CN109475120A - 抗微生物组合物 - Google Patents
抗微生物组合物 Download PDFInfo
- Publication number
- CN109475120A CN109475120A CN201680086406.3A CN201680086406A CN109475120A CN 109475120 A CN109475120 A CN 109475120A CN 201680086406 A CN201680086406 A CN 201680086406A CN 109475120 A CN109475120 A CN 109475120A
- Authority
- CN
- China
- Prior art keywords
- acid
- salt
- ester
- group
- hydroxypropyl acrylate
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 200
- 230000000845 anti-microbial effect Effects 0.000 title claims description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 106
- 238000002360 preparation method Methods 0.000 claims abstract description 62
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims abstract description 34
- 239000004599 antimicrobial Substances 0.000 claims abstract description 29
- -1 hydroxyl ethyl Chemical group 0.000 claims description 275
- 150000003839 salts Chemical class 0.000 claims description 102
- 150000002148 esters Chemical class 0.000 claims description 89
- 239000002253 acid Substances 0.000 claims description 79
- 239000003795 chemical substances by application Substances 0.000 claims description 63
- 239000003921 oil Substances 0.000 claims description 57
- 235000019441 ethanol Nutrition 0.000 claims description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- 239000000126 substance Substances 0.000 claims description 47
- 210000003491 skin Anatomy 0.000 claims description 37
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 31
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 29
- 239000004094 surface-active agent Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 25
- 235000013305 food Nutrition 0.000 claims description 22
- 210000004209 hair Anatomy 0.000 claims description 22
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 22
- 150000001408 amides Chemical class 0.000 claims description 20
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 19
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 14
- 239000006071 cream Substances 0.000 claims description 14
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 14
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 14
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 14
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 13
- 241000228212 Aspergillus Species 0.000 claims description 12
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 229960005082 etohexadiol Drugs 0.000 claims description 11
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 claims description 10
- 239000005711 Benzoic acid Substances 0.000 claims description 10
- MXOAEAUPQDYUQM-UHFFFAOYSA-N chlorphenesin Chemical compound OCC(O)COC1=CC=C(Cl)C=C1 MXOAEAUPQDYUQM-UHFFFAOYSA-N 0.000 claims description 10
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims description 10
- 239000006210 lotion Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 9
- 150000001299 aldehydes Chemical class 0.000 claims description 9
- 235000010233 benzoic acid Nutrition 0.000 claims description 9
- GHBFNMLVSPCDGN-UHFFFAOYSA-N caprylic acid monoglyceride Natural products CCCCCCCC(=O)OCC(O)CO GHBFNMLVSPCDGN-UHFFFAOYSA-N 0.000 claims description 9
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical class CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 9
- WSDISUOETYTPRL-UHFFFAOYSA-N dmdm hydantoin Chemical compound CC1(C)N(CO)C(=O)N(CO)C1=O WSDISUOETYTPRL-UHFFFAOYSA-N 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 9
- 239000002562 thickening agent Substances 0.000 claims description 9
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- ZCTXEAQXZGPWFG-UHFFFAOYSA-N imidurea Chemical compound O=C1NC(=O)N(CO)C1NC(=O)NCNC(=O)NC1C(=O)NC(=O)N1CO ZCTXEAQXZGPWFG-UHFFFAOYSA-N 0.000 claims description 8
- 150000002576 ketones Chemical class 0.000 claims description 8
- 235000014655 lactic acid Nutrition 0.000 claims description 7
- 239000004310 lactic acid Substances 0.000 claims description 7
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims description 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 7
- 239000002453 shampoo Substances 0.000 claims description 7
- 159000000000 sodium salts Chemical class 0.000 claims description 7
- MXOAEAUPQDYUQM-QMMMGPOBSA-N (S)-chlorphenesin Chemical compound OC[C@H](O)COC1=CC=C(Cl)C=C1 MXOAEAUPQDYUQM-QMMMGPOBSA-N 0.000 claims description 6
- ZXPLGLMEXWSLCX-UHFFFAOYSA-N 2-chloro-3,5-dimethylphenol Chemical compound CC1=CC(C)=C(Cl)C(O)=C1 ZXPLGLMEXWSLCX-UHFFFAOYSA-N 0.000 claims description 6
- 241000228197 Aspergillus flavus Species 0.000 claims description 6
- 241001225321 Aspergillus fumigatus Species 0.000 claims description 6
- 241000228245 Aspergillus niger Species 0.000 claims description 6
- 229920001661 Chitosan Polymers 0.000 claims description 6
- 241001480035 Epidermophyton Species 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 241000555676 Malassezia Species 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- 241000223238 Trichophyton Species 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229940091771 aspergillus fumigatus Drugs 0.000 claims description 6
- 229960003993 chlorphenesin Drugs 0.000 claims description 6
- 150000002440 hydroxy compounds Chemical class 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 229960004889 salicylic acid Drugs 0.000 claims description 6
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 5
- IJALWSVNUBBQRA-UHFFFAOYSA-N 4-Isopropyl-3-methylphenol Chemical compound CC(C)C1=CC=C(O)C=C1C IJALWSVNUBBQRA-UHFFFAOYSA-N 0.000 claims description 5
- 229940073735 4-hydroxy acetophenone Drugs 0.000 claims description 5
- 241000186162 Brevibacterium epidermidis Species 0.000 claims description 5
- LKUNXBRZDFMZOK-GFCCVEGCSA-N Capric acid monoglyceride Natural products CCCCCCCCCC(=O)OC[C@H](O)CO LKUNXBRZDFMZOK-GFCCVEGCSA-N 0.000 claims description 5
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 5
- 239000005770 Eugenol Substances 0.000 claims description 5
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 235000013985 cinnamic acid Nutrition 0.000 claims description 5
- 229930016911 cinnamic acid Natural products 0.000 claims description 5
- 210000002615 epidermis Anatomy 0.000 claims description 5
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- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 5
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- LKUNXBRZDFMZOK-UHFFFAOYSA-N rac-1-monodecanoylglycerol Chemical compound CCCCCCCCCC(=O)OCC(O)CO LKUNXBRZDFMZOK-UHFFFAOYSA-N 0.000 claims description 5
- 210000004761 scalp Anatomy 0.000 claims description 5
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 claims description 4
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 claims description 4
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 4
- CFKMVGJGLGKFKI-UHFFFAOYSA-N 4-chloro-m-cresol Chemical compound CC1=CC(O)=CC=C1Cl CFKMVGJGLGKFKI-UHFFFAOYSA-N 0.000 claims description 4
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 4
- 241001331781 Aspergillus brasiliensis Species 0.000 claims description 4
- 241000193755 Bacillus cereus Species 0.000 claims description 4
- 241000589513 Burkholderia cepacia Species 0.000 claims description 4
- 241000222122 Candida albicans Species 0.000 claims description 4
- 241000186245 Corynebacterium xerosis Species 0.000 claims description 4
- 241000186427 Cutibacterium acnes Species 0.000 claims description 4
- 241000588724 Escherichia coli Species 0.000 claims description 4
- 241000186429 Propionibacterium Species 0.000 claims description 4
- 241000191967 Staphylococcus aureus Species 0.000 claims description 4
- 241000191963 Staphylococcus epidermidis Species 0.000 claims description 4
- 230000000844 anti-bacterial effect Effects 0.000 claims description 4
- 229940095731 candida albicans Drugs 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 claims description 4
- YSRSBDQINUMTIF-UHFFFAOYSA-N decane-1,2-diol Chemical compound CCCCCCCCC(O)CO YSRSBDQINUMTIF-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 4
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- CDSMSBUVCWHORP-UHFFFAOYSA-N perillic acid Chemical compound CC(=C)C1CCC(C(O)=O)=CC1 CDSMSBUVCWHORP-UHFFFAOYSA-N 0.000 claims description 4
- PETXWIMJICIQTQ-UHFFFAOYSA-N phenylmethoxymethanol Chemical compound OCOCC1=CC=CC=C1 PETXWIMJICIQTQ-UHFFFAOYSA-N 0.000 claims description 4
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- 229940055019 propionibacterium acne Drugs 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- ARIWANIATODDMH-UHFFFAOYSA-N rac-1-monolauroylglycerol Chemical compound CCCCCCCCCCCC(=O)OCC(O)CO ARIWANIATODDMH-UHFFFAOYSA-N 0.000 claims description 4
- ICUTUKXCWQYESQ-UHFFFAOYSA-N triclocarban Chemical compound C1=CC(Cl)=CC=C1NC(=O)NC1=CC=C(Cl)C(Cl)=C1 ICUTUKXCWQYESQ-UHFFFAOYSA-N 0.000 claims description 4
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- WYVVKGNFXHOCQV-UHFFFAOYSA-N 3-iodoprop-2-yn-1-yl butylcarbamate Chemical compound CCCCNC(=O)OCC#CI WYVVKGNFXHOCQV-UHFFFAOYSA-N 0.000 claims description 3
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- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims description 3
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- 241000191940 Staphylococcus Species 0.000 claims description 3
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- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 claims description 3
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- UHNYQOSYULALJU-UHFFFAOYSA-N benzoic acid 3-hydroxypropyl prop-2-enoate Chemical compound C(C1=CC=CC=C1)(=O)O.C(C=C)(=O)OCCCO UHNYQOSYULALJU-UHFFFAOYSA-N 0.000 claims description 3
- SOROIESOUPGGFO-UHFFFAOYSA-N diazolidinylurea Chemical compound OCNC(=O)N(CO)C1N(CO)C(=O)N(CO)C1=O SOROIESOUPGGFO-UHFFFAOYSA-N 0.000 claims description 3
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- YQUVCSBJEUQKSH-UHFFFAOYSA-N protochatechuic acid Natural products OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 claims description 3
