CN1564675A - 抗刺激剂 - Google Patents
抗刺激剂 Download PDFInfo
- Publication number
- CN1564675A CN1564675A CN02819876.XA CN02819876A CN1564675A CN 1564675 A CN1564675 A CN 1564675A CN 02819876 A CN02819876 A CN 02819876A CN 1564675 A CN1564675 A CN 1564675A
- Authority
- CN
- China
- Prior art keywords
- ester
- oxyalkylated
- carbon atom
- oxyalkylated ester
- ppg
- 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.)
- Pending
Links
- 239000002085 irritant Substances 0.000 title abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 278
- 150000002148 esters Chemical class 0.000 claims abstract description 208
- 230000007794 irritation Effects 0.000 claims abstract description 72
- 239000012895 dilution Substances 0.000 claims abstract description 44
- 238000010790 dilution Methods 0.000 claims abstract description 44
- 239000002453 shampoo Substances 0.000 claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000002537 cosmetic Substances 0.000 claims abstract description 37
- 230000000694 effects Effects 0.000 claims abstract description 34
- 150000001991 dicarboxylic acids Chemical class 0.000 claims abstract description 14
- 150000003628 tricarboxylic acids Chemical class 0.000 claims abstract description 7
- 238000004851 dishwashing Methods 0.000 claims abstract description 3
- -1 phenyl aryl Chemical group 0.000 claims description 164
- 229910052799 carbon Inorganic materials 0.000 claims description 67
- 150000001721 carbon Chemical group 0.000 claims description 65
- 239000004094 surface-active agent Substances 0.000 claims description 45
- 239000002253 acid Substances 0.000 claims description 34
- 125000003118 aryl group Chemical group 0.000 claims description 31
- 210000004209 hair Anatomy 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000002585 base Substances 0.000 claims description 24
- 230000000638 stimulation Effects 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- 239000004902 Softening Agent Substances 0.000 claims description 19
- BNWJOHGLIBDBOB-UHFFFAOYSA-N myristicine Natural products COC1=CC(CC=C)=CC2=C1OCO2 BNWJOHGLIBDBOB-UHFFFAOYSA-N 0.000 claims description 18
- 229920006395 saturated elastomer Polymers 0.000 claims description 17
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 claims description 15
- 239000002280 amphoteric surfactant Substances 0.000 claims description 14
- 230000002421 anti-septic effect Effects 0.000 claims description 13
- 229940020947 fluorescein sodium Drugs 0.000 claims description 13
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 12
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 12
- 239000003093 cationic surfactant Substances 0.000 claims description 11
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
- 239000006260 foam Substances 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- 239000003599 detergent Substances 0.000 claims description 8
- 239000002562 thickening agent Substances 0.000 claims description 8
- 239000003945 anionic surfactant Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 239000003605 opacifier Substances 0.000 claims description 7
- 230000000699 topical effect Effects 0.000 claims description 7
- 239000000080 wetting agent Substances 0.000 claims description 7
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 6
- 235000013336 milk Nutrition 0.000 claims description 6
- 239000008267 milk Substances 0.000 claims description 6
- 210000004080 milk Anatomy 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 230000000475 sunscreen effect Effects 0.000 claims description 5
- 239000000516 sunscreening agent Substances 0.000 claims description 5
- 241001465754 Metazoa Species 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000004745 nonwoven fabric Substances 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 125000005189 alkyl hydroxy group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000010408 film Substances 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 235000016068 Berberis vulgaris Nutrition 0.000 claims 1
- 241000335053 Beta vulgaris Species 0.000 claims 1
- 239000012190 activator Substances 0.000 claims 1
- 239000011521 glass Substances 0.000 claims 1
- 239000004033 plastic Substances 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 11
- 238000012360 testing method Methods 0.000 abstract description 5
- 231100000021 irritant Toxicity 0.000 abstract description 2
- 239000003788 bath preparation Substances 0.000 abstract 1
- NJDNXYGOVLYJHP-UHFFFAOYSA-L disodium;2-(3-oxido-6-oxoxanthen-9-yl)benzoate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=CC(=O)C=C2OC2=CC([O-])=CC=C21 NJDNXYGOVLYJHP-UHFFFAOYSA-L 0.000 abstract 1
- 230000003834 intracellular effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 57
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 55
- 239000003921 oil Substances 0.000 description 34
- 235000019198 oils Nutrition 0.000 description 34
- 244000060011 Cocos nucifera Species 0.000 description 31
- 235000013162 Cocos nucifera Nutrition 0.000 description 31
- 150000001875 compounds Chemical class 0.000 description 29
- 150000001412 amines Chemical class 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 22
- 229920001296 polysiloxane Polymers 0.000 description 20
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical class C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 18
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 125000003696 stearoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 18
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 16
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 14
- 229940063557 methacrylate Drugs 0.000 description 14
- 229920002907 Guar gum Polymers 0.000 description 13
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 13
- 239000000665 guar gum Substances 0.000 description 13
- 235000010417 guar gum Nutrition 0.000 description 13
- 229960002154 guar gum Drugs 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 13
- 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 12
- 241000498779 Myristica Species 0.000 description 12
- 235000009421 Myristica fragrans Nutrition 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 12
