WO1997002002A2 - Use of polyolpoly-12-hydroxystearates - Google Patents
Use of polyolpoly-12-hydroxystearates Download PDFInfo
- Publication number
- WO1997002002A2 WO1997002002A2 PCT/EP1996/002750 EP9602750W WO9702002A2 WO 1997002002 A2 WO1997002002 A2 WO 1997002002A2 EP 9602750 W EP9602750 W EP 9602750W WO 9702002 A2 WO9702002 A2 WO 9702002A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- polyglycerol
- poly
- acid
- hydroxystearates
- Prior art date
Links
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000002537 cosmetic Substances 0.000 claims abstract description 8
- 239000000825 pharmaceutical preparation Substances 0.000 claims abstract description 6
- 229920000223 polyglycerol Polymers 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 14
- 229920005862 polyol Polymers 0.000 claims description 13
- 150000003077 polyols Chemical class 0.000 claims description 11
- 229940114069 12-hydroxystearate Drugs 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- ULQISTXYYBZJSJ-UHFFFAOYSA-M 12-hydroxyoctadecanoate Chemical compound CCCCCCC(O)CCCCCCCCCCC([O-])=O ULQISTXYYBZJSJ-UHFFFAOYSA-M 0.000 claims 2
- 239000000839 emulsion Substances 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 21
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 12
- 239000000194 fatty acid Substances 0.000 description 11
- 235000014113 dietary fatty acids Nutrition 0.000 description 10
- 229930195729 fatty acid Natural products 0.000 description 10
- 150000004665 fatty acids Chemical class 0.000 description 9
- -1 Alkyl glucosides Chemical class 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000006071 cream Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- BARWIPMJPCRCTP-CLFAGFIQSA-N oleyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC BARWIPMJPCRCTP-CLFAGFIQSA-N 0.000 description 4
- WBHHMMIMDMUBKC-QJWNTBNXSA-N ricinoleic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(O)=O WBHHMMIMDMUBKC-QJWNTBNXSA-N 0.000 description 4
- 229960003656 ricinoleic acid Drugs 0.000 description 4
- 229920001661 Chitosan Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000007764 o/w emulsion Substances 0.000 description 3
- 235000010958 polyglycerol polyricinoleate Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000000035 biogenic effect Effects 0.000 description 2
- 239000007957 coemulsifier Substances 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000001815 facial effect Effects 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- PMMXXYHTOMKOAZ-UHFFFAOYSA-N hexadecyl 7-methyloctanoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)CCCCCC(C)C PMMXXYHTOMKOAZ-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 150000005846 sugar alcohols Chemical class 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 1
- BZANQLIRVMZFOS-ZKZCYXTQSA-N (3r,4s,5s,6r)-2-butoxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound CCCCOC1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O BZANQLIRVMZFOS-ZKZCYXTQSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical class CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- SZSSMFVYZRQGIM-UHFFFAOYSA-N 2-(hydroxymethyl)-2-propylpropane-1,3-diol Chemical compound CCCC(CO)(CO)CO SZSSMFVYZRQGIM-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 241001440269 Cutina Species 0.000 description 1
- 244000007835 Cyamopsis tetragonoloba Species 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 229920000727 Decyl polyglucose Polymers 0.000 description 1
- FPVVYTCTZKCSOJ-UHFFFAOYSA-N Ethylene glycol distearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCCCCCCCC FPVVYTCTZKCSOJ-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 241000206672 Gelidium Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000004166 Lanolin Substances 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 241000384110 Tylos Species 0.000 description 1
- 239000004904 UV filter Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229940073669 ceteareth 20 Drugs 0.000 description 1
- 229940081733 cetearyl alcohol Drugs 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000000973 cosmetic coloring agent Substances 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- SASYSVUEVMOWPL-NXVVXOECSA-N decyl oleate Chemical compound CCCCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC SASYSVUEVMOWPL-NXVVXOECSA-N 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000002337 glycosamines Chemical class 0.000 description 1
- UBHWBODXJBSFLH-UHFFFAOYSA-N hexadecan-1-ol;octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO.CCCCCCCCCCCCCCCCCCO UBHWBODXJBSFLH-UHFFFAOYSA-N 0.000 description 1
- 229920002674 hyaluronan Polymers 0.000 description 1
- 229960003160 hyaluronic acid Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229940039717 lanolin Drugs 0.000 description 1
- 235000019388 lanolin Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 229920002601 oligoester Polymers 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- LADGBHLMCUINGV-UHFFFAOYSA-N tricaprin Chemical compound CCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCC)COC(=O)CCCCCCCCC LADGBHLMCUINGV-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 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
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/39—Derivatives containing from 2 to 10 oxyalkylene groups
-
- 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
-
- 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
- A61K8/062—Oil-in-water 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
- A61K8/37—Esters of carboxylic acids
- A61K8/375—Esters of carboxylic acids the alcohol moiety 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
- A61Q19/10—Washing or bathing preparations
Definitions
- the invention relates to the use of polyol poly-12-hydroxystearates as O / W emulsifiers for the production of cosmetic and / or pharmaceutical preparations.
- Polyglycerol polyricinoleates have long been known as W / O emulsifiers and can be used to formulate low-viscosity W / O emulsions [cf. EP-AI 0 559 013 (Th. Goldschmidt), EP-AI 0 440 203 (Lotte Co.) and WO 85/04346 (Meiji Milk Prods.). It turns out, however, that polyglycerol polyrinoleates on the market do not form emulsions with all oils conventionally used in cosmetics, but only with those of a certain polarity range; moreover, these emulsions have only a limited shelf life. A major disadvantage is that the commercially available products are not able to adequately stabilize emulsions with strongly polar oils such as vegetable oils. In view of the particular ecotoxicological compatibility of such emulsions, however, this is precisely what is desired in the market.
- polyglycerol polyricinoleates are not suitable for producing O / W emulsions because of their high lipophilicity; this requires significantly more hydrophilic, usually surfactant, emulsifiers.
- the latter again have the disadvantage that they generally contain ethylene oxide groups, which is not always desirable from the market point of view.
- the stability of the emulsions obtainable using known hydrophilic O / W emulsifiers is in many cases unsatisfactory.
