JPH026729B2 - - Google Patents
Info
- Publication number
- JPH026729B2 JPH026729B2 JP56010561A JP1056181A JPH026729B2 JP H026729 B2 JPH026729 B2 JP H026729B2 JP 56010561 A JP56010561 A JP 56010561A JP 1056181 A JP1056181 A JP 1056181A JP H026729 B2 JPH026729 B2 JP H026729B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- fatty acid
- branched
- water
- acid
- 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.)
- Expired
Links
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 42
- 239000000194 fatty acid Substances 0.000 claims description 42
- 229930195729 fatty acid Natural products 0.000 claims description 42
- -1 fatty acid cholesteryl ester Chemical class 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007762 w/o emulsion Substances 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- 239000006071 cream Substances 0.000 description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 22
- 150000004665 fatty acids Chemical class 0.000 description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- 239000011541 reaction mixture Substances 0.000 description 12
- 210000003491 skin Anatomy 0.000 description 12
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 239000008213 purified water Substances 0.000 description 10
- 229940099259 vaseline Drugs 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 229940057995 liquid paraffin Drugs 0.000 description 9
- 229940060184 oil ingredients Drugs 0.000 description 9
- WNWHHMBRJJOGFJ-UHFFFAOYSA-N 16-methylheptadecan-1-ol Chemical compound CC(C)CCCCCCCCCCCCCCCO WNWHHMBRJJOGFJ-UHFFFAOYSA-N 0.000 description 8
- 239000004166 Lanolin Substances 0.000 description 8
- 235000019388 lanolin Nutrition 0.000 description 8
- 229940039717 lanolin Drugs 0.000 description 8
- 235000019198 oils Nutrition 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 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 8
- 238000003756 stirring Methods 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol group Chemical group [C@@H]1(CC[C@H]2[C@@H]3CC=C4C[C@@H](O)CC[C@]4(C)[C@H]3CC[C@]12C)[C@H](C)CCCC(C)C HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- HIQIXEFWDLTDED-UHFFFAOYSA-N 4-hydroxy-1-piperidin-4-ylpyrrolidin-2-one Chemical compound O=C1CC(O)CN1C1CCNCC1 HIQIXEFWDLTDED-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- UGMCXQCYOVCMTB-UHFFFAOYSA-K dihydroxy(stearato)aluminium Chemical compound CCCCCCCCCCCCCCCCCC(=O)O[Al](O)O UGMCXQCYOVCMTB-UHFFFAOYSA-K 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 229910001651 emery Inorganic materials 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000037323 metabolic rate Effects 0.000 description 4
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 4
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 description 4
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 4
- 229960002216 methylparaben Drugs 0.000 description 4
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 229940032094 squalane Drugs 0.000 description 4
- MBGYSHXGENGTBP-UHFFFAOYSA-N 6-(2-ethylhexoxy)-6-oxohexanoic acid Chemical compound CCCCC(CC)COC(=O)CCCCC(O)=O MBGYSHXGENGTBP-UHFFFAOYSA-N 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000012000 cholesterol Nutrition 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 230000037336 dry skin Effects 0.000 description 3
- 230000029142 excretion Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 235000010232 propyl p-hydroxybenzoate Nutrition 0.000 description 3
- 239000004405 propyl p-hydroxybenzoate Substances 0.000 description 3
- QELSKZZBTMNZEB-UHFFFAOYSA-N propylparaben Chemical compound CCCOC(=O)C1=CC=C(O)C=C1 QELSKZZBTMNZEB-UHFFFAOYSA-N 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 150000004671 saturated fatty acids Chemical class 0.000 description 3
- 125000002345 steroid group Chemical group 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 208000024891 symptom Diseases 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- NBBOKGSPCURQHM-UHFFFAOYSA-N 1-chloro-16-methylheptadecane Chemical compound CC(C)CCCCCCCCCCCCCCCCl NBBOKGSPCURQHM-UHFFFAOYSA-N 0.000 description 2
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 2
- LFDKQJVNMJFNGG-UHFFFAOYSA-N 16-methylheptadecanoyl chloride Chemical compound CC(C)CCCCCCCCCCCCCCC(Cl)=O LFDKQJVNMJFNGG-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000007869 Guerbet synthesis reaction Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005882 aldol condensation reaction Methods 0.000 description 2
- POJWUDADGALRAB-UHFFFAOYSA-N allantoin Chemical compound NC(=O)NC1NC(=O)NC1=O POJWUDADGALRAB-UHFFFAOYSA-N 0.000 description 2
- 239000002260 anti-inflammatory agent Substances 0.000 description 2
- 229940121363 anti-inflammatory agent Drugs 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000000787 lecithin Substances 0.000 description 2
- 235000010445 lecithin Nutrition 0.000 description 2
- 229940067606 lecithin Drugs 0.000 description 2
- 239000002075 main ingredient Substances 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002674 ointment Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 description 2
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 description 2
- NEOZOXKVMDBOSG-UHFFFAOYSA-N propan-2-yl 16-methylheptadecanoate Chemical compound CC(C)CCCCCCCCCCCCCCC(=O)OC(C)C NEOZOXKVMDBOSG-UHFFFAOYSA-N 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 230000001225 therapeutic effect Effects 0.000 description 2
- 229940088594 vitamin Drugs 0.000 description 2
- 239000011782 vitamin Substances 0.000 description 2
- 235000013343 vitamin Nutrition 0.000 description 2
- 229930003231 vitamin Natural products 0.000 description 2
- CUNWUEBNSZSNRX-RKGWDQTMSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;(z)-octadec-9-enoic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O CUNWUEBNSZSNRX-RKGWDQTMSA-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