- 239000001913 cellulose Substances 0.000 description 12
- 229920002678 cellulose Polymers 0.000 description 12
- 239000001702 nutmeg Substances 0.000 description 12
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 description 12
- 235000011152 sodium sulphate Nutrition 0.000 description 12
- 239000000600 sorbitol Substances 0.000 description 12
- 125000002091 cationic group Chemical group 0.000 description 11
- 125000005456 glyceride group Chemical group 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 150000003839 salts Chemical group 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 10
- 229910019142 PO4 Inorganic materials 0.000 description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 10
- 239000010452 phosphate Substances 0.000 description 10
- 239000002953 phosphate buffered saline Substances 0.000 description 10
- 238000012216 screening Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 229960003237 betaine Drugs 0.000 description 9
- 150000005690 diesters Chemical class 0.000 description 9
- 239000004615 ingredient Substances 0.000 description 9
- 229960001173 oxybenzone Drugs 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000001294 propane Substances 0.000 description 9
- 229940099259 vaseline Drugs 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 241001597008 Nomeidae Species 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 8
- 229940063953 ammonium lauryl sulfate Drugs 0.000 description 8
- 235000012677 beetroot red Nutrition 0.000 description 8
- 235000002185 betanin Nutrition 0.000 description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 8
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 8
- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical compound NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 description 7
- DHHFDKNIEVKVKS-MVUYWVKGSA-N Betanin Natural products O=C(O)[C@@H]1NC(C(=O)O)=C/C(=C\C=[N+]/2\[C@@H](C(=O)[O-])Cc3c\2cc(O)c(O[C@H]2[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O2)c3)/C1 DHHFDKNIEVKVKS-MVUYWVKGSA-N 0.000 description 7
- 229930006000 Sucrose Natural products 0.000 description 7
- 235000011037 adipic acid Nutrition 0.000 description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 7
- 235000011130 ammonium sulphate Nutrition 0.000 description 7
- 239000001654 beetroot red Substances 0.000 description 7
- 238000005660 chlorination reaction Methods 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 7
- 230000007246 mechanism Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 239000005720 sucrose Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
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- 150000004665 fatty acids Chemical class 0.000 description 6
- 150000002194 fatty esters Chemical class 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 6
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 6
- 230000000474 nursing effect Effects 0.000 description 6
- IIGMITQLXAGZTL-UHFFFAOYSA-N octyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCCCCCC IIGMITQLXAGZTL-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 239000000419 plant extract Substances 0.000 description 6
- 239000010497 wheat germ oil Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- DHHFDKNIEVKVKS-FMOSSLLZSA-N Betanin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC(C(=C1)O)=CC(C[C@H]2C([O-])=O)=C1[N+]2=C\C=C\1C=C(C(O)=O)N[C@H](C(O)=O)C/1 DHHFDKNIEVKVKS-FMOSSLLZSA-N 0.000 description 5
- 244000147568 Laurus nobilis Species 0.000 description 5
- 235000017858 Laurus nobilis Nutrition 0.000 description 5
- 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 5
- 235000005212 Terminalia tomentosa Nutrition 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- 150000007942 carboxylates Chemical class 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 230000003750 conditioning effect Effects 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
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- 238000000338 in vitro Methods 0.000 description 5
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- 239000013642 negative control Substances 0.000 description 5
- 229960001679 octinoxate Drugs 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- QELSKZZBTMNZEB-UHFFFAOYSA-N propylparaben Chemical compound CCCOC(=O)C1=CC=C(O)C=C1 QELSKZZBTMNZEB-UHFFFAOYSA-N 0.000 description 5
- 239000002888 zwitterionic surfactant Substances 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 4
- YBGZDTIWKVFICR-JLHYYAGUSA-N Octyl 4-methoxycinnamic acid Chemical compound CCCCC(CC)COC(=O)\C=C\C1=CC=C(OC)C=C1 YBGZDTIWKVFICR-JLHYYAGUSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- 230000021523 carboxylation Effects 0.000 description 4
- 238000006473 carboxylation reaction Methods 0.000 description 4
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- IIRDTKBZINWQAW-UHFFFAOYSA-N hexaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCO IIRDTKBZINWQAW-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
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Abstract
具有抗刺激活性的二羧酸或三羧酸的烷氧基化的酯,采用含有5%烷氧基化的酯的试验组合物,在1∶50稀释度时测得荧光素钠的胞内渗漏减少了15%或更多,在1∶100稀释度时减少了40%或更多。这些烷氧基化的酯可有效用于化妆品和个人护理用品,尤其是婴儿香波、洗手液和泡泡浴液之类的产品。采用这种减弱刺激的方法可将对人体有刺激的刺激剂与烷氧基化的酯一起用于个人护理或美容化妆产品。
Description
发明领域
本发明涉及化妆和/或个人护理产品领域。更具体的,本发明涉及在化妆和/或个人护理产品中用作抗刺激剂的化合物以及相关的减弱刺激的方法。
发明背景
个人护理产品,如洗发液,调理剂,脱毛剂,遮光剂等的配方和制造中存在许多难题。用于这类产品的一些成分可能会对皮肤和眼睛造成刺激。例如,洗发液通常含有各种表面活性化合物或表面活性剂,脱毛剂的配方中含有有机或无机碱,某些皮肤护理产品含有羟酸,这些都会造成刺激。此外,一些产品(例如肥皂、去污剂、清洁剂、剃须膏等)可能会除去一些皮肤的保护性脂类从而增加皮肤对其它本来不会造成刺激的成分的敏感性。
无论刺激的原因怎样,人们采取了许多方法来减弱个人护理和化妆产品的刺激性,其中包括确定造成刺激的成分,降低此这种成分的浓度或将它们完全除去。然而,在许数情况下,减少或除去所述刺激成分可能是不可行或不合需要的,因为它们通常是配方的活性成分。例如,洗发液、脱毛剂和某些皮肤护理产品中分别含有表面活性剂、碱和羟酸以实现这种产品的主要目的。因此,不是除去刺激剂,而是在化妆品和个人护理产品中包含抗刺激剂可能更符合需要。
已有人提仪将抗刺激剂用于化妆品,例如可参见R.L.Goldemberg的《将抗刺激剂用于化妆品》(Use of Anti-Irritants in Cosmetic Formulating),J.Soc.Cosmetic Chemists,6:317-340(1965)和《抗刺激剂》(Anti-irritants),J.Soc.Cosmetic Chemists,30:415-427(1979),在此将其并入以供参考。Goldemberg将抗刺激剂定义为任何一种″当与皮肤或眼刺激剂同时使用时足以将它们的刺激降至身体可以忍受的程度″的试剂。广义上可认为,如果一种化合物与刺激剂同时使用时对人体的刺激低于相同条件下不含抗刺激剂的相同刺激剂对人体的刺激,则这种化合物就可被认为是抗刺激剂。
换句话说,如果当一种化合物与刺激剂一起使用可降低刺激则被认为是抗刺激剂。有了这个定义,任何与产品的刺激性成分分开使用,例如在使用产品前使用,的物质通常都不被认为是抗刺激剂。例如,已知可在使用高pH松弛剂(relaxer)前在头皮上施加一层矿脂。即便矿脂确实可以减弱松弛剂造成的头皮刺激,但它不是抗刺激剂,因为它是分开使用的,除非当矿脂被用于松弛剂的配方时还能减弱刺激。