- the complex object of the invention was therefore to provide O / W emulsifiers which on the one hand are free of ethylene oxide and on the other hand allow the production of finely divided and at the same time storage-stable emulsions.
- the invention relates to the use of polyol poly-12-hydroxystearates as O / W emulsifiers for the production of cosmetic and / or pharmaceutical preparations.
- condensation products of polyols preferably technical polyglycerol
- poly-12-hydroxystearic acid which are known to be suitable as W / O emulsifiers
- condensation products based on the 12-hydroxystearic acid are liquid, although the acid used has a melting point in the range of 75 ° C.
- the invention relates to the use of polyglycerol poly-12-hydroxystearates, which is obtained by poly-12-hydroxy stearic acid having a degree of self-condensation in the range from 2 to 20, preferably 2 to 10, with a polyglycerol mixture of the composition ( GC method)
- polyols is understood to mean substances which have at least two, preferably 3 to 12 and in particular 3 to 8 hydroxyl groups and 2 to 12 carbon atoms. Typical examples are:
- Allkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol;
- Methyl compounds such as, in particular, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
- Sugar alcohols having 5 to 12 carbon atoms such as, for example, sorbitol or mannitol,
- reaction products based on polyglycerol are of particular importance among the O / W emulsifiers to be used according to the invention because of their excellent performance properties. It has proven particularly advantageous to use selected polyglycerols which have the following homolog distribution (the preferred ranges are given in brackets):
- the polyol poly-12-hydroxystearates can be prepared in a manner known per se.
- the polyglycerol and then the polyhydroxystearic acid are preferably first produced and finally both are esterified.
- the preparation of a polyglycerol of the abovementioned composition can be carried out by self-condensation of glycerol in the presence of suitable catalysts such as, for example, potassium carbonate, silicates according to DE-Al 40 29 323 (Henkel) or borates according to DE-Al 41 17 033 (Henkel) at temperatures in the range of 200 to 260 ° C are carried out.
- the poly-12-hydroxystearic acid is prepared, for example, by alkaline-catalyzed polycondensation of 12-hydroxystearic acid, which is obtained by curing ricinic acid or technical castor oil fatty acid. Linear esterification products having 2 to 10 and in particular 2 to 8 fatty acid units are preferably formed.
- the following distribution (GPC method) is typically achieved:
- mixtures of 12-hydroxystearic acid and ricinoleic acid or technical castor oil fatty acid which consists of approximately 90% by weight of ricinoleic acid, are used in a weight ratio of 99: 1 to 1:99 and preferably 75:25 to 10:90 .
- polystyrene resin for example the polyglycerol with the poly-12-hydroxystearic acid or the mixtures with polyricinoleic acid
- a complex mixture of homologous polyester is formed.
- the proportions of mono-, di-, tri- and oligoesters in the polyol poly-12-hydroxystearates to be used according to the invention and preferably polyglycerol poly-12-hydroxystearates depend on the conditions of use of the starting compounds.
- a polyol poly-12-hydroxystearate with particularly advantageous application properties is used, which is obtained by subjecting about 1000 kg of 12-hydroxystearic acid to self-condensation until a product with an acid number in the range from 50 to 55 results and this is then further esterified with about 150 kg of polyglycerol of the composition indicated above until the acid number has decreased to a value less than 2.
- Condensation products based on polyglycerol and poly-12-hydroxystearic acid or poly-12-hydroxystearic acid / polyricinoleic acid can be characterized by their iodine number.
- Typical examples are polyesters with an iodine number ⁇ 10 (based on 100% 12-hydroxystearic acid) or 65 to 80 (based on 90% 12-hydroxystearic acid, 10% ricinoleic acid).
- the O / W emulsions or cosmetic or pharmaceutical preparations obtainable using the polyol poly-12-hydroxystearates can be used as further components, inter alia. Contain oil oils, co-emulsifiers, fats and waxes, stabilizers, thickeners, biogenic agents, film formers, fragrances, dyes, pearlescent agents, preservatives, UV filters, pigments, electrolytes (e.g. magnesium sulfate) and pH regulators.
- suitable co-emulsifiers are hardened and ethoxylated castor oil, ethoxylated fatty alcohols or partial glycerides, alkyl oligoglycosides, polyglycerol fatty acid esters or polyglycerol polyricinoleates.
- Substances such as polyethoxylated lanolin derivatives, lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used as superfatting agents, the latter simultaneously serving as foam stabilizers.
- Suitable thickeners are, for example, polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, and also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as fatty alcohol ethoxylates with a narrow homolog distribution or alkyl oligoglucosides and electrolytes such as table salt and ammonium chloride.
- Biogenic active substances are understood to mean, for example, plant extracts and vitamin complexes.
- Common film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid or its salts and similar compounds.
- Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid.
- Suitable pearlescent agents are, for example, glycol distearic acid esters such as ethylene glycol distearate, but also fatty acid mono-glycol esters.
- the dyes which can be used are the substances which are suitable and approved for cosmetic purposes, such as are listed, for example, in the publication "Cosmetic Dyes” by the Dye Commission of the German Research Foundation, Verlag Chemie, Weinheim, 1984, pp. 81-106. These dyes are usually used in concentrations of 0.001 to 0.1% by weight, based on the overall mixture.
- the total proportion of auxiliaries and additives can be 1 to 50, preferably 5 to 40% by weight, based on the composition.
- the O / W emulsions can be prepared in a manner known per se by the cold / cold, hot / hot, hot / cold or PIT method.
- a facial cleansing cream To prepare a facial cleansing cream, the constituents I were melted at 80 ° C. and stirred until homogeneous. The components of phase II were also heated to 80 ° C., added slowly to phase I with stirring and emulsified at 80 ° C. for 5 minutes. The emulsion was cooled with stirring and carefully homogenized at about 50 ° C. After a temperature of 30 ° C. had been reached, the stirring was stopped and the emulsion was vented after cooling to room temperature. Using polyglycerol poly-12-hydroxystearate as an O / W emulsifier, a viscous cream was obtained which was still stable even after 12 weeks of storage. When using a known hydrophilic O / W emulsifier from the prior art, the mixture remained two-phase. The composition of the mixtures can be found in Table 1 (quantitative data as% by weight).
