JP6796949B2 - Manufacturing method of oil-in-water emulsified cosmetics - Google Patents
Manufacturing method of oil-in-water emulsified cosmetics Download PDFInfo
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- JP6796949B2 JP6796949B2 JP2016102393A JP2016102393A JP6796949B2 JP 6796949 B2 JP6796949 B2 JP 6796949B2 JP 2016102393 A JP2016102393 A JP 2016102393A JP 2016102393 A JP2016102393 A JP 2016102393A JP 6796949 B2 JP6796949 B2 JP 6796949B2
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- Prior art keywords
- oil
- acid
- preferable
- particle size
- water emulsified
- Prior art date
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- 239000002537 cosmetic Substances 0.000 title claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 55
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000002245 particle Substances 0.000 claims description 81
- -1 organic acid salts Chemical class 0.000 claims description 57
- 239000000839 emulsion Substances 0.000 claims description 48
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 229920001296 polysiloxane Polymers 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 17
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 13
- 239000000194 fatty acid Substances 0.000 claims description 13
- 229930195729 fatty acid Natural products 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 150000001413 amino acids Chemical class 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 150000004676 glycans Chemical class 0.000 claims description 6
- 229920001282 polysaccharide Polymers 0.000 claims description 6
- 239000005017 polysaccharide Substances 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- HSINOMROUCMIEA-FGVHQWLLSA-N (2s,4r)-4-[(3r,5s,6r,7r,8s,9s,10s,13r,14s,17r)-6-ethyl-3,7-dihydroxy-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-17-yl]-2-methylpentanoic acid Chemical compound C([C@@]12C)C[C@@H](O)C[C@H]1[C@@H](CC)[C@@H](O)[C@@H]1[C@@H]2CC[C@]2(C)[C@@H]([C@H](C)C[C@H](C)C(O)=O)CC[C@H]21 HSINOMROUCMIEA-FGVHQWLLSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 239000003613 bile acid Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000003921 oil Substances 0.000 description 48
- 235000019198 oils Nutrition 0.000 description 48
- 238000003860 storage Methods 0.000 description 37
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 30
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 20
- 239000002253 acid Substances 0.000 description 18
- 239000004094 surface-active agent Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- 235000001014 amino acid Nutrition 0.000 description 11
- 239000008346 aqueous phase Substances 0.000 description 11
- 239000003945 anionic surfactant Substances 0.000 description 10
- 235000011187 glycerol Nutrition 0.000 description 10
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 8
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 8
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 8
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 8
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 8
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 8
- 229920002125 Sokalan® Polymers 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 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 6
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229920002545 silicone oil Polymers 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- LEEDMQGKBNGPDN-UHFFFAOYSA-N 2-methylnonadecane Chemical compound CCCCCCCCCCCCCCCCCC(C)C LEEDMQGKBNGPDN-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 150000005690 diesters Chemical class 0.000 description 4
- 229940008099 dimethicone Drugs 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010696 ester oil Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- 229940057995 liquid paraffin Drugs 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 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 3
- OVYMWJFNQQOJBU-UHFFFAOYSA-N 1-octanoyloxypropan-2-yl octanoate Chemical compound CCCCCCCC(=O)OCC(C)OC(=O)CCCCCCC OVYMWJFNQQOJBU-UHFFFAOYSA-N 0.000 description 3
- 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 3
- OCIQZTICBOLUJQ-UHFFFAOYSA-N 2,2,3,3-tetraethylhexanoic acid Chemical compound CCCC(CC)(CC)C(CC)(CC)C(O)=O OCIQZTICBOLUJQ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229930064664 L-arginine Natural products 0.000 description 3
- 235000014852 L-arginine Nutrition 0.000 description 3
- 125000002059 L-arginyl group Chemical group O=C([*])[C@](N([H])[H])([H])C([H])([H])C([H])([H])C([H])([H])N([H])C(=N[H])N([H])[H] 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 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 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 241000894007 species Species 0.000 description 3
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- 150000005846 sugar alcohols Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OILXMJHPFNGGTO-UHFFFAOYSA-N (22E)-(24xi)-24-methylcholesta-5,22-dien-3beta-ol Natural products C1C=C2CC(O)CCC2(C)C2C1C1CCC(C(C)C=CC(C)C(C)C)C1(C)CC2 OILXMJHPFNGGTO-UHFFFAOYSA-N 0.000 description 2
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 2
- XMFUMMRWIFOQDQ-UHFFFAOYSA-N 1-(4-methylpentan-2-yloxy)hexadecane Chemical compound CCCCCCCCCCCCCCCCOC(C)CC(C)C XMFUMMRWIFOQDQ-UHFFFAOYSA-N 0.000 description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 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 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
- OQMZNAMGEHIHNN-UHFFFAOYSA-N 7-Dehydrostigmasterol Natural products C1C(O)CCC2(C)C(CCC3(C(C(C)C=CC(CC)C(C)C)CCC33)C)C3=CC=C21 OQMZNAMGEHIHNN-UHFFFAOYSA-N 0.000 description 2
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
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- 239000012190 activator Substances 0.000 description 2
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- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
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- 125000001204 arachidyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
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- 238000012790 confirmation Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
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- 238000002050 diffraction method Methods 0.000 description 2
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- 238000000691 measurement method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 125000004079 stearyl 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])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229930193551 sterin Natural products 0.000 description 1
- 229940032091 stigmasterol Drugs 0.000 description 1
- HCXVJBMSMIARIN-PHZDYDNGSA-N stigmasterol 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)/C=C/[C@@H](CC)C(C)C)[C@@]1(C)CC2 HCXVJBMSMIARIN-PHZDYDNGSA-N 0.000 description 1
- 235000016831 stigmasterol Nutrition 0.000 description 1
- BFDNMXAIBMJLBB-UHFFFAOYSA-N stigmasterol Natural products CCC(C=CC(C)C1CCCC2C3CC=C4CC(O)CCC4(C)C3CCC12C)C(C)C BFDNMXAIBMJLBB-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- BORJONZPSTVSFP-UHFFFAOYSA-N tetradecyl 2-hydroxypropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)C(C)O BORJONZPSTVSFP-UHFFFAOYSA-N 0.000 description 1
- DZKXJUASMGQEMA-UHFFFAOYSA-N tetradecyl tetradecanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCC DZKXJUASMGQEMA-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- DUXYWXYOBMKGIN-UHFFFAOYSA-N trimyristin Chemical compound CCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCC DUXYWXYOBMKGIN-UHFFFAOYSA-N 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
Landscapes
- Cosmetics (AREA)
Description
本発明は、水中油型乳化化粧料の製造方法に関する。 The present invention relates to a method for producing an oil-in-water emulsified cosmetic.
近年、化粧料等として、界面活性剤の含有量が低減されたものや、含有しないものが求められている。
しかしながら、界面活性剤の含有量が低減されたものや、含有しない乳化化粧料では、乳化粒子径が大きくなり、十分な保存安定性を得ることができない。このため、界面活性剤の含有量が低減されたものや、含有しない乳化物を得るため、種々の検討がなされている。
In recent years, as cosmetics and the like, those having a reduced content of surfactants and those not containing them have been required.
However, in the case of emulsified cosmetics in which the content of the surfactant is reduced or not contained, the emulsified particle size becomes large and sufficient storage stability cannot be obtained. Therefore, various studies have been conducted in order to obtain an emulsion having a reduced content of a surfactant and an emulsion containing no surfactant.
例えば、特許文献１には、特定の両親媒性高分子を用いて、保存安定性に優れた水中油型乳化化粧料を得ることが開示されている。特許文献２には、特定の有機酸とスフィンゴシン類を用いて、ｐＨ変化に対する安定性や保存安定性に優れたベシクル組成物を得ることが開示されている。 For example, Patent Document 1 discloses that an oil-in-water emulsified cosmetic having excellent storage stability can be obtained by using a specific amphipathic polymer. Patent Document 2 discloses that a vesicle composition having excellent stability against pH change and storage stability can be obtained by using a specific organic acid and sphingosines.
しかしながら、特許文献１の化粧料は、界面活性剤を含有しないものの、特定のアミド化合物を含むことが必須となっている。また、特許文献２では、酸性側ではスフィンゴシン類がカチオン化して界面活性剤として働き、塩基性側では特定の有機酸が界面活性剤として働いており、製品としては低分子界面活性剤が含まれている。
本発明は、界面活性剤の含有量を低減するか、もしくは含有せずに、乳化粒子径を小さくする水中油型乳化化粧料の製造方法に関する。また、塗布後の肌のさっぱり感を良好にすることができる。
However, although the cosmetic of Patent Document 1 does not contain a surfactant, it is essential that it contains a specific amide compound. Further, in Patent Document 2, sphingosines are cationized and act as a surfactant on the acidic side, and a specific organic acid acts as a surfactant on the basic side, and the product includes a low molecular weight surfactant. ing.
The present invention relates to a method for producing an oil-in-water emulsified cosmetic that reduces the emulsified particle size with or without reducing the content of a surfactant. In addition, the refreshing feeling of the skin after application can be improved.
本発明者らは、特定の有機酸塩及び脂肪酸塩から選ばれる化合物と特定の高分子を組合せ、乳化物を調製した後、ｐＨを下げることにより、界面活性剤の含有量を低減するか、もしくは含有せずに、乳化粒子径を小さくし、さっぱり感が良好な水中油型乳化化粧料が得られることを見出した。
なお、ここでの界面活性剤は、分子量２０００以下のものを示す。
以下、本発明における「水中油型乳化化粧料」を、適宜単に「乳化化粧料」とも呼ぶ。
The present inventors prepare a emulsion by combining a compound selected from a specific organic acid salt and a specific fatty acid salt with a specific polymer, and then lower the pH to reduce the content of the surfactant. Alternatively, it has been found that an oil-in-water emulsified cosmetic having a good refreshing feeling can be obtained by reducing the emulsified particle size without containing it.
The surfactant here has a molecular weight of 2000 or less.
Hereinafter, the "oil-in-water emulsified cosmetic" in the present invention is also appropriately simply referred to as "emulsified cosmetic".
本発明は、以下の工程を有する水中油型乳化化粧料の製造方法に関する。
工程１：
（Ａ）一般式（１）
The present invention relates to a method for producing an oil-in-water emulsified cosmetic having the following steps.
Step 1:
(A) General formula (1)
（式中、Ｒ1は、１個の水酸基を有する天然ステリン若しくはその水素添加物、又は胆汁酸の水酸基の水素原子を除いたあとに残る残基を示し、Ｒ2は、炭素数１〜２４の２価の炭化水素基を示し、Ｍは、アルカリ金属、アルカリ土類金属、アンモニウム（ＮＨ4 +）、有機アンモニウム、又は塩基性アミノ酸を示す）
で表される有機酸塩及び炭素数１２〜２４の脂肪酸塩から選ばれる１種又は２種以上、
（Ｂ）アルキル変性された多糖類系ポリマー、Ｎ−アシルアルキレンイミンを繰り返し単位とする親水性セグメントと、オルガノポリシロキサンセグメントとを構成単位とするポリマー及びポリエーテル変性シリコーンから選ばれる１種又は２種以上の高分子、
（Ｃ）油剤、及び
（Ｄ）水
を含む組成物を混合して、乳化物を得る工程、
工程２：
工程１で得られた乳化物のｐＨを下げる工程。
(In the formula, R 1 indicates the residue remaining after removing the hydrogen atom of the hydroxyl group of natural sterine having one hydroxyl group or its hydrogen additive, or the hydroxyl group of bile acid, and R 2 has 1 to 24 carbon atoms. represents a divalent hydrocarbon group, M represents an alkali metal, alkaline earth metal, ammonium (NH 4 +), organic ammonium, or basic amino acid)
One or more selected from organic acid salts represented by and fatty acid salts having 12 to 24 carbon atoms.