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- QBTIHZIVENIGSW-UHFFFAOYSA-N 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctanoic acid Chemical compound CC(C)(C)CC(C)CCC(C(O)=O)C(C)CC(C)(C)C QBTIHZIVENIGSW-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
- UBHGDYHAWJOMOF-UHFFFAOYSA-N 2-[[2-hydroxy-2-(hydroxymethyl)-18-methylnonadecoxy]methyl]-18-methylnonadecane-1,2-diol Chemical compound C(CCCCCCCCCCCCCCC(C)C)C(COCC(O)(CO)CCCCCCCCCCCCCCCC(C)C)(O)CO UBHGDYHAWJOMOF-UHFFFAOYSA-N 0.000 description 1
- KUIYXYIWGVFQPD-UHFFFAOYSA-N 2-octyldodecanoic acid Chemical compound CCCCCCCCCCC(C(O)=O)CCCCCCCC KUIYXYIWGVFQPD-UHFFFAOYSA-N 0.000 description 1
- YNXFWNKTAOTVGR-UHFFFAOYSA-N 2-pentylnonanoic acid Chemical compound CCCCCCCC(C(O)=O)CCCCC YNXFWNKTAOTVGR-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
- VTDOEFXTVHCAAM-UHFFFAOYSA-N 4-methylpent-3-ene-1,2,3-triol Chemical compound CC(C)=C(O)C(O)CO VTDOEFXTVHCAAM-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- POJWUDADGALRAB-PVQJCKRUSA-N Allantoin Natural products NC(=O)N[C@@H]1NC(=O)NC1=O POJWUDADGALRAB-PVQJCKRUSA-N 0.000 description 1
- 241001340526 Chrysoclista linneella Species 0.000 description 1
- ZAKOWWREFLAJOT-CEFNRUSXSA-N D-alpha-tocopherylacetate Chemical compound CC(=O)OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C ZAKOWWREFLAJOT-CEFNRUSXSA-N 0.000 description 1
- 239000011626 DL-alpha-tocopherylacetate Substances 0.000 description 1
- 235000001809 DL-alpha-tocopherylacetate Nutrition 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010020649 Hyperkeratosis Diseases 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 208000001126 Keratosis Diseases 0.000 description 1
- 240000008415 Lactuca sativa Species 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
- 239000004264 Petrolatum Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229960000458 allantoin Drugs 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000000043 antiallergic agent Substances 0.000 description 1
- 208000010668 atopic eczema Diseases 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- YZIYKJHYYHPJIB-UUPCJSQJSA-N chlorhexidine gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O.C1=CC(Cl)=CC=C1NC(=N)NC(=N)NCCCCCCNC(=N)NC(=N)NC1=CC=C(Cl)C=C1 YZIYKJHYYHPJIB-UUPCJSQJSA-N 0.000 description 1
- 229960003333 chlorhexidine gluconate Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 210000000245 forearm Anatomy 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000011874 heated mixture Substances 0.000 description 1
- XJNUECKWDBNFJV-UHFFFAOYSA-N hexadecyl 2-ethylhexanoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(CC)CCCC XJNUECKWDBNFJV-UHFFFAOYSA-N 0.000 description 1
- JMOLZNNXZPAGBH-UHFFFAOYSA-N hexyldecanoic acid Chemical compound CCCCCCCCC(C(O)=O)CCCCCC JMOLZNNXZPAGBH-UHFFFAOYSA-N 0.000 description 1
- 229950004531 hexyldecanoic acid Drugs 0.000 description 1
- 239000008309 hydrophilic cream Substances 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229940093629 isopropyl isostearate Drugs 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001333 moisturizer Effects 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002889 oleic acids Chemical class 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000012045 salad Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 208000017520 skin disease Diseases 0.000 description 1
- 230000036620 skin dryness Effects 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 229960005078 sorbitan sesquioleate Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 210000000434 stratum corneum Anatomy 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229940042585 tocopherol acetate Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/63—Steroids; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/064—Water-in-oil emulsions, e.g. Water-in-silicone emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/34—Alcohols
- A61K8/345—Alcohols containing more than one hydroxy group
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/007—Preparations for dry skin
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Dermatology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Dispersion Chemistry (AREA)
- Cosmetics (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Medicinal Preparation (AREA)
Description
本発明は油中水型(W/O)エマルシヨンに関
し、詳しくはα−モノグリセリルエーテルと特定
のコレステリルエステルを含有し、特に乾燥皮膚
の保護あるいは治療用に適当な油中水型エマルシ
ヨンに関する。
冬季の外気条件、陶磁器類の洗浄、家庭におけ
る雑用等により、特に女性の皮膚にはヒビ、アカ
ギレ、肌荒れを生じ易く、主婦湿疹、進行性指掌
角皮症などを悪化させることが知られている。こ
のような乾燥性皮膚疾患の改善、治療の為に種々
のクリーム、軟膏類が開発、上市されているのも
かかわらず顕著な効果のあるクリーム、軟膏は見
出しがたい。
皮膚の乾燥症状の主な原因として皮表脂質の減
少、角質層内水分の減少の2つがあることがほぼ
定説となつている。このことより皮表水分蒸散を
抑制できる、即ち水分閉塞性のあるクリーム基剤
は皮膚乾燥症状を軽減、治癒する効果の高いこと
が考えられる。このような目的の為にワセリン、
ラノリン等は油成分として多く使用されている
が、これらは水分閉塞効果が高いにもかかわら
ず、べたついた感じがするため好まれないという
傾向にあり、事実調査によると肌の荒れている人
ほどクリームはさらつとして、伸びが良く、肌に
なじみ、なめらかであるものが良いという結果が
得られている(日本化粧品技術者連合会会誌、6
(2)21−27(1970))。また水中油型(O/W)クリ
ームは、親水性乳化剤の使用により水分閉塞効果
が下げられ、また撥水性が劣ることにより当然の
ことながらクリーム基剤による治療効果は低いも
のとなる欠点がある。
本発明者らは乾燥症状を伴う皮膚疾患の治療効
果を高める皮表水分蒸散抑制効果即ち水分閉塞効
果が高くしかもべたつきが少ない油中水型エマル
シヨンを得るべく鋭意研究した結果、α−モノグ
リセリルエーテルと特定の分岐脂肪酸コレステリ
ルエステルを併用することによりこの目的が達成
されることを見出し本発明を完成した。
すなわち本発明は、
式();
〔式中Rは次の式()
(式中mは2ないし14の整数、nは3ないし11の
整数であり、mとnの和は9ないし21である)
で表される分岐鎖アルキル基である〕
で表されるα−モノグリセリルエーテルと式
();
(式中R′は合計11〜23個の炭素原子を有し、カ
ルボキシル結合位から主鎖の中央までに、少なく
とも1つのアルキル置換基を有する飽和脂肪族炭
化水素基である)
で表される分岐脂肪酸コレステリルエステルを含
有することを特徴とする油中水型エマルシヨン
を提供するものである。
式()で表わされるモノメチル分岐アルキル
基を有するモノグリセリルエーテルは、例えばオ
レイン酸等の不飽和酸のダイマー製造時の副産物
として得られる(例えばJ.Amer.Oil Chem.Soc.、
51、522(1974))上記式を有するカルボン酸を還
元してアルコールとし、これから導くことができ
る(特願昭54−113188)。
式()で表わされるα−モノグリセリルエー
テルのうちでは、分岐鎖アルキル基を有するも
の、特に式()で表わされるモノメチル分岐ア
ルキル基を有するものが本発明の目的上好適であ
る。
本発明で使用される分岐脂肪酸コレステリルエ
ステルは、次の式()で表わされる。
(式中R′は合計11〜23個の炭素原子を有し、カ
ルボキシル結合位から主鎖の中央までに少くとも
1つのアルキル置換基を有する飽和脂肪族炭化水
素基である)
本発明の分岐脂肪酸コレステリルエステルの製
造に用いられる分岐脂肪酸(R′COOH)は、炭
素数12〜24(R′としての炭素数として11ないし
23)のものが使用できるが、炭素数14〜20(R′と
しての炭素数13〜19)のものが好ましい。
分岐脂肪酸は、カルボキシル基結合位から主鎖
の中央までに少くとも1つのアルキル置換基を有
する飽和分岐脂肪酸である。このような飽和分岐
脂肪酸は、石油化学工業原料又は油脂化学工業原
料より容易に得られる。
石油化学工業原料より得られるこのような分岐