- Emulgade® PL 1618 Hexadecyl Polyglucose and Hexadecyl Alcohol
- Plantaren® 1200 decyl polyglucose
- Myritol® 312 Caprylic / Capric Triglyceride
- Dehymuls® PGPH polyglyceryl poly-12-hydroxystearate
- Example 2 The procedure for producing a care cream was as described in Example 1.
- the cream produced using the polyglycerol poly-12-hydroxystearate was still stable even after storage for more than 12 weeks; without the O / W emulsifier, the cream separated into an oily and an aqueous phase within 8 weeks.
- the composition of the mixtures can be found in Table 2 (quantitative data as% by weight).
Landscapes
- 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)
- Dispersion Chemistry (AREA)
- Dermatology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Cosmetics (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Verwendung von PolyolpoIy-12-hydroxystearaten Use of polyol poly-12-hydroxystearates
Gebiet der ErfindungField of the Invention
Die Erfindung betrifft die Verwendung von Polyolpoly-12-hydroxystearaten als O/W- Emulgatoren für die Herstellung von kosmetischen und/oder pharmazeutischen Zubereitungen.The invention relates to the use of polyol poly-12-hydroxystearates as O / W emulsifiers for the production of cosmetic and / or pharmaceutical preparations.
Stand der TechnikState of the art
Polyglycerinpolyricinoleate sind seit langem als W/O-Emulgatoren bekannt und können zur Formulierung von niedrigviskosen W/O-Emulsionen eingesetzt werden [vgl. EP-AI 0 559 013 (Th. Goldschmidt), EP-AI 0 440 203 (Lotte Co.) und WO 85/04346 (Meiji Milk Prods.). Es zeigt sich jedoch, daß Polyglycerinpolyrinoleate des Marktes nicht mit allen in der Kosmetik üblicherweise eingesetzten Öle Emulsionen bilden, sondern nur mit solchen eines bestimmten Polaritätsbereiches; zudem sind diese Emulsionen nur eingeschränkt lagerstabil. Ein we¬ sentlicher Nachteil besteht vor allem darin, daß die handelsüblichen Produkte nicht in der Lage sind, Emulsionen mit stark polaren Ölen wie beispielsweise Pflanzenölen ausreichend zu stabilisieren. Im Hinblick auf die besondere ökotoxikologische Verträglichkeit derartiger Emul¬ sionen wird jedoch gerade dies im Markt gewünscht.Polyglycerol polyricinoleates have long been known as W / O emulsifiers and can be used to formulate low-viscosity W / O emulsions [cf. EP-AI 0 559 013 (Th. Goldschmidt), EP-AI 0 440 203 (Lotte Co.) and WO 85/04346 (Meiji Milk Prods.). It turns out, however, that polyglycerol polyrinoleates on the market do not form emulsions with all oils conventionally used in cosmetics, but only with those of a certain polarity range; moreover, these emulsions have only a limited shelf life. A major disadvantage is that the commercially available products are not able to adequately stabilize emulsions with strongly polar oils such as vegetable oils. In view of the particular ecotoxicological compatibility of such emulsions, however, this is precisely what is desired in the market.
Weiterhin sind Polyglycerinpolyricinoleate wegen ihrer hohen Lipophilie nicht zur Herstellung von O/W-Emulsionen geeignet; hierfür werden deutlich hydrophilere, in der Regel tensidische Emulgatoren benötigt. Letztgenannte haben aber wiederum den Nachteil, daß sie in der Regel Ethylenoxidgruppen beinhalten, was aus Sicht des Marktes nicht immer erwünscht ist. Ferner ist die Stabilität der unter Verwendung bekannter hydrophiler O/W-Emulgatoren erhältlichen Emulsionen in vielen Fällen nicht zufriedenstellend. Die komplexe Aufgabe der Erfindung hat somit darin bestanden, O/W-Emulgatoren zur Verfügung zu stellen, die einerseits frei von Ethylenoxidanteilen sind und zum anderen die Her¬ stellung feinteiliger und gleichzeitig lagerstabiler Emulsionen erlauben.Furthermore, polyglycerol polyricinoleates are not suitable for producing O / W emulsions because of their high lipophilicity; this requires significantly more hydrophilic, usually surfactant, emulsifiers. However, the latter again have the disadvantage that they generally contain ethylene oxide groups, which is not always desirable from the market point of view. Furthermore, the stability of the emulsions obtainable using known hydrophilic O / W emulsifiers is in many cases unsatisfactory. The complex object of the invention was therefore to provide O / W emulsifiers which on the one hand are free of ethylene oxide and on the other hand allow the production of finely divided and at the same time storage-stable emulsions.
Beschreibung der ErfindungDescription of the invention
Gegenstand der Erfindung ist die Verwendung von Polyolpoly-12-hydroxystearaten als O/W-Emulgatoren zur Herstellung von kosmetischen und/oder pharmazeutischen Zuberei¬ tungen.The invention relates to the use of polyol poly-12-hydroxystearates as O / W emulsifiers for the production of cosmetic and / or pharmaceutical preparations.