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- NCKMMSIFQUPKCK-UHFFFAOYSA-N 2-benzyl-4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1CC1=CC=CC=C1 NCKMMSIFQUPKCK-UHFFFAOYSA-N 0.000 claims description 2
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- KCLRQIRQHGDVMV-UHFFFAOYSA-N 2-bromo-5-nitro-1,3-dioxane Chemical class [O-][N+](=O)C1COC(Br)OC1 KCLRQIRQHGDVMV-UHFFFAOYSA-N 0.000 claims description 2
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- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
本发明涉及式(I)的化合物或其(药用)盐其中(a)X代表CH=CH或CZ1=CZ2,其中如果Z1是H则Z2代表选自组包括OH、NH2、NHMe、NMe2、OMe和OEt的基团,和如果Z2是H则Z1代表选自组包括OH、NH2、NHMe、NMe2、OMe和OEt的基团,Y代表选自组包括NH2、NHMe、NMe2、NHEt,O‑(CH2)n‑OH的基团,其中n是2至5并且R代表选自组包括H、OH、Me、Et、OMe、OEt、NH2、NHMe、NMe2、NHEt和NEt2的基团,或(b)X代表O,Y代表选自组包括NH2、NHMe、NMe2、NHEt、O‑(CH2)n‑OH和OMe的基团,其中n是2至5并且R代表H、OH、Me、Et、OMe、OEt、NH2、NHMe、NMe2、NHEt、NEt2。作为抗微生物制剂的用涂以及含有该制剂的组合物。
Description
发明领域
本发明属于用于个人护理、家居和营养产品的抗微生物制剂领域并且涉及新的抗微生物制剂及其在不同领域消费产品中的用途。
现有技术
在化妆和药物以及食品工业持续需要具备抗微生物性能的制剂,特别是用于易腐物质的防腐(例如化妆、家居、药物产品或食品),以及用于直接化妆或治疗处理对人体或动物体有不良影响的微生物。可以例如参考可以导致体味、粉刺、真菌病等的微生物。
在所述的技术领域已经使用了大量抗微生物活性化合物,但是为了能够进行有目的的治疗和/或减小副作用,仍然在寻找替代品。
然而在寻找具备抗微生物活性的替代制剂中,并且特别是防腐作用产品时,应当注意化妆品、家居用品、药品和/或食品领域中使用的物质必须
·毒理学上可接受的
·容易被皮肤耐受的
·稳定的(特别是在常规化妆、家居和/或药物制剂中)
·基本并且优选完全无味
·制备廉价(即采用标准工艺和/或由标准前体开始)
·易于制备(即优选液态)并且对最终产品无害。
此外,它们应当具备满足各种标准的抗微生物活性。应当
·提供抗革兰氏阳性和革兰氏阴性菌、酵母和霉菌的广谱抗微生物性能
·对霉菌如巴西曲霉(Aspergillus brasiliensis)的孢子表现出特别强的活性
·在不同pH值下不同化妆和家居制剂中有活性。
本发明涉及式(I)的化合物或其(药用)可接受的盐
其中
(a)X代表CH=CH或CZ1=CZ2,其中
如果Z1是H则Z2代表选自组包括OH、NH2、NHMe、NMe2、OMe和OEt的基团,和
如果Z2是H则Z1代表选自组包括OH、NH2、NHMe、NMe2、OMe和OEt的基团,Y代表选自组包括NH2、NHMe、NMe2、NHEt,O-(CH2)n-OH的基团,其中
n是2至5
并且
R代表选自组包括H、OH、Me、Et、OMe、OEt、NH2、NHMe、NMe2、NHEt和NEt2的基团,
或
(b)X代表O,
Y代表选自组包括NH2、NHMe、NMe2、NHEt、O-(CH2)n-OH和OMe的基团,其中
n是2至
并且
R代表H、OH、Me、Et、OMe、OEt、NH2、NHMe、NMe2、NHEt、NEt2。
特别地,本发明涉及所述式(I)化合物的某些用途。如下文更详细地说明,本发明的第一个方面是所述化合物或混合物作为抗微生物制剂用于使微生物失活的用途,即一种具备抗微生物活性的制剂以及含有所述制剂的组合物。
事实上,式(I)的一些化合物已知。然而据我们所知没有记载其抗微生物活性。
WO 90/00859 A1(Nelson and Robertson Pty.Ltd)公开了含有特定驱虫剂的驱虫条皂组合物。根据该发明,这些制剂的用量基于组合物总量计为18至20重量%。提出1,3-丙二醇单苯甲酸酯是一个可以使用的驱虫剂实例。但是在整篇专利中没有提及1,3-丙二醇单苯甲酸酯的抗微生物活性以及乳液型制剂。
WO 2007/137128 A1(Mary Kay Inc.)公开了皮肤护理局部制剂,含有水杨酸甘油酯以降低皮肤的水分蒸发,保护皮肤抵抗UV射线,处理年老或受损皮肤。丙二醇单苯甲酸酯是成分之一。没有记载不同成分的抗微生物活性。此外,没有提及与甘油酯(例如辛酸甘油酯、癸酸甘油酯)或中链二醇(例如1,2-戊二醇、1,2-己二醇、1,2-辛二醇、1,2-癸二醇)的结合使用。
US 2016/0000066 A1(Rhodia Operations)公开了糠醛衍生物作为溶剂用于植物保护产品和/或树脂。一种要求的糠醛衍生物是糠酸羟丙酯。没有提到化妆产品或局部或全身施用于人类或动物的产品,并且没有提供任何方面类似化妆产品的组合物。此外,该文件没有提及糠醛衍生物并且特别是糠酸羟丙酯的抗微生物活性。
不同文件涉及了茴香酸羟丙基酯的化学合成(Journal of the Korean ChemicalSociety,2002,46(5),479-485;Synthesis,2003,(15),2373-2377)。然而,没有提及合成产品的特定用途或优势。特别地,没有提及化妆用途和作为具备抗微生物性质的制剂的用途。
寻找适当的(活性)物质,其具备足够程度的一种或多种所述性质,对于本领域技术人员有难度,因为物质的化学结构与其对某些微生物(细菌、酵母、真菌、小型真核生物)的生物活性之间没有清楚的依赖性。这使得在实验室实验中测试物质是不可避免的。
此外,在化装制剂中的抗微生物性能无法由标准抗菌筛选试验,如记载于DIN58940或ISO 20776的生长抑制试验,得出。许多特征在于低最低抑菌浓度(MICs)的抗微生物物质无法在更先进和应用分析中进行。对于产品防腐,必须使用根据ISO 11930,European Pharmacopoeia 7-5.1.3,或United States Pharmacopoeia 35的费力费时的“防腐抗菌测试报告”(“preservative challenge test”)。进一步地,化学结构和其他化妆品领域的物理化学参数之间没有可以预见的关联,即毒理学可接受性、皮肤耐受性、稳定性、溶解性和制剂性质以及物质味道。
因此,本发明的第一个主题是提供满足上述复杂性质并且特别是在低浓度下对各种不同微生物有活性的新的抗微生物制剂。
另一方面,以前,包括杀菌和杀真菌活性在内的广谱防腐效果只在个人护理产品中部分实现,或仅通过加入某些杀真菌剂,特别是甲醛,甲醛供体,卤代化合物,异噻唑啉酮类,属于对羟基苯甲酸酯类的化合物和各种特定的杀菌剂实现。
因此,以下经典杀菌剂,特别是杀真菌剂化合物通常用于个人护理产品:
-甲醛供体特别包括双咪唑烷基脲(CAS 78491-02-8)、咪唑烷基脲(CAS 39236-46-9)、和DMDM乙内酰脲(CAS 6440-58-0)。
-卤代化合物特别包括2,4-二氯苄醇(CAS 1777-82-8)、对氯间二甲苯酚(也称作4-氯-3,5-二甲基苯酚,CAS 88-04-0)、溴硝醇(也称作2-溴-2-硝基丙-1,3-二醇,CAS 52-51-7)、碘丙炔基丁基氨基甲酸酯(CAS 55406-53-6)、氯苯甘醚(也称作3-(4-氯苯氧基)-1,2-丙二醇,CAS 104-29-0)。
-对羟基苯甲酸酯类化合物特别包括对羟基苯甲酸甲酯(CAS 99-76-3)、对羟基苯甲酸乙酯(CAS 120-47-8)、对羟基苯甲酸丙酯(CAS 94-13-3)、对羟基苯甲酸丁酯(CAS 94-26-8)、对羟基苯甲酸异丙酯(CAS 4191-73-5),和对羟基苯甲酸苄酯(CAS 94-18-8)。
-其它杀真菌剂包括季铵盐-15(Quaternium-15)(CAS 51229-78-8)、甲基-氯异噻唑啉酮(CAS 26172-55-4),和甲基异噻唑啉酮(CAS 2682-20-4)。
人们担心这些杀真菌剂中的一些可能对健康构成危害,例如碘丙炔基丁基氨基甲酸酯、甲醛和甲醛供体、甲基-氯异噻唑啉酮(CAS 26172-55-4),和甲基异噻唑啉酮被认为是高度致敏/光敏的。
因此,重要的是替换施用于人类皮肤或头皮的个人护理产品中的上述化合物,但同时保持良好的广谱防腐活性,包括杀孢子作用。
因此,本发明的另一个主题是提供含有新的抗微生物制剂的抗微生物混合物,其中所述抗微生物混合物能够在不存在上述化合物的情况下抑制微生物的生长或将其杀灭或同时抑制和杀灭。
发明内容
如上所述,本发明的一个方面是式(I)化合物或其(药用)可接受的盐
其中
(a)X代表CH=CH或CZ1=CZ2,其中
如果Z1是H则Z2代表选自组包括OH、NH2、NHMe、NMe2、OMe和OEt的基团,和
如果Z2是H则Z1代表选自组包括OH、NH2、NHMe、NMe2、OMe和OEt的基团,Y代表选自组包括NH2、NHMe、NMe2、NHEt,O-(CH2)n-OH的基团,其中
n是2至5
并且
R代表选自组包括H、OH、Me、Et、OMe、OEt、NH2、NHMe、NMe2、NHEt和NEt2的基团,
或
(b)X代表O,
Y代表选自组包括NH2、NHMe、NMe2、NHEt、O-(CH2)n-OH和OMe的基团,其中
n是2至5
并且
R代表H、OH、Me、Et、OMe、OEt、NH2、NHMe、NMe2、NHEt、NEt2。
作为抗微生物制剂的用途。
优选地上述式(I)化合物或其(药用)可接受的盐的用途并不是通过手术或治疗方法治疗人类或动物体的方法或在人类或动物体上进行的诊断方法。
术语“其相应的(药用)可接受的盐”是指可安全用于药用目的的式(I)化合物的盐。这并不意味着本发明或其任何方面被限于式(I)化合物或相应混合物用于药用目的的用途。通常,如果一种盐可用于药用目的,其同样可用于化妆目的,或在食品或饮料制剂中。式(I)化合物的(药用)可接受的盐(或相应的溶剂化物)可以通过标准方法制备。因此,涉及如上定义的式(I)化合物应理解为包括涉及其相应的(药用)可接受的盐。
本发明基于令人惊异的发现,根据本发明的式(I)化合物作为保存各种易腐制剂以抵抗微生物腐败的制剂表现出非常好的广谱活性。
根据本发明的式(I)化合物表现出针对大量革兰氏阳性菌、革兰氏阴性菌、霉菌和酵母的抗微生物活性,其特别为各种化妆品制剂提供了可能的保护和抗微生物处理。特别好的活性在于抵抗革兰氏阳性菌,如金黄色葡萄球菌(Staphylococcus aureus)、表皮葡萄球菌(Staphylococcus epidermidis)、蜡样芽孢杆菌(Bacillus cereus)、结膜干燥棒状杆菌(Corynebacterium xerosis)和疮疱丙酸杆菌(Propionibacterium acnes),抵抗革兰氏阴性菌,如大肠杆菌(Escherichia coli)、洋葱伯克霍尔德菌(Burkholderia cepacia)、和荧光假单胞菌(Pseudomonas aeruginosa)、抵抗酵母,如白色念珠菌(Candida albicans)、糠批马拉色菌(Malassezia furfur)和球形马拉色菌(Malassezia globosa),以及确切地—如上所述—抵抗真菌及其孢子,如曲霉(Aspergillus)属的霉菌种类。特别有利的是,根据本发明的混合物抵抗曲霉(Aspergillus)属的霉菌—一种非常难以抵抗的真菌—的非常好的活性。
式(I)化合物特别有利的抵抗曲霉(Aspergillus)属的霉菌种类,如巴西曲霉(Aspergillus brasiliensis)、黑曲霉(Aspergillus niger)、黄曲霉(Aspergillusflavus)、烟曲霉(Aspergillus fumigatus)及其他微生物。已知霉菌,由于其形成孢子的能力并因此对不同pH、温度、渗透压和营养条件的高耐受性以及其抵抗并降解不同化合物的能力,非常难以抵抗。
更特别的是,发现根据本发明的式(I)化合物具备抵抗表皮葡萄球菌(Staphylococcus epidermidis)、结膜干燥棒状杆菌(Corynebacterium xerosis)、表皮短杆菌(Brevibacterium epidermidis)、疮疱丙酸杆菌(Propionibacterium acnes)、马拉色菌属(Malassezia)以及抵抗毛癣菌属(Trichophyton)和表皮癣菌属(Epidermophyton)的良好活性,因此它们一般可被用作处理或抵抗腋下和足部气味或体味的制剂,作为抗痤疮剂、去屑剂以及用于治疗真菌病特别是皮肤真菌病。
值得一提的是尽管本领域技术人员已经已知有机酸的抗微生物性能,这些化合物广泛地基于例如苯甲酸、糠酸或茴香酸。然而,这些酸仅在最大至5.5的较低pH值下有效。许多化妆和家居制剂具备大于5.5的pH值并因此无法通过这些酸有效防腐。迄今为止没有迹象表明式(I)的酯化合物具备显著改善的抗微生物活性,特别是在5.5或更高的相对pH值下。因此特别令人惊讶地是根据本发明的式(I)化合物在大部分化妆和家居制品的相对pH范围内表现出处理曲霉(Aspergillus)属霉菌的高活性。
根据本发明的一个优选用途是式(I)化合物或其(药用)可接受的盐作为抗真菌剂和/或抗细菌剂,更特别是作为抑制生长或杀灭或抑制生长并杀灭选自组包括巴西曲霉(Aspergillus brasiliensis)、黑曲霉(Aspergillus niger)、黄曲霉(Aspergillusflavus)、烟曲霉(Aspergillus fumigatus)、表皮葡萄球菌(Staphylococcusepidermidis)、结膜干燥棒状杆菌(Corynebacterium xerosis)、表皮短杆菌(Brevibacterium epidermidis)、疮疱丙酸杆菌(Propionibacterium acnes)、马拉色菌属(Malassezia)、毛癣菌属(Trichophyton)和表皮癣菌属(Epidermophyton)的微生物制剂的用途。
优选某些特定的式(I)化合物。特别地,根据本发明的用途,其中式(I)化合物选自组包括式(Ia)-(Im)
·苯甲酸-3-羟丙酯
·苯甲酸-3羟乙酯
·糠酸-3-羟丙酯
·糠酸-3-羟乙酯
·糠酸甲酯
·茴香酸-3-羟丙酯
·茴香酸-3-羟乙酯
·N-甲基水杨酰胺
·水杨酰胺
·水杨酸羟乙酯
·水杨酸羟丙酯
·香草酸羟丙酯
·氨基苯甲酸羟丙酯
根据本发明的另一个优选用途是式(I)化合物或其(药用)可接受的盐
其中
X代表O、CH=CH或CZ1=CZ2,其中
如果Z1是H则Z2代表选自组包括OH、NH2、NHMe、NMe2、OMe和OEt的基团,和
如果Z2是H则Z1代表选自组包括OH、NH2、NHMe、NMe2、OMe和OEt的基团,Y代表选自组包括NH2、NHMe、NMe2、NHEt,O-(CH2)n-OH的基团,其中
n是2至3
并且
R代表选自组包括H、OH、Me、Et、OMe、OEt、NH2、NHMe、NMe2、NHEt和NEt2的基团,
作为抗微生物制剂的用途。
根据本发明的另一个优选用途是式(I)化合物或其(药用)可接受的盐
其中
X代表O、CH=CH或CZ1=CZ2,其中
如果Z1是H则Z2代表选自组包括OH、NH2、NHMe、NMe2、OMe和OEt的基团,和
如果Z2是H则Z1代表选自组包括OH、NH2、NHMe、NMe2、OMe和OEt的基团,Y代表O-(CH2)n-OH,其中
n是2至3
并且
R代表选自组包括H、OH、Me、Et、OMe、OEt、NH2、NHMe、NMe2、NHEt和NEt2的基团,
作为抗微生物制剂的用途。
根据本发明的另一个优选用途是式(I)化合物或其(药用)可接受的盐
其中
X代表CH=CH或CZ1=CZ2,其中
如果Z1是H则Z2代表选自组包括OH、NH2、NHMe、NMe2、OMe和OEt的基团,和
如果Z2是H则Z1代表选自组包括OH、NH2、NHMe、NMe2、OMe和OEt的基团,
Y代表O-(CH2)n-OH,其中
n是2至3
并且
R代表选自组包括H、OH、Me、Et、OMe、OEt、NH2、NHMe、NMe2、NHEt和NEt2的基团,
作为抗微生物制剂的用途。
特别优选的式(I)化合物是
·苯甲酸-3-羟丙酯
·苯甲酸-3羟乙酯
·茴香酸-3-羟丙酯
·茴香酸-3-羟乙酯
·N-甲基水杨酰胺
·水杨酰胺
·水杨酸羟乙酯
·水杨酸羟丙酯
·香草酸羟丙酯
·氨基苯甲酸羟丙酯
本发明的主题是一种抗微生物制剂或抗微生物组合物,含有至少一种如上定义的通式(I)的芳香酯或酰胺衍生物或其(药用)盐。优选地抗微生物组合物含有如上定义优选的通式(I)的组合物,段落[0033]-[0037]。
在一个优选实施方案中,上述抗微生物组合物含有浓度为约0.01至约10重量%,更优选约0.02至约5重量%,并且特别优选浓度位于0.05至约2重量%的式(I)化合物或其(药用)可接受的盐,基于总组合物计。
特别优选一种抗微生物制剂或抗微生物组合物,含有至少一种如上定义的通式(I)的芳香酯或酰胺衍生物或其(药用)盐,前提是该组合物不含有杀菌、杀真菌、杀孢子有效或防腐浓度的选自下组的化合物:
-甲醛,甲醛供体化合物包括双咪唑烷基脲、咪唑烷基脲、和DMDM乙内酰脲;-选自组包括对羟基苯甲酸甲酯、对羟基苯甲酸乙酯、对羟基苯甲酸丙酯、对羟基苯甲酸异丙酯、对羟基苯甲酸丁酯、对羟基苯甲酸异丁酯、和对羟基苯甲酸苄酯(CAS 94-18-8)的对羟基苯甲酸酯类化合物;
-卤代化合物包括2,4-二氯苄醇、4-氯-3,5-二甲基苯酚、2-溴-2-硝基丙-1,3-二醇和碘丙炔基丁基氨基甲酸酯、氯苯甘醚(也称作3-(4-氯苯氧基)-1,2-丙二醇,CAS 104-29-0);
-选自季铵盐-15(CAS 51229-78-8)、甲基-氯异噻唑啉酮,甲基异噻唑啉酮和苯并异噻唑啉酮(CAS 2634-33-5)的杀真菌剂。
本发明也包括抗微生物制剂的混合物。本发明主题的第一混合物含有(a)至少一种选自式(I)的芳香酯或酰胺衍生物的第一抗微生物制剂,和
(b)至少一种第二抗微生物制剂,选自组包括苯甲酸和对羟基苯甲酸、其酯和盐、苯甲酸苄酯、丙酸及其盐、水杨酸及其盐、2,4-己二烯酸(山梨酸)及其盐、乙酰丙酸及其盐、茴香酸及其盐、紫苏酸及其盐、肉桂酸及其盐、甲醛和多聚甲醛、4-羟基苯甲醛、邻-、间-和对-茴香醛、胡椒醛、肉桂醛、肉桂醇、2-羟基二苯醚及其盐、2-锌-磺酰亚胺基吡啶N-氧化物、无机亚硫酸盐和亚硫酸氢盐、碘酸钠、三氯叔丁醇、4-乙基汞(II)-5-氨基-1,3-二(2-羟基苯甲酸)及其盐和酯、脱氢乙酸、甲酸、1,6-二(4-脒基-2-溴苯氧基)-正己烷及其盐、乙基汞(II)-硫代水杨酸的钠盐、苯基汞及其盐、10-十一碳烯酸及其盐、5-氨基-1,3-二(2-乙基己基)-5-甲基-六氢嘧啶、5-溴-5-硝基-1,3-二噁烷、2-溴-2-硝基-1,3-丙二醇、2,4-二氯苄醇、N-(4-氯苯基)-N’-(3,4-二氯苯基)-脲、4-氯-间甲酚、2,4,4’-三氯-2’-羟基-二苯醚、4-氯-3,5-二甲基苯酚、1,1’-亚甲基-二(3-(1-羟甲基-2,4-二氧代咪唑烷-5-基)脲)、聚-(六亚甲基双胍)盐酸盐、(苄氧基甲氧基)-甲醇六亚甲基四胺、1-(3-氯代烯丙基)-3,5,7-三氮杂-1-氮鎓杂金刚烷氯化物、1-(4-氯苯氧基)-1-(1H-咪唑-1-基)-3,3-二甲基-2-丁酮、1,3-二-(羟甲基)-5,5-二甲基-2,4-咪唑烷二酮、1,2-二溴-2,4-二氰基丁烷、2,2’-亚甲基-二(6-溴-4-氯-苯酚)、溴氯苯、5-氯-2-甲基-3(2H)-异噻唑啉酮、2-甲基-3(2H)-异噻唑啉酮与氯化镁和硝酸镁的混合物、2-辛基-2H-异噻唑-3-酮、1,2-苯并异噻唑啉-3(2H)-酮、2-苄基-4-氯苯酚、3-(4-氯苯氧基)-1,2-丙二醇(Chlorphenesin)、2-氯乙酰胺、氯己定、醋酸氯己定、葡糖酸氯己定、盐酸氯己定、N-烷基(C12-C22)三甲基溴化铵和N-烷基(C12-C22)三甲基氯化铵、4,4-二甲基-1,3-噁唑烷、N-羟甲基-N-(1,3-二(羟甲基)-2,5-二氧代咪唑烷-4-基)-N’-羟基-甲基脲、1,6-二(4-脒基-苯氧基)-正己烷及其盐、戊二醛、5-乙基-1-氮杂-3,7-二氧杂二环(3.3.0)辛烷、3-(4-氯苯氧基)-1,2-丙二醇、季铵盐、烷基-(C8-C18)-二甲基-苄基氯化铵、烷基-(C8-C18)-二甲基-苄基溴化铵、烷基-(C8-C18)-二甲基-苄基-糖精铵、苄基半缩甲醛、3-碘-2-丙炔基丁基氨基甲酸酯、羟甲基-氨基醋酸钠、咪唑烷基脲、双咪唑烷基脲、羟甲基甘氨酸钠、DMDM己内酰脲、环庚三烯酚酮、亚乙基二氧基二甲醇、2-溴-2-(溴乙基)戊二腈、N-(3-氨丙基)-N-十二烷基丙烷-1,3-二胺、α,α‘,α“-三甲基-1,3,5-三嗪-1,3,5(2H,4H,6H)-三乙醇、吡啶-2-硫醇-1-氧化物、钠盐、四氢-1,3,4,6-四(羟甲基)咪唑并[4,5-d]咪唑-2,5(1H,3H)-二酮,1,3-双(羟甲基)-1-(1,3,4-三(羟甲基)-2,5-二氧代咪唑烷-4-基)脲(Diazolidinyl Urea)、1,3-双(羟甲基)-5,5-二甲基咪唑烷-2,4-二酮、3-乙酰基-2-羟基-6-甲基-4H-吡喃-4-酮、氯化十六烷基铵基吡啶、N-α-月桂酰-L-精氨酸乙酯盐酸盐、辛酰氧肟酸、山梨醇异羟肟酸及其混合物,和/或
(c)至少一种羟基化合物选自组包括1,3-丙二醇、甲基丙二醇、1,2-戊二醇、1,2-己二醇、1,2-辛二醇、乙基己基甘油、辛酸甘油酯、癸酸甘油酯、3-苯基丙醇、2-苯基乙醇、2-苯氧基乙醇、苄醇、4-异丙基-3-甲基苯酚和4-羟基苯乙酮。
本发明的更优选混合物含有
(a)至少一种选自式(I)的芳香酯或酰胺衍生物的第一抗微生物制剂和
(b)1,3-丙二醇、1,2-戊二醇、1,2-己二醇、1,2-辛二醇、辛酸甘油酯、乙基己基甘油、4-羟基苯乙酮、4-异丙基-3-甲基苯酚、苄醇、2-苯氧基乙醇。
令人惊异地发现式(I)的化合物协同增效地改善了抗微生物制剂(b)的抗微生物活性和/或羟基化合物(c)的抗微生物活性。
特别优选上文定义的抗微生物混合物,前提是该组合物不含有杀菌、杀真菌、杀孢子有效或防腐浓度的选自下组的化合物:
-甲醛,甲醛供体化合物包括双咪唑烷基脲、咪唑烷基脲、和DMDM乙内酰脲;
-选自组包括对羟基苯甲酸甲酯、对羟基苯甲酸乙酯、对羟基苯甲酸丙酯、对羟基苯甲酸异丙酯、对羟基苯甲酸丁酯、对羟基苯甲酸异丁酯、和对羟基苯甲酸苄酯的对羟基苯甲酸酯类化合物;
-卤代化合物包括2,4-二氯苄醇、4-氯-3,5-二甲基苯酚、2-溴-2-硝基丙-1,3-二醇和碘丙炔基丁基氨基甲酸酯、氯苯甘醚(也称作3-(4-氯苯氧基)-1,2-丙二醇,CAS 104-29-0);
-选自季铵盐-15(CAS 51229-78-8)、甲基-氯异噻唑啉酮,甲基异噻唑啉酮和苯并异噻唑啉酮(CAS 2634-33-5)的杀真菌剂。
因此,特别令人惊异地是在施用于人类皮肤或头皮的个人护理产品中上述化合物可以被式(I)化合物替代,而保持良好的广谱防腐活性,包括杀孢子效果。