曾经讨论了抗刺激活性的多种机制。一种机制认为由于刺激剂与抗刺激化合物络合从而减弱了刺激剂的刺激能力。聚乙烯基吡咯烷酮(PVP),已知它可减弱碘的刺激能力,被认为是通过这种机制的抗刺激剂的一个例子。当将PVP加入碘溶液时,后者就不会再刺激粘液组织同时保持其杀菌活性。
另一种机制认为抗刺激剂封闭了皮肤角蛋白的化学活性位点,从而可阻止刺激剂与此活性位点接触。例如,聚季铵-10(polyquaternium-10)和硬脂基二甲基胺氧化物以这种机制发挥作用。
还有另一种机制认为是减少了刺激剂和皮肤之间的物理性接触。通过这种机制发挥作用的原材料的例子有增稠剂,它减缓了刺激剂充满皮肤/制剂界面的速度。
一些方法被用来测量刺激值。测量刺激和抗刺激效果的体内方法的例子包括重复攻击试验(Repeated Insult Patch Testing)(RIPT)和Draize法,这两者方法都是精通此领域的技术人员熟知的。体外方法的例子有InVitro International的EyetexTM,以及MatTek公司的EpiDermTM和EpiOcularTM。R.Goldemberg在《局部刺激的减弱》(Reduction of Topical Irritation),J.Soc.Cosmetic Chemists,28,667-679(1977)中描述了另一种测量刺激的方法,在此将其并入以供参考。
减弱刺激的方法还不完善,因此仍需要有效的抗刺激剂。例如,需要有可减弱基于表面活性剂的化妆和/或个人护理产品的刺激的成分。特别需要易于和个人护理产品相容的抗刺激剂和/或能够带来其它有利特性,如稳定化作用、保湿性、延展性、粘度等,的抗刺激剂。特别需要既能使产品有较好的用后感觉和/或能作为清洁产品配方的抗刺激剂。
发明概述
在一个优选的方面,本发明实现这些需求是通过提供具有上述抗刺激活性的二羧酸或三羧酸的烷氧基化的酯,测量所述活性的方法是对相同的皮肤表面施加相同时间的同样制剂,所述制剂含或不含本发明抗刺激化合物,并比较所得结果,刺激程度的降低即为抗刺激活性。还可通过显示试验组合物与对照组合物相比荧光素钠胞内渗漏的降低来测量抗刺激特性。采用含有5%重量的烷氧基化的酯的试验组合物,优选的烷氧基化的酯的抗刺激活性在1∶50稀释度时为15%或更高或在1∶100稀释度时为40%或更高。本发明另一个优选的方面提供了具有确定的化学结构的烷氧基化的酯。更加优选地,特定化学结构的烷氧基化的酯也具有抗刺激活性。
根据另一个优选的方面,本发明提供了减弱因使用含有刺激剂的个人护理品或化妆品而对人或动物造成的刺激的方法。所述方法包括施用个人护理品或化妆品,所述产品含有刺激剂和至少一种二羧酸或三羧酸的烷氧基化的酯,该酯具有确定的抗刺激活性。本发明的方法对于减弱表面活性剂,尤其是个人护理品或化妆品中的表面活性剂造成的刺激特别有效。
根据再一个优选的方面,本发明提供了含有刺激剂(优选为表面活性剂)和至少一种这里所述烷氧基化的酯的组合物。优选地,该组合物的烷氧基化的酯具有上述抗刺激活性。优选地,所述组合物可作为可稀释的预先混合的混合物或作为产品配方。所述组合物中还可含有各种其它成分。参照优选实施方案进一步描述了本发明。
优选实施方案的详细描述
人们惊奇地发现,当某些烷氧基化的酯和刺激剂一起存在于组合物中时可减弱含有刺激剂的组合物的刺激性,因而显示出抗刺激活性。二羧酸的烷氧基化的酯是烷氧基化的醇和二羧酸的单酯或二酯。三羧酸的烷氧基化的酯是烷氧基化的醇和三羧酸的二酯或三酯。一些这样的酯描述在美国专利5,382,377;5,455,025和5,597,555和美国专利申请09/410,585中,所有这些在此全文并入以供参考,并由本专利申请的代理人,新泽西的Croda Incorporated of Piscataway代理。这些化合物是优秀的软化剂。其它的也在这里描述。
以下实施例说明了某些烷氧基化的酯的抗刺激活性。制备了试验组合物A和对照组合物B。试验组合物A含有5%二-PPG-3-PEG-4肉豆蔻醚己二酸酯,三丙氧基-四乙氧基肉豆寇基醇和己二酸的烷氧基化的(三丙氧基-四乙氧基)二酯以及10%月桂基硫酸钠(SLS),一种已知的刺激剂,溶于磷酸缓冲的盐水(PBS),pH为6.8-7.2。对照组合物B含有10%SLS,溶于相同pH的PBS,但不含烷氧基化的酯。将单独的PBS溶液(无SLS和所述酯)用作阴性对照溶液。实验在MatTek公司的EpiOcularTM组织模型(OCL-200)上进行。EpiOcularTM插入物在测定培养基上平衡过夜。试验组合物A和B和阴性对照溶液然后分别与细胞直接接触。在1、5和10分钟时测定各个试验物质的细胞死亡过程。将阴性对照插入插入物暴露于磷酸缓冲盐水(PBS)10分钟。插入物用PBS洗涤,在Eagle极限必需培养基(EMEM)中平衡,然后在MTT(3-{4,5-二甲基噻唑-2-基]-2,5-二苯基溴化四唑)中培养并用异丙醇提取过夜。试验培养样品的光密度与阴性对照插入物PBS(100%存活)比较。
表1显示了试验组合物A和对照组合物B的细胞存活比例:
表1
时间(min) | 细胞存活(%) | |
组合物A(SLS+二-PPG-3-PEG-4肉豆蔻醚己二酸酯) | 组合物B(只有SLS) | |
0 | 100 | 100 |
1 | 97.79 | 72.56 |
5 | 82.18 | 52.16 |
10 | 64.25 | 31.75 |
由表1可见,加入二-PPG-3-PEG-4肉豆蔻醚己二酸酯大大降低了细胞死亡,这说明二-PPG-3-PEG-4肉豆蔻醚己二酸酯具有抗刺激活性。
不是所有的二羧酸或三羧酸的烷氧基化的酯都具有所需抗刺激活性。在这点上,只有具有这种最小抗刺激活性的烷氧基化的酯适合用作抗刺激剂(称为抗刺激活性)。此外,具有较大抗刺激活性的烷氧基化的酯是优选的。
根据本发明优选的实施方案,上述抗刺激活性标准被用于筛选优选的烷氧基化的酯。满足这一标准的烷氧基化的酯被优先选择用于制造含有刺激剂的个人护理和化妆产品。被试验的烷氧基化的酯基于测量试验组合物(含有刺激剂和备选的烷氧基化的酯)和对照组合物(组成实质上相同但不含备选的烷氧基化的酯)的刺激潜能来评价。比较测得的试验组合物和对照组合物的刺激潜能。试验组合物相对于对照的刺激潜能的减弱的幅度(如果有的话)是对备选烷氧基化的酯抗刺激活性的量度。上述筛选标准是刺激潜能减弱的阈值。活性大于上述标准的候选物被选择。上述选择标准还被用于将酯类按其抗刺激活性的幅度进行分类。
测量烷氧基化的酯刺激潜能的实验方法是跨上皮渗透性(Trans-EpithelialPermeability)(TEP)测定。所述TEP测定测量合适的标记试剂,如荧光素钠,通过暴露于含有刺激剂的组合物的细胞的胞内渗漏。渗漏越小则说明细胞的损伤程度越低。如果将细胞暴露于有和没有抗刺激剂的含有刺激剂的组合物,则胞内渗漏的降低幅度说明了抗刺激剂的抗刺激能力。为了解关于TEP测定的其它内容可参见Tchao,R.,《在体外通过荧光素的跨上皮渗透性测定眼刺激剂》(Trans-EpithelialPermeability of Fluorescein In Vitro As An Assay To Determine EyeIrritants),《体外毒理学进展》(Progress in In Vitro Toxicology),AM Goldberg编,6:271-283(1988);Drewitt-Barlow,B.,McPherson,J.,Broyd,J.和Williamson,2000.《婴儿不流眼泪》(No Tears for Baby).《全球化妆品工业》(Global CosmeticIndustry),(2000年10月):16-20;Burke,J.和Joseph,L.B.,2000,《PEG-150季戊四醇四硬脂酸酯刺激减轻的体外分析》(In Vitro Analysis of the IrritationMitigating Properties of PEG-150季戊四基四硬脂酸酯),《化妆品科学》(Society of Cosmetic Chemists),2000 Technology Showcase,NY,NY,所有这些在此并入以供参考。
以下实施例阐述了制造和筛选烷氧基化的酯的实验方法。制备了试验组合物I,II和III和对照组合物IV。表2列出了组合物I,II,III和IV的组成:
表2
I | II | III | IV | |
组成 | ||||
椰油酰氨基丙基羟基磺基甜菜碱 | 12% | 12% | 12% | 12% |
SLES(3)* | 20% | 20% | 20% | 20% |
二-PPG-2-PEG-10月桂基己二酸酯** | 5% | - | - | - |
二-PPG-2 Myreth-10己二酸酯*** | - | 5% | - | - |
二-PPG-2硬脂基聚氧乙烯-10己二酸酯**** | - | - | 5% | - |
水 | qs | qs | qs | qs |
*月桂醚硫酸钠(三-乙氧基化)
**二-(丙氧基)-十-(乙氧基)月桂基(C12)醇和己二酸的二酯;
***二-(丙氧基)-十-(乙氧基)肉豆寇基(C14)醇和己二酸的二酯;
****二-(丙氧基)-十-(乙氧基)硬脂基(C18)醇和己二酸的二酯。
将以上成分溶于蒸馏水并将pH调至6.8-7.2。月桂醚硫酸钠(三乙氧基化)是已知的刺激剂。用TEP测定如下测定组合物I,II,III和IV的刺激潜能。
将购自美国模式培养物保藏所的MDCK(肾,犬类)NBL-2品系(CCL 34)培养在标准条件下。实验3天前以每个插入物1×105细胞的密度将细胞传代培养到Corning6.5mm Transwell多孔细胞培养插入物上。细胞在3天内生长至融合。实验前立即用磷酸缓冲盐水(PBS)洗涤插入物5次。在实验之前制备所有试剂,但用盐溶液稀释的最终的溶液除外,稀释液在实验当天制备。
将组合物I,II,III和IV用Hanks缓冲盐溶液(HBSS)稀释至1∶50和1∶100。例如,为制备试验组合物I的1∶50稀释液,可将1份试验组合物I与49份HBSS混合。将稀释的样品置于插入物的腹侧(两份)与细胞直接接触15分钟。将两份HBSS插入物作为阴性对照,没有细胞的插入物作为100%渗漏的参照。加入试验物后,用大量PBS洗涤插入物。
将荧光素钠直接加到细胞单层,并将1ml HBSS放在孔的下面。在室温下培养30分钟后,从孔中取出三份200μl的样品并测定孔内液体的光密度(OD)。然后将实验OD与100%渗漏的参考(无细胞滤光片)OD进行比较以得到试验组合物刺激潜能的数值。
表3显示了当细胞暴露于试验组合物I,II,III和对照组合物IV时荧光素钠的胞内渗漏比例:
表3
组合物 | 酯 | 渗漏百分率(1∶50稀释) | 渗漏百分率(1∶100稀释) |
I | 二-PPG-2-PEG-10月桂基己二酸酯 | 69% | 64% |
II | 二-PPG-2-PEG-10肉豆寇基己二酸酯 | 65% | 43% |
III | 二-PPG-2-PEG-10硬脂基聚氧乙烯己二酸酯 | 44% | 27% |
IV(对照) | ------ | 73% | 68% |
由表3可见,与对照组合物IV相比,在试验组合物中观察到胞内渗漏以及由此而产生的刺激潜能的实质降低,尤其是试验组合物II和III。刺激潜能的降低是用相对于对照制剂的绝对降低的比例计算的(对照作为100%,降低的比例用100%减去(观察到的渗漏)/(观察到的对照的渗漏)×100%计算)。计算结果列在表4中:
表4
组合物 | 酯 | 刺激潜能的降低(1∶50稀释) | 刺激潜能的降低(1∶50稀释) |
I | 二-PPG-2-PEG-10月桂酰己二酸酯 | 5.4%* | 5.8% |
II | 二-PPG-2-PEG-10肉豆寇基己二酸酯 | 11% | 36.7% |
III | 二-PPG-2-PEG-10硬脂基聚氧乙烯己二酸酯 | 39.8% | 60.2% |
IV(对照) | ------ | 0% | 0% |
*例如(100%-(69/73)×100%=5.4%)。
由表4可见,不同烷氧基化的酯的抗刺激活性有显著差异而无论其化学结构有多么类似。同时,上述实验方法可区别烷氧基化的酯的抗刺激活性并为优选的具有抗刺激活性的烷氧基化的酯创造选择标准。
因此,根据本发明一个优选的方面,本发明提供了具有抗刺激活性的二羧酸或三羧酸的烷氧基化的酯,与对照组合物相比,试验组合物在1∶50稀释度时荧光素钠的胞内渗漏减少了15%或更多,在1∶100稀释度时减少了40%或更多。更加优选的烷氧基化的酯在1∶50稀释度时使荧光素钠的胞内渗漏减少了20%或更多,在1∶100稀释度时使其减少了50%或更多。再优选的烷氧基化的酯在1∶50稀释度时使荧光素钠的胞内渗漏减少了50%或更多,在1∶100稀释度时使其减少了75%或更多。荧光素钠的胞内渗漏的减少按上述方法用跨上皮渗透性(TEP)测定,并被作为抗刺激活性的尺度。所述试验组合物是5%的备选烷氧基化的酯、12%的椰油酰氨基丙基羟基磺基甜菜碱和20%的三-乙氧基化月桂醚硫酸钠溶于蒸馏水所得的溶液,对照组合物是12%的椰油酰氨基丙基羟基磺基甜菜碱和20%的三-乙氧基化月桂醚硫酸钠溶于蒸馏水所得的溶液,其中不含备选烷氧基化的酯,所述成分以重量计。
本发明还提供了一些具有特殊结构的烷氧基化的酯。更加优选地,具有所述化学结构烷氧基化的酯也能满足上述抗刺激活性的筛选标准。
在一个优选的实施方案中,所述烷氧基化的酯具有式(I):
其中,-COR1CO-是脂肪族二羧酸的二羧基,R1是有0-20个碳原子、优选有0-18个碳原子、更优选有0-8个碳原子、最优选有0-6个碳原子的饱和或不饱和的、直链或支链的、取代或未取代的、有环或无环的烷基。
或者,-COR1CO-是芳香二羧酸的二羧基,R1是含有6-20个碳原子、优选有6-14个碳原子、更优选有6或10个碳原子的芳香二羧酸的芳香环。所述芳香环的非限制性例子有芳基-,苯基芳基-,烷基芳基-和萘。
在式(I)的酯中,R2O-,R4O-,可以相同或不同,是下式的烷氧基化的部分
其中,[O(CH2)2-]是乙氧基,[OCH(CH3)CH2-]是丙氧基,所述烷氧基化的部分的乙氧基和丙氧基可以有任何排列顺序,即可以随机排列、嵌段排列或交替排列。
x从0-200,优选从1-100,y从0-200,优选从0-100。
R3,R5,可以相同或不同,独立为氢或含有6-30个碳原子的直链或支链、饱和或不饱和、取代或未取代的烷基、烷基芳基或芳基烷基,条件是R3,R5中最多有一个是氢。