(B) One or 2 selected from an alkyl-modified polysaccharide polymer, a hydrophilic segment having N-acylalkyleneimine as a repeating unit, a polymer having an organopolysiloxane segment as a constituent unit, and a polyether-modified silicone. More than seed polymer,
Step of mixing (C) an oil agent and (D) a composition containing water to obtain an emulsion,
Step 2:
A step of lowering the pH of the emulsion obtained in step 1.
本発明において、成分（Ａ）は、工程１では、有機酸塩又は脂肪酸塩として存在し、アニオン界面活性剤として機能すると考えられる。すなわち、工程１で得られる乳化物中において、成分（Ａ）はアニオン界面活性剤として存在していると考えられる。
そして、工程２でｐＨを下げることにより、成分（Ａ）は、一部又は全てが、成分（Ａ）を構成する酸と塩に解離し、酸は油中に取り込まれると考えられる。その結果、工程２で得られる乳化物中では、アニオン界面活性剤の含有量が低減されるか、含有しない状態となると考えられる。
In the present invention, the component (A) is considered to exist as an organic acid salt or a fatty acid salt in step 1 and function as an anionic surfactant. That is, it is considered that the component (A) is present as an anionic surfactant in the emulsion obtained in step 1.
Then, by lowering the pH in step 2, it is considered that part or all of the component (A) is dissociated into the acid and the salt constituting the component (A), and the acid is incorporated into the oil. As a result, it is considered that the content of the anionic surfactant is reduced or is not contained in the emulsion obtained in step 2.
本発明によれば、界面活性剤の含有量を低減するか、もしくは含有せずに、乳化粒子径を小さくすることができ、特に高温での保存安定性に優れ、さっぱり感が良好な水中油型乳化化粧料を得ることができる。 According to the present invention, the emulsified particle size can be reduced with or without the content of the surfactant, and the oil in water has excellent storage stability at a particularly high temperature and a good refreshing feeling. Molded emulsified cosmetics can be obtained.
（工程１）
本発明の工程１は、成分（Ａ）、（Ｂ）、（Ｃ）及び（Ｄ）を含む組成物を混合して、乳化物を得る工程である。
(Step 1)
Step 1 of the present invention is a step of mixing a composition containing the components (A), (B), (C) and (D) to obtain an emulsion.
成分（Ａ）のうち、前記一般式（１）で表される有機酸塩において、式中、Ｒ1で示される１個の水酸基を有する天然ステリンとしては、例えば、コレステロール、スチグマステロール、シトステロール、カンペステロール、ラノステロール、エルゴステロール等が挙げられ、その中でも、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、コレステロールが好ましい。
また、一般式（１）において、Ｒ2は、炭素数１〜２４の２価の炭化水素基であり、直鎖又は分岐鎖のアルキレン基又はアルケニレン基が挙げられ、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、次式
Among the components (A), in the organic acid salt represented by the general formula (1), as the natural sterin having one hydroxyl group represented by R 1 in the formula, for example, cholesterol, stigmasterol, citosterol, etc. , Campesterol, lanosterol, ergosterol and the like, and among them, cholesterol is preferable from the viewpoint of reducing the emulsified particle size and improving the storage stability at high temperature.
Further, in the general formula (1), R 2 is a divalent hydrocarbon group having 1 to 24 carbon atoms, and examples thereof include a linear or branched alkylene group or an alkenylene group, which reduces the emulsified particle size. From the viewpoint of improving storage stability at high temperatures, the following equation
（式中、Ｒ3は、炭素数６〜２０の直鎖又は分岐鎖のアルキル基又はアルケニル基を示す）で表される基が好ましい（なお、いずれも、＊側には、カルボキシル基が結合する）。 In the formula, R 3 is preferably a group represented by an alkyl group or an alkenyl group of a linear or branched chain having 6 to 20 carbon atoms (in each case, a carboxyl group is bonded to the * side). To do).
Ｒ3としては、直鎖又は分岐鎖の２−ヘキセニル基、２−オクテニル基、２−デセテル基、２−ドデセニル基、２−テトラデセニル基、２−ヘキサデセニル基、２−オクタデセニル基、２−エイコセニル基、ヘキシル基、オクチル基、デシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、エイコシル基等が挙げられ、その中でも、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、２−テトラデセニル基、２−ヘキサデセニル基、２−オクタデセニル基、２−エイコセニル基、テトラデシル基、ヘキサデシル基、オクタデシル基、エイコシル基が好ましく、２−ヘキサデセニル基、２−オクタデセニル基、がより好ましい。 R 3 is a linear or branched 2-hexenyl group, 2-octenyl group, 2-decetter group, 2-dodecenyl group, 2-tetradecenyl group, 2-hexadecenyl group, 2-octadeceny group, 2-eicosenyl group. , Hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, etc. Among them, from the viewpoint of reducing the emulsified particle size and improving the storage stability at high temperature. , 2-Tetradecenyl group, 2-Hexadecenyl group, 2-Ocdecenyl group, 2-Eicosenyl group, Tetradecyl group, Hexadecyl group, Octadecil group, Eicosyl group are preferable, and 2-Hexadecenyl group and 2-Octadecenyl group are more preferable.
このような化合物（１）は、例えば、特開平５−２９４９８９号公報に記載の方法に従い、ステリン類をアルケニルコハク酸無水物若しくはアルキルコハク酸無水物と反応させ、アルカリ性物質で中和することにより得ることができる。
具体的には、ｎ−ヘキサデセニルコハク酸コレステリル塩、ｎ−オクタデセニルコハク酸コレステリル塩等が挙げられ、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、ｎ−ヘキサデセニルコハク酸コレステリル塩、ｎ−オクタデセニルコハク酸コレステリル塩から選ばれる少なくとも１種又は２種以上が好ましい。
Such a compound (1) is produced, for example, by reacting sterines with an alkenyl succinic anhydride or an alkyl succinic anhydride and neutralizing with an alkaline substance according to the method described in JP-A-5-294899. Obtainable.
Specific examples thereof include n-hexadecenyl succinate cholesteryl salt, n-octadecenyl succinate cholesteryl salt, etc., from the viewpoint of reducing the emulsified particle size and improving storage stability at high temperatures. At least one or more selected from n-hexadecenyl succinate cholesteryl salt and n-octadecenyl succinate cholesteryl salt is preferable.
また、成分（Ａ）のうち、炭素数１２〜２４の脂肪酸塩は、直鎖の脂肪酸塩または分岐の脂肪酸塩でもよく、飽和の脂肪酸塩または不飽和の脂肪酸塩でも良い。炭素数１２〜２４の脂肪酸塩において、炭素数は、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、１４〜２２が好ましく、１６〜２０がより好ましく、１８〜２０がさらに好ましい。 Further, among the component (A), the fatty acid salt having 12 to 24 carbon atoms may be a linear fatty acid salt or a branched fatty acid salt, or may be a saturated fatty acid salt or an unsaturated fatty acid salt. Among the fatty acid salts having 12 to 24 carbon atoms, the number of carbon atoms is preferably 14 to 22, more preferably 16 to 20, and 18 to 20 from the viewpoint of reducing the emulsified particle size and improving the storage stability at high temperature. More preferred.
成分（Ａ）の塩としては、ナトリウム塩、カリウム塩等のアルカリ金属塩；カルシウム塩、マグネシウム塩等のアルカリ土類金属塩；アンモニウム（ＮＨ4 +）塩；モノエタノールアミン塩、ジエタノールアミン塩、トリエタノールアミン塩等の有機アンモニウム塩；アルギニン塩、リシン塩、ヒスチジン塩等の塩基性アミノ酸塩などが挙げられる。これらの中で、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、アルカリ金属塩、有機アンモニウム塩、塩基性アミノ酸塩から選ばれる少なくとも１種又は２種以上が好ましく、アルカリ金属塩、塩基性アミノ酸塩から選ばれる少なくとも１種又は２種以上がより好ましい。 The salt of component (A), sodium salts, alkali metal salts such as potassium salts; calcium salts, alkaline earth metal salts such as magnesium salts; ammonium (NH 4 +) salt; monoethanolamine salts, diethanolamine salts, triethanolamine Organic ammonium salts such as ethanolamine salts; basic amino acid salts such as arginine salts, lysine salts and histidine salts can be mentioned. Among these, at least one or two or more selected from alkali metal salts, organic ammonium salts, and basic amino acid salts are preferable from the viewpoint of reducing the emulsified particle size and improving the storage stability at high temperatures, and alkali. At least one or more selected from metal salts and basic amino acid salts is more preferable.
成分（Ａ）は、成分（Ａ）を構成する酸を、酸として配合し、塩基によって中和して塩として含有されることもできる。この場合の成分（Ａ）を中和する塩基は、水酸化ナトリウム、水酸化カリウム等のアルカリ金属の水酸化物；水酸化カルシウム等のアルカリ土類金属の水酸化物；アンモニウム（ＮＨ4 +）；モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等の有機アンモニウム；アルギニン、リシン、ヒスチジン等の塩基性アミノ酸などが挙げられる。
これらのうち、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、アルカリ金属の水酸化物、有機アンモニウム、塩基性アミノ酸から選ばれる少なくとも１種又は２種以上が好ましく、アルカリ金属の水酸化物、塩基性アミノ酸から選ばれる少なくとも１種又は２種以上がより好ましい。
The component (A) can also be contained as a salt by blending the acid constituting the component (A) as an acid and neutralizing it with a base. Bases for neutralizing the component (A) in this case, sodium hydroxide, alkali metal hydroxides such as potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; ammonium (NH 4 +) Organic ammonium such as monoethanolamine, diethanolamine, triethanolamine; basic amino acids such as arginine, lysine, and histidine can be mentioned.
Of these, at least one or two or more selected from alkali metal hydroxides, organic ammonium, and basic amino acids are preferable from the viewpoint of reducing the emulsified particle size and improving storage stability at high temperatures, and alkali. More preferably, at least one or more selected from metal hydroxides and basic amino acids.
成分（Ａ）は、１種又は２種以上を用いることができ、さっぱり感を向上させ、塗布時の液垂れを抑制し、乳化粒子径を小さくする観点から、その含有量は、乳化化粧料中に酸として、０．０３〜６質量％であるのが好ましく、０．０８〜４質量％がより好ましく、０．２〜２．８質量％がさらに好ましい。 As the component (A), one type or two or more types can be used, and the content thereof is an emulsified cosmetic from the viewpoint of improving the refreshing feeling, suppressing the dripping during application, and reducing the emulsified particle size. The acid content is preferably 0.03 to 6% by mass, more preferably 0.08 to 4% by mass, and even more preferably 0.2 to 2.8% by mass.
また、本発明において、水中油型乳化化粧料は、成分（Ａ）以外のアニオン界面活性剤を含有することができる。乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、水中油型乳化化粧料中における全アニオン界面活性剤中の成分（Ａ）の含有割合は、６０質量％以上が好ましく、７０質量％以上がより好ましく、９０質量％以上がさらに好ましく、１００質量％であることがよりさらに好ましい。 Further, in the present invention, the oil-in-water emulsified cosmetic may contain an anionic surfactant other than the component (A). From the viewpoint of reducing the size of the emulsified particles and improving the storage stability at high temperatures, the content ratio of the component (A) in the total anionic surfactant in the oil-in-water emulsified cosmetic is preferably 60% by mass or more. 70% by mass or more is more preferable, 90% by mass or more is further preferable, and 100% by mass is even more preferable.