替代地,防腐混合物可以含有
(a)至少一种选自式(I)的芳香酯或酰胺衍生物的第一抗微生物制剂和
(b)至少一种第二抗微生物制剂,选自组包括4-羟基苯乙酮、1,2-辛二醇、1,2-癸二醇、1,5-戊二醇、1,6-己二醇、1,8-辛二醇、1,2-癸二醇、己氧基-丙-1,2-二醇、庚氧基-丙-1,2-二醇、辛氧基-丙-1,2-二醇、3-苯氧基-丙-1,2-二醇、3-苄氧基-丙-1,2-二醇、3-苯基乙氧基-丙-1,2-二醇、3-苯基丙氧基-丙-1,2-二醇、3-甲基苄氧基-丙-1,2-二醇、辛酸甘油酯、癸酸甘油酯、月桂酸甘油酯、脫水山梨糖醇辛酸酯、乳酸丙酯、乳酸丁酯、乳酸戊酯、乳酸异戊酯、乳酸顺己-3-烯基酯、乳酸苄酯、三氯生、二唑丁酮、Octopirox(1-羟基-4-甲基-6-(2,4,4-三甲基戊基)-2(1H)-吡啶酮,2-氨基乙醇)、壳聚糖、金合欢醇、2-丁基辛酸、2-苄基庚-1-醇、甘油单月桂酸酯、双(2-嘧啶硫代)锌1,1'-二氧化物、N,N'-(癸-1,10-二基二吡啶-1-基-4-基亚基)-双辛胺-1-胺二盐酸化物(盐酸奥替尼啶)、麝香草酚、丁香油酚、4-异丙基-3-甲基苯酚、苄醇、4-甲基苄醇、2-苯乙醇、1-苯氧基-丙-2-醇、3-苯氧基丙醇、苄氧基甲醇,
和/或
(c)至少一种羟基化合物选自组包括1,3-丙二醇、甲基丙二醇、1,2-戊二醇、1,2-己二醇、1,2-辛二醇、乙基己基甘油、3-苯基丙醇、2-苯基乙醇和2-苯氧基乙醇。
令人惊讶地发现式(I)的化合物协同增效地改善了抗微生物制剂(b)的抗微生物活性和/或羟基化合物(c)的抗微生物活性。
特别优选上文定义的抗微生物混合物,前提是该组合物不含有杀菌、杀真菌、杀孢子有效或防腐浓度的选自下组的化合物:
-甲醛,甲醛供体化合物包括双咪唑烷基脲、咪唑烷基脲、和DMDM乙内酰脲;
-选自组包括对羟基苯甲酸甲酯、对羟基苯甲酸乙酯、对羟基苯甲酸丙酯、对羟基苯甲酸异丙酯、对羟基苯甲酸丁酯、对羟基苯甲酸异丁酯、和对羟基苯甲酸苄酯的对羟基苯甲酸酯类化合物;
-卤代化合物包括2,4-二氯苄醇、4-氯-3,5-二甲基苯酚、2-溴-2-硝基丙-1,3-二醇和碘丙炔基丁基氨基甲酸酯、氯苯甘醚(也称作3-(4-氯苯氧基)-1,2-丙二醇,CAS 104-29-0);
-选自季铵盐-15(CAS 51229-78-8)、甲基-氯异噻唑啉酮,甲基异噻唑啉酮和苯并异噻唑啉酮(CAS 2634-33-5)的杀真菌剂。
因此,特别令人惊异地是在施用于人类皮肤或头皮的个人护理产品中上述化合物可以被式(I)化合物替代,而保持良好的广谱防腐活性,包括杀孢子效果。
在优选实施方案中上述抗微生物组合物可以含有浓度为约0.01至约10重量%,更优选约0.02至约5重量%,并且特别优选浓度为约0.05至约2重量%的式(I)化合物或其(药用)可接受的盐,基于总组合物计。
混合物可以含有重量比为约1:99至约99:1,优选约20:80至约80:20并且更优选约40:60至约60:40的成分(a)和(b)。
成分(c)的含量可以为约1至25,优选2至20并且更优选约5至10重量%,基于总混合物计。
工业应用
个人护理组合物
本发明的另一个实施方案涉及个人护理或化妆组合物,含有有效量的至少一种式(I)的化合物或其(药用)盐,其与其他防腐剂和/或抗微生物制剂的混合物,其含量可以为约0.01至约10,优选约0.02至约5,并且更优选约0.05至约2重量%—基于总组合物计。
个人护理或化妆组合物可以含有研磨剂、抗痤疮剂、抗皮肤老化剂、溶脂剂、去头屑剂、抗炎剂、防刺激剂、抑制刺激剂,抗氧化剂、收敛剂、抑汗剂、杀菌剂、抗静电剂、粘合剂、缓冲剂、载体、螯合剂、细胞刺激剂、清洗剂、护理剂、脱毛剂、表面活性物质、除臭剂、止汗剂、柔软剂、乳化剂、酶、精油、纤维、成膜剂、固色剂、泡沫形成剂、泡沫稳定剂、消泡剂、泡沫促进剂、胶凝剂、凝胶形成剂、头发护理剂、毛发定型剂、头发拉直剂、增湿剂、润湿剂、保湿剂、漂白剂、加强剂、去污剂、光学增亮剂、浸溃剂、驱污剂、减摩剂、润滑剂、保湿霜、软膏、遮光剂、增塑剂、覆盖剂、上光剂、光泽剂、聚合物、粉末、蛋白质、加脂剂、磨蚀剂、硅酮、皮肤舒缓剂、皮肤清洁剂、护肤剂、皮肤愈合剂、皮肤光亮剂、皮肤保护剂、皮肤软化剂、冷却剂、皮肤冷却剂、加温剂、皮肤升温剂、稳定剂、UV吸收剂、UV滤光剂、洗涤剂、织物柔顺剂、助悬剂、皮肤美黑剂、增稠剂、维生素、油、蜡、脂肪、磷脂、饱和脂肪酸、单或多不饱和脂肪酸、α-羟基酸、多羟基脂肪酸、液化剂、染料、颜色保护剂、颜料、防蚀剂、芳香物质、调味物质、气味物质、多元醇、表面活性剂、电解质、有机溶剂或硅酮衍生物等额外助剂和添加剂。
A.表面活性剂
其他优选的助剂和添加剂是阴离子和/或两性或两性离子表面活性剂。阴离子表面活性剂的典型实例为肥皂、烷基苯磺酸盐、烷烃磺酸盐、烯烃磺酸盐、烷基醚磺酸盐、甘油醚磺酸盐、甲酯磺酸盐、磺基脂肪酸、烷基硫酸盐、脂肪醇醚硫酸盐、甘油醚硫酸盐、脂肪酸醚硫酸盐、羟基混合醚硫酸盐、单甘油酯(醚)硫酸盐、脂肪酸酰胺(醚)硫酸盐、单-和二烷基磺基丁二酸盐、单-和二烷基磺基琥珀酰胺酸盐、磺基甘油三酯、酰胺皂、醚羧酸及其盐、脂肪酸羟乙磺酸盐、脂肪酸肌氨酸盐、脂肪酸牛磺酸盐、N-酰氨酸如,例如酰基乳酸盐、酰基酒石酸盐、酰基谷氨酸盐和酰基天冬氨酸盐、烷基低聚葡糖苷硫酸盐、蛋白质脂肪酸缩合物(特别是小麦基植物产品)和烷基(醚)磷酸盐。如果阴离子表面活性剂含有聚乙二醇醚链,则它们可具有常规的同族分布,但优选具有窄同族分布。两性或两性离子表面活性剂的典型实例为烷基甜菜碱、烷基酰胺基甜菜碱、氨基丙酸盐、氨基甘氨酸盐、咪唑啉甜菜碱和磺基甜菜碱。所述表面活性剂均为已知化合物。其结构和制备信息可见于相关概述作品,参见,例如J.Falbe(编辑),“Surfactants in Consumer Products”,Springer Verlag,Berlin,1987,页54至124或J.Falbe(编辑),“Katalysatoren,Tenside und(Catalysts,Surfactants and矿物油Additives)”,Thieme Verlag,Stuttgart,1978,页123-217。表面活性剂在制剂中的百分含量可以为0.1至10重量%且优选0.5至5重量%,基于制剂计。
B.油体
适当的构成O/W乳液成分的油体是,例如,基于含有6至18个,优选8至10个碳原子的脂肪醇的Guerbet醇,直链C6-C22-脂肪酸与直链或支链C6-C22-脂肪醇的酯或支链C6-C13-羧酸与直链或支链C6-C22-脂肪醇的酯,如例如肉豆蔻酸十四烷酯、棕榈酸十四烷酯、硬脂酸十四烷酯、异硬脂酸十四烷酯、油酸十四烷酯、山嵛酸十四烷酯、芥酸十四烷酯、肉豆蔻酸十六烷酯、棕榈酸十六烷酯、硬脂酸十六烷酯、异硬脂酸十六烷酯、油酸十六烷酯、山嵛酸十六烷酯、芥酸十六烷酯、肉豆蔻酸十八烷酯、棕榈酸十八烷酯、硬脂酸十八烷酯、异硬脂酸十八烷酯、油酸十八烷酯、山嵛酸十八烷酯、芥酸十八烷酯、肉豆蔻酸异十八烷酯、棕榈酸异十八烷酯、硬脂酸异十八烷酯、异硬脂酸异十八烷酯、油酸异十八烷酯、山嵛酸异十八烷酯、油酸异十八烷酯、油醇肉豆蔻酸酯、棕榈酸油醇酯、油醇硬脂酸酯、油醇异硬脂酸酯、油酸油醇酯、山嵛酸油醇酯、芥酸油醇酯、肉豆蔻酸二十二烷酯、棕榈酸二十二烷酯、硬脂酸二十二烷酯、异硬脂酸二十二烷酯、油酸二十二烷酯、山嵛酸二十二烷酯、芥酸二十二烷酯、肉豆蔻酸芥醇酯、棕榈酸芥醇酯、硬脂酸芥醇酯、异硬脂酸芥醇酯、油酸芥醇酯、山嵛酸芥醇酯和芥酸芥醇酯。同样适当的是直链C6-C22-脂肪酸与支链醇,特别是2-乙基己醇的酯、C18-C38-烷基羟基羧酸与直链或支链C6-C22-脂肪醇的酯,特别是苹果酸二辛酯、直链和/或支链脂肪酸与多元醇(如,例如丙二醇、二聚二元醇(dimerdiol)或三聚三元醇(trimertriol))和/或Guerbet醇的酯、基于C6-C10-脂肪酸的甘油三酯、基于C6-C18-脂肪酸的液态单-/二-/三酸甘油酯混合物、C6-C22-脂肪醇和/或Guerbet醇与芳族羧酸,特别是苯甲酸的酯、C2-C12-二羧酸与具有1至22个碳原子的直链或支链醇或者具有2至10个碳原子和2至6个羟基的多元醇的酯、植物油、支链伯醇、取代环己烷、直链和支链C6-C22-脂肪醇的碳酸酯,如例如碳酸二辛酯(CC)、基于具有6至18个优选8至10个碳原子的脂肪醇的Guerbet碳酸酯、苯甲酸与直链和/或支链C6-C22-醇的酯(例如TN)、每个烷基具有6至22个碳原子的直链或支链、对称或非对称的二烷基醚,如例如二辛酰基醚(OE)、环氧化脂肪酸酯与多元醇的开环产物、硅油(环聚二甲基硅氧烷、硅酮甲基硅油等级,等)、脂肪烃或环烷烃,如例如角鲨烷、角鲨烯或二烷基环己烷。
C.乳化剂
也可以向制剂中加入其他表面活性剂作为乳化剂,包括例如:
·2至30摩尔环氧乙烷和/或0至5摩尔环氧丙烷与直链C8-22脂肪醇、与C12-22脂肪酸、与烷基中具有8-15个碳原子的烷基苯酚的加成产物;
·1至30摩尔环氧乙烷与甘油的加成产物的C12/18脂肪酸单酯和二酯;
·具有6至22个碳原子的饱和和不饱和脂肪酸的甘油单酯和二酯以及脱水山梨醇单酯和二酯,及其环氧乙烷加成产物;
·15至60摩尔环氧乙烷与蓖麻油和/或氢化蓖麻油的加成产物;
·多元醇酯以及,特别是聚甘油酯类如,例如,聚蓖麻酸聚甘油酯、聚-12-羟基硬脂酸聚甘油酯或聚甘油二聚合油异硬脂酸酯(polyglycerol dimerate isostearate)。本组中的一些化合物的混合物同样适当;
·2至15摩尔环氧乙烷与蓖麻油和/或氢化蓖麻油的加成产物;
·基于直链、支链、不饱和或饱和C6/22脂肪酸、蓖麻酸和12-羟基硬脂酸和甘油、聚甘油、季戊四醇、二季戊四醇、糖醇类(例如山梨糖醇)、烷基糖苷类(例如甲基糖苷、丁基糖苷、月桂基糖苷)以及多苷类(例如纤维素)的偏酯类;
·磷酸单-、二-和三烷酯类以及磷酸单-、二-和/或三-PEG烷酯类及其盐;
·羊毛蜡醇类;
·聚硅氧烷/聚烷基-聚醚共聚物及相应衍生物;
·季戊四醇、脂肪酸、柠檬酸和脂肪醇的混合酯和/或C6-22脂肪酸、甲基葡萄糖和多元醇类、优选甘油或聚甘油的混合酯;
·聚二醇类以及
·碳酸甘油酯。
环氧乙烷和/或环氧丙烷与脂肪醇、脂肪酸、烷基苯酚、脂肪酸的甘油单酯和二酯以及脂肪酸的脱水山梨醇单酯和二酯或与蓖麻油的加成产物是市售可得的公知产品。它们是同族混合物,其中烷氧基化的平均程度对应于进行加成反应的环氧乙烷和/环氧丙烷和底物的用量比例。环氧乙烷与甘油的加成产物的C12/18脂肪酸单酯和二酯已知用作化妆品制剂的脂质层强化剂。
优选的乳化剂详细记载如下:
(i)偏甘油酯。适当的偏甘油酯的典型实例是羟基硬脂酸单甘油酯、羟基硬脂酸二甘油酯、异硬脂酸单甘油酯、异硬脂酸二甘油酯、油酸单甘油酯、油酸二甘油酯、蓖麻酸单甘油酯、蓖麻酸二甘油酯、亚油酸单甘油酯、亚油酸二甘油酯、亚油酸单甘油酯、亚油酸二甘油酯、芥酸单甘油酯、芥酸二甘油酯、酒石酸单甘油酯、酒石酸二甘油酯、柠檬酸单甘油酯、柠檬酸二甘油酯、苹果酸单甘油酯、苹果酸二甘油酯及其仍含有少量源自生产过程的甘油三酯的技术混合物。1至30且优选5至10摩尔环氧乙烷与上述偏甘油酯的加成产物同样适当。
(ii)脱水山梨醇酯。适当的脱水山梨醇酯是脱水山梨醇单异硬脂酸酯、脱水山梨醇倍半异硬脂酸酯、脱水山梨醇二异硬脂酸酯、脱水山梨醇三异硬脂酸酯、脱水山梨醇单油酸酯、脱水山梨醇倍半油酸酯、脱水山梨醇二油酸酯、脱水山梨醇三油酸酯、脱水山梨醇单芥酸酯、脱水山梨醇倍半芥酸酯、脱水山梨醇二芥酸酯、脱水山梨醇三芥酸酯、脱水山梨醇单蓖麻酸酯、脱水山梨醇倍半蓖麻酸酯、脱水山梨醇二蓖麻酸酯、脱水山梨醇三蓖麻酸酯、脱水山梨醇单羟基硬脂酸酯、脱水山梨醇倍半羟基硬脂酸酯、脱水山梨醇二羟基硬脂酸酯、脱水山梨醇三羟基硬脂酸酯、脱水山梨醇单酒石酸酯、脱水山梨醇倍半酒石酸酯、脱水山梨醇二酒石酸酯、脱水山梨醇三酒石酸酯、脱水山梨醇单柠檬酸酯、脱水山梨醇倍半柠檬酸酯、脱水山梨醇二柠檬酸酯、脱水山梨醇三柠檬酸酯、脱水山梨醇单马来酸酯、脱水山梨醇倍半马来酸酯、脱水山梨醇二马来酸酯、脱水山梨醇三马来酸酯及其技术混合物。1至30且优选5至10摩尔环氧乙烷与上述脱水山梨醇的加成产物同样适当。
(iii)聚甘油酯。适当的聚甘油酯的典型实例是聚甘油-2二聚羟基硬脂酸酯(PGPH)、聚甘油-3-二异硬脂酸酯(TGI)、聚甘油-4异硬脂酸酯(GI 34)、聚甘油-3油酸酯、聚甘油-3二异硬脂酸酯(PDI)、聚甘油-3甲基葡糖二硬脂酸酯(Tego450)、聚甘油-3蜂蜡(Cera)、聚甘油-4癸酸酯(聚甘油癸酸酯T2010/90)、聚甘油-3鲸蜡基醚(NL)、聚甘油-3二硬脂酸酯(GS 32)和聚甘油聚蓖麻酸酯(WOL 1403)、聚甘油二异硬脂酸(polyglyceryl dimerateisostearate)酯及其混合物。其它适当的多元醇酯的实例是任选与1至30摩尔环氧乙烷反应的月桂酸、椰油酸、牛油酸、棕榈酸、硬脂酸、油酸、山嵛酸等与三羟甲基丙烷或季戊四醇的单酯、二酯和三酯。
(iv)阴离子乳化剂。典型的阴离子乳化剂是脂肪族C12-22脂肪酸,如例如棕榈酸、硬脂酸或山嵛酸,以及C12-22的二羧酸,如例如壬二酸或癸二酸。
(v)两性乳化剂。其他适当的乳化剂是两性或两性离子表面活性剂。两性离子表面活性剂是分子中含有至少一个季铵基团和至少一个羧酸酯基团和一个磺酸酯基团的表面活性化合物。特别适当的两性离子表面活性剂为所谓的甜菜碱,如N-烷基-N,N-二甲基甘氨酸铵,例如椰油烷基二甲基甘氨酸铵、N-酰胺基丙基-N,N-二甲基甘氨酸铵,例如椰油酰胺基丙基二甲基甘氨酸铵、和烷基或酰基中具有8-18个碳原子的2-烷基-3-羧甲基-3-羟乙基咪唑啉和椰油酰胺基乙基羟乙基羧甲基甘氨酸盐。特别优选已知CTFA名为椰油酰胺丙基甜菜碱的脂肪酸酰胺衍生物。同样适当的乳化剂为两性表面活性剂。两性表面活性剂是除了C8/18烷基或酰基外,分子中还含有至少一个游离氨基和至少一个-COOH或-SO3H基团且能形成内盐的表面活性化合物。适当的两性表面活性剂的实例为烷基中具有约8-18个碳原子的N-烷基甘氨酸、N-烷基丙酸、N-烷基氨基丁酸、N-烷基亚氨基二丙酸、N-羟乙基-N-烷基酰胺基丙基甘氨酸、N-烷基牛磺酸、N-烷基肌氨酸、2-烷基氨基丙酸和烷基氨基乙酸。特别优选的两性表面活性剂为N-椰油烷基氨基丙酸酯、椰油酰胺基乙基氨基丙酸酯和C12/18酰基肌氨酸。
D.富脂剂和稠度因子
富脂剂可以选自物质如例如,羊毛脂和卵磷脂以及聚乙氧基化或酰基化羊毛脂和卵磷脂衍生物、多元醇脂肪酸酯、单甘油酯和脂肪酸烷醇酰胺;脂肪酸烷醇酰胺也可用作泡沫稳定剂。
常用稠度因子是具有12至22个并且优选16至18个碳原子的脂肪醇或羟基脂肪醇以及偏甘油酯、脂肪酸或羟基脂肪酸。优选使用这些物质与烷基多糖苷和/或具有相同链长的脂肪酸N-甲基葡糖酰胺和/或聚甘油聚-12-羟基硬脂酸酯的组合。
E.增稠剂和流变添加剂
适当的增稠剂是聚合增稠剂,如类(亲水性二氧化硅)、多糖,更特别是黄原胶、瓜尔胶、琼脂、藻酸盐和纤基乙酸钠(tyloses)、羧甲基纤维素和羟乙基纤维素、以及脂肪酸的相对高分子量聚乙二醇单酯和二酯、聚丙烯酸酯(例如[Goodrich]或[Sigma])、聚丙烯酰胺、聚乙烯醇和聚乙烯吡咯烷酮、表面活性剂如,例如乙氧基化脂肪酸甘油酯、脂肪酸与多元醇如季戊四醇或三羟甲基丙烷的酯、窄分布的脂肪醇乙氧基化物(fatty alcohol ethoxylates)和电解质如氯化钠和氯化铵。
F.聚合物
适当的阳离子聚合物是例如,阳离子纤维素衍生物,例如以商品名Polymer JR由Amerchol得到的季铵化羟乙基纤维素、阳离子淀粉、二烯丙基铵盐和丙烯酰胺的共聚物、季铵化乙烯基吡咯烷酮/乙烯基咪唑聚合物如,例如(BASF)、聚乙二醇和胺的缩合产物、季铵化胶原多肽如,例如月桂基二甲基铵羟丙基胺水解胶原(Lame-L,Grünau)、季铵化小麦多肽、聚乙烯亚胺、阳离子硅氧烷聚合物如,例如氨基二甲聚硅氧烷(amo二甲基硅氧烷)、己二酸和二甲基氨基羟丙基二亚乙基三胺的共聚物(Sandoz)、丙烯酸与二甲基二烯丙基氯化铵的共聚物(550,Chemviron)、聚氨基聚酰胺及其交联水溶性聚合物、阳离子角质素衍生物如,例如任选以微晶分布的季铵化壳聚糖、二卤代烷基如二溴丁烷与双二烷基胺的缩合产物,例如双-二甲基氨基-1,3-丙烷、阳离子瓜尔胶如,例如Celanese的CBS、C-17、C-16、季铵盐聚合物如,例如Miranol的A-15、AD-1、AZ-1以及各种聚季铵盐类(例如6、7、32或37),其可以商品名CC或300由市场可得。
适当的阴离子、两性离子、两性和非离子聚合物是例如,乙酸乙烯酯/巴豆酸共聚物、乙烯基吡咯烷酮/丙烯酸乙烯酯共聚物、乙酸乙烯酯/马来酸丁酯/丙烯酸异冰片酯共聚物、甲基乙烯基醚/马来酸酐共聚物及其酯、未交联的和与多元醇交联的聚丙烯酸、丙烯酰胺基丙基三甲基氯化铵/丙烯酸酯共聚物、辛基丙烯酰胺/甲基丙烯酸甲酯/甲基丙烯酸叔丁基氨基乙酯/甲基丙烯酸2-羟丙酯共聚物、聚乙烯吡咯烷酮、乙烯基吡咯烷酮/乙酸乙烯酯共聚物、乙烯基吡咯烷酮/甲基丙烯酸二甲基氨基乙酯/乙烯基己内酰胺三元共聚物和任选衍生的纤维素醚和硅氧烷。
G.珠光蜡
适当的珠光蜡是,例如,烷二醇酯,尤其是乙二醇二硬脂酸酯;脂肪酸烷醇酰胺,尤其是椰油脂肪酸二乙醇酰胺;偏甘油酯,尤其是硬脂酸单甘油酯;多元、任选羟基取代的羧酸与具有6-22个碳原子的脂肪醇的酯,尤其是酒石酸的长链酯;具有总计至少24个碳原子的脂肪物质,如例如脂肪醇、脂肪酮、脂肪醛、脂肪醚和脂肪碳酸酯,尤其是月桂酮和二硬脂醚;脂肪酸如硬脂酸、羟基硬脂酸或山嵛酸、具有12-22个碳原子的环氧烯烃与具有12-22个碳原子的脂肪醇和/或具有2-15个碳原子和2-10个羟基的多元醇的开环产物、及其混合物。
H.硅氧烷化合物
适当的硅氧烷化合物是,例如二甲基聚硅氧烷、甲基苯基聚硅氧烷、环硅氧烷以及氨基、脂肪酸、醇、聚醚、环氧、氟、糖苷和/或烷基改性的硅氧烷化合物,在室温下它们可以是液态以及呈树脂态。其它适当的硅氧烷化合物是有机硅树脂,其为平均链长为200至300个二甲基硅氧烷单元的二甲基硅油与氢化硅酸盐的混合物。适当的挥发性硅氧烷的具体综述还可见于Todd等人的Cosm.Toil.91,27(1976)。
I.蜡和稳定剂
除了使用的天然油脂,制剂中也可以存在蜡,更特别是天然蜡如,例如小烛树蜡、巴西棕榈蜡、日本蜡、芦华草腊(espartograss wax)、软木蜡、小冠椰子腊(guaruma wax)、米糠油蜡、糖甘蔗蜡、小冠巴西棕蜡(ouricury wax)、褐煤蜡、蜂蜡、紫胶蜡(schellacwax)、鲸蜡、羊毛脂(羊毛蜡)、尾脂脂肪(uropygial fat)、(纯)地蜡、地蜡(石蜡)、凡士林、石油蜡和微蜡;化学改性的蜡类(硬蜡类)如,例如,褐煤酯蜡(montan ester waxes)、德国沙索集团石油蜡(Sasol Wax)、氢化霍霍巴蜡(jojoba waxes)以及合成蜡类如,例如,聚亚烷基蜡类和聚乙二醇蜡类。
脂肪酸的金属盐如,例如硬脂酸或蓖麻酸的镁盐、铝盐和/或锌盐用作稳定剂。
J.主要防晒剂
在本发明中主要防晒剂是,例如,在室温下是液体或晶体,并且能够吸收紫外辐射并以长波辐射,例如热的形式释放能量的有机物(滤光物质)。
本发明的制剂可有利地含有至少一种UV-A过滤物质和/或至少一种UV-B过滤物质和/或一种宽波过滤物质和/或至少一种无机颜料。本发明的制剂优选含有至少一种UV-B过滤物质或一种宽波过滤物质,更特别优选至少一种UV-A过滤物质和至少一种UV-B过滤物质。
根据本发明优选的化妆品组合物,优选地,局部制剂,含有一种、两种、三种或更多种防晒剂,选自组包括4-氨基苯甲酸和衍生物、水杨酸衍生物、二苯酮衍生物、二苯酰甲烷衍生物、丙烯酸二苯酯、3-咪唑基-4-基丙烯酸及其酯、苯并呋喃衍生物、丙二酸亚苄酯衍生物、含有一个或多个有机硅自由基的聚合UV吸收剂、肉桂酸衍生物、樟脑衍生物、三苯胺基-s-三嗪衍生物、2-羟基苯基苯并三唑衍生物、苯基苯并咪唑磺酸衍生物及其盐、邻氨基苯甲酸薄荷酯、苯并三唑衍生物和吲哚衍生物。
此外,有利地将式(I)的化合物与活性成分结合,所述活性成分渗透进入皮肤并由内保护细胞免受阳光导致的损害并降低皮肤基质金属蛋白酶水平。WO 2007/128723记载了被称为芳香烃受体拮抗剂的各个优选成分,并在此引用。优选的是2-亚苄基-5,6-二甲氧基-3,3-二甲基茚满-1-酮。
下文引用的可在本发明中使用的UV过滤物质是优选的,但不限于这些物质。
优选使用的UV过滤物质选自组包括:
·对氨基苯甲酸
·乙氧基化(25mol)对氨基苯甲酸乙酯(INCI名称:PEG-25PABA)
·对二甲基氨基苯甲酸-2-乙基己酯
·N-丙氧基化(2mol)对氨基苯甲酸乙酯
·对氨基苯甲酸甘油酯
·水杨酸高薄荷醇酯(胡莫柳酯)(NeoHMS)
·水杨酸-2-乙基己酯(NeoOS)
·三乙醇胺水杨酸酯
·水杨酸4-异丙基苄酯
·邻氨基苯甲酸薄荷醇酯(NeoMA)
·二异丙基肉桂酸乙酯
·对甲氧基肉桂酸2-乙基己酯(NeoAV)
·二异丙基肉桂酸甲酯
·对甲氧基肉桂酸异戊酯(NeoE 1000)
·对甲氧基肉桂酸二乙醇胺盐
·对甲氧基肉桂酸异丙酯
·2-苯基苯并咪唑磺酸和盐(NeoHydro)
·3-(4'-三甲基铵)-亚苄基-莰基-2-酮硫酸甲酯
·β-咪唑-4(5)-丙烯酸(尿刊酸)
·3-(4'-磺基)亚苄基-莰基-2-酮和盐
·3-(4'-甲基亚苄基)-D,L-樟脑(NeoMBC)
·3-亚苄基-D,L-樟脑
·N-[(2和4)-[2-(氧代亚冰片-3-亚基)甲基]苄基]-丙烯酰胺聚合物
·4,4'-[(6-[4-(1,1-二甲基)-氨基羰基)苯基氨基]-1,3,5-三嗪-2,4-二基)二亚氨基]-二-(苯甲酸2-乙基己酯)(HEB)
·亚苄基丙二酸酯-聚硅氧烷(SLX)
·甘油基乙基己酸二甲氧基肉桂酸酯
·双丙二醇水杨酸酯
·4,4',4”-(1,3,5-三嗪-2,4,6-三基三亚氨基)-三-苯甲酸三(2-乙基己酯)(2,4,6-三苯胺基-(对-羰基-2'-乙基己基-1'-氧基)-1,3,5-三嗪)(T150)
在本发明的制剂中优选与一种或多种式(A)的化合物结合的宽波过滤物质选自组包括
·2-氰基-3,3-二苯基丙烯酸-2-乙基己酯(Neo303)
·2-氰基-3,3′-二苯基丙烯酸乙酯
·2-羟基-4-甲氧基二苯酮(NeoBB)
·2-羟基-4-甲氧基二苯酮-5-磺酸
·二羟基-4-甲氧基二苯酮
·2,4-二羟基二苯酮
·四羟基二苯酮
·2,2′-二羟基-4,4′-二甲氧基二苯酮
·2-羟基-4-正辛氧基二苯酮
·2-羟基-4-甲氧基-4′-甲基二苯酮
·羟基甲氧基二苯酮磺酸钠
·2,2’-二羟基-4,4’-二甲氧基-5,5’-二磺基-二苯酮二钠
·苯酚,2-(2H-苯并三唑-2-基)-4-甲基-6-(2-甲基-3(1,3,3,3-四甲基-1-(三甲基甲硅烷基)-氧)-二甲硅氧基)-丙基)(XL)
·2,2′-亚甲基-二-(6-(2H-苯并三唑-2-基)-4-1,1,3,3-四甲基丁基)-苯酚)(M)
·2,4-二-[4-(2-乙基己氧基)-2-羟苯基]-1,3,5-三嗪
·2,4-二-[{(4-(2-乙基己氧基)-2-羟基}苯基]-6-(4-甲氧基苯基)-1,3,5-三嗪(S)
·2,4-二-[{(4-(3-磺酸基)-2-羟基丙氧基)-2-羟基}苯基]-6-(4-甲氧基苯基)-1,3,5-三嗪钠盐
·2,4-二-[{(3-(2-丙氧基)-2-羟基丙氧基)-2-羟基}苯基]-6-(4-甲氧基苯基)-1,3,5-三嗪
·2,4-二-[{4-(2-乙基己氧基)-2-羟基}苯基]-6-[4-(2-甲氧乙基羰基)苯基氨基]-1,3,5-三嗪
·2,4-二-[{4-(3-(2-丙氧基)-2-羟基丙氧基)-2-羟基}苯基]-6-[4-(2-乙基羰基)苯基氨基]-1,3,5-三嗪