Überraschenderweise wurde gefunden, daß Kondensationsprodukte von Polyolen, vorzugsweise technischem Polyglycerin, mit Poly-12-hydroxystearinsäure, von denen bekannt ist, daß sie sich als W/O-Emulgatoren eignen, gleichzeitig auch O/W-emulgierende Eigen¬ schaften besitzen. Bei der Verwendung von Polyglycerinpoly-12-hydroxystearaten als O/W- Emulgatoren werden Emulsionen erhalten, die gegenüber dem Stand der Technik eine signifikant höhere Lagerstabilität aufweisen. Ferner wurde überraschenderweise festgestellt, daß die Kondensationsprodukte auf Basis der 12-Hydroxystearinsäure flüssig sind, obwohl die eingesetzte Säure einen Schmelzpunkt im Bereich von 75°C aufweist. Somit ist neben der klassischen "Heiß-Heiß-Herstellung auch eine energiesparende "Kalt-Kalf-Herstellung der Emulsionen problemlos möglich. In einer bevorzugten Ausführungsform betrifil die Erfindung die Verwendung von Polyglycerinpoly-12-hydroxystearaten, die man erhält, indem man Poly- 12-hy droxy Stearinsäure mit einem Eigenkondensationsgrad im Bereich von 2 bis 20, vorzugsweise 2 bis 10, mit einem Polyglyceringemisch der Zusammensetzung (GC-Methode)Surprisingly, it was found that condensation products of polyols, preferably technical polyglycerol, with poly-12-hydroxystearic acid, which are known to be suitable as W / O emulsifiers, also have O / W emulsifying properties. When using polyglycerol poly-12-hydroxystearates as O / W emulsifiers, emulsions are obtained which have a significantly higher storage stability compared to the prior art. It was also surprisingly found that the condensation products based on the 12-hydroxystearic acid are liquid, although the acid used has a melting point in the range of 75 ° C. In addition to the classic "hot-hot production", an energy-saving "cold-cold" production of the emulsions is also possible without any problems. In a preferred embodiment, the invention relates to the use of polyglycerol poly-12-hydroxystearates, which is obtained by poly-12-hydroxy stearic acid having a degree of self-condensation in the range from 2 to 20, preferably 2 to 10, with a polyglycerol mixture of the composition ( GC method)
Glycerin 5 bis 35 (15 bis 30) Gew.-%Glycerin 5 to 35 (15 to 30) wt%
Diglycerine 15 bis 40 (20 bis 32) Gew.-%Diglycerols 15 to 40 (20 to 32) wt%
Triglycerine 10 bis 35 (15 bis 25) Gew. -%Triglycerols 10 to 35 (15 to 25)% by weight
Tetraglycerine 5 bis 20 ( 8 bis 15) Gew. -%Tetraglycerols 5 to 20 (8 to 15) wt.%
Pentaglycerine 2 bis 10 ( 3 bis 8) Gew.-%Pentaglycerols 2 to 10 (3 to 8) wt%
Oligoglycerine ad 100 Gew.-%Oligoglycerols ad 100% by weight
in an sich bekannter Weise verestert (in Klammern angegeben sind die bevorzugten Bereiche).. Polyoleesterified in a manner known per se (the preferred ranges are given in brackets). Polyols
Unter dem Begriff Polyole sind Stoffe zu verstehen, die über mindestens zwei, vor¬ zugsweise 3 bis 12 und insbesondere 3 bis 8 Hydroxylgruppen und 2 bis 12 Kohlenstoffatome verfügen. Typische Beispiele sind:The term polyols is understood to mean substances which have at least two, preferably 3 to 12 and in particular 3 to 8 hydroxyl groups and 2 to 12 carbon atoms. Typical examples are:
• Glycerin und Polyglycerin;• glycerin and polyglycerin;
• Allkylenglycole wie beispielsweise Ethylenglycol, Diethylenglycol, Propylenglycol;• Allkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol;
• Methyolverbindungen, wie insbesondere Trimethylolethan, Trimethylolpropan, Trime- thylolbutan, Pentaerythrit und Dipentaerythrit;• Methyl compounds, such as, in particular, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
• Alkylglucoside mit 1 bis 22, vorzugsweise 1 bis 8 und insbesondere 1 bis 4 Kohlen¬ stoffen im Alkylrest wie beispielsweise Methyl- und Butylglucosid;Alkyl glucosides with 1 to 22, preferably 1 to 8 and in particular 1 to 4 carbons in the alkyl radical, such as, for example, methyl and butyl glucoside;
• Zuckeralkohole mit 5 bis 12 Kohlenstoffatomen wie beispielsweise Sorbit oder Mannit,Sugar alcohols having 5 to 12 carbon atoms, such as, for example, sorbitol or mannitol,
• Zucker mit 5 bis 12 Kohlenstoffatomen wie beispielsweise Glucose oder Saccharose;• Sugar with 5 to 12 carbon atoms, such as glucose or sucrose;
• Aminozucker wie beispielweise Glucamin.• Aminosugars such as glucamine.
PolyglycerinPolyglycerin
Wie schon erwähnt, kommen unter den erfindungsgemäß zu verwendenden O/W- Emulgatoren Umsetzungsprodukten auf Basis von Polyglycerin wegen ihrer ausgezeichneten anwendungstechnischen Eigenschaften eine besondere Bedeutung zu. Als besonders vorteilhaft hat sich die Verwendung von ausgewählten Polyglycerinen erwiesen, die die folgende Homologenverteilung aufweisen (in Klammern angegeben sind die bevorzugten Bereiche):As already mentioned, reaction products based on polyglycerol are of particular importance among the O / W emulsifiers to be used according to the invention because of their excellent performance properties. It has proven particularly advantageous to use selected polyglycerols which have the following homolog distribution (the preferred ranges are given in brackets):
Glycerin 5 bis 35 (15 bis 30) Gew.-%Glycerin 5 to 35 (15 to 30) wt%
Diglycerine 15 bis 40 (20 bis 32) Gew.-%Diglycerols 15 to 40 (20 to 32) wt%
Triglycerine 10 bis 35 (15 bis 25) Gew.-%Triglycerols 10 to 35 (15 to 25)% by weight
Tetraglycerine 5 bis 20 ( 8 bis l5) Gew.-%Tetraglycerols 5 to 20 (8 to 15) wt%
Pentaglycerine 2 bis 10 ( 3 bis 8) Gew.-%Pentaglycerols 2 to 10 (3 to 8) wt%
Oligoglycerine ad 100 Gew.-% Herstellung der Polyolpolv-12-hvdroxystearateOligoglycerols ad 100% by weight Production of Polyolpolv-12-hvdroxystearate
Die Herstellung der Polyolpoly-12-hydroxystearate kann in an sich bekannter Weise erfolgen. Im Fall der Polyglycerinpoly-12-hydroxystearate wird dabei vorzugsweise zunächst das Polyglycerin und dann die Polyhydroxystearinsäure hergestellt und schließlich beide verestert. Die Herstellung eines Polyglycerins der oben genannten Zusammensetzung kann durch Eigenkondensation von Glycerin in Gegenwart von geeigneten Katalysatoren wie beispielsweise Kaliumcarbonat, Silicaten gemäß DE-Al 40 29 323 (Henkel) oder Boraten gemäß DE-Al 41 17 033 (Henkel) bei Temperaturen im Bereich von 200 bis 260°C durchgeführt werden.The polyol poly-12-hydroxystearates can be prepared in a manner known per se. In the case of the polyglycerol poly-12-hydroxystearates, the polyglycerol and then the polyhydroxystearic acid are preferably first produced and finally both are esterified. The preparation of a polyglycerol of the abovementioned composition can be carried out by self-condensation of glycerol in the presence of suitable catalysts such as, for example, potassium carbonate, silicates according to DE-Al 40 29 323 (Henkel) or borates according to DE-Al 41 17 033 (Henkel) at temperatures in the range of 200 to 260 ° C are carried out.
