44
- 150000003722 vitamin derivatives Chemical class 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- ZAKOWWREFLAJOT-ADUHFSDSSA-N [2,5,7,8-tetramethyl-2-[(4R,8R)-4,8,12-trimethyltridecyl]-3,4-dihydrochromen-6-yl] acetate Chemical group CC(=O)OC1=C(C)C(C)=C2OC(CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C ZAKOWWREFLAJOT-ADUHFSDSSA-N 0.000 claims description 22
- 125000003289 ascorbyl group Chemical group [H]O[C@@]([H])(C([H])([H])O*)[C@@]1([H])OC(=O)C(O*)=C1O* 0.000 claims description 22
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 16
- 239000002562 thickening agent Substances 0.000 claims description 15
- 239000006071 cream Substances 0.000 claims description 14
- 238000005259 measurement Methods 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 8
- 235000011009 potassium phosphates Nutrition 0.000 claims description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 33
- 239000003921 oil Substances 0.000 description 33
- 210000003491 skin Anatomy 0.000 description 30
- 229910019142 PO4 Inorganic materials 0.000 description 29
- 239000010452 phosphate Substances 0.000 description 29
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 28
- 235000019198 oils Nutrition 0.000 description 25
- 235000014113 dietary fatty acids Nutrition 0.000 description 22
- 239000000194 fatty acid Substances 0.000 description 22
- 229930195729 fatty acid Natural products 0.000 description 22
- 229960005070 ascorbic acid Drugs 0.000 description 19
- 239000012071 phase Substances 0.000 description 19
- 239000011668 ascorbic acid Substances 0.000 description 18
- 235000010323 ascorbic acid Nutrition 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 16
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 14
- 238000003860 storage Methods 0.000 description 14
- 150000005846 sugar alcohols Polymers 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000002537 cosmetic Substances 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 12
- 239000000839 emulsion Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 239000004205 dimethyl polysiloxane Substances 0.000 description 9
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 9
- 238000009472 formulation Methods 0.000 description 9
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 239000008346 aqueous phase Substances 0.000 description 7
- 238000013329 compounding Methods 0.000 description 7
- 229940008099 dimethicone Drugs 0.000 description 7
- 230000001953 sensory effect Effects 0.000 description 7
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229930003268 Vitamin C Natural products 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000002845 discoloration Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 235000019154 vitamin C Nutrition 0.000 description 6
- 239000011718 vitamin C Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- DBSABEYSGXPBTA-RXSVEWSESA-N (2r)-2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one;phosphoric acid Chemical compound OP(O)(O)=O.OC[C@H](O)[C@H]1OC(=O)C(O)=C1O DBSABEYSGXPBTA-RXSVEWSESA-N 0.000 description 4
- 239000004166 Lanolin Substances 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- OQILCOQZDHPEAZ-UHFFFAOYSA-N Palmitinsaeure-octylester Natural products CCCCCCCCCCCCCCCC(=O)OCCCCCCCC OQILCOQZDHPEAZ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- GJQLBGWSDGMZKM-UHFFFAOYSA-N ethylhexyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC(CC)CCCCC GJQLBGWSDGMZKM-UHFFFAOYSA-N 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 229940119170 jojoba wax Drugs 0.000 description 4
- 235000019388 lanolin Nutrition 0.000 description 4
- 229940039717 lanolin Drugs 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- 229940043375 1,5-pentanediol Drugs 0.000 description 3
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229920006037 cross link polymer Polymers 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 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
- 239000003814 drug Substances 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 3
- 239000004006 olive oil Substances 0.000 description 3
- 235000008390 olive oil Nutrition 0.000 description 3
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 3
- 229960005323 phenoxyethanol Drugs 0.000 description 3
- 235000010384 tocopherol Nutrition 0.000 description 3
- 239000011732 tocopherol Substances 0.000 description 3
- 229960001295 tocopherol Drugs 0.000 description 3
- 229930003799 tocopherol Natural products 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 3
- 229940058015 1,3-butylene glycol Drugs 0.000 description 2
- JSOVGYMVTPPEND-UHFFFAOYSA-N 16-methylheptadecyl 2,2-dimethylpropanoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)C(C)(C)C JSOVGYMVTPPEND-UHFFFAOYSA-N 0.000 description 2
- DCVMAYAWOPBYKB-UHFFFAOYSA-N 3-[methyl(tetradecanoyl)amino]propanoic acid Chemical compound CCCCCCCCCCCCCC(=O)N(C)CCC(O)=O DCVMAYAWOPBYKB-UHFFFAOYSA-N 0.000 description 2
- YDNKGFDKKRUKPY-JHOUSYSJSA-N C16 ceramide Natural products CCCCCCCCCCCCCCCC(=O)N[C@@H](CO)[C@H](O)C=CCCCCCCCCCCCCC YDNKGFDKKRUKPY-JHOUSYSJSA-N 0.000 description 2
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 2
- QZKRHPLGUJDVAR-UHFFFAOYSA-K EDTA trisodium salt Chemical compound [Na+].[Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O QZKRHPLGUJDVAR-UHFFFAOYSA-K 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MLSJBGYKDYSOAE-DCWMUDTNSA-N L-Ascorbic acid-2-glucoside Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O[C@@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)=C1O MLSJBGYKDYSOAE-DCWMUDTNSA-N 0.000 description 2
- XUMBMVFBXHLACL-UHFFFAOYSA-N Melanin Chemical compound O=C1C(=O)C(C2=CNC3=C(C(C(=O)C4=C32)=O)C)=C2C4=CNC2=C1C XUMBMVFBXHLACL-UHFFFAOYSA-N 0.000 description 2
- CRJGESKKUOMBCT-VQTJNVASSA-N N-acetylsphinganine Chemical compound CCCCCCCCCCCCCCC[C@@H](O)[C@H](CO)NC(C)=O CRJGESKKUOMBCT-VQTJNVASSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- JAZBEHYOTPTENJ-JLNKQSITSA-N all-cis-5,8,11,14,17-icosapentaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O JAZBEHYOTPTENJ-JLNKQSITSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 description 2
- 229940106189 ceramide Drugs 0.000 description 2
- ZVEQCJWYRWKARO-UHFFFAOYSA-N ceramide Natural products CCCCCCCCCCCCCCC(O)C(=O)NC(CO)C(O)C=CCCC=C(C)CCCCCCCCC ZVEQCJWYRWKARO-UHFFFAOYSA-N 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 229940105990 diglycerin Drugs 0.000 description 2
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000002552 dosage form Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 235000020673 eicosapentaenoic acid Nutrition 0.000 description 2
- 229960005135 eicosapentaenoic acid Drugs 0.000 description 2
- JAZBEHYOTPTENJ-UHFFFAOYSA-N eicosapentaenoic acid Natural products CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O JAZBEHYOTPTENJ-UHFFFAOYSA-N 0.000 description 2
- 239000010696 ester oil Substances 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-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
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- PUGFCQQOYJMKOO-UHFFFAOYSA-N n-(3-hexadecoxy-2-hydroxypropyl)-n-(2-hydroxyethyl)hexadecanamide Chemical compound CCCCCCCCCCCCCCCCOCC(O)CN(CCO)C(=O)CCCCCCCCCCCCCCC PUGFCQQOYJMKOO-UHFFFAOYSA-N 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- VVGIYYKRAMHVLU-UHFFFAOYSA-N newbouldiamide Natural products CCCCCCCCCCCCCCCCCCCC(O)C(O)C(O)C(CO)NC(=O)CCCCCCCCCCCCCCCCC VVGIYYKRAMHVLU-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 210000004927 skin cell Anatomy 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- HTJNEBVCZXHBNJ-XCTPRCOBSA-H trimagnesium;(2r)-2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one;diphosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.OC[C@H](O)[C@H]1OC(=O)C(O)=C1O HTJNEBVCZXHBNJ-XCTPRCOBSA-H 0.000 description 2
- 229960005066 trisodium edetate Drugs 0.000 description 2
- IRJHMGSFUSXXQJ-JBEKKHDOSA-K trisodium;(2r)-2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one;phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O.OC[C@H](O)[C@H]1OC(=O)C(O)=C1O IRJHMGSFUSXXQJ-JBEKKHDOSA-K 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 229940088594 vitamin Drugs 0.000 description 2
- 229930003231 vitamin Natural products 0.000 description 2
- 235000013343 vitamin Nutrition 0.000 description 2
- 239000011782 vitamin Substances 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- DVSZKTAMJJTWFG-SKCDLICFSA-N (2e,4e,6e,8e,10e,12e)-docosa-2,4,6,8,10,12-hexaenoic acid Chemical compound CCCCCCCCC\C=C\C=C\C=C\C=C\C=C\C=C\C(O)=O DVSZKTAMJJTWFG-SKCDLICFSA-N 0.000 description 1
- JSPNNZKWADNWHI-PNANGNLXSA-N (2r)-2-hydroxy-n-[(2s,3r,4e,8e)-3-hydroxy-9-methyl-1-[(2r,3r,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoctadeca-4,8-dien-2-yl]heptadecanamide Chemical compound CCCCCCCCCCCCCCC[C@@H](O)C(=O)N[C@H]([C@H](O)\C=C\CC\C=C(/C)CCCCCCCCC)CO[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O JSPNNZKWADNWHI-PNANGNLXSA-N 0.000 description 1
- BJDAUCLANVMIOB-UHFFFAOYSA-N (3-decanoyloxy-2,2-dimethylpropyl) decanoate Chemical compound CCCCCCCCCC(=O)OCC(C)(C)COC(=O)CCCCCCCCC BJDAUCLANVMIOB-UHFFFAOYSA-N 0.000 description 1
- 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
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- JNAYPSWVMNJOPQ-UHFFFAOYSA-N 2,3-bis(16-methylheptadecanoyloxy)propyl 16-methylheptadecanoate Chemical compound CC(C)CCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCC(C)C)COC(=O)CCCCCCCCCCCCCCC(C)C JNAYPSWVMNJOPQ-UHFFFAOYSA-N 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
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- QOOALSWUUBYFCT-UHFFFAOYSA-N 2-[2-(7-methyloctanoyloxy)propoxy]propyl 7-methyloctanoate Chemical compound CC(C)CCCCCC(=O)OCC(C)OCC(C)OC(=O)CCCCCC(C)C QOOALSWUUBYFCT-UHFFFAOYSA-N 0.000 description 1
- OSCJHTSDLYVCQC-UHFFFAOYSA-N 2-ethylhexyl 4-[[4-[4-(tert-butylcarbamoyl)anilino]-6-[4-(2-ethylhexoxycarbonyl)anilino]-1,3,5-triazin-2-yl]amino]benzoate Chemical compound C1=CC(C(=O)OCC(CC)CCCC)=CC=C1NC1=NC(NC=2C=CC(=CC=2)C(=O)NC(C)(C)C)=NC(NC=2C=CC(=CC=2)C(=O)OCC(CC)CCCC)=N1 OSCJHTSDLYVCQC-UHFFFAOYSA-N 0.000 description 1
- BXCRLBBIZJSWNS-UHFFFAOYSA-N 2-hydroxyethyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCCO BXCRLBBIZJSWNS-UHFFFAOYSA-N 0.000 description 1
- XATHTZNVYDUDGS-UHFFFAOYSA-N 2-octadecylpropane-1,2,3-triol Chemical compound CCCCCCCCCCCCCCCCCCC(O)(CO)CO XATHTZNVYDUDGS-UHFFFAOYSA-N 0.000 description 1