成分（Ｂ）の高分子は、アルキル変性された多糖類系ポリマー、Ｎ−アシルアルキレンイミンを繰り返し単位とする親水性セグメントと、オルガノポリシロキサンセグメントとを構成単位とするポリマー及びポリエーテル変性シリコーンから選ばれる１種又は２種以上のものである。
アルキル変性された多糖類系ポリマーとしては、例えば、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、メチルセルロース、カルボキシメチルセルロースナトリウム、ステアロキシヒドロキシプロピルメチルセルロース、ラウレス−１３ＰＧヒドロキシエチルセルロース、ステアロキシＰＧヒドロキシエチルセルローススルホン酸塩等が挙げられる。
これらのうち、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、ヒドロキシプロピルメチルセルロース、ステアロキシヒドロキシプロピルメチルセルロース、ラウレス−１３ＰＧヒドロキシエチルセルロース、ステアロキシＰＧヒドロキシエチルセルローススルホン酸塩から選ばれる少なくとも１種又は２種以上が好ましく、ヒドロキシプロピルメチルセルロース、ステアロキシＰＧヒドロキシエチルセルローススルホン酸塩から選ばれる少なくとも１種又は２種以上がより好ましく、ヒドロキシプロピルメチルセルロース、ステアロキシＰＧヒドロキシエチルセルローススルホン酸塩を共に含有することがさらに好ましい。
市販品としては、例えば、ヒドロキシプロピルメチルセルロースとして、メトローズ６０ＳＨ−４０００（信越化学工業社製）等が挙げられ；ステアロキシヒドロキシプロピルメチルセルロースとして、サンジェロース６０Ｍ（大同化成工業社製）等が挙げられ；ステアロキシＰＧヒドロキシエチルセルローススルホン酸塩として、ポイズ３１０（花王社製）等が挙げられる。
The polymer of the component (B) is composed of an alkyl-modified polysaccharide polymer, a hydrophilic segment having N-acylalkyleneimine as a repeating unit, a polymer having an organopolysiloxane segment as a constituent unit, and a polyether-modified silicone. One or more selected species.
Examples of the alkyl-modified polysaccharide polymer include hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, sodium carboxymethyl cellulose, stearoxy hydroxypropyl methyl cellulose, laureth-13PG hydroxyethyl cellulose, stearoxy PG hydroxyethyl cellulose sulfonate and the like. Can be mentioned.
Of these, at least selected from hydroxypropylmethyl cellulose, stearoxy hydroxypropyl methyl cellulose, laureth-13PG hydroxyethyl cellulose, and stearoxy PG hydroxyethyl cellulose sulfonate from the viewpoint of reducing the emulsified particle size and improving storage stability at high temperatures. One or more are preferable, and at least one or two or more selected from hydroxypropyl methylcellulose and stearoxy PG hydroxyethyl cellulose sulfonate are more preferable, and both hydroxypropyl methylcellulose and stearoxy PG hydroxyethyl cellulose sulfonate are contained. Is even more preferable.
Examples of commercially available products include Metroz 60SH-4000 (manufactured by Shin-Etsu Chemical Co., Ltd.) as hydroxypropylmethyl cellulose; and Sangelose 60M (manufactured by Daido Kasei Kogyo Co., Ltd.) as stearoxy hydroxypropyl methyl cellulose; Examples of stearoxy PG hydroxyethyl cellulose sulfonate include Poise 310 (manufactured by Kao Corporation).
Ｎ−アシルアルキレンイミンを繰り返し単位とする親水性セグメントと、オルガノポリシロキサンセグメントとを構成単位とするポリマー（以下、オキサゾリン変性シリコーンという場合がある）において、Ｎ−アシルアルキレンイミンを繰り返し単位とする親水性セグメントに対するオルガノポリシロキサンセグメントの質量比（オルガノポリシロキサンセグメントａ／Ｎ−アシルアルキレンイミンを繰り返し単位とする親水性セグメントｂ）は、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、４５／５５〜７５／２５の範囲が好ましく、４７／５３〜７４／２６がより好ましく、４８／５２〜７３／２７がさらに好ましく、４９／５１〜７２／２８がよりさらに好ましく、５０／５０〜７０／３０がことさら好ましい。
なお、本発明において、上記質量比は、本発明で用いるオルガノポリシロキサンを重クロロホルム中に５質量％で溶解させ、核磁気共鳴（1Ｈ−ＮＭＲ）分析により、オルガノポリシロキサンセグメント中のアルキル基またはフェニル基と、ポリ（Ｎ−アシルアルキレンイミン）セグメント中のメチレン基の積分比より求めた値をいう。
In a polymer having an N-acylalkyleneimine as a repeating unit and an organopolysiloxane segment as a constituent unit (hereinafter, may be referred to as oxazoline-modified silicone), hydrophilicity having N-acylalkyleneimine as a repeating unit. The mass ratio of the organopolysiloxane segment to the sex segment (hydrophilic segment b with the organopolysiloxane segment a / N-acylalkyleneimine as a repeating unit) reduces the size of the emulsified particle and improves the storage stability at high temperature. From the viewpoint, the range of 45/55 to 75/25 is preferable, 47/53 to 74/26 is more preferable, 48/52 to 73/27 is more preferable, 49/51 to 72/28 is even more preferable, and 50 / 50-70 / 30 is particularly preferable.
In the present invention, the above mass ratio is determined by dissolving the organopolysiloxane used in the present invention in 5% by mass in heavy chloroform and analyzing the alkyl group in the organopolysiloxane segment by nuclear magnetic resonance ( 1 H-NMR) analysis. Alternatively, it refers to a value obtained from the integral ratio of the phenyl group and the methylene group in the poly (N-acylalkyleneimine) segment.
オキサゾリン変性シリコーンにおいて、オルガノポリシロキサンセグメントの重量平均分子量は、乳化粒子径を小さく、高温での保存安定性を向上させる観点から、たとえば１×１０4以上であり、好ましくは２×１０4以上、さらに好ましくは３．５×１０4以上であり、また、たとえば３×１０5以下であり、好ましくは２×１０5以下、さらに好ましくは１．５×１０5以下である。
なお、主鎖を構成するオルガノポリシロキサンは、原料化合物である変性オルガノポリシロキサンと共通の骨格を有するため、主鎖を構成するオルガノポリシロキサンの重量平均分子量は変性オルガノポリシロキサンの平均分子量と略同一である。
ここで、変性オルガノポリシロキサンの重量平均分子量は、ゲルパーミエションクロマトグラフィ（ＧＰＣ）により下記条件で測定されたポリスチレン換算の重量平均分子量である。
カラム：Super HZ4000 + Super HZ2000（東ソー社製）
溶離液：１ｍＭトリエチルアミン／ＴＨＦ
流量：０．３５ｍＬ／ｍｉｎ
カラム温度：４０℃
検出器：ＵＶ検出器
サンプル：５０μＬ
In the oxazoline-modified silicone, the weight average molecular weight of the organopolysiloxane segment is, for example, 1 × 10 4 or more, preferably 2 × 10 4 or more, from the viewpoint of reducing the emulsified particle size and improving the storage stability at high temperature. more preferably not more 3.5 × 10 4 or more, for example, a 3 × 10 5 or less, preferably 2 × 10 5 or less, more preferably 1.5 × 10 5 or less.
Since the organopolysiloxane constituting the main chain has the same skeleton as the modified organopolysiloxane which is the raw material compound, the weight average molecular weight of the organopolysiloxane constituting the main chain is abbreviated as the average molecular weight of the modified organopolysiloxane. It is the same.
Here, the weight average molecular weight of the modified organopolysiloxane is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) under the following conditions.
Column: Super HZ4000 + Super HZ2000 (manufactured by Tosoh)
Eluent: 1 mM triethylamine / THF
Flow rate: 0.35 mL / min
Column temperature: 40 ° C
Detector: UV detector sample: 50 μL
また、オキサゾリン変性シリコーンにおいて、ポリ（Ｎ−アシルアルキレンイミン）セグメントの数平均分子量は、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、たとえば５×１０2以上であり、好ましくは７×１０2以上、さらに好ましくは８×１０2以上であり、また、たとえば４×１０3以下であり、好ましくは３．５×１０3以下、さらに好ましくは３×１０3以下である。
なお、ポリ（Ｎ−アシルアルキレンイミン）セグメントの数平均分子量は、Ｎ−アシルアルキレンイミン単位の分子量と重合度とから算出する方法または上記ＧＰＣ測定法により測定することが可能であるが、本実施形態においてはＧＰＣ測定法により測定される数平均分子量をいう。
Further, in the oxazoline-modified silicone, the number average molecular weight of the poly (N-acylalkyleneimine) segment is, for example, 5 × 10 2 or more from the viewpoint of reducing the emulsified particle size and improving the storage stability at high temperature. It is preferably 7 × 10 2 or more, more preferably 8 × 10 2 or more, and for example, 4 × 10 3 or less, preferably 3.5 × 10 3 or less, still more preferably 3 × 10 3 or less. ..
The number average molecular weight of the poly (N-acylalkyleneimine) segment can be measured by a method calculated from the molecular weight and the degree of polymerization of each N-acylalkyleneimine unit or by the above GPC measurement method. In the form, it refers to the number average molecular weight measured by the GPC measurement method.
オキサゾリン変性シリコーンの具体例として、下記一般式（２）で示すものが挙げられる。 Specific examples of the oxazoline-modified silicone include those represented by the following general formula (2).
（式中、ｎは１〜５の数を示し、Ｒ4は水素原子又は炭素数１〜５のアルキル基を示し、ｍはモノマーの重合度であって、１〜１０００の数を示し、ｒは平均で１０〜２０００、ｐは平均で０〜２０、ｑは平均で１〜２０の数を示し、Ｘ-は四級アンモニウムイオンの対イオンを示し、エチル硫酸イオン、メチル硫酸イオン、塩素イオン、ヨウ素イオン、硫酸イオン、ｐ−トルエンスルホン酸イオン又は過塩素酸イオンを示す。なお、Ｎ−アシルアルキレンイミンの繰り返し単位のＮ末端には、重合開始剤残基が結合する。）
重合開始剤としては、ジエチル硫酸、ジメチル硫酸、塩酸、ヨウ化水素、硫酸、ｐ−トルエンスルホン酸、過塩素酸等が用いられ、これらの残基が重合後のＮ−末端に結合する。
(In the formula, n represents a number of 1 to 5, R 4 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, m is the degree of polymerization of the monomer, and represents a number of 1 to 1000, r. Is 10 to 2000 on average, p is 0 to 20 on average, q is 1 to 20 on average, X - is a pair ion of quaternary ammonium ion, ethyl sulfate ion, methyl sulfate ion, chlorine ion. , Iodine ion, sulfate ion, p-toluenesulfonate ion or perchlorate ion. Note that a polymerization initiator residue is bound to the N-terminal of the repeating unit of N-acylalkyleneimine.)
As the polymerization initiator, diethylsulfate, dimethylsulfate, hydrochloric acid, hydrogen iodide, sulfuric acid, p-toluenesulfonic acid, perchloric acid and the like are used, and these residues are bonded to the N-terminal after polymerization.
オキサゾリン変性シリコーンとして、Ｎ−プロピオニルポリエチレンイミン・メチルポリシロキサン共重合体（ＰＯＬＹＳＩＬＩＣＯＮＥ−９）が好ましい。ＰＯＬＹＳＩＬＩＣＯＮＥ−９として、例えば特開２０１６−６０２９号公報に記載のものを用いることができる。 As the oxazoline-modified silicone, N-propionylpolyethylenimine-methylpolysiloxane copolymer (POLYSILICONE-9) is preferable. As POLYSILICONE-9, for example, those described in JP-A-2016-6029 can be used.
ポリエーテル変性シリコーンとしては、例えば次の一般式（３）で表されるものが挙げられる。 Examples of the polyether-modified silicone include those represented by the following general formula (3).