脂肪酸の例としては、α位に側鎖を有する分岐脂
肪酸があり、次式()で表わされる。
(式中R1及びR2はそれぞれ直鎖又は分岐鎖の飽
和脂肪族炭化水素基であり、R1及びR2の炭素原
子数の和は、12〜18である)
上記の式()で表わされるα位に側鎖を有す
る分岐脂肪酸は、例えば炭素数7〜10の直鎖又は
分岐鎖のアルデヒドのアルドール縮合によりα−
分岐不飽和アルデヒドとし、次いでこれを水素添
加、酸化させて分岐飽和脂肪酸とする方法によつ
て製造することができる。この方法によつて製造
される最も入手し易い分岐飽和脂肪酸は、イソブ
チレン2量体のオキソ反応により炭素数9の分岐
アルデヒドとし、次いでこのアルデヒドのアルド
ール縮合により炭素数18の分岐不飽和アルデヒド
とし、次いで水素添加、酸化により得られる炭素
数18の分岐脂肪酸、5,7,7−トリメチル−2
−(1,3,3−トリメチルブチル)−オクタン酸
〔例えば日産化学(株)より市販されている〕である。
上記の式で表わされるα位に側鎖を有する分岐
脂肪酸は、また、炭素数7〜10の直鎖又は分岐鎖
1級アルコールのゲルベ反応
(Guerbetreaction)によりβ−分岐アルコール
とし、次いでこれを酸化することにより得られ
る。この方法によつて製造することができる最も
入手し易い分岐飽和脂肪酸は、ノニルアルコール
のゲルベ反応、続いて酸化反応により得られる2
−ヘプチルウンデカン酸〔例えば三菱化成(株)より
市販されている〕である。
上記の式()で表わされるα位に側鎖を有す
る分岐脂肪酸は、上述のいずれかの方法により製
造されたもので良く、さらに他のいずれかの方法
(例えば炭素数13〜19を有するオレフインのオキ
ソ反応によりα位に側鎖を有するアルデヒドと
し、次いでこれを酸化する等の方法)によるかを
問わず本発明において使用することができる。
α位に側鎖を有する飽和分岐脂肪酸の好ましい
具体例としては、上記の5,7,7−トリメチル
−2−(1,3,3−トリメチルブチル)−オクタ
ン酸、2−ヘブチルウンデカン酸の他に、2−ヘ
キシルデカン酸、2−オクチルドデカン酸、2−
ペンチルノナン酸等がある。
油脂化学工業原料より得られる飽和分岐脂肪酸
の例としては、次の式()で表わされるメチル
分岐鎖を有する脂肪酸がある。
(式中m′とn′の和は14であり、m′=n′=7を中心
とする分布を有する)
このようなメチル分岐鎖脂肪酸は、例えばオレ
イン酸のダイマー製造時の副産物として得られ
(例えば、J・Amer・Oil Chem・Soc..、51、
522(1974))、本明細書中では、メチル分岐イソス
テアリン酸と称する。メチル分岐イソステアリン
酸は、例えばそのイソプロピルエステルとして市
販されている(米国エメリー社など)。
本発明の分岐脂肪酸コレステリルエステルは、
上記の分岐脂肪酸又はその誘導体とコレステロー
ルから通常のエステルを製造する方法によつて製
造される。脂肪酸とコレステロールをそのまま反
応させてエステル化することもできるし、いずれ
か一方をより反応性の高い誘導体(例えば酸ハラ
イド)に導き次いでエステル化することもでき
る。これらの分岐脂肪酸コレステリルエステルは
新規物質であり、既に特許出願した(特願昭54−
139788)。
本発明の油中水型エマルシヨン中には、式
()で表わされるα−モノグリセリルエーテル
を0.1〜10.0wt.%、好ましくは0.5〜5.0wt.%、ま
た式()で表わされる分岐コレステリルエステ
ルを0.5〜25.0wt.%、好ましくは2〜15wt.%配合
するのが適当である。
本発明の油中水型エマルシヨンを調製するに当
つては、上記必須成分の他に、油成分としてワセ
リン、ラノリン、流動パラフイン、天然油脂、高
級脂肪酸アルキルエステル、高級脂肪族アルコー
ル、高級脂肪酸、スクワラン等を1〜80wt.%加
えることができる。α−モノグリセリルエーテル
自身が乳化剤であるので特に他の乳化剤を必要と
しないが、乳化剤又は乳化安定剤としてレシチ
ン、ソルビタン脂肪酸エステル、脂肪酸モノグリ
セリド、脂肪酸金属塩、硫酸マグネシウム等を
0.5〜20wt.%加えることができる。残部は主に水
である。
本発明の油中水型エマルシヨンは、種々の目的
のために使用することができるが、皮膚外用薬基
剤、皮膚化粧料等に使用するのに特に適してい
る。皮膚外用基剤として使用する場合には、通常
さらに抗炎症剤、殺菌剤、抗アレルギー剤、ビタ
ミン剤、保湿剤等の薬剤を0.001〜30wt.%配合す
る。また皮膚化粧料として使用する場合にはさら
に香料等を配合する。
本発明によれば、α−モノグリセリルエーテル
と分岐脂肪酸コレステリルエステルとを組み合わ
せることにより、水分蒸散抑制効果即ち水分閉塞
効果が高められると同時に、この水分閉塞効果を
低下させることなくべたつきも軽減される。
以下に本発明を実施例をもつて説明する。併せ
て実施例で使用する新規物質の製造法を参考例と
して示した。
参考例 1
20オートクレーブに、イソステアリン酸イソ
プロピルエステル〔エメリー(Emery)2310イ
ソステアリン酸イソプロピルエステル、米国エメ
リー社より市販されている〕4770g及び銅クロム
触媒(日揮製)239gを仕込む。つぎに、150Kg/
cm2の圧力にて水素ガスを充填せしめ、次いで反応
混合物を275℃に加熱昇温させる。150Kg/cm2/
275℃で約7時間水素添加した後、反応生成物を
冷却して、触媒残渣をろ別により除き、粗生成物
3500gを得た。粗生成物を減圧蒸留することによ
り、80〜167℃/0.6mmHgの留分として、無色透
明のイソステアリルアルコール3300gを得た。得
られたイソステアリルアルコール(メチル分岐イ
ソステアリルアルコール)は、酸価0.05、ケン化
価5.5、水酸基価181.4を示した。IR(液膜)にお
いては3340、1055cm-1に、NMR(CCl4溶媒)に
おいてはδ3.50(ブロード三重線、−CH2−OH)に
それぞれ吸収を示した。このアルコールの主成分
は、そのガスクロマトグラフからアルキル基の合
計炭素数が18(式におけるmとnの和が15)で
あるものが約75%を占め、残りの成分は、合計炭
素数14、16のものであり、分岐メチル基はいずれ
もアルキル主鎖の中央部付近に位置するものの混
合物であることがわかつた。
参考例 2
(i) 温度計、還流冷却器、滴下ろうと、窒素ガス
導入管、及び攪拌器を備えた容量5の反応容
器に、参考例1で得られたイソステアリルアル
コール2444gを仕込んだ。攪拌しながら、窒素
ガス通気下に、滴下ろうとより塩化チオニルを
室温で滴下した。反応混合物は発熱し、同時に
ガスを発生した。反応混合物の温度は、反応初
期には31℃まで上昇するが、塩化チオニルの添
加量が増すに従つて次第に低下し、18℃付近ま
で低下した。ここで反応混合物を約40℃に加熱
昇温して、さらに塩化チオニルの滴下を続け
た。ガスの発生が弱くなつた後、反応混合物を
70〜80℃に加熱昇温したところ再びガスの発生
が激しくなつたので、塩化チオニルを引き続き
滴下した。ガスの発生が全く認められなくなつ
た時点で塩化チオニルの滴下を止めた。滴下し
た塩化チオニルの総量は2200gであつた。反応
生成物を冷却し、さらに70〜80℃で約1時間攪
拌を継続した。
反応生成物を冷却し、常圧下、40〜50℃で低
沸点留分(主に未反応塩化チオニル)を留去
し、残渣を氷冷し、攪拌しながら氷塊を少量ず
つ加えた。激しいガスの発生が止まつた事を確
認して、エーテルを加え、さらに水を加えて十
分攪拌した。エーテル層を分取し、重炭酸ナト
リウムで中和し、溶媒を留去した後、減圧蒸留
して、103〜163℃/0.1〜1.0mmHgの留分からイ
ソステアリルクロライド2217gを得た。
IR(液膜):725、650cm-1
NMR(CCl4):δ3.50(三重線−CH2Cl)
(ii) 温度計、攪拌器、滴下ろうと及びデイーンス
タークトラツプを備えた容量5の反応容器
に、イソプロピリデングリセロール798g、キ
シレン1500ml、93%水酸化ナトリウム340g及
び水300gを仕込み、攪拌しながら130〜140℃
で加熱還流した。留出する水/キシレン混合物
から、デイーンスタークトラツプ中で水を分離
して反応系外へ除き、キシレンを反応系に戻し
た。約16時間の加熱還流の後、水の留出が認め
られなくなつた時点で、滴下ろうとより、(i)で
製造したイソステアリルクロライド777gを約
30分を要して滴下した。滴下終了後、反応混合
物をさらに約9時間130〜140℃で加熱還流して
反応を完結させた。冷却後、反応器中に沈澱し
た塩化ナトリウムをろ別除去し、減圧下に溶媒
を留去し、次いで176〜206℃/0.25〜0.50mmHg
の留分800gを得た。これは2,3−O−イソ
プロピリデン−1−O−イソステアリルグリセ
リルエーテルである。
IR(液膜):cm-1
1200〜1260、1050〜1120(C−O伸縮振動)
NMR(CCl4):δ3.1〜4.2(多重線、
The present invention relates to water-in-oil (W/O) emulsions, and more particularly to water-in-oil emulsions containing α-monoglyceryl ether and specific cholesteryl esters, and which are particularly suitable for the protection or treatment of dry skin. Women's skin is especially susceptible to cracks, redness, and rough skin due to outdoor air conditions in winter, washing chinaware, and household chores, and is known to worsen housewife's eczema and progressive palmar keratoderma. There is. Although various creams and ointments have been developed and put on the market to improve and treat such dry skin diseases, it is difficult to find any cream or ointment that is particularly effective. It is almost an established theory that the main causes of dry skin symptoms are a decrease in skin surface lipids and a decrease in moisture within the stratum corneum. This suggests that cream bases that can suppress water evaporation from the skin surface, that is, have water-occlusive properties, are highly effective in alleviating and curing skin dryness symptoms. Vaseline for this purpose,
Lanolin and other oils are often used as oil ingredients, but although they have a high water-occluding effect, they tend not to be liked because they have a sticky feel. Results have shown that creams that are silky, spread well, blend well with the skin, and are smooth are best (Journal of the Japan Cosmetic Engineers Association, 6)