- LEACJMVNYZDSKR-UHFFFAOYSA-N 2-octyldodecan-1-ol Chemical compound CCCCCCCCCCC(CO)CCCCCCCC LEACJMVNYZDSKR-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-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
- DJMBNBIFHBZPFR-UHFFFAOYSA-N 3-(7-methyloctanoyloxy)butyl 7-methyloctanoate Chemical compound C(CCCCCC(C)C)(=O)OCCC(C)OC(CCCCCC(C)C)=O DJMBNBIFHBZPFR-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- GZJLLYHBALOKEX-UHFFFAOYSA-N 6-Ketone, O18-Me-Ussuriedine Natural products CC=CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O GZJLLYHBALOKEX-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HJCMDXDYPOUFDY-WHFBIAKZSA-N Ala-Gln Chemical compound C[C@H](N)C(=O)N[C@H](C(O)=O)CCC(N)=O HJCMDXDYPOUFDY-WHFBIAKZSA-N 0.000 description 1
- AYQFHOICBJDUFS-UHFFFAOYSA-K C(CCCCCCCCCCCCCCC)(=O)[O-].[Na+].[Na+].[Na+].C(CCCCCCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCCCCCC)(=O)[O-] Chemical compound C(CCCCCCCCCCCCCCC)(=O)[O-].[Na+].[Na+].[Na+].C(CCCCCCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCCCCCC)(=O)[O-] AYQFHOICBJDUFS-UHFFFAOYSA-K 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 101100256637 Drosophila melanogaster senju gene Proteins 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- 102000011782 Keratins Human genes 0.000 description 1
- 108010076876 Keratins Proteins 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 150000000996 L-ascorbic acids Chemical class 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 102100037611 Lysophospholipase Human genes 0.000 description 1
- 235000018330 Macadamia integrifolia Nutrition 0.000 description 1
- 240000000912 Macadamia tetraphylla Species 0.000 description 1
- 235000003800 Macadamia tetraphylla Nutrition 0.000 description 1
- 239000004909 Moisturizer Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 102000016387 Pancreatic elastase Human genes 0.000 description 1
- 108010067372 Pancreatic elastase Proteins 0.000 description 1
- 108010058864 Phospholipases A2 Proteins 0.000 description 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 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
- HOAKDRHIAARPFN-UHFFFAOYSA-K [Na+].[Na+].[Na+].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O Chemical compound [Na+].[Na+].[Na+].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HOAKDRHIAARPFN-UHFFFAOYSA-K 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229960002648 alanylglutamine Drugs 0.000 description 1
- 108010044940 alanylglutamine Proteins 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- BTFJIXJJCSYFAL-UHFFFAOYSA-N arachidyl alcohol Natural products CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 description 1
- 229940071097 ascorbyl phosphate Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000010495 camellia oil Substances 0.000 description 1
- 239000004204 candelilla wax Substances 0.000 description 1
- 235000013868 candelilla wax Nutrition 0.000 description 1
- 229940073532 candelilla wax Drugs 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229930183167 cerebroside Natural products 0.000 description 1
- RIZIAUKTHDLMQX-UHFFFAOYSA-N cerebroside D Natural products CCCCCCCCCCCCCCCCC(O)C(=O)NC(C(O)C=CCCC=C(C)CCCCCCCCC)COC1OC(CO)C(O)C(O)C1O RIZIAUKTHDLMQX-UHFFFAOYSA-N 0.000 description 1
- 229940082500 cetostearyl alcohol Drugs 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 235000019868 cocoa butter Nutrition 0.000 description 1
- 229940110456 cocoa butter Drugs 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 239000008406 cosmetic ingredient Substances 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- 229940113120 dipropylene glycol Drugs 0.000 description 1
- 235000020669 docosahexaenoic acid Nutrition 0.000 description 1
- KAUVQQXNCKESLC-UHFFFAOYSA-N docosahexaenoic acid (DHA) Natural products COC(=O)C(C)NOCC1=CC=CC=C1 KAUVQQXNCKESLC-UHFFFAOYSA-N 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 229940009662 edetate Drugs 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 235000008524 evening primrose extract Nutrition 0.000 description 1
- 229940089020 evening primrose oil Drugs 0.000 description 1
- 239000010475 evening primrose oil Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 230000007760 free radical scavenging Effects 0.000 description 1
- 229940107187 fructooligosaccharide Drugs 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 229960005150 glycerol Drugs 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- IUJAMGNYPWYUPM-UHFFFAOYSA-N hentriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC IUJAMGNYPWYUPM-UHFFFAOYSA-N 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 229940100554 isononyl isononanoate Drugs 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 229940114937 microcrystalline wax Drugs 0.000 description 1
- 230000001333 moisturizer Effects 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000010466 nut oil Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000008385 outer phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 210000004694 pigment cell Anatomy 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- VIHIKSJKXIMMLV-FZTHFCCHSA-M potassium;[(2r)-2-[(1s)-1,2-dihydroxyethyl]-3-hydroxy-5-oxo-2h-furan-4-yl] [(2r)-2,5,7,8-tetramethyl-2-[(4r,8r)-4,8,12-trimethyltridecyl]-3,4-dihydrochromen-6-yl] phosphate Chemical compound [K+].C([C@@](OC1=C(C)C=2C)(C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)CC1=C(C)C=2OP([O-])(=O)OC1=C(O)[C@@H]([C@@H](O)CO)OC1=O VIHIKSJKXIMMLV-FZTHFCCHSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 235000019615 sensations Nutrition 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 231100000245 skin permeability Toxicity 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229940032094 squalane Drugs 0.000 description 1
- 229940031439 squalene Drugs 0.000 description 1
- TUHBEKDERLKLEC-UHFFFAOYSA-N squalene Natural products CC(=CCCC(=CCCC(=CCCC=C(/C)CCC=C(/C)CC=C(C)C)C)C)C TUHBEKDERLKLEC-UHFFFAOYSA-N 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 210000000434 stratum corneum Anatomy 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- OULAJFUGPPVRBK-UHFFFAOYSA-N tetratriacontyl alcohol Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO OULAJFUGPPVRBK-UHFFFAOYSA-N 0.000 description 1
- LADGBHLMCUINGV-UHFFFAOYSA-N tricaprin Chemical compound CCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCC)COC(=O)CCCCCCCCC LADGBHLMCUINGV-UHFFFAOYSA-N 0.000 description 1
- DPLMNCOVYWAZDG-XQTBVMIOSA-K trisodium dihydrogen phosphate (2R)-2-[(1S)-1,2-dihydroxyethyl]-3-hydroxy-5-oxo-2H-furan-4-olate hexadecanoate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O.OC[C@H](O)[C@H]1OC(=O)C(O)=C1O.CCCCCCCCCCCCCCCC(O)=O DPLMNCOVYWAZDG-XQTBVMIOSA-K 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 150000003700 vitamin C derivatives Chemical class 0.000 description 1
- 239000010497 wheat germ oil Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Description
本発明は、安定性と使用感に優れた油中水型乳化組成物に関する。 The present invention relates to a water-in-oil emulsion composition having excellent stability and usability.
多価アルコールのポリ（１２−ヒドロキシステアリン酸）エステルは、高温および低温安定性に優れた流動性のある低粘度乳化組成物を製造できることが特徴である（非特許文献１：ＦＲＡＧＲＡＮＣＥ ＪＯＵＲＮＡＬ １９９９年９月）。多価アルコールのポリ（１２−ヒドロキシステアリン酸）エステルはそれ自身が軽い感触でべたついたりしないので、とかく油っぽく重たい使用感が敬遠されがちな化粧料用の油中水型乳化組成物の乳化剤として広く使用されている。特許文献１：特許第４１４６９７９号公報には、多価アルコールのポリ（１２−ヒドロキシステアリン酸）エステルを含有する多層乳化剤型の皮膚外用剤が開示されている。
一般に、油中水型乳化組成物は電荷を持たない為、乳化粒子同士の静電反発によって粒子の合一を防止し、安定化を図ることができず、乳化組成物中に沈殿や分離が発生するなどの問題に対しては、外相(油)を増粘剤により増粘させる、他の乳化剤との併用により界面を強化する(粘度の増加はあまり期待できない) 等の方法が採用されている。
増粘剤を配合した例として、例えば、増粘ゲル化剤であるフラクトオリゴ糖脂肪酸エステルとポリ（１２−ヒドロキシステアリン酸）エステルとトリアシルグリセリンを１〜５０質量％含有する油剤と水を含む油中水型乳化組成物が提案されている(特許文献２：特許第４６７６６３４号公報）。しかしながら、べたつき感が残るなど使用感は十分ではない。先に示した非特許文献１（ＦＲＡＧＲＡＮＣＥ ＪＯＵＲＮＡＬ １９９９年９月）には、増粘剤濃度が高すぎると皮膚当たりが悪くなることが、注意事項として記されている。
A poly (12-hydroxystearic acid) ester of a polyhydric alcohol is characterized in that a low-viscosity emulsified composition having excellent flow stability at high and low temperatures can be produced (Non-patent Document 1: FRAGRANCE JOURNAL 1999 September. Moon). Since the poly (12-hydroxystearic acid) ester of polyhydric alcohol itself is not light and sticky, the emulsifier of the water-in-oil emulsion composition for cosmetics, which tends to be avoided in any way because it is oily and heavy. As widely used. Patent Document 1: Japanese Patent No. 4146969 discloses a multilayer emulsifier type skin external preparation containing a poly (12-hydroxystearic acid) ester of a polyhydric alcohol.
In general, since water-in-oil emulsion compositions do not have a charge, electrostatic repulsion between emulsified particles prevents particles from being coalesced and cannot be stabilized, and precipitation or separation occurs in the emulsion composition. For problems such as occurrence, methods such as thickening the outer phase (oil) with a thickener, strengthening the interface by using in combination with other emulsifiers (increase in viscosity cannot be expected) are adopted. Yes.
As an example of blending a thickener, for example, an oil containing 1 to 50% by mass of fructooligosaccharide fatty acid ester, poly (12-hydroxystearic acid) ester, and triacylglycerin, which is a thickening gelling agent, and water A water-in-water emulsified composition has been proposed (Patent Document 2: Japanese Patent No. 4676634). However, the feeling of use is not sufficient, for example, a sticky feeling remains. The non-patent document 1 (FRAGRANJO JOURNAL, September 1999) shown above indicates that the skin contact becomes worse when the thickener concentration is too high.
非特許文献１には、多価アルコールのポリ（１２−ヒドロキシステアリン酸）エステルの配合を過剰にし、内水相の体積率を高くした（９０％）場合に油中水型乳化組成物の粘度が増大することが記載されている。しかしながら、高内水相の油中水型乳化組成物は、独特のスプラッシュ感（塗布時に内水相が弾け出る感触）が生じ肌に自然に馴染む感覚が得られず使用感に優れた組成物とは言い難い。 Non-Patent Document 1 discloses the viscosity of a water-in-oil emulsion composition when the poly (12-hydroxystearic acid) ester of polyhydric alcohol is excessively mixed to increase the volume fraction of the inner aqueous phase (90%). Is described as increasing. However, the water-in-oil emulsified composition with a high inner water phase is a composition that has a unique splash feeling (feeling that the inner water phase bounces at the time of application) and does not have a natural feeling of conforming to the skin, and has an excellent feeling of use. It's hard to say.