［式中、Ｒ6〜Ｒ8及びＲ10〜Ｒ11は、それぞれメチル基又はフェニル基を示し、Ｒ5、Ｒ9及びＲ12は、それぞれメチル基、フェニル基、又は基Ｒ13（ＯＣ3Ｈ6）f（ＯＣ2Ｈ4）gＯ（ＣＨ2）h−（Ｒ13は水素原子又は炭素数１〜１２のアルキル基を示し、ｆ及びｇは平均値で、それぞれ０〜３５の数を示し、ｈは１〜５の数を示す）を示す。ただし、Ｒ5、Ｒ9及びＲ12のうち少なくとも１つは基Ｒ13（ＯＣ3Ｈ6）f（ＯＣ2Ｈ4）gＯ（ＣＨ2）h−を示す。ｄ及びｅは平均値で、ｄは１〜２００の数を示し、ｅは０〜５０の数を示す］ [In the formula, R 6 to R 8 and R 10 to R 11 represent a methyl group or a phenyl group, respectively, and R 5 , R 9 and R 12 are a methyl group, a phenyl group, or a group R 13 (OC 3), respectively. H 6 ) f (OC 2 H 4 ) g O (CH 2 ) h − (R 13 indicates a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and f and g are average values of 0 to 35, respectively. , And h indicates a number from 1 to 5). However, at least one of R 5 , R 9 and R 12 indicates the group R 13 (OC 3 H 6 ) f (OC 2 H 4 ) g O (CH 2 ) h −. d and e are average values, d indicates a number from 1 to 200, and e indicates a number from 0 to 50]
ポリエーテル変性シリコーンとしては、一般式（３）で示されるポリオキシエチレン・メチルポリシロキサン共重合体、ポリ（オキシエチレン・オキシプロピレン）・メチルポリシロキサン共重合体から選ばれる少なくとも１種又は２種以上が好ましく、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、ポリオキシエチレン・メチルポリシロキサン共重合体が好ましい。
市販品としては、例えば、信越化学工業社から販売されている「ＫＦ−６０１５」（ＰＥＧ−３ジメチコン）、「ＫＦ−６０１９」（ＰＥＧ−９ジメチコン）、東レ・ダウコーニング・シリコーン社から販売されている「ＳＨ−３７７５Ｍ」（ＰＥＧ−１２ジメチコン）、「ＳＨ−３７７１Ｍ」（ＰＥＧ−１２ジメチコン）、「ＳＳ−２８０４」（ＰＥＧ−１２ジメチコン）等が挙げられる。
As the polyether-modified silicone, at least one or two kinds selected from the polyoxyethylene / methylpolysiloxane copolymer represented by the general formula (3) and the poly (oxyethylene / oxypropylene) / methylpolysiloxane copolymer. The above is preferable, and a polyoxyethylene / methylpolysiloxane copolymer is preferable from the viewpoint of reducing the size of the emulsified particles and improving the storage stability at high temperatures.
Commercially available products include, for example, "KF-6015" (PEG-3 dimethicone), "KF-6019" (PEG-9 dimethicone) sold by Shin-Etsu Chemical Industry Co., Ltd., and Toray Dow Corning Silicone Co., Ltd. Examples thereof include "SH-3775M" (PEG-12 dimethicone), "SH-3771M" (PEG-12 dimethicone), and "SS-2804" (PEG-12 dimethicone).
成分（Ｂ）としては、高温での保存安定性を向上させ、乳化粒子径を小さくする観点から、アルキル変性された多糖類系ポリマー、Ｎ−アシルアルキレンイミンを繰り返し単位とする親水性セグメントと、オルガノポリシロキサンセグメントとを構成単位とするポリマーから選ばれる少なくとも１種又は２種以上が好ましく、アルキル変性された多糖類系ポリマーがより好ましい。 The component (B) includes a hydrophilic segment having N-acylalkyleneimine as a repeating unit, an alkyl-modified polysaccharide polymer, from the viewpoint of improving storage stability at high temperature and reducing the emulsion particle size. At least one or more selected from polymers having an organopolysiloxane segment as a constituent unit is preferable, and an alkyl-modified polysaccharide-based polymer is more preferable.
成分（Ｂ）は、１種又は２種以上を用いることができ、さっぱり感、塗布時の伸ばしやすさを向上させ、乳化粒子径を小さくする観点から、含有量は、乳化化粧料中に０．００６〜２．５質量％であるのが好ましく、０．００８〜１．０質量％であるのがより好ましく、０．０１〜０．６５質量％がより好ましく、０．０４〜０．４質量％がさらに好ましい。 As the component (B), one type or two or more types can be used, and the content is 0 in the emulsified cosmetic from the viewpoint of improving the refreshing feeling, the ease of spreading at the time of application, and reducing the emulsified particle size. It is preferably .006 to 2.5% by mass, more preferably 0.008 to 1.0% by mass, more preferably 0.01 to 0.65% by mass, and 0.04 to 0.4% by mass. Mass% is more preferred.
成分（Ｃ）の油剤としては、例えば、炭化水素油、エステル油、エーテル油、シリコーン油、炭素数１０〜２４の高級アルコール、炭素数１０~２４の高級脂肪酸等が挙げられる。 Examples of the oil agent of the component (C) include hydrocarbon oils, ester oils, ether oils, silicone oils, higher alcohols having 10 to 24 carbon atoms, higher fatty acids having 10 to 24 carbon atoms, and the like.
より具体的には、炭化水素油としては、スクワラン、流動パラフィン、流動イソパラフィン、重質流動イソパラフィン等が挙げられる。これらの炭化水素油のうち、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、流動パラフィン、流動イソパラフィン及びスクワランから選ばれる少なくとも１種又は２種以上が好ましく、流動イソパラフィン及びスクワランから選ばれる少なくとも１種がより好ましい。 More specifically, examples of the hydrocarbon oil include squalane, liquid paraffin, liquid isoparaffin, heavy liquid isoparaffin and the like. Of these hydrocarbon oils, at least one or two or more selected from liquid paraffin, liquid isoparaffin and squalane are preferable from the viewpoint of reducing the emulsified particle size and improving the storage stability at high temperature, and the liquid isoparaffin and At least one selected from squalane is more preferred.
エステル油としては、モノエステル油、ジエステル油、トリエステル油及びテトラエステル油が挙げられる。
モノエステル油としては、炭素数２〜２４の脂肪族又は芳香族のモノカルボン酸又はジカルボン酸のモノエステルが挙げられ、具体例としては、２−エチルヘキサン酸セチル、オクタン酸セチル、イソノナン酸イソノニル、イソノナン酸イソトリデシル、ラウリン酸ヘキシル、ミリスチン酸イソプロピル、ミリスチン酸オクチルドデシル、ミリスチン酸ミリスチル、ミリスチン酸２−ヘキシルデシル、パルミチン酸イソプロピル、パルミチン酸オクチル、パルミチン酸２−ヘキシルデシルステアリン酸ブチル、ステアリン酸イソセチル、イソステアリン酸イソセチル、オレイン酸デシル、イソデシルベンゾエート、メトキシケイヒ酸オクチル、ジメチルオクタン酸ヘキシルデシル、乳酸セチル、乳酸ミリスチル、酢酸ラノリン、コハク酸２−エチルヘキシル、アジピン酸２−ヘキシルデシル、安息香酸アルキル（Ｃ１２〜Ｃ１５）等が挙げられる。これらの中では、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、イソノナン酸イソノニル、イソノナン酸イソトリデシル、ミリスチン酸イソプロピル及びメトキシケイヒ酸オクチルから選ばれる少なくとも１種が好ましく、イソノナン酸イソノニル及びイソノナン酸イソトリデシルから選ばれる少なくとも１種又は２種以上がより好ましい。
Examples of the ester oil include monoester oil, diester oil, triester oil and tetraester oil.
Examples of the monoester oil include monoesters of aliphatic or aromatic monocarboxylic acids or dicarboxylic acids having 2 to 24 carbon atoms, and specific examples thereof include cetyl 2-ethylhexanoate, cetyl octanoate, and isononyl isononanoate. , Isotridecyl isononanoate, hexyl laurate, isopropyl myristate, octyldodecyl myristate, myristyl myristate, 2-hexyldecyl myristate, isopropyl palmitate, octyl palmitate, butyl palmitate 2-hexyldecyl stearate, isocetyl stearate , Isocetyl isostearate, decyl oleate, isodecylbenzoate, octyl methoxycinnamate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, 2-ethylhexyl succinate, 2-hexyldecyl adipate, alkyl benzoate ( C12 to C15) and the like can be mentioned. Among these, at least one selected from isononyl isononanoate, isotridecyl isononanoate, isopropyl myristate and octyl methoxycinnamonate is preferable from the viewpoint of reducing the emulsified particle size and improving the storage stability at high temperature, and isononan. More preferably, at least one or more selected from isononyl acid acid and isotridecyl isononanoate.
ジエステル油としては、炭素数３〜１８のジカルボン酸のジエステル、多価アルコールのジ脂肪酸エステル等が挙げられ、具体例としては、ジカプリル酸プロピレングリコール、ジカプリン酸ネオペンチルグリコール、ジステアリン酸グリコール、ジイソステアリン酸プロピレングリコール、ジイソステアリン酸グリセリル、モノイソステアリン酸モノミリスチン酸グリセリル、ジ２−ヘプチルウンデカン酸グリセリン、コハク酸ジ２−エチルヘキシル、セバシン酸ジイソプロピル、リンゴ酸ジイソステアリル、ジ２−エチルヘキサン酸エチレングリコール、アジピン酸ジイソブチル、アジピン酸ジ−２−ヘプチルウンデシル、セバシン酸ジ−２−エチルヘキシル等が挙げられる。これらの中では、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、ジカプリル酸プロピレングリコール、ジカプリン酸ネオペンチルグリコール、ジステアリン酸グリコール及びジイソステアリン酸プロピレングリコールから選ばれる少なくとも１種が好ましく、ジカプリル酸プロピレングリコール及びジカプリン酸ネオペンチルグリコールから選ばれる少なくとも１種又は２種以上がより好ましい。 Examples of the diester oil include diesters of dicarboxylic acids having 3 to 18 carbon atoms and difatty acid esters of polyhydric alcohols. Specific examples thereof include propylene glycol dicaprylate, neopentyl glycol dicaprate, glycol distearate, and diisostearic acid. Propylene glycol, glyceryl diisostearate, glyceryl monomylystearate monoisostearate, glycerin di2-heptylundecanoate, di2-ethylhexyl succinate, diisopropyl sebacate, diisostearyl malate, ethylene glycol di2-ethylhexanoate, adipine Examples thereof include diisobutyl acid acid, di-2-heptylundesyl adipate, and di-2-ethylhexyl sebacate. Among these, at least one selected from propylene glycol dicaprylate, neopentyl glycol dicaprate, glycol distearate and propylene glycol diisostearate is selected from the viewpoint of reducing the emulsified particle size and improving storage stability at high temperatures. Preferably, at least one or more selected from propylene glycol dicaprylate and neopentyl glycol dicaprate is more preferable.
トリエステル油としては、３価以上の多価アルコールのトリ脂肪酸エステルが挙げられ、具体的には、トリミリスチン酸グリセリン、トリイソパルミチン酸グリセリン、トリ２−ヘプチルウンデカン酸グリセリン、トリエチルヘキサン酸トリメチロールプロパン、トリオクタン酸トリメチロールプロパン、トリ（カプリル・カプリン酸）グリセリン、トリオレイン酸グリセリン、トリ２−エチルヘキサン酸グリセリン、トリイソステアリン酸グリセリン、オリーブ油、ホホバ油等が挙げられる。これらの中では、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、トリ（カプリル・カプリン酸）グリセリン、トリオレイン酸グリセリン、トリ２−エチルヘキサン酸グリセリン及びトリイソステアリン酸グリセリンから選ばれる少なくとも１種又は２種以上が好ましく、トリ（カプリル・カプリン酸）グリセリンがより好ましい。 Examples of the triester oil include trifatty acid esters of trivalent or higher polyhydric alcohols, and specifically, glycerin trimyristate, glycerin triisopalmitate, glycerin tri2-heptylundecanoate, and trimethyl triethylhexanoate. Examples thereof include propane, trimethylol propane trioctanoate, glycerin tri (capril capric acid), glycerin trioleate, glycerin tri2-ethylhexanoate, glycerin triisostearate, olive oil, and jojoba oil. Among these, tri (caprylic capric acid) glycerin, trioleate glycerin, tri2-ethylhexanoate glycerin and triisostearate glycerin from the viewpoint of reducing the emulsified particle size and improving storage stability at high temperatures. At least one or more selected from the above is preferable, and tri (caprylic capric acid) glycerin is more preferable.