(2)21-27 (1970)). In addition, oil-in-water (O/W) creams have the disadvantage that the use of hydrophilic emulsifiers reduces the water occlusion effect, and that the therapeutic effects of cream bases are naturally lower due to poor water repellency. . The present inventors conducted intensive research to obtain a water-in-oil emulsion that has a high skin surface water evaporation suppressing effect, that is, a water occlusion effect that enhances the therapeutic effect of skin diseases accompanied by dryness symptoms, and is less sticky. The present invention was completed based on the discovery that this object could be achieved by using a specific branched fatty acid cholesteryl ester in combination with a specific branched fatty acid cholesteryl ester. That is, the present invention has the following formula: [In the formula, R is the following formula () (In the formula, m is an integer of 2 to 14, n is an integer of 3 to 11, and the sum of m and n is 9 to 21.) Monoglyceryl ether and formula (); (wherein R' is a saturated aliphatic hydrocarbon group having a total of 11 to 23 carbon atoms and having at least one alkyl substituent from the carboxyl bond position to the center of the main chain) A water-in-oil emulsion characterized by containing a branched fatty acid cholesteryl ester is provided. Monoglyceryl ether having a monomethyl branched alkyl group represented by the formula () is obtained, for example, as a by-product during dimer production of unsaturated acids such as oleic acid (for example, J.Amer.Oil Chem.Soc.
51, 522 (1974)) The carboxylic acid having the above formula is reduced to an alcohol, which can be derived from this (Japanese Patent Application No. 113,188/1988). Among the α-monoglyceryl ethers represented by formula (), those having a branched alkyl group, particularly those having a monomethyl branched alkyl group represented by formula (), are suitable for the purpose of the present invention. The branched fatty acid cholesteryl ester used in the present invention is represented by the following formula (). (In the formula, R′ is a saturated aliphatic hydrocarbon group having a total of 11 to 23 carbon atoms and having at least one alkyl substituent from the carboxyl bond position to the center of the main chain) Branches of the present invention Branched fatty acids (R′COOH) used in the production of fatty acid cholesteryl esters have 12 to 24 carbon atoms (11 to 24 carbon atoms as R′).
23) can be used, but those having 14 to 20 carbon atoms (13 to 19 carbon atoms as R') are preferable. A branched fatty acid is a saturated branched fatty acid having at least one alkyl substituent from the carboxyl group bonding position to the center of the main chain. Such saturated branched fatty acids can be easily obtained from petrochemical raw materials or oleochemical raw materials. An example of such a branched fatty acid obtained from petrochemical raw materials is a branched fatty acid having a side chain at the α position, which is represented by the following formula (). (In the formula, R 1 and R 2 are each a linear or branched saturated aliphatic hydrocarbon group, and the sum of the number of carbon atoms of R 1 and R 2 is 12 to 18.) In the above formula () The branched fatty acid having a side chain at the α-position can be obtained by, for example, aldol condensation of a linear or branched aldehyde having 7 to 10 carbon atoms.
It can be produced by forming a branched unsaturated aldehyde and then hydrogenating and oxidizing this to form a branched saturated fatty acid. The most easily available branched saturated fatty acid produced by this method is a branched aldehyde having 9 carbon atoms through the oxo reaction of an isobutylene dimer, and then a branched unsaturated aldehyde having 18 carbon atoms by aldol condensation of this aldehyde. Next, a branched fatty acid having 18 carbon atoms, 5,7,7-trimethyl-2, obtained by hydrogenation and oxidation.
-(1,3,3-trimethylbutyl)-octanoic acid (commercially available, for example, from Nissan Chemical Co., Ltd.). The branched fatty acid having a side chain at the α-position represented by the above formula can also be converted into a β-branched alcohol by Guerbet reaction of a linear or branched primary alcohol having 7 to 10 carbon atoms, and then oxidized. It can be obtained by The most readily available branched saturated fatty acids that can be produced by this method are those obtained by the Guerbet reaction of nonyl alcohol followed by an oxidation reaction.
-heptylundecanoic acid (commercially available, for example, from Mitsubishi Kasei Corporation). The branched fatty acid having a side chain at the α-position represented by the above formula () may be produced by any of the methods described above, or may be produced by any other method (for example, an olefin having 13 to 19 carbon atoms). It can be used in the present invention regardless of the method (such as a method in which an aldehyde having a side chain at the α-position is formed by an oxo reaction of Preferred specific examples of saturated branched fatty acids having a side chain at the α-position include the above-mentioned 5,7,7-trimethyl-2-(1,3,3-trimethylbutyl)-octanoic acid and 2-hebutylundecanoic acid. In addition, 2-hexyldecanoic acid, 2-octyldodecanoic acid, 2-
Examples include pentylnonanoic acid. An example of a saturated branched fatty acid obtained from oleochemical raw materials is a fatty acid having a methyl branched chain represented by the following formula (). (In the formula, the sum of m' and n' is 14, and the distribution is centered around m' = n' = 7.) Such methyl branched chain fatty acids are obtained, for example, as a by-product during the production of oleic acid dimer. (e.g., J. Amer. Oil Chem. Soc.., 51 ,
522 (1974)), herein referred to as methyl branched isostearic acid. Methyl branched isostearic acid is commercially available, for example as its isopropyl ester (eg Emery, USA). The branched fatty acid cholesteryl ester of the present invention is
It is produced by a conventional method for producing esters from the above-mentioned branched fatty acids or derivatives thereof and cholesterol. A fatty acid and cholesterol can be reacted as they are to esterify them, or either one can be converted into a more reactive derivative (for example, an acid halide) and then esterified. These branched fatty acid cholesteryl esters are new substances, and a patent application has already been filed for them (patent application filed in 1983).