Die Herstellung der Poly-12-hydroxystearinsäure erfolgt beispielsweise durch alkalisch katalysierte Polykondensation von 12-Hydroxystearinsäure, die durch Härtung von Ricino- säure bzw. technischer Ricinusölfettsäure gewonnen wird. Vorzugsweise werden dabei lineare Veresterungsprodukte mit 2 bis 10 und insbesondere 2 bis 8 Fettsäureeinheiten gebildet. Typi¬ scherweise wird die folgende Verteilung (GPC-Methode) erreicht:The poly-12-hydroxystearic acid is prepared, for example, by alkaline-catalyzed polycondensation of 12-hydroxystearic acid, which is obtained by curing ricinic acid or technical castor oil fatty acid. Linear esterification products having 2 to 10 and in particular 2 to 8 fatty acid units are preferably formed. The following distribution (GPC method) is typically achieved:
Monomere 1 bis 10 Gew.-%Monomers 1 to 10% by weight
Dimere 5 bis 15 Gew.-%Dimers 5 to 15% by weight
Trimere 5 bis 15 Gew.-%Trimers 5 to 15% by weight
Tetramere 5 bis 15 Gew.-%Tetramers 5 to 15% by weight
Pentamere 5 bis 15 Gew.-%Pentamers 5 to 15% by weight
Hexamere 5 bis 15 Gew.-%Hexamers 5 to 15% by weight
Heptamere 5 bis 15 Gew.-%Heptamers 5 to 15% by weight
Octamere 1 bis 10 Gew.-%Octamers 1 to 10% by weight
Oligomere ad 100 Gew.-%Oligomers ad 100% by weight
In einer besonderen Ausführungsform der Erfindung werden Gemische von 12- Hydroxystearinsäure und Ricinolsäure bzw. technischer Ricinusölfettsäure, die zu etwa 90 Gew.-% aus Ricinolsäure besteht, im Gewichtsverhältnis 99 : 1 bis 1 : 99 und vorzugsweise 75 : 25 bis 10 : 90 eingesetzt. In gleicher Weise ist es möglich, die Säuren einzeln zu kondensieren und anschließend die Kondensate abzumischen.In a particular embodiment of the invention, mixtures of 12-hydroxystearic acid and ricinoleic acid or technical castor oil fatty acid, which consists of approximately 90% by weight of ricinoleic acid, are used in a weight ratio of 99: 1 to 1:99 and preferably 75:25 to 10:90 . In the same way, it is possible to condense the acids individually and then to mix the condensates.
Bei der nachfolgenden Kondensation der Polyolkomponente, beispielsweise des Polyglycerins mit der Poly-12-hydroxystearinsäure bzw. den Gemischen mit Polyricinolsäure, wird eine komplexe Mischung homologer Polyester gebildet. Die Anteile an Mono-, Di-, Tri- und Oligoestem in den erfindungsgemaß einzusetzenden Polyolpoly-12-hydroxystearaten und vorzugsweise Polyglycerinpoly-12-hydroxystearaten richtet sich nach den Einsatzverhältnissen der Ausgangsverbindungen. In einer bevorzugten Ausführungsform der Erfindung wird ein Polyolpoly-12-hydroxystearat mit besonders vorteilhaften anwendungstechnischen Eigen¬ schaften eingesetzt, das man erhält, indem man etwa 1000 kg 12-Hydroxystearinsäure solange einer Eigenkondensation unterwirft, bis ein Produkt mit einer Säurezahl im Bereich von 50 bis 55 resultiert und dieses dann mit etwa 150 kg Polyglycerin der oben angegebenen Zusam¬ mensetzung weiter verestert, bis die Säurezahl bis auf einen Wert kleiner 2 abgenommen hat.In the subsequent condensation of the polyol component, for example the polyglycerol with the poly-12-hydroxystearic acid or the mixtures with polyricinoleic acid, a complex mixture of homologous polyester is formed. The proportions of mono-, di-, tri- and oligoesters in the polyol poly-12-hydroxystearates to be used according to the invention and preferably polyglycerol poly-12-hydroxystearates depend on the conditions of use of the starting compounds. In a preferred embodiment of the invention, a polyol poly-12-hydroxystearate with particularly advantageous application properties is used, which is obtained by subjecting about 1000 kg of 12-hydroxystearic acid to self-condensation until a product with an acid number in the range from 50 to 55 results and this is then further esterified with about 150 kg of polyglycerol of the composition indicated above until the acid number has decreased to a value less than 2.
Kondensationsprodukte auf Basis von Polyglycerin und Poly-12-hydroxystearinsäure bzw. Poly-12-hydroxystearinsäure/Polyricinolsäure können über ihre lodzahl charakterisiert werden. Typische Beispiele sind Polyester mit einer lodzahl < 10 (Basis 100 % 12-Hydroxy- stearinsäure) bzw 65 bis 80 (Basis 90 % 12-Hydroxystearinsäure, 10 % Ricinolsäure).Condensation products based on polyglycerol and poly-12-hydroxystearic acid or poly-12-hydroxystearic acid / polyricinoleic acid can be characterized by their iodine number. Typical examples are polyesters with an iodine number <10 (based on 100% 12-hydroxystearic acid) or 65 to 80 (based on 90% 12-hydroxystearic acid, 10% ricinoleic acid).