テトラエステル油としては、４価以上の多価アルコールのテトラ脂肪酸エステルが挙げられ、具体的には、テトラ（ベヘン酸／安息香酸／エチルヘキサン酸）ペンタエリスリット、テトラエチルヘキサン酸ペンタエリスリット、テトラオクタン酸ペンタエリスリット、テトラ２−エチルヘキサン酸ペンタエリスリットが挙げられる。これらの中では、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、テトラエチルヘキサン酸ペンタエリスリット、テトラオクタン酸ペンタエリスリット及びテトラ２−エチルヘキサン酸ペンタエリスリットから選ばれる少なくとも１種又は２種以上が好ましく、テトラエチルヘキサン酸ペンタエリスリットがより好ましい。また、テトラエステル油は、テトラエチルヘキサン酸ペンタエリスリットを含むことがさらに好ましい。 Examples of the tetraester oil include tetrafatty acid esters of tetrahydric or higher polyhydric alcohols, and specifically, tetra (behenic acid / benzoic acid / ethylhexanoic acid) pentaerythlit, tetraethylhexanoic acid pentaerythlit, tetra. Examples thereof include pentaerislit octanate and pentaerislit tetra2-ethylhexanoate. Among these, pentaethylhexanoate pentaerythlit, tetraoctanoate pentaerythlit and tetra2-ethylhexanoate pentaerythlit are selected from the viewpoint of reducing the emulsified particle size and improving storage stability at high temperatures. At least one or more are preferable, and pentaerythlit tetraethylhexanoate is more preferable. Further, it is more preferable that the tetraester oil contains a tetraethylhexanoic acid pentaerythlit.
エーテル油としては、ジアルキルエーテルが挙げられ、具体的には、ジヘキシルエーテル、ジカプリリルエーテル、セチル−１，３−ジメチルブチルエーテル等が挙げられる。これらの中では、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、ジカプリリルエーテル及びセチル−１，３−ジメチルブチルエーテルから選ばれる少なくとも１種又は２種以上が好ましく、セチル−１，３−ジメチルブチルエーテルがより好ましい。 Examples of the ether oil include dialkyl ether, and specific examples thereof include dihexyl ether, dicaprylyl ether, and cetyl-1,3-dimethylbutyl ether. Among these, at least one or more selected from dicaprylyl ether and cetyl-1,3-dimethylbutyl ether are preferable from the viewpoint of reducing the emulsified particle size and improving the storage stability at high temperature, and cetyl is preferable. -1,3-Dimethylbutyl ether is more preferable.
シリコーン油としては、メチルポリシロキサン、架橋型メチルポリシロキサン、網状型メチルポリシロキサン、ジメチルポリシロキサン、ジメチルシクロポリシロキサン、メチルフェニルポリシロキサン、高級アルコール変性オルガノポリシロキサン等が挙げられる。これらの中では、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、メチルポリシロキサン、架橋型メチルポリシロキサン及び網状型メチルポリシロキサンから選ばれる少なくとも１種又は２種以上が好ましく、メチルポリシロキサンがより好ましい。また、シリコーン油は、メチルポリシロキサンを含むことがさらに好ましい。 Examples of the silicone oil include methylpolysiloxane, crosslinked methylpolysiloxane, reticulated methylpolysiloxane, dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, and higher alcohol-modified organopolysiloxane. Among these, at least one or more selected from methylpolysiloxane, crosslinked methylpolysiloxane and reticulated methylpolysiloxane from the viewpoint of reducing the emulsified particle size and improving the storage stability at high temperature. Preferably, methylpolysiloxane is more preferred. Further, it is more preferable that the silicone oil contains methylpolysiloxane.
炭素数１０〜２４の高級アルコールとしては、乳化粒子径を小さくし、さっぱり感をより向上させる観点から、炭素数１２〜２２の高級アルコールが好ましく、炭素数１６〜２２の高級アルコールがより好ましく、炭素数１８〜２２の高級アルコールがさらに好ましく、炭素数１８と２２の高級アルコールを含有するのがよりさらに好ましい。
炭素数１０〜２４の高級脂肪酸としては、乳化粒子径を小さくし、さっぱり感をより向上させる観点から、炭素数１２〜２２の高級脂肪酸が好ましく、炭素数１６〜２２の高級脂肪酸がより好ましく、炭素数１８〜２２の高級脂肪酸がさらに好ましい。
As the higher alcohol having 10 to 24 carbon atoms, a higher alcohol having 12 to 22 carbon atoms is preferable, and a higher alcohol having 16 to 22 carbon atoms is more preferable, from the viewpoint of reducing the emulsified particle size and further improving the refreshing feeling. Higher alcohols having 18 to 22 carbon atoms are more preferable, and higher alcohols having 18 to 22 carbon atoms are even more preferable.
As the higher fatty acid having 10 to 24 carbon atoms, a higher fatty acid having 12 to 22 carbon atoms is preferable, and a higher fatty acid having 16 to 22 carbon atoms is more preferable, from the viewpoint of reducing the emulsified particle size and further improving the refreshing feeling. Higher fatty acids having 18 to 22 carbon atoms are more preferable.
成分（Ｃ）の油剤としては、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、炭化水素油、エステル油、シリコーン油、炭素数１０〜２４の高級アルコールから選ばれる少なくとも１種又は２種以上が好ましく、エステル油の中ではジエステル油が好ましく、さらに炭化水素油、シリコーン油、炭素数１０〜２４の高級アルコールから選ばれる少なくとも１種又は２種以上がより好ましい。また、乳化粒子径を小さくし、さっぱり感を向上させ、肌に塗布時の液垂れを抑制する観点から、炭素数１０〜２４の高級アルコールを含有することがさらに好ましい。 The oil component (C) is selected from at least hydrocarbon oil, ester oil, silicone oil, and higher alcohol having 10 to 24 carbon atoms from the viewpoint of reducing the emulsified particle size and improving the storage stability at high temperature. One or more of them are preferable, diester oil is preferable among ester oils, and at least one or more selected from hydrocarbon oils, silicone oils, and higher alcohols having 10 to 24 carbon atoms is more preferable. Further, from the viewpoint of reducing the diameter of the emulsified particles, improving the refreshing feeling, and suppressing dripping when applied to the skin, it is more preferable to contain a higher alcohol having 10 to 24 carbon atoms.
成分（Ｃ）は、１種又は２種以上を用いることができ、乳化粒子径を小さく、高温での保存安定性を向上させる観点から、含有量は、乳化化粧料中に３〜３５質量％であるのが好ましく、８〜２８質量％がより好ましく、１０〜１８質量％がさらに好ましい。 As the component (C), one type or two or more types can be used, and the content is 3 to 35% by mass in the emulsified cosmetic from the viewpoint of reducing the emulsified particle size and improving the storage stability at high temperature. It is preferably 8 to 28% by mass, more preferably 10 to 18% by mass.
本発明において、成分（Ｃ）に対する成分（Ａ）の酸としての質量割合［〔（Ａ）の酸としての質量〕／（Ｃ）］は、乳化粒子径を小さくし、さっぱり感を向上させる観点から、０．００２〜０．３５が好ましく、０．０２０〜０．３０がより好ましく、０．０３０〜０．２５がさらに好ましい。 In the present invention, the mass ratio of the component (A) to the component (C) as an acid [[mass of (A) as an acid] / (C)] is a viewpoint of reducing the emulsified particle size and improving the refreshing feeling. Therefore, 0.002 to 0.35 is preferable, 0.020 to 0.30 is more preferable, and 0.030 to 0.25 is further preferable.
成分（Ｄ）の水の含有量は、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、乳化化粧料中に４０〜９５質量％が好ましく、５０〜９２質量％がより好ましく、６０〜８８質量％がさらに好ましい。
成分（Ｄ）の水は、工程１及び工程２に分けて用いることが好ましい。
工程１で水を用いる場合、その含有量（Ｄ１）は、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、乳化化粧料中に５〜３０質量％が好ましく、８〜２５質量％がより好ましく、１０〜２０質量％がさらに好ましい。
また、工程２での水を用いる場合、その含有量（Ｄ２）は、残部であり、乳化化粧料中に３５〜９０質量％が好ましく、４０〜８０質量％がより好ましく、４５〜７５質量％がさらに好ましい。
The water content of the component (D) is preferably 40 to 95% by mass, more preferably 50 to 92% by mass in the emulsified cosmetic, from the viewpoint of reducing the emulsified particle size and improving the storage stability at high temperature. It is preferable, and 60 to 88% by mass is more preferable.
The water of the component (D) is preferably used separately in step 1 and step 2.
When water is used in step 1, the content (D1) is preferably 5 to 30% by mass, preferably 8 to 30% by mass, in the emulsified cosmetic from the viewpoint of reducing the emulsified particle size and improving the storage stability at high temperature. 25% by mass is more preferable, and 10 to 20% by mass is further preferable.
When water in step 2 is used, the content (D2) is the balance, preferably 35 to 90% by mass, more preferably 40 to 80% by mass, and 45 to 75% by mass in the emulsified cosmetic. Is even more preferable.
工程１においては、前記成分（Ａ）、（Ｂ）、（Ｃ）及び（Ｄ）を含む成分を混合して、乳化物を得る。
これら成分の混合方法は特に制限されず、通常の方法により行うことができる。例えば、成分（Ａ）、（Ｂ）、（Ｃ）を含む油相を調製し、成分（Ｄ）を含む水相を調製し、前記水相に油相を加え、混合することにより乳化物を得ることができる。
In step 1, the components containing the components (A), (B), (C) and (D) are mixed to obtain an emulsion.
The method for mixing these components is not particularly limited, and can be carried out by a usual method. For example, an oil phase containing the components (A), (B), and (C) is prepared, an aqueous phase containing the component (D) is prepared, and the oil phase is added to the aqueous phase and mixed to form an emulsion. Obtainable.
工程１で得られる乳化物は、乳化粒子径を小さくする観点から、ｐＨ７．５以上であるのが好ましく、ｐＨ８．０以上がより好ましく、ｐＨ８．３以上がさらに好ましく、ｐＨ８．８以上がよりさらに好ましい。また、乳化粒子径を小さくする観点から、ｐＨ１２．５以下が好ましく、ｐＨ１２．０以下がより好ましく、ｐＨ１１．６以下がさらに好ましい。
なお、本発明において、ｐＨは、ｐＨメーター（堀場製作所製、型番Ｆ−２２）を用い、２５℃で測定する。
工程１で得られる乳化物のｐＨを７．５以上とするのが好ましいことは、後記参考例１に示すｐＨと乳化粒子径の実験より、確認することができる。
The emulsion obtained in step 1 is preferably pH 7.5 or higher, more preferably pH 8.0 or higher, further preferably pH 8.3 or higher, and more preferably pH 8.8 or higher, from the viewpoint of reducing the emulsified particle size. More preferred. Further, from the viewpoint of reducing the emulsified particle size, pH 12.5 or less is preferable, pH 12.0 or less is more preferable, and pH 11.6 or less is further preferable.