优选地,R3,R5有12-22个碳原子,优选有16-22个碳原子,最优选有18-22个碳原子;x从1-40,再优选从2-20,最优选的是x从3-10;y从0-40,优选有1-10,最优选的是y从1-5;x/y从1-2.5,最优选的是从1-2;根据基团R3O(R2O)-和R5O(R4O)-的分子量,基团(R2O)和(R4O)中乙氧基的重量百分比分别是20%或更高,更优选为20-80%,最优选为24-35%。
在另一个优选的实施方案中,所述烷氧基化的酯具有式(II):
其中,-COR6CO-是脂肪族三羧酸的三羧基,R6是烷基,取代或未取代,饱和或不饱和,直链或支链,有环或无环的,有1-19个碳原子,优选有1-15个碳原子,更优选有1-8个碳原子,最优选有1-6个碳原子。
或者,-COR6CO-是芳香三羧酸的三羧基,R6是有6-20个碳原子的芳香三羧酸的芳香环,优选有6-14个碳原子,更优选有6或10个碳原子。R6核的非限制性例子是芳基-,苯基芳基-,烷基芳基-和萘。
在式(II)的酯类中,R7O-,RgO,R11O-,可以相同或不同,是下式的烷氧基化的部分
其中,[O(CH2)2-]是乙氧基和[OCH(CH3)CH2-]是丙氧基,所述烷氧基化的部分的乙氧基和丙氧基可以有任何排列顺序,即可以随机排列、嵌段排列或交替排列。
x从0-200,优选从1-100;y从0-200,更优选从0-100;。
R8,R10,R12分别独立是氢或烷基,烷基芳基或芳基烷基,直链或支链,饱和或不饱和,取代或未取代,含有6-30个碳原子,条件是R8,R10,R12最多有一个是氢。
优选地,R8,R10,R12有12-22个碳原子,优选有16-22个碳原子,最优选有18-22个碳原子;x从1-40,更优选从2-20;y从O-40,更优选从1-10;最优选x从3-10,y从1-5,x/y为2或更大,且x>y;基团R8O(R7O)-、R10O(R9O)-、R12O(R11O)-的分子量,基团(R7O),(R9O)和(R11O)中乙氧基的重量百分比分别为20%或更高,更加优选为20-80%,最优选为24-35%。
发现带有较长末端烷基链的烷氧基化的酯具有较好的抗刺激活性。参考表4,二-PPG-2-PEG-10硬脂基聚氧乙烯己二酸酯的抗刺激活性大于二-PPG-2-PEG-10肉豆寇基己二酸酯,而二-PPG-2-PEG-10肉豆寇基己二酸酯的抗刺激活性大于二-PPG-2-PEG-10月桂酰己二酸酯。抗刺激活性随链长的增加而显著增加。
在另一个优选的实施方案中,所述烷氧基化的酯具有式(III):
其中,-OCR13CO-是脂肪族二羧酸的二羧酸基,R13是直链烷基,饱和或不饱和,取代或未取代,有环或无环的,有0-20个碳原子,或
-COR13CO-是芳香二羧酸的二羧基,R13是芳香二羧酸的芳香环有6-20个碳原子;
x1和x2,可以相同或不同,范围从0-200,y1和y2,可以相同或不同,范围从0-200;。
R14,R15可以相同或不同,是含有16-30个碳原子的直链或支链、饱和或不饱和、取代或未取代的烷基,更优选有16-22个碳原子,最优选有18-22个碳原子。
优选地,x1和x2范围从0-100,更优选从1-20;再优选从2-10:y1和y2范围从0-100,更优选从1-10,更优选有y1和y2范围是1-5;x1/y1和x2/y2,相同或不同,大于1;基团-OCR13CO-带有末端羧基,R13具有结构(CHm)n或-(CHm)nX,其中,X如果存在是选自低级烷基,包括甲基、羟基、烷基羟基)和卤素包括氯和溴的支链取代基,可在末端羧基之间的任何位置,,m是1或2,n从3-10,更优选从3-7,最优选n是4。
一组特别优选的式(III)的酯类中,n是4,R14,R15有18-22个碳原子,x1和x2是4和y1和y2是3。在这一组特别优选的酯类中,当R14,R15有18个碳原子时是二-PEG-4-PPG-3硬脂基聚氧乙烯醚己二酸酯。另一组特别优选的式(III)的酯类中,n是4,R14,R15有18-22个碳原子,x1和x2是10,y1和y2是2。在这一组特别优选的酯类中,当R14,R15有18个碳原子时是二-PEG-2-PPG-10硬脂基聚氧乙烯醚己二酸酯。
式(III)的烷氧基化的酯的非限制性例子包括
二-PPG-2-PEG-10十六烷基醚己二酸酯
二-PPG-2-PEG-10硬脂基聚氧乙烯醚己二酸酯
和。
二-PPG-5-PEG-8二十二烷基醚己二酸酯
二-PPG-3-PEG-4硬脂基聚氧乙烯醚己二酸酯。
发现具有某些烷氧基化模式的烷氧基化的酯有增强的抗刺激活性。根据本发明另一个优选的方面,所述烷氧基化的酯具有式(IV):
其中,-OCR16CO-是脂肪族二羧酸的二羧基,R16饱和或不饱和、直链或支链、取代或未取代、有环或无环的烷基,有0-20个碳原子;
R17,R18是烷基,可以相同或不同,饱和或不饱和,取代或未取代,有6-22个碳原子,优选有12-22个碳原子,最优选有16-22个碳原子;
x1和x2,可以相同或不同,范围是1-100,y1和y2,可以相同或不同,范围是0-100;以及
x1/y1,x2/y2从1-2.5。
优选地,x1/y1和x2/y2从1-2,更优选从1-1.5;x1和x2范围是1-40,更优选从2-20,最优选是从3-10,y1和y2范围是0-40,更优选从1-10,最优选是从1-5;R16是结构为-(CHm)n或-(CHm)nX的基团,其中,n和X如对式(III)的定义。
一组特别优选的式(IV)的酯类中,R16是结构为-(CH2)4的基团,R17,R18有14-22个碳原子,x1和x2是4和y1和y2是3。在这一组特别优选的酯类中,当R17,R18有14个碳原子时是二-PEG-4-PPG-3肉豆蔻醚己二酸酯。
式(IV)的烷氧基化的酯的非限制性例子包括
和
二-PPG-3-PEG-4肉豆蔻醚己二酸酯
二-PPG-4-PEG-5十五烷基醚己二酸酯。
本发明的化合物可通过将相应的二-或三羧酸与所需的烷氧基化的脂肪醇反应制得。因此,根据本发明另一个方面,本发明提供了通过使酸与化学计量过量的一种或多种烷氧基化的脂肪醇反应形成的化合物。
实际上,本发明的化合物可用这种方式使饱和或不饱和的、取代或未取代的、脂肪族或芳香脂肪醇与环氧乙烷和/或环氧丙烷或其混合物反应制得,反应可相继进行或以混合形式进行,且需要有酸性或碱性催化剂存在。适合此反应的催化剂是此领域已知的,包括,例如,碱金属氧化物和氢氧化物,例如氢氧化钾、甲醇钠、硼氢化钠、质子酸和路易斯酸,例如三氟化硼、氯化锡和硫酸。也可使用胺类,季铵化合物,水和其它酸类。还可使用催化剂的混合物。某些活性物质是此领域已知的,例如使用炔醇就无需使用催化剂。无机催化剂如锡催化剂也可使用。
优选地,碱性催化剂被用于该反应,最优选是占醇的重量约0.1-2.0重量百分比的氢氧化钾或氢氧化钠、甲醇钠、硼氢化钠或它们的混合物。反应在无水条件下进行以避免形成副产物,反应温度优选为约110℃-200℃,尽管也可采用较高温度。反应可在大气压下进行,尽管反应优选在高压灭菌器中在约10psi-80psi的压力下进行。环氧乙烷和/或环氧丙烷可以混合物的形式加入或以任何所需顺序加入,包括交替加入和相继加入。加入反应区的环氧乙烷或环氧丙烷的量以及反应时间决定了在脂肪醇的脂肪部分R中加入的这种成分的摩尔数。
化学计量量的脂肪醇、环氧乙烷和环氧丙烷可以一起发生反应,化学计量量的聚烷氧基化的脂肪醇和二羧酸可以一起发生反应。例如,反应可以按顺序进行,即使脂肪醇首先与环氧丙烷反应,然后在反应完全后在反应混合物中加入环氧乙烷,或者反之。
所得聚烷氧基化的脂肪醇然后与合适的二羧酸或三羧酸反应。合适的脂肪族二羧酸的例子包括己二酸、癸二酸、丙二酸和琥珀酸。己二酸是优选的。合适的芳香二羧酸的特别的例子有邻苯二甲酸和萘二羧酸。
醇和酸之间的反应是常规的酯化反应。反应可在有或没有催化剂的条件下进行。优选的催化剂包括甲磺酸和对甲苯磺酸。酯化反应通常是将化学计量量的聚烷氧基化的脂肪醇和要被酯化的酸混合。精通此领域的技术人员应该知道,当要在酸中加入两个聚烷氧基化的脂肪醇链时,聚烷氧基化的脂肪醇和要被酯化的酸应以2∶1的摩尔比混合。然而,略为过量可确保充分酯化和低酸度。酯化反应可在溶剂中进行或不在溶剂中进行。
通常,聚烷氧基化的脂肪醇、酸和催化剂被混合以形成反应混合物。将此反应混合物搅拌下加热至约155℃-250℃,优选约170℃和220℃,直到酸值小于8mgKOH,优选小于5mg KOH。然后将反应混合物冷却至85℃以下并用水洗涤,最好无需中和催化剂。应避免高温以防止聚烷氧基化的脂肪醇损失,这会造成不完全酯化以及酸度高于所需酸度。将酯层分离并在真空下加热直至水分含量小于0.2%。
如上所述,聚烷氧基化的脂肪醇可通过将脂肪醇与环氧乙烷和环氧丙烷的混合物反应制得。因此,所得聚烷氧基化的脂肪醇可含有由脂肪醇混合物的乙氧基化和丙氧基化所得的混合物。
根据另一个优选的方面,本发明提供了减弱个人护理品或化妆品中刺激剂刺激的方法,所述刺激剂如表面活性剂,羟酸等。美国专利6,312,714,6,379,716和5,876,737描述了一些刺激剂和含有刺激剂的组合物,在此将其并入以供参考。根据本发明的方法,制造了含有刺激剂和至少一种具有上述抗刺激特性的二羧酸或三羧酸的烷氧基化的酯的个人护理品或化妆品,然后将其用于人或动物个体。所述产品可以该产品的常规使用方式用于个体的身体,包括头发、皮肤和眼睛。例如,洗发液或调节剂可用于头发,然后冲洗;皮肤护理产品可局部用于皮肤;等等。优选地,烷氧基化的酯被用来减轻表面活性剂的刺激。
具有抗刺激活性的烷氧基化的酯优选用于实践本发明的方法,所述抗刺激活性以荧光素钠胞内渗漏的减少测量,在1∶50稀释度时测得减少了10%或更多,在1∶100稀释度时测得减少了40%或更多。更加优选的烷氧基化的酯的抗刺激活性为,1∶50稀释度时减少20%或更多,1∶100稀释度时减少50%或更多,再优选的烷氧基化的酯的抗刺激活性为,1∶50稀释度时减少了40%或更多,在1∶100稀释度时减少了75%或更多。如果烷氧基化的酯的抗刺激活性在1∶50稀释度时减少不到15%,在1∶100稀释度时减少不到40%则不是优选的。本发明的方法也可用于这种烷氧基化的酯,其中包括抗刺激活性在1∶50稀释度时减少10%或更多在1∶100稀释度时减少20%或更多的烷氧基化的酯。
本发明还提供了含有至少一种二羧酸或三羧酸的烷氧基化的酯和刺激剂的组合物。在优选的实施方案中,本发明的组合物是可稀释的预混合混合物,含有至少一种烷氧基化的酯和用于洗发液、沐浴液、泡沫洁面乳、泡泡浴、洗手液的表面活性剂和其它根据需要使用的表面活性剂。在优选的实施方案中,本发明的混合物含有3-20%本发明的烷氧基化的酯以及表5所示的表面活性剂:
表5
表面活性剂 | 含量(%) |
阴离子表面活性剂 | 0-97 |
甜菜碱 | 0-97% |
两性表面活性剂 | 0-97% |
非离子表面活性剂 | 0-30% |
阳离子表面活性剂 | 0-10% |
链烷醇酰胺 | 0-30% |
可稀释的混合物中可含有一种或多种表面活性剂或其混合物。可加入足量的水以及防腐剂、芳香剂、泡沫促进剂、调理剂、软化剂和化妆成分以得到最终的制品,与没有烷氧基化的酯的制品相比,这种制品的刺激减弱了。
根据另一方面,本发明还提供了各种化妆和/或个人护理产品形式的组合物。所述组合物可称为最终产品组合物,并且可以有以下形式,例如用于头发和/或皮肤的遮光剂组合物,如洗剂、凝胶剂、喷雾剂等,洗手液,沐浴组合物,防晒油,防汗组合物,香水和古龙水,冷霜,剃须膏,除臭剂,局部药用软膏剂,软化剂,洁面乳,清洁乳,皮肤凝胶,洗发液,头发调理剂,去污剂,家用清洁产品,化妆品,唇膏,染眉毛和染发产品。
本发明的的最终产品组合物,包括用于皮肤和头发的制品,包括至少一种上述二羧酸或三羧酸的烷氧基化的酯。产品中具有所述抗刺激特性的烷氧基化的酯的量取决于特定的应用,可占产品组合物重量的约0.1%-40%,更优选从约0.1%-10%,再优选从约0.5%-2%。然而,根据产品的特性,不同的量可能是优选的。
本发明的烷氧基化的酯特别适合用于更可能造成刺激或特别需要减弱刺激的化妆品和个人护理产品。优选的产品包括洗发液,头发调理剂,防晒剂,婴儿洗发液,婴儿沐浴产品,洗手液,沐浴液,洗面奶,无纺布,婴儿抹布和泡泡浴产品。更加优选的产品是婴儿洗发液,婴儿沐浴产品,洗手液,婴儿抹布和泡泡浴产品。
含有烷氧基化的酯的洗发液可含有多种其它成分,包括常规的洗发液所含的成分。这种成分的非限制性例子有月桂基硫酸铵,月桂基聚氧乙烯基醚硫酸铵,月桂基硫酸钠,月桂基聚氧乙烯基醚硫酸钠,两性表面活性剂(如椰油两性甘氨酸盐,椰油酰氨基丙基甜菜碱(cocoamido丙基betaine)等),氧化胺,如椰油胺氧化物(cocoamine oxide)等,纤维素和阳离子纤维素,如,Polyquat 10,瓜尔胶和阳离子瓜尔胶,UV吸收化合物,如二苯甲酮3和辛基甲氧基肉桂酸盐,液体硅酮(环二甲硅酮),修饰的液体硅酮(Amodimethicone),植物提取物,脂肪酯和甘油三酸酯,如硬脂酸辛酯和麦芽油。其它合适的特别成分描述在常规成分部分。
含有烷氧基化的酯的婴儿洗发液和婴儿沐浴液还可含有多种其它成分,包括它们常规所含的成分。这种成分的非限制性例子有月桂基硫酸铵,月桂基聚氧乙烯基醚硫酸铵,月桂基硫酸钠,月桂基聚氧乙烯基醚硫酸钠,两性表面活性剂(如椰油两性甘氨酸盐,椰油酰氨基丙基甜菜碱等),氧化胺,如椰油胺氧化物等,纤维素和阳离子纤维素,如,Polyquat 10,瓜尔胶和阳离子瓜尔胶,UV吸收化合物,如二苯甲酮3和辛基甲氧基肉桂酸盐,液体硅酮(环二甲硅酮),修饰的液体硅酮(Amodimethicone),植物提取物,脂肪酯和甘油三酸酯,如硬脂酸辛酯和麦芽油,烷氧基化的甘油酯如PEG-30甘油基椰油酯,烷氧基化的山梨糖醇酯如聚山梨醇酯20,羧化表面活性剂如Trideceth-10羧酸酯。其它合适的特别成分描述在常规成分部分。
含有烷氧基化的酯的身体洗液和洗面奶还可含有多种其它成分,包括它们常规所含的成分。这种成分的非限制性例子有月桂基硫酸铵,月桂基聚氧乙烯基醚硫酸铵,月桂基硫酸钠,月桂基聚氧乙烯基醚硫酸钠,两性表面活性剂(如椰油两性甘氨酸盐,椰油酰氨基丙基甜菜碱等),氧化胺,如椰油氨基氧化物等,纤维素和阳离子纤维素,如,Polyquat 10,瓜尔胶和阳离子瓜尔胶,UV吸收化合物,如二苯甲酮3和辛基甲氧基肉桂酸盐,液体硅酮(环二甲硅酮),修饰的液体硅酮(Amodimethicone),植物提取物,脂肪酯和甘油三酸酯,如硬脂酸辛酯和麦芽油,烷氧基化的甘油酯如PEG-30甘油基椰油酯,烷氧基化的山梨糖醇酯如聚山梨醇酯20,羧化表面活性剂如Trideceth-10羧酸酯,羊毛脂和羊毛脂季盐(Lanolin quat),矿脂。其它合适的特别成分描述在常规成分部分。