Kosmetische und pharmazeutische ZubereitungenCosmetic and pharmaceutical preparations
Die unter Verwendung der Polyolpoly-12-hydroxystearate erhältlichen O/W-Emul¬ sionen bzw. kosmetischen oder pharmazeutischen Zubereitungen können als weitere Bestand¬ teile u.a. Ölkörper, Co-Emulgatoren, Fette und Wachse, Stabilisatoren, Verdickungsmittel, biogene Wirkstoffe, Filmbildner, Duftstoffe, Farbstoffe, Perlglanzmittel, Konservierungsmittel, UV-Filter, Pigmente, Elektrolyte (z.B. Magnesiumsulfat) und pH-Regulatoren enthalten.The O / W emulsions or cosmetic or pharmaceutical preparations obtainable using the polyol poly-12-hydroxystearates can be used as further components, inter alia. Contain oil oils, co-emulsifiers, fats and waxes, stabilizers, thickeners, biogenic agents, film formers, fragrances, dyes, pearlescent agents, preservatives, UV filters, pigments, electrolytes (e.g. magnesium sulfate) and pH regulators.
Als Ölkörper kommen beispielsweise Guerbetalkohole auf Basis von Fettalkoholen mit 6 bis 18, vorzugsweise 8 bis 10 Kohlenstoffatomen, Ester von linearen C6-C2o-Fettsäuren mit linearen C6-C2o-Fettalkoholen, Ester von verzweigten Cβ-Cι3- Carbonsäuren mit linearen Cβ- C2o-Fettalkoholen, Ester von linearen Cβ-C.g-Fettsäuren mit verzweigten Alkoholen, ins¬ besondere 2-Ethylhexanol, Ester von linearen und/oder verzweigten Fettsäuren mit mehr¬ wertigen Alkoholen (wie z.B. Dimerdiol oder Trimerdiol) und/oder Guerbetalkoholen, Trigly¬ ceride auf Basis Cβ-Cio-Fettsäuren, pflanzliche Öle, verzweigte primäre Alkohole, substituierte Cyclohexane, Guerbetcarbonate, Dialkylether und/oder aliphatische bzw. naphthenische Koh¬ lenwasserstoffe in Betracht. Als Co-Emulgatoren kommen beispielsweise gehärtetes und ethoxyliertes Ricinusöl, ethoxylierte Fettalkohole bzw. Partialglyceride, Alkyloligoglykoside, Polyglycerinfettsäureester oder Polyglycerinpolyricinoleate in Frage. Als Überfettungsmittel können Substanzen wie bei¬ spielsweise polyethoxylierte Lanolinderivate, Lecithinderivate, Polyolfettsäureester, Monogly¬ ceride und Fettsäurealkanolamide verwendet werden, wobei die letzteren gleichzeitig als Schaumstabilisatoren dienen. Geeignete Verdickungsmittel sind bei-spielsweise Polysaccha¬ ride, insbesondere Xanthan-Gum, Guar-Guar, Agar-Agar, Alginate und Tylosen, Carboxy¬ methylcellulose und Hydroxyethylcellulose, ferner höhermolekulare Polyethylenglycolmono- und -diester von Fettsäuren, Polyacrylate, Polyvinylalkohol und Polyvinylpyrrolidon, Tenside wie beispielsweise Fettalkoholethoxylate mit eingeengter Homologenverteilung oder Alkyl- oligoglucoside sowie Elektrolyte wie Kochsalz und Ammoniumchlorid. Unter biogenen Wirkstoffen sind beispielsweise Pflanzenextrakte und Vitaminkomplexe zu verstehen. Ge¬ bräuchliche Filmbildner sind beispielsweise Chitosan, πükrokristallines Chitosan, quaterniertes Chitosan, Polyvinylpyrrolidon, Vinylpyrrolidon-Vinylacetat-Copolymerisate, Polymere der Acrylsäurereihe, quaternäre Cellulose-Derivate, Kollagen, Hyaluronsäure bzw. deren Salze und ähnliche Verbindungen. Als Konservierungsmittel eignen sich beispielsweise Phenoxyethanol, Formaldehydlösung, Parabene, Pentandiol oder Sorbinsäure. Als Perlglanz-mittel kommen beispielsweise Glycoldistearinsäureester wie Ethylenglycoldistearat, aber auch Fettsäuremono- glycolester in Betracht. Als Farbstoffe können die für kosmetische Zwecke geeigneten und zu¬ gelassenen Substanzen verwendet werden, wie sie beispielsweise in der Publikation "Kosme¬ tische Färbemittel" der Farbstoffkommission der Deutschen Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, S.81-106 zusammengestellt sind. Diese Farbstoffe werden üblicherweise in Konzentrationen von 0,001 bis 0,1 Gew.-%, bezogen auf die gesamte Mi¬ schung, eingesetzt.Guerbet alcohols based on fatty alcohols with 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C6-C 2 o-fatty acids with linear C6-C 2 o-fatty alcohols, esters of branched Cβ-C 3 -carboxylic acids come as oil bodies, for example linear Cβ-C2o fatty alcohols, esters of linear Cβ-Cg fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of linear and / or branched fatty acids with polyhydric alcohols (such as dimer diol or trimer diol) and / or Guerbet alcohols , Triglycerides based on Cβ-cio fatty acids, vegetable oils, branched primary alcohols, substituted cyclohexanes, Guerbet carbonates, dialkyl ethers and / or aliphatic or naphthenic hydrocarbons. Examples of suitable co-emulsifiers are hardened and ethoxylated castor oil, ethoxylated fatty alcohols or partial glycerides, alkyl oligoglycosides, polyglycerol fatty acid esters or polyglycerol polyricinoleates. Substances such as polyethoxylated lanolin derivatives, lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used as superfatting agents, the latter simultaneously serving as foam stabilizers. Suitable thickeners are, for example, polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, and also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as fatty alcohol ethoxylates with a narrow homolog distribution or alkyl oligoglucosides and electrolytes such as table salt and ammonium chloride. Biogenic active substances are understood to mean, for example, plant extracts and vitamin complexes. Common film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid or its salts and similar compounds. Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid. Suitable pearlescent agents are, for example, glycol distearic acid esters such as ethylene glycol distearate, but also fatty acid mono-glycol esters. The dyes which can be used are the substances which are suitable and approved for cosmetic purposes, such as are listed, for example, in the publication "Cosmetic Dyes" by the Dye Commission of the German Research Foundation, Verlag Chemie, Weinheim, 1984, pp. 81-106. These dyes are usually used in concentrations of 0.001 to 0.1% by weight, based on the overall mixture.