アスコルビン酸リン酸脂肪酸エステル及び（アスコルビル／トコフェリル）リン酸塩は、親油性と親水性の両方の性質を持つ両親媒性のビタミン誘導体である。皮膚浸透性に優れ、優れた美白効果や酸化抑制老化防止効果を有することから皮膚化粧料への配合が試みられている。しかしながら、これらの両親媒性のビタミン誘導体は、処方中で徐々に加水分解され、変色や異臭が発生したり、沈殿物が析出したりするため、長期安定性を保つことが困難である。
アスコルビン酸リン酸脂肪酸エステルを安定に配合する技術が提案されている。たとえば、アスコルビン酸リン酸脂肪酸エステルとトコフェリルリン酸エステルを組み合わせた化粧料 (特許文献３：特許第３８９８６２９号公報）、アスコルビン酸リン酸脂肪酸エステルと液状環状ジメチルポリシロキサンと多糖類脂肪酸エステルと水から成る油中水型乳化組成物 (特許文献４：特開２００７−２０４３９９号公報)が提案されている。また、出願人は、アスコルビン酸リン酸脂肪酸エステルとアラニルグルタミンを含有する水溶液の凍結乾燥製剤の技術を提案している（特願２０１０−１５６２９５号）。
また、（アスコルビル／トコフェリル）リン酸塩を安定に配合する技術としては、シクロデキストリンまたはヒドロキシアルキル化シクロデキストリンにビタミンＥ−ビタミンＣリン酸ジエステルが包接された包接物（特許文献５：特開平１０−６７６３９号公報）が提案されている。
Ascorbic acid phosphate fatty acid esters and (ascorbyl / tocopheryl) phosphate are amphiphilic vitamin derivatives with both lipophilic and hydrophilic properties. Since it has excellent skin permeability and has an excellent whitening effect and oxidation-inhibiting anti-aging effect, it has been tried to be incorporated into skin cosmetics. However, these amphiphilic vitamin derivatives are gradually hydrolyzed in the formulation, causing discoloration and off-flavors, and precipitates are deposited, making it difficult to maintain long-term stability.
Techniques for stably blending ascorbic acid phosphate fatty acid esters have been proposed. For example, cosmetics combining ascorbic acid phosphate fatty acid ester and tocopheryl phosphate ester (Patent Document 3: Japanese Patent No. 3898629), ascorbic acid phosphate fatty acid ester, liquid cyclic dimethylpolysiloxane, polysaccharide fatty acid ester and water A water-in-oil emulsion composition (Patent Document 4: Japanese Patent Application Laid-Open No. 2007-204399) is proposed. In addition, the applicant has proposed a technique of a freeze-dried preparation of an aqueous solution containing ascorbic acid phosphate fatty acid ester and alanylglutamine (Japanese Patent Application No. 2010-156295).
Further, as a technique for stably blending (ascorbyl / tocopheryl) phosphate, a clathrate in which vitamin E-vitamin C phosphate diester is clathrated in cyclodextrin or hydroxyalkylated cyclodextrin (Patent Document 5: Special) No. 10-67639 has been proposed.
本発明者は、前記の両親媒性のビタミン誘導体と多価アルコールのポリ（１２−ヒドロキシステアリン酸）エステルを組み合わせた油中水型乳化組成物が、安定性、使用感ともに優れた化粧料になることを見出し、本発明を完成させた。 The present inventor has found that a water-in-oil emulsion composition combining the above-mentioned amphiphilic vitamin derivative and poly (12-hydroxystearic acid) ester of polyhydric alcohol is a cosmetic with excellent stability and usability. As a result, the present invention has been completed.
保存安定性が高く、使用感の良好な油中水型乳化組成物を提供することを課題とする。 It is an object of the present invention to provide a water-in-oil emulsion composition having high storage stability and good usability.
本発明の主な構成は、次のとおりである。
（１）（Ａ）：両親媒性のビタミン誘導体であるＬ−アスコルビン酸リン酸パルミチン酸三ナトリウム０．１〜６質量％又は（アスコルビル／トコフェリル）リン酸カリウム０．３〜６質量％、
（Ｂ）：ジポリヒドロキシステアリン酸ポリエチレングリコール、
（Ｃ）：油剤、
（Ｄ）：水、
を含有する油中水型乳化組成物であって、
測定温度２５℃において、Ｂ型粘度計、４号ローターを用いて測定した粘度が、４８００〜５００００ｍＰａ・ｓを示し、
ポリエチレングリコールおよび増粘剤を含有しない油中水型乳化組成物。
（２）油中水型乳化組成物中の水相の合計量が組成物全体の６５〜８４質量％である（１）に記載の油中水型乳化組成物。
（３）クリーム剤型である（１）又は（２）に記載の油中水型乳化組成物。
The main configuration of the present invention is as follows.
(1) (A): L-ascorbic acid palmitate trisodium 0.1-6 mass% or (ascorbyl / tocopheryl) potassium phosphate 0.3-6 mass% which is an amphipathic vitamin derivative
(B): polyethylene glycol dipolyhydroxystearate,
(C): oil agent,
(D): water,
A water-in-oil emulsion composition containing,
At a measurement temperature of 25 ° C., the viscosity measured using a B-type viscometer, No. 4 rotor is 4800 to 50000 mPa · s,
A water-in-oil emulsion composition containing no polyethylene glycol and thickener .
(2) The water-in-oil emulsion composition according to (1), wherein the total amount of the water phase in the water-in-oil emulsion composition is 65 to 84% by mass of the entire composition.
(3) The water-in-oil emulsion composition according to (1) or (2), which is a cream type.
安定性に優れ、使用感の良好な油中水型乳化組成物を提供できる。
この組成物を用いて調製した化粧料、皮膚外用剤(医薬部外品、医薬品)は、さっぱりとしたべたつかない使用感を維持しながら、クリーム状の粘性があり、製剤を塗布する際に液だれすることがなく、高級なクリーム状の使用感を実現することができる。
It is possible to provide a water-in-oil emulsion composition having excellent stability and good usability.
Cosmetics and skin external preparations (quasi-drugs, pharmaceuticals) prepared using this composition have a creamy viscosity while maintaining a refreshing and non-sticky feeling, and liquids are applied when the formulation is applied. It is possible to realize a high quality creamy feeling without anybody.
以下に、本発明の構成成分について説明する。
必須成分
Below, the component of this invention is demonstrated.
Essential ingredients
本発明の（Ａ）成分である両親媒性のビタミン誘導体は、親油性と親水性の両方の性質を持つ両親媒性のビタミン誘導体である。アスコルビン酸リン酸脂肪酸エステル及び（アスコルビル／トコフェリル）リン酸塩を例示することができる。
〔（Ａ）１：アスコルビン酸リン酸脂肪酸エステル〕
本発明に用いるアスコルビン酸リン酸脂肪酸エステル及びその塩としては、Ｌ−アスコルビン酸リン酸ラウリン酸、Ｌ−アスコルビン酸リン酸ミリスチン酸、Ｌ−アスコルビン酸リン酸パルミチン酸、Ｌ−アスコルビン酸リン酸ステアリン酸、Ｌ−アスコルビン酸リン酸ラウリン酸三ナトリウム、Ｌ−アスコルビン酸リン酸ミリスチン酸三ナトリウム、Ｌ−アスコルビン酸リン酸パルミチン酸三ナトリウム、Ｌ−アスコルビン酸リン酸ステアリン酸三ナトリウム、Ｌ−アスコルビン酸リン酸ラウリン酸マグネシウム、Ｌ−アスコルビン酸リン酸ミリスチン酸マグネシウム、Ｌ−アスコルビン酸リン酸パルミチン酸マグネシウム、Ｌ−アスコルビン酸リン酸ステアリン酸マグネシウム等が挙げられる。特に好ましくは、Ｌ−アスコルビン酸リン酸パルミチン酸三ナトリウムである。
Ｌ−アスコルビン酸リン酸パルミチン酸三ナトリウムは、ビタミンＣにパルミチン酸とリン酸が結合しており、親水性と親油性の両方の性質を有するので皮膚の細胞膜を透過しやすく皮膚の細胞に効率よく取り込まれる。Ｌ−アスコルビン酸リン酸パルミチン酸三ナトリウムは、皮膚内のエラスターゼやフォスファターゼなどの酵素によりビタミンＣに変換される。変換されたビタミンＣは、活性酸素除去作用や皮膚角質バリアーを担う脂質合成を高める作用を発揮して肌荒れやしわを改善したり、色素細胞に取り込まれたメラニン色素産生を抑制したり産生された色素を還元したりするので、その美容効果を期待して化粧料などの皮膚外用剤に配合される。本発明においてもビタミンＣの供給を目的として配合されている。アスコルビン酸リン酸脂肪酸エステルの市販品されているものとして、昭和電工(株)製のアプレシエ(Ｒ)（Ｌ−アスコルビン酸リン酸パルミチン酸三ナトリウム）を用いることができる。
The amphiphilic vitamin derivative as component (A) of the present invention is an amphiphilic vitamin derivative having both lipophilic and hydrophilic properties. Ascorbic acid phosphate fatty acid ester and (ascorbyl / tocopheryl) phosphate can be exemplified.
[(A) 1: Ascorbic acid fatty acid ester]
Ascorbic acid phosphate fatty acid esters and salts thereof used in the present invention include L-ascorbic acid phosphate lauric acid, L-ascorbic acid phosphate myristic acid, L-ascorbic acid phosphate palmitic acid, L-ascorbic acid phosphate stearin Acid, L-ascorbic acid trisodium phosphate, L-ascorbic acid phosphate, trisodium myristic acid, L-ascorbic acid phosphate, trisodium palmitate, L-ascorbic acid phosphate, trisodium stearate, L-ascorbic acid Examples thereof include magnesium laurate phosphate, L-ascorbic acid phosphate magnesium myristate, L-ascorbic acid phosphate palmitate, L-ascorbate phosphate magnesium stearate, and the like. Particularly preferred is L-ascorbic acid trisodium palmitate.
L-ascorbic acid trisodium palmitate is a combination of vitamin C and palmitic acid and phosphoric acid, and has both hydrophilic and lipophilic properties, so it easily penetrates the skin cell membrane and is efficient for skin cells. Well taken in. L-ascorbic acid trisodium palmitate is converted to vitamin C by enzymes such as elastase and phosphatase in the skin. The converted vitamin C was produced by demonstrating the action of removing active oxygen and enhancing the synthesis of lipids responsible for the skin keratin barrier to improve rough skin and wrinkles, and to suppress the production of melanin pigment incorporated into pigment cells. Since the pigment is reduced, it is blended into an external preparation for skin such as cosmetics in anticipation of its beauty effect. Also in the present invention, it is blended for the purpose of supplying vitamin C. As a commercial product of ascorbic acid phosphate fatty acid ester, Apressie® (L-ascorbic acid palmitate trisodium phosphate) manufactured by Showa Denko KK can be used.