含有烷氧基化的酯的头发调理剂还可含有多种其它成分,包括它们常规所含的成分。这种成分的非限制性例子有月桂基硫酸铵,月桂基聚氧乙烯基醚硫酸铵,月桂基硫酸钠,月桂基聚氧乙烯基醚硫酸钠,两性表面活性剂(如椰油两性甘氨酸盐,椰油酰氨基丙基甜菜碱等),氧化胺,如椰油氨基氧化物等,纤维素和阳离子纤维素,如Polyquat 10,瓜尔胶和阳离子瓜尔胶,UV吸收化合物,如二苯甲酮3和辛基甲氧基肉桂酸盐,液体硅酮(环二甲硅酮),修饰的液体硅酮(Amodimethicone),植物提取物,脂肪酯和甘油三酸酯,如硬脂酸辛酯和麦芽油,脂肪烷基磷酸酯如联十六烷基磷酸酯和PEG-20十六烷基磷酸酯。其它合适的特别成分描述在常规成分部分。
含有烷氧基化的酯的洗手液还可含有多种其它成分,包括它们常规所含的成分。这种成分的非限制性例子有月桂基硫酸铵,月桂基聚氧乙烯基醚硫酸铵,月桂基硫酸钠,月桂基聚氧乙烯基醚硫酸钠,十二烷基苯磺酸钠和十二烷基苯磺酸镁,链烷醇酰胺,如椰油酰胺DEA或Cocoamide MEA,两性表面活性剂,如椰油两性甘氨酸盐,椰油酰氨基丙基甜菜碱等等,氧化胺,如椰油胺氧化物等。
含有烷氧基化的酯的无纺布和婴儿抹布还可含有多种其它成分,包括它们常规所含的成分。这种成分的非限制性例子有月桂基硫酸铵,月桂基聚氧乙烯基醚硫酸铵,月桂基硫酸钠,月桂基聚氧乙烯基醚硫酸钠,两性表面活性剂(如椰油两性甘氨酸盐,椰油酰氨基丙基甜菜碱等),氧化胺,如椰油氨基氧化物等,纤维素和阳离子纤维素,如,Polyquat 10,瓜尔胶和阳离子瓜尔胶,UV吸收化合物,如二苯甲酮3和辛基甲氧基肉桂酸盐,液体硅酮(环二甲硅酮),修饰的液体硅酮(Amodimethicone),植物提取物,脂肪酯和甘油三酸酯,如硬脂酸辛酯和麦芽油,烷氧基化的甘油酯如PEG-30甘油基椰油酯,peg-75羊毛脂,烷氧基化的山梨糖醇酯如聚山梨醇酯20,羧化表面活性剂如Trideceth-10羧酸酯,非羧化的醇磷酸酯如十六烷基磷酸酯或联十六烷基磷酸酯,烷氧基化的醇磷酸酯如PEG-10十六烷基磷酸酯等。其它合适的特别成分描述在常规成分部分。
含有烷氧基化的酯的泡泡浴产品还可含有多种其它成分,包括它们常规所含的成分。这种成分的非限制性例子有月桂基硫酸铵,月桂基聚氧乙烯基醚硫酸铵,月桂基硫酸钠,月桂基聚氧乙烯基醚硫酸钠,两性表面活性剂(如椰油两性甘氨酸盐,椰油酰氨基丙基甜菜碱等),氧化胺,如椰油氨基氧化物等,纤维素和阳离子纤维素,如,Polyquat 10,瓜尔胶和阳离子瓜尔胶,UV吸收化合物,如二苯甲酮3和辛基甲氧基肉桂酸盐,液体硅酮(环二甲硅酮),修饰的液体硅酮(Amodimethicone),植物提取物,脂肪酯和甘油三酸酯,如硬脂酸辛酯和麦芽油。其它合适的特别成分描述在常规成分部分。
含有所述烷氧基化的酯是最终产品组合物可以是液体、凝胶、霜剂、乳剂、泡沫和固体;可以是透明或不透明的;并且可以被制成含水制品或不含水制品,包括但不限于局部制品。因此,根据本发明另一个实施方案,提供了供局部使用的含有一种或多种活性成分和本发明的脂肪烷氧基化的酯试剂的组合物。
本发明的含水局部制品含有一种或多种烷氧基化的酯和一种或多种活性成分,余量为水。如上所述,也可含有矿物油、矿脂等单独的软化剂。然而,本发明的化合物具有软化特性。用于这种局部制品的合适的活性剂包括遮光剂,色素,润湿剂,成膜剂,去污剂,增稠剂,乳化剂,防腐剂,调节剂和除臭剂。
本发明的局部制品除了含有本发明的组合物,一种或多种活性成分,水和任选的软化剂外还可含有赋形剂,如芳香剂、蛋白质、润湿剂,盐、防腐剂,精油等。这些额外的成分可以化妆品制造业熟知的各种量加入。
本发明的典型含水局部制品含有本发明的烷氧基化的酯,其含量约为组合物重量的0.20-40.0%,优选为3.0-20.0%。所述一种或多种活性成分的量可占组合物重量的约0.20-40.0%,优选为约3.0-20.0%。使用时,其它软化剂以约10∶1-1∶10份本发明的酯试剂的比例与本发明的试剂混合。余量通常是赋形剂和水或一些含水溶剂系统。
也可制造本发明的非水性局部制品。所述制品含有本发明的试剂和一种或多种上述活性成分。可任选包含矿物油,矿脂等软化剂,以及上述赋形剂、芳香剂、蛋白质、润湿剂,盐、防腐剂,精油等。
本发明的典型非水性局部制品含有本发明的烷氧基化的酯,其含量约为组合物重量的0.20-99.0%,优选为约10-90.0%,更优选为约25-75%。所述一种或多种活性成分的量可占组合物重量的约0.20-99.0%,优选为约10-90.0,更优选为约25-75%。
和含水局部制品一样,如果存在软化剂,软化剂以约10∶1-1∶10份本发明的酯试剂的比例与本发明的试剂混合。
优选地,最终的产品组合物是在水或水和一种合适的辅助溶剂的混合物中的分散体或溶液。合适的惰性溶剂包括各种低级烷醇和二醇。含有1-4个碳原子的低级烷醇适合用于本发明,含有2-3个碳原子的低级烷醇是优选的。含有3-8个碳原子的二醇适合用于本发明,含有3-6个碳原子的二醇是优选的。合适的低级烷醇和二醇的例子包括甲醇、乙醇、异丙醇、丁醇、己二醇、1,3-丁二醇、1,2-和1,3-丙二醇、2-甲基1,3-丙二醇、丙二醇、二甘醇等。溶剂的重量可占到组合物重量的98%,优选约占20%-90%,更优选约占50%-90%。然而同时,根据产品的特性不同的溶剂量可以是优选的。如果使用水和辅助溶剂的混合物,辅助溶剂的量可占到组合物重量的90%,优选约为25%-80%。
除了烷氧基化的酯,本发明的组合物可包括各种常规的或非常规的活性成分和添加成分。当然,含有何种成分以及选择特殊的活性成分和添加成分取决于特定的用途和产品类型。同时,“活性”成分和“添加”成分的划分是人为的,并取决于特定的用途和产品类型。一种物质在一种用途或产品中是“活性”成分而在另一种用途或产品中则可能是“添加”成份,反之亦然。
因此,本发明的组合物可包括一种或多种活性成分,所述活性成分对组合物的应用对象,如头发或皮肤,有好处。所述活性成分可包括一种或多种物质,如清洁剂、头发调理剂、皮肤调理剂、头发定型剂、止屑剂、头发生长促进剂、香料、防晒化合物、色素、润湿剂、成膜剂、染发剂、化妆品、去污剂、增稠剂、乳化剂、防腐剂、除臭剂、表面活性剂和对透皮输递有用的药物。
活性成分的选择取决于所需的化妆或个人护理产品的特性。例如,防晒化合物可用于遮光液、洗发液、药用洗发液、头发护理液等。对于每种类型的活性成分可有一种或多种化合物。同样,可以有多种活性成分。
本发明的组合物中可含有以下成分。
表面活性剂。
本发明的组合物中可有各种表面活性剂,包括一种或多种非离子表面活性剂,阴离子表面活性剂,阳离子表面活性剂,两性表面活性剂,两性离子表面活性剂以及它们的混合物。一些表面活性剂可与本发明的组合物联合使用,可参见McCutcheon的《去污剂和乳化剂》,(1986),美国专利5,51,210,5,151,209,5,120,532,5,011,681,4,788,006,4,741,855,美国专利4,704,272,4,557,853,4,421,769,3,755,560;在此将它们全文并入。
阳离子表面活性剂
本发明的烷氧基化的酯是适合用于个人护理用品尤其是头发护理产品如调理剂和洗发液的阳离子表面活性剂。此外,本发明的组合物中还可含有其它阳离子表面活性剂。本发明组合物中阳离子表面活性剂的量和性质取决于组合物的性质。在最终的产品组合物中,阳离子表面活性剂(包括这里所述的其烷氧基化的酯)的重量占产品组合物重量的0.1%-40%,更优选从约0.1%-15%,再优选从约0.5%-2%。然而,根据产品的性质,不同的阳离子表面活性剂的量可以是优选的。其它合适的阳离子表面活性剂描述在McCutcheon的《去污剂和乳化剂》一书,(M.C.PublishingCo.1979);美国专利3,155,591,3,929,678,3,959,461,4,387,090,在此将它们并入以供参考。
季铵
本发明的组合物可包括下式所示的季铵阳离子表面活性剂
其中,X和a如上所述,Q1是C12-C22烷基,C12-C22烷基酰氨基C1-C6亚烷基,C12-C22烷基羟基;Q2是C12-C22烷基,C12-C22烷基酰氨基C1-C6亚烷基,C12-C22烷基羟基,苄基或C1-C6烷基;Q3和Q4独立为C1-C6烷基或苄基。
合适的季铵表面活性剂的例子包括十六烷基氯化铵,十六烷基溴化铵,月桂基氯化铵,月桂基溴化铵,硬脂基氯化铵,硬脂基溴化铵,十六烷基二甲基氯化铵,十六烷基二甲基溴化铵,月桂基二甲基氯化铵,月桂基二甲基溴化铵,硬脂基二甲基氯化铵,硬脂基二甲基溴化铵,十六烷基三甲基氯化铵,十六烷基三甲基溴化铵,月桂酰三甲基氯化铵,月桂基三甲基溴化铵,硬脂基三甲基氯化铵,硬脂基三甲基溴化铵,月桂基二甲基氯化铵,硬脂基二甲基十六烷基二牛油基二甲基氯化铵,二十六烷基氯化铵,二十六烷基溴化铵,二月桂基氯化铵,二月桂基溴化铵,二硬脂基氯化铵,二硬脂基溴化铵,二十六烷基甲基氯化铵,二十六烷基甲基溴化铵,二月桂基甲基氯化铵,二月桂基甲基溴化铵,二硬脂基甲基氯化铵,二硬脂基二甲基氯化铵,二硬脂基甲基溴化铵以及它们的混合物。
其它季铵盐包括以下这些,其中,C12-C22烷基衍生自牛油脂肪酸或椰油脂肪酸。衍生自这些牛脂和椰油来源的季铵盐包括二牛油基二甲基氯化铵,二牛油基二甲基甲基硫酸铵,二(氢化牛脂)二甲基氯化铵,二(氢化牛脂)二甲基乙酸铵,二牛油基二丙基磷酸铵,二牛油基二甲基硝酸铵,二(椰油烷基)二甲基氯化铵,二(椰油烷基)二甲基溴化铵,牛脂氯化铵,椰油氯化铵,硬脂酰氨基丙基PG-氯化dimonium磷酸盐(stearamidopropyl PG-dimonium chloride phosphate),硬脂酰氨基丙基乙基乙基硫酸dimonium(stearamidopropyl ethyldimonium ethosulfate),硬脂酰氨基丙基二甲基(肉豆寇基乙酸酯)氯化铵,硬脂酰氨基丙基二甲基酯芳基甲苯磺酸铵,硬脂酰氨基丙基二甲基氯化铵,硬脂酰氨基丙基二甲基乳酸铵以及它们的混合物。
更加优选的季铵表面活性剂是二月桂基二甲基氯化铵,二硬脂基二甲基氯化铵,二肉豆寇基二甲基氯化铵,二软酯基二甲基氯化铵,二硬脂基二甲基氯化铵,硬脂酰氨基丙基PG-氯化dimonium磷酸盐,硬脂酰氨基丙基乙基乙基硫酸dimonium,硬脂酰氨基丙基二甲基(肉豆寇基乙酸酯)氯化铵,硬脂酰氨基丙基二甲基酯芳基甲苯磺酸铵,硬脂酰氨基丙基二甲基氯化铵,硬脂酰氨基丙基二甲基乳酸铵以及它们的混合物。
脂肪胺
本发明的组合物还可包含C12-C22的伯胺、仲胺和叔胺。合适的胺的例子包括硬脂酰氨基丙基二甲基胺,二乙基氨基乙基硬脂酰胺,二甲基硬脂胺,二甲基豆胺(dimethyl soyamine),豆胺(soyamine),三(癸基)胺,乙基硬脂基胺,乙氧基化硬脂基胺,二羟基乙基硬脂基胺和花生四烯基山嵛基胺。合适的胺盐包括卤化物、乙酸盐、磷酸盐、硝酸盐、柠檬酸盐、乳酸盐和烷基硫酸盐。所述盐包括盐酸硬脂基胺,氯化豆胺(soyamine chloride),甲酸硬脂基胺,N-牛脂丙烷二胺二氯化物和硬脂酰氨基丙基二甲基胺柠檬酸盐。可用于本发明组合物的一些阳离子胺表面活性剂描述在美国专利4,275,055,将其并入以供参考。
酰氨基胺
本发明的组合物还可包含酰氨基胺,如Croda公司的美国专利申请09/409,203所述,在此将其并入以供参考。
非离子表面活性剂
本发明的组合物还包括各种非离子表面活性剂。合适的非离子表面活性剂包括C8-C30醇和糖或淀粉聚合物的缩合产物。这些化合物可用式(S)n--O-R表示,其中,S是糖部分,如葡萄糖、果糖、甘露糖和半乳糖;n是1-1000的整数,R是C8-C30烷基。合适的C8-C30醇的例子包括R基团衍生自癸醇,十六烷醇,十八烷醇,月桂醇,肉豆蔻醇,油醇等的那些。这些表面活性剂的特例包括癸基多聚葡萄糖苷和月桂基多聚葡萄糖苷。
其它合适的非离子表面活性剂包括环氧烷烃和脂肪酸的缩合产物(即脂肪酸的环氧烷烃酯)。这些物质具有通式RCO(X)nOH,其中,R是C10-C30烷基,X是-OCH2CH2-(衍生自环氧乙烷)或-OCH2CHCH3-(衍生自环氧丙烷),n是1-200的整数。
其它合适的非离子表面活性剂有环氧烷烃和脂肪酸的缩合产物(即脂肪酸的环氧烷烃二酯),它们具有通式RCO(X)nOOCR,其中,R是C10-C30烷基,X是-OCH2CH2-(衍生自环氧乙烷)或-OCH2CHCH3-(衍生自环氧丙烷),n是1-200的整数。
其它合适的非离子表面活性剂有环氧烷烃和脂肪醇的缩合产物(即脂肪醇的环氧烷烃醚),它们具有通式R(X)nOR’,其中,R是C10-C30烷基,n是1-200的整数,R’是或C10-C30烷基。
其它非离子表面活性剂是具有式RCO(X)nOR’的化合物,其中,R,R’是C10-C30烷基,X是-OCH2CH2-(衍生自环氧乙烷)或-OCH2CHCH3-(衍生自环氧丙烷),n是1-200的整数。
环氧烷烃衍生的非离子表面活性剂的例子包括十六烷基聚氧乙烯醚-1,十六烷基聚氧乙烯醚-2,十六烷基聚氧乙烯醚-6,十六烷基聚氧乙烯醚-10,十六烷基聚氧乙烯醚-12,十六烷基十八烷基聚氧乙烯醚-2,十六烷基十八烷基聚氧乙烯醚-6,十六烷基十八烷基聚氧乙烯醚-10,十六烷基十八烷基聚氧乙烯醚-12,十八烷基聚氧乙烯醚-1,十八烷基聚氧乙烯醚-2,十八烷基聚氧乙烯醚-6,十八烷基聚氧乙烯醚-10,十八烷基聚氧乙烯醚-12,PEG-2硬脂酸盐,PEG4硬脂酸盐,PEG6硬脂酸盐,PEG-10硬脂酸盐,PEG-12硬脂酸酯,PEG-20硬脂酸甘油酯,PEG-80牛酸甘油酯(glyceryl tallowate),PPG-10硬脂酸甘油酯,PEG-30椰油甘油酯(glycerylcocoate),PEG-80椰油甘油酯,PEG-200牛酸甘油酯,PEG-8二月桂酸酯,PEG-10二硬脂酸酯以及它们的混合物。
其它有用的非离子表面活性剂包括多羟基脂肪酸酰胺,如美国专利2,965,576,2,703,798和1,985,424所述,在此将其并入以供参考。
阴离子表面活性剂
本发明的组合物还包括各种阴离子表面活性剂。一些合适的阴离子表面活性剂的例子描述在美国专利3,929,678,在此将其并入以供参考。合适的阴离子表面活性剂的其它例子包括烷酰基羟乙磺酸盐和烷基醚硫酸盐。