·2,4-二-[{4-(2-乙基己氧基)-2-羟基}苯基]-6-(1-甲基吡咯-2-基)-1,3,5-三嗪
·2,4-二-[{4-三-(三甲基硅氧基甲硅烷基丙氧基)-2-羟基}苯基]-6-(4-甲氧基苯基)-1,3,5-三嗪
·2,4-二-[{4-(2″-甲基丙氧烯基)-2-羟基}苯基]-6-(4-甲氧基苯基)-1,3,5-三嗪
·2,4-二-[{4-(1′,1′,1′,3′,5′,5′,5′-七甲基硅氧基-2″-甲基丙氧基)-2-羟基}苯基]-6-(4-甲氧基苯基)-1,3,5-三嗪
在本发明的制剂中优选与一种或多种式(A)的化合物结合的UV-A过滤物质选自组包括
·4-异丙基二苯甲酰甲烷
·对苯二亚甲基-二莰烷磺酸和盐(SX)
·4-叔丁基-4′-甲氧基二苯甲酰基甲烷(阿伏苯宗)/(Neo357)
·亚苯基-二-苯并咪唑基-四磺酸二钠盐(NeoAP)
·2,2′-(1,4-亚苯基)-二-(1H-苯并咪唑-4,6-二磺酸),一钠盐
·2-(4-二乙氨基-2-羟基苯甲酰基)-苯甲酸己酯(A Plus)
·根据DE 100 55 940A1(=WO 2002038537)的茚满亚基化合物
在本发明的制剂中与一种或多种式(A)的化合物优选结合的UV过滤物质选自组包括
·对氨基苯甲酸
·3-(4′-三甲基铵)-亚苄基莰基-2-酮硫酸甲酯
·水杨酸高薄荷醇酯(NeoHMS)
·2-羟基-4-甲氧基二苯酮(NeoBB)
·2-苯基苯并咪唑磺酸(NeoHydro)
·对苯二亚甲基-二莰烷磺酸和盐(SX)
·4-叔丁基-4′-甲氧基二苯甲酰基甲烷(Neo357)
·3-(4′-磺基)亚苄基-莰基-2-酮和盐
·2-氰基-3,3-二苯基丙烯酸-2-乙基己酯(Neo303)
·N-[(2和4)-[2-(氧代亚冰片-3-亚基)甲基]苄基]-丙烯酰胺聚合物
·对甲氧基肉桂酸2-乙基己酯(NeoAV)
·乙氧基化(25mol)对氨基苯甲酸乙酯(INCI名称:PEG-25PABA)
·对甲氧基肉桂酸异戊酯(NeoE 1000)
·2,4,6-三苯胺基-(对-羰基-2′-乙基己基-1′-氧基)-1,3,5-三嗪(T150)
·苯酚,2-(2H-苯并三唑-2-基)-4-甲基-6-(2-甲基-3(1,3,3,3-四甲基-1-(三甲基甲硅烷基)-氧)-二甲硅氧基)-丙基)(XL)
·4,4′-[(6-[4-(1,1-二甲基)-氨基羰基)苯基氨基]-1,3,5-三嗪-2,4-二基)二亚氨基]-二-(苯甲酸2-乙基己基酯)(Uvasorb HEB)
·3-(4′-甲基亚苄基)-D,L-樟脑(NeoMBC)
·3-亚苄基-樟脑
·水杨酸-2-乙基己酯(NeoOS)
·4-二甲基氨基苯甲酸-2-乙基己酯(Padimate O)
·羟基-4-甲氧基二苯酮-5-磺酸和钠盐
·2,2′-亚甲基-二-(6-(2H-苯并三唑-2-基)-4-1,1,3,3-四甲基丁基)-苯酚)(M)
·亚苯基-二-苯并咪唑基-四磺酸二钠盐(NeoAP)
·2,4-二-[{(4-(2-乙基己氧基)-2-羟基}苯基]-6-(4-甲氧基苯基)-1,3,5-三嗪(S)
·亚苄基丙二酸酯-聚硅氧烷(SLX)
·邻氨基苯甲酸薄荷醇酯(NeoMA)
·2-(4-二乙氨基-2-羟基苯甲酰基)-苯甲酸己酯(A Plus)
·根据DE 100 55 940(=WO 02/38537)的茚满亚基化合物
有利的主要以及二级防晒剂记载于WO 2005 123101 A1。有利地这些制剂含有至少一种UVA过滤物质和/或至少一种UVB过滤物质和/或至少一种无机颜料。该制剂在本发明中可以各种形式存在,如通常用于防晒制剂的形式。因此,它们的形式可以为溶液、油包水型(W/O)或水包油型(O/W)乳剂或多重乳剂,例如水包油包水型(W/O/W)、凝胶、水分散体、固体棒或气雾剂。
在另一个优选实施方案中本发明的制剂含有遮光剂,即,特别是UV过滤物质和/或无机颜料(UV过滤颜料)的总量能够使本发明的制剂具备大于或等于2的光照防护系数(优选大于或等于5)。本发明的该制剂特别适用于保护皮肤和头发。
H.二级防晒剂
除了上述主要防晒剂组,也可以使用抗氧化剂型的二级防晒剂。抗氧化剂型的二级防晒剂阻断了当紫外线渗透进入皮肤时引发的光化学反应链。典型实例是氨基酸类(例如甘氨酸、组氨酸、酯氨酸、色氨酸)及其衍生物、咪唑类(例如尿刊酸)及其衍生物、肽类例如D,L-肌肽、D-肌肽,L-肌肽及其衍生物(例如鹅肌肽)、类胡萝卜素类、胡萝卜素类(例如α-胡萝卜素、β-胡萝卜素、番茄红素)及其衍生物、绿原酸及其衍生物、脂酮酸及其衍生物(例如二氢脂酮酸)、金硫葡糖、丙基硫氧嘧啶和其他硫醇(例如硫氧还蛋白、谷胱甘肽、半胱氨酸、胱氨酸、胱胺及其糖基、N-乙酰基、甲基、乙基、丙基、戊基、丁基和月桂基、棕榈酰基、油烯基、α-亚油酰基、胆甾醇基和其甘油酯)及其盐、硫代二丙酸二月桂酯、硫代二丙酸双十八酯、硫代二丙酸及其衍生物(酯类、醚类、肽类、脂类、核苷酸类、核苷类和盐)以及非常低的耐药剂量的亚砜亚胺化合物(例如丁硫氨酸亚砜亚胺、同型半胱氨酸亚砜亚胺、丁硫氨酸砜、五-、六-和七-硫氨酸亚砜亚胺)、以及(金属)螯合剂类(例如,α-羟基脂肪酸类、棕榈酸、植酸、乳铁蛋白)、α-羟基酸类(例如柠檬酸、乳酸、苹果酸)、腐殖酸、胆汁酸、胆汁提取物、胆红素、胆绿素、EDTA、EGTA及其衍生物、不饱和脂肪酸及其衍生物(例如亚油酸、油酸)、叶酸及其衍生物、泛醌和泛醇及其衍生物、维生素C及其衍生物(例如抗坏血酸棕榈酸酯、抗坏血酸磷酸镁、抗坏血酸乙酸酯)、生育酚及衍生物(例如维生素E乙酸酯)、维生素A及衍生物(维生素A棕榈酸酯)以及安息香树脂的苯甲酸松酯、芸香十烯酸及其衍生物、糖基芦丁、阿魏酸、亚糠基山梨醇、肌肽、丁基羟甲苯、丁基羟基茴香醚、去甲二氢愈创木酸木脂酸、去甲二氢愈创木酸、三羟基丁酰苯、尿酸及其衍生物、甘露糖及其衍生物、超氧化物歧化酶、二氧化钛(例如乙醇中的分散体)、锌及其衍生物(例如ZnO、ZnSO4)、硒及其衍生物(例如蛋氨酸硒)、芪类及其衍生物(例如均二苯乙烯氧化物、反-均二苯乙烯氧化物)及这些活性化合物的适合本发明目的的衍生物(盐类、酯类、醚类、糖类、核苷酸类、核苷类、肽类和脂类)。
有利的无机二级光照防护颜料精细分散于金属氧化物和金属盐中,其记载于WO2005 123101 A1中。无机颜料,特别是疏水性无机微颜料,在本发明的最终化妆品制剂中的总量有利地是0.1至30重量%,优选0.5至10.0重量%,基于制剂总量计。
同样优选的是使用微粒状UV过滤物质或无机颜料,其可任选为疏水性的,如钛的氧化物(TiO2)、锌的氧化物(ZnO)、铁的氧化物(Fe2O3)、锆的氧化物(ZrO2)、硅的氧化物(SiO2)、镁的氧化物(例如MnO)、铝的氧化物(Al2O3)、铈的氧化物(例如Ce2O3)和/或其混合物。
J.抗老化活性物
在本发明中抗老化剂或生物活性剂是,例如抗氧化剂、基质金属蛋白酶抑制剂(MMPI)、皮肤保湿剂、粘多糖刺激剂(glycosaminglycan stimulkators)、抗炎剂、TRPV1拮抗剂和植物提取物。
(i)抗氧化剂。氨基酸类(优选甘氨酸,组氨酸,酪氨酸,色氨酸)及其衍生物、咪唑类(优选尿刊酸)及其衍生物、肽类,优选D,L-肌肽、D-肌肽、L-肌肽及其衍生物(优选鹅肌肽)、肉碱、肌酸、马曲金(matrikine)肽类(优选赖氨酰-苏氨酰-苏氨酰-赖氨酰-丝氨酸)和棕榈酰化五肽类、类胡萝卜素类、胡萝卜素类(优选α-胡萝卜素、β-胡萝卜素、番茄红素)及其衍生物、硫辛酸及其衍生物(优选二氢硫辛酸)、金硫葡萄糖、丙基硫氧嘧啶和其他硫醇(优选硫氧还蛋白、谷胱甘肽、半胱氨酸、胱氨酸、胱胺和糖基、N-乙酰基、甲基、乙基、丙基、戊基、丁基和月桂基、棕榈酰基、油烯基、γ-亚油烯基、胆甾醇基、甘油基及其寡甘油酯)及其盐、硫代二丙酸二月桂酯、硫代二丙酸二硬脂酯、硫代二丙酸及其衍生物(优选酯类、醚类、肽类、脂类、核苷酸类、核苷类和盐)和非常低的耐药剂量(例如pmol至μmol/kg)的亚砜亚胺化合物(优选丁硫氨酸亚砜亚胺、同型半胱氨酸亚砜亚胺、丁硫氨酸砜、五-、六-和七-硫氨酸亚砜亚胺)、以及(金属)螯合剂(优选α-羟基脂肪酸、棕榈酸、植酸、乳铁蛋白)、α-羟基酸(优选柠檬酸、乳酸、苹果酸)、腐殖酸、胆汁酸、胆汁提取物、单宁类、胆红素、胆绿素、EDTA、EGTA及其衍生物、不饱和脂肪酸及其衍生物(优选γ-亚麻酸,亚油酸,油酸)、叶酸及其衍生物、泛醌及其衍生物,泛醇及其衍生物、维生素C及衍生物(优选抗坏血酸棕榈酸酯、抗坏血酸磷酸镁、抗坏血酸基乙酸酯、抗坏血酸葡糖苷)、生育酚及衍生物(优选维生素E乙酸酯)、维生素A及衍生物(维生素A棕榈酸酯)以及安息香树脂的苯甲酸松酯、芸香十烯酸及其衍生物、黄酮类及其糖基化前体,具体而言,槲皮素及其衍生物,优选α-葡糖基芦丁、迷迭香酸、鼠尾草酚、卡诺酸、白藜芦醇、咖啡酸及其衍生物、芥子酸及其衍生物、阿魏酸及其衍生物、姜黄素类、绿原酸及其衍生物、类视黄醇类,优选类视黄醇棕榈酸酯、视黄醇或维甲酸、乌索酸、乙酰丙酸、丁基羟基甲苯、丁基羟基茴香醚、去二氢愈创木酸、去甲二氢愈创木酸、三羟基丁酰苯、尿酸及其衍生物、甘露糖及其衍生物、锌及其衍生物(优选ZnO、ZnSO4)、硒及其衍生物(优选硒蛋氨酸)、超氧化物歧化酶、二苯乙烯类及其衍生物(优选二苯乙烯氧化物、反式-二苯乙烯氧化物)及这些引用的活性成分的适合本发明的衍生物(盐、酯类、醚类、糖类、核苷酸类、核苷类、肽类和脂类)或者具有抗氧化作用的植物的提取物或馏分,优选绿茶、路易波士(rooibos)茶、蜜树茶、葡萄、迷迭香、鼠尾草、蜜蜂花、百里香、薰衣草、橄榄、燕麦、可可、银杏、人参、甘草、金银花、苦参、葛根、松、柑橘、余甘子或St.John麦汁、葡萄籽、小麦胚芽、余甘子、辅酶,优选辅酶Q10、质体醌和甲基萘醌。优选的抗氧化剂选自组包括维生素A及衍生物,维生素C及衍生物,生育酚及衍生物,优选生育酚醋酸酯、以及泛醌。
(ii)基质金属蛋白酶抑制剂(MMPI)。优选的组合物包含基质金属蛋白酶抑制剂,尤其是那些抑制基质金属蛋白酶裂解胶原的抑制剂,选自组包括:熊果酸、视黄醇棕榈酸酯、没食子酸丙酯、早熟素类、6-羟基-7-甲氧基-2,2-二甲基-1(2H)-苯并吡喃、3,4-二氢-6-羟基-7-甲氧基-2,2-二甲基-1(2H)-苯并吡喃、盐酸苯甲脒、半胱氨酸蛋白酶抑制剂N-乙基马来酰胺和丝氨酸蛋白酶抑制剂的ε-氨基-正己酸:苯基甲基磺酰基氟化物、collhibin(Pentapharm公司;INCI:水解大米蛋白)、oenotherol(Soliance公司;INCI:丙二醇、水、月见草根提取物、鞣花酸和鞣花单宁类,例如来自石榴的提取物)、磷酸阿米酮桧木醇、EDTA、加拉定(galardin)、Equistat(Collaborative Group公司;苹果提取物、大豆种子提取物、熊果酸、大豆异黄酮类和大豆蛋白类)、鼠尾草提取物、MDI(Atrium公司;INCI:粘多糖(glycosaminoglycans)),fermiskin(Silab/MAWI公司;INCI:水和香菇提取物)、actimp1.9.3(Expanscience/Rahn公司;INCI:水解羽扇豆蛋白),lipobelle大豆糖苷配基(Mibelle公司;INCI:醇、聚山梨醇酯80、卵磷脂和大豆异黄酮)、绿茶和黑茶提取物以及WO02069992A1中列出的其它植物提取物(见其中的表1-12,通过引用并入本文)、大豆蛋白或大豆糖蛋白、来自大米、豌豆或羽扇豆的水解蛋白、抑制MMP的植物提取物,优选香菇提取物、蔷薇科、蔷薇亚科的叶提取物,特别是黑莓叶提取物(优选地,如WO2005123101A1中所述,通过引用并入本文),例如SymMatrix(Symrise公司,INCI:麦芽糖糊精、欧洲黑莓(RubusFruticosus)叶提取物)。优选的活性物质选自组包括视黄醇棕榈酸酯、熊果酸、蔷薇科、蔷薇亚科的叶提取物、染料木素和黄豆苷元。
(III)皮肤保湿剂。优选的皮肤保湿剂选自组包括含有3至12个碳原子的烷二醇或烷三醇,优选C3-C10-烷二醇和C3-C10-烷三醇。更优选地,所述皮肤保湿剂选自组包括:甘油、1,2-丙二醇、1,2-丁二醇、1,3-丁二醇、1,2-戊二醇、1,2-己二醇、1,2-辛二醇和1,2-癸二醇。
(iv)粘多糖刺激剂。优选的组合物含有刺激粘多糖合成的物质,选自组包括透明质酸和衍生物或盐,Subliskin(Sederma,INCI:苜蓿中华根瘤菌发酵滤液、十六烷基羟乙基纤维素、卵磷脂)、Hyalufix(BASF,INCI:水、丁二醇、高良姜叶提取物、黄原胶、辛酸/癸酸甘油三酯、Stimulhyal(Soliance,INCI:酮葡糖酸钙(Calcium ketogluconate))、Syn-Glycan(DSM,INCI:十四烷基氨基丁酸基缬氨酰氨基丁脲三氟乙酸酯(TetradecylAminobutyroylvalylaminobutyric脲Trifluoroacetate)、甘油、氯化镁)、Kalpariane(Biotech Marine)、DC Upregulex(Distinctive Cosmetic成分,INCI:水、丁二醇、磷脂质类、水解丝胶蛋白)、葡萄糖胺、N-乙酰基葡萄糖胺、类视黄醇类,优选视黄醇和维生素A、牛蒡果提取物、枇杷提取物、芫花素、N-甲基-L-丝氨酸、(-)-α-没药醇或合成的α-没药醇,例如Symrise的Dragosantol和Dragosantol100、燕麦葡聚糖、松果菊提取物和大豆蛋白水解物。优选的活性物质选自组包括透明质酸和衍生物或盐、视黄醇和衍生物、(-)-α-没药醇或合成的α-没药醇,例如Symrise的Dragosantol和Dragosantol100、燕麦葡聚糖、松果菊提取物、苜蓿根瘤菌发酵滤液、酮葡糖酸钙、高良姜叶提取物和十四烷基氨基丁酸基缬氨酰氨基丁脲三氟醋酸酯。
(v)抗炎剂。所述组合物还可含有抗炎和/或抗发红和/或瘙痒缓解成分,特别是,选自以下的皮质类固醇的甾类物质有利地用作抗炎活性成分或缓解发红和瘙痒的活性成分:皮质醇(hydrocortisone)、地塞美松、磷酸地塞美松、甲基脱氢皮质或可的松,还包括其它甾类抗炎剂。还可使用非甾类抗炎剂。本文可引用的实例为昔康类,如吡罗昔康或替诺昔康;水杨酸盐类如阿司匹林、双水杨酸(disalcid)、solprin或芬度柳;乙酸衍生物如双氯芬酸、氯芬酸、吲哚美辛、舒林酸、托美丁或clindanac;灭酸酯类如甲灭酸、甲氯灭酸、氟芬那酸或尼氟灭酸;丙酸衍生物如布洛芬、萘普生、苯恶洛芬或吡唑类如保泰松、羟保松、非普拉宗(febrazone)或阿扎丙宗。邻氨基苯甲酸衍生物,特别是WO 2004047833A1中描述的燕麦蒽酰胺(avenanthramides),为本发明的组合物中的优选的抗瘙痒成分。
同样有用的是天然或天然生成的抗炎物质混合物或缓解发红和/或瘙痒的物质混合物,特别是洋甘菊、芦荟、没药类、茜草类、柳树、柳叶菜、燕麦、金盏花、山金车、St John’s麦汁、金银花、迷迭香、西番莲、金缕梅、姜或紫锥菊的提取物或馏分;优选地选自组包括洋甘菊、芦荟、燕麦、金盏花、山金车、金银花、迷迭香、金缕梅、姜或紫锥菊的提取物或馏分、和/或纯物质,优选地α-没药醇、芹黄素、芹黄素-7-葡萄糖苷、姜酚类、姜烯酚类、姜二醇类、脱氢姜二酮类、姜酮酚类(paradols)、天然或天然生成的燕麦蒽酰胺,优选曲尼司特(tranilast)、燕麦蒽酰胺A、燕麦蒽酰胺B、燕麦蒽酰胺C、非天然或非天然生成的燕麦蒽酰胺,优选二氢燕麦蒽酰胺D、二氢燕麦蒽酰胺E、燕麦蒽酰胺D、燕麦蒽酰胺E、燕麦蒽酰胺F、乳香脂酸、植物甾醇、甘草甜素、光甘草定和甘草查尔酮A;优选地,选自组包括α-没药醇、天然燕麦蒽酰胺、非天然燕麦蒽酰胺,优选二氢燕麦蒽酰胺D(如WO2004047833A1中描述)、乳香脂酸、植物甾醇、甘草甜素、和甘草查尔酮A、和/或尿囊素、泛醇、羊毛脂、(假-)神经酰胺类[优选神经酰胺2、羟丙基双棕榈酰胺MEA、十六基氧丙基甘油基甲氧基丙基十四酰胺、N-(1-十六酰)-4-羟基-L-脯氨酸(1-十六基)酯、羟乙基棕榈基氧羟丙基棕榈酰胺]、鞘糖脂、植物甾醇、壳聚糖、甘露糖、乳糖和β-葡聚糖,特别是燕麦的1,3-1,4-β-葡聚糖。
(vi)TRPV1拮抗剂。基于作为TRPV1拮抗剂的作用减轻皮肤神经过敏性的适当化合物包括例如WO2009087242A1中描述的反式-4-叔丁基环己醇,或者通过活化μ-受体的TRPV1间接调节剂,例如乙酰基四肽-15,是优选的。
(vii)植物提取物。所述组合物还可含有植物的各种提取物,如银杏(Ginkgobiloba)、木犀(Oleacea europensis)、Glyzyrrhiza glabra、越桔(Vacciniummyrtillus)、红三叶(Trifolium pratense)、荔枝(Litchi sinensis)、葡萄(Vitis)、酿酒葡萄(vinifera)、甘蓝(Brassica oleracea)、石榴(Punica granatum)、Petroseliniumcrispum、雷公根(Centella asiatica)、西番莲(Passiflora incarnata)、紫花苜蓿(Medicago sativa)、香蜂草(Melissa officinalis)、缬草(Valeriana officinalis)、欧洲板栗(Castanea sativa)、白柳(Salix alba)和Hapagophytum procumbens的提取物。
K.清凉剂
所述组合物还可含有一种或多种具有生理清凉作用的物质(清凉剂),其优选自以下列表:薄荷醇和薄荷醇衍生物(例如L-薄荷醇、D-薄荷醇、外消旋薄荷醇、异薄荷醇、新异薄荷醇、新薄荷醇)、薄荷基醚(例如(I-薄荷氧基)-1,2-丙二醇、(I-薄荷氧基)-2-甲基-1,2-丙二醇、I-薄荷基-甲醚)、薄荷酯(例如甲酸薄荷酯、乙酸薄荷酯、异丁酸薄荷酯、乳酸薄荷酯、L-乳酸L-薄荷酯、D-乳酸L-薄荷酯、(2-甲氧基)-乙酸薄荷酯、(2-甲氧基乙氧基)乙酸薄荷酯、焦谷氨酸薄荷酯)、碳酸薄荷酯(例如丙二醇碳酸薄荷酯、乙二醇碳酸薄荷酯、甘油碳酸薄荷酯或其混合物)、薄荷醇与二元羧酸的半酯或其衍生物(例如琥珀酸单薄荷酯、戊二酸单薄荷酯、丙二酸单薄荷酯、O-薄荷基琥珀酸酯-N,N-(二甲基)酰胺、O-薄荷基丁二酸酯酰胺)、薄荷烷羧酸酰胺(在这种情况下优选如US 4,150,052中所描述的薄荷烷羧酸-N-乙酰胺[WS3]或Nα-(薄荷烷羰基)甘氨酸乙酯[WS5]、如WO2005049553A1中描述的薄荷烷羧酸-N-(4-氰基苯基)酰胺或薄荷烷羧酸-N-(4-氰基甲基苯基)酰胺、甲烷羧酸-N-(烷氧基烷基)酰胺类)、薄荷酮和薄荷酮衍生物(例如L-薄荷酮甘油缩酮)、2,3-二甲基-2-(2-丙基)-丁酸衍生物(例如2,3-二甲基-2-(2-丙基)-丁酸-N-甲酰胺[WS23])、异胡薄荷醇或其酯(I-(-)-异胡薄荷醇、I-(-)-异胡薄荷醇乙酸酯)、薄荷烷衍生物(例如p-薄荷烷-3,8-二醇)、荜澄茄醇或含有荜澄茄醇的合成或天然混合物、环烷基二酮衍生物的吡咯烷酮衍生物(例如3-甲基-2(1-吡咯烷基)-2-环戊烯-1-酮)或四氢嘧啶-2-酮(例如WO2004/026840中描述的iciline或相关化合物)、其它甲酰胺(例如N-(2-(吡啶-2-基)乙基)-3-p-薄荷烷甲酰胺或相关化合物)、(1R,2S,5R)-N-(4-甲氧基苯基)-5-甲基-2-(1-异丙基)环己烷-甲酰胺[WS12]、草氨酸酯(优选EP 2033688A2中描述的)。
L.抗微生物剂
适当的其他抗微生物剂原则上是对革兰氏阳性细菌有效的所有物质,例如4-羟基苯甲酸及其盐和酯、N-(4-氯苯基)-N'-(3,4-二氯苯基)脲、2,4,4'-三氯-2'-羟基-二苯基醚(三氯生)、4-氯-3,5-二甲基-苯酚、2,2'-亚甲基双(6-溴-4-氯苯酚)、3-甲基-4-(1-甲基乙基)苯酚、2-苄基-4-氯-苯酚、3-(4-氯苯氧基)-1,2-丙二醇、丁基氨基甲酸3-碘-2-丙炔酯、氯己定、3,4,4'-三氯碳酰替苯胺(TTC)、抗菌芳香剂、麝香草酚、麝香草油、丁香酚、丁香油、薄荷醇、薄荷油、金合欢醇、苯氧乙醇、甘油单癸酸酯、单辛酸甘油酯、月桂酸单甘油酯(GML)、双甘油单癸酸酯(DMC)、水杨酸N-烷基胺,例如,正辛基水杨酰胺或正癸基水杨酰胺。
M.酶抑制剂
适当的酶抑制剂是例如酯酶抑制剂。这些酶抑制剂优选为柠檬酸三烷酯,例如柠檬酸三甲酯、柠檬酸三丙酯、柠檬酸三异丙酯、柠檬酸三丁酯和,特别是,柠檬酸三乙酯(Hydagen CAT)。上述物质抑制酶活性,由此减少气味的生成。适合作为酯酶抑制剂的其它物质为甾醇硫酸酯或甾醇磷酸酯,例如,羊毛甾醇硫酸酯或磷酸酯、胆固醇硫酸酯或磷酸酯、菜油甾醇硫酸酯或磷酸酯、豆甾醇硫酸酯或磷酸酯和谷甾醇硫酸酯或磷酸酯;二羧酸和其酯,例如戊二酸、戊二酸单乙酯、戊二酸二乙酯、己二酸、己二酸单乙酯、己二酸二乙酯、丙二酸和丙二酸二乙酯;羟基羧酸及其酯,例如柠檬酸、苹果酸、酒石酸或酒石酸二乙酯,以及甘氨酸锌。
N.气味吸收剂和止汗活性剂
适当的气味吸收剂是能够吸收并在很大程度上保留形成味道的化合物的物质。它们降低各成分的分压,由此还可降低其扩散速率。重要的是在该过程中芳香剂必须保持未受损害。气味吸收剂对细菌没有作用。它们含有例如作为主成分的蓖麻油酸的复合锌盐,或作为“固香剂”为本领域技术人员所知晓的特定的主要中和气味的芳香剂,例如,岩蔷薇或苏合香的提取物或一些松香酸衍生物。气味掩蔽剂为芳香剂或芳香油,除了其作为气味掩蔽剂的功能之外,还向除臭剂提供其各自香味。可以提及的芳香油是例如天然和合成芳香剂的混合物。天然芳香剂为花、茎和叶、果实、果皮、根、木材、草本植物和禾本植物、松针和树枝以及树脂和香脂的提取物。还适当的是动物产品,例如麝猫香和海狸香。典型的合成芳香化合物为酯、醚、醛、酮、醇和烃类产物。酯类芳香剂化合物是例如,乙酸苄基酯、乙酸p-叔丁基环己酯、乙酸芳樟酯、乙酸苯乙酯、苯甲酸芳樟酯、甲酸苄酯、环己基丙酸烯丙酯、丙酸苏合香酯和水杨酸苄酯。醚类包括,例如苄基乙基醚;醛类包括,例如含有8至18个碳原子的直链烷醛、柠檬醛、香茅醛、香茅基氧基乙醛、仙客来醛、羟基香茅醛、铃兰醛和波洁红醛(bourgeonal);酮包括,例如紫罗兰酮和甲基柏木酮;醇包括茴香脑、香茅醇、丁香酚、异丁香酚、香叶醇、芳樟醇,苯乙醇和松油醇;烃类主要包括萜烯和香脂。然而,优选使用不同芳香剂化合物的混合物,它们一起产生令人愉快的香味。通常用作芳香成分的挥发性较低的精油也适用作芳香油,例如鼠尾草油、甘菊油、丁香油、蜂花油、薄荷油、肉桂叶油、椴树花油、杜松子油、香根草油、乳香油、白松香油(galbanum oil)、岩蔷薇油和熏衣草油。优选单独使用或以混合物使用佛手柑油、二氢月桂烯醇、铃兰醛、新铃兰醛、香茅醇、苯乙醇、α-己基肉桂醛、香叶醇、苄丙酮、仙客来醛、芳樟醇、乙氧基甲氧基环十一烷(boisambreneforte)、龙涎呋喃、吲哚、二氢茉莉酮酸甲酯、sandelice、柠檬油、柑橘油、橙油、异戊氧基乙酸烯丙酯、cyclovertal、熏衣草油、鼠尾草油、β-大马酮、波旁香叶油、水杨酸环己酯、Vertofix Coeur、Iso-E-Super、Fixolide NP、evernyl、iraldein gamma、苯乙酸、乙酸香叶酯、乙酸苄酯、玫瑰醚、romilat、2-乙基-己酸乙酯(irotyl)和2-叔丁基环己基乙基碳酸酯(floramat)。
适当的收敛止汗活性成分主要是铝,锆或锌的盐。这类适当的antihydrotic活性成分是例如,氯化铝、氢氯酸铝、二氢氯酸铝、倍半氢氯酸铝及其络合物,例如与1,2-丙二醇的络合物、尿囊素羟基铝(aluminium hydroxyallantoinate)、酒石酸氯化铝、三氢氯酸铝锆、四氢氯酸铝锆、五氢氯酸铝锆及其络合物,例如与氨基酸如甘氨酸的络合物。