139788). The water-in-oil emulsion of the present invention contains 0.1 to 10.0 wt.%, preferably 0.5 to 5.0 wt.%, of α-monoglyceryl ether represented by the formula (), and branched cholesteryl ester represented by the formula (). It is appropriate to blend 0.5 to 25.0 wt.%, preferably 2 to 15 wt.%. In preparing the water-in-oil emulsion of the present invention, in addition to the above-mentioned essential ingredients, petrolatum, lanolin, liquid paraffin, natural oils, higher fatty acid alkyl esters, higher fatty alcohols, higher fatty acids, and squalane are used as oil components. etc. can be added in an amount of 1 to 80 wt.%. Since α-monoglyceryl ether itself is an emulsifier, it does not require any other emulsifier, but lecithin, sorbitan fatty acid ester, fatty acid monoglyceride, fatty acid metal salt, magnesium sulfate, etc. may be used as an emulsifier or emulsion stabilizer.
0.5-20wt.% can be added. The remainder is mainly water. Although the water-in-oil emulsion of the present invention can be used for various purposes, it is particularly suitable for use in skin external drug bases, skin cosmetics, and the like. When used as an external skin base, 0.001 to 30 wt.% of drugs such as anti-inflammatory agents, bactericidal agents, anti-allergic agents, vitamins, and moisturizers are usually added. Further, when used as a skin cosmetic, fragrances and the like are further added. According to the present invention, by combining α-monoglyceryl ether and branched fatty acid cholesteryl ester, the water evaporation suppressing effect, that is, the water occlusion effect is enhanced, and at the same time, the stickiness is reduced without reducing this water occlusion effect. . The present invention will be explained below using examples. In addition, a method for producing a new substance used in the Examples is shown as a reference example. Reference Example 1 4770 g of isostearate isopropyl ester (Emery 2310 isopropyl isostearate, commercially available from Emery Company, USA) and 239 g of a copper chromium catalyst (manufactured by JGC) are placed in a 20-meter autoclave. Next, 150Kg/
Fill with hydrogen gas at a pressure of cm 2 and then heat the reaction mixture to 275°C. 150Kg/ cm2 /
After hydrogenation at 275°C for about 7 hours, the reaction product was cooled and the catalyst residue was removed by filtration to obtain the crude product.
Obtained 3500g. The crude product was distilled under reduced pressure to obtain 3300 g of colorless and transparent isostearyl alcohol as a fraction of 80 to 167°C/0.6 mmHg. The obtained isostearyl alcohol (methyl branched isostearyl alcohol) had an acid value of 0.05, a saponification value of 5.5, and a hydroxyl value of 181.4. It showed absorption at 3340 and 1055 cm -1 in IR (liquid film) and at δ3.50 (broad triplet, -CH 2 -OH) in NMR (CCl 4 solvent). As for the main component of this alcohol, approximately 75% has an alkyl group with a total carbon number of 18 (the sum of m and n in the formula is 15), and the remaining components have a total carbon number of 14, It was found that all of the branched methyl groups were a mixture of those located near the center of the alkyl main chain. Reference Example 2 (i) 2444 g of isostearyl alcohol obtained in Reference Example 1 was charged into a reaction vessel with a capacity of 5 equipped with a thermometer, a reflux condenser, a dropping funnel, a nitrogen gas inlet tube, and a stirrer. While stirring, thionyl chloride was added dropwise from a dropping funnel at room temperature under nitrogen gas flow. The reaction mixture exothermed and evolved gas at the same time. The temperature of the reaction mixture rose to 31°C at the beginning of the reaction, but gradually decreased to around 18°C as the amount of thionyl chloride added increased. At this point, the reaction mixture was heated to about 40° C., and thionyl chloride was continued to be added dropwise. After gas evolution has subsided, the reaction mixture is
When the temperature was raised to 70 to 80°C, gas generation became intense again, so thionyl chloride was successively added dropwise. The dropping of thionyl chloride was stopped when no gas was observed to be generated at all. The total amount of thionyl chloride added dropwise was 2200 g. The reaction product was cooled, and stirring was continued for about 1 hour at 70-80°C. The reaction product was cooled, and the low-boiling fraction (mainly unreacted thionyl chloride) was distilled off at 40 to 50° C. under normal pressure. The residue was ice-cooled, and ice cubes were added little by little while stirring. After confirming that the intense gas generation had stopped, ether was added, then water was added, and the mixture was thoroughly stirred. The ether layer was separated, neutralized with sodium bicarbonate, the solvent was distilled off, and then distilled under reduced pressure to obtain 2217 g of isostearyl chloride from the fraction at 103-163°C/0.1-1.0 mmHg. IR (liquid film): 725, 650 cm -1 NMR (CCl 4 ): δ 3.50 (triplet line - CH 2 Cl) (ii) Capacity 5 with thermometer, stirrer, addition funnel and Dean Stark trap. 798 g of isopropylidene glycerol, 1500 ml of xylene, 340 g of 93% sodium hydroxide, and 300 g of water were placed in a reaction vessel, and heated to 130-140°C while stirring.
The mixture was heated to reflux. Water was separated from the distilled water/xylene mixture in a Dean Stark trap and removed from the reaction system, and xylene was returned to the reaction system. After heating under reflux for about 16 hours, when no more water was observed to be distilled out, about 777 g of isostearyl chloride produced in (i) was added to the dropping funnel.
It took 30 minutes to drip. After the dropwise addition was completed, the reaction mixture was further heated under reflux at 130 to 140° C. for about 9 hours to complete the reaction. After cooling, the sodium chloride precipitated in the reactor was removed by filtration, the solvent was distilled off under reduced pressure, and then 176-206℃/0.25-0.50mmHg
800g of fraction was obtained. This is 2,3-O-isopropylidene-1-O-isostearyl glyceryl ether. IR (liquid film): cm -1 1200-1260, 1050-1120 (C-O stretching vibration) NMR (CCl 4 ): δ3.1-4.2 (multiplet,
【式】)
(iii) 攪拌器、温度計、還流冷却器を備えた容量5
の反応容器に、(ii)で得られたイソプロピリデ
ンイソステアリルグリセリルエーテル1103gを
仕込み、これにエタノール1500ml及び0.1規定
硫酸2000mlを加えた。混合物を攪拌しながら80
〜85℃で加熱還流し、約10時間後に、ガスクロ
マトグラフによつて追跡し、イソプロピリデン
イソステアリルグリセリルエーテルの加水分解
が完全に行なわれていることが認められた。放
冷後、静置して油層と水層に分離した。水層を
エーテルで抽出し、先の油層と併せて、重炭酸
ナトリウム溶液を加えて残存する酸を中和し
た。有機層を分取後、減圧下で溶媒を留去し、
さらに100℃/0.1mmHgで3時間加熱乾燥した。
無色透明液体のα−モノ(イソステアリル)グ
リセリルエーテル900gが得られた。
IR(液膜):3400、1050〜1140cm-1
NMR(CCl4):δ3.2〜3.8(多重線、
[Formula]) (iii) Capacity 5 equipped with stirrer, thermometer and reflux condenser
1,103 g of isopropylidene isostearyl glyceryl ether obtained in step (ii) was placed in a reaction vessel, and 1,500 ml of ethanol and 2,000 ml of 0.1N sulfuric acid were added thereto. 80 while stirring the mixture
The mixture was heated to reflux at ~85°C, and after about 10 hours, it was observed by gas chromatography that the isopropylidene isostearyl glyceryl ether was completely hydrolyzed. After cooling, the mixture was allowed to stand still and separated into an oil layer and an aqueous layer. The aqueous layer was extracted with ether, combined with the previous oil layer, and sodium bicarbonate solution was added to neutralize the remaining acid. After separating the organic layer, the solvent was distilled off under reduced pressure,
Further, it was dried by heating at 100°C/0.1mmHg for 3 hours.