烷酰基羟乙磺酸盐通常具有式RCO--OCH2CH2-SO3M,其中,R是C10-C30烷基,M是水溶性阳离子,如铵、钠、钾或三乙醇胺。合适的羟乙磺酸盐的例子包括椰油酰基羟乙磺酸铵、椰油酰基羟乙磺酸钠、月桂酰基羟乙磺酸钠、硬脂酰基羟乙磺酸钠以及它们的混合物。这里优选使用的是椰油酰基羟乙磺酸铵、椰油酰基羟乙磺酸钠以及它们的混合物。
烷基醚磷酸盐通常具有式ROSO3M,RO(C2H4O)xSO3M,其中,R是C10-C30烷基,x为1-10,M是水溶性阳离子,如铵、钠、钾或三乙醇胺。
其它合适的阴离子表面活性剂是C8-C30羧酸和具有式R1-SO3M(其中R1是C8-C30烷基;优选为C12-C22烷基和M是阳离子)的烷基磺酸盐的碱金属盐,,包括琥珀酰胺酸盐和和C12-C24烯烃磺酸盐和羧酸盐。
两性表面活性剂
本发明的组合物还包括两性离子和两性表面活性剂。合适的两性和两性离子表面活性剂有,例如,单-或二-C8-C24仲胺和叔胺的衍生物,如烷基亚氨基乙酸盐、羧酸盐、磺酸盐、硫酸盐、磷酸盐和膦酸盐,包括结构式为RN(CH2)mCO2M2,和RNH(CH2)mCO2M的亚氨基二烷酸盐和氨基烷酸盐,其中m从1-4,R是C8-C30烷基;优选C12-C22烷基,M是H碱金属、碱土金属、铵或烷醇铵(alkanolammonium)。
其它合适的两性和两性离子表面活性剂是咪唑啉鎓盐和铵的衍生物。这种两性表面活性剂的合适的例子包括3-十二烷基-氨基丙酸钠,3-十二烷基氨基丙烷磺酸钠,N-烷基牛磺酸;N-高级烷基天冬氨酸和coamido丙基PG-氯化dimonium磷酸盐。合适的两性和两性离子表面活性剂其它例子可参见美国专利2,658,072,2,438,091和2,528,378,在此将其并入以供参考。
其它合适的两性和两性离子表面活性剂是甜菜碱。合适的甜菜碱的例子包括椰油二甲基羧甲基甜菜碱,月桂基二甲基羧甲基甜菜碱,月桂基二甲基α羧基乙基甜菜碱,十六烷基二甲基羧甲基甜菜碱,十六烷基二甲基甜菜碱,月桂酰二-(2-羟乙基)羧甲基甜菜碱,硬脂基二-(2-羟丙基)羧甲基甜菜碱,油酰基二甲基γ-羧丙基甜菜碱,月桂酰二-(2-羟丙基)α-羧乙基甜菜碱,椰油二甲基磺基丙基甜菜碱,硬脂基二甲基磺基丙基甜菜碱,月桂基二甲基磺基乙基甜菜碱,月桂基二-(2-羟乙基)磺基丙基甜菜碱和酰氨基甜菜碱和酰氨基磺基甜菜碱,油酰基甜菜碱和椰油酰氨基丙基甜菜碱。
防晒化合物
许多防晒化合物都适合用于本发明的组合物。根据组合物的性质,防晒化合物的加入量可占到组合物重量的40%,优选约1%-30%。然而,优选的量可根据组合物的性质加以调整。因此,对于洗发液或调理剂形式的最终产品组合物,合适的防晒剂的量约为组合物重量的40%,优选从约0.5%-5%,更优选从约0.5-1.5%。合适的防晒化合物包括,例如,对-氨基苯甲酸,其盐及其衍生物;邻氨基苯甲酸盐;水杨酸盐;肉桂酸衍生物;二羟基肉桂酸衍生物;三羟基肉桂酸衍生物;烃;二亚苄基丙酮和亚苄基苯乙酮;萘酚磺酸盐;二羟基-萘酚酸及其盐;香豆素衍生物;二唑;奎宁盐;喹啉衍生物;羟基-或甲氧基-取代的二苯甲酮;尿酸和vilouric acids;丹宁酸及其衍生物;氢醌;氨基苯甲酸酯,水杨酸盐,阿魏酸(ferrulic acid)衍生物,苯基苯并咪唑磺酸,二苯甲酮磺酸,硫辛酸衍生物,油溶性肉桂酸酯和二苯甲酮。要了解其它合适的防晒化合物,请参见Segarin等,美容科学和技术,第VIII章,189页开始,在此将其并入以供参考。
特别合适的防晒化合物包括2-乙基己基对-甲氧基肉桂酸酯,4,4’-叔-丁基甲氧基二苯甲酰甲烷,2-羟基-4-甲氧基二苯甲酮,辛基二甲基对-氨基苯甲酸,二没食子酰三油酸酯,2,2-二羟基-4-甲氧基二苯甲酮,乙基-4-二(羟丙基)-氨基苯甲酸酯,2-乙基己基-2-氰基-3,3-二苯基丙烯酸酯,2-乙基己基水杨酸酯,甘油基对-氨基苯甲酸酯,3,3,5-三甲基环己基水杨酸酯,甲基邻氨基苯甲酸酯,对-二甲基-氨基苯甲酸或氨基苯甲酸酯,2-乙基己基对-二甲基氨基苯甲酸酯,2-苯基苯并咪唑-5-磺酸,2-(对-二甲基-氨基苯基)-5-磺酸基苯并噁酸,对-氨基苯甲酸,二苯甲酮-1,二苯甲酮-1,二苯甲酮-2,二苯甲酮-3,二苯甲酮-4,二苯甲酮-5,二苯甲酮-6,二苯甲酮-8,二苯甲酮-12,甲氧基肉桂酸酯,阿伏苯宗,乙基二羟丙基对-氨基苯甲酸酯,甘油基对-氨基苯甲酸酯,甲基邻氨基苯甲酸酯,octocrylene,辛基二甲基对-氨基苯甲酸酯,辛基甲氧基肉桂酸酯,辛基水杨酸酯,氧化锌,二氧化钛,红色矿脂(red petrolatum)。
软化剂
本发明的组合物还包括一种或多种软化剂化合物,如脂肪、蜡、类脂、硅酮、烃、脂肪醇和多种溶剂物质。软化剂的量取决于用途。在最终的产品组合物中,软化剂可占到组合物重量的50%,优选从约0.1%-20%和更优选从约0.5%-10%。
合适的软化剂的例子包括C8-30羧酸的C8-30烷基酯;C8-30羧酸的C1-6二醇单酯和二酯;C8-30羧酸的甘油一酯,甘油二酯和甘油三酯,C8-30羧酸的胆固醇酯,胆固醇和烃。这些物质的例子包括己二酸二异丙酯,肉豆蔻酸异丙酯,棕榈酸异丙酯,棕榈酸乙基己基酯,新戊酸异癸酯,C12-15醇的苯甲酸酯,马来酸二乙基己基酯,PPG-14丁基醚,PPG-2肉豆寇基醚丙酸酯,蓖麻油酸十六醇酯,胆固醇硬脂酸酯,胆固醇异硬脂酸酯,胆固醇乙酸酯,霍霍巴油,可可脂,牛油树脂,羊毛脂,羊毛脂酯,矿物油,矿脂和直链和支链C16-C30烃。
同样有用的有直链和支链脂肪C8-C30醇,例如,十八烷醇,异十八烷醇,ehenyl醇,十六烷醇,异十六烷醇以及它们的混合物。其它合适的软化剂是例子如美国专利4,919,934中所述;在此将其全文并入以供参考。
其它合适的软化剂是各种烷氧基化的醚、二醚、酯、二酯和三酯。合适的烷氧基化的醚的例子包括PPG-10丁基醚,PPG-11丁基醚,PPG-12丁基醚,PPG-13丁基醚,PPG-14丁基醚,PPG-15丁基醚,PPG-16丁基醚,PPG-17丁基醚,PPG-18丁基醚,PPG-19丁基醚,PPG-20丁基醚,PPG-22丁基醚,PPG-24丁基醚,PPG-30丁基醚,PPG-11硬脂基醚,PPG-15硬脂基醚,PPG-10油基醚,PPG-7月桂醚,PPG-30异十六烷基醚,PPG-10甘油醚,PPG-15甘油醚,PPG-10丁二醇醚,PPG-15丁二醇醚,PPG-27甘油醚,PPG-30十六烷基醚,PPG-28十六烷基醚,PPG-10十六烷基醚,PPG-10己二醇醚,PPG-15己二醇醚,PPG-10 1,2,6-己三醇醚,PPG-15 1,2,6-己三醇醚以及它们的混合物。
烷氧基化的二醚的例子包括PPG-10 1,4-丁二醇二醚,PPG-12 1,4-丁二醇二醚,PPG-14 1,4-丁二醇二醚,PPG-2丁二醇二醚,PPG-10 1,6-己二醇二醚,PPG-12 1,6-己二醇二醚,PPG-14己二醇二醚,PPG-20己二醇二醚以及它们的混合物。优选的是选自PPG-10 1,4-丁二醇二醚,PPG-12 1,4-丁二醇二醚,PPG-10 1,6-己二醇二醚和PPG-12己二醇二醚以及它们的混合物。
合适的脂类包括C8-C20醇单失水山梨醇酯,C8-C20醇失水山梨醇二酯,C8-C20醇失水山梨醇三酯,C8-C20醇蔗糖单酯,C8-C20醇蔗糖二酯,C8-C20醇蔗糖三酯和C2-C62-羟酸的C8-C20脂肪醇酯。特别合适的类脂的例子是失水山梨醇二异硬脂酸酯,失水山梨醇二油酸酯,失水山梨醇二硬脂酸酯,失水山梨醇异硬脂酸酯,失水山梨醇月桂酸酯,失水山梨醇油酸酯,失水山梨醇棕榈酸酯,失水山梨醇倍半油酸酯,失水山梨醇倍半硬脂酸酯,失水山梨醇硬脂酸盐,失水山梨醇三异硬脂酸酯,失水山梨醇三油酸酯,失水山梨醇三硬脂酸酯,蔗糖可可脂,蔗糖月桂酸酯,蔗糖二硬脂酸酯,蔗糖月桂酸酯,蔗糖肉豆蔻酸酯,蔗糖油酸酯,蔗糖棕榈酸酯,蔗糖蓖麻油酸酯,蔗糖硬脂酸酯,蔗糖三山嵛酸酯,蔗糖三硬脂酸酯,肉豆寇基乳酸酯,硬脂基乳酸酯,异硬脂基乳酸酯,十六烷基乳酸酯,棕榈基乳酸酯,可可基乳酸酯以及它们的混合物。
其它合适的软化剂包括矿物油、矿脂、胆固醇、二甲硅油、二甲基硅醇(dimethiconol)、十八烷醇,十六烷醇,二十二烷醇,己二酸二异丙酯,肉豆蔻酸异丙酯,肉豆蔻酸肉豆蔻酯,蓖麻油酸十六醇酯,失水山梨醇二硬脂酸酯,失水山梨醇二月桂酸酯,失水山梨醇硬脂酸盐,失水山梨醇月桂酸酯,蔗糖月桂酸酯,蔗糖二月桂酸酯,异硬脂基乳酸钠,月桂酰pidolate,失水山梨醇硬脂酸酯,硬脂醇,十六烷醇,二十二烷醇,PPG-14丁基醚,PPG-15硬脂基醚以及它们的混合物。
乳化剂
本发明的组合物还包括各种乳化剂。在本发明的最终产品组合物中,乳化剂可占到组合物重量的10%,优选为0.5%-5%。合适的乳化剂的例子包括硬脂酰氨基丙基PG-氯化dimonium磷酸盐,硬脂酰氨基丙基乙基乙基硫酸dimonium,硬脂酰氨基丙基二甲基(肉豆寇基乙酸盐)氯化铵,硬脂酰氨基丙基二甲基十六十八烷基甲苯磺酸铵(stearamidopropyl dimethyl cetearyl ammonium tosylate),硬脂酰氨基丙基二甲基氯化铵,硬脂酰氨基丙基二甲基乳酸铵,聚乙二醇,聚丙二醇以及它们的混合物。
止屑剂
本发明的组合物还包括止屑剂。合适的止屑剂的例子包括羟基吡啶硫酮锌、硫磺和硫化硒。
毛发氧化剂
本发明的组合物还包括头发的氧化/还原剂,合适的头发氧化/还原试剂包括过氧化氢、过硼酸盐、巯基乙酸盐和过硫酸盐。
增稠剂
本发明的组合物还包括各种增稠剂,如交联丙烯酸酯,非离子聚丙烯酰胺,黄原胶,瓜尔胶,gellan gum等;聚烷基硅氧烷,聚芳基硅氧烷和氨基硅酮。在本发明组合物的最终产品中,增稠剂可占到组合物重量的10%,优选为0.2%-5%。
合适的增稠硅化合物的特别的例子包括聚二甲基硅氧烷,苯基硅酮,聚二乙基硅氧烷和聚甲基苯基硅氧烷。一些合适的硅化合物描述在欧洲专利申请EP 95,238和美国专利4,185,017中,在此将其并入以供参考。本发明的组合物还包括硅酮聚合物,它既可以保持发型也可以调理头发。这种物质描述在美国专利4,902,499中,在此将其并入以供参考。
头发调理剂
本发明的组合物还包括水解的动物蛋白头发调理剂。其例子之一是Croda有限公司出售的一种物质,其商品名为Crotein Q-RTM。其它例子包括尿素、甘油和丙氧基化甘油,这些描述在美国专利4,976,953中,在此将其并入以供参考。
头发定型剂
本发明的组合物还包括使头发定型的头发定型剂。所述设定发型的聚合物可以是均聚物、共聚物、三元共聚物等。为便于描述这些聚合物,聚合物中的单体单元可称为用来制造聚合物的单体。所述单体可以是离子的(例如阴离子的,阳离子的,两性的,两性离子的)或非离子的。
阴离子单体的例子包括不饱和羧酸单体,如丙烯酸,甲基丙烯酸,马来酸,马来酸半酯,衣康酸,延胡索酸和巴豆酸;不饱和多元酸酐的半酯,如琥珀酸酐,邻苯二甲酸酐,或含有羟基的丙烯酸酯和/或异丁烯酸酯,如羟乙基丙烯酸酯和羟乙基甲基丙烯酸酯,羟丙基丙烯酸酯等;带有磺酸基的单体,如苯乙烯磺酸,磺乙基丙烯酸酯和甲基丙烯酸酯等;和带有磷酸基团的单体,如酸性磷酸氧基乙基丙烯酸酯和甲基丙烯酸酯,3-氯-2-酸性磷酸氧基丙基丙烯酸酯和甲基丙烯酸酯等。
阳离子单体的例子包括从丙烯酸或甲基丙烯酸衍生的单体和三烷基胺的季化的表卤代醇产品,所述烷基含有1-5个碳原子,如(甲基)丙烯酰氧基丙基三甲基氯化铵和(甲基)丙烯酰氧基丙基三乙基溴化铵;甲基丙烯酸的胺衍生物或衍生自甲基丙烯酸或甲基丙烯酰胺的甲基丙烯酰胺的胺衍生物和二烷基链烷醇胺,所述烷基含有1-6个碳原子,如二甲基氨基乙基(甲基)丙烯酸酯,二乙基氨基乙基(甲基)丙烯酸酯,二甲基氨基丙基(甲基)丙烯酸酯或二甲基氨基丙基(甲基)丙烯酰胺。
两性单体是例子包括被卤代脂肪酸盐(如单氯代醋酸钾、单溴代丙酸钠、单氯代醋酸的氨基甲基丙醇盐、单氯代醋酸的三乙醇胺盐等)两性离子化的上述(甲基)丙烯酸的胺衍生物或(甲基)丙烯酰胺的胺衍生物的衍生物,如二甲基氨基乙基(甲基)丙烯酸酯,二甲基氨基丙基(甲基)丙烯酰胺;以及(甲基)丙烯酸或(甲基)丙烯酰胺的胺衍生物,如上所述,被丙磺酸内酯修饰。
非离子单体的例子有C1-C24醇的丙烯酸或甲基丙烯酸酯,如甲醇,乙醇,1-丙醇,2-丙醇,1-丁醇,2-甲基-1-丙醇,1-戊醇,2-戊醇,3-戊醇,2-甲基-1-丁醇,1-甲基-1-丁醇,3-甲基-1-丁醇,1-甲基-1-戊醇,2-甲基-1-戊醇,3-甲基-1-戊醇,叔-丁醇,环己醇,2-乙基-1-丁醇,3-庚醇,苄醇,2-辛醇,6-甲基-1-庚醇,2-乙基-1-己醇,3,5-二甲基-1-己醇,3,5,5-三甲基-1-己醇,1-癸醇,1-十二碳醇,1-十六碳醇,1-十八碳醇,苯乙烯;氯苯乙烯;乙烯基酯如乙酸乙烯酯;氯乙烯;偏二氯乙烯;丙烯腈;α-甲基苯乙烯;叔-丁基苯乙烯;丁二烯;环己二烯;乙烯;丙烯;乙烯基甲苯;烷氧基烷基(甲基)丙烯酸酯,甲氧基乙基(甲基)丙烯酸酯,丁氧基乙基(甲基)丙烯酸酯;烯丙基丙烯酸酯,烯丙基甲基丙烯酸酯,环己基丙烯酸酯和甲基丙烯酸酯,油基丙烯酸酯和甲基丙烯酸酯,苄基丙烯酸酯和甲基丙烯酸酯,四氢糠基丙烯酸酯和甲基丙烯酸酯,乙二醇二-丙烯酸酯和-甲基丙烯酸酯,1,3-丁二醇二-丙烯酸酯和-甲基丙烯酸酯,二丙酮丙烯酰胺,异冰片基(甲基)丙烯酸酯,正-丁基甲基丙烯酸酯,异丁基甲基丙烯酸酯,2-乙基己基甲基丙烯酸酯,甲基丙烯酸甲酯,叔-丁基丙烯酸酯,叔-丁基甲基丙烯酸酯以及它们的混合物。
阴离子头发定型聚合物的例子有乙酸乙烯酯和巴豆酸的共聚物,乙酸乙烯酯、巴豆酸和α-支链饱和的脂肪族单羧酸的乙烯酯(如乙烯基新癸酸酯)的三元共聚物;以及甲基乙烯醚和马来酸酐的共聚物,丙烯酸共聚物和含有丙烯酸或甲基丙烯酸的三元共聚物。
阳离子头发定型聚合物的例子有带有氨基官能团的丙烯酸酯单体(如低级烷基氨基烷基丙烯酸酯)或甲基丙烯酸酯单体(如二甲基氨基乙基甲基丙烯酸酯)与兼容单体,如N-乙烯基吡咯烷酮或烷基甲基丙烯酸酯(如甲基丙烯酸甲酯和甲基丙烯酸乙酯)和烷基丙烯酸酯(如丙烯酸甲酯和丙烯酸丁酯)的共聚物。
其它组分
本发明的组合物还包括多种其它多种成分。通常用于化妆品和个人护理用品工业的一些合适的其它成分描述在《CTFA化妆品成分手册》(第二版,1992),在此将其并入以供参考。