O.成膜剂和抗头皮屑剂
标准成膜剂是例如,壳聚糖、微晶壳聚糖、季铵壳聚糖、聚乙烯吡咯烷酮、乙烯基吡咯烷酮/乙酸乙烯酯共聚物、丙烯酸系聚合物、季纤维素衍生物、胶原、透明质酸及其盐和类似化合物。
适当的抗头皮屑剂是Pirocton Olamin(1-羟基-4-甲基-6-(2,4,4-三甲基戊基)-2-(1H)-吡啶酮单乙醇胺盐)、(氯咪巴唑)、(4-乙酰基-1-{4-[2-(2,4-二氯苯基)r-2-(1H-咪唑-1-基甲基)-1,3-二氧戊(dioxylan)-c-4-基甲氧基苯基}-哌嗪、酮康唑、新康唑、二硫化硒、胶体硫、硫聚乙二醇脱水山梨醇单油酸酯、硫蓖麻醇聚乙氧基化物、硫磺焦油馏分、水杨酸(或结合六氯酚)、十一碳烯酸、单乙醇酰胺磺基琥珀酸钠盐、UD(蛋白质/十一烯酸浓缩物)、吡啶硫酮锌、吡啶硫酮铝和吡啶硫酮镁/双吡硫翁硫酸镁。
P.载体和助水溶物
优选的化妆品载体材料在25℃和1013mbar下为固体或液体(包括高粘度物质),例如甘油、1,2-丙二醇、1,2-丁二醇、1,3-丙二醇、1,3-丁二醇、乙醇、水以及两种或多种所述液体载体物质与水的混合物。任选地,本发明的这些制剂可使用防腐剂或助溶剂制备。可作为本发明制剂的成分的其它优选的液体载体物质选自组包括油类,例如植物油、中性油和矿物油。
可作为本发明制剂的成分的优选的固体载体物质为水胶体,例如淀粉、降解淀粉、化学或物理改性淀粉、糊精、(粉末状)麦芽糊精(优选地具备葡糖值为5至25,优选10-20)、乳糖、二氧化硅、葡萄糖、改性纤维素、阿拉伯树胶、印度树胶、胺黄树胶、梧桐胶、卡拉胶、普鲁兰多糖、凝胶多糖、黄原胶、结冷胶、瓜尔豆胶、角豆粉、藻酸盐、琼脂、果胶和菊粉以及两种或两种以上这些固体物质的混合物,特别是,麦芽糊精(优选地,葡糖值为15至20)、乳糖,二氧化硅和/或葡萄糖。
此外,助水溶物,例如乙醇、异丙醇或多元醇,可用于改善流动性。适当的多元醇优选含有2至15个碳原子和至少两个羟基。这种多元醇可含有其它官能团,更具体地为氨基,或可被氮修饰。
典型实例为:
·甘油;
·烷二醇,例如乙二醇、二乙二醇、丙二醇、丁二醇、己二醇和平均分子量为100至1000道尔顿的聚乙二醇;
·自缩合度为1.5至10的寡甘油技术混合物,如二甘油含量为40至50重量%的二甘油技术混合物;
·羟甲基化合物,特别是,例如三羟甲基乙烷、三羟甲基丙烷、三羟甲基丁烷、季戊四醇和二季戊四醇;
·低级烷基糖苷,尤其是烷基中含有1至8个碳原子的那些烷基糖苷,例如甲基糖苷和丁基糖苷;
·含有5至12个碳原子的糖醇,例如山梨醇或甘露糖醇;
·含有5至12个碳原子的糖,例如葡萄糖或蔗糖;
·氨基糖,例如葡糖胺;
·二醇胺,例如二乙醇胺或2-氨基丙烷-1,3-二醇。
Q.防腐剂
适当的防腐剂是例如,苯氧基乙醇、甲醛溶液、对羟基苯甲酸酯类、戊二醇或山梨酸以及Kosmetikverordnung(“化妆品指南”)中附录6,A和B部分中列举的其它类别的化合物。
R.芳香油和芳香剂
适当的芳香油是天然芳香剂与合成芳香剂的混合物。天然芳香剂包括花(百合、薰衣草、玫瑰、茉莉、橙花、依兰)、茎和叶(天竺葵、广藿香、苦橙)、水果(茴香、胡荽、香菜、杜松)、果皮(佛手柑、柠檬、橙)、根(肉豆蔻、当归、芹菜、小豆蔻、木香、虹膜、菖蒲)、木材(松木、檀香、愈创木、雪松木、花梨木)、草本植物和禾本植物(龙蒿、柠檬草、鼠尾草、百里香)、松针和树枝(云杉、冷杉、松树、矮松)、树脂和香脂(格蓬、榄香脂、安息香、没药、乳香、红没药)的提取物。还可使用动物原料,例如麝猫香和海狸香。典型的合成芳香剂化合物是酯、醚、醛、酮、醇和烃类产物。酯类芳香剂化合物实例是乙酸苄酯,异丁酸苯氧基乙酯、环己基乙酸p-叔丁酯、乙酸芳樟酯、乙酸二甲基苄基原酯(dimethyl benzyl carbinyl acetate)、乙酸苯乙酯、苯甲酸芳樟酯、甲酸苄酯、苯基甘氨酸乙基甲酯、环己基丙酸烯丙酯、丙酸苏合香酯和水杨酸苄酯。醚类包括,例如苄基乙基醚;而醛类包括,例如含有8至18个碳原子的直链烷醛、柠檬醛、香茅醛、香茅基氧基乙醛、仙客来醛、羟基香茅醛、铃兰醛和波洁红醛。适当的酮类的实例是紫罗兰酮、α-异甲基紫罗酮和甲基柏木酮。适当的醇类是茴香脑、香茅醇、丁香酚、异丁香酚、香叶醇、芳樟醇、苯乙醇和松油醇。烃类主要包括萜烯类和香脂类。然而,优选使用不同芳香剂化合物的混合物,它们一起产生令人愉快的香味。其它适当的芳香油为大多用作芳香成分的挥发性较低的精油。实例是鼠尾草油、甘菊油、丁香油、蜂花油、薄荷油、肉桂叶油、莱姆花油、杜松子油、香根草油、乳香油、白松香油、岩蔷薇油和熏衣草油。以下为单独或以混合形式优选使用的物质:佛手柑油、二氢月桂烯醇、铃兰醛、新铃兰醛、香茅醇、苯乙醇、己基肉桂醛、香叶醇、苄丙酮、仙客来醛、芳樟醇、乙氧基甲氧基环十一烷、龙涎呋喃、吲哚、二氢茉莉酮酸甲酯(hedione)、sandelice、柑橘类精油、柑橘油、橙油、乙醇酸烯丙基戊酯、cyclovertal、醒目熏衣草油、鼠尾草油、大马酮、波旁香叶油、水杨酸环己酯、Vertofix Coeur、Iso-E-Super、Fixolide NP、evernyl、iraldein gamma、苯乙酸、乙酸香叶酯、乙酸苄酯、玫瑰醚、romilat、2-乙基-己酸乙酯(irotyl)和2-叔丁基环己基乙基碳酸酯(floramat)。
S.染料
适合的染料是例如德国研究学会染料协会(Farbstoff-kommission derDeutschen Forschungsgemeinschaft)的公开物“Kosmetische ”,VerlagChemie,Weinheim,1984,页81至106中列举的适于并批准用于化妆品的物质中的任何一种。实例包括胭脂红A(C.I.16255)、专利蓝V(C.I.42051)、靛蓝(C.I.73015)、叶绿酸(C.I.75810)、喹啉黄(C.I.47005)、二氧化钛(C.I.77891)、阴丹士林蓝RS(C.I.69800)和茜草红(C.I.58000)。鲁米诺(Luminol)也可用作荧光染料。有利的着色颜料是例如二氧化钛、云母、铁氧化物(例如Fe2O3、Fe3O4、FeO(OH))和/或氧化锡。有利的染料是例如胭脂红、柏林蓝、氧化铬绿、群青和/或锰紫
式(I)化合物或其(药用)可接受的盐的抗微生物活性特别适用于防止含有水和至少一种选自组包括表面活性剂、乳化剂、增稠剂和油体,如那些对微生物生长特别敏感的组合物,微生物腐烂。优选的油体是硅油。
因此,在另一个实施方案中,本发明也涉及化妆品组合物,含有水和至少一种选自组包括表面活性剂、乳化剂、增稠剂和油体的制剂,其中该组合物进一步含有用量为0.01至约10,优选约0.02至约5并且更优选约0.05至约2重量%的至少一种式(I)化合物或其(药用)盐或上述抗微生物组合物,基于组合物总量计。
本发明的优选组合物选自用于治疗、防护、护理和清洁皮肤和/或毛发的产品或作为化妆产品,优选地,作为滞留(leave-on)产品(是指与洗去(rinse-off)产品相比,一种或多种式(I)的化合物停留在皮肤和/或毛发上持续更长的时间,从而使其保湿和/或抗老化和/或伤口治愈的促进作用更显著)。
本发明的制剂优选以乳剂形式,例如W/O(油包水)、O/W(水包油)、W/O/W(水包油包水)、O/W/O(油包水包油)乳剂、PIT乳剂、皮克林(Picking)乳剂、油含量低的乳剂、微米乳剂或纳米乳剂;溶液,例如在油(脂肪油或脂肪酸酯,特别是C6-C32脂肪酸C2-C30酯)或硅油、分散体、悬浮液、乳霜、乳液或奶液中的溶液,取决于制备方法和成分;凝胶(包括水凝胶、水分散凝胶、油凝胶);喷雾剂(例如泵喷雾剂或含有推进剂的喷雾剂)或用于擦拭化妆品的泡沫或浸渍溶液;洗涤剂,如肥皂、合成洗涤剂、洗涤液、淋浴和沐浴制剂、沐浴产品(胶囊、油剂、片剂、盐、浴盐、肥皂等);泡腾制剂、皮肤护理产品,如乳剂(如上所述)、软膏剂、糊剂、凝胶(如上所述)、油、香油、乳清、粉末(如擦脸粉、身体粉)、面膜、眉笔、唇膏、走珠、泵剂、气雾剂(发泡、非发泡或后发泡)、除臭剂和/或止汗剂、漱口水和口腔清洗剂、足部护理产品(包括去角质、除臭剂)、驱虫剂、防晒霜、晒后用品、剃须产品、须后膏、剃须前和剃须后洗剂、脱毛剂、头发护理产品,如洗发香波(包括2合1香波,去屑香波,婴儿香波,干性发质香波,浓缩香波)、护发素、生发油、生发水、染发液、造型膏、润发油、烫发和卷发药水、发胶、定型助剂(如凝胶或蜡)、头发光滑剂(护发剂、松弛剂)、染发剂如短时直接染发剂、半永久性染发剂、永久性染发、护发素、护发摩丝、眼睛护理产品、化妆、卸妆或婴儿产品。
本发明的制剂尤其优选以乳剂形式,特别是W/O、O/W、W/O/W、O/W/O乳剂形式、PIT乳剂、皮克林乳剂、油含量低的乳剂、微米乳剂或纳米乳剂、凝胶(包括水凝胶、水分散凝胶、油凝胶)、溶液,例如在油(脂肪油或脂肪酸酯,特别是C6-C32脂肪酸C2-C30酯)或硅油中的溶液、或喷雾剂(例如泵喷雾剂或具有推进剂的喷雾剂)。
辅助物质和添加剂的含量为5至99重量%,优选10至80重量%,基于制剂总量计。本领域技术人员容易根据特定产品的性质通过简单试凑法确定在各情况下所使用的化妆品或护肤用品助剂和添加剂以及芳香剂的的量。
根据本发明的化妆组合物特别地被局部施用于哺乳动物角质组织,如特别是人类皮肤或人类头皮和毛发。
本应用使用的术语“化妆组合物”涉及Rompp Lexikon Chemie,10th edition1997,Georg Thieme Verlag Stuttgart中条目"Kosmetika"下定义的化妆组合物,以及A.Domsch,"Cosmetic Compositions",Verlag fur chemische Industrie(ed.H.Ziolkowsky),4thedition,1992中公开的化妆组合物。
根据本发明的化妆组合物优选地还含有生理上可接受的介质,即与角质物质,如皮肤、粘膜、和角质纤维相容的介质。特别地,生理上可接受的介质是化妆用可接受载体。
术语化妆用可接受载体是指通常在化妆组合物中使用的所有载体和/或辅料和/或稀释剂。
在一个特别优选的实施方案中,化妆组合物是洗发香波、护发素、O/W乳液、W/O乳液或凝胶。
优选地,根据本发明的化妆组合物是液体、乳液、增稠乳液、凝胶、霜剂、奶液、软膏或糊剂形式。
根据本发明的化妆组合物具备3-10,优选4-8,最优选5-7的pH值。通过本领域已知的方法调节pH,例如使用酸如羟基酸包括乙醇酸、乳酸、苹果酸、柠檬酸和酒石酸或碱如氢氧化钠或钾或氢氧化铵及其混合物。
优选地,在根据本发明的组合物中使用至少0.0001重量%,例如0.01-1重量%,特别是0.01至0.5重量%的柠檬酸或氢氧化钠或钾进行pH调节。
根据本发明的化妆组合物特别是皮肤护理制剂、功能制剂和/或毛发护理制剂,特别是皮肤或毛发护理制剂。
皮肤护理制剂的实例特别是光保护制剂、抗老化制剂、用于处理光老化的制剂、身体油、身体乳液、身体凝胶、治疗霜剂、护肤软膏、保湿剂如保湿凝胶或保湿喷雾、面部和/或身体保湿剂、仿晒剂(即用于人类皮肤的人工/无阳光晒黑和/或变棕),例如自晒黑霜剂以及皮肤美白制剂。
制剂也可以含有最多约99重量%,优选5至80重量%的水,基于制剂的总量计。
清洁剂组合物
本发明的另一个实施方案涉及一种清洁剂组合物,其通常含有有效量的至少一种芳香酯或酰胺衍生物或其与其他防腐剂和/或抗微生物制剂的混合物,其含量为约0.01至约10,优选约0.02至约5并且更优选约0.05至约2重量%,基于总组合物计。
根据本发明的清洁剂组合物可以含有任何一般用于此类组合物的成分,例如阴离子、非离子、阳离子、两性或两性离子(辅助)表面活性剂、有机溶剂、助洗剂、酶和其他助剂如驱污剂、增稠剂、着色剂和芳香剂等。
阴离子辅助表面活性剂
优选地,磺酸盐类表面活性剂,烷(烯)基磺酸盐、烷氧基化烷(烯)基磺酸盐、酯磺酸盐和/或肥皂用作阴离子表面活性剂。适当的磺酸盐类表面活性剂有利的是C9-13烷基苯磺酸盐、烯烃磺酸盐,即烯基磺酸盐和羟基烷基磺酸盐的混合物,以及二磺酸盐,例如它们是通过用气态的三氧化硫磺化末端为双健或中部为双键的C12-18单烯烃,并随后碱水解或酸水解磺化产品而获得的。
(i)烷(烯)基磺酸盐。优选的烷(烯)基磺酸盐是C12-C18脂肪醇,例如椰油醇、牛脂醇、月桂醇、肉豆蔻醇、鲸蜡醇或硬酯醇或C8-C20羰基合成醇的磺酸半酯以及这些长链仲醇半酯的碱盐并特别是钠盐。也优选石化生产的含有合成直链烷基的所述长链烷(烯)基磺酸盐。基于洗衣性能特别优选C12-C16烷基磺酸盐和C12-C15烷基磺酸盐以及C14-C15烷基磺酸盐和C14-C16烷基磺酸盐。Shell Oil公司的商品名为DANTM的2,3-烷烃磺酸盐也是适当的阴离子表面活性剂。
(ii)烷(烯)基醚磺酸盐。同样适当的是与1至6摩尔环氧乙烷乙氧基化的直链或支链C7-C21烷醇,如平均3.5摩尔环氧乙烷(EO)的2-甲基C9-C11醇或具有1至4个EO的C12-C18脂肪醇的硫酸单酯。
(iii)酯磺酸盐。同样适当的是α-磺基脂肪酸(酯磺酸盐),例如,氢化椰油酸、棕榈酸或牛脂酸的α-磺化甲酯。
(iv)皂类。特别地皂可以是其他阴离子表面活性剂。特别适当的饱和脂肪酸皂,如月桂酸盐、肉豆蔻酸盐、棕榈酸盐、硬脂酸盐、氢化芥酸盐和山嵛酸盐,以及特别是源自天然脂肪酸的盐,如椰油脂肪酸盐、棕榈仁脂肪酸盐或牛油脂肪酸盐的皂混合物。特别优选这些皂混合物由50至100重量%的饱和C12-C24脂肪酸盐和0至50重量%的油酸皂构成。
(v)醚羧酸。另一类阴离子表面活性剂是醚羧酸,其在碱催化剂存在下通过使用氯乙酸钠处理脂肪醇乙氧基化物得到。其通式为RO(CH2CH2O)pCH2COOH,R=C1-C18并且p=0.1至20。醚羧酸对水硬度不灵敏并且具备优异的表面活性剂性能。
B.非离子(辅助)表面活性剂
(i)醇烷氧基化物。加入的非离子表面活性剂优选是烷氧基化和/或丙氧基化,特别是优选每摩尔醇含有8-18个碳原子以及平均1至12摩尔环氧乙烷(EO)和/或1至10摩尔环氧丙烷(PO)的伯醇。特别优选乙氧基化度为2至10,优选3至8,和/或丙氧基化度为1至6,优选1.5至5的C8-C16-醇烷氧基化物,有利的是乙氧基化物和/或丙氧基化物C10-C15-醇烷氧基化物,特别是C12-C14醇烷氧基化物。所述的乙氧基化度和丙氧基化度构成统计平均值,对于特定产物其可能为整数或分数。优选的醇乙氧基化物和丙氧基化物具有窄同系物分布(窄范围乙氧基化物/丙氧基化物,NRE/NRP)。除了这些非离子表面活性剂之外,也可使用具有大于12EO的脂肪醇。其实例为具有14EO、16EO、20EO、25EO、30EO或40EO的(牛油)脂肪醇。
(ii)烷基糖苷此外,作为额外的非离子表面活性剂,可以加入满足通式RO(G)x的烷基糖苷,例如作为化合物,特别是与非离子表面活性剂一起,其中R为直链或甲基-支化,尤其是2-甲基支化的,具有8至22,优选12至18个碳原子的脂族基团,G代表具有5或6个碳原子的单糖单元,优选葡萄糖。糖基化度x,其定义了单糖苷和低聚糖苷的分布,为1至10,优选1.1至1.4之间的数值。
(iii)脂肪酸酯烷氧基化物。另一类优选的非离子表面活性剂,其或作为单独的非离子表面活性剂或与其他非离子表面活性剂,特别是与烷氧基化脂肪醇和/或烷基糖苷结合使用,是烷氧基化,优选乙氧基化或乙氧基化和丙氧基化脂肪酸烷基酯,优选烷基链中含有1至4个碳原子,更特别地是,例如在日本专利申请中JP-A-58/217598记载的或优选通过国际专利申请WO-A-90/13533记载的方法制备的脂肪酸甲酯。特别优选含有平均3至15个EO,特别是含有约5至12个EO的C12-C18脂肪酸甲酯。
(iv)胺氧化物。胺氧化物类型的非离子表面活性剂,如N-椰油烷基-N,N-二甲基胺氧化物和N-牛油脂烷基-N,N-二羟乙胺氧化物,以及脂肪酸链烷醇酰胺类型也是适当的。这些非离子表面活性剂的量优选不大于乙氧基化脂肪醇的量,尤其是不大于其一半的量。
(v)双子表面活性剂。其他的表面活性剂是所谓的双子表面活性剂。通常这类化合物是指每分子含有两个亲水基团和两个疏水基团的化合物。这些基团通常通过“间隔子”相互分隔。这种间隔子通常是碳链,其长度应足以使亲水基团有充足的距离能够相互独立的起作用。这类表面活性剂的特征通常在于非常小的临界胶束浓度并且极大地降低水的表面张力。然而特殊情况下双子表面活性剂不仅指二聚也指三聚表面活性。适当的双子表面活性剂是例如德国专利申请DE 4321022 A1的硫酸化羟基混合醚,或根据国际专利申请96/23768 A1的二聚醇-双-和三聚醇-三-硫酸盐和-醚硫酸盐。根据德国专利申请DE 19513391A1,封端的二聚和三聚混合醚的特征是其双官能性和多官能性。也可以使用如那些记载于国际专利申请WO 95/19953 A1、WO 95/19954 A1和WO 95/19955 A1中的双子聚羟基脂肪酸酰胺或聚羟基脂肪酸酰胺。
C.辅助表面活性剂
(i)四烷基季铵盐。水溶液中阳离子活性表面活性剂含有解离阳离子中表面活性所需的疏水高分子基团。阳离子表面活性剂的重要代表是通式(R1R2R3R4N+)X-的四烷基季铵盐。其中R1代表C1-C8烷(烯)基,R2、R3和R4相互独立地代表含有1至22个碳原子的烷(烯)基。X是反离子,优选自卤素、烷基硫酸盐和烷基碳酸盐。特别优选阳离子表面活性剂,其中氮原子被两个长酰基和两个短烷(烯)基取代。
(ii)酯季铵盐。特别用作本发明的辅助表面活性剂的阳离子表面活性剂由所述酯季铵盐代表。酯季铵盐通常被理解为季铵化的脂肪酸三乙醇胺酯盐。这些是可以通过制备有机化学的相关方法得到的已知化合物。可以参考国际专利申请WO 91/01295A1,其中三乙醇胺在次磷酸的存在下使用脂肪酸部分酯化,将空气通入反应混合物,随后使用硫酸二甲酯或环氧乙烷整体季铵化。此外,德国专利DE 4308794 C1记载了制备固体酯季铵盐的方法,其中三乙醇胺酯的季铵化在适当分散剂,优选脂肪醇的存在下进行。
根据本发明适当使用的酯季铵盐的典型实例是一种产品,其酰基成分源自对应于式RCOOH的单羧酸,其中RCO是含有6至10个碳原子的酰基,并且氨基成分是三乙醇胺(TEA)。这类单羧酸的实例是己酸、辛酸、癸酸及其技术混合物,如例如所谓的头分馏脂肪酸。优选使用的酯季铵盐,其酰基成分源自含有8至10个碳原子的单羧酸。其他酯季铵盐是那些产物,其酰基成分源自二元碳酸如丙二酸、琥珀酸、马来酸、富马酸、戊二酸、山梨酸、庚二酸、壬二酸、癸二酸和/或十二烷二酸,但优选己二酸。总之优选其酰基源自含有6至22个碳原子的单羧酸和己二酸的混合物的酯季铵盐。在最终的酯季铵盐中单羧酸和二元羧酸的摩尔比为1:99至99:1并且优选50:50至90:10并且特别是70:30至80:20。除了季铵化脂肪酸三乙醇胺酯盐,其他适当的酯季铵盐是单/二元羧酸混合物与二乙醇烷基胺或1,2-二羟基丙基二烷基胺。酯季铵盐可以由脂肪酸和相应的甘油三酯与相应二元羧酸混合得到。一种这类方法,其可以为被看为相关现有技术的代表,记载于欧洲专利EP 0750606 B1。为了生产季铵化酯,单和二元羧酸和三乙醇胺的混合物—基于可用的羧基功能—摩尔比可以为1.1:1至3:1。考虑到酯季铵盐的性能,已经证明特别有利的比例是1.2:1至2.2:1,并且优选1.5:1至1.9:1。优选的酯季铵盐是平均酯化度为1.5至1.9的单、二和三酯的技术混合物。
D.两性或两性离子辅助表面活性剂
(i)内铵盐。两性或两性离子表面活性剂具备多种可以在水溶液中离子化的官能团并从而—取决于介质条件—赋予化合物阴离子或阳离子属性(参见DIN 53900,1972年7月)。接近等电点(约pH4),两性表面活性剂形成内盐,从而在水中变得弱溶解或不溶。两性表面活性剂细分为两性物和内铵盐,后者在溶液中表现为两性离子。两性物是两性的电解质,即,同时具有酸性和碱性亲水基团,并因此依赖于条件表现为酸或表现为碱的化合物。尤其,内铵盐是已知的表面活性剂,其主要通过胺化合物的羧基烷基化,优选羧基甲基化生产。起始原料优选与卤代羧酸或其盐,尤其是氯乙酸钠缩合,每摩尔内铵盐形成一摩尔盐。不饱和羧酸,例如丙烯酸的加成也是可能的。适合的内铵盐的例子是仲胺,尤其是叔胺的羧基烷基化产物,其对应于通式R1R2R3N-(CH2)qCOOX,其中R1是具有6-22个碳原子的烷基基团,R2是氢或含有1-4个碳原子的烷基基团,R3是含有1-4个碳原子的烷基基团,q是1-6的数,以及X是碱和/或碱土金属或铵。典型的例子是己基甲基胺、己基二甲基胺、辛基二甲基胺、癸基二甲基胺、C12/14-椰子烷基二甲基胺、肉豆蔻基二甲基胺、鲸蜡基二甲基胺、硬脂基二甲基胺、硬脂基乙基甲基胺、油基二甲基胺、C16/18-牛脂烷基二甲基胺和它们的工业混合物,以及特别是十二烷基甲基胺、十二烷基二甲基胺、十二烷基乙基甲基胺和其工业混合物的羧基甲基化产物。
(ii)烷基酰胺基内铵盐。其它合适的内铵盐是酰胺基胺的羧基烷基化产物,其对应于通式R1CO(R3)(R4)-NH-(CH2)p-N-(CH2)qCOOX,其中R1CO是具有6-22个碳原子以及0或1至3个双键的脂族酰基基团,R2是氢或具有1-4个碳原子的烷基基团,R3是具有1-4个碳原子的烷基基团,P是1-6的数,q是1-3的数,和X是碱和/或碱土金属或铵。典型的例子是具有6-22个碳原子的脂肪酸,例如己酸、辛酸、癸酸、月桂酸、肉豆蔻酸、棕榈酸,棕榈油酸、硬脂酸、异硬脂酸、油酸、反油酸、岩芹酸、亚油酸、亚麻酸、桐酸、花生四烯酸、顺(9)-二十碳烯酸、山嵛酸、芥酸和它们的工业混合物与N,N-二甲基氨基乙胺、N,N-二甲基氨基丙胺、N,N-二乙基氨基乙胺和N,N-二乙基氨基丙胺的反应产物,该产物与氯乙酸钠缩合。市售可得产品包括K和PK(Cognis Deutschland GmbH&Co.,KG)以及Betaine(Goldschmidt)。
(iii)咪唑啉。用于本发明目的的内铵盐的其它合适的起始原料是咪唑啉。这些物质也是已知的并且可以例如通过1或2摩尔的C6-C22脂肪酸与多官能胺例如氨基乙基乙醇胺(AEEA)或二亚乙基三胺的环化缩合获得。相应的羧基烷基化产物是不同的开链内铵盐的混合物。典型的实例是以上提及的脂肪酸与AEEA的缩合产物,优选基于月桂酸的咪唑啉,其随后用氯乙酸钠内铵盐化。市售可得产品包括G(Cognis Deutschland GmbH&Co.,KG)。
本发明的组合物中(辅助)表面活性剂的用量优选0.1至90重量%,特别是10至80重量%,并且特别优选20至70重量%。
E.有机溶剂
液态轻垢或重垢型洗涤剂可以含有有机溶剂,优选那些与水互溶的。为此用量为0至90重量%,优选0.1至70重量%,特别是0.1至60重量%的聚二醇、醚、醇、酮、酰胺和/或酯优选用作有机溶剂。优选低分子量极性物质,如甲醇、乙醇、碳酸丙烯酯、丙酮、丙酮基丙酮、二丙酮醇、乙酸乙酯、2-丙醇、乙二醇、丙二醇、甘油、二乙二醇、二丙二醇单甲醚和二甲基甲酰胺或其混合物。
F.酶