〔（Ａ）２：（アスコルビル／トコフェリル）リン酸塩〕
本発明に用いる（アスコルビル／トコフェリル）リン酸塩の塩類はいずれでもよいが、ナトリウム塩、カリウム塩、等の金属塩が好ましい。特に好ましくは（アスコルビル／トコフェリル）リン酸カリウムである。
（アスコルビル／トコフェリル）リン酸カリウムは、抗酸化作用及びラジカルスカベンジャーとしての作用が期待される化合物で、過酸化脂質抑制作用、フリーラジカル消去作用、ホスホリパーゼＡ２阻害作用、保湿作用、角質層の生成周期の正常化等を有し、トコフェロールやアスコルビン酸の単独および併用投与とは異なった作用を有することが確認されている物質である。本発明においてもビタミンＣとトコフェロールの供給を目的として配合されている。（アスコルビル／トコフェリル）リン酸塩の市販品としては、千寿製薬（株）製のＥＰＣ−Ｋ（（アスコルビル／トコフェリル）リン酸カリウム）を用いることができる。
[(A) 2: (Ascorbyl / tocopheryl) phosphate]
Any salt of (ascorbyl / tocopheryl) phosphate used in the present invention may be used, but metal salts such as sodium salt and potassium salt are preferred. Particularly preferred is (ascorbyl / tocopheryl) potassium phosphate.
(Ascorbyl / tocopheryl) potassium phosphate is a compound that is expected to act as an antioxidant and as a radical scavenger. Lipid peroxide inhibitory action, free radical scavenging action, phospholipase A2 inhibitory action, moisturizing action, stratum corneum formation cycle It is a substance that has been confirmed to have an action different from that of tocopherol or ascorbic acid alone or in combination. Also in the present invention, it is blended for the purpose of supplying vitamin C and tocopherol. As a commercially available product of (ascorbyl / tocopheryl) phosphate, EPC-K ((ascorbyl / tocopheryl) potassium phosphate) manufactured by Senju Pharmaceutical Co., Ltd. can be used.
本発明に用いる（Ａ）１：アスコルビン酸リン酸脂肪酸エステル、（Ａ）２：（アスコルビル／トコフェリル）リン酸塩は、単独で用いても、組み合わせて配合しても構わない。成分(Ａ)の両親媒性ビタミンの配合量は、化粧料や皮膚外用剤に所望される、皮膚にビタミンＣやトコフェロールを供給できる量を配合することができる。通常、組成物の安定性を考慮して配合するが、０．０５〜１０質量％が好ましく、特に好ましくは０．１〜６質量％である。０．０５質量％に満たないと、安定性を向上させる効果が不十分になる恐れがある。１０質量％を超えると、べたついた使用感になる恐れがある。 (A) 1: Ascorbic acid phosphate fatty acid ester and (A) 2: (ascorbyl / tocopheryl) phosphate used in the present invention may be used alone or in combination. The compounding amount of the amphiphilic vitamin of component (A) can be an amount that can supply vitamin C and tocopherol to the skin, which is desired for cosmetics and external preparations for skin. Usually, it mix | blends considering the stability of a composition, However, 0.05-10 mass% is preferable, Especially preferably, it is 0.1-6 mass%. If it is less than 0.05% by mass, the effect of improving the stability may be insufficient. If it exceeds 10% by mass, there may be a sticky feeling of use.
〔（Ｂ）：多価アルコールのポリ（１２−ヒドロキシステアリン酸）エステル〕
本発明に用いる多価アルコールのポリ（１２−ヒドロキシステアリン酸）エステルは、ポリエチレングリコール等の多価アルコールをアルカリ存在下、ポリ（１２−ヒドロキシステアリン酸）と塩化チオニル等のハロゲン化剤を反応させて調製した酸クロライドを反応させることにより得ることができる。
多価アルコ−ルとしては、プロピレングリコール、ブタンジオール、ペンタンジオール、（ポリ）グリセリン、（ポリ）プロピレングリコール、ポリエチレングリコールなどが好ましく例示でき、ポリエチレングリコールが特に好ましい。この場合のポリエチレングリコールのサイズは、平均分子量で４００〜６０００が好ましい。一方、疎水基となるポリ（１２−ヒドロキシステアリン酸）は、そのサイズが平均分子量１０００〜３０００であることが好ましい。
ポリエチレングリコールのジ（１２−ヒドロキシステアリン酸）エステルを用いることが好ましく、ＩＮＣＩ名がジポリヒドロキシステアリン酸ＰＥＧ−３０と収載されているものが好ましく、市販品としては、ユニケマ社製のアラセルＰ−１３５、クローダジャパン（株）社製のシスロールＤＰＨＳがある。
多価アルコールのポリ（１２−ヒドロキシステアリン酸）エステルの配合量は、０．１〜５質量％が好ましく、特に好ましくは１〜５質量％である。０．１質量％に満たないと、乳化が不十分になる恐れがある。５質量％を超えると、べたついた使用感になる恐れがある。
[(B): poly (12-hydroxystearic acid) ester of polyhydric alcohol]
Poly (12-hydroxystearic acid) ester of polyhydric alcohol used in the present invention is obtained by reacting poly (12-hydroxystearic acid) with a halogenating agent such as thionyl chloride in the presence of an alkali such as polyethylene glycol. It can be obtained by reacting the acid chloride prepared above.
Preferred examples of the polyhydric alcohol include propylene glycol, butanediol, pentanediol, (poly) glycerin, (poly) propylene glycol, and polyethylene glycol, with polyethylene glycol being particularly preferred. In this case, the polyethylene glycol preferably has an average molecular weight of 400 to 6000. On the other hand, the poly (12-hydroxystearic acid) serving as a hydrophobic group preferably has an average molecular weight of 1000 to 3000.
It is preferable to use di (12-hydroxystearic acid) ester of polyethylene glycol, and those whose INCI name is listed as dipolyhydroxystearic acid PEG-30 are preferable. 135, and Cisroll DPHS manufactured by Croda Japan Co., Ltd. is available.
The blending amount of the poly (12-hydroxystearic acid) ester of the polyhydric alcohol is preferably 0.1 to 5% by mass, particularly preferably 1 to 5% by mass. If it is less than 0.1% by mass, emulsification may be insufficient. If it exceeds 5 mass%, there is a risk of having a sticky feel.
〔（Ｃ）：油剤〕
本発明に用いる油剤としては、エステル油、植物油のような油脂類、炭化水素類、高級脂肪酸、高級アルコール、シリコ−ン油などが例示できる。
エステル油としては、例えば、エチルヘキサン酸セチル、ジイソノナン酸１，３−ブチレングリコール、ジ２−エチルヘキサン酸１，３−ブチレングリコール、ジイソノナン酸ジプロピレングリコール、ジ２−エチルヘキサン酸ジプロピレングリコール、イソノナン酸イソノニル、トリ２−エチルヘキサン酸グリセリル、トリカプリン酸グリセリル、トリイソステアリン酸グリセリル、ジカプリン酸ネオペンチルグリコール、パルミチン酸エチルヘキシル、ネオペンタン酸イソステアリル等が挙げられる。
油脂類としては、例えば、ツバキ油、月見草油、マカデミアナッツ油、オリーブ油、ナタネ油、トウモロコシ油、ゴマ油、ホホバ油、胚芽油、小麦胚芽油、等の液体油脂、カカオ脂、ヤシ油、硬化ヤシ油、パーム油、パーム核油、モクロウ、モクロウ核油、硬化油、硬化ヒマシ油等の固体油脂、ミツロウ、キャンデリラロウ、綿ロウ、ヌカロウ、ラノリン、酢酸ラノリン、液状ラノリン、サトウキビロウ等のロウ類が挙げられる。
炭化水素類としては、例えば、流動パラフィン、スクワレン、スクワラン、マイクロクリスタリンワックス等が挙げられる。
高級脂肪酸としては、例えば、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、リノール酸、リノレン酸、ドコサヘキサエン酸（ＤＨＡ）、エイコサペンタエン酸（ＥＰＡ）等が挙げられる。
高級アルコールとしては、例えば、ラウリルアルコール、ステアリルアルコール、セチルアルコール、セトステアリルアルコール等の直鎖アルコール、モノステアリルグリセリンエーテル、ラノリンアルコール、コレステロール、フィトステロール、オクチルドデカノール等の分枝鎖アルコール等が挙げられる。
シリコ−ン油として、例えば、鎖状ポリシロキサンのジメチルポリシロキサン、メチルフェニルポリシロキサン等、環状ポリシロキサンのデカメチルシクロペンタシロキサン、シクロペンタシロキサン、（ジメチコン／ビニルジメチコン）クロスポリマー等が挙げられる。
ホホバ油、パルミチン酸エチルヘキシル、ネオペンタン酸イソステアリルを用いることが使用感の観点から好ましい。本発明における油剤の配合量は特に限定されないが、好ましくは１０〜４０％である。
[(C): Oil agent]
Examples of the oil used in the present invention include fats and oils such as ester oils and vegetable oils, hydrocarbons, higher fatty acids, higher alcohols, and silicone oils.
Examples of ester oils include cetyl ethylhexanoate, 1,3-butylene glycol diisononanoate, 1,3-butylene glycol di-2-ethylhexanoate, dipropylene glycol diisononanoate, dipropylene glycol di-2-ethylhexanoate, Examples include isononyl isononanoate, glyceryl tri-2-ethylhexanoate, glyceryl tricaprate, glyceryl triisostearate, neopentyl glycol dicaprate, ethylhexyl palmitate, isostearyl neopentanoate, and the like.
Examples of the fats and oils include camellia oil, evening primrose oil, macadamia nut oil, olive oil, rapeseed oil, corn oil, sesame oil, jojoba oil, germ oil, wheat germ oil, and other liquid oils, cocoa butter, coconut oil, and hardened coconut oil. , Solid oils such as palm oil, palm kernel oil, mole owl, owl kernel oil, hydrogenated oil, hydrogenated castor oil, waxes such as beeswax, candelilla wax, cotton wax, nuka wax, lanolin, lanolin acetate, liquid lanolin, sugarcane wax Is mentioned.
Examples of the hydrocarbons include liquid paraffin, squalene, squalane, and microcrystalline wax.
Examples of the higher fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, docosahexaenoic acid (DHA), eicosapentaenoic acid (EPA), and the like.
Examples of the higher alcohol include linear alcohols such as lauryl alcohol, stearyl alcohol, cetyl alcohol, and cetostearyl alcohol, branched alcohols such as monostearyl glycerin ether, lanolin alcohol, cholesterol, phytosterol, and octyldodecanol. .
Examples of the silicone oil include linear polysiloxanes such as dimethylpolysiloxane and methylphenylpolysiloxane, cyclic polysiloxanes such as decamethylcyclopentasiloxane, cyclopentasiloxane, and (dimethicone / vinyl dimethicone) crosspolymer.
Use of jojoba oil, ethylhexyl palmitate, and isostearyl neopentanoate is preferable from the viewpoint of feeling of use. Although the compounding quantity of the oil agent in this invention is not specifically limited, Preferably it is 10 to 40%.
〔（Ｄ）：水〕
本発明において水の配合は、油中水型のエマルジョンを形成させるために必須の成分である。配合量は特に限定されないが、好ましくは３０〜８０質量％である。
[(D): Water]
In the present invention, the formulation of water is an essential component for forming a water-in-oil emulsion. The blending amount is not particularly limited, but is preferably 30 to 80% by mass.