因此,本发明的组合物还包括一种或多种吸收剂、抗痤疮剂、防汗剂、抗结剂、消泡剂、抗菌剂、抗氧化剂、止屑剂、收敛剂、粘合剂、缓冲液、生物添加剂、缓冲剂、填充剂、螯合剂、化学添加剂、偶联剂、调理剂、着色剂、化妆品收敛剂、化妆品抗微生物剂、变性剂、药用收敛剂、去污剂、分散剂、外用镇痛剂、成膜剂、起泡剂、芳香剂组分、保湿剂、角质软化剂、遮光剂、pH调节剂、防腐剂、推进剂、蛋白质、类视色素、还原剂、螯合剂、皮肤增白剂、皮肤调节剂(保湿剂、多种且隐藏)、皮肤缓和剂、皮肤愈合剂、软化剂、增溶剂、润滑剂、渗透剂、增塑剂、溶剂和辅助溶剂、遮光添加剂、盐、精油和维生素。
合适的pH调节剂的例子包括氢氧化钠、三乙醇胺和氨基甲基丙醇以及它们的混合物。如果最终从产品组合物中含有pH调节剂,其含量可占组合物重量的约0.01%-5%,优选从约0.1%-2%。
合适的成膜剂的例子包括甘油/二甘醇肉豆蔻酸酯(diethylene glycolmyrystate)的共聚物,甘油/二甘醇己二酸酯共聚物,PVM/MA共聚物的乙酯,PVP/二甲基硅油基丙烯酸酯/聚氨基甲酰/聚二醇酯以及它们的混合物。如果最终的产品组合物中含有成膜剂,其含量可占组合物重量的约0.1%-15.0%,优选从约0.1%-2.5%。
合适的维生素的例子包括维生素E、维生素E乙酸酯、视黄酸、视黄醇、类视色素。
合适的抗痤疮药物的例子有间苯二酚、硫、水杨酸、红霉素、锌和过氧苯甲酰。
合适的皮肤增白剂或淡化剂的例子包括氢醌和曲酸。合适的美观组分的例子有芳香剂、色素、染色剂等,包括泛醌及其衍生物(例如乙基泛醌)、芦荟(aloe vera)、泛酸及其衍生物、丁香油、薄荷醇、樟脑、桉树油、丁香油酚、甲基乳酸酯、北美金缕梅精华、尿囊素、没药醇和甘草酸二钾。
本发明的组合物将在以下实施例中进一步描述。
实施例1.PPG-3-PEG-4十六烷基醚的制备
将2351克(9.7摩尔)十六烷醇置于充有氮气的干燥的搅拌式压力容器中。将十六烷醇加热至熔化,然后边搅拌边加入5.75克NaOH,NaOH是40%的水溶液。在容器中充入氮气并再加热至110℃。施加1小时真空从容器顶端除去水蒸气,然后将混合物再加热至155℃。加入1690克环氧丙烷和1709克环氧乙烷并混合后,将反应混合物再搅拌1.5小时以使反应完全进行。通过取出试剂并测量容器内的压力来控制反应过程。将反应混合物冷却至110℃并施加1小时真空。为中和反应混合物中的NaOH,加入42克25%的硫酸。将混合物再搅拌10分钟并将pH调至7。冷却后就得到了粘稠液体状的PEG-4-PPG-3十六烷基醚,将其作为主要产品分离。
实施例2.二-PPG-3-PEG-4十六烷基醚己二酸酯的制备
在装有机械搅拌器、温度计并充有氮气的四颈烧瓶中加入1778克(2.96摩尔)PPG-3-PEG-4十六烷基醚、221克(1.52摩尔)己二酸和1.5克SnO。将混合物加热至220C。通过测量反应混合物的酸值控制反应进程。一旦酸值稳定便将混合物冷却至22℃。加入4g 30%的H2O2水溶液和70克水,并在加热至75℃。在真空下脱水,制得主要产品二-PPG-3-PEG-4。
实施例3.评价洗发液基料中3%烷氧基化的酯的抗刺激性
用含有3%烷氧基化的酯的专利洗发液基料评价二-PPG-2-PEG-10肉豆蔻醚己二酸酯和二-PPG-3-PEG-4十六烷基醚己二酸酯的抗刺激活性。除非离子表面活性剂和增稠剂外,该洗发液基料中含有常规洗发液所有有效成分。用上述TEP测定实验法进行抗刺激活性的评估。表6显示了试验组合物A1(二-PPG-2-PEG-10肉豆蔻醚己二酸酯)和B1(二-PPG-3-PEG-4十六烷基醚己二酸酯)以及对照组合物C1的含量:
表6
A1 | B1 | ------ | C1 | |
洗发液基料 | 96% | 96% | 99% | |
Crothix液* | 1% | 1% | 1% | |
二-PPG-2-PEG-10肉豆蔻醚己二酸酯 | 3% | - | - | |
二-PPG-3-PEG-4十六烷基醚己二酸酯 | - | 3% | - |
*PEG-150季戊四基四硬脂酸酯(和)PEG-6甘油辛酯/癸酯(和)水。
表7显示了组合物A1,B1和C1的荧光素钠的胞内渗漏百分比:
表7
组合物 | 1∶50稀释度时的渗漏百分比 | 1∶50稀释度时的渗漏百分比 |
A1 | 48% | 15% |
B1 | 36% | 6% |
C1 | 64% | 47% |
由表7可见,二-PPG-2-PEG-10肉豆蔻醚己二酸酯和二-PPG-3-PEG-4十六烷基醚己二酸酯都显示出抗刺激活性,二-PPG-3-PEG-4十六烷基醚己二酸酯(试验组合物B1)的活性幅度明显较高。
实施例4.参比市售的婴儿洗发液评价抗刺激性
市售的J&J婴儿洗发液样品(产品编号1199NB)购自市场。试验组合物A2在J&J婴儿洗发液中添加了烷氧基化的酯,J&J婴儿洗发液同时用作对照。在化妆品工业中,涉及表面活性剂系统的体外实验通常将J&J婴儿洗发液作为对照。表8比较了试验组合物A2和市售的J&J婴儿洗发液样品:
表8
1∶50稀释度时的渗漏百分比 | 1∶100稀释度时的渗漏百分比 | |
试验组合物A2 | 48% | 15% |
市售婴儿洗发液 | 60% | 39% |
从上述比较可见,含有烷氧基化的酯的组合物A2能够产生与其它未经处理的市售产品同样的或更好的抗刺激效果。
实施例5.评价二-PPG-3-PEG-4肉豆蔻醚己二酸酯对比市售婴儿洗发液的抗刺激活性
试验组合物A3是在J&J婴儿洗发液中加入二-PPG-3-PEG-4肉豆蔻醚己二酸酯制备的(含有5%的酯和95%的洗发液)。将不含酯的洗发液用作对照。用TEP测定按上述方法试验组合物A3和对照的刺激潜能。测量结果显示在表9(荧光素钠的胞内渗漏):
表9
1∶50稀释度时的渗漏百分比 | 1∶100稀释度时的渗漏百分比 | |
试验组合物A3 | 14.2% | 17.4% |
市售婴儿洗发液 | 64.5% | 44.8% |
由表9可见,二-PPG-3-PEG-4肉豆蔻醚己二酸酯使洗发液的刺激潜能大大降低,这说明其显著的抗刺激活性。
实施例6.合成液体皂
成分 | % |
A部分 | |
CRODASINIC LS-30(月桂酰基肌氨酸钠) | 7.0 |
INCROMIDE CA(椰油酰胺DEA) | 5.0 |
月桂基聚氧乙烯醚硫酸钠 | 18.0 |
二-PPG-2硬脂基聚氧乙烯-10己二酸酯 | 3.0 |
GLYCEROX HE(PEG-7甘油椰油酯) | 2.5 |
SUPER SOLAN(PEG-75羊毛脂) | 2.5 |
氯化钠 | 1.0 |
去离子水 | 58.5 |
乙二醇单硬脂酸酯 | 1.5 |
B部分 | |
丙二醇(和)甲基对羟基苯甲酸酯(和)丙基对羟基苯甲酸酯(和)二唑烷基尿素)(1) | 1.0 |
加入乳酸至pH7.00 | |
过程:将成分混合并加热至75-80℃。冷却至40℃。加入B部分。冷却至所需填充温度。如果需要用乳酸调节pH。
实施例7.透明沐浴液
成分 | % |
A部分 | |
去离子水 | 51.9 |
SLES(3摩尔) | 20.0 |
二-PPG-2硬脂基聚氧乙烯-10己二酸酯 | 3.0 |
CROSULTAINE C-50(椰油酰氨基丙基羟基磺基甜菜碱) | 12.0 |
EDTA二钠 | 0.1 |
B部分 | |
INCROMIDE CA(椰油酰胺DEA) | 3.0 |
GLYCEROX 767(PEG-6癸酸/辛酸甘油三酸酯) | 3.0 |
CROTHIX LIQUID(PEG-150季戊四基四硬脂酸酯(和)PEG-6辛酸/癸酸甘油酯(和)水) | 3.0 |
C部分 | |
CROTEIN C-50(水解的胶原) | 1.0 |
INCROMECTANT LAMEA(乙酰胺MEA(和)乳酰胺MEA) | 1.0 |
10%柠檬酸溶液 | 1.0 |
丙二醇(和)Diazolidinyl Urea(和)甲基对羟基苯甲酸酯(和)丙基对羟基苯甲酸酯(1) | 1.0 |
pH=5.0+0.5 | |
粘度=5,500+10%(RVT Spindle #3,10rpm,25℃) |
过程:将A部分成分混合。将B部分成分混合并加热至50℃。边搅拌边将B部分缓慢加入A部分。将C部分的成分分别加入A部分。混合均匀。
实施例8.温和洗碗液(diswashing liquid)
成分 | 供应商 | 重量百分比 |
水 | - | 60 |
Calsoft L-40 | Pilot Chemical | 18.0 |
Calfoam ES-303 | Pilot Chemical | 12.0 |
INCROMIDE OXIDE C | Croda | 5.0 |
二-PPG-2硬脂基聚氧乙烯-10己二酸酯 | Croda | 3.0 |
氯化钠 | Various | 1-2 |
染料,芳香剂,防腐剂 | Various | q.s. |
实施例9.柔滑泡泡浴液
成分 | % |
A相 | |
INCROSUL OTS(油基聚氧乙烯醚-3磺基琥珀酸二钠) | 35.00 |
INCROMINE OXIDE C(椰油酰氨基丙胺氧化物) | 3.50 |
INCROMIDE LR(月桂酰胺DEA) | 2.00 |
CROVOL PK-70(PEG-45棕榈仁甘油酯) | 5.00 |
二-PPG-2硬脂基聚氧乙烯-10己二酸酯 | 3.00 |
氯化钠 | 1.25 |
去离子水 | 45.75 |
B相 | |
CRODAPEARL液(月桂基聚氧乙烯醚硫酸钠(和)羟乙基硬脂酰胺MIPA) | 3.00 |
CROSILK液(蚕丝氨基酸) | .50 |
Germaben II(1) | 1.00 |
柠檬酸将pH调至6.0 |
过程:将A相合并并略为加热至65℃。当溶液澄清时停止加热,继续混合并冷却至45℃。在45℃加入B相。混合并继续冷却至室温,然后调节pH。
实施例10.婴儿洗发液
成分 | % |
A部分 | |
SLES(3摩尔) | 20.0 |
CROSULTAINE C-50(椰油酰氨基丙基羟基磺基甜菜碱) | 12.0 |
去离子水 | 45.5 |
B部分 | |
CROVOL A-70(PEG-60杏仁甘油酯) | 15.0 |
二-PPG-2硬脂基聚氧乙烯-10己二酸酯 | 3.0 |
CROTHIX液(PEG-150季戊四基四硬脂酸酯和PEG-6辛酸/癸酸甘油酯(和)水) | 3.5 |
C部分 | |
丙二醇(和)Diazolidinyl Urea(和)甲基对羟基苯甲酸酯(和)丙基对羟基苯甲酸酯(1) | 1.0 |
过程:将A部分的成分混合。将B部分的成分混合并加热至50℃。将B部分加入A部分。分别加入C部分的成分。如果需要用10%HCl水溶液调节pH。将混合物冷却至所需的填充温度。
PH=6.22+0.5;粘度:9,200CPS+10%(RVT SPINDLE #4,10RPM,@25℃)
实施例11.遮光液
A遮光液包括以下成分:
A相
成分 | %W/W |
二-芥酸四咪唑啉季盐(di-erucic imidazoline quat) | 1.0 |
二苯甲酮3 | 6.0 |
十六十八烷基醇 | 4.0 |
二-PPG-3-PEG-4硬脂基聚氧乙烯己二酸酯 | 5.0 |
辛基甲氧基肉桂酸酯 | 7.5 |
B相
成分 | W/W% |
水 | 65.50 |
C相
成分 | W/W% |
Germaben II(防腐剂) | 1.0 |
所述遮光液按如下制备。将A相的成分合并并加热至75℃。在另外的容器中将B相的成分合并并加热至75℃。边搅拌边将A相加入B相,继续搅拌将混合相冷却至40℃。加入C相,继续冷却至25℃,得到了所需的液体。
实施例12.遮光剂喷射剂
A遮光剂喷射剂包括以下成分:
A相
成分 | %W/W |
二山嵛基二甲基氯化铵 | 1.0 |
二-PPG-3肉豆蔻醚己二酸酯 | 11.0 |
二苯甲酮3 | 6.0 |
辛基甲氧基肉桂酸酯 | 7.0 |
薄荷基邻氨基苯甲酸酯 | 5.0 |
二-PPG-2硬脂基聚氧乙烯-10己二酸酯 | 3.0 |
B相
成分 | W/W% |
水 | 66 |
氢氧化钠 | 0.1 |
C相
成分 | W/W% |
Germaben II(防腐剂) | 1.0 |
所述遮光剂喷射剂按以下方法制备。将A相的成分合并并加热至75℃。在单独的容器中将B相的成分合并并加热至75℃。边搅拌边将A相加入B相,继续搅拌将混合相冷却至40℃。加入C相,继续冷却至25℃,得到了所需的液体。
实施例13。头发调理剂
A头发调理剂包括以下成分:
A相
成分 | %W/W |
二-C20-24咪唑啉季盐(Immidazoline Quat) | 1.0 |
Cromollient SCE(二-PPG-2硬脂基聚氧乙烯-10己二酸酯) | 5.0 |
十六烷醇 | 4.0 |
B相
成分 | W/W% |
水 | 89 |
C相
成分 | W/W% |
Germaben II(防腐剂) | 1.0 |
所述头发调理剂按以下方法制备。将A相的成分合并并加热至75℃。在单独的容器中将B相的成分合并并加热至75℃。边搅拌边将A相加入B相,继续搅拌将混合相冷却至40℃。加入C相,继续冷却至25℃,得到了所需的液体。
实施例14.调理洗发液
A调理洗发液包括以下成分:
A相
成分 | %W/W |
月桂基硫酸铵 | 25.0 |
月桂基聚氧乙烯醚硫酸铵 | 12.0 |
CrosultaineC-50(椰油酰氨基丙基羟基磺基甜菜碱) | 3.0 |
月桂酰胺DEA | 1.0 |
Cromollient DCA34(二-PPG-3 Myreth-4己二酸酯) | 4.0 |
Germaben II(防腐剂) | 1.0 |
B相
成分 | W/W% |
二-芥酸咪唑啉季盐 | 2.0 |
所述调理洗发液按以下方法制备。将A相的成分合并并加热至60℃。将B相加入A相,继续搅拌将混合物冷却至25℃。
除非另有说明,术语“包含”、“包括”、“含有”、“具有”等是指“没有限制地含有”,不能理解为将一般状态限制于它后面紧跟的特定或类似项目或物质。尽管已经参考特定实施方案描述了本发明,应该理解,这些实施方案仅仅是为了产生本发明的原则和应用。因此应该理解,不背离由附加的权利要求书所限定的本发明精神和范围的情况下,可对所例举的实施方案进行各种修改以及设计出其它组合。
尽管已经参照特定实施方案描述了本发明,应该理解,这些实施方案仅仅是为了产生本发明的原则和应用。因此应该理解,不背离由附加的权利要求书所限定的本发明精神和范围的情况下,可对所例举的实施方案进行各种修改以及设计出其它组合。
Claims (93)
1.一种具有抗刺激活性的二羧酸或三羧酸的烷氧基化的酯,其抗刺激活性检测为,采用含有5%所述烷氧基化的酯的试验组合物,在1∶50稀释度时荧光素钠的胞内渗漏减少了15%或更多,在1∶100稀释度时减少了40%或更多。