Der Gesamtanteil der Hilfs- und Zusatzstoffe kann 1 bis 50, vorzugsweise 5 bis 40 Gew.-% - bezogen auf die Mittel - betragen. Die Herstellung der O/W-Emulsionen kann in an sich bekannter Weise nach der Kalt/Kalt-, Heiß/Heiß-, Heiß/Kalt- oder PIT-Methode erfolgen.The total proportion of auxiliaries and additives can be 1 to 50, preferably 5 to 40% by weight, based on the composition. The O / W emulsions can be prepared in a manner known per se by the cold / cold, hot / hot, hot / cold or PIT method.
Die nachfolgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn darauf einzuschränken. BeispieleThe following examples are intended to explain the subject matter of the invention in more detail without restricting it. Examples
Beispiel 1, Vergleichsbeispiel VIExample 1, Comparative Example VI
Zur Herstellung einer Gesichtsreinigungscreme wurden die Bestandteile I bei 80°C geschmolzen und homogen verrührt. Die Bestandteile der Phase II wurden ebenfalls auf 80°C erhitzt, langsam unter Rühren zu Phase I gegeben und 5 min bei 80°C emulgiert. Die Emulsion wurde unter Rühren abgekühlt und bei ca. 50°C vorsichtig homogenisiert. Nach Erreichen einer Temperatur von 30°C wurde das Rühren eingestellt und die Emulsion nach Abkühlen auf Raumtemperatur entlüftet. Unter Verwendung von Polyglycerinpoly-12-hydroxystearat als O/W-Emulgator wurde eine viskose Creme erhalten, die auch nach 12wöchiger Lagerung noch stabil war. Bei Verwendung eines bekannten hydrophilen O/W-Emulgators des Stands der Technik blieb die Mischung zweiphasig. Die Zusammensetzung der Mischungen kann Tabelle 1 entnommen werden (Mengenangaben als Gew.-%).To prepare a facial cleansing cream, the constituents I were melted at 80 ° C. and stirred until homogeneous. The components of phase II were also heated to 80 ° C., added slowly to phase I with stirring and emulsified at 80 ° C. for 5 minutes. The emulsion was cooled with stirring and carefully homogenized at about 50 ° C. After a temperature of 30 ° C. had been reached, the stirring was stopped and the emulsion was vented after cooling to room temperature. Using polyglycerol poly-12-hydroxystearate as an O / W emulsifier, a viscous cream was obtained which was still stable even after 12 weeks of storage. When using a known hydrophilic O / W emulsifier from the prior art, the mixture remained two-phase. The composition of the mixtures can be found in Table 1 (quantitative data as% by weight).
Tabelle 1Table 1
Zusammensetzung Ges-chtsre-nigungscremeComposition facial cleansing cream
(JesϊchtsreiiugHngscreme(JesutstsreiiugHngscreme
Phase Zusammensetzung Beispiel l Vergleichsbeispiel VIPhase Composition Example 1 Comparative Example VI
I EmulgadeΘ PL 1618 10,0 15,0I EmulgadeΘ PL 1618 10.0 15.0
Plantaren® 1200 10,0 10,0Plantaren® 1200 10.0 10.0
Dehymuls® PGPH 5,0 _Dehymuls® PGPH 5.0 _
Myritol® 312 3,0 _Myritol® 312 3.0 _
Cetiol® SN _ 3,0 π Glycerin, 86 Gew.-%ig 3,0 3,0Cetiol® SN _ 3.0 π glycerol, 86% by weight 3.0 3.0
Wasser ad 100Water ad 100
Viskosität [Pa*s] 112 _Viscosity [Pa * s] 112 _
Stabilität > 12 Wochen zweiphasig n. Herstell.Stability> 12 weeks two-phase after manufacturing
Legende: Emulgade® PL 1618 = Hexadecyl Polyglucose and Hexadecyl AlcoholLegend: Emulgade® PL 1618 = Hexadecyl Polyglucose and Hexadecyl Alcohol
Plantaren® 1200 = Decyl PolyglucosePlantaren® 1200 = decyl polyglucose
Myritol® 312 = Caprylic/Capric TriglycerideMyritol® 312 = Caprylic / Capric Triglyceride
Dehymuls® PGPH = Polyglyceryl Poly- 12-hydroxystearateDehymuls® PGPH = polyglyceryl poly-12-hydroxystearate
Cetiol® SN = Cetearyl Isononanoate Beispiel 2. Vergleichsbeispiel V2Cetiol® SN = Cetearyl Isononanoate Example 2. Comparative Example V2
Zur Herstellung einer Pflegecreme wurde wie unter Beispiel 1 beschrieben verfahren. Die unter Verwendung des Polyglycerinpoly-12-hydroxystearates hergestellte Creme war auch nach einer Lagerung von mehr als 12 Wochen noch stabil, die ohne den O/W-Emulgator trennte sich innerhalb von 8 Wochen in eine ölige und eine wäßrige Phase. Die Zusammen¬ setzung der Mischungen kann Tabelle 2 entnommen werden (Mengenangaben als Gew.-%).The procedure for producing a care cream was as described in Example 1. The cream produced using the polyglycerol poly-12-hydroxystearate was still stable even after storage for more than 12 weeks; without the O / W emulsifier, the cream separated into an oily and an aqueous phase within 8 weeks. The composition of the mixtures can be found in Table 2 (quantitative data as% by weight).