900 g of α-mono(isostearyl)glyceryl ether as a colorless transparent liquid was obtained. IR (liquid film): 3400, 1050~1140cm -1 NMR ( CCl4 ): δ3.2~3.8 (multiplet,
【式】)
酸価:0.08、ケン化価:0.36、水酸基価:
313.8、ヨウ素価:0.32
参考例 3
温度計、還流冷却器、滴下ろうと、攪拌器を備
えた容量3の反応容器に、イソステアリン酸
(式で表わされるメチル分岐脂肪酸であつて
Emery875イソステアリン酸として市販されてい
る)568g(2.0モル)を仕込んだ。攪拌しなが
ら、窒素ガス通気下で、滴下ろうとより塩化チオ
ニル520g(4.4モル)を室温で滴下した。塩化チ
オニルの滴下が進行するに従つて、反応混合物
は、無色、淡黄色、黒かつ色に着色し、同時にガ
スの発生が認められた。塩化チオニルの滴下中、
反応混合物の温度を室温に保つた。塩化チオニル
を約3時間を要して滴下した後、油浴にて反応混
合物を60〜70℃に約3時間保つた。ガスの発生が
ほとんど認められなくなつた事を確認後、減圧下
で低沸点物を留去した後、減圧蒸留により、153
〜170℃/1.0〜3.0mmHgの留分454g(収率75%)
を得た。このものはメチル分岐イソステアリン酸
クロライドであつた。
IRスペクトル(液膜法)
2950、2920、2850、1800(C=O伸縮)、1460、
1400、1380、950、720、680、590cm-1
H1−NMRスペクトル(CCl4):δ
0.6〜1.0(m、CH3 CH2−及び[Formula]) Acid value: 0.08, saponification value: 0.36, hydroxyl value:
313.8, iodine value: 0.32 Reference example 3 In a reaction vessel with a capacity of 3 equipped with a thermometer, reflux condenser, dropping funnel, and stirrer, isostearic acid (a methyl branched fatty acid represented by the formula
568 g (2.0 mol) of Emery 875 isostearic acid (commercially available as Emery 875 isostearic acid) was charged. While stirring, 520 g (4.4 mol) of thionyl chloride was added dropwise from a dropping funnel at room temperature under nitrogen gas flow. As the dropwise addition of thionyl chloride progressed, the reaction mixture changed from colorless to pale yellow to black, and at the same time, gas evolution was observed. During the dropwise addition of thionyl chloride,
The temperature of the reaction mixture was kept at room temperature. After adding thionyl chloride dropwise over a period of about 3 hours, the reaction mixture was kept at 60-70°C in an oil bath for about 3 hours. After confirming that gas generation was almost no longer observed, low-boiling substances were distilled off under reduced pressure, and then 153
~170℃/1.0~3.0mmHg fraction 454g (yield 75%)
I got it. This was methyl branched isostearic acid chloride. IR spectrum (liquid film method) 2950, 2920, 2850, 1800 (C=O stretching), 1460,
1400, 1380, 950, 720, 680, 590 cm -1 H 1 -NMR spectrum (CCl 4 ): δ 0.6-1.0 (m, CH 3 CH 2 - and
【式】 1.0〜1.5(m、−CH2−) 1.5〜2.0(m、[Formula] 1.0 to 1.5 (m, -CH 2 -) 1.5 to 2.0 (m,
【式】)
2.77(t、−CH2 COCl)
参考例 4
温度計、滴下ろうと、還流冷却器、攪拌器を備
えた3の反応容器に、コレステロール281g
(0.73モル)、ベンゼン1500ml、ピリジン100g
(1.27モル)をこの順に加えた。反応混合物を攪
拌しながら、窒素ガス通気下で25〜30℃に保ち滴
下ろうとより参考例3で得られたメチル分岐イソ
ステアリン酸クロライド212g(0.70モル)を滴
下した。滴下終了後、反応混合物の温度を約50℃
に約3時間保ち、さらに70〜80℃に約8時間保つ
た。この加熱処理によりエステル化反応は完成に
進行し、反応混合物中に酸クロライドは全く含ま
れていない事がIRスペクトルにより確認された。
反応生成物中のピリジン塩酸塩の白色沈澱物をろ
過により除去し、得られたろ液を、減圧下で溶媒
留去させた。ベンゼン(1000ml)及び希塩酸
(1000ml)中に混合し激しくかきまぜた後、分液
によりベンゼン層を採取した。ベンゼン層を無水
硫酸ナトリウムを加えて乾燥した後、減圧下でベ
ンゼンを留去し、淡黄色の粘稠な液体状のメチル
分岐イソステアリン酸コレステリルエステル460
g(収率94%)を得た。
IRスペクトル(液膜)
2950、2920、2850、1730(C=O伸縮)、1460、
1370、1160、1000cm-1
H1−NMRスペクトル(CCl4溶媒):δ
0.70(s、3H、ステロイド骨格C−18メチル
基)
0.80(d、6H、ステロイド骨格側鎖C−26、C
−27メチル基)
1.00(s、3H、ステロイド骨格C−19メチル
基)
0.80〜1.0(m、6H、分岐脂肪酸CH3 CH2−及び
[Formula]) 2.77 (t, -C H 2 COCl) Reference Example 4 281 g of cholesterol was placed in reaction vessel 3 equipped with a thermometer, dropping funnel, reflux condenser, and stirrer.
(0.73 mol), benzene 1500ml, pyridine 100g
(1.27 mol) were added in this order. While stirring the reaction mixture, 212 g (0.70 mol) of methyl branched isostearic acid chloride obtained in Reference Example 3 was added dropwise through a dropping funnel while maintaining the temperature at 25 to 30° C. under nitrogen gas flow. After the dropwise addition is complete, the temperature of the reaction mixture is reduced to approximately 50°C.
It was kept at 70-80°C for about 3 hours, and then kept at 70-80°C for about 8 hours. Through this heat treatment, the esterification reaction proceeded to completion, and it was confirmed by IR spectrum that no acid chloride was contained in the reaction mixture.
The white precipitate of pyridine hydrochloride in the reaction product was removed by filtration, and the resulting filtrate was subjected to solvent distillation under reduced pressure. After mixing in benzene (1000 ml) and dilute hydrochloric acid (1000 ml) and stirring vigorously, the benzene layer was collected by liquid separation. After drying the benzene layer by adding anhydrous sodium sulfate, the benzene was distilled off under reduced pressure to obtain a pale yellow viscous liquid methyl branched isostearic acid cholesteryl ester 460.