In the present invention, the pH is measured at 25 ° C. using a pH meter (manufactured by HORIBA, Ltd., model number F-22).
It can be confirmed from the experiment of pH and emulsified particle size shown in Reference Example 1 below that the pH of the emulsion obtained in step 1 is preferably 7.5 or more.
（工程２）
工程２は、工程１で得られた乳化物のｐＨを下げる工程である。
工程１において、乳化粒子径が小さい乳化物を得た後、ｐＨを下げることにより、成分（Ａ）の含有量を低減するか、含有しない状態にすることができ、乳化粒子径が小さいまま維持され、高温での保存安定性に優れた水中油型乳化化粧料を得ることができると考えられる。
工程２において、ｐＨを下げるには、工程１で得られた乳化物に、ｐＨを下げる成分（Ｅ）を添加した後、混合して、ｐＨを下げることが好ましい。
(Step 2)
Step 2 is a step of lowering the pH of the emulsion obtained in Step 1.
In step 1, after obtaining an emulsion having a small emulsified particle size, the content of the component (A) can be reduced or not contained by lowering the pH, and the emulsified particle size remains small. Therefore, it is considered that an oil-in-water emulsified cosmetic having excellent storage stability at high temperature can be obtained.
In step 2, in order to lower the pH, it is preferable to add the pH lowering component (E) to the emulsion obtained in step 1 and then mix the mixture to lower the pH.
ｐＨを下げる成分（Ｅ）としては、無機酸、炭素数８以下の有機酸、アクリル酸若しくはスルホン酸由来の構成単位を有する酸性の高分子から選ばれる１種または２種以上が好ましい。
無機酸としては、塩酸、硝酸、亜硝酸、硫酸、亜硫酸、リン酸、ホスホン酸、ホスフィン酸が挙げられ、乳化粒子径を小さくする観点から、リン酸、ホスホン酸、ホスフィン酸から選ばれる少なくとも１種又は２種以上が好ましく、リン酸、ホスホン酸から選ばれる少なくとも１種又は２種以上がより好ましく、リン酸がさらに好ましい。
As the component (E) for lowering the pH, one or more selected from an acidic polymer having a structural unit derived from an inorganic acid, an organic acid having 8 or less carbon atoms, an acrylic acid or a sulfonic acid is preferable.
Examples of the inorganic acid include hydrochloric acid, nitrate, nitrite, sulfuric acid, sulfite, phosphoric acid, phosphonic acid, and phosphinic acid, and at least one selected from phosphoric acid, phosphonic acid, and phosphinic acid from the viewpoint of reducing the emulsified particle size. Species or two or more are preferable, at least one or two or more selected from phosphoric acid and phosphonic acid are more preferable, and phosphoric acid is further preferable.
炭素数８以下の有機酸としては、酢酸、プロピオン酸、酪酸等のモノカルボン酸；コハク酸、フタル酸、フマル酸、シュウ酸、マロン酸、グルタル酸等のジカルボン酸；グリコール酸、クエン酸、乳酸、ピルビン酸、リンゴ酸、酒石酸等のオキシカルボン酸；グルタミン酸、アスパラギン酸等の酸性アミノ酸が挙げられ、乳化粒子径を小さくする観点から、モノカルボン酸、ジカルボン酸、酸性アミノ酸から選ばれる少なくとも１種又は２種以上が好ましく、ジカルボン酸、酸性アミノ酸から選ばれる少なくとも１種又は２種以上がより好ましく、酸性アミノ酸がさらに好ましい。 Examples of organic acids having 8 or less carbon atoms include monocarboxylic acids such as acetic acid, propionic acid and butyric acid; dicarboxylic acids such as succinic acid, phthalic acid, fumaric acid, oxalic acid, malonic acid and glutaric acid; glycolic acid, citric acid, etc. Oxycarboxylic acids such as lactic acid, pyruvate, malic acid and tartrate; acidic amino acids such as glutamic acid and aspartic acid can be mentioned, and at least one selected from monocarboxylic acid, dicarboxylic acid and acidic amino acid from the viewpoint of reducing the emulsified particle size. Species or two or more are preferable, at least one or two or more selected from dicarboxylic acids and acidic amino acids are more preferable, and acidic amino acids are even more preferable.
アクリル酸またはスルホン酸由来の構成単位を有する酸性の高分子としては、カルボキシビニルポリマー、アルキル変性されたカルボキシビニルポリマー、ポリアクリル酸、少なくともアクリル酸塩またはアクリル酸ヒドロキシアルキルとアクリロイルジメチルタウリン塩とを共重合して得られた共重合体が挙げられ、乳化粒子径を小さくする観点から、カルボキシビニルポリマー、アルキル変性されたカルボキシビニルポリマー、ポリアクリル酸が好ましく、カルボキシビニルポリマー、アルキル変性されたカルボキシビニルポリマーがより好ましい。 Examples of the acidic polymer having a structural unit derived from acrylic acid or sulfonic acid include a carboxyvinyl polymer, an alkyl-modified carboxyvinyl polymer, a polyacrylic acid, at least an acrylate or a hydroxyalkyl acrylate, and an acryloyldimethyltaurine salt. Examples thereof include copolymers obtained by copolymerization, and from the viewpoint of reducing the emulsified particle size, carboxyvinyl polymers, alkyl-modified carboxyvinyl polymers and polyacrylic acids are preferable, and carboxyvinyl polymers and alkyl-modified carboxys are preferable. Vinyl polymers are more preferred.
成分（Ｅ）としては、乳化粒子径を小さくし、塗布時の液垂れを抑制する観点から、アクリル酸またはスルホン酸由来の構成単位を有する酸性の高分子が好ましい。
成分（Ｅ）は、１種又は２種以上を用いることができ、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、含有量は、乳化化粧料中に０．０１〜２質量％であるのが好ましく、０．０１５〜１．５質量％がより好ましく、０．０２〜１．２質量％がさらに好ましい。
成分（Ｅ）として、アクリル酸またはスルホン酸由来の構成単位を有する酸性の高分子を含有する場合の含有量は、乳化粒子径を小さくし、塗布時の伸ばしやすさを向上させる観点から、乳化化粧料中に０．０５〜０．７質量％であるのが好ましく、０．０６〜０．４質量％がより好ましく、０．０８〜０．３質量％がさらに好ましい。
As the component (E), an acidic polymer having a structural unit derived from acrylic acid or sulfonic acid is preferable from the viewpoint of reducing the diameter of the emulsified particles and suppressing dripping during coating.
As the component (E), one type or two or more types can be used, and the content is 0.01 to 0.01 in the emulsified cosmetic from the viewpoint of reducing the emulsified particle size and improving the storage stability at high temperature. It is preferably 2% by mass, more preferably 0.015 to 1.5% by mass, and even more preferably 0.02 to 1.2% by mass.
When the component (E) contains an acidic polymer having a structural unit derived from acrylic acid or sulfonic acid, the content is emulsified from the viewpoint of reducing the emulsified particle size and improving the ease of spreading during application. It is preferably 0.05 to 0.7% by mass, more preferably 0.06 to 0.4% by mass, and even more preferably 0.08 to 0.3% by mass in the cosmetic.
工程２において、成分（Ｅ）を、工程１で得られた乳化物に添加する際には、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、予め成分（Ｅ）を成分（Ｄ）の水の一部（Ｄ２）と混合して、添加するのが好ましい。
工程２においては、成分（Ｅ）を添加することにより、工程１で得られた乳化物のｐＨを下げることが好ましい。
工程２で得られる乳化物は、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、ｐＨ７．５未満であるのが好ましく、ｐＨ７．４以下がより好ましく、ｐＨ７．３以下がさらに好ましい。また、ｐＨ２．６以上が好ましく、ｐＨ２．７以上がより好ましく、ｐＨ２．８以上がさらに好ましい。
なお、ｐＨは、工程１の乳化物のｐＨの測定と同様の方法で測定される。
In step 2, when the component (E) is added to the emulsion obtained in step 1, the component (E) is previously added from the viewpoint of reducing the emulsified particle size and improving the storage stability at high temperature. It is preferable to add the component (D) by mixing it with a part of water (D2).
In step 2, it is preferable to lower the pH of the emulsion obtained in step 1 by adding the component (E).
The emulsion obtained in step 2 preferably has a pH of less than 7.5, more preferably pH 7.4 or less, and a pH of 7.3 or less, from the viewpoint of reducing the emulsified particle size and improving the storage stability at high temperatures. Is even more preferable. Further, pH 2.6 or higher is preferable, pH 2.7 or higher is more preferable, and pH 2.8 or higher is even more preferable.
The pH is measured by the same method as the measurement of the pH of the emulsion in step 1.
工程１で得られる乳化物のｐＨと、工程２で得られる乳化物のｐＨの差の変化率、[〔（工程１の乳化物のｐＨ）-（工程２の乳化物のｐＨ）〕/（工程１の乳化物のｐＨ）]は、乳化粒子径を小さくし、高温での保存安定性を向上させる観点から、０．１８〜０．８０であるのが好ましく、０．２２〜０．７７がより好ましく、０．２５〜０．７４がさらに好ましい。 The rate of change in the difference between the pH of the emulsion obtained in step 1 and the pH of the emulsion obtained in step 2, [[(pH of emulsion in step 1)-(pH of emulsion in step 2)] / ( The pH of the emulsion in step 1)] is preferably 0.18 to 0.80, preferably 0.22 to 0.77, from the viewpoint of reducing the emulsion particle size and improving the storage stability at high temperatures. Is more preferable, and 0.25 to 0.74 is even more preferable.
このようにして得られる水中油型乳化化粧料は、乳化粒子径（Ｄ５０）が１〜１０μｍであるのが好ましく、１〜９μｍであるのがより好ましい。
なお、本発明において、乳化粒子径は、レーザ回折／散乱式粒度分布測定装置（Partica LA-950V2、ＨＯＲＩＢＡ社製）にて測定される体積粒径である。また、乳化粒子径（Ｄ５０）は、体積分率で計算した累積体積頻度が粒径の小さい方から計算して５０％になる粒径であり、同様に、乳化粒子径（Ｄ９０）は、体積分率で計算した累積体積頻度が粒径の小さい方から計算して９０％になる粒径である。
The oil-in-water emulsified cosmetic obtained in this manner preferably has an emulsified particle size (D50) of 1 to 10 μm, more preferably 1 to 9 μm.
In the present invention, the emulsified particle size is the volume particle size measured by a laser diffraction / scattering type particle size distribution measuring device (Partica LA-950V2, manufactured by HORIBA). The emulsified particle size (D50) is a particle size in which the cumulative volume frequency calculated by the volume fraction is 50% calculated from the smaller particle size. Similarly, the emulsified particle size (D90) is a volume. The cumulative volume frequency calculated by fraction is 90% calculated from the smaller particle size.
また、本発明により得られる水中油型乳化化粧料は、肌に塗布時の液垂れを抑制し、塗布時の伸ばしやすさを向上させる観点から、２５℃における粘度が、９００〜３５，０００ｍＰａ・ｓであるのが好ましく、４，０００〜３０，０００ｍＰａ・ｓがより好ましく、８，０００〜２４，０００ｍＰａ・ｓがさらに好ましく、１０，０００〜１６，０００ｍＰａ・ｓがよりさらに好ましい。
なお、本発明において、粘度は、Ｂ型粘度計（ＴＶＢ−１０Ｒ形回転粘度計、東機産業社製、ローターＮｏ.４、６ｒｐｍ、２５℃）を用いて測定する。
Further, the oil-in-water emulsified cosmetic obtained by the present invention has a viscosity at 25 ° C. of 900 to 35,000 mPa. From the viewpoint of suppressing dripping when applied to the skin and improving the ease of spreading during application. It is preferably s, more preferably 4,000 to 30,000 mPa · s, further preferably 8,000 to 24,000 mPa · s, even more preferably 10,000 to 16,000 mPa · s.