Legende: Cutina® MD Glyceiyl Stearate Eumulgin® B2 Ceteareth-20 Eumulgin® Bl Ceteareth-12 Lanette® O Cetearyl Alcohol Cetiol® V Decyl Oleate Cetiol® SN Cetearyl Isononanoate Legend: Cutina® MD Glyceiyl Stearate Eumulgin® B2 Ceteareth-20 Eumulgin® Bl Ceteareth-12 Lanette® O Cetearyl Alcohol Cetiol® V Decyl Oleate Cetiol® SN Cetearyl Isononanoate
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19524210.6 | 1995-07-03 | ||
| DE19524210A DE19524210A1 (en) | 1995-07-03 | 1995-07-03 | Use of polyol poly-12-hydroxystearates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO1997002002A2 true WO1997002002A2 (en) | 1997-01-23 |
| WO1997002002A3 WO1997002002A3 (en) | 1997-02-13 |
Family
ID=7765899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1996/002750 WO1997002002A2 (en) | 1995-07-03 | 1996-06-24 | Use of polyolpoly-12-hydroxystearates |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE19524210A1 (en) |
| WO (1) | WO1997002002A2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005005199A1 (en) * | 2005-02-03 | 2006-08-10 | Beiersdorf Ag | Use of alkyl glucoside for obtaining or improving the microbiological stability of cosmetic or dermatological preparations, which contain preservatives and for protecting organic products from the attack of the mycobiont |
| JPWO2013069690A1 (en) * | 2011-11-07 | 2015-04-02 | 日清オイリオグループ株式会社 | Cleaning composition and cleaning material |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19548345C2 (en) * | 1995-12-22 | 1998-10-15 | Henkel Kgaa | Use of mixtures of special emulsifiers and oil bodies |
| DE19650473C1 (en) * | 1996-12-05 | 1998-04-02 | Henkel Kgaa | Instant sun tan lotion formulations containing di:hydroxy:acetone |
| DE19651478A1 (en) * | 1996-12-11 | 1998-06-18 | Beiersdorf Ag | Sunscreen preparations containing surface-active mono- or oligoglyceryl compounds, water-soluble UV filter substances and optionally inorganic micropigments |
| DE19751221A1 (en) * | 1997-11-19 | 1999-05-20 | Beiersdorf Ag | Use of alkyl hydroxystearoyl-stearate in sunscreen compositions |
| DE19752564A1 (en) * | 1997-11-27 | 1999-07-01 | Henkel Kgaa | Pigment dispersions |
| DE19917493A1 (en) * | 1999-04-17 | 2000-10-19 | Cognis Deutschland Gmbh | Use of mixtures for the production of make-up removers |
| US7129276B2 (en) * | 2001-05-04 | 2006-10-31 | L'oreal S.A. | Composition comprising at least one liquid fatty phase structured by at least one semi-crystalline polymer |
| WO2003061613A1 (en) | 2002-01-24 | 2003-07-31 | L'oreal | Composition containing a semi-crystalline polymer and an ester |
| US7255870B2 (en) | 2002-01-24 | 2007-08-14 | L'oreal | Composition containing a semicrystalline polymer, uses thereof, and method for making |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0731413A (en) * | 1993-07-14 | 1995-02-03 | Ajinomoto Co Inc | Emulsion composition stable over wide temperature range |
| DE4420516C2 (en) * | 1994-06-13 | 1998-10-22 | Henkel Kgaa | Polyglycerol polyhydroxystearates |
-
1995
- 1995-07-03 DE DE19524210A patent/DE19524210A1/en not_active Withdrawn
-
1996
- 1996-06-24 WO PCT/EP1996/002750 patent/WO1997002002A2/en active Application Filing
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005005199A1 (en) * | 2005-02-03 | 2006-08-10 | Beiersdorf Ag | Use of alkyl glucoside for obtaining or improving the microbiological stability of cosmetic or dermatological preparations, which contain preservatives and for protecting organic products from the attack of the mycobiont |
| JPWO2013069690A1 (en) * | 2011-11-07 | 2015-04-02 | 日清オイリオグループ株式会社 | Cleaning composition and cleaning material |
| US9428715B2 (en) | 2011-11-07 | 2016-08-30 | The Nisshin Oillio Group, Ltd. | Composition for cleansing agent and cleansing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1997002002A3 (en) | 1997-02-13 |
| DE19524210A1 (en) | 1997-01-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0766661B1 (en) | Polyolpolyhydroxystearates | |
| EP0735853B1 (en) | W/o/w emulsions | |
| EP0853494B1 (en) | Oil-water emulsifiers | |
| EP1500427B1 (en) | Emulsifier for low-viscosity w/o emulsions, based on partially crosslinked polyglycerin esters of polyhydroxystearic acid. | |
| EP0835862B1 (en) | Partial esters of polyglycerine with fatty acids and polyfunctional carboxylic acids, their preparation and use | |
| DE10211801B4 (en) | Cosmetic and pharmaceutical preparations containing an oxalkylated polyglycerol ester | |
| EP0554292A1 (en) | Oil-in-water emulsions. | |
| DE3222471A1 (en) | EMULSIFIERS AND EMULSIFIED COSMETICS | |
| EP0780112A1 (en) | Method of elaboration of O/W- or O/W/O emulsions and emulsions therefrom | |
| WO1997002002A2 (en) | Use of polyolpoly-12-hydroxystearates | |
| WO1998044903A1 (en) | USE OF LOW MOLECULAR OLIGOMER ESTERS OF α-HYDROXY ACIDS AND/OR AROMATIC OF o-HYDROXY ACIDS IN COSMETIC FORMULATIONS | |
| EP0804146B1 (en) | Polyglycerine polyricinoleates | |
| EP1071466B2 (en) | Glycolipid creams | |
| DE3338890A1 (en) | NEW O / W EMULSIFIERS FOR COSMETIC PURPOSES | |
| DE19523478C1 (en) | Cosmetic and / or pharmaceutical preparations | |
| EP1426401B1 (en) | Water-based emulgator wax gels | |
| WO1996028245A1 (en) | Multiple w/o/w emulsions | |
| EP1178044B1 (en) | Tocopherylalkoxylates, their preparation and their use in cosmetic and pharmaceutical forms | |
| EP0904050B1 (en) | Use of lactic acid esters | |
| DE19505004C1 (en) | Multiple W / O / W emulsions and process for their preparation | |
| DE19643062A1 (en) | Use of poly:ol-poly-12-hydroxy-stearate compounds as pigment dispersants | |
| WO1996016924A1 (en) | Process for producing complex esters | |
| DE19525108A1 (en) | Cosmetic or pharmaceutical emulsion, e.g. for skin- and hair care - comprises ethoxylated poly:glycerol fatty acid ester emulsifier in specific amt. giving temp.-stable viscosity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A2 Designated state(s): JP US |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A2 Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
| AK | Designated states |
Kind code of ref document: A3 Designated state(s): JP US |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A3 Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
| DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| 122 | Ep: pct application non-entry in european phase |