适当的酶特别包括水解酶类如蛋白酶、酯酶、脂肪酶和起到分解脂肪作用的酶、淀粉酶、纤维素酶或其他糖苷水解酶以及所述酶的混合物。所有这些水解酶在洗涤中用于移除污迹如含有蛋白、脂肪或淀粉的污迹和变色。此外纤维素酶和其他糖苷水解酶通过移除毛球和微纤维用于保持织物的颜色和提高柔软度。也可以使用氧化还原酶用于漂白和防止染料转移。特别合适的是由细菌菌株或真菌如枯草杆菌(Bacillus subtilis)、地衣芽孢杆菌(Bacillus licheniformis)、灰色链霉菌(Streptomyceus griseus)和特异腐质霉(Humicolainsolens)得到的酶活性物。优选使用枯草杆菌蛋白酶类的蛋白酶并且特别是由迟缓芽孢杆菌(Bacillus lentus)得到的蛋白酶。特别重要的是酶混合物,如由蛋白酶和淀粉酶或蛋白酶和酯酶,特别是起到分解脂肪作用的酶或蛋白酶和纤维素酶构成的混合物,或者由纤维素酶和酯酶,特别是起到分解脂肪作用的酶构成的混合物,或者蛋白酶、淀粉酶和酯酶特别是起到分解脂肪作用的酶或蛋白酶、酯酶特别是起到分解脂肪作用的酶和纤维素酶构成的混合物,然而特别是含有蛋白酶和/或酯酶的混合物以及含有起到分解脂肪作用的酶的混合物。这类起到分解脂肪作用的酶是已知的角质酶。在有些情况下过氧化酶或氧化酶也合适。适当的淀粉酶特别包括α-淀粉酶、异淀粉酶、支链淀粉酶和果胶酶。作为淀粉酶优选使用纤维二糖水解酶、内切葡聚糖酶和也被称为纤维素酶的p-葡糖苷酶及其混合物。由于不同的纤维素酶类型通过CMCase-和Avicelase-活性区别,可以通过有目的的混合纤维素酶调节想要的活性。酶或酶混合物的含量可以是例如约0.1至5重量%并且优选0.1至约3重量%。
G.助洗剂
(i)沸石。含有结合水的细晶合成沸石,优选沸石A和/或沸石P可以用作助洗剂。特别优选的沸石P是沸石MAP.RTM.(Crosfield公司的市售产品)。然而,沸石X以及沸石A、X、Y和/或P的混合物也是适合的。特别优选以商品名Vegobond(Condea Augusta S.p.A.的市售产品)可得的沸石X和沸石A的共结晶硅铝酸钠/钾。优选地可使用喷雾干燥粉末状的沸石。在以悬浮液形式加入沸石的情况下,可添加少量的非离子表面活性剂作为稳定剂,例如基于沸石计1至3重量%的、具有2至5个环氧乙烷基团的乙氧基化C12-C18脂肪醇、具有4至5个环氧乙烷基团的C12-C14脂肪醇或乙氧基化的异十三烷醇。合适的沸石具有的平均颗粒尺寸小于10微米(测量方法:体积分布Coulter计数器),并优选含有18至22重量%,更优选20至22重量%的结合水。此外,磷酸盐也可用作助洗剂。
(ii)层状硅酸盐。磷酸盐和沸石的适当替代品或部分替代品是结晶、层状硅酸钠。这类结晶层状硅酸钠记载于,例如欧洲专利申请EP 0164514A1。优选的结晶层状硅酸盐是通过,例如国际专利申请WO 91/08171A1中记载的方法得到的那些。
(iii)无定型硅酸盐。优选的助洗剂也包括模数(Na2O:SiO2比例)为1:2至1:3.3,优选1:2至1:2.8并且更优选1:2至1:2.6的无定型硅酸钠,其具有延时溶解和多次循环洗涤的特性。与传统的无定形硅酸钠相比这种延迟溶解特性可由各种方式获得,例如通过表面处理、复合、密实/压缩或通过过度干燥而获得。在本发明的范围内,术语“无定形”也指“X射线无定形”。换句话说在X射线衍射试验中,硅酸盐没有产生任何晶态物质的典型X射线反射,而是充其量具有一个或多个散射X射线的峰值,其具有几度衍射角的宽度。但是,当硅酸盐颗粒在电子衍射试验中产生不明显或者甚至清晰的衍射峰值时,可以实现特别好的助洗剂特性。这可理解为产品具有10至几百纳米的微晶范围,其中优选该值最大是50纳米,尤其最大为20纳米。在德国专利申请DE 4400024 A1中公开了与常规水玻璃相比,同样具有延迟溶解特性的这类X射线无定形硅酸盐。特别优选的是压缩/密实的无定形硅酸盐、复合的无定形硅酸盐和过度干燥的X射线无定形硅酸盐。
(iv)磷酸盐。也可使用通常已知的磷酸盐作为助洗剂,只要这种使用不会由于生态方面的原因而应当避免。特别合适的是正磷酸、焦磷酸以及尤其是三聚磷酸盐的钠盐。其含量通常不大于25重量%,优选不大于20重量%,基于最终组合物计。在有些情况下特别是三聚磷酸盐,在最大为10重量%的低含量下,基于最终组合物计,与其他助洗剂结合已经表现出二次洗涤功率的增效改善。磷酸盐的优选用量低于10重量%,特别是0重量%。
H.辅助助洗剂
(i)聚羧酸。有用的有机辅助助洗剂是,例如可以其聚羧酸钠盐形式使用的聚羧酸,其中聚羧酸是指带有多于一个酸官能的羧酸。包括例如柠檬酸、己二酸、琥珀酸、戊二酸、苹果酸、酒石酸、马来酸、富马酸、糖酸、氨基羧酸、氨三乙酸(NTA)及其衍生物和混合物。优选的盐是聚羧酸如柠檬酸、己二酸、琥珀酸、戊二酸、酒石酸、糖酸的盐及其混合物。
(ii)有机酸。也可以使用酸本身。除了其助洗作用,酸通常也具有酸化成分的作用,因此可以在洗涤剂或清洁组合物中建立相对低和温和的pH值。特别可以提到柠檬酸、琥珀酸、戊二酸、己二酸、葡糖酸及其混合物。其他适当的酸化剂是已知的pH调节剂如碳酸氢钠和硫酸氢钠。
(iii)聚合物。特别适合的聚合物类辅助助洗剂是聚丙烯酸酯,其优选分子量为2000至20000g/mol。基于其出色的溶解性,本组中优选摩尔量为2000至10000g/mol,且特别优选3000至5000g/mol的短链聚丙烯酸酯。适当的聚合物也可以包括部分或完全由乙烯醇单元或其衍生物构成的物质。
其他适当的共聚羧酸盐特别是丙烯酸与甲基丙烯酸以及丙烯酸或甲基丙烯酸与马来酸的共聚物。已经证明丙烯酸与马来酸的共聚物,其含有50至90重量%的丙烯酸与50至10重量%的马来酸,特别合适。其相对分子量,基于自由酸计,通常为2000至70000g/mol,优选20000至50000g/mol并且尤其是30000至40000g/mol。(共)聚羧酸盐可以水溶液或优选以粉末加入。为了改善水溶解度,聚合物也可以含有烯丙基磺酸单体,如例如EP 0727448B1中的烯丙氧基苯磺酸和甲基烯丙基磺酸。
特别优选含有多于两种不同单体单元的可生物降解聚合物,实例是DE 4300772A1中含有丙烯酸盐和马来酸盐,以及乙烯醇或乙烯醇衍生物作为单体的那些,或含有丙烯酸和2-烷基烯丙基磺酸盐,以及糖衍生物作为单体的那些。其他优选的共聚物是记载于德国专利申请DE 4303320 A1和DE 4417734 A1中的那些并且优选包括丙烯醛和丙烯酸/丙烯酸盐或丙烯醛和乙酸乙烯酯作为单体。
同样地,其他优选的助洗剂是聚合物类氨基二羧酸,其盐或其前体物质。特别优选的是德国专利申请DE 19540086 A1中公开的聚天冬氨酸或其盐和衍生物,它们除了辅助助洗剂性能也具备漂白稳定作用。
其它适合的助洗剂是聚缩醛,它们是通过将二醛与具有5至7个碳原子和至少3个羟基的多羟基羧酸进行反应而获得的,如记载于欧洲专利申请EP 0280223A1。优选的聚缩醛是由二醛例如乙二醛、戊二醛、对苯二甲醛及其混合物与多羟基羧酸,例如葡糖酸和/或葡庚糖酸获得的。
(iv)碳水化合物。其它合适的有机辅助助洗剂是糊精,例如碳水化合物的低聚物或聚合物,它们是通过淀粉部分水解而获得的。水解可以常规方法,例如酸催化或酶催化方法进行。优选的是平均摩尔量是400至500000g/mol的水解产物。优选一种具有葡萄糖当量(DE)为0.5至40,更特别是2至30的多糖,其中DE是与DE为100的葡萄糖相比,该多糖还原作用的可接受量度。可以使用DE是3至20的麦芽糊精和DE是20至37的干燥葡萄糖糖浆,以及所谓的具有2000至30000g/mol的较高分子量的黄糊精和白糊精。优选的糊精记载于英国专利申请94 19 091。
这类糊精的氧化衍生物涉及的是糊精与氧化剂的反应产物,其能至少使糖环的醇官能团氧化成羧酸官能团。这类氧化糊精和用于其制备的方法由例如欧洲专利申请EP0232202 A1已知。一种在糖环的C6上氧化的产物是特别优选的。
(v)其它适合的辅助助洗剂是氧代二琥珀酸酯和二琥珀酸酯(Disuccinaten)的其它衍生物,优选乙基二胺二琥珀酸酯。优选使用钠盐或镁盐形式的乙二胺-N,N'-二琥珀酸(EDDS),其合成记载于例如US 3,158,615。在本文中特别优选的是甘油二琥珀酸酯和甘油三琥珀酸酯,如记载于US 4,524,009。在含有沸石和/或含有硅酸盐的制剂中加入量为3至15重量%。
(vi)内酯。其它可使用的有机辅助助洗剂例如是乙酰化的羟基羧酸或其盐,其任选也可以内酯的形式存在,且其含有至少4个碳原子,至少1个羟基以及至多2个酸基。这类辅助助洗剂记载于例如国际专利申请WO 95/20029 A1。
I.驱污剂
此外,组合物还可含有对织物的去油和去脂肪有积极作用的其它组分(所谓的驱污剂)。当织物脏污并已经用含有这种含有去油和去脂肪组分的强效洗涤剂清洗时,这种效果特别明显。优选的去油和去脂肪组分包括例如非离子纤维素醚,如甲基纤维素和甲基羟丙基纤维素,其含有基于非离子纤维素醚计15至30重量%的甲氧基和1至15重量%的羟丙氧基,以及由现有技术已知的邻苯二甲酸和/或对苯二甲酸或其衍生物的聚合物,特别是苯二甲酸乙二醇酯和/或聚乙二醇对苯二甲酸酯的聚合物或其阴离子和/或非离子改性衍生物。特别优选的是邻苯二甲酸聚合物和对苯二甲酸聚合物的磺化衍生物。
J.无机盐
组合物的其他适当成分是水溶性无机盐如碳酸氢盐、碳酸盐、无定型硅酸盐或其混合物;特别使用碱金属碳酸盐和无定型硅酸盐,主要是Na2O:SiO2摩尔比为1:1至1:4.5,优选1:2至1:3.5的硅酸钠。优选的组合物含有碱金属盐、助洗剂和/或辅助助洗剂,优选碳酸钠、沸石、晶体层状硅酸钠和/或柠檬酸三钠,含量为0.5至70重量%,优选0.5至50重量%,特别是0.5至30重量%的无水物质。
K.泡沫抑制剂
尤其是在自动洗涤过程中可以向组合物中有利的加入常规泡沫抑制剂。适当的泡沫抑制剂包括例如天然或合成皂,其含有大量C18-C24脂肪酸。非表面活性类型的泡沫抑制剂是,例如有机多分子硅醚以及其与微细,任选硅烷化二氧化硅的混合物,以及石蜡、蜡、微晶蜡以及其与硅烷化二氧化硅或二硬脂酰二亚乙基二胺的混合物。优选使用各种泡沫抑制剂的混合物,例如硅酮、石蜡或蜡的混合物。优选地,泡沫抑制剂,尤其是含有硅酮和/或石蜡的泡沫抑制剂,负载到颗粒,水溶性或可分散载体材料上。尤其是在这种情况下优选石蜡和二硬脂酰二亚乙基二胺的混合物。
L.螯合剂
多磷酸盐可被认为是螯合剂或稳定剂,特别是用于对重金属离子敏感的过氧化合物和酶。例如1-羟基乙烷-1,1-二磷酸钠盐、二亚乙基三胺五亚甲基膦酸钠或乙二胺四亚甲基膦酸钠的用量为0.1至5重量%。
M.变褐抑制剂
变褐抑制剂的任务是,使由纤维脱离的污物保持悬浮在清洗液体中,并从而避免污物的再次吸附。为此大部分有机天然的水溶性溶胶,例如(共)聚羧酸、胶料、明胶的盐、淀粉或纤维素的醚羧酸或醚磺酸盐、或纤维素或淀粉的酸性硫酸酯的盐是适合的。同样适用于此目的的是含有酸性基团的水溶性聚酰胺。此外可溶解的淀粉制剂等,例如水解淀粉、醛淀粉等可以用作上述淀粉产品。同样可以使用的是聚乙烯吡咯酮。然而优选纤维素醚是如羧甲基纤维素(钠盐)、甲基纤维素、羟烷基纤维素和混合醚如甲基羟乙基纤维素、甲基羟丙基纤维素、甲基羧甲基纤维素及其混合物,以及聚乙烯吡咯烷酮,使用量为0.1至5重量%,基于组合物计。
N.荧光增白剂和UV-吸收剂
组合物可以含有例如,二氨芪二磺酸衍生去及其碱金属盐作为荧光增白剂。适当的荧光增白剂是例如4,4'-双(2-苯胺基-4-吗啉基-1,3,5-三嗪基-6-氨基)芪-2,2'-二磺酸或类似结构的化合物,该化合物携带有二乙醇氨基、甲基氨基、苯氨基或2-甲氧基乙基氨基以代替吗啉基。此外可以存在取代的联苯苯乙烯基类增白剂,例如4,4’-双(2-磺基苯乙烯基)-联苯、4,4’-双(4-氯-3-磺基苯乙烯基)-联苯或4-(4-氯苯乙烯基)-4’-(2-磺基苯乙烯基)-联苯的碱金属盐。也可以使用上述荧光增白剂的混合物。
此外可以加入UV吸收剂。UV吸收剂是对紫外线辐射具备出色吸收性能的化合物,其作为UV稳定剂还可以改善用于纺织纤维的颜料和染料的光稳定性以及通过防止UV辐射渗透过纤维保护纤维产品穿戴者的皮肤。通常高效的无辐射惰化化合物是由羟基和/或烷氧基取代,特别是2位和/或4位的二苯酮的衍生物。同样适当的是取代的苯并三唑,3位苯基取代并任选2位氰基取代的丙烯酸酯(肉桂酸衍生物)、水杨酸酯、有机Ni配合物、以及天然产物如络合物以及天然产物如伞形酮以及本体尿刊酸。在优选实施方案中UV吸收剂吸收UV-A和UV-B辐射以及可能的UV-C辐射并再次放射蓝光波长的光,使其额外地具有光学增亮效果。优选的UV吸收剂含有三嗪衍生物,例如羟基芳基-1,3,5-三嗪、磺化1,3,5-三嗪、o-羟苯基苯并三唑和2-芳基-2H-苯并三唑以及双(苯胺基三嗪基-氨基)芪二磺酸及其衍生物。也可以使用紫外吸收染料如二氧化钛作为UV吸收剂。
O.增稠剂
组合物也可以含有常规增稠剂和抗沉积组合物以及粘度调节剂如聚丙烯酸酯、聚羧酸、多糖及其衍生物、聚氨酯、聚乙烯吡咯烷酮、蓖麻油衍生物、多胺衍生物如季铵化和/或乙氧基化六亚甲基二胺及其混合物。优选的组合物粘度小于10,000mPa*s,使用Brookfield粘度计在20℃的温度和50min-1剪切速率下测定。
P.芳香剂和着色剂
组合物可以含有其他典型洗涤剂和清洗组合物成分如芳香剂和/或着色剂,其中优选在洗涤纤维上不留下或仅留下不显著着色的任何着色剂。加入着色剂的总量优选小于1重量%,优选低于0.1重量%,基于组合物计。组合物也可以含有白色染料如TiO2。
食品组合物
本发明的另一个实施方案涉及一种食品组合物,其含有有效量的至少一种芳香酯或酰胺衍生物或其与其他防腐剂和/或抗微生物制剂的混合物,其含量为约0.01至约10,优选约0.02至约5并且更优选约0.05至约2重量%,基于总组合物计。
根据本发明的食品组合物是任何适用于消费并用于营养或享受目的的制剂或组合物,以及旨在被引入人类或动物口腔并在其中停留一段时间并随后被食用的产品(例如即食食品或饲料,见下文)或被由口腔移除的产品(例如口香糖)。这类产品包括任何在加工、部分加工或未加工状态下被人或动物消化的任何物质或产物。它们也包括在口服消费产品生产、制备或处理过程中加入并旨在引入人或动物口腔的物质。
根据本发明的食品组合物也包括在未改变、处理或制备状态下被人或动物吞下并消化的物质;在这方面本发明的口服消费产品也包括其他同时被吞食或预期被吞食的肠衣、糖衣或其他胶囊。表述“口服消费产品”是指即食食品和饲料,也就是对于味道重要的物质已经完成的食品和饲料。表述“即食食品”和“即食饲料”也包括饮料以及固体或半固体即食食品或饲料。可以提及的实例是冷冻产品,其在食用前必须解冻并加热至食用温度。产品如酸奶或冰激凌以及口香糖或硬焦糖也属于即食食品或饲料。
根据本发明优选的食品组合物也包括“半成产品”。在本发明中半成产品是指口服消费产品,其由于高含量的香料和味道赋予物质不适用作即食口服产品(特别是食品或饲料)。半成产品仅通过与至少一种其他成分混合(例如通过减少所述香料或味道赋予物质的浓度)并且任选进一步加工步骤(例如加热、冷冻)转化为即食口服产品(特别是食品或饲料)。半成产品的实例此处提到。
本发明的食品组合物优选包含一种或多种用于营养或享受目的的制剂。这特别包括(低卡路里)烘焙产品(例如面包、干饼干、蛋糕、其他烘烤产品)、糕饼(例如巧克力、巧克力棒、其他棒状产品、水果软糖、糖衣片、硬的和软的焦糖、口香糖)、无醇饮料(例如可可、咖啡、绿茶、红茶、富含(绿、红)茶提取物的(绿、红)茶饮品、rooibos茶、其他草本茶、含有水果的软饮、等张饮料、清爽饮料、甜美饮料(nectars)、水果和蔬菜果汁、水果或蔬菜果汁制品)、速溶饮料(例如速溶可可饮料、速溶茶饮料、速溶咖啡饮料)、肉质品(例如火腿、新鲜香肠或生香肠制品、五香或腌制的新鲜或腌肉制品)、蛋或蛋制品(干蛋、蛋白、蛋黄)、谷物制品(例如早餐谷物、麦片棒、预煮即食米饭制品)、奶制品(例如全脂或低脂或脱脂奶饮料、米粉布丁、酸奶、克菲尔(kefir)、奶油奶酪、软奶酪、硬奶酪、干燥奶粉、乳清、黄油、白脱牛奶、含有部分或全部水解乳蛋白的制品)、由大豆蛋白或其他大豆馏分得到的制品(例如豆奶和由其制得的制品、含有分离的或酶加工的大豆蛋白的饮料、含有大豆粉的饮料、含有大豆卵磷脂的制品、发酵产品如豆腐或豆豉或由其制得的制品和与水果制品以及任选香料的混合物)、水果制品(例如果酱、果汁冰糕(sorbets)、蜜饯、水果馅料)、蔬菜制品(例如番茄酱、调味汁、干燥蔬菜、冷冻蔬菜、预煮蔬菜、熬煮蔬菜)、小吃(例如烤制或炸制薯片或土豆球产品、玉米或花生为主的挤出物)、脂肪或油基制品或其乳液(例如蛋黄酱、加料蛋黄酱、调料、各个均为全脂或低脂)、其他即食菜品和汤(例如汤粉、速溶汤粉、预煮汤)、香料、香料混合物以及特别是在例如小吃领域使用的佐料、甜味剂制品、片剂或袋剂、其他用于将饮料或其他食品调成甜味或调白的制品。本发明范围内的制品也可以半成品的形式用于生产其他用于营养或享受目的的制品。本发明范围内的制品也可以胶囊、片剂(未包衣和包衣片剂,例如肠溶衣)、糖衣片、颗粒、丸剂、固体混合物、液体相中分散体的形式、乳液形式、粉末形式、溶液形式、浆剂或其他可以被吞食或咀嚼的制剂的形式,以及食品添加剂的形式。
制剂可以为胶囊、片剂(未包衣和包衣片剂,例如肠溶衣)、糖衣片、颗粒、丸剂、固体混合物、液体相中分散体的形式、乳液形式、粉末形式、溶液形式、浆剂或其他可以被吞食或咀嚼的制剂的形式,例如食品添加剂的形式。
半成品通常用于生产用于营养或享受目的的即用或即食制剂。
用于营养或享受目的的即食制剂或半成品制品的其他成分可以是用于食品或享受食品的常规底物、辅助物质和添加剂,例如水、新鲜或加工的蔬菜或动物为主或生料混合物(例如生的、烘烤、干燥、发酵、熏制和/或煮制肉类、骨头、软骨、鱼、蔬菜、草药、坚果、蔬菜汁、蔬菜泥或其混合物)、易消化或不易消化的碳水化合物(例如蔗糖、麦芽糖、果糖、葡萄糖、糊精、直链淀粉、支链淀粉、菊粉、木聚糖、纤维素、塔格糖)、糖醇(例如山梨糖醇、赤藻糖醇)、天然或硬化脂肪(例如牛脂、猪油、棕榈脂、椰子油、氢化植物脂肪)、油(例如向日葵油、花生油、玉米油、橄榄油、鱼油、豆油、芝麻油)、脂肪酸或其盐(例如硬脂酸钾)、蛋白或非蛋白氨基酸和相关化合物(例如γ-氨基丁酸、牛磺酸)、肽(例如谷胱甘肽)、天然或加工蛋白质(例如明胶)、酶(例如肽酶)、核酸、核苷酸、令人不愉快味道印象的味道矫正剂、用于其它通常不是令人不愉快味道印象的其它味道调节剂、其它味道调节物质(例如环己六醇磷酸酯、核苷酸如鸟苷单磷酸盐、腺苷单磷酸盐或其它物质,如谷氨酸钠或2-苯氧基丙酸)、乳化剂(例如卵磷脂、甘油二酯、阿拉伯胶)、稳定剂(例如角叉菜胶、藻酸盐)、防腐剂(例如苯甲酸及其盐、山梨糖酸及其盐)、抗氧化剂(例如生育酚、抗坏血酸)、螯合剂(例如柠檬酸)、有机或无机酸(例如乙酸、磷酸)、苦味素(例如奎宁、咖啡因、柠檬苦素、苦龙胆脂苷、律草酮(humolone)、蛇麻酮(lupolone)、儿荼酚、鞣酸)、防止酶促褐变的物质(例如亚硫酸盐、抗坏血酸)、醚油、植物提取物、天然或合成的着色剂或着色颜料(例如类胡萝卜素、类黄酮、花色素、叶绿素及其衍生物)、辛香料、三叉神经活性物质或包含这种三叉神经活性物质的植物提取物、合成的、天然的或等同天然的香料或芳香剂以及气味矫正剂。
根据本发明的食品组合物,例如以制品或半成品形式的那些,优选含有调味组合物用于完善和改良味道和/或气味。一种制品可以含有固体载体和调味组合物成分。适当的调味组合物包括,例如,合成、天然或等同天然的香料、香精和味道赋予物质、反应香料、烟熏香料或其他香味赋予制品(例如蛋白(部分)水解物,优选具有高精氨酸含量的蛋白(部分)水解物、烤肉香料、植物提取物、辛香料、调味制品、蔬菜和/或蔬菜制品)以及适当的辅助物质和载体。此处特别适当的是产生烘烤、肉香(特别是鸡肉、鱼肉、海鲜、牛肉、猪肉、羔羊肉、羊肉、山羊肉)、类蔬菜(特别是番茄、洋葱、大蒜、芹菜、韭菜、蘑菇、茄子、海藻)、香辛料(特别是黑胡椒和白胡椒、小豆蔻、肉豆蔻、西班牙甘椒、芥末和芥末制品)、炸制、类酵母、煮制、脂肪、咸味和/或辛辣的味道印象并因此可以增强辣味印象。香料组合物通常含有多于一种所述的成分。
本发明的食品组合物优选自组包括
·糕饼,优选低热量或无热量糕饼,优选自组包括麦片棒产品、水果糖、糖衣片、硬焦糖和口香糖,
·无醇饮料,优选自组包括绿茶、红茶、富含(绿、红)茶提取物的(绿、红)茶饮品、rooibos茶、其他草本茶、含有水果的低糖或无糖软饮、等张饮料、甜美饮料(nectars)、水果和蔬菜果汁、水果或蔬菜果汁制品,
·速溶饮料,优选自组包括速溶(绿、红、rooibos、草本)茶饮料,
·谷物制品,优选自组包括低糖和无糖早餐谷物和麦片棒,
·奶制品,优选自组包括低脂和脱脂奶饮料、酸奶、克菲尔、乳清、白脱牛奶或冰激凌,
·由大豆蛋白或其他大豆馏分得到的制品,优选自组包括豆奶、由豆奶制得的制品、含有分离的或酶加工的大豆蛋白的饮料、含有大豆粉的饮料、含有大豆卵磷脂的制品、由含有大豆卵磷脂和水果制品以及任选香料的混合物的制品制得的产品,
·甜味剂制品、片剂或袋剂,
·无糖糖衣
·冰激凌,含有或不含奶基成分,优选无糖。
A.香味或香料化合物
本领域熟知的香味化合物或香料制剂可以加入本发明的香料组合物。这些香料制剂可以选自合成香料液体和/或源自植物叶、花、果实等的油及其结合。香料液体的代表包括:人工、天然或合成水果香料如桉树油、柠檬油、橙油、香蕉油、葡萄油、白柠檬油、杏仁油和葡萄柚油和水果香精包括苹果、草莓、樱桃、橙子、菠萝等;豆类和坚果产生的味道如咖啡、可可、可乐、花生、杏仁等;以及根产生的味道如甘草或姜。
香料制剂优选自组包括精油和提取物、酊剂和香膏,例如茴香醚、罗勒油、佛手柑油、苦杏仁油、樟脑油、香茅油、柠檬油;柠檬桉油、桉树油、茴香油、葡萄柚油、洋甘菊油、荷兰薄荷油、蒿子油、白柠檬油、橘子油、肉豆蔻油(特别是肉豆蔻花油)、没药油、丁香油、丁香花油、橙油、牛至油、欧芹(籽)油、辣薄荷油、迷迭香油、鼠尾草油(香鼠尾草油、达尔马提亚或西班牙鼠尾草油)、八角油、百里香油、香草精、桧油(特别是杜松子油)、冬青油、肉桂叶油、桂皮油及其馏分,或由其分离的成分。
特别有利是本发明的香料组合物含有至少一种,优选两种、三种、四种、五种、六种、七种、八种或更多种香料制剂,其选自以下组:薄荷醇(优选左旋薄荷醇和/或消旋薄荷醇)、茴香脑、茴香醚、茴香醛、茴香醇、(外消旋)新薄荷醇、桉树脑(1,8-桉树脑)、薄荷酮(优选L-薄荷酮)、异薄荷酮(优选D-异薄荷酮)、异胡薄荷醇、乙酸薄荷酯(优选L-乙酸薄荷酯)、丙酸薄荷酯、香芹酮(优选(-)-香芹酮,任选作为荷兰薄荷油的组分)、水杨酸甲酯(任选作为冬青油的组分)、丁香酚乙酸酯、异丁香酚甲醚、β-环高柠檬醛、丁香酚、异丁醛、3-辛醇、二甲基硫醚、己醇、己醛、反式-2-己醛、顺式-3-己烯醇、4-萜品醇、薄荷烯酮、里哪醇、乙酸8-罗勒烯酯、异戊醇、异戊醛、α-蒎烯、β-蒎烯、苧烯(优选D-苧烯,任选作为精油的组分)、薄荷酮、反式-水合桧烯、薄荷呋喃、石竹烯、大根香叶烯D、肉桂醛、薄荷内酯、百里酚、γ-辛内酯、γ-壬内酯、γ-癸内酯、(1,3E,5Z)-十一烷三烯、2-丁酮、甲酸乙酯、乙酸3-辛酯、异戊酸异戊酯、顺式-和反式-乙酸香芹酯、对聚伞花素、大马酮、突厥酮、顺式-氧化玫瑰、反式-氧化玫瑰、葑醇、乙醛二乙缩醛、乙酸1-乙氧基乙酯、顺式-4-庚烯醛、顺式-茉莉酮、二氢茉莉酸甲酯、2'-羟基苯丙酮、薄荷基甲基醚、乙酸桃金娘烯酯、2-苯乙醇、异丁酸2-苯乙酯、异戊酸2-苯乙酯、香叶醇、橙花醇和绿花白千层醇。
特别优选的香味或香料化合物包括薄荷醇、桉油酚、丁香酚、麝香草酚、肉桂醛、辣薄荷油、荷兰薄荷油、桉树油、百里香油、肉桂油、丁香油、云杉针油、茴香油、鼠尾草油、茴香油、八角油、春黄菊油、和蒿子油及其混合物。
B.甜味剂
本文中术语“甜味剂”代表基于蔗糖甜度(因此甜度为1)的相对甜度至少为25的物质。根据本发明(a)在口服消费产品(特别是食品、饲料或药品)中使用的甜味剂优选防龋齿和/或每克口服消费产品的热量不大于5kcal。
在本发明优选的食品组合物中有利的甜味剂选自下组:
(i)天然存在的甜味剂,优选自组包括
·神秘果素、莫内林、马宾灵、奇异果甜蛋白、仙茅甜蛋白、布拉齐因、皮泰亭(pentaidin)、D-苯丙氨酸、D-色氨酸以及获自含有这些氨基酸和/或蛋白质的自然资源中得到的提取物或馏分,以及这些氨基酸和/或蛋白质的生理上可接受的盐,尤其是钠、钾、钙或铵盐;