g (yield 94%) was obtained. IR spectrum (liquid film) 2950, 2920, 2850, 1730 (C=O stretching), 1460,
1370, 1160, 1000 cm -1 H 1 -NMR spectrum (CCl 4 solvent): δ 0.70 (s, 3H, steroid skeleton C-18 methyl group) 0.80 (d, 6H, steroid skeleton side chain C-26, C
-27 methyl group) 1.00 (s, 3H, steroid skeleton C-19 methyl group) 0.80 to 1.0 (m, 6H, branched fatty acid CH 3 CH 2 - and
【式】) 1.0〜2.0(m) 2.2(t、2H、−CH2−CH2 −COO−) 4.4(m、1H、[Formula]) 1.0 ~ 2.0 (m) 2.2 (t, 2H, -CH 2 -CH 2 -COO-) 4.4 (m, 1H,
【式】)
5.25(m、1H、ステロイド骨格、C−6オレフ
インプロトン)
酸 価 0.8(計算値0)
ケン化価 84.8(計算値86.0)
水酸基価 0.7(計算値0)
ヨウ素価 41.4(計算値39.0)
実験例 1
In vitroにおける水分閉塞効果を当業界で広く
採用しているカツプ試法(J.Soc.Cosmet、
Chem.Japan、13(2)、14〜19(1979))により測定
した。
(方 法)
50ml容量のガラスビンの口に紙(桐山ロート
用紙、No.4 40mm径)をあて、一定の面積にく
り抜いたキヤツプで紙を固定する。紙はあら
かじめ被検クリームに浸漬しておく。ガラスビン
に一定量の水を入れ、一定条件(20℃、50%相対
湿度)に24時間放置する。放置前後の重量変化に
より透過水分量を求め、未処理紙の水分透過量
で割り水分透過率(%)とした。紙への被検ク
リームの付着量は100mgに換算統一して計算をし
た。
(被検クリーム処方)
処方A W/O型クリーム(本発明品)
分岐脂肪酸コレステリルエステル(参考例4で
製造したもの) 10wt.%
α−モノ(メチル分岐アルキル)グリセリルエ
ーテル(参考例2で製造したもの) 2 〃
ワセリン 5 〃
ラノリン 5 〃
硫動パラフイン 5 〃
イソプロピルミリステート 5 〃
精製水 68 〃
処方B W/O型クリーム(対象)
α−モノ(メチル分岐アルキル)グリセリルエ
ーテル(参考例2で製造したもの) 2wt.%
ワセリン 15 〃
ラノリン 5 〃
流動パラフイン 5 〃
イソプロピルミリステート 5 〃
精製水 68 〃
処方C O/W型クリーム(対象)
分岐脂肪酸コレステリルエステル(参考例4で
製造したもの) 10wt.%
ワセリン 5 〃
ラノリン 5 〃
流動パラフイン 5 〃
イソプロピルミリステート 5 〃
ステアリン酸モノグリセリド 2 〃
ソルビタンモノステアレート 3 〃
ポリオキシエチレンソルビタンモノステアレー
ト 3 〃
精製水 62 〃
市販品A O/Wクリーム(対象)
(主成分のみ、詳細不明)
固型パラフイン
ヘキサデシル−2−エチルヘキサノエート
オリーブ油
ステアリン酸モノグリセリド
ポリオキシエチレンソルビタンモノステアレー
ト
精製水
市販品B W/O型クリーム(対象)
(主成分のみ、詳細不明)
流動パラフイン
ワセリン
ラノリンアルコール
ステアリン酸アルミニウム
精製水
(結 果)[Formula]) 5.25 (m, 1H, steroid skeleton, C-6 olefin proton) Acid value 0.8 (calculated value 0) Saponification value 84.8 (calculated value 86.0) Hydroxyl value 0.7 (calculated value 0) Iodine value 41.4 (calculated value 39.0) Experimental example 1 In vitro water occlusion effect was measured using the cup test method (J.Soc.Cosmet,
Chem. Japan, 13(2), 14-19 (1979)). (Method) Place paper (Kiriyama Roto paper, No. 4 40 mm diameter) over the mouth of a 50 ml glass bottle and secure the paper with a cap cut out to a certain area. Soak the paper in the test cream in advance. Fill a glass bottle with a certain amount of water and leave it under certain conditions (20°C, 50% relative humidity) for 24 hours. The amount of permeated water was determined from the change in weight before and after standing, and was divided by the amount of water permeated through the untreated paper to obtain the water permeation rate (%). The amount of the test cream adhered to the paper was calculated by converting it into 100 mg. (Test cream formulation) Prescription A W/O type cream (product of the present invention) Branched fatty acid cholesteryl ester (produced in Reference Example 4) 10wt.% α-mono(methyl branched alkyl) glyceryl ether (produced in Reference Example 2) 2 Vaseline 5 Lanolin 5 Sulfuric paraffin 5 Isopropyl myristate 5 Purified water 68 Prescription B W/O cream (target) α-mono(methyl branched alkyl) glyceryl ether (in reference example 2) 2wt.% Vaseline 15 Lanolin 5 Liquid paraffin 5 Isopropyl myristate 5 Purified water 68 Prescription C O/W cream (target) Branched fatty acid cholesteryl ester (manufactured in Reference Example 4) 10wt .% Vaseline 5 Lanolin 5 Liquid paraffin 5 Isopropyl myristate 5 Stearic acid monoglyceride 2 Sorbitan monostearate 3 Polyoxyethylene sorbitan monostearate 3 Purified water 62 Commercial product A O/W cream (targeted) ) (Main ingredient only, details unknown) Solid paraffin Hexadecyl-2-ethylhexanoate Olive oil Stearic acid monoglyceride polyoxyethylene sorbitan monostearate Purified water Commercial product B W/O cream (Target) (Main ingredient only, details Unknown) Liquid paraffin Vaseline Lanolin alcohol Aluminum stearate Purified water (results)
【表】
実験例 2
In vivoにおける水分閉塞効果を、ヒトを使用
する場合の一般的な方法として採用されている皮
膚不感蒸泄測定法(日本皮膚科学会誌86(12)、815
〜823(昭51))に従つて測定した。
(方 法)
女性の前腕屈側部の定めた部位にカツプをあ
て、エーテル(1):アセトン(1)混液を注ぎ、30秒間
2回当てて脱脂する。一定条件(20℃、50%相対
湿度)に設定した環験可変室に20分間安静させ、
各部位の不感蒸泄量を測定する。半径20cm
(12.56cm2)に一定量の被検クリームを塗布し、塗
布後30分後、60分後の不感蒸泄量を測定する。閉
塞率は下記の式により求める。
(クリーム塗布前の不感蒸泄量)−(クリ
ーム塗布後の不感蒸泄量)/(クリーム塗布前の不感蒸
泄量)×100
不感蒸泄量の測定にはEvapori meterを使用
し、皮膚に接触して1分後の値を読み取つた。
(結 果)[Table] Experimental example 2 In vivo water occlusion effect was measured using the skin-insensitive excretion measurement method, which is commonly used in humans (Journal of the Japanese Dermatological Association 86(12), 815
~823 (Sho 51)). (Method) Place a cup on a designated area on the flexor side of a woman's forearm, pour a mixture of ether (1) and acetone (1), and apply the cup twice for 30 seconds to degrease. Rest for 20 minutes in a variable environment room set at constant conditions (20°C, 50% relative humidity).