In the present invention, the viscosity is measured using a B-type viscometer (TVB-10R type rotational viscometer, manufactured by Toki Sangyo Co., Ltd., rotor No. 4, 6 rpm, 25 ° C.).
本発明により得られる水中油型乳化化粧料は、前記成分以外に、更に、通常の化粧料に用いられる成分、例えば、炭素数１〜３のアルコール、保湿剤、酸化防止剤、防腐剤、冷汗剤、キレート剤、美白剤、紫外線吸収剤、ビタミン類、植物抽出物、その他各種薬効成分、粉体、香料、色材などを配合することができる。これらの各剤は、各剤としての用途に限られず、目的に応じて他の用途、たとえば、冷感剤を香料として使用したり、他の用途との併用として、例えば、制汗剤と香料としての効果を奏するものとして使用することができる。
本発明の水中油型乳化化粧料は、皮膚、中でも頭髪を除く皮膚、好ましくは顔、身体、手足等のいずれかに適用、好ましくは塗布することにより使用することができる。
In addition to the above-mentioned components, the oil-in-water emulsified cosmetic obtained by the present invention further contains components used in ordinary cosmetics, such as alcohols having 1 to 3 carbon atoms, moisturizers, antioxidants, preservatives, and cold sweats. Agents, chelating agents, whitening agents, ultraviolet absorbers, vitamins, plant extracts, various other medicinal ingredients, powders, fragrances, coloring materials, etc. can be blended. Each of these agents is not limited to the use as each agent, and may be used for other purposes depending on the purpose, for example, a cooling sensation agent may be used as a fragrance, or in combination with other applications, for example, an antiperspirant and a fragrance. It can be used as one that produces the effect of.
The oil-in-water emulsified cosmetic of the present invention can be applied to, and preferably applied to, the skin, especially the skin excluding hair, preferably the face, body, limbs, and the like.
参考例１（ｐＨと乳化粒子径の実験）
表１に示す組成の乳化物を製造し、ｐＨ及び乳化粒子径（Ｄ５０）を測定した。結果を表２に示した。
（乳化物の製造方法）
８０℃にて、流動パラフィン及びオレイン酸をディスパー３０００rpm、５分で混合して、油相を調製した。水酸化カリウム及び水を混合して、水相を調製した。前記油相に水相を加え、ディスパー３０００rpm、５分で混合し、さらに、ホモミキサー７０００rpm、１分で混合した。その後、プロペラ攪拌機３００ｒｐｍで混合しながら、１℃／分の速さで２５℃まで冷却して、乳化物を得た。
得られた乳化物について、ｐＨ及び乳化粒子径（Ｄ５０）を測定した。
なお、乳化物中の水酸化カリウムの含有量を変えることで、異なるｐＨの乳化物を得た。
Reference Example 1 (Experiment of pH and emulsified particle size)
An emulsion having the composition shown in Table 1 was produced, and the pH and emulsion particle size (D50) were measured. The results are shown in Table 2.
(Manufacturing method of emulsion)
At 80 ° C., liquid paraffin and oleic acid were mixed at disper 3000 rpm for 5 minutes to prepare an oil phase. An aqueous phase was prepared by mixing potassium hydroxide and water. An aqueous phase was added to the oil phase, and the mixture was mixed at disper 3000 rpm for 5 minutes, and further mixed at a homomixer 7000 rpm for 1 minute. Then, while mixing with a propeller stirrer at 300 rpm, the mixture was cooled to 25 ° C. at a speed of 1 ° C./min to obtain an emulsion.
The pH and emulsified particle size (D50) of the obtained emulsion were measured.
By changing the content of potassium hydroxide in the emulsion, emulsions having different pH were obtained.
（測定方法）
（１）ｐＨ：
ｐＨメーター（堀場製作所社製、型番Ｆ−２２）を用い、乳化物を２５℃まで冷却後、２４時間後に２５℃で測定した。
（２）乳化粒子径：
各乳化物について、レーザー散乱／回折法により、HORIBA LA-920（堀場製作所社製）を用いて、乳化粒子径（Ｄ５０）を測定した。
(Measuring method)
(1) pH:
Using a pH meter (manufactured by HORIBA, Ltd., model number F-22), the emulsion was cooled to 25 ° C., and then measured at 25 ° C. 24 hours later.
(2) Emulsified particle size:
For each emulsion, the emulsified particle size (D50) was measured using HORIBA LA-920 (manufactured by HORIBA, Ltd.) by a laser scattering / diffraction method.
表２の結果より、ｐＨ６．９〜７．７の範囲で乳化粒子径（Ｄ５０）が小さくなっていることがわかる。従って、工程１で得られる乳化物のｐＨを７．５以上とするのが好ましいことが確認された。 From the results in Table 2, it can be seen that the emulsified particle size (D50) is small in the pH range of 6.9 to 7.7. Therefore, it was confirmed that the pH of the emulsion obtained in step 1 is preferably 7.5 or higher.
実施例１〜３、比較例１〜８
表３に示す組成の水中油型乳化化粧料を製造し、水中油型乳化化粧料中の乳化粒子径（Ｄ５０）及び粘度を測定するとともに、保存安定性、さっぱり感を評価した。結果を表３に併せて示す。
なお、工程１で得られた乳化物、工程２で得られた乳化物のｐＨは、ｐＨメーター（堀場製作所社製、型番Ｆ−２２）を用いて、２５℃で測定した。工程２で得られた乳化物は、製造後、２４時間後に測定した。
Examples 1 to 3 and Comparative Examples 1 to 8
An oil-in-water emulsified cosmetic having the composition shown in Table 3 was produced, the diameter (D50) and viscosity of the emulsified particles in the oil-in-water emulsified cosmetic were measured, and the storage stability and refreshing feeling were evaluated. The results are also shown in Table 3.
The pH of the emulsion obtained in step 1 and the emulsion obtained in step 2 was measured at 25 ° C. using a pH meter (manufactured by HORIBA, Ltd., model number F-22). The emulsion obtained in step 2 was measured 24 hours after production.
（製造方法）
（１）実施例１：
（工程１）
８０℃にて、ｎ−オクタデセニルコハク酸コレステリル、ｎ−ヘキサデセニルコハク酸コレステリル、成分（Ｂ）及び（Ｃ）を、ディスパー３０００rpm、５分で混合し、油相を調製した。その後、水酸化カリウムと一部の水（Ｄ１）を混合して水相を調製した。その後、前記油相に水相を加え、ディスパー３０００rpm、１０分で混合し、さらに、ホモミキサー７０００rpm、１０分で混合した。その後、プロペラ攪拌機３００ｒｐｍで混合しながら、１℃／１分の速さで２５℃まで冷却して、ｐＨ８．５の乳化物を得た。
（工程２）
工程１で得られたｐＨ８．５の乳化物に、成分（Ｅ）と残りの成分（Ｄ２）を混合した水相を更に加え、プロペラ攪拌機３００ｒｐｍ、５分で混合して、ｐＨ５．５の水中油型乳化化粧料を得た。
なお、工程１において、ｎ−オクタデセニルコハク酸コレステリル及びｎ−ヘキサデセニルコハク酸コレステリル、は、組成物中では、水酸化カリウムと塩を形成し、成分（Ａ）であるｎ−オクタデセニルコハク酸コレステリルカリウム塩及びｎ−ヘキサデセニルコハク酸コレステリルカリウム塩として存在すると考えられる。
(Production method)
(1) Example 1:
(Step 1)
At 80 ° C., cholesteryl n-octadecenyl succinate, cholesteryl n-hexadecenyl succinate, components (B) and (C) were mixed at disper 3000 rpm for 5 minutes to prepare an oil phase. Then, potassium hydroxide and a part of water (D1) were mixed to prepare an aqueous phase. Then, the aqueous phase was added to the oil phase and mixed at disper 3000 rpm for 10 minutes, and further mixed at homomixer 7000 rpm for 10 minutes. Then, while mixing with a propeller stirrer at 300 rpm, the mixture was cooled to 25 ° C. at a speed of 1 ° C./1/1 minute to obtain an emulsion having a pH of 8.5.
(Step 2)
An aqueous phase in which the component (E) and the remaining component (D2) are mixed is further added to the pH 8.5 emulsion obtained in step 1, and the mixture is mixed with a propeller stirrer at 300 rpm for 5 minutes to make water at pH 5.5. An oil-type emulsified cosmetic was obtained.
In step 1, cholesteryl n-octadecenyl succinate and cholesteryl n-hexadecenyl succinate form a salt with potassium hydroxide in the composition, and n- is a component (A). It is believed to be present as potassium octadecenyl succinate and potassium cholesteryl n-hexadecenyl succinate.
（２）実施例２及び３：
ｎ−オクタデセニルコハク酸コレステリル及びｎ−ヘキサデセニルコハク酸コレステリルをオレイン酸に、水酸化カリウムをＬ−アルギニンに置き換えた以外は、実施例１と同様にして、水中油型乳化化粧料を得た。
(2) Examples 2 and 3:
Oil-in-water emulsified cosmetics in the same manner as in Example 1 except that cholesteryl n-octadecenyl succinate and cholesteryl n-hexadecenyl succinate were replaced with oleic acid and potassium hydroxide was replaced with L-arginine. I got a fee.
（３）比較例１：
８０℃にて、成分（Ｂ）及び（Ｃ）を、ディスパー３０００rpm、５分で混合し、油相を調製した。その後、前記油相に８０℃に加熱した水を加え、ディスパー３０００rpm、１０分で混合し、さらに、ホモミキサー７０００rpm、１０分で混合した、その後、プロペラ攪拌機３００ｒｐｍで混合しながら、１℃／１分の速さで２５℃まで冷却して、水中油型乳化化粧料を得た。
(3) Comparative Example 1:
At 80 ° C., the components (B) and (C) were mixed at disper 3000 rpm for 5 minutes to prepare an oil phase. Then, water heated to 80 ° C. was added to the oil phase, mixed at disper 3000 rpm for 10 minutes, further mixed at homomixer 7000 rpm for 10 minutes, and then mixed with a propeller stirrer 300 rpm at 1 ° C./1. The mixture was cooled to 25 ° C. at a rate of 1 minute to obtain an oil-in-water emulsified cosmetic.
（４）比較例２及び３：
比較例１と同様にして、水中油型乳化化粧料を得た。
(4) Comparative Examples 2 and 3:
An oil-in-water emulsified cosmetic was obtained in the same manner as in Comparative Example 1.
（５）比較例４：
８０℃にて、ｎ−オクタデセニルコハク酸コレステリル、ｎ−ヘキサデセニルコハク酸コレステリル、及び成分（Ｃ）を、ディスパー３０００rpm、５分で混合し、油相を調製した。８０℃にて、水酸化カリウムと水を混合して水相を調製した。その後、前記油相に水相を加え、ディスパー３０００rpm、１０分で混合し、さらに、ホモミキサー７０００rpm、１０分で混合した。その後、プロペラ攪拌機３００で混合しながら、１℃／１分の速さで２５℃まで冷却して、水中油型乳化化粧料を得た。
(5) Comparative Example 4:
At 80 ° C., cholesteryl n-octadecenyl succinate, cholesteryl n-hexadecenyl succinate, and component (C) were mixed at disper 3000 rpm for 5 minutes to prepare an oil phase. An aqueous phase was prepared by mixing potassium hydroxide and water at 80 ° C. Then, the aqueous phase was added to the oil phase and mixed at disper 3000 rpm for 10 minutes, and further mixed at homomixer 7000 rpm for 10 minutes. Then, while mixing with a propeller stirrer 300, the mixture was cooled to 25 ° C. at a speed of 1 ° C./1/1 minute to obtain an oil-in-water emulsified cosmetic.