·神秘果素、莫内林、马宾灵、奇异果甜蛋白、仙茅甜蛋白、布拉齐因、皮泰亭(pentaidin)、D-苯丙氨酸、D-色氨酸以及获自含有这些氨基酸和/或蛋白质的自然资源中得到的提取物或馏分,以及这些氨基酸和/或蛋白质的生理上可接受的盐,尤其是钠、钾、钙或铵盐;extracts or concentrated fractions of the extracts,selected from thegroup comprising thaumatococcus extracts(katamfe plant),extracts from Steviassp.(in particular Stevia rebaudiana),swingle extracts(Momordica or Siratiagrosvenorii,Luo-Han-Guo),extracts from Glycerrhyzia ssp.(in particularGlycerrhyzia glabra),extracts from Rubus ssp.(in particular Rubussuavissimus),citrus extracts and extracts from Lippia dulcis;
(ii)合成的甜味物质,优选地选自组包括,唛甘浦(magap)、环拉酸钠或环拉酸的其它生理上可接受的盐、安赛蜜K或其它生理上可接受的盐、新橙皮苷二氢查尔酮、柚苷二氢查尔酮、沙卡林(saccharin)、沙卡林钠盐、阿斯巴甜、超级阿斯巴甜、纽甜、阿力甜、糖精、紫苏葶、三氯蔗糖、胍乙酸、卡瑞来、苏洛内特和苏洛奥内特(sucrooctate)。
C.增稠剂
在本发明优选的口服消费产品(特别是食品、饲料或药品)中有利的增稠剂选自下组包括:交联聚丙烯酸及其衍生物、多糖及其衍生物,如黄原胶、琼脂、海藻酸盐或tyloses、纤维素衍生物,例如羧甲基纤维素和羟基羧甲基纤维素、脂肪醇、甘油单酯和脂肪酸、聚乙烯醇和聚乙烯吡咯烷酮。
根据本发明优选的口服消费产品(特别是食品或饲料)含有使用乳酸菌增稠的奶和/或使用乳酸菌增稠的奶油,并优选自组包括酸奶、克菲尔和夸克。
根据本发明的含有使用乳酸菌增稠奶和/或使用乳酸菌增稠奶油的食品组合物有利地是含有益生菌的口服消费产品,其中益生菌优选自组包括动物双歧杆菌乳亚种BB-12、动物双歧杆菌乳亚种DN-173 010、动物双歧杆菌乳亚种HN019、嗜酸乳杆菌LA5、NCFM、约氏乳酸杆菌La1、干酪乳酸杆菌immunitass/defensis、干酪乳酸杆菌代田菌(DSM 20312)、干酪乳酸杆菌CRL431、罗伊氏乳酸杆菌(ATCC 55730)和鼠李糖乳酸杆菌(ATCC 53013)。
D.口香糖添加剂
根据本发明特别优选的口服消费产品(特别是食品、饲料或药品)是口香糖并包括口香糖胶基。口香糖胶基优选自组包括口香糖或泡泡糖胶基。后者更软,从而可以形成泡泡。根据本发明优选的口香糖胶基,除了常规使用的天然树脂或latex树胶,包括弹性体如聚乙酸乙烯酯(PVA)、聚乙烯(低分子量和中等分子量)、聚异丁烯(PIB)、聚丁二烯、异丁烯-异戊二烯共聚物(丁基橡胶)、聚乙烯基乙醚(PVE)、聚乙烯基丁醚、乙烯基酯和乙烯基醚的共聚物、苯乙烯-丁二烯共聚物(苯乙烯-丁二烯橡胶,SBR)或乙烯基弹性体,例如基于乙酸乙烯酯/月桂酸乙烯酯、乙酸乙烯酯/硬脂酸乙烯酯或乙酸亚乙酯/乙酸乙烯酯,及所述弹性体的混合物,例如如EP 0 242 325、US 4,518,615、US 5,093,136、US 5,266,336、US 5,601,858或US 6,986,709中所述。此外,根据本发明优选的口香糖胶基还包含其他组分,例如(矿物)填料、增塑剂、乳化剂、抗氧化剂、蜡、脂肪或脂肪油,如硬化(氢化)植物或动物脂肪、甘油单酯、甘油二酯或甘油三酯。适合的(矿物)填料有例如碳酸钙、二氧化钛、二氧化硅、滑石、氧化铝、磷酸二钙、磷酸三钙、氢氧化镁及其混合物。适合的增塑剂或防粘剂(脱粘剂)是例如羊毛脂、硬脂酸、硬脂酸钠、乙酸乙酯、二醋精(二乙酸甘油酯)、三醋精(三乙酸甘油酯)、柠檬酸三乙酯。适合的蜡是例如石蜡、小烛树蜡、巴西棕榈蜡、微晶蜡和聚乙烯蜡。适合的乳化剂是例如磷脂如卵磷脂、脂肪酸的甘油单酯和甘油二酯,例如单硬脂酸甘油酯。
本发明的口香糖(特别是上文公开的)优选包含成分如不同类型的糖、糖替代品、其他甜味物质、糖醇(特别是山梨糖醇、木糖醇、甘露醇)、具有清凉效果的成分、令人不愉快味道印象的味道矫正剂、其他味道矫正物质(例如磷酸肌醇、核苷酸如单磷酸鸟苷、单磷酸腺苷或其他物质如谷氨酸钠或2-苯氧基丙酸)、保湿剂、增稠剂、乳化剂、稳定剂、气味校正剂和香料(例如桉树-薄荷脑、樱桃、草莓、葡萄柚、香草、香蕉、柑橘、桃、黑醋栗、热带水果、姜、咖啡、肉桂、(所述香料)与薄荷香料的结合以及单独的荷兰薄荷和辣薄荷)。特别优选的是香料与其他具有清凉、温暖和/或令人垂涎特性物质的结合。
用于防腐和抵抗体味的方法
如上所述,根据本发明的式(I)化合物表现出抵抗大量革兰氏阳性菌、革兰氏阴性菌、霉菌和酵母的抗微生物活性,其特别可以对大量化妆制剂进行防腐和抗微生物处理。特别良好的作用是抵抗革兰氏阳性菌,如金黄色葡萄球菌(Staphylococcus aureus)、表皮葡萄球菌(Staphylococcus epidermidis)、蜡样芽孢杆菌(Bacillus cereus)、结膜干燥棒状杆菌(Corynebacterium xerosis)和疮疱丙酸杆菌(Propionibacterium acnes),抵抗革兰氏阴性菌,如大肠杆菌(Escherichia coli)、洋葱伯克霍尔德菌(Burkholderia cepacia)、和荧光假单胞菌(Pseudomonas aeruginosa)、抵抗酵母,如白色念珠菌(Candidaalbicans)、糠批马拉色菌(Malassezia furfur)和球形马拉色菌(Malassezia globosa),以及确切地—如上所述—抵抗真菌及其孢子,如曲霉(Aspergillus)属的霉菌种类。特别有利的是,根据本发明的混合物抵抗曲霉(Aspergillus)属的霉菌—一种非常难以抵抗的真菌—的非常好的活性。
因此,本发明的另一个主题涉及一种个人护理组合物、清洁剂组合物或食品组合物的防腐方法,通过加入有效量的至少一种式(I)化合物或其(药用)盐或其与其他防腐化合物或抗微生物制剂(b)和/或(c)的混合物。
本发明的另一个主题涉及一种抵抗微生物的方法,通过向个人护理、清洁剂或食品组合物加入有效量的至少一种式(I)化合物或其(药用)盐或其与其他防腐化合物或抗微生物制剂(b)和/或(c)的混合物。
本发明的一个主题是一种防止化妆组合物、清洁剂组合物或食品组合物微生物腐败的方法,所述方法包括向所述组合物加入0.01至10重量%,优选约0.02至约5和更优选约0.05至约2重量%的至少一种式(I)化合物或其(药用)盐或段落[0038]-[0052]的混合物,基于组合物总量计。
在一个优选实施方案中,化妆组合物还含有水和至少一种选自组包括表面活性剂、乳化剂、增稠剂和油体的制剂。
在另一个优选实施方案中,化妆组合物是洗发香波、护发素、O/W乳液、W/O乳液或凝胶。
本发明也包括至少一种式(I)化合物或其(药用)盐或其与其他防腐化合物或抗微生物制剂(b)和/或(c)的混合物作为防腐剂的用途,特别是用于个人护理、清洁剂或食品组合物,用量优选约0.01至约10,优选约0.02至约5并且更优选约0.05至约2重量%,基于组合物总量计。
本发明的另一个主题涉及一种抵抗微生物的方法,通过加入有效量的至少一种式(I)化合物或其(药用)盐或其与其他防腐化合物或抗微生物制剂(b)和/或(c)的混合物。
式(I)化合物或其(药用)盐或其与其他防腐化合物或抗微生物制剂(b)和/或(c)的混合物对于引发体味、痤疮和/或霉菌病的微生物特别有效。有利地,将防腐剂或防腐混合物以浓度为0.01至约10,优选约0.02至约5,并且更优选约0.05至约2重量%施用至人类皮肤,任何情况下基于含有混合物的化妆或药物产品的总量计。协同增效的活性混合物可以(a)预防性地或(b)按需使用。施用活性化合物的浓度可以例如根据客体生理状态和特定参数,如年龄或体重,每日改变。根据本发明的协同增效活性混合物可以单独使用或与其他抗微生物活性物质结合使用。
因此本发明的另一个主题包括一种处理不良体味,特别是腋下和足部气味的方法,通过向皮肤局部施用有效量的至少一种式(I)化合物或其(药用)盐或其与其他防腐化合物或抗微生物制剂(b)和/或(c)的混合物。最后,本发明涉及至少一种芳香酯或酰胺衍生物或其与第二防腐剂或抗微生物制剂的混合物作为除臭剂的用途。
应当理解上述针对芳香酯和酰胺衍生物及其混合物解释和优选实施方案必要修订后也可用于要求的方法和用途,因此无需额外重复。
实施例
本发明在下文基于实施例进一步描述。实施例用于说明发明,而不限定权利要求书的保护范围。实施例1至11,根据欧洲药典7.0(5.1.3.Efficacy of antimicrobialpreservation)的防腐效率试验。实施例12,根据DIN 58940通过测定最小抑制浓度(MIC数值)测定活性。所有数值信息涉及重量,除非另外说明。
实施例1
苯甲酸-3-羟丙酯(BAHP)抵抗微生物大肠杆菌(E.coli)、荧光假单胞菌(P.aeruginosa)、金黄色葡萄球菌(S.aureus)、白色念珠菌(C.albicans)和巴西曲霉(A.brasiliensis)孢子的活性在Dracorin CE作为乳化剂的阴离子乳液中进行评估。乳液的pH值为5.5。
表1
苯甲酸-3-羟丙酯(BAHP)的活性
实施例2
糠酸-3-羟丙酯(FAHP)抵抗微生物大肠杆菌(E.coli)、荧光假单胞菌(P.aeruginosa)、金黄色葡萄球菌(S.aureus)、白色念珠菌(C.albicans)和巴西曲霉(A.brasiliensis)孢子的活性在Dracorin CE作为乳化剂的阴离子乳液中进行评估。乳液的pH值为5.5。
表2
糠酸-3-羟丙酯(FAHP)的活性
实施例3
茴香酸-3-羟丙酯(AAHP)抵抗微生物大肠杆菌(E.coli)、荧光假单胞菌(P.aeruginosa)、金黄色葡萄球菌(S.aureus)、白色念珠菌(C.albicans)和巴西曲霉(A.brasiliensis)孢子的活性在Dracorin CE作为乳化剂的阴离子乳液中进行评估。乳液的pH值为5.5。
表3
茴香酸-3-羟丙酯(AAHP)的活性
实施例4
N-甲基水杨酰胺(MSA)抵抗微生物巴西曲霉(A.brasiliensis)的活性在DracorinCE作为乳化剂的阴离子乳液中进行评估。乳液的pH值为5.5。
表4
N-甲基水杨酰胺(MSA)的活性
实施例5
糠酸甲酯(FAME)抵抗微生物巴西曲霉(A.brasiliensis)的活性在Dracorin CE作为乳化剂的阴离子乳液中进行评估。乳液的pH值为5.5。
表5
糠酸甲酯(FAME)的活性
实施例6
水杨酰胺(SA)抵抗微生物巴西曲霉(A.brasiliensis)的活性在Dracorin CE作为乳化剂的阴离子乳液中进行评估。乳液的pH值为5.5。
表6
水杨酰胺(SA)的活性
实施例7
水杨酸羟乙酯(SAHE)抵抗微生物巴西曲霉(A.brasiliensis)的活性在DracorinCE作为乳化剂的阴离子乳液中进行评估。乳液的pH值为5.5。
表7
水杨酸羟乙酯(SAHE)的活性
实施例8
水杨酸羟丙酯(SAHP)抵抗微生物巴西曲霉(A.brasiliensis)的活性在DracorinCE作为乳化剂的阴离子乳液中进行评估。乳液的pH值为5.5。
表8
水杨酸羟丙酯(SAHP)的活性
实施例9
苯甲酸-3-羟丙酯(BAHP)抵抗微生物巴西曲霉(A.brasiliensis)孢子的活性在Dracorin CE作为乳化剂的阴离子乳液中进行评估。乳液的pH值为7。
表9
pH为7时苯甲酸-3-羟丙酯(BAHP)的活性
实施例10
茴香酸-3-羟丙酯(AAHP)抵抗微生物巴西曲霉(A.brasiliensis)孢子的活性在Dracorin CE作为乳化剂的阴离子乳液中进行评估。乳液的pH值为7。
表10
pH为7时茴香酸-3-羟丙酯(AAHP)的活性
实施例11
测定了苯甲酸-3-羟丙酯(BAHP)和1,2-辛二醇的协同增效效果。BAHP、1,2-辛二醇以及BAHP和1,2-辛二醇结合抵抗微生物大肠杆菌(E.coli)、荧光假单胞菌(P.aeruginosa)、金黄色葡萄球菌(S.aureus)、白色念珠菌(C.albicans)和巴西曲霉(A.brasiliensis)孢子的活性在Dracorin CE作为乳化剂的阴离子乳液中进行评估。乳液的pH值为5.5。
表11
苯甲酸-3-羟丙酯(BAHP)的活性
表12
1,2-辛二醇的活性
表12
苯甲酸-3-羟丙酯(BAHP)和1,2-辛二醇的活性
相对于单一成分揭示了BAHP和1,2-辛二醇结合的明显协同增效的效果,特别是抵抗巴西曲霉的孢子以及白色念珠菌。
实施例12
测定了苯甲酸-3-羟丙酯(BAHP)、糠酸-3-羟丙酯(FAHP)和茴香酸-3-羟丙酯(AAHP)、水杨酸羟乙酯(SAHE)和水杨酸羟丙酯(SAHP)抵抗微生物金黄色葡萄球菌(Staphylococcus aureus)、白色念珠菌(Candida albicans)、和巴西曲霉(Aspergillusbrasiliensis)、荧光假单胞菌(Pseudomonas aeruginosa)和大肠杆菌(Escherichiacoli)的活性。测定了N-甲基水杨酰胺(MSA)、糠酸甲酯(FAME)和水杨酰胺(SA)抵抗微生物巴西曲霉(Aspergillus brasiliensis)的活性。结果示于表14。
表14
不同抗微生物制剂的最小抑制浓度
制剂实施例
本发明通过以下实施例进一步说明。如果没有另外指出,“式(A)物质”涉及苯甲酸-3-羟丙酯(BAHP)、糠酸-3-羟丙酯(FAHP)或茴香酸-3-羟丙酯(AAHP)。然而,“式(A)物质”可以由任何其他式(A)化合物替代。
表IA
芳香油(含量以重量%计)
表IB
芳香油P2(用量为%b.w.)
表IC
芳香油P3(用量为%b.w.)
表ID
具备白花香气的芳香油P4(用量为%b.w.)
由上述实施例得到的芳香油P1、P2、P3和P4被分别加工为以下制剂。
表II
液体皂,透明(用量为%b.w.)
表II中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表III
合成皂,液态(用量为%b.w.)
成分 | INCI名称 | 成分 |
Elfan OS 46 | C14-16烯基磺酸钠 | 35.5 |
Armoteric LB | 月桂基甜菜碱 | 8.0 |
Elfan SG | 10.0 | |
Elfacos GT 282L | 牛脂醇聚醚-60肉豆蔻基甘醇 | 3.0 |
PCL-液体100 | 鲸蜡硬脂醇乙基己酸酯 | 4.0 |
芳香油P1、P2、P3或P4 | 香精 | 0.4 |
防腐剂 | 甲基氯异噻唑啉酮,甲基异噻唑啉酮 | 0.1 |
式(I)的物质 | 苯甲酸-3-羟丙酯 | 0.4 |
水 | 水 | 加至100 |
表III中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表IV
用于沐浴的化妆乳液(用量为%b.w.)
表IV中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表V
用于沐浴的含有三氯生的化妆乳液(用量为%b.w.)
表V中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表VI
敏感部位清洁液(用量为%b.w.)
表VI中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表VII
液体皂(用量为%b.w.)
表VII中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表VIII
香波(用量为%b.w.)
成分 | 用量 |
月桂基乙醚硫酸钠(例如Texapon NSO) | 12 |
椰油酰胺丙基甜菜碱(例如Dehyton K) | 2 |
氯化钠 | 1.4 |
柠檬酸 | 1.3 |
芳香油P1、P2、P3或P4 | 0.3 |
苯氧基乙醇、羟苯甲酯、羟苯乙酯、羟苯丁酯和羟苯丙酯 | 0.5 |
苯甲酸-3-羟丙酯 | 0.5 |
水 | 加至100 |
表VIII中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表IX
2合1香波(用量为%b.w.)
表IX中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表X
抗头皮屑香波(用量为%b.w.)
成分 | 用量 |
氯咪巴唑 | 0.50 |
月桂醇聚醚硫酸酯钠 | 37.00 |
椰油酰胺丙基甜菜碱 | 8.00 |
PEG-6辛酸/癸酸甘油酯类 | 2.50 |
月桂醇聚醚-2 | 2.00 |
水、甘油、麝香草(THYMUS VULGARIS)花/叶提取物 | 0.50 |
迷迭香(Rosmarinus Officinalis)叶水、水、丁二醇、戊二醇 | 0.50 |
红没药醇 | 0.10 |
泛醇 | 0.50 |
聚季铵盐-10 | 0.40 |
芳香油P1、P2、P3或P4 | 0.50 |
苯氧基乙醇、羟苯甲酯、羟苯乙酯、羟苯丁酯、羟苯丙酯、羟苯异丙酯 | 0.70 |
苯甲酸-3-羟丙酯 | 0.30 |
水 | 加至100 |
表X中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XI
含有Crinipan的护发素,洗除(用量为%b.w.)
表XI中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XII
含有吡硫鎓锌的可喷护发素,免洗(用量为%b.w.)
表XII中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XIII
含有UV防晒因子的护发素(用量为%b.w.)
表XIII中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XIV
沐浴露(用量为%b.w.)
表XIV中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XV
剃须膏(用量为%b.w.)
表XV中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XVI
脱毛霜(用量为%b.w.)
成分 | 用量 |
鲸蜡硬脂醇 | 10.0 |
鲸蜡硬脂醇聚醚-12 | 2.0 |
PCL-Liquid(鲸蜡硬脂醇乙基己酸酯、肉豆蔻酸异丙酯) | 3.0 |
没药醇(红没药醇、金合欢醇) | 0.1 |
Edenor L2SM(硬脂酸.棕榈酸) | 1.0 |
去离子水 | 52.2 |
脲 | 5.0 |
去离子水 | 10.0 |
巯基乙酸钙 | 6.0 |
氢氧化钠溶液10% | 10.0 |
芳香油P1、P2、P3或P4 | 0.5 |
Neo Dragocid Powder(羟苯甲酯、山梨酸、脱氢乙酸、羟苯丙酯) | 0.2 |
苯甲酸-3-羟丙酯 | 0.4 |
表XVI中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XVII
须后水(用量为%b.w.)
表XVII中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XVIII
滚珠凝胶形式的除臭制剂(用量为%b.w.)
表XVIII中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XIX
除臭止汗滚珠(用量为%b.w.)
表XIX中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XX
除臭棒(用量为%b.w.)
表XX中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXI
锆悬浮胶体止汗棒(用量为%b.w.)
成分 | INCI名称 | 用量 |
PCL Liquid 100 | 鲸蜡硬脂醇乙基己酸酯 | 加至100 |
Silicone Fluid 345 | 环聚二甲基硅氧烷 | 10.00 |
CRODACOL C90 | 鲸蜡醇 | 8.00 |
SYNCROWAX HGLC | C18-36甘油三酯 | 8.00 |
CRODAMOL PTC | 季戊四醇四辛酸酯/季戊四醇四癸酸酯 | 5.00 |
SYNCROWAX HRC | 三山嵛精 | 4.00 |
VOLPO N5 | 油醇聚醚-5 | 1.00 |
二氧化钛 | 1.00 | |
Rezal 36GP | 四氯水合甘氨酸铝 | 20.00 |
Dry Flo C | 淀粉辛烯基琥珀酯铝盐 | 22.50 |
芳香油P1、P2、P3或P4 | 香精 | 0.60 |
防腐剂 | 苯氧基乙醇 | 0.40 |
己氧基-1.2-丙二醇 | 0.10 | |
式(I)的物质 | 苯甲酸-3-羟丙酯 | 0.40 |
表XXI中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXII
含有SymClariol的除臭喷剂(用量为%b.w.)
表XXII中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXIII
止汗制剂(用量为%b.w.)
表XXIII中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXIV
含有三氯生的除臭喷雾(用量为%b.w.)
表XXIV中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXV
O/W乳液(用量为%b.w.)
成分 | 用量 |
石蜡油 | 5.00 |
棕榈酸异丙酯 | 5.00 |
鲸蜡醇 | 2.00 |
蜂蜡 | 2.00 |
鲸蜡硬脂醇聚醚-20 | 2.00 |
PEG-20-甘油硬脂酸酯 | 1.50 |
甘油 | 3.00 |
芳香油P1、P2、P3或P4 | 0.30 |
羟苯甲酯 | 0.30 |
苯甲酸-3-羟丙酯 | 0.60 |
水 | 加至100.00 |
表XXV中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXVI
身体乳液(用量为%b.w.)
表XXVI中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXVII
霜剂(用量为%b.w.)
成分 | 用量 |
石蜡油 | 10.00 |
地蜡 | 4.00 |
凡士林 | 4.00 |
植物油 | 10.00 |
羊毛蜡醇 | 2.00 |
硬脂酸铝 | 0.40 |
芳香油P1、P2、P3或P4 | 0.70 |
1.2-戊二醇 | 2.00 |
苯氧基乙醇 | 0.50 |
苯甲酸-3-羟丙酯 | 0.50 |
水 | 加至100.00 |
表XXVII中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXVIII
霜剂(用量为%b.w.)