Measure the amount of insensible excretion at each site. radius 20cm
(12.56 cm 2 ), apply a certain amount of the test cream, and measure the amount of insensible excretion 30 and 60 minutes after application. The occlusion rate is determined by the following formula. (Insensible metabolic rate before cream application) - (Insensible metabolic rate after cream application) / (Insensible metabolic rate before cream application) x 100 To measure the insensible metabolic rate, use an Evapori meter and apply it to the skin. The value was read 1 minute after contact. (Result)
【表】
実験例 3
管能評価によるクリームのべたつきの評価
(方 法)
20人の女性パネラーの手の甲に被検クリームを
一定量塗り、そのべたつきを評価した。
(結 果)[Table] Experimental Example 3 Evaluation of stickiness of cream by tube function evaluation (method) A certain amount of the test cream was applied to the backs of the hands of 20 female panelists, and the stickiness was evaluated. (Result)
【表】
実験例1および実験例2の結果より、α−モノ
グリセリルエーテル及び分岐脂肪酸コレステリル
エステルを配合した本発明に係る処方AのW/O
型クリームと、分岐脂肪酸コレステリルエステル
に代えてワセリンを配合した処方BのW/O型ク
リームの水分閉塞効果(即ち皮表水分蒸散抑制効
果)に優れることがわかる。一方実験例3の結果
より、処方AのW/O型クリームが処方BのW/
O型クリームにくらべてべたつきが少ないことが
わかる。
以下に本発明のW/O型クリームの実施例を示
す。使用した分岐脂肪酸コレステリルエステル、
α−モノグリセリルエーテルは参考例で製造した
ものである。
実施例 1
〔1〕 分岐脂肪酸コレステリルエステル 10.0wt.%
〔2〕 ワセリン 5.0 〃
〔3〕 ラノリン 5.0 〃
〔4〕 流動パラフイン 5.0 〃
〔5〕 α−モノグリセリルエーテル 2.0 〃
〔6〕 ステアリン酸アルミニウム 0.05 〃
〔7〕 安息香酸ナトリウム 0.3 〃
〔8〕 精製水 残部
〔1〕〜〔6〕を混合し60℃に加熱した。60℃
に加熱した〔7〕〔8〕の混合物を加えながら攪
拌乳化した。乳化室温まで冷却してW/O型クリ
ームとした。
実施例 2
消炎剤含有W/O型クリーム
分岐脂肪酸コレステリルエステル 5.0%
ワセリン 5.0
スクワラン 5.0
流動パラフイン 5.0
2−エチルヘキシルアジペート 5.0
パラヒドロキシ安息香酸プロピル 0.1
レシチン 0.5
ソルビタンセスキオレエート 2.0
アルミニウムモノステアレート 0.05
α−モノグリセリルエーテル 2.0%
アラントイン 1.5
パラヒドロキシ安息香酸メチル 0.1
硫酸マグネシウム 0.5
精製水 残量
実施例 3
殺菌剤含有W/O型クリーム
分岐脂肪酸コレステリルエステル 10.0%
ワセリン 5.0
ラノリン 5.0
流動パラフイン 5.0
イソプロピルミリステート 5.0
パラヒドロキシ安息香酸プロピル 0.1
アルミニウムモノステアレート 0.05
α−モノグリセリルエーテル 2.0
パラヒドロキシ安息香酸メチル 0.1
グルコン酸クロルヘキシジン(20%) 0.5
精製水 残量
実施例 4
ビタミン剤含有W/O型クリーム
分岐脂肪酸コレステリルエステル 5.0%
サラシミツロウ 3.0
スクワラン 2.0
流動パラフイン 5.0
2−エチルヘキシルアジペート 5.0
パラヒドロキシ安息香酸プロピル 0.1
アルミニウムモノステアレート 0.05
α−モノグリセリルエーテル 2.0
酢酸dl−α−トコフエロール 0.2
パラヒドロキシ安息香酸メチル 0.1
製*** 残量
実施例 5
保湿剤含有W/O型クリーム
分岐脂肪酸コレステリルエステル 10.0%
ワセリン 5.0
スクワラン 5.0
流動パラフイン 5.0
2−エチルヘキシルアジペート 5.0
アルミニウムモノステアレート 0.05
α−モノグリセリルエーテル 2.0%
パラヒドロキシ安息香酸プロピル 0.1
パラヒドロキシ安息香酸メチル 0.1
硫酸マグネシウム 0.5
尿 素 5.0
精製水 残量[Table] From the results of Experimental Examples 1 and 2, W/O of formulation A according to the present invention containing α-monoglyceryl ether and branched fatty acid cholesteryl ester
It can be seen that the W/O type cream of Formulation B, which contains Vaseline in place of the branched fatty acid cholesteryl ester, has an excellent water occlusion effect (that is, an effect of suppressing water evaporation from the skin surface). On the other hand, from the results of Experimental Example 3, it was found that the W/O type cream of Prescription A was different from the W/O type cream of Prescription B.
It can be seen that it is less sticky than O type cream. Examples of the W/O type cream of the present invention are shown below. Branched fatty acid cholesteryl ester used,
α-Monoglyceryl ether was produced in Reference Example. Example 1 [1] Branched fatty acid cholesteryl ester 10.0wt.% [2] Vaseline 5.0 [3] Lanolin 5.0 [4] Liquid paraffin 5.0 [5] α-monoglyceryl ether 2.0 [6] Ste. Aluminum phosphate 0.05 [7] Sodium benzoate 0.3 [8] Purified water The remainder [1] to [6] were mixed and heated to 60°C. 60℃
While adding the heated mixture of [7] and [8], the mixture was stirred and emulsified. The emulsion was cooled to room temperature to obtain a W/O type cream. Example 2 W/O type cream containing anti-inflammatory agent Branched fatty acid cholesteryl ester 5.0% Vaseline 5.0 Squalane 5.0 Liquid paraffin 5.0 2-ethylhexyl adipate 5.0 Propyl parahydroxybenzoate 0.1 Lecithin 0.5 Sorbitan sesquioleate 2.0 Aluminum monostearate 0.05 α-mono Glyceryl ether 2.0% Allantoin 1.5 Methyl para-hydroxybenzoate 0.1 Magnesium sulfate 0.5 Purified water Remaining amount example 3 W/O type cream containing bactericide Branched fatty acid cholesteryl ester 10.0% Vaseline 5.0 Lanolin 5.0 Liquid paraffin 5.0 Isopropyl myristate 5.0 Para-hydroxybenzoin Propyl acid 0.1 Aluminum monostearate 0.05 α-monoglyceryl ether 2.0 Methyl para-hydroxybenzoate 0.1 Chlorhexidine gluconate (20%) 0.5 Purified water Remaining amount example 4 W/O type cream containing vitamins Branched fatty acid cholesteryl ester 5.0% Salad Beeswax 3.0 Squalane 2.0 Liquid paraffin 5.0 2-ethylhexyl adipate 5.0 Propyl para-hydroxybenzoate 0.1 Aluminum monostearate 0.05 α-monoglyceryl ether 2.0 dl-α-tocopherol acetate 0.2 Methyl para-hydroxybenzoate 0.1 Purified water Remaining amount example 5 Moisturizing agent-containing W/O type cream Branched fatty acid cholesteryl ester 10.0% Vaseline 5.0 Squalane 5.0 Liquid paraffin 5.0 2-ethylhexyl adipate 5.0 Aluminum monostearate 0.05 α-monoglyceryl ether 2.0% Propyl para-hydroxybenzoate 0.1 Methyl para-hydroxybenzoate 0.1 Magnesium sulfate 0.5 Urea 5.0 Purified water remaining amount
Claims (1)
整数であり、mとnの和は9ないし21である) で表される分岐鎖アルキル基である〕 で表されるα−モノグリセリルエーテルと式
(); (式中R′は合計11〜23個の炭素原子を有し、カ
ルボキシル結合位から主鎖の中央までに、少なく
とも1つのアルキル置換基を有する飽和脂肪族炭
化水素基である) で表される分岐脂肪酸コレステリルエステルを含
有することを特徴とする油中水型エマルシヨン。[Claims] 1 Formula (); [In the formula, R is the following formula () (In the formula, m is an integer of 2 to 14, n is an integer of 3 to 11, and the sum of m and n is 9 to 21.) Monoglyceryl ether and formula (); (wherein R' is a saturated aliphatic hydrocarbon group having a total of 11 to 23 carbon atoms and having at least one alkyl substituent from the carboxyl bond position to the center of the main chain) A water-in-oil emulsion characterized by containing branched fatty acid cholesteryl ester.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56010561A JPS57123108A (en) | 1981-01-26 | 1981-01-26 | Water-in-oil type emulsion |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56010561A JPS57123108A (en) | 1981-01-26 | 1981-01-26 | Water-in-oil type emulsion |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS57123108A JPS57123108A (en) | 1982-07-31 |
JPH026729B2 true JPH026729B2 (en) | 1990-02-13 |
Family
ID=11753649
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP56010561A Granted JPS57123108A (en) | 1981-01-26 | 1981-01-26 | Water-in-oil type emulsion |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS57123108A (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6272611A (en) * | 1985-09-27 | 1987-04-03 | Kao Corp | Skin external preparation |
JPH0659164B2 (en) * | 1985-12-23 | 1994-08-10 | 理研ビタミン株式会社 | Sterin-containing composition |
JPS62230896A (en) * | 1985-12-28 | 1987-10-09 | 三洋化成工業株式会社 | Refining agent |
-
1981
- 1981-01-26 JP JP56010561A patent/JPS57123108A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS57123108A (en) | 1982-07-31 |
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