2.如权利要求1所述的烷氧基化的酯,所述抗刺激活性为,在1∶50稀释度时为了20%或更多,在1∶100稀释度时为50%或更多。
3.如权利要求1所述的烷氧基化的酯,所述抗刺激活性为,在1∶50稀释度时为40%或更多,在1∶100稀释度时为75%或更多。
5.如权利要求4所述的烷氧基化的酯,其中,-COR1CO-是脂肪族二羧酸的二羧基,R1有0-6个碳原子。
6.如权利要求4所述的烷氧基化的酯,其中,R1是具有6或10个碳原子的芳香环。
7.如权利要求4所述的烷氧基化的酯,其中,R1选自芳基,苯基芳基,烷基芳基和萘。
8.如权利要求4所述的烷氧基化的酯,其中,R3或R5是氢。
9.如权利要求4所述的烷氧基化的酯,其中,R3,R5有6-22个碳原子。
10.如权利要求4所述的烷氧基化的酯,其中,R3,R5有12-22个碳原子。
11.如权利要求4所述的烷氧基化的酯,其中,R3,R5有16-22个碳原子。
12.如权利要求4所述的烷氧基化的酯,其中,R3,R5有18-22个碳原子。
13.如权利要求4所述的烷氧基化的酯,其中,x/y从1-2.5。
14.如权利要求4所述的烷氧基化的酯,其中,x/y从1-2。
15.如权利要求4所述的烷氧基化的酯,其中,根据基团R3O(R2O)-和R5O(R4O)-的分子量,基团(R2O)和(R4O)中乙氧基的重量百分比分别超过20%。
16.如权利要求4所述的烷氧基化的酯,其中,根据基团R3O(R2O)-和R5O(R4O)-的分子量,基团(R2O)和(R4O)中乙氧基的重量百分比分别从20-80%。
17.如权利要求4所述的烷氧基化的酯,其中,根据基团R3O(R2O)-和R5O(R4O)-的分子量,基团(R2O)和(R4O)中乙氧基的重量百分比分别从24-35%。
18.如权利要求1所述的烷氧基化的酯,具有下式:
其中,-COR6CO-是脂肪族三羧酸的三羧基,R6是有1-19个碳原子的取代或未取代的、饱和或不饱和的、直链或支链、有环或无环的烷基,或
-COR6CO-是芳香三羧酸的三羧基,R6是有6-20个碳原子的芳香三羧酸的芳香环;
R7O-、R9O、R11O-可以相同或不同,是下式的烷氧基化的部分
x从0-200,y从0-200;
R8,R10,R12分别独立是含有6-30个碳原子的直链或支链、饱和或不饱和、取代或未取代的烷基、烷基芳基或芳基烷基基团,或是氢,条件是R8,R10,R12中至多有一个是氢。
19.如权利要求18所述的烷氧基化的酯,其中,-COR6CO-是脂肪族三羧酸的三羧基,R6有1-6个碳原子。
20.如权利要求18所述的烷氧基化的酯,其中,R6是芳香环有6或10个碳原子。
21.如权利要求20所述的烷氧基化的酯,其中,R6选自芳基,苯基芳基,烷基芳基和萘。
22.如权利要求18所述的烷氧基化的酯,其中,R8,R10或R12是氢。
23.如权利要求18所述的烷氧基化的酯,其中,根据基团R8O(R7O)-、R10O(R9O)-、R12O(R11O)-的分子量,基团(R7O),(R9O)和(R11O)中乙氧基的重量百分比分别超过20%。
24.如权利要求18所述的烷氧基化的酯,其中,根据基团R8O(R7O)-、R10O(R9O)-、R12O(R11O)-的分子量,基团(R7O),(R9O)和(R11O)中乙氧基的重量百分比分别为20-80%。
25.如权利要求18所述的烷氧基化的酯,其中,根据基团R8O(R7O)-、R10O(R9O)-、R12O(R11O)-的分子量,基团(R7O),(R9O)和(R11O)中乙氧基的重量百分比分别为24-35%。
26.如权利要求18所述的烷氧基化的酯,其中,R8,R10,R12有6-22个碳原子。
27.如权利要求18所述的烷氧基化的酯,其中,R8,R10,R12有12-22个碳原子。
28.如权利要求18所述的烷氧基化的酯,其中,R8、R10、R12有16-22个碳原子。
29.如权利要求18所述的烷氧基化的酯,其中,R8、R10、R12有18-22个碳原子。
30.如权利要求18所述的烷氧基化的酯,其中,x/y是2或更大且x>y。
31.如权利要求4或18所述的烷氧基化的酯,其中,x从1-100,y从0-100。
32.如权利要求4或18所述的烷氧基化的酯,其中,x从1-40,y从0-40。
33.如权利要求4或18所述的烷氧基化的酯,其中,x从2-20,y从1-5。
34.如权利要求4或18所述的烷氧基化的酯,其中,x从3-10,y从1-10。
36.如权利要求35所述的烷氧基化的酯,其中,R14、R15有16-22个碳原子。
37.如权利要求35所述的烷氧基化的酯,其中,R14、R15有18-22个碳原子。
38.如权利要求35所述的烷氧基化的酯,其中,x1和x2范围从1-100,y1和y2范围从0-100。
39.如权利要求35所述的烷氧基化的酯,其中,x1和x2范围从1-20,y1和y2范围从1-10。
40.如权利要求35所述的烷氧基化的酯,其中,x1和x2范围是2-10,y1和y2范围是1-5。
41.如权利要求35所述的烷氧基化的酯,其中,R13具有结构(CHm)n或-(CHm)nX-,m是1或2,n是0-20,X如果存在是选自低级烷基,包括甲基、羟基、烷基羟基和卤素的支链取代基,卤素包括氯和溴。
42.如权利要求41所述的烷氧基化的酯,其中,n是4。
43.如权利要求42所述的烷氧基化的酯,其中,R14、R15有18-22个碳原子。
44.如权利要求43所述的烷氧基化的酯,其中,x1和x2是4,y1和y2是3。
45.如权利要求44所述的烷氧基化的酯,是PEG-4-PPG-3硬脂基聚氧乙烯醚己二酸酯。
46.如权利要求43所述的烷氧基化的酯,其中,x1和x2是10,y1和y2是2。
47.如权利要求44所述的烷氧基化的酯,是PEG-2-PPG-10硬脂基聚氧乙烯醚己二酸酯。
48.具有式(IV)的烷氧基化的酯:
其中,-OCR16CO-是脂肪族二羧酸的二羧基,R16是有0-20个碳原子的饱和或不饱和、直链或支链、取代或未取代、有环或无环的烷基;
R17、R18是有6-22个碳原子的相同或不同、饱和或不饱和、取代或未取代的烷基;
x1和x2,可以相同或不同,范围是1-100;
y1和y2,可以相同或不同,范围是0-100;以及
x1/y1和x2/y2从1-2.5。
49.如权利要求41所述的烷氧基化的酯,其中,x1/y1和x2/y2从1-2。
50.如权利要求41所述的烷氧基化的酯,其中,x1/y1和x2/y2从1-1.5。
51.如权利要求41所述的烷氧基化的酯,其中,R17,R18有12-22个碳原子。
52.如权利要求48所述的烷氧基化的酯,其中,R17,R18有16-22个碳原子。
53.如权利要求48所述的烷氧基化的酯,其中,x1和x2范围是1-40,y1和y2范围是0-40。
54.如权利要求48所述的烷氧基化的酯,其中,x1和x2范围是3-10,y1和y2从1-5。
55.如权利要求48所述的烷氧基化的酯,其中,R16具有结构(CHm)n或-(CH1-2)nX-,m是1或2,n是0-20,X是选自低级烷基,包括甲基、羟基、烷基羟基和卤素的支链取代基,卤素包括氯和溴。
56.如权利要求55所述的烷氧基化的酯,其中,n是3-7。
57.如权利要求55所述的烷氧基化的酯,其中,n是4。
58.如权利要求57所述的烷氧基化的酯,其中,x1和x2是4,y1和y2是3,R17,R18有14-22个碳原子。
59.如权利要求55所述的烷氧基化的酯,是PEG-4-PPG-3肉豆蔻醚己二酸酯。
60.减弱含有刺激剂的个人护理品或化妆品对人或动物的刺激的方法,其特征在于,所述方法包括将所述个人护理品或化妆品用于所述个体,所述个人护理品或化妆品含有所述刺激剂和至少一种二羧酸或三羧酸的烷氧基化的酯,所述烷氧基化的酯的抗刺激活性检测为,采用含有5%烷氧基化的酯的试验组合物,在1∶50稀释度时测得荧光素钠的胞内渗漏减少了15%或更多,在1∶100稀释度时减少了40%或更多。
61.如权利要求60所述的方法,其中,在1∶50稀释度时所述抗刺激活性为20%或更多,或在1∶100稀释度时为50%或更多。
62.如权利要求61所述的方法,其中,在1∶50稀释度时所述抗刺激活性为40%或更多,或在1∶100稀释度时为75%或更多。
63.如权利要求60所述的方法,其中,所述施用步骤包括对皮肤局部施用。
64.如权利要求60所述的方法,其中,所述施用步骤包括对头发局部施用。
65.如权利要求60所述的方法,其中,所述刺激剂是表面活性剂。
66.如权利要求65所述的方法,其中,所述表面活性剂选自非离子表面活性剂,阴离子表面活性剂,阳离子表面活性剂和两性表面活性剂。
67.如权利要求60所述的方法,其中,所述产品选自洗发液,头发调理剂,防晒剂,婴儿洗发液,婴儿沐浴产品,手洗碗液,沐浴液,洗面奶,无纺布,婴儿抹布和泡泡浴产品。
68.如权利要求60所述的方法,其中,所述至少一种烷氧基化的酯是权利要求4、18、35或48所述的酯。
69.如权利要求60所述的方法,其中,所述烷氧基化的酯是二-PPG-3-PEG-4肉豆蔻醚己二酸酯。
70.如权利要求60所述的方法,其中,所述烷氧基化的酯是二-PPG-2-PEG-10硬脂基聚氧乙烯醚己二酸酯。
71.如权利要求60所述的方法,其中,所述烷氧基化的酯是二-PPG-3-PEG-4硬脂基聚氧乙烯醚己二酸酯。
72.一种组合物,其特征在于,所述组合物含有刺激剂和至少一种权利要求1,35或48所述的烷氧基化的酯。
73.如权利要求72所述的组合物,其中,所述刺激剂是表面活性剂。
74.如权利要求73所述的组合物,其中,所述刺激剂和烷氧基化的酯被制成预混合混合物。
75.如权利要求74所述的组合物,还含有水。
76.如权利要求75所述的组合物,其中,所述烷氧基化的酯占混合物重量的3-20%。
77.如权利要求76所述的组合物,其中,所述表面活性剂是甜菜碱表面活性剂,占混合物重量的0-97%。
78.如权利要求76所述的组合物,其中,所述表面活性剂是两性表面活性剂,占0-97%重。
79.如权利要求76所述的组合物,其中,所述表面活性剂是非离子表面活性剂,占0-30%重。
80.如权利要求76所述的组合物,其中,所述表面活性剂是阳离子表面活性剂,占0-30%重。
81.如权利要求76所述的组合物,其中,所述表面活性剂链烷醇酰胺,占0-30%重。
82.如权利要求76所述的组合物,还含有一种或更多防腐剂,芳香剂,泡沫促进剂,调理剂和软化剂。
83.如权利要求74所述的组合物,其中,所述烷氧基化的酯是二-PPG-3-PEG-4肉豆蔻醚己二酸酯。
84.如权利要求74所述的组合物,其中,所述烷氧基化的酯是二-PPG-2-PEG-10硬脂基聚氧乙烯醚己二酸酯。
85.如权利要求74所述的组合物,其中,所述烷氧基化的酯是二-PPG-3-PEG-4硬脂基聚氧乙烯醚己二酸酯。
86.如权利要求73所述的组合物,其中,所述刺激剂和所述表面活性剂包含在选自洗发液,头发调理剂,防晒剂,婴儿洗发液,婴儿沐浴产品,洗手液,沐浴液,洗面奶,无纺布,婴儿抹布和泡泡浴产品的化妆品或个人护理产品中。
87.如权利要求73所述的组合物,其中,所述烷氧基化的酯约占0.20-40.0%,还含有约0.20-40.0%重量的活性成分。
88.如权利要求87所述的组合物,其中,所述活性成分是遮光剂,色素,润湿剂,成膜剂,去污剂,增稠剂,乳化剂,防腐剂,调节剂或除臭剂。
89.如权利要求73所述的组合物,其中,所述烷氧基化的酯是二-PPG-3-PEG-4肉豆蔻醚己二酸酯。
90.如权利要求73所述的组合物,其中,所述烷氧基化的酯是二-PPG-2-PEG-10硬脂基聚氧乙烯醚己二酸酯。
91.如权利要求73所述的组合物,其中,所述烷氧基化的酯是二-PPG-3-PEG-4硬脂基聚氧乙烯醚己二酸酯。
92.如权利要求87所述的组合物,它是含水的局部组合物。
93.如权利要求87所述的组合物,它是非-水性局部组合物。
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US31101001P | 2001-08-09 | 2001-08-09 | |
US60/311,010 | 2001-08-09 | ||
US31660801P | 2001-08-31 | 2001-08-31 | |
US60/316,608 | 2001-08-31 |
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CN1564675A true CN1564675A (zh) | 2005-01-12 |
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EP (1) | EP1414397A4 (zh) |
JP (1) | JP2005511493A (zh) |
CN (1) | CN1564675A (zh) |
AU (1) | AU2002327437A1 (zh) |
WO (1) | WO2003013439A2 (zh) |
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- 2002-08-09 WO PCT/US2002/025448 patent/WO2003013439A2/en not_active Application Discontinuation
- 2002-08-09 EP EP02763428A patent/EP1414397A4/en not_active Withdrawn
- 2002-08-09 JP JP2003518453A patent/JP2005511493A/ja active Pending
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US20030114520A1 (en) | 2003-06-19 |
WO2003013439A3 (en) | 2003-07-10 |
US7091243B2 (en) | 2006-08-15 |
JP2005511493A (ja) | 2005-04-28 |
WO2003013439A2 (en) | 2003-02-20 |
EP1414397A2 (en) | 2004-05-06 |
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