本発明における油中水型乳化組成物は、油の中に水が分散している乳化組成物のことであり、水相を、乳化組成物の連続相となる油相へ添加して調製することが出来る。ここで、水相とは、その組成物中に含有される水、多価アルコール等の水溶性成分、両親媒性のビタミン誘導体が該当する。油相とは、その組成物中に含有される天然動・植物油、合成油等のすべての油性成分、乳化剤である多価アルコールのポリ（１２−ヒドロキシステアリン酸）エステルが該当する。水相には、通常化粧料に配合される水溶性の成分を配合できる。水相が水と両親媒性のビタミン誘導体のみで構成されていても構わない。
本発明の油中水型乳化組成物では、水相の合計量が乳化組成物全体の６５〜８４質量％、より好ましくは６５〜８０質量％、さらに好ましくは７０〜８０質量％であることが好ましい。６５質量％に満たないと、クリーム状の粘性が得られない恐れがある。８４質量％を超えた高内水相の油中水型乳化組成物としても、クリーム状の粘性で安定性に優れたものが調製できるが、独特のスプラッシュ感（塗布時に内水相が弾け出る感触）が生じ肌に自然に馴染む感覚が得られず使用感に優れた組成物が得られにくくなる恐れがある。
The water-in-oil emulsion composition in the present invention is an emulsion composition in which water is dispersed in oil, and is prepared by adding an aqueous phase to an oil phase that becomes a continuous phase of the emulsion composition. I can do it. Here, the water phase corresponds to water, water-soluble components such as polyhydric alcohols, and amphiphilic vitamin derivatives contained in the composition. The oil phase corresponds to all oily components such as natural animal and vegetable oils and synthetic oils contained in the composition, and poly (12-hydroxystearic acid) ester of polyhydric alcohol which is an emulsifier. In the aqueous phase, water-soluble components that are usually blended in cosmetics can be blended. The aqueous phase may be composed only of water and an amphiphilic vitamin derivative.
In the water-in-oil emulsion composition of the present invention, the total amount of the aqueous phase is 65 to 84% by mass, more preferably 65 to 80% by mass, and still more preferably 70 to 80% by mass of the entire emulsion composition. preferable. If it is less than 65% by mass, a creamy viscosity may not be obtained. A water-in-oil emulsified composition with a high internal water phase exceeding 84% by mass can also be prepared with a creamy viscosity and excellent stability, but a unique splash feeling (the internal water phase pops out during application) There is a risk that it will be difficult to obtain a composition having an excellent feeling in use due to a feeling) that does not give the skin a natural sensation.
本発明の油中水型乳化組成物の粘度は、Ｎｏ．４ローターを備えたＢ型粘度計を使用し、測定温度２５℃、ローター回転速度１２ｒｐｍ、測定開始後３０秒後の条件で測定するとき、４８００〜５００００ｍＰａ・ｓの範囲にあることが好ましい。この粘度の範囲では、さっぱりとしたべたつかない使用感を維持しながら、製剤を塗布する際の、高級なクリーム状の使用感を実現することができる。 The viscosity of the water-in-oil emulsion composition of the present invention is No. When a B-type viscometer equipped with 4 rotors is used and measurement is performed under the conditions of a measurement temperature of 25 ° C., a rotor rotation speed of 12 rpm, and 30 seconds after the start of measurement, it is preferably in the range of 4800 to 50000 mPa · s. Within this viscosity range, it is possible to realize a high-grade creamy feeling when applying the preparation while maintaining a refreshing and non-sticky feeling.
任意成分
本発明の油中水型乳化組成物には、任意成分として本発明の効果を損なわない範囲で、化粧料に通常用いられている成分、例えば、非イオン性界面活性剤、陰イオン性界面活性剤、陽イオン性界面活性剤、両性界面活性剤、油剤、多価アルコール等の保湿剤、抗酸化剤、紫外線吸収剤、塩類、ＰＨ調整剤、防腐剤、抗菌剤、キレート剤、着色剤、香料等を配合することができる。また、セラミド、植物抽出液等の美容成分を配合することができる。
Optional components In the water-in-oil emulsion composition of the present invention, components that are usually used in cosmetics, for example, nonionic surfactants, anionic properties, as long as the effects of the present invention are not impaired as optional components Surfactant, Cationic surfactant, Amphoteric surfactant, Oil agent, Moisturizer such as polyhydric alcohol, Antioxidant, UV absorber, Salts, PH adjuster, Preservative, Antibacterial agent, Chelating agent, Coloring An agent, a fragrance | flavor, etc. can be mix | blended. In addition, cosmetic ingredients such as ceramide and plant extract can be blended.
保湿剤としては、グリセリン、ジグリセリン、１，３−ブチレングリコール、ジプロピレングリコール、ペンチレングリコール等が挙げられる。
塩類としては、塩化ナトリウム、硫酸マグネシウム等が挙げられる。
ＰＨ調製剤としては、クエン酸、クエン酸ナトリウム、リン酸、リン酸ナトリウム、水酸化カリウム等が挙げられる。
防腐剤としては、フェノキシエタノール、パラベン等が挙げられる。
アスコルビン酸誘導体としては、Ｌ−アスコルビン酸リン酸エステルマグネシウム塩、Ｌ−アスコルビン酸リン酸エステルナトリウム塩、２−Ｏ−α−Ｄ−グルコピラノシル−Ｌ−アスコルビン酸等が挙げられる。
セラミドとしては、セチルＰＧヒドロキシエチルパルミタイド、セレブロシド等が挙げられる。
Examples of the humectant include glycerin, diglycerin, 1,3-butylene glycol, dipropylene glycol, and pentylene glycol.
Examples of the salts include sodium chloride and magnesium sulfate.
Examples of the pH adjusting agent include citric acid, sodium citrate, phosphoric acid, sodium phosphate, potassium hydroxide and the like.
Examples of the preservative include phenoxyethanol and paraben.
Examples of the ascorbic acid derivative include L-ascorbic acid phosphate magnesium salt, L-ascorbic acid phosphate sodium salt, 2-O-α-D-glucopyranosyl-L-ascorbic acid and the like.
Examples of ceramide include cetyl PG hydroxyethyl palmitate, cerebroside and the like.
本発明の油中水型乳化組成物に、さらにキレート剤を含有させると、油中水型乳化組成物の保管温度による粘度の差をより小さくする場合がある。キレート剤としては、エデト酸二ナトリウム、エデト酸三ナトリウム、エデト酸四ナトリウム、エデト酸二カリウムを例示することができる。エデト酸三ナトリウムを用いることが好ましい。市販されているキレスト株式会社製のキレスト２Ｃ-ＳＤを用いることができる。油中水型乳化組成物は、キレート剤を０．０００１質量％〜０．２質量％含有することが好ましい。 When the water-in-oil emulsion composition of the present invention further contains a chelating agent, the difference in viscosity depending on the storage temperature of the water-in-oil emulsion composition may be further reduced. Examples of the chelating agent include disodium edetate, trisodium edetate, tetrasodium edetate, and dipotassium edetate. It is preferable to use trisodium edetate. A commercially available Kirest 2C-SD manufactured by Kirest Co., Ltd. can be used. The water-in-oil emulsion composition preferably contains 0.0001% by mass to 0.2% by mass of a chelating agent.
本発明の構成をとる油中水型乳化組成物は、水溶性高分子や油溶性高分子などの増粘剤を配合しなくても好ましいクリーム状の粘度になる。したがって、粘度を上げることを目的とした増粘剤の配合は必要としない。しかし、つるつるとした感触を付与したい場合などに、本発明の効果を損なわない程度に水溶性高分子などを少量配合することができる。 The water-in-oil emulsified composition taking the constitution of the present invention has a preferable cream-like viscosity without blending a thickener such as a water-soluble polymer or oil-soluble polymer. Therefore, it is not necessary to add a thickener for the purpose of increasing the viscosity. However, a small amount of a water-soluble polymer or the like can be blended to such an extent that the effect of the present invention is not impaired when it is desired to give a smooth feel.
本発明の油中水型乳化組成物は乳液、クリーム、美容液、日焼け止め、リキッドファンデーション等の化粧料や、皮膚外用剤として医薬部外品や医薬品として使用することができる。本発明の特性から、クリーム状剤型が特に好ましい。 The water-in-oil emulsified composition of the present invention can be used as a quasi-drug or pharmaceutical as cosmetics such as milky lotion, cream, cosmetic liquid, sunscreen, liquid foundation, etc., or as a skin external preparation. A creamy dosage form is particularly preferred because of the properties of the present invention.
〔実施例〕
以下に実施例を挙げて、本発明の特徴と効果をさらに詳細に説明する。
〔Example〕
Hereinafter, the features and effects of the present invention will be described in more detail with reference to examples.
表１の組成にて、実施例１、２、比較例１〜３の油中水型乳化組成物を、以下の調製方法により調製した。 With the composition of Table 1, the water-in-oil emulsion compositions of Examples 1 and 2 and Comparative Examples 1 to 3 were prepared by the following preparation method.
（調製方法）
ジポリヒドロキシステアリン酸ＰＥＧ−３０（成分（Ｂ））に各油剤（Ｃ）を加え８０℃に加熱して、十分に攪拌し油相を調製する。また、成分（Ａ）と水、多価アルコールを混合後、８０℃に加熱して、十分に攪拌し水相を調製する。次いで水相を油相へ徐々に添加しながら、ホモミキサーで６０００ｒｐｍ、２分攪拌して乳化し、その後、室温まで攪拌しながら冷却する。
(Preparation method)
Each oil agent (C) is added to dipolyhydroxystearic acid PEG-30 (component (B)), heated to 80 ° C., and sufficiently stirred to prepare an oil phase. Moreover, after mixing a component (A), water, and a polyhydric alcohol, it heats at 80 degreeC and fully stirs and prepares an aqueous phase. Next, while gradually adding the aqueous phase to the oil phase, the mixture is emulsified by stirring at 6000 rpm for 2 minutes with a homomixer, and then cooled to room temperature with stirring.
乳化状態の顕微鏡観察、粘度の測定、安定性・使用感の評価
実施例と比較例の組成物を、下記に示す方法により測定、評価した。
Microscopic observation of emulsified state, measurement of viscosity, evaluation of stability / use feeling The compositions of Examples and Comparative Examples were measured and evaluated by the methods described below.
＜乳化状態の顕微鏡観察＞
OLYMPUS社製のシステム偏光顕微鏡BX-50-33P-Dを用いて２５℃に１日間保存した油中水型乳化組成物を倍率４００で観察し、下記の基準で判定した。
◎；粒子径が細かく（３μｍ以下）均一 である
○；粒子径が細かくはないが均一である
△；粒子径が不揃である
×；粒子径が揃っておらず、合一が見られる
尚、調製直後に分離したりＷ／Ｏ型乳化を形成しなかった乳化組成物については「×」と評価した。
<Microscopic observation of emulsified state>
The water-in-oil emulsion composition stored at 25 ° C. for 1 day was observed at a magnification of 400 using a system polarizing microscope BX-50-33P-D manufactured by OLYMPUS, and judged according to the following criteria.
◎: Particle size is fine (3 μm or less) and uniform ○: Particle size is not fine but uniform △: Particle size is uneven ×: Particle size is not uniform and unity is seen
In addition, it evaluated as "x" about the emulsion composition which isolate | separated immediately after preparation or did not form W / O type | mold emulsification.