表XXVIII中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXIX
护手霜和护体霜(用量为%b.w.)
表XXIX中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXX
面霜(用量为%b.w.)
表XXX中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXXI
滋润护体霜(用量为%b.w.)
成分 | 用量 |
PEG-7氢化蓖蔴油 | 6.00 |
鲸蜡硬脂醇乙基己酸酯 | 10.00 |
肉豆蔻酸异丙酯 | 5.00 |
矿物油 | 7.00 |
牛油树脂酸酯(牛油果树Butyrospermum parkii) | 0.50 |
硬脂酸铝 | 0.50 |
硬脂酸镁 | 0.50 |
红没药醇 | 0.20 |
季铵盐-18-水辉石 | 0.70 |
二丙二醇 | 5.0 |
硫酸镁 | 0.70 |
1,2-戊二醇 | 4.00 |
芳香油P1、P2、P3或P4 | 0.30 |
防腐剂(苯氧基乙醇) | 0.20 |
苯甲酸-3-羟丙酯 | 0.40 |
软化水 | 58.90 |
表XXXI中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXXII
抗皱霜(用量为%b.w.)
表XXXII中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXXIII
功能性皮肤用消毒油(用量为%b.w.)
表XXXIII中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXXIV
感染伤口用膏(用量为%b.w.)
成分(INCI) | 用量 |
失水山梨醇异硬脂酸酯、氢化蓖蔴油、纯地蜡、蜂蜡(白蜂蜡) | 6.00 |
石蜡油 | 21.00 |
白蜂蜡 | 5.00 |
鲸蜡硬脂醇 | 7.00 |
Prunus Dulcis | 7.00 |
羊毛脂 | 5.00 |
液体石蜡 | 12.00 |
芳香油P1、P2、P3或P4 | 0.30 |
水 | 加至100 |
泛醇 | 7.00 |
硫酸镁 | 0.70 |
1,2-戊二醇 | 1.00 |
生育酚乙酸酯 | 1.00 |
盐酸奥替尼啶 | 0.10 |
苯氧基乙醇 | 0.50 |
苯甲酸-3-羟丙酯 | 0.50 |
表XXXIV中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXXV
保湿和消毒面膜(用量为%b.w.)
表XXXV中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXXVI
可喷消毒凝胶(用量为%b.w.)
表XXXVI中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXXVII
矿物清洗和清洁凝胶(用量为%b.w.)
表XXXVII中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXXVIII
抗痤疮洗剂(用量为%b.w.)
表XXXVIII中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXXIX
化妆品防晒组合物(用量为%b.w.)
表XXXIX中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXXX
防晒喷雾(用量为%b.w.)
表XXXX中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXXXI
防晒喷雾O/W.SPE 15-20(用量为%b.w.)
表XXXXI中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXXXII
防晒软膏(W/O),SPF 40(用量为%b.w.)
表XXXXII中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXXXIII
防晒乳(W/O)(用量为%b.w.)
表XXXXIII中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXXXIV
晒后凝胶(用量为%b.w.)
表XXXXIV中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXXXV
晒后乳液(用量为%b.w.)
成分 | 用量 |
丙烯酸酯/丙烯酸C10-30烷酯交联聚合物 | 0.4 |
鲸蜡硬脂醇乙基己酸酯 | 15.0 |
红没药醇 | 0.2 |
生育酚乙酸酯 | 1.0 |
泛醇 | 1.0 |
醇 | 15.0 |
甘油 | 3.0 |
芳香油P1、P2、P3或P4 | 0.30 |
1.2-己二醇 | 0.60 |
苯甲酸-3-羟丙酯 | 0.30 |
1,2-戊二醇 | 4.0 |
软化水 | 加至100 |
三乙醇胺 | 0.2 |
表XXXXV中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXXXVI
头发定型发胶(用量为%b.w.)
表XXXXVI中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXXXVII
硅油乳液(用量为%b.w.)
表XXXXVII中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXXXVIII
微乳凝胶(用量为%b.w.)
表XXXXVIII中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表XXXXIX
凝胶形式的空气清新剂(用量为%b.w.)
表XXXXIX中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表L
清洁剂,APC液体,碱性pH 8-10(用量为%b.w.)
成分(INCI) | 用量 |
水 | 59.06 |
二水合柠檬酸三钠盐 | 3.00 |
月桂醇聚醚硫酸酯钠 | 30.00 |
十三烷醇聚醚-9 | 5.00 |
乙醇 | 2.00 |
10%柠檬酸溶液 | 0.24 |
芳香油P1、P2、P3或P4 | 0.50 |
5-氯-2-甲基-2H-异噻唑-3-酮和2-甲基-2H-异噻唑-3-酮的混合物 | 0.10 |
苯甲酸-3-羟丙酯 | 0.30 |
表L中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表LI
织物柔软剂(用量为%b.w.)
成分(INCI) | 用量 |
水 | 72.10 |
双烷基酯基甲基硫酸甲酯铵 | 16.60 |
聚二甲基硅氧烷 | 0.30 |
氯化镁 | 10.00 |
芳香油P1、P2、P3或P4 | 0.60 |
5-氯-2-甲基-2H-异噻唑-3-酮和2-甲基-2H-异噻唑-3-酮的混合物 | 0.10 |
苯甲酸-3-羟丙酯 | 0.40 |
表LI中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表LII
洗涤液(用量为%b.w.)
成分 | 用量 |
去离子水 | 39.60 |
荧光增白剂 | 0.10 |
椰油脂肪酸(C12-C18) | 7.50 |
50%氢氧化钾溶液 | 4.30 |
丙-1.2-二醇 | 5.00 |
脂肪醇C12-C15,8EO | 12.00 |
(C13-C17)仲烷基磺酸钠盐 | 17.00 |
三乙醇胺 | 2.00 |
二水合柠檬酸三钠盐 | 5.00 |
Dequest 2066二乙三胺五亚甲基磷酸 | 3.00 |
乙醇 | 3.00 |
酶 | 0.70 |
芳香油P1、P2、P3或P4 | 0.50 |
苯甲酸-3-羟丙酯 | 1.00 |
表LII中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表LIII
洗涤液浓缩物(用量为%b.w.)
表LIII中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表LIV
厕所清洁剂(用量为%b.w.)
成分 | 用量 |
水 | 930 |
Kelzan ASX-T | 05 |
石蜡磺酸钠盐 | 10 |
柠檬酸 | 5.0 |
染料(FD&C黄色No.6) | 0.1 |
芳香油P1、P2、P3或P4 | 0.3 |
防腐剂(苯并异噻唑啉酮、戊二醛) | 005 |
苯甲酸-3-羟丙酯 | 0.6 |
表LIV中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表LV
洗洁精浓缩物(用量为%b.w.)
表LV中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表LVI
洗洁精浓缩物(用量为%b.w.)
成分 | 用量 |
棕榈树苷 | 4.0 |
月桂醇硫酸酯钠 | 450 |
可可甜菜碱 | 80 |
96%乙醇 | 10 |
染料(C.I.染料蓝15) | 0.05 |
芳香油P1、P2、P3或P4 | 0.2 |
苯甲酸-3-羟丙酯 | 0.7 |
水 | 加至100 |
表LVI中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表LVII
用于湿纸巾的溶液(用量为%b.w.)
表LVII中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
湿清洁纸巾
制备用于使用湿清洁纸巾中和令人不愉快气味和/或消毒的组合物或混合物:将以下成分混合形成组合物或混合物:20重量份二丙二醇,25重量份式(I)的物质,15重量份肉豆蔻酸异丙酯、15重量份柠檬酸三乙酯和15重量份苯甲酸苄酯。使用乳化剂(DracorinGOC)制得该组合物的0.05%水溶液并用于生产湿清洁纸巾。
表LVIIIA
薄荷香料PF1(用量为%b.w.)
成分 | 用量 |
异丁醛 | 0.5 |
3-辛醇l | 0.5 |
二甲硫醚 | 0.5 |
反式-2-己烯醛 | 1.0 |
顺式-3-己烯醇 | 1.0 |
天然4-松油醇 | 1.0 |
异胡薄荷醇 | 1.0 |
由桉树得到天然薄荷酮 | 2.0 |
芳樟醇 | 3.0 |
三醋精中10%的8-乙酸罗勒烯酯 | 5.0 |
异戊醇 | 10.0 |
异戊醛 | 10.0 |
天然α-蒎烯 | 25.0 |
天然β-蒎烯 | 25.0 |
外消旋新薄荷醇 | 40.0 |
天然桉油醇(1.8-桉树脑) | 50.0 |
式D的左旋乙酸薄荷酯 | 70.0 |
左旋薄荷酮 | 220.0 |
D-异薄荷酮 | 50.0 |
左旋薄荷醇 | 483.5 |
Nonenolide | 1.0 |
表LVIIIB
冬青香精PF2(用量为%b.w.)
表LVIIIC
乙酸异戊酯类香料PF3(用量为%b.w.)
成分 | 用量I | 用量II |
乙酸异戊酯 | 2 | 2 |
丁酸乙酯 | 0.5 | - |
丁酸丁酯 | - | 0.5 |
乙基香兰素 | 2 | - |
香草醛 | - | 1 |
Frambinon<sup>TM</sup>[4-(4-羟苯基)-2-丁酮] | 0.5 | 0.5 |
左旋薄荷醇 | 8 | 11 |
三醋精 | 85 | |
1.2-丙二醇 | 87 |
表LVIIID
肉桂类清凉香料PF4(用量为%b.w.)
表LIX
牙膏(用量为%b.w.)
成分 | 用量 |
去离子水 | 加至100 |
山梨醇70% | 45.00 |
磷酸三钠 | 0.10 |
糖精 | 0.20 |
单氟磷酸钠 | 1.14 |
PEG 1500 | 5.00 |
Sident 9(二氧化硅磨料) | 10.00 |
Sident 22S(增稠二氧化硅) | 8.00 |
羧甲基纤维素钠 | 1.10 |
氧化钛(IV) | 0.50 |
去离子水 | 4.50 |
月桂基硫酸钠(SLS) | 1.50 |
香精(PF1、PF2、PF3和PF4) | 1.00 |
Solbrol M(钠盐)(羟苯甲酯) | 0.15 |
苯甲酸-3-羟丙酯 | 0.40 |
表LIX中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表LX
含有柠檬酸锌的牙膏(用量为%b.w.)
表LX中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表LXI
漱口水(用量为%b.w.)
表LXI中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表LXII
凝胶牙膏(用量为%b.w.)
成分 | 用量 |
羧甲基纤维素钠 | 0.40 |
水中70%山梨醇 | 72.00 |
聚乙二醇(PEG)1500 | 3.00 |
糖精钠 | 0.07 |
氟化钠 | 0.24 |
香精(PF1、PF2、PF3或PF4) | 1.00 |
二氧化硅磨料 | 11.00 |
增稠二氧化硅 | 6.00 |
十二烷基硫酸钠(SDS) | 1.40 |
蒸馏水 | 加至100 |
对羟基苯甲酸(PHB)乙酯 | 0.15 |
苯甲酸-3-羟丙酯 | 0.20 |
表LXII中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表LXIII
对抗牙斑牙膏(用量为%b.w.)
表LXIII中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表LXIV
用于敏感牙齿的牙膏(用量为%b.w.)
表LXIV中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表LXV
牙膏和漱口水的2合一产品
成分 | 用量 |
山梨醇 | 40.00 |
甘油 | 20.00 |
乙醇 | 5.00 |
水 | 加至100 |
单氟磷酸钠 | 0.75 |
糖精 | 0.20 |
Sident 9(二氧化硅磨料) | 20.00 |
Sident 22S(增稠二氧化硅) | 2.00 |
羧甲基纤维素钠 | 0.30 |
月桂醇硫酸酯钠(SDS) | 1.20 |
染料(水中1%悬浮液)C.I.染料蓝15 | 0.50 |
香精(PF1、PF2、PF3或PF4) | 0.90 |
Solbrol M.钠盐(羟苯甲酯、钠盐) | 0.20 |
苯甲酸-3-羟丙酯 | 0.30 |
表LXV中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表LXVI
含氯即用漱口水(用量为%b.w.)
表LXVI中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺
表LXVII
无糖口香糖(用量为%b.w.)
成分 | 用量 |
口香糖基料 | 30.00 |
山梨醇粉末 | 加至100 |
Palatinite | 9.50 |
木糖醇 | 2.00 |
甘露醇 | 3.00 |
阿斯巴甜 | 0.10 |
安赛蜜 | 0.10 |
Emulgum/乳化剂 | 0.30 |
水中70%山梨醇 | 14.00 |
甘油 | 1.00 |
香精(PF1、PF2、PF3或PF4) | 1.50 |
Benzoic acid-3-hydroxypropylester | 0.20 |
表LXVII中给出的制剂,替代“苯甲酸-3-羟丙酯”,可以含有:
a)糠酸-3-羟丙酯
b)茴香酸-3-羟丙酯
c)N-甲基水杨酰胺。
Claims (15)
1.式(I)的化合物或其(药用)盐
其中
(a)X代表CH=CH或CZ1=CZ2,其中
如果Z1是H则Z2代表选自组包括OH、NH2、NHMe、NMe2、OMe和OEt的基团,
和
如果Z2是H则Z1代表选自组包括OH、NH2、NHMe、NMe2、OMe和OEt的基团,
Y代表选自组包括NH2、NHMe、NMe2、NHEt,O-(CH2)n-OH的基团,其中
n是2至5
并且
R代表选自组包括H、OH、Me、Et、OMe、OEt、NH2、NHMe、NMe2、NHEt和NEt2的基团,
或
(b)X代表O,
Y代表选自组包括NH2、NHMe、NMe2、NHEt、O-(CH2)n-OH和OMe的基团,其中
n是2至5
并且
R代表H、OH、Me、Et、OMe、OEt、NH2、NHMe、NMe2、NHEt、NEt2。
作为抗微生物制剂的用途。
2.根据权利要求1所述的用途,其中抗抗微生物制剂是抗真菌和/或抗细菌制剂。
3.根据权利要求2所述的用途,其中抗真菌和/或抗细菌制剂是抑制巴西曲霉(Aspergillus brasiliensis)、黑曲霉(Aspergillus niger)、黄曲霉(Aspergillusflavus)、烟曲霉(Aspergillus fumigatus)、表皮葡萄球菌(Staphylococcusepidermidis)、结膜干燥棒状杆菌(Corynebacterium xerosis)、表皮短杆菌(Brevibacterium epidermidis)、疮疱丙酸杆菌(Propionibacterium acnes)、马拉色菌属(Malassezia)、毛癣菌属(Trichophyton)和表皮癣菌属(Epidermophyton)、金黄色葡萄球菌(Staphylococcus aureus)、蜡样芽孢杆菌(Bacillus cereus)、大肠杆菌(Escherichiacoli)、洋葱伯克霍尔德菌(Burkholderia cepacia)和荧光假单胞菌(Pseudomonasaeruginosa)、白色念珠菌(Candida albicans)、糠批马拉色菌(Malassezia furfur)生长的制剂。
4.根据前述权利要求所述的用途,其中式(I)的化合物选自组包括式(Ia)-(Im):
·苯甲酸-3-羟丙酯
·苯甲酸-3羟乙酯
·糠酸-3-羟丙酯
·糠酸-3-羟乙酯
·糠酸甲酯
·茴香酸-3-羟丙酯
·茴香酸-3-羟乙酯
·N-甲基水杨酰胺
·水杨酰胺
·水杨酸羟乙酯
·水杨酸羟丙酯
·香草酸羟丙酯
·氨基苯甲酸羟丙酯
5.一种抗微生物混合物含有
(a)至少一种选自式(I)的芳香酯或酰胺衍生物的第一抗微生物制剂,和
(b)至少一种第二抗微生物制剂,选自组包括苯甲酸和对羟基苯甲酸、其酯和盐、苯甲酸苄酯、丙酸及其盐、水杨酸及其盐、2,4-己二烯酸(山梨酸)及其盐、乙酰丙酸及其盐、茴香酸及其盐、紫苏酸及其盐、肉桂酸及其盐、甲醛和多聚甲醛、4-羟基苯甲醛、邻-、间-和对-茴香醛、胡椒醛、肉桂醛、肉桂醇、2-羟基二苯醚及其盐、2-锌-磺酰亚胺基吡啶N-氧化物、无机亚硫酸盐和亚硫酸氢盐、碘酸钠、三氯叔丁醇、4-乙基汞(II)-5-氨基-1,3-二(2-羟基苯甲酸)及其盐和酯、脱氢乙酸、甲酸、1,6-二(4-脒基-2-溴苯氧基)-正己烷及其盐、乙基汞(II)-硫代水杨酸的钠盐、苯基汞及其盐、10-十一碳烯酸及其盐、5-氨基-1,3-二(2-乙基己基)-5-甲基-六氢嘧啶、5-溴-5-硝基-1,3-二噁烷、2-溴-2-硝基-1,3-丙二醇、2,4-二氯苄醇、N-(4-氯苯基)-N’-(3,4-二氯苯基)-脲、4-氯-间甲酚、2,4,4’-三氯-2’-羟基-二苯醚、4-氯-3,5-二甲基苯酚、1,1’-亚甲基-二(3-(1-羟甲基-2,4-二氧代咪唑烷-5-基)脲)、聚-(六亚甲基双胍)盐酸盐、(苄氧基甲氧基)-甲醇六亚甲基四胺、1-(3-氯代烯丙基)-3,5,7-三氮杂-1-氮鎓杂金刚烷氯化物、1-(4-氯苯氧基)-1-(1H-咪唑-1-基)-3,3-二甲基-2-丁酮、1,3-二-(羟甲基)-5,5-二甲基-2,4-咪唑烷二酮、1,2-二溴-2,4-二氰基丁烷、2,2’-亚甲基-二(6-溴-4-氯-苯酚)、溴氯苯、5-氯-2-甲基-3(2H)-异噻唑啉酮、2-甲基-3(2H)-异噻唑啉酮与氯化镁和硝酸镁的混合物、2-辛基-2H-异噻唑-3-酮、1,2-苯并异噻唑啉-3(2H)-酮、2-苄基-4-氯苯酚、3-(4-氯苯氧基)-1,2-丙二醇(Chlorphenesin)、2-氯乙酰胺、氯己定、醋酸氯己定、葡糖酸氯己定、盐酸氯己定、N-烷基(C12-C22)三甲基溴化铵和N-烷基(C12-C22)三甲基氯化铵、4,4-二甲基-1,3-噁唑烷、N-羟甲基-N-(1,3-二(羟甲基)-2,5-二氧代咪唑烷-4-基)-N’-羟基-甲基脲、1,6-二(4-脒基-苯氧基)-正己烷及其盐、戊二醛、5-乙基-1-氮杂-3,7-二氧杂二环(3.3.0)辛烷、3-(4-氯苯氧基)-1,2-丙二醇、季铵盐、烷基-(C8-C18)-二甲基-苄基氯化铵、烷基-(C8-C18)-二甲基-苄基溴化铵、烷基-(C8-C18)-二甲基-苄基-糖精铵、苄基半缩甲醛、3-碘-2-丙炔基丁基氨基甲酸酯、羟甲基-氨基醋酸钠、咪唑烷基脲、双咪唑烷基脲、羟甲基甘氨酸钠、DMDM己内酰脲、环庚三烯酚酮、亚乙基二氧基二甲醇、2-溴-2-(溴乙基)戊二腈、N-(3-氨丙基)-N-十二烷基丙烷-1,3-二胺、α,α‘,α“-三甲基-1,3,5-三嗪-1,3,5(2H,4H,6H)-三乙醇、吡啶-2-硫醇-1-氧化物、钠盐、四氢-1,3,4,6-四(羟甲基)咪唑并[4,5-d]咪唑-2,5(1H,3H)-二酮,1,3-双(羟甲基)-1-(1,3,4-三(羟甲基)-2,5-二氧代咪唑烷-4-基)脲(Diazolidinyl Urea)、1,3-双(羟甲基)-5,5-二甲基咪唑烷-2,4-二酮、3-乙酰基-2-羟基-6-甲基-4H-吡喃-4-酮、氯化十六烷基铵基吡啶、N-α-月桂酰-L-精氨酸乙酯盐酸盐、辛酰氧肟酸、山梨醇异羟肟酸及其混合物,
和/或
(c)至少一种羟基化合物选自组包括1,3-丙二醇、甲基丙二醇、1,2-戊二醇、1,2-己二醇、1,2-辛二醇、乙基己基甘油、辛酸甘油酯、癸酸甘油酯、3-苯基丙醇、2-苯基乙醇、2-苯氧基乙醇、苄醇、4-异丙基-3-甲基苯酚和4-羟基苯乙酮。
6.一种抗微生物混合物含有
(a)至少一种选自式(I)的芳香酯或酰胺衍生物的第一抗微生物制剂,和
(b)至少一种第二抗微生物制剂,选自组包括4-羟基苯乙酮、1,2-辛二醇、1,2-癸二醇、1,5-戊二醇、1,6-己二醇、1,8-辛二醇、1,2-癸二醇、己氧基-丙-1,2-二醇、庚氧基-丙-1,2-二醇、辛氧基-丙-1,2-二醇、3-苯氧基-丙-1,2-二醇、3-苄氧基-丙-1,2-二醇、3-苯基乙氧基-丙-1,2-二醇、3-苯基丙氧基-丙-1,2-二醇、3-甲基苄氧基-丙-1,2-二醇、辛酸甘油酯、癸酸甘油酯、月桂酸甘油酯、脫水山梨糖醇辛酸酯、乳酸丙酯、乳酸丁酯、乳酸戊酯、乳酸异戊酯、乳酸顺己-3-烯基酯、乳酸苄酯、三氯生、二唑丁酮、Octopirox(1-羟基-4-甲基-6-(2,4,4-三甲基戊基)-2(1H)-吡啶酮,2-氨基乙醇)、壳聚糖、金合欢醇、2-丁基辛酸、2-苄基庚-1-醇、甘油单月桂酸酯、双(2-嘧啶硫代)锌1,1'-二氧化物、N,N'-(癸-1,10-二基二吡啶-1-基-4-基亚基)-双辛胺-1-胺二盐酸化物(盐酸奥替尼啶)、麝香草酚、丁香油酚、4-异丙基-3-甲基苯酚、苄醇、4-甲基苄醇、2-苯乙醇、1-苯氧基-丙-2-醇、3-苯氧基丙醇、苄氧基甲醇,
(c)至少一种羟基化合物选自组包括1,3-丙二醇、甲基丙二醇、1,2-戊二醇、1,2-己二醇、1,2-辛二醇、乙基己基甘油、3-苯基丙醇、2-苯基乙醇和2-苯氧基乙醇。
7.一种个人护理组合物,含有有效量的至少一种式(I)的化合物或其(药用)盐或根据权利要求5或6所述的混合物。
8.一种清洁剂组合物,含有有效量的至少一种式(I)的化合物或其(药用)盐或根据权利要求5或6所述的混合物。
9.一种食品组合物,含有有效量的至少一种式(I)的化合物或其(药用)盐或根据权利要求5或6所述的混合物。
10.根据权利要求7所述的个人护理组合物、根据权利要求8所述的清洁剂组合物或根据权利要求9所述的食品组合物含有约0.01至约10重量%的至少一种式(I)的化合物或其(药用)盐或根据权利要求5或6所述的混合物—基于总组合物计。
11.一种用于局部施用的化妆组合物,含有水和至少一种选自组包括表面活性剂、乳化剂、增稠剂和油体的制剂,其中该组合物进一步含有0.01至10重量%的至少一种式(I)的化合物或其(药用)盐或根据权利要求5或6所述的混合物—基于总组合物计。
12.根据权利要求11所述的组合物,其中该组合物是洗发香波、护发素、O/W乳液、W/O乳液或凝胶。
13.根据权利要求11至12任一项所述的组合物,其中该组合物是施用至人类皮肤、头皮和/或毛发的局部制剂。
14.一种防止化妆组合物、清洁剂组合物或食品组合物微生物腐败的方法,所述方法包括向所述组合物加入0.01至10重量%的至少一种式(I)化合物或其(药用)盐或根据权利要求5或6所述的混合物—基于总组合物计。
15.一种抵抗不想要的体味的方法,向人类皮肤局部施用有效量的至少一种式(I)化合物或其(药用)盐或根据权利要求5或6所述的混合物。
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EP (2) | EP4450128A2 (zh) |
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WO2021243669A1 (en) * | 2020-06-05 | 2021-12-09 | Henkel Ag & Co. Kgaa | Use of a compound containing two or more alcoholic hydroxyl groups or phenolic hydroxyl groups as a microbiome regulator on scalp |
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CN115650808A (zh) * | 2022-09-21 | 2023-01-31 | 南京理工大学 | 一种硝酸羟胺基绿色无污染凝胶推进剂及其制备方法 |
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JP6828136B2 (ja) | 2021-02-10 |
EP4450128A2 (en) | 2024-10-23 |
BR112018073863B1 (pt) | 2022-08-23 |
CN109475120B (zh) | 2022-03-29 |
KR102637286B1 (ko) | 2024-02-16 |
KR20190069346A (ko) | 2019-06-19 |
WO2018068825A1 (en) | 2018-04-19 |
MX2018014358A (es) | 2019-03-14 |
US11116710B2 (en) | 2021-09-14 |
EP3525587A1 (en) | 2019-08-21 |
JP2019536733A (ja) | 2019-12-19 |
US20190282478A1 (en) | 2019-09-19 |
BR112018073863A2 (pt) | 2019-02-26 |
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