（６）比較例５：
ｎ−オクタデセニルコハク酸コレステリル及びｎ−ヘキサデセニルコハク酸コレステリルをオレイン酸に、水酸化カリウムをＬ−アルギニンに置き換えた以外は、比較例４と同様にして、水中油型乳化化粧料を得た。
(6) Comparative Example 5:
Oil-in-water emulsified makeup in the same manner as in Comparative Example 4, except that cholesteryl n-octadecenyl succinate and cholesteryl n-hexadecenyl succinate were replaced with oleic acid and potassium hydroxide was replaced with L-arginine. I got a fee.
（７）比較例６：
８０℃にて、ｎ−オクタデセニルコハク酸コレステリル、ｎ−ヘキサデセニルコハク酸コレステリル、成分（Ｂ）及び（Ｃ）を、ディスパー３０００rpm、５分で混合し、油相を調製した。８０℃にて、水酸化カリウムと水を混合して水相を調製した。その後、前記油相に水相を加え、ディスパー３０００rpm、１０分で混合し、さらに、ホモミキサー７０００rpm、１０分で混合した。その後、プロペラ攪拌機３００rpmで混合しながら、１℃／１分の速さで２５℃まで冷却して、水中油型乳化化粧料を得た。
(7) Comparative Example 6:
At 80 ° C., cholesteryl n-octadecenyl succinate, cholesteryl n-hexadecenyl succinate, components (B) and (C) were mixed at disper 3000 rpm for 5 minutes to prepare an oil phase. An aqueous phase was prepared by mixing potassium hydroxide and water at 80 ° C. Then, the aqueous phase was added to the oil phase and mixed at disper 3000 rpm for 10 minutes, and further mixed at homomixer 7000 rpm for 10 minutes. Then, while mixing with a propeller stirrer at 300 rpm, the mixture was cooled to 25 ° C. at a speed of 1 ° C./1/1 minute to obtain an oil-in-water emulsified cosmetic.
（８）比較例７及び８：
ｎ−オクタデセニルコハク酸コレステリル及びｎ−ヘキサデセニルコハク酸コレステリルをオレイン酸に、水酸化カリウムをＬ−アルギニンに置き換えた以外は、比較例６と同様にして、水中油型乳化化粧料を得た。
(8) Comparative Examples 7 and 8:
Oil-in-water emulsified cosmetics in the same manner as in Comparative Example 6 except that cholesteryl n-octadeceenyl succinate and cholesteryl n-hexadecenyl succinate were replaced with oleic acid and potassium hydroxide was replaced with L-arginine. I got a fee.
（評価方法）
（１）乳化粒子径：
各水中油型乳化化粧料について、レーザー散乱／回折法により、HORIBA LA-920（堀場製作所社製）を用いて、乳化粒子径（Ｄ５０）を測定した。
(Evaluation method)
(1) Emulsified particle size:
The emulsified particle size (D50) of each oil-in-water emulsified cosmetic was measured by a laser scattering / diffraction method using HORIBA LA-920 (manufactured by HORIBA, Ltd.).
（２）粘度：
各水中油型乳化化粧料を、２５℃にて、Ｂ型粘度計（ＴＶＢ−１０Ｒ形回転粘度計、東機産業社製、ローターＮｏ.４、６rpm）を用いて、粘度を測定した。
(2) Viscosity:
The viscosity of each oil-in-water emulsified cosmetic was measured at 25 ° C. using a B-type viscometer (TVB-10R type rotational viscometer, manufactured by Toki Sangyo Co., Ltd., rotor No. 4, 6 rpm).
（３）保存安定性：
各水中油型乳化化粧料をガラス瓶（広口規格瓶、ＰＳ-Ｎｏ．６、５０ｇ、東京硝子社製）に４０ｇ充填して密閉し、６０℃で２週間保存した。２週間後、各乳化化粧料を取り出し、外観を目視観察し、ガラス瓶の上層または下層に透明に分離した液の量（mm）を、目視で評価した。
(3) Storage stability:
40 g of each oil-in-water emulsified cosmetic was filled in a glass bottle (wide-mouth standard bottle, PS-No. 6, 50 g, manufactured by Tokyo Glass Co., Ltd.), sealed, and stored at 60 ° C. for 2 weeks. After 2 weeks, each emulsified cosmetic was taken out, the appearance was visually observed, and the amount (mm) of the liquid transparently separated into the upper layer or the lower layer of the glass bottle was visually evaluated.
（４）さっぱり感：
専門パネラー１名により、各水中油型乳化化粧料０．２ｇを手の甲に塗布した。その後、直径６cmの円を描くように１秒間に１回の速さで２０秒間マッサージし、マッサージ終了後の皮膚を手で触り、さっぱり感を評価した。評価は、非常にさっぱりすると感じた場合を５、さっぱりしないと感じた場合を１とした５段階で評価した。
(4) Refreshing feeling:
One expert panelist applied 0.2 g of each oil-in-water emulsified cosmetic to the back of the hand. Then, the skin was massaged for 20 seconds at a rate of once per second in a circle having a diameter of 6 cm, and the skin after the massage was touched with hands to evaluate the refreshing feeling. The evaluation was made on a five-point scale, with 5 being the case of feeling very refreshed and 1 being the case of feeling not refreshing.
試験例１（乳化確認試験）
実施例１及び比較例６で得られた水中油型乳化化粧料（１）について、前記の方法により、乳化粒子径（Ｄ５０）及び（Ｄ９０）を測定した後、油剤（流動パラフィン１０質量％）を加え、ホモミキサー７０００rpm、１分で混合することにより、水中油型乳化化粧料（２）を得た。水中油型乳化化粧料（２）について、同様に、乳化粒子径（Ｄ５０）及び（Ｄ９０）を測定した。結果を表４に示す。
Test Example 1 (emulsification confirmation test)
With respect to the oil-in-water emulsified cosmetics (1) obtained in Example 1 and Comparative Example 6, after measuring the emulsified particle diameters (D50) and (D90) by the above method, an oil agent (liquid paraffin 10% by mass). Was added and mixed at 7000 rpm for 1 minute with a homomixer to obtain an oil-in-water emulsified cosmetic (2). For the oil-in-water emulsified cosmetic (2), the emulsified particle diameters (D50) and (D90) were measured in the same manner. The results are shown in Table 4.
本発明の製造方法は、工程１でアニオン界面活性剤を用いて乳化を行っている。しかし、工程２で、乳化物のｐＨを下げることにより、最終的に得られる乳化物においては、アニオン界面活性剤は、酸と塩基に解離し、酸は油として乳化粒子中に取り込まれるため、アニオン界面活性剤が存在しないか、存在していても微量と考えられる。
これを確認するため、本発明で得られる水中油型乳化化粧料（１）に油剤を添加する乳化確認試験を行った。
添加された油剤が乳化される大きさ（油滴の大きさ）は、水中油型乳化化粧料（１）に存在するアニオン界面活性剤の量に反比例する。アニオン界面活性剤が存在しない場合は、油剤は系内で分離し、また、微量しか存在しない場合も、活性能が弱いために、大きい油滴しかできず、結果として、平均粒径は大きくなり、特に、油滴を含む乳化粒子径の分布は、大粒径側を多く含むものとなると考えられる。
一方、界面活性剤量が増えるにしたがい、活性能が強くなるため、油滴の大きさは小さくなり、油滴を含む乳化粒子径の分布は、油剤を添加する前の乳化粒子径と差が小さくなると考えられる。
結果は、表４に示すとおり、実施例１では、乳化粒子径は、メジアン径である（Ｄ５０）、大粒径側の粒径割合を示す（Ｄ９０）が大きくなり、特に、油剤の添加後は、添加前に比較して、（Ｄ５０）は３．５倍であるのに対して、（Ｄ９０）は１７倍となり、非常に大きな油滴が形成されている、すなわち、活性剤が少ないこことが確認された。
これに対し、比較例６では、乳化粒子径（Ｄ５０）、（Ｄ９０）とも、油剤の添加前後での差が、（Ｄ５０）は１．６倍、（Ｄ９０）は２．２倍程度であり、活性能が強い、すなわち、活性剤が多いことが確認された。
他の実施例においても同様であると考えられる。
In the production method of the present invention, emulsification is performed using an anionic surfactant in step 1. However, in the emulsion finally obtained by lowering the pH of the emulsion in step 2, the anionic surfactant dissociates into an acid and a base, and the acid is incorporated into the emulsified particles as an oil. Anionic surfactants are not present, or even if they are present, they are considered to be in trace amounts.
In order to confirm this, an emulsification confirmation test was conducted in which an oil agent was added to the oil-in-water emulsified cosmetic (1) obtained in the present invention.
The size of the added oil that is emulsified (the size of the oil droplets) is inversely proportional to the amount of the anionic surfactant present in the oil-in-water emulsified cosmetic (1). In the absence of anionic surfactants, the oils separate in the system, and in the presence of only trace amounts, the weak activity results in only large oil droplets, resulting in a large average particle size. In particular, the distribution of the emulsified particle size including oil droplets is considered to include a large amount on the large particle size side.
On the other hand, as the amount of the surfactant increases, the activity becomes stronger, so that the size of the oil droplets becomes smaller, and the distribution of the emulsified particle size including the oil droplets is different from the emulsified particle size before the oil agent is added. It is thought to be smaller.
As a result, as shown in Table 4, in Example 1, the emulsified particle size is the median size (D50), and the particle size ratio on the large particle size side is increased (D90), particularly after the addition of the oil agent. (D50) is 3.5 times as much as (D90) is 17 times as much as before addition, and very large oil droplets are formed, that is, there are few activators here. Was confirmed.
On the other hand, in Comparative Example 6, the difference between the emulsified particle diameters (D50) and (D90) before and after the addition of the oil agent was about 1.6 times for (D50) and about 2.2 times for (D90). It was confirmed that the activity was strong, that is, there were many activators.
It is considered that the same applies to other examples.
実施例４〜２１
実施例１〜３と同様にして、表５〜表７に示す組成の水中油型乳化化粧料を製造し、水中油型乳化化粧料中の乳化粒子径（Ｄ５０）及び粘度を測定するとともに、保存安定性、さっぱり感を評価した。結果を表５〜表７に併せて示す。
Examples 4-21
In the same manner as in Examples 1 to 3, oil-in-water emulsified cosmetics having the compositions shown in Tables 5 to 7 were produced, and the emulsified particle size (D50) and viscosity in the oil-in-water emulsified cosmetics were measured, and at the same time. The storage stability and refreshing feeling were evaluated. The results are also shown in Tables 5 to 7.
Claims (5)
工程１：
（Ａ）一般式（１）
で表される有機酸塩及び炭素数１２〜２４の脂肪酸塩から選ばれる１種又は２種以上、
（Ｂ）アルキル変性された多糖類系ポリマー、Ｎ−アシルアルキレンイミンを繰り返し単位とする親水性セグメントと、オルガノポリシロキサンセグメントとを構成単位とするポリマー及びポリエーテル変性シリコーンから選ばれる１種又は２種以上の高分子、
（Ｃ）油剤、及び
（Ｄ）水
を含む組成物を混合して、乳化物を得る工程、
工程２：
工程１で得られた乳化物のｐＨを下げる工程。 A method for producing an oil-in-water emulsified cosmetic having the following steps.
Step 1:
(A) General formula (1)
One or more selected from organic acid salts represented by and fatty acid salts having 12 to 24 carbon atoms.
(B) One or 2 selected from an alkyl-modified polysaccharide polymer, a hydrophilic segment having N-acylalkyleneimine as a repeating unit, a polymer having an organopolysiloxane segment as a constituent unit, and a polyether-modified silicone. More than seed polymer,
Step of mixing (C) an oil agent and (D) a composition containing water to obtain an emulsion,
Step 2:
A step of lowering the pH of the emulsion obtained in step 1.
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