＜粘度＞
（調製翌日の粘度）
得られた油中水型乳化組成物を直径約３ｃｍのガラス容器に充填し２５℃に保存して、調製翌日の粘度を、Ｎｏ．４ローターを備えたＢ型粘度計を使用し、測定温度２５℃、ローター回転速度１２ｒｐｍ、測定開始後３０秒後の条件で測定した。
<Viscosity>
(Viscosity the day after preparation)
The obtained water-in-oil emulsion composition was filled in a glass container having a diameter of about 3 cm and stored at 25 ° C. A B-type viscometer equipped with 4 rotors was used, and measurement was performed under the conditions of a measurement temperature of 25 ° C., a rotor rotation speed of 12 rpm, and 30 seconds after the start of measurement.
＜乳化安定性の評価＞
乳化組成物を、それぞれ直径約３ｃｍのガラス容器に充填し、５℃、２５℃、４０℃、５０℃に３０日間保存して、乳化安定性を以下の基準により目視評価した。
（各温度での判定基準）
○：外観に異常がない
×：分離している
<Evaluation of emulsion stability>
The emulsified composition was filled in glass containers each having a diameter of about 3 cm, stored at 5 ° C., 25 ° C., 40 ° C., and 50 ° C. for 30 days, and the emulsion stability was visually evaluated according to the following criteria.
(Criteria at each temperature)
○: Appearance is not abnormal ×: Separated
＜両親媒性のビタミン誘導体の安定性の評価＞
得られた乳化組成物を、それぞれ直径３ｃｍのガラス容器に充填し、５℃、２５℃、４０℃、５０℃に３０日間保存して、両親媒性のビタミン誘導体（アスコルビン酸リン酸脂肪酸エステル、（アスコルビル／トコフェリル）リン酸塩）の安定性を以下の基準により目視評価した。
（判定基準）
○：両親媒性のビタミン誘導体の析出がなく、変色もない
△：両親媒性のビタミン誘導体による変色がある
×：両親媒性のビタミン誘導体の析出があり、変色している
尚、調製翌日の観察で、分離していた組成物又はＯ／Ｗ型乳化を形成してＷ／Ｏ型乳化を形成しなかった組成物については粘度の測定、安定性の評価はしていない。また、保存途中で分離した組成物についてはそれ以後の観察による評価を行わなかった。表中で記号（−）は評価していないことを示す。また、表に示された安定性の評価（乳化安定性の評価、両親媒性のビタミン誘導体の安定性の評価）とは、５℃、２５℃、４０℃、５０℃のすべての保管温度帯において、○の評価になった場合にのみ○と記入した。
<Evaluation of stability of amphiphilic vitamin derivatives>
The obtained emulsified composition was filled in a glass container having a diameter of 3 cm and stored at 5 ° C., 25 ° C., 40 ° C., and 50 ° C. for 30 days, and an amphiphilic vitamin derivative (ascorbic acid phosphate fatty acid ester, The stability of (ascorbyl / tocopheryl) phosphate) was visually evaluated according to the following criteria.
(Criteria)
○: No precipitation of amphiphilic vitamin derivatives and no discoloration △: Discoloration due to amphipathic vitamin derivatives ×: Discoloration due to precipitation of amphiphilic vitamin derivatives
In addition, by the observation on the next day of preparation, the measurement of the viscosity and the evaluation of the stability were not performed for the separated composition or the composition that formed the O / W type emulsion and did not form the W / O type emulsion. . Further, the composition separated during storage was not evaluated by subsequent observation. The symbol (-) in the table indicates that no evaluation is made. In addition, the evaluation of stability shown in the table (emulsification stability evaluation, stability evaluation of amphiphilic vitamin derivatives) is all storage temperature ranges of 5 ° C, 25 ° C, 40 ° C, and 50 ° C. In “”, “○” was entered only when the evaluation was “Good”.
＜使用感の評価＞
実施例、比較例の調製翌日の各配合の試料を用いて、各評価項目（塗布のしやすさ、べたつき）について、官能評価に優れたパネル（１０名）がブラインドにより評価した。
（塗布のしやすさの判定基準)
○；良い （７名以上が液だれせずに肌に塗布しやすいと答えた）
△；普通 （４〜６名が液だれせずに肌に塗布しやすいと答えた）
×；悪い （液だれせずに肌に塗布しやすいと答えたのが３名以下であった。）
（べたつきの判定基準)
○；良い （７名以上がべたつかないと答えた）
△；普通 （４〜６名がべたつかないと答えた）
×；悪い （べたつかないと答えたのが３名以下であった。）
<Evaluation of feeling of use>
Panels (10 persons) excellent in sensory evaluation were evaluated blindly for each evaluation item (ease of application, stickiness) using samples of each formulation on the day after preparation of Examples and Comparative Examples.
(Criteria for ease of application)
○: Good (7 or more responded that it was easy to apply to the skin without dripping)
△: Normal (4-6 people answered that it was easy to apply to the skin without dripping)
X: Poor (less than 3 people answered that it was easy to apply to the skin without dripping.)
(Criteria for stickiness)
○; Good (7 or more people said they were not sticky)
△: Normal (4-6 people answered they were not sticky)
×: Bad (less than 3 respondents answered that they were not sticky)
結果１
（Ａ）成分である両親媒性ビタミン誘導体を配合せずに、（Ｂ）成分であるジポリヒドロキシステアリン酸ＰＥＧ−３０のみを配合した比較例１の乳化組成物は、粘度が２１００ｍＰａ・ｓと低めであり、べたつきはないものの液だれして肌に塗布しにくかった。また、比較例１の油中水型乳化組成物は、１４日目に観察すると５０℃で保存したものが分離しており安定性が悪かった。（Ｂ）成分であるジポリヒドロキシステアリン酸ＰＥＧ−３０を配合せずに（Ａ）成分である両親媒性ビタミン誘導体のみを配合した比較例２、３は、油中水型乳化組成物は得られなかった。
これに対して、(Ａ）成分である両親媒性ビタミン誘導体(アスコルビン酸リン酸脂肪酸エステル又は（アスコルビル／トコフェリル）リン酸塩)を配合し、（Ｂ）成分であるジポリヒドロキシステアリン酸ＰＥＧ−３０を配合した実施例１、２の油中水型乳化組成物は、１６９００ｍＰａ・ｓ、７６００ｍＰａ・ｓとクリーム状で高い粘性があり、官能評価試験でも、液だれすることなく肌に塗布しやすいと評価された。また、べたつくことなくさっぱりとした感触で使用感に優れていると評価された。実施例１、２の油中水型乳化組成物は、３０日保存後もすべての保管温度帯（５℃、２５℃、４０℃、５０℃）で分離がみられず安定であった。両親媒性ビタミン誘導体の安定性については、実施例１の油中水型乳化組成物を５０℃に３０日間保管したものについてのみ上部が黒っぽく変色していた。しかし、アスコルビン酸リン酸脂肪酸エステルの析出はみられず、５℃、２５℃、４０℃に保管したものには変色がなかったことから、両親媒性ビタミン誘導体の安定性についても概ね良好であると判断した。
表１の試験結果から、成分（Ａ）両親媒性ビタミン誘導体(アスコルビン酸リン酸脂肪酸エステル又は（アスコルビル／トコフェリル）リン酸塩)と、成分（Ｂ）多価アルコールのポリ（１２−ヒドロキシステアリン酸）エステルを配合した油中水型乳化組成物は、使用感に優れ、保存安定性に優れたクリーム状の組成物となることが確認できた。
Result 1
The emulsified composition of Comparative Example 1 in which only the dipolyhydroxystearic acid PEG-30 as the component (B) is blended without blending the amphiphilic vitamin derivative as the component (A) has a viscosity of 2100 mPa · s. Although it was low and there was no stickiness, it was difficult to apply to the skin due to dripping. Moreover, the water-in-oil emulsion composition of Comparative Example 1 was poor in stability because it was separated from the one stored at 50 ° C. when observed on the 14th day. Comparative Examples 2 and 3 in which only the amphiphilic vitamin derivative as the component (A) was blended without blending the dipolyhydroxystearic acid PEG-30 as the component (B) were obtained as a water-in-oil emulsion composition. I couldn't.
On the other hand, (A) component amphiphilic vitamin derivative (ascorbic acid phosphate fatty acid ester or (ascorbyl / tocopheryl) phosphate) is blended, and (B) component dipolyhydroxystearic acid PEG- The water-in-oil emulsified composition of Examples 1 and 2 blended with 30 is creamy with high viscosity of 16900 mPa · s and 7600 mPa · s, and is easy to apply to the skin without dripping even in sensory evaluation tests. It was evaluated. In addition, it was evaluated as being excellent in usability with a refreshing feel without stickiness. The water-in-oil emulsion compositions of Examples 1 and 2 were stable with no separation observed in all storage temperature zones (5 ° C., 25 ° C., 40 ° C., 50 ° C.) even after storage for 30 days. Regarding the stability of the amphiphilic vitamin derivative, the upper part of the water-in-oil emulsion composition of Example 1 stored at 50 ° C. for 30 days was blackish in color. However, precipitation of ascorbic acid phosphate fatty acid ester was not observed, and the products stored at 5 ° C., 25 ° C., and 40 ° C. were not discolored, and the stability of the amphiphilic vitamin derivative was generally good. It was judged.
From the test results of Table 1, component (A) amphiphilic vitamin derivative (ascorbic acid phosphate fatty acid ester or (ascorbyl / tocopheryl) phosphate) and component (B) poly (12-hydroxystearic acid) of polyhydric alcohol It was confirmed that the water-in-oil emulsion composition containing the ester was a cream-like composition having excellent usability and excellent storage stability.
Ａ成分の配合量と油中水型乳化組成物の粘度の関係
次に、（Ａ）成分であるアスコルビン酸リン酸脂肪酸エステル（以下（Ａ）１成分）、または（Ａ）成分である（アスコルビル／トコフェリル）リン酸塩（以下（Ａ）２成分）の配合量の違いが本発明の油中水型乳化組成物の粘度にどのように影響するか調べた。（Ａ）１成分であるアスコルビン酸リン酸脂肪酸エステルの試験結果を表２に、（Ａ）２成分である（アスコルビル／トコフェリル）リン酸塩の試験結果を表３に示す。
Relation between blending amount of component A and viscosity of water-in-oil emulsion composition Next, component (A) is ascorbic acid fatty acid ester (hereinafter referred to as component (A) 1), or component (A) (ascorbyl) / Tocopheryl) phosphate (hereinafter referred to as component (A) 2 component) was examined how the difference in blending amount affects the viscosity of the water-in-oil emulsion composition of the present invention. The test results of (A) one component ascorbic acid phosphate fatty acid ester are shown in Table 2, and the test results of (A) two component (ascorbyl / tocopheryl) phosphate are shown in Table 3.
結果２
表２から、Ｌ−アスコルビン酸リン酸パルミチン酸三ナトリウムを配合すると概ね配合量の増加に応じて粘度が高くなることが分かった（実施例３〜１１）。Ｌ−アスコルビン酸リン酸パルミチン酸三ナトリウムを０．１質量％配合した実施例３の粘度は４８００ｍＰａ・ｓ、６質量％配合した実施例１１の粘度は８５００ｍＰａ・ｓであり、実施例４〜１０の粘度（１３３００〜２３２５０ｍＰａ・ｓ）と比べるとやや低めの粘度であったが、クリーム状を保てる粘度（４８００ｍＰａ・ｓ以上）であった。
実施例３〜１１の油中水型乳化組成物は、４８００〜２３２５０Ｐａ・ｓ(２５℃に保存した調製翌日の粘度；Ｂ型粘度計、Ｎｏ．４ローター、ローター回転速度１２ｒｐｍ、測定開始後３０秒後)であり、いずれもクリーム状を保つ高い粘性があり、官能評価試験でも、液だれすることなく肌に塗布しやすいと評価された。
実施例３〜１１の油中水型乳化組成物は、べたつくことなくさっぱりとした感触で使用感に優れていると評価された。また、実施例３〜１１の油中水型乳化組成物は、３０日保存後もすべての保管温度帯（５℃、２５℃、４０℃、５０℃）で分離がみられず安定であった。両親媒性ビタミン誘導体の変色(保管したガラス容器内での上部表面付近の黒変または黄変)は、実施例３〜１１のすべてでわずかに観察されたが、特に問題となる変化ではなかった。またこの変化は高温度帯（４０、５０℃）においてのみであり、実使用の温度帯（２５℃）ではまったく発生しなかった。
Result 2
From Table 2, when L-ascorbic acid trisodium palmitate was mix | blended, it turned out that a viscosity becomes high according to the increase in the compounding quantity (Examples 3-11). The viscosity of Example 3 containing 0.1% by mass of trisodium L-ascorbic acid palmitate is 4800 mPa · s, and the viscosity of Example 11 containing 6% by mass is 8500 mPa · s. Examples 4 to 10 Compared to the viscosity (13300 to 23250 mPa · s), the viscosity was slightly lower, but it was a viscosity (4800 mPa · s or more) that kept the cream shape.
The water-in-oil emulsion compositions of Examples 3 to 11 were 4800 to 23250 Pa · s (viscosity on the day after preparation stored at 25 ° C .; B-type viscometer, No. 4 rotor, rotor rotation speed 12 rpm, 30 after the start of measurement) 2 seconds later), both of which have a high viscosity to maintain a cream shape, and were evaluated as being easy to apply to the skin without dripping in the sensory evaluation test.
The water-in-oil emulsion compositions of Examples 3 to 11 were evaluated as being excellent in usability with a refreshing feel without stickiness. Moreover, the water-in-oil emulsion compositions of Examples 3 to 11 were stable with no separation observed in all storage temperature zones (5 ° C, 25 ° C, 40 ° C, 50 ° C) even after storage for 30 days. . Discoloration of the amphiphilic vitamin derivative (blackening or yellowing near the upper surface in the stored glass container) was slightly observed in all of Examples 3-11, but was not a particularly problematic change. . This change was only in the high temperature zone (40, 50 ° C.) and did not occur at all in the actual use temperature zone (25 ° C.).
結果３
表３から、（アスコルビル／トコフェリル）リン酸カリウムの配合量を増加させると、概ね配合量の増加に応じて粘度が高くなることが分かった（実施例１２〜１９）。実施例１２〜１９の油中水型乳化組成物は、７４５０〜２６６００ｍＰａ・ｓ（２５℃に保存した調製翌日の粘度；Ｂ型粘度計、Ｎｏ．４ローター、ローター回転速度１２ｒｐｍ、測定開始後３０秒後）であり、いずれもクリーム状を保つ高い粘性があり、官能評価試験でも、液だれすることなく肌に塗布しやすいと評価された。実施例１２〜１９の油中水型乳化組成物は、皮膚に塗布したとき、べたつくことなくさっぱりとした感触で使用感に優れていると評価された。また、実施例１２〜１９の油中水型乳化組成物は、３０日保存後もすべての保管温度帯（５℃、２５℃、４０℃、５０℃）で分離がみられず安定であった。両親媒性ビタミン誘導体（（アスコルビル／トコフェリル）リン酸カリウム）の変色(保管したガラス容器内での上部表面付近の黄変)は、実施例１６〜１９で、わずかに観察されたが、特に問題となる変化ではなかった。またこの変化は高温度帯（４０、５０℃）においてのみであり、実使用の温度帯ではまったく発生しなかった。
以上、表１〜３に示すとおり、実施例１〜１９の組成物は、べたつかず、さっぱりとした使用感を有していた。また適切なクリーム状態を示す粘度を有している。すなわち、本発明の構成とすることで、使用感に優れ、保存安定性に優れたクリーム状の乳化組成物が調製できることが確認できた。
Result 3
From Table 3, when the compounding quantity of (ascorbyl / tocopheryl) potassium phosphate was increased, it turned out that a viscosity becomes high according to the increase in the compounding quantity (Examples 12-19). The water-in-oil emulsion compositions of Examples 12 to 19 were 7450 to 26600 mPa · s (viscosity on the day after preparation stored at 25 ° C .; B-type viscometer, No. 4 rotor, rotor rotational speed 12 rpm, 30 after measurement start) 2 seconds later), both of which have a high viscosity to maintain a cream shape, and were evaluated as easy to apply to the skin without dripping in the sensory evaluation test. The water-in-oil emulsified compositions of Examples 12 to 19 were evaluated as being excellent in use feeling with a refreshing feel without stickiness when applied to the skin. Moreover, the water-in-oil emulsion compositions of Examples 12 to 19 were stable without separation in all storage temperature zones (5 ° C, 25 ° C, 40 ° C, 50 ° C) even after 30 days of storage. . Discoloration of the amphiphilic vitamin derivative ((ascorbyl / tocopheryl) potassium phosphate) (yellowing near the upper surface in the stored glass container) was slightly observed in Examples 16 to 19, but it was particularly problematic. It was not a change to become. This change was only in the high temperature zone (40, 50 ° C.) and did not occur at all in the actual use temperature zone.
As described above, as shown in Tables 1 to 3, the compositions of Examples 1 to 19 were not sticky and had a refreshing feeling of use. Moreover, it has the viscosity which shows a suitable cream state. That is, it was confirmed that a creamy emulsion composition having excellent usability and storage stability can be prepared by using the constitution of the present invention.
電解質や増粘剤の配合試験（比較例）
油中水型乳化組成物は、電解質や増粘剤を含ませると安定化する（場合によっては増粘する）といわれている。（Ａ）成分に代えて電解質又は増粘剤を配合して以下の試験を行った。
表４は、（Ｂ）成分としてジポリヒドロキシステアリン酸ＰＥＧ−３０を配合し（Ａ）成分の両親媒性ビタミン誘導体に代えて電解質又は増粘剤を配合した油中水型乳化組成物（比較例４〜１４）の試験結果である。
Combination test of electrolyte and thickener (comparative example)
It is said that a water-in-oil emulsion composition is stabilized (thickened in some cases) when an electrolyte or a thickener is included. (A) It replaced with the component and mix | blended the electrolyte or the thickener, and performed the following tests.
Table 4 shows a water-in-oil emulsion composition in which dipolyhydroxystearic acid PEG-30 is blended as component (B) and an electrolyte or thickener is blended in place of the amphiphilic vitamin derivative of component (A) (comparison) It is a test result of Examples 4-14.
結果４
比較例４は硫酸マグネシウムを配合した組成物で、その粘度は２８５０ｍＰａ・ｓであった。クリーム状を保つ組成物は得られず、肌への塗布のしやすさの判定は「×；悪い（液だれせずに肌に塗布しやすいと答えたのが３名以下）」と評価された。
比較例５は、電解質である塩化ナトリウムと増粘剤((ジメチコン／ビニルジメチコン)クロスポリマー)を配合した組成物である。その粘度は３６００ｍＰａ・ｓであり、クリーム状を保つ粘度を有する組成物は得られなかった。また、肌への塗布のしやすさの判定は「×；悪い」と評価された。
Result 4
Comparative Example 4 was a composition containing magnesium sulfate and had a viscosity of 2850 mPa · s. A composition that maintains a creamy form cannot be obtained, and the judgment of ease of application to the skin is evaluated as “×; poor (less than 3 people answered that it is easy to apply to the skin without dripping)” It was.
Comparative Example 5 is a composition containing sodium chloride as an electrolyte and a thickener ((dimethicone / vinyl dimethicone) crosspolymer). The viscosity was 3600 mPa · s, and a composition having a viscosity maintaining a creamy shape was not obtained. In addition, the evaluation of ease of application to the skin was evaluated as “x; bad”.
比較例６〜１２は、電解質であるＬ−アスコルビン酸リン酸エステルマグネシウム塩、水酸化カリウムおよびクエン酸と、増粘剤を含む組成である。その粘度は、それぞれ４５００ｍＰａ・ｓ、４５００ｍＰａ・ｓ、１５００ｍＰａ・ｓ、３８５０ｍＰａ・ｓ、４５００ｍＰａ・ｓ、２２００ｍＰａ・ｓ、２６００ｍＰａ・ｓであり、クリーム状を保つ粘度の組成物は得られなかった。肌への塗布のしやすさの評価では、「△；４〜６名が液だれせずに肌に塗布しやすいと答えた」または「×；悪い（液だれせずに肌に塗布しやすいと答えたのが３名以下）」と評価され、粘度が低い方が肌に塗布しやすいと評価するパネル（官能評価員）の数が減る傾向が認められた。比較例６〜１２では併用した増粘剤や電解質に由来するべたつき感を感じるパネル（官能評価員）もいた。 Comparative Examples 6-12 are compositions containing L-ascorbic acid phosphate magnesium salt, potassium hydroxide and citric acid, which are electrolytes, and a thickener. The viscosities were 4500 mPa · s, 4500 mPa · s, 1500 mPa · s, 3850 mPa · s, 4500 mPa · s, 2200 mPa · s, 2600 mPa · s, respectively, and a composition having a viscosity that kept cream was not obtained. In the evaluation of ease of application to the skin, “△; 4-6 people answered that it was easy to apply to the skin without dripping” or “×; bad (easy to apply to the skin without dripping) The number of panels (sensory evaluators) that evaluate that the lower viscosity is easier to apply to the skin was observed. In Comparative Examples 6 to 12, there were also panels (sensory evaluators) that felt stickiness derived from the thickener and electrolyte used in combination.
両親媒性ビタミン誘導体ではないビタミンＣ誘導体であるアスコルビン酸２−グルコシド、アスコルビルエチルと成分（Ｂ）ジポリヒドロキシステアリン酸ＰＥＧ−３０を組み合わせた比較例１３、１４は、クリーム状を保つ粘性はいずれも得られず低粘度（２３００ｍＰａ・ｓ、１９５０ｍＰａ・ｓ）であった。粘度が低いため肌に塗布しにくく、比較例１３では併用した増粘剤や電解質に由来するべたつき感を感じるパネル（官能評価員）もいた。 Comparative Examples 13 and 14 in which ascorbic acid 2-glucoside and ascorbyl ethyl which are vitamin C derivatives which are not amphiphilic vitamin derivatives and component (B) dipolyhydroxystearic acid PEG-30 are combined have a viscosity that keeps the cream. Was not obtained, and the viscosity was low (2300 mPa · s, 1950 mPa · s). Since the viscosity was low, it was difficult to apply to the skin, and in Comparative Example 13, there was a panel (sensory evaluator) that felt a sticky feeling derived from the thickener and electrolyte used in combination.
以上、表１〜４の結果から、成分（Ａ）両親媒性ビタミン誘導体（アスコルビン酸リン酸脂肪酸エステル又は（アスコルビル／トコフェリル）リン酸塩）と、成分（Ｂ）ジポリヒドロキシステアリン酸ポリエチレングリコールとを組み合わせることで、べたつきのないさっぱりとした使用感を維持しながら粘度を増大させた、使用感、使用性、安定性のすべてにおいて良好な油中水型乳化組成物が作成できることが証明できた。
本発明のジポリヒドロキシステアリン酸ポリエチレングリコールと特定の両親媒性ビタミン誘導体（アスコルビン酸リン酸脂肪酸エステル及び／又は（アスコルビル／トコフェリル）リン酸塩）とを組み合わせた油中水型乳化組成物は、べたつきのない優れた使用感であり、粘度の高い高級感のあるクリーム状の剤型を実現できるので、化粧料や皮膚外用剤として有用である。
As described above, from the results of Tables 1 to 4, component (A) amphiphilic vitamin derivative (ascorbic acid phosphate fatty acid ester or (ascorbyl / tocopheryl) phosphate) and component (B) polyethylene glycol dipolyhydroxystearate In combination, it was proved that a water-in-oil emulsified composition with improved usability, usability, and stability can be created with increased viscosity while maintaining a refreshing feeling without stickiness. .
A water-in-oil emulsion composition comprising a combination of the polyethylene glycol dipolyhydroxystearate of the present invention and a specific amphiphilic vitamin derivative (ascorbyl phosphate fatty acid ester and / or (ascorbyl / tocopheryl) phosphate), Since it has an excellent feeling of use without stickiness and can realize a creamy dosage form with high viscosity and high quality, it is useful as a cosmetic or skin external preparation.
以下に、本発明の構成を使用した油中水型乳化組成物（クリーム）の処方、製法、特性を示す。
処方例１ クリーム
（配合成分） （質量％）
１． ジポリヒドロキシステアリン酸ＰＥＧ−３０ ２
２． ミリストイルメチル−β−アラニン（フィトステリル
／デシルテトラデシル） ２
３． オリーブ油 ５
４． ホホバ油 ４
５． パルミチン酸エチルヘキシル ３
６． セチルＰＧヒドロキシエチルパルミタミド ０．５
７． トリエチルヘキサノイン １
８． （ジメチコン／ビニルジメチコン）クロスポリマー １
９． グリセリン ５
１０．ペンチレングリコール ２
１１．フェノキシエタノール ０．２
１２．Ｌ−アスコルビン酸リン酸パルミチン酸三ナトリウム ２
１３．精製水 残余
Below, the formulation of a water-in-oil type emulsion composition (cream) using the structure of this invention, a manufacturing method, and a characteristic are shown.
Formulation Example 1 Cream
(Compounding ingredients) (mass%)
1. Dipolyhydroxystearic acid PEG-30 2
2. Myristoylmethyl-β-alanine (phytosteryl / decyltetradecyl) 2
3. Olive oil 5
4). Jojoba oil 4
5. Ethyl hexyl palmitate 3
6). Cetyl PG hydroxyethyl palmitamide 0.5
7). Triethylhexanoin 1
8). (Dimethicone / Vinyl Dimethicone) Cross Polymer 1
9. Glycerin 5
10. Pentylene glycol 2
11. Phenoxyethanol 0.2
12 L-ascorbic acid trisodium palmitate 2
13. Purified water residue
（製法）
油相（１〜８）と水相（９〜１３）をそれぞれ別に８０℃に加熱して、十分に攪拌後、水相を油相へ添加し、ホモミキサーで６０００ｒｐｍ、２分攪拌して乳化し、その後、室温まで攪拌冷却する。
(Manufacturing method)
The oil phase (1-8) and the water phase (9-13) are separately heated to 80 ° C. and sufficiently stirred, and then the water phase is added to the oil phase and emulsified by stirring at 6000 rpm for 2 minutes with a homomixer. Then, the mixture is stirred and cooled to room temperature.
処方例１のクリームは、心地よい使用感であり、保存安定性に優れていた。 The cream of Formulation Example 1 had a pleasant feeling of use and was excellent in storage stability.
処方例２ クリーム
（配合成分） （質量％）
１． ジポリヒドロキシステアリン酸ＰＥＧ−３０ ２
２． ミリストイルメチル−β−アラニン（フィトステリル
／デシルテトラデシル） ２
３． オリーブ油 ３
４． ホホバ油 １
５． パルミチン酸エチルヘキシル ２
６． セチルＰＧヒドロキシエチルパルミタミド ０．５
７． ２−エチルヘキサン酸セチル １
８． ジメチコン １
９． ジグリセリン ５
１０．ペンチレングリコール ２
１１．フェノキシエタノール ０．２
１２．（アスコルビル／トコフェリル）リン酸カリウム ４
１３．精製水 残余
Formulation Example 2 Cream
(Compounding ingredients) (mass%)
1. Dipolyhydroxystearic acid PEG-30 2
2. Myristoylmethyl-β-alanine (phytosteryl / decyltetradecyl) 2
3. Olive oil 3
4). Jojoba oil 1
5. Ethyl hexyl palmitate 2
6). Cetyl PG hydroxyethyl palmitamide 0.5
7). Cetyl 2-ethylhexanoate 1
8). Dimethicone 1
9. Diglycerin 5
10. Pentylene glycol 2
11. Phenoxyethanol 0.2
12 (Ascorbyl / tocopheryl) potassium phosphate 4
13. Purified water residue
（製法）
油相（１〜８）と水相（９〜１３）をそれぞれ別に８０℃に加熱して、十分に攪拌後、水相を油相へ添加し、ホモミキサーで６０００ｒｐｍ、２分攪拌して乳化し、その後、室温まで攪拌冷却する。
(Manufacturing method)
The oil phase (1-8) and the water phase (9-13) are separately heated to 80 ° C. and sufficiently stirred, and then the water phase is added to the oil phase and emulsified by stirring at 6000 rpm for 2 minutes with a homomixer. Then, the mixture is stirred and cooled to room temperature.
処方例２のクリームは、心地よい使用感であり、保存安定性に優れていた。 The cream of Formulation Example 2 had a pleasant feeling of use and was excellent in storage stability.
Claims (3)
（Ｂ）：ジポリヒドロキシステアリン酸ポリエチレングリコール、
（Ｃ）：油剤、
（Ｄ）：水、
を含有する油中水型乳化組成物であって、
測定温度２５℃において、Ｂ型粘度計、４号ローターを用いて測定した粘度が、４８００〜５００００ｍＰａ・ｓを示し、
ポリエチレングリコールおよび増粘剤を含有しない油中水型乳化組成物。 (A): L-ascorbic acid trisodium palmitate trisodium 0.1-6 mass% or (ascorbyl / tocopheryl) potassium phosphate 0.3-6 mass% which is an amphipathic vitamin derivative
(B): polyethylene glycol dipolyhydroxystearate,
(C): oil agent,
(D): water,
A water-in-oil emulsion composition containing,
At a measurement temperature of 25 ° C., the viscosity measured using a B-type viscometer, No. 4 rotor is 4800 to 50000 mPa · s,
A water-in-oil emulsion composition containing no polyethylene glycol and thickener .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011234490A JP5869296B2 (en) | 2011-10-26 | 2011-10-26 | Water-in-oil emulsion composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011234490A JP5869296B2 (en) | 2011-10-26 | 2011-10-26 | Water-in-oil emulsion composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2013091617A JP2013091617A (en) | 2013-05-16 |
| JP5869296B2 true JP5869296B2 (en) | 2016-02-24 |
Family
ID=48615048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2011234490A Active JP5869296B2 (en) | 2011-10-26 | 2011-10-26 | Water-in-oil emulsion composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5869296B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3060361B1 (en) * | 2016-12-21 | 2018-12-07 | L'oreal | WATER-IN-OIL EMULSION COMPRISING A PARTICULAR EMULSIFYING SYSTEM, A LIPOPHILIC CLAY, AN ELASTOMERIC ORGANOPOLYSILOXANE POWDER COATED WITH A SILICONE RESIN |
| JP7022422B2 (en) * | 2017-12-18 | 2022-02-18 | 日本メナード化粧品株式会社 | Water-in-oil emulsification composition |
| CN116270299A (en) * | 2023-03-27 | 2023-06-23 | 芜湖美的智能厨电制造有限公司 | Skin-moistening composition, skin-moistening emulsion and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59219295A (en) * | 1983-05-30 | 1984-12-10 | Senjiyu Seiyaku Kk | Phosphoric diester, its salt, and their preparation |
| JPH09165394A (en) * | 1995-10-13 | 1997-06-24 | Senju Pharmaceut Co Ltd | New phosphoric diester |
| JPH10298174A (en) * | 1997-04-30 | 1998-11-10 | Showa Denko Kk | Ascorbic acid derivative and vitamin c agent containing the same |
| JP4212209B2 (en) * | 2000-02-28 | 2009-01-21 | 日本メナード化粧品株式会社 | Whitening cosmetics |
| JP2007204399A (en) * | 2006-01-31 | 2007-08-16 | Haba Laboratories Inc | Water-in-oil type emulsion composition |
| JP5053683B2 (en) * | 2006-03-31 | 2012-10-17 | 株式会社コーセー | Water-in-oil emulsified cosmetic |
-
2011
- 2011-10-26 JP JP2011234490A patent/JP5869296B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013091617A (en) | 2013-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6010418B2 (en) | Emulsified composition | |
| JP4341983B2 (en) | Topical skin preparation | |
| JP4527530B2 (en) | Vesicle dispersion and cosmetics containing the same | |
| US20120022160A1 (en) | Composition for external use on skin | |
| KR20120022822A (en) | External preparation for skin | |
| JP6281744B2 (en) | Oil-in-water emulsified cosmetic | |
| JP6339376B2 (en) | Cosmetics | |
| JP2012017318A (en) | Liquid crystal and skin external preparation containing the same | |
| JP5203623B2 (en) | Oil-in-water emulsified cosmetic | |
| JP2014101344A (en) | Cosmetic | |
| JP2009242326A (en) | Skin-lightening liquid cosmetic | |
| JP7384518B2 (en) | Composition for stabilizing poorly soluble ingredients and cosmetic compositions containing the same | |
| WO2012017733A1 (en) | Skin cosmetic | |
| JP5833810B2 (en) | Oil-in-water emulsified cosmetic | |
| JP6133618B2 (en) | Water-in-oil emulsion composition | |
| JP5869296B2 (en) | Water-in-oil emulsion composition | |
| WO2013021775A1 (en) | Liquid skin-conditioning composition | |
| JP5662794B2 (en) | Water-in-oil emulsion composition | |
| JP6116966B2 (en) | Oily composition | |
| JP6792353B2 (en) | Water-in-oil emulsified composition | |
| JP2011213621A (en) | Oil-in-water type emulsified composition | |
| JP2006306793A (en) | Emulsion type cosmetic | |
| JP5824323B2 (en) | Water-in-oil emulsion composition | |
| JP5793056B2 (en) | Cosmetics | |
| JP2013091620A (en) | Water-in-oil type emulsion composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20140516 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20150107 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150120 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150226 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20150818 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20151117 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20151124 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20160105 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160107 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5869296 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |