CN1902353A - 经稳定的身体护理品、家用制品、纺织品和织物 - Google Patents
经稳定的身体护理品、家用制品、纺织品和织物 Download PDFInfo
- Publication number
- CN1902353A CN1902353A CNA2004800397449A CN200480039744A CN1902353A CN 1902353 A CN1902353 A CN 1902353A CN A2004800397449 A CNA2004800397449 A CN A2004800397449A CN 200480039744 A CN200480039744 A CN 200480039744A CN 1902353 A CN1902353 A CN 1902353A
- Authority
- CN
- China
- Prior art keywords
- carbon atom
- hydroxyl
- tetramethyl
- alkyl
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004744 fabric Substances 0.000 title claims abstract description 35
- 239000004753 textile Substances 0.000 title claims abstract description 23
- 239000000047 product Substances 0.000 title abstract description 32
- -1 hydroxylamine salt compounds Chemical class 0.000 claims abstract description 247
- 239000004904 UV filter Substances 0.000 claims abstract description 57
- 239000002537 cosmetic Substances 0.000 claims abstract description 20
- 239000003599 detergent Substances 0.000 claims abstract description 16
- 239000002979 fabric softener Substances 0.000 claims abstract description 7
- 239000000551 dentifrice Substances 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 294
- 150000001721 carbon Chemical group 0.000 claims description 272
- 125000000217 alkyl group Chemical group 0.000 claims description 170
- 239000000203 mixture Substances 0.000 claims description 111
- 229910052739 hydrogen Inorganic materials 0.000 claims description 95
- 239000001257 hydrogen Substances 0.000 claims description 90
- 238000002360 preparation method Methods 0.000 claims description 87
- 239000002253 acid Substances 0.000 claims description 83
- 239000003795 chemical substances by application Substances 0.000 claims description 75
- 150000001875 compounds Chemical class 0.000 claims description 62
- 150000002431 hydrogen Chemical class 0.000 claims description 59
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 58
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 55
- 125000001118 alkylidene group Chemical group 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 49
- 210000004209 hair Anatomy 0.000 claims description 49
- 239000003921 oil Substances 0.000 claims description 45
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 44
- 150000002148 esters Chemical class 0.000 claims description 43
- 229910052760 oxygen Inorganic materials 0.000 claims description 43
- YYTYIUAYFBFKHX-UHFFFAOYSA-N n-(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)acetamide Chemical class CC(=O)NC1CC(C)(C)N(O)C(C)(C)C1 YYTYIUAYFBFKHX-UHFFFAOYSA-N 0.000 claims description 34
- 239000002585 base Substances 0.000 claims description 32
- 239000001301 oxygen Substances 0.000 claims description 31
- CSGAUKGQUCHWDP-UHFFFAOYSA-N 1-hydroxy-2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1O CSGAUKGQUCHWDP-UHFFFAOYSA-N 0.000 claims description 30
- KMEUSKGEUADGET-UHFFFAOYSA-N 1-hydroxy-2,2,6,6-tetramethylpiperidin-4-one Chemical class CC1(C)CC(=O)CC(C)(C)N1O KMEUSKGEUADGET-UHFFFAOYSA-N 0.000 claims description 30
- 229960003330 pentetic acid Drugs 0.000 claims description 29
- 229960001484 edetic acid Drugs 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 23
- 238000005192 partition Methods 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 20
- 239000003963 antioxidant agent Substances 0.000 claims description 20
- 230000003078 antioxidant effect Effects 0.000 claims description 20
- 235000006708 antioxidants Nutrition 0.000 claims description 20
- 229920001577 copolymer Polymers 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 239000000975 dye Substances 0.000 claims description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 19
- QNLIVQOXNYYXKO-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;1-hydroxy-2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1O.OC(=O)CC(O)(C(O)=O)CC(O)=O QNLIVQOXNYYXKO-UHFFFAOYSA-N 0.000 claims description 18
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 16
- 239000007921 spray Substances 0.000 claims description 16
- 125000001931 aliphatic group Chemical group 0.000 claims description 15
- 238000011282 treatment Methods 0.000 claims description 15
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 14
- 239000012459 cleaning agent Substances 0.000 claims description 14
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 14
- 229910019142 PO4 Inorganic materials 0.000 claims description 13
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 13
- 238000009472 formulation Methods 0.000 claims description 13
- 239000010452 phosphate Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 12
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 12
- 229940009662 edetate Drugs 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 235000013599 spices Nutrition 0.000 claims description 11
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 claims description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 10
- 125000004450 alkenylene group Chemical group 0.000 claims description 10
- 230000000474 nursing effect Effects 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 239000002453 shampoo Substances 0.000 claims description 10
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 9
- 235000010323 ascorbic acid Nutrition 0.000 claims description 9
- 229960005070 ascorbic acid Drugs 0.000 claims description 9
- 239000011668 ascorbic acid Substances 0.000 claims description 9
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 9
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 9
- 239000002304 perfume Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000002252 acyl group Chemical group 0.000 claims description 8
- 150000001408 amides Chemical class 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 125000002091 cationic group Chemical group 0.000 claims description 8
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical class C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003205 fragrance Substances 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- 241000370738 Chlorion Species 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 239000010985 leather Substances 0.000 claims description 7
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims description 7
- 239000000419 plant extract Substances 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 7
- 239000000344 soap Substances 0.000 claims description 7
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 229940088594 vitamin Drugs 0.000 claims description 7
- 229930003231 vitamin Natural products 0.000 claims description 7
- 235000013343 vitamin Nutrition 0.000 claims description 7
- 239000011782 vitamin Substances 0.000 claims description 7
- 150000003722 vitamin derivatives Chemical class 0.000 claims description 7
- 125000006839 xylylene group Chemical group 0.000 claims description 7
- HEOCBCNFKCOKBX-RELGSGGGSA-N (1s,2e,4r)-4,7,7-trimethyl-2-[(4-methylphenyl)methylidene]bicyclo[2.2.1]heptan-3-one Chemical compound C1=CC(C)=CC=C1\C=C/1C(=O)[C@]2(C)CC[C@H]\1C2(C)C HEOCBCNFKCOKBX-RELGSGGGSA-N 0.000 claims description 6
- UIERETOOQGIECD-ARJAWSKDSA-M 2-Methyl-2-butenoic acid Natural products C\C=C(\C)C([O-])=O UIERETOOQGIECD-ARJAWSKDSA-M 0.000 claims description 6
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims description 6
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-M benzoate Chemical compound [O-]C(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-M 0.000 claims description 6
- 229940006460 bromide ion Drugs 0.000 claims description 6
- 238000004043 dyeing Methods 0.000 claims description 6
- 239000001530 fumaric acid Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 6
- 229940049920 malate Drugs 0.000 claims description 6
- IWYDHOAUDWTVEP-UHFFFAOYSA-N mandelic acid Chemical group OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 6
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 6
- 150000003053 piperidines Chemical class 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 6
- 229940095064 tartrate Drugs 0.000 claims description 6
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 claims description 6
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical class C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims description 5
- VTQVLCXOOIFPBB-UHFFFAOYSA-N 4-ethyl-5-hexyl-1H-triazin-6-one Chemical compound C(C)C1=C(C(NN=N1)=O)CCCCCC VTQVLCXOOIFPBB-UHFFFAOYSA-N 0.000 claims description 5
- 229930003427 Vitamin E Natural products 0.000 claims description 5
- 238000005034 decoration Methods 0.000 claims description 5
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 claims description 5
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 5
- 229940046009 vitamin E Drugs 0.000 claims description 5
- 235000019165 vitamin E Nutrition 0.000 claims description 5
- 239000011709 vitamin E Substances 0.000 claims description 5
- QCJDXHSSMDQRBO-UHFFFAOYSA-N 1-hydroxy-2,2,6,6-tetramethylpiperidin-1-ium-4-ol;chloride Chemical compound [Cl-].CC1(C)CC(O)CC(C)(C)[NH+]1O QCJDXHSSMDQRBO-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- XHGLDJYVOVYQHP-UHFFFAOYSA-N C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.NCCNCCN.ON1C(CC(CC1(C)C)=O)(C)C Chemical compound C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.NCCNCCN.ON1C(CC(CC1(C)C)=O)(C)C XHGLDJYVOVYQHP-UHFFFAOYSA-N 0.000 claims description 4
- HBKBRFMRGDUJOU-UHFFFAOYSA-N C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.NCCNCCN.ON1C(CC(CC1(C)C)O)(C)C Chemical compound C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.NCCNCCN.ON1C(CC(CC1(C)C)O)(C)C HBKBRFMRGDUJOU-UHFFFAOYSA-N 0.000 claims description 4
- 241001446187 Kermes Species 0.000 claims description 4
- CZBNQEHYRAWYJW-UHFFFAOYSA-N S(=O)(=O)(O)OS(=O)(=O)O.ON1C(CC(CC1(C)C)O)(C)C Chemical compound S(=O)(=O)(O)OS(=O)(=O)O.ON1C(CC(CC1(C)C)O)(C)C CZBNQEHYRAWYJW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052770 Uranium Inorganic materials 0.000 claims description 4
- 229920006387 Vinylite Polymers 0.000 claims description 4
- LUTRAMFAYXFIQK-UHFFFAOYSA-N acetic acid;1-hydroxy-2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC([O-])=O.CC1(C)CC(O)CC(C)(C)[NH+]1O LUTRAMFAYXFIQK-UHFFFAOYSA-N 0.000 claims description 4
- QTONSPKDOKVNBJ-UHFFFAOYSA-N acetic acid;n'-(2-aminoethyl)ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCN QTONSPKDOKVNBJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001449 anionic compounds Chemical group 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 230000000844 anti-bacterial effect Effects 0.000 claims description 4
- 230000003115 biocidal effect Effects 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229960004697 enzacamene Drugs 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000005556 hormone Substances 0.000 claims description 4
- 229940088597 hormone Drugs 0.000 claims description 4
- CXORMDKZEUMQHX-UHFFFAOYSA-N kermesic acid Chemical compound O=C1C2=C(O)C(O)=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C CXORMDKZEUMQHX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004611 light stabiliser Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 150000002891 organic anions Chemical group 0.000 claims description 4
- AFDXODALSZRGIH-UHFFFAOYSA-N p-coumaric acid methyl ether Natural products COC1=CC=C(C=CC(O)=O)C=C1 AFDXODALSZRGIH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229940116351 sebacate Drugs 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- ZAKOWWREFLAJOT-CEFNRUSXSA-N D-alpha-tocopherylacetate Chemical compound CC(=O)OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C ZAKOWWREFLAJOT-CEFNRUSXSA-N 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 3
- 239000002386 air freshener Substances 0.000 claims description 3
- 210000000476 body water Anatomy 0.000 claims description 3
- 235000021466 carotenoid Nutrition 0.000 claims description 3
- 150000001747 carotenoids Chemical class 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229940114081 cinnamate Drugs 0.000 claims description 3
- 239000008294 cold cream Substances 0.000 claims description 3
- ZAKOWWREFLAJOT-UHFFFAOYSA-N d-alpha-Tocopheryl acetate Natural products CC(=O)OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C ZAKOWWREFLAJOT-UHFFFAOYSA-N 0.000 claims description 3
- 230000001877 deodorizing effect Effects 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229930003935 flavonoid Natural products 0.000 claims description 3
- 150000002215 flavonoids Chemical class 0.000 claims description 3
- 235000017173 flavonoids Nutrition 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 230000003711 photoprotective effect Effects 0.000 claims description 3
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 3
- 235000013824 polyphenols Nutrition 0.000 claims description 3
- 229940042585 tocopherol acetate Drugs 0.000 claims description 3
- OIQXFRANQVWXJF-QBFSEMIESA-N (2z)-2-benzylidene-4,7,7-trimethylbicyclo[2.2.1]heptan-3-one Chemical compound CC1(C)C2CCC1(C)C(=O)\C2=C/C1=CC=CC=C1 OIQXFRANQVWXJF-QBFSEMIESA-N 0.000 claims description 2
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Abstract
本发明披露了经稳定的身体护理品、家用制品、纺织品和织物,其包含某些受阻硝酰基化合物、受阻羟胺化合物和受阻羟胺盐化合物以及选定的有机UV滤光材料。所述经稳定的制品例如是护肤品、头发护理用品、洁齿剂、化妆品、洗衣用洗涤剂和织物软化剂、基于非洗涤剂的织物护理用品、家用清洁剂和纺织品护理用品。
Description
本发明涉及选定的受阻硝酰基化合物、羟胺和羟胺盐化合物以及选定的有机UV滤光材料的用途,其用于保护身体护理品、个人护理品、家用制品、织物护理品、公共设施与工业用制品、纺织品(textile)和织物(fabrics)不受光、热和氧气的有害影响。
由于当今的消费者可以挑选众多的家用和个人护理品,制造商需要清楚地表明其品牌如何独特。以透明和半透明包装呈现的、在多种色彩的组合物中包含新型香味和活性成分的专业化产品如今十分常见。
即使当严重暴露于UV光下时,消费品的合意外观、产品功效和清新气味在其整个产品寿命周期中也会维持,这对于商业上的成功是必要的。这样的暴露可以导致破坏制品外观、活性成分和香味的分解过程和强烈的褪色。
多种通过吸收UV光的透明包装制品稳定技术是常用和公知的。例如,与主要吸收UV-B光线的其他吸收剂如二苯甲酮类相比,苯并三唑类的宽谱带UV光稳定剂由于它们良好的UV-A和UV-B吸收性能而提高制品的稳定性和保存期限。
然而,仅仅通过UV光的吸收,并没有阻断所有潜在的退化途径。
令人惊讶地,发现用选自硝酰基化合物、受阻羟胺化合物和受阻羟胺盐化合物的特定化合物以及特定的有机UV吸收剂可以实现有效的保护。
背景技术
WO 01/07550教导用受阻胺稳定剂处理纤维。
美国专利6,254,724教导用基于受阻胺的化合物的稳定化纸浆和纸张。
发明内容
本发明涉及一种经稳定的组合物(stabilized composition),其包含:
(a)身体护理品、家用制品、纺织品或织物,和
(b)有效稳定量的至少一种化合物,其选自:
(i)式(I)的受阻硝酰基化合物
(ii)式(II)的受阻羟胺化合物
和
其中
G1和G2独立地是1-4个碳原子的烷基,或一起为五亚甲基(pentamethylene),
Z1和Z2各自为甲基,或Z1和Z2一起形成可以另外地被酯、醚、羟基、氧代(oxo)、氰醇(cyanohydrin)、酰胺、氨基、羧基或氨基甲酸酯基团取代的连接部分(linking moiety),
X是无机或有机阴离子,如磷酸根,膦酸根,碳酸根,碳酸氢根,硝酸根,氯离子,溴离子,亚硫酸氢根,亚硫酸根,硫酸氢根,硫酸根,硼酸根,甲酸根,乙酸根,苯甲酸根,柠檬酸根,草酸根,酒石酸根,丙烯酸根,聚丙烯酸根(polyacrylate),富马酸根,马来酸根,衣康酸根,乙醇酸根,葡糖酸根,苹果酸根,扁桃酸根,惕各酸根(tiglate),抗坏血酸根,聚甲基丙烯酸根(polymethacrylate),次氮基三乙酸的羧酸根、羟乙基乙二胺三乙酸的羧酸根、乙二胺四乙酸的羧酸根或二亚乙基三胺五乙酸的羧酸根,二亚乙基三胺五亚甲基膦酸根、烷基磺酸根或芳基磺酸根,以及
其中阳离子的总电荷h等于阴离子的总电荷j;和
(c)选自下列物质的有机UV滤光材料:
(c1)二苯甲酰甲烷衍生物;
(c2)肉桂酸酯;
(c3)樟脑衍生物;和
(c4)三苯胺基-s-三嗪衍生物。
举例来说,X是氯离子、亚硫酸氢根、亚硫酸根、硫酸根、磷酸根、硝酸根、抗坏血酸根、乙酸根、柠檬酸根或乙二胺四乙酸的羧酸根或二亚乙基三胺五乙酸的羧酸根;例如,X是亚硫酸氢根或柠檬酸根。
组分(b)的受阻硝酰基化合物、受阻羟胺化合物以及受阻羟胺盐化合物例如是式A至EE以及A*至EE*的化合物。
其中
E是氧基(oxyl)或羟基,
R是氢或甲基。
在式A和A*中
n是1或2,
当n是1时,
R1是氢,1-18个碳原子的烷基,2-18个碳原子的烯基,炔丙基,缩水甘油基,被1-20个氧原子隔断的2-50个碳原子的烷基、被1-10个羟基取代的所述烷基或者既被所述氧原子隔断又被所述羟基取代的所述烷基,或
R1是被羧基或-COOZ取代的1-4个碳原子的烷基,其中Z是氢、1-4个碳原子的烷基或苯基,或者其中Z是被-(COO-)nMn+取代的所述烷基,其中n是1-3以及M是周期表中第一、第二或第三族的金属离子或Zn、Cu、Ni或Co,或者M是基团Nn+(R2)4,其中R2是1-8个碳原子的烷基或苄基,
当n是2时,
R1是1-12个碳原子的亚烷基,4-12个碳原子的亚烯基,亚二甲苯基(xylylene)或被1-20个氧原子隔断的、被1-10个羟基取代的或者既被所述氧原子隔断又被所述羟基取代的1-50个碳原子的亚烷基,
在式B和B*中,
m是1-4,
当m是1时,
R2是1-18个碳原子的烷基,被-COO-隔断的3-18个碳原子的烷基,或者R2是-CH2(OCH2CH2)nOCH3,其中n是1-12,或
R2是5-12个碳原子的环烷基,6-12个碳原子的芳基,或被1-4个具有1-4个碳原子的烷基取代的所述芳基,或
R2是-NHR3,其中R3是1-18个碳原子的烷基、5-12个碳原子的环烷基、6-12个碳原子的芳基,或被1-4个具有1-4个碳原子的烷基取代的所述芳基,或
R2是-N(R3)2,其中R3如上所定义,
当m是2时,
R2是1-12个碳原子的亚烷基,4-12个碳原子的亚烯基,亚二甲苯基,被-COO-隔断的2-12个碳原子的亚烷基,或者R2是-CH2(OCH2CH2)nOCH2-,其中n是1-12,或
R2是5-12个碳原子的亚环烷基,7-15个碳原子的亚芳烷基(aralkylene),或6-12个碳原子的亚芳基,或
R2是-NHR4NH-,其中R4是2-18个碳原子的亚烷基、5-12个碳原子的亚环烷基、8-15个碳原子的亚芳烷基或6-12个碳原子的亚芳基,或
R2是-N(R3)R4N(R3)-,其中R3和R4如上所定义,或
R2是-CO-或-NH-CO-NH-,
当m是3时,
R2是3-8个碳原子的烷三基(alkanetriyl)或苯三基(benzenetriyl),或
当m是4时,
R2是5-8个碳原子的烷四基(alkanetetrayl)或苯四基(benzenetetrayl),
在式C和C*中,
R10是氢,1-18个碳原子的烷基,5-12个碳原子的环烷基,7-15个碳原子的芳烷基,2-18个碳原子的烷酰基,3-5个碳原子的烯酰基或苯甲酰基,
x是1或2
当x是1时,
R11是氢,1-18个碳原子的烷基,2-18个碳原子的烯基,炔丙基,缩水甘油基,被1-20个氧原子隔断的2-50个碳原子的烷基、被1-10个羟基取代的所述烷基或者既被所述氧原子隔断又被所述羟基取代的所述烷基,或
R11是被羧基或-COOZ取代的1-4个碳原子的烷基,其中Z是氢、1-4个碳原子的烷基或苯基,或者其中Z是被-(COO-)nMn+取代的所述烷基,其中n是1-3以及M是周期表中第一、第二或第三族的金属离子或Zn、Cu、Ni或Co,或者M是基团Nn+(R2)4,其中R2是氢、1-8个碳原子的烷基或苄基,
当x是2时,
R11是1-12个碳原子的亚烷基,4-12个碳原子的亚烯基,亚二甲苯基或被1-20个氧原子隔断的、被1-10个羟基取代的或者既被所述氧原子隔断又被所述羟基取代的1-50个碳原子的亚烷基,
在式D和D*中,
R10如上所定义,
y是1-4,和
R12如上述R2所定义的,
在式E和E*中,
k是1或2
当k是1时,
R20和R21独立地是1-12个碳原子的烷基,2-12个碳原子的烯基或7-15个碳原子的芳烷基,或R20还可以是氢,或
R20和R21一起为2-8个碳原子的亚烷基或被羟基取代的所述亚烷基,或是4-22个碳原子的酰氧基-亚烷基,或
当k是2时,
R20和R21一起为(-CH2)2C(CH2-)2,
在式F和F*中,
R30是氢,1-18个碳原子的烷基,苄基,缩水甘油基,或2-6个碳原子的烷氧基烷基,
g是1或2,
当g是1时,R31如上述n为1时R1所定义,
当g是2时,R31如上述n为2时R1所定义,
在式G和G*中,
Q1是-NR41-或-O-,
E1是1-3个碳原子的亚烷基,或E1是-CH2-CH(R42)-O-,其中R42是氢、甲基或苯基,或E1是-(CH2)3-NH-或E1是直键(direct bond),
R40是氢或1-18个碳原子的烷基,
R41是氢,1-18个碳原子的烷基,5-12个碳原子的环烷基,7-15个碳原子的芳烷基,6-10个碳原子的芳基,或R41是-CH2-CH(R42)-OH,其中R42如上所定义,
在式H和H*中,
p是1或2
T4如x是1或2时R11所定义的,
M和Y独立地是亚甲基或羰基,例如M是亚甲基和Y是羰基,
在式I和I*中,
该式表示聚合物的重复结构单元,其中T1是乙烯或1,2-丙烯或是衍生自α-烯烃与丙烯酸烷基酯或甲基丙烯酸烷基酯的共聚物的重复结构单元,以及其中,
q是2-100,
Q1是-N(R41)-或-O-,其中R41如上所定义,
在式J和J*中,
r是1或2
T7如式A中当n是1或2时R1所定义的,
例如当r是2时T7是八亚甲基(octamethylene),
在式L和L*中,
u是1或2,
T13如式A中n是1或2时R1所定义的,条件是当u是1时T13不是氢,
在式M和M*中,
E1和E2不同,且各自为-CO-或-N(E5)-,其中E5是氢、1-12个碳原子的烷基或4-22个碳原子的烷氧羰基烷基,例如E1是-CO-和E2是-N(E5)-,
E3是氢,1-30个碳原子的烷基,苯基,萘基,被氯或1-4个碳原子的烷基取代的所述苯基或所述萘基,或7-12个碳原子的苯基烷基,或被1-4个碳原子的烷基取代的所述苯基烷基,
E4是氢,1-30个碳原子的烷基,苯基,萘基或7-12个碳原子的苯基烷基,或
E3和E4一起为4-17个碳原子的聚亚甲基(polymethylene),或被1-4个具有1-4个碳原子的烷基如甲基所取代的所述聚亚甲基,
在式N中,
R1如式A中n是1时对R1所定义的,
G3是直键,1-12个碳原子的亚烷基,亚苯基或-NH-G1-NH-,其中G1是1-12个碳原子的亚烷基,
在式O和O*中,
R10如式C中对R10所定义的,
在式P和P*中,
E6是脂族或芳族四价基团,例如新戊四基或苯四基,
在式T和T*中,
R51是氢,1-18个碳原子的烷基,5-12个碳原子的环烷基,或6-10个碳原子的芳基,
R52是氢或1-18个碳原子的烷基,或
R51和R52一起为4-8个碳原子的亚烷基,
f是1或2,
当f是1时,
R50如式C中x是1时对R11所定义的,或R50是-(CH2)zCOOR54,其中z是1-4以及R54是氢或1-18个碳原子的烷基,或R54是周期表第一、第二或第三族的金属离子或基团-N(R55)4,其中R55是氢、1-12个碳原子的烷基或苄基,
当f是2时,R50如式C中x是2时对R11所定义的,
在式U和U*中,
R53、R54、R55和R56独立地是1-4个碳原子的烷基或一起为五亚甲基,
在式V和V*中,
R57、R58、R59和R60独立地是1-4个碳原子的烷基或一起为五亚甲基,
在式W和W*中,
R61、R62、R63和R64独立地是1-4个碳原子的烷基或一起为五亚甲基,
R65是1-5个碳原子的烷基,
M是氢或氧,
其中在式X至CC和X*至CC*中,
n是2-3,
G1是氢、甲基、乙基、丁基或苄基,
m是1-4,
x是1-4,
当x是1时,
R1和R2独立地是1-18个碳原子的烷基,被1-5个氧原子隔断的所述烷基,被1-5个羟基取代的所述烷基,或者既被所述氧原子隔断又被所述羟基取代的所述烷基;5-12个碳原子的环烷基,7-15个碳原子的芳烷基,6-10个碳原子的芳基或被1-3个具有1-8个碳原子的烷基取代的所述芳基,或R1还可以是氢,
或R1和R2一起为四亚甲基、五亚甲基、六亚甲基或3-氧杂五亚甲基基,
当x是2时,
R1是氢,1-8个碳原子的烷基,被1或2个氧原子隔断的所述烷基,被羟基取代的所述烷基,或者既被1或2个氧原子隔断又被羟基取代的所述烷基,
R2是2-18个碳原子的亚烷基,被1-5个氧原子隔断的所述亚烷基,被1-5个羟基取代的所述亚烷基,或者既被所述氧原子隔断又被所述羟基取代的所述亚烷基;邻-、间-或对-亚苯基,或被1或2个具有1-4个碳原子的烷基取代的所述亚苯基,或
R2是-(CH2)kO[(CH2)kO]h(CH2)k-,其中k是2-4以及h是1-40,或
R1和R2与连接至其上的两个N原子一起为哌嗪-1,4-二基,
当x是3时,
R1是氢,
R2是被1个氮原子隔断的4-8个碳原子的亚烷基,
当x是4时,
R1是氢,
R2是被2个氮原子隔断的6-12个碳原子的亚烷基,
R3是氢,1-8个碳原子的烷基,被1或2个氧原子隔断的所述烷基,被羟基取代的所述烷基,或者既被1或2个氧原子隔断又被羟基取代的所述烷基,
P是2或3,以及
Q是碱金属盐、铵或N+(G1)4,
在式DD和DD*中,
m是2或3,
当m是2时,
G是-(CH2CHR-O)rCH2CHR-,其中r是0-3,以及R是氢或甲基,和
当m是3时,
G是甘油基,
在式EE和EE*中,
G2是-CN、-CONH2或-COOG3,其中G3是氢、1-18个碳原子的烷基或苯基,
X是无机或有机阴离子,如磷酸根,膦酸根,碳酸根,碳酸氢根,硝酸根,氯离子,溴离子,亚硫酸氢根,亚硫酸根,硫酸氢根,硫酸根,硼酸根,甲酸根,乙酸根,苯甲酸根,柠檬酸根,草酸根,酒石酸根,丙烯酸根,聚丙烯酸根,富马酸根,马来酸根,衣康酸根,乙醇酸根,葡糖酸根,苹果酸根,扁桃酸根,惕各酸根,抗坏血酸根,聚甲基丙烯酸根,次氮基三乙酸的羧酸根、羟乙基乙二胺三乙酸的羧酸根、乙二胺四乙酸的羧酸根或二亚乙基三胺五乙酸的羧酸根,二亚乙基三胺五亚甲基膦酸根、烷基磺酸根或芳基磺酸根,以及
其中阳离子的总电荷h等于阴离子的总电荷j。
例如,组分(b)的化合物为式A、A*、B、B*、C、C*、D、D*、Q、Q*、R、R*、S、S*、X、X*、Y、Y*、Z和Z*的那些,
R是氢,
在式A和A*中
n是1或2,
当n是1时,
R1是氢,1-6个碳原子的烷基,2-6个碳原子的烯基,炔丙基,缩水甘油基,被1-10个氧原子隔断的2-20个碳原子的烷基,被1-5个羟基取代的所述烷基或者既被所述氧原子隔断又被所述羟基取代的所述烷基,或
R1是被羧基或-COOZ取代的1-4个碳原子的烷基,其中Z是氢、1-4个碳原子的烷基,
当n是2时,
R1是1-8个碳原子的亚烷基,4-8个碳原子的亚烯基,被1-10个氧原子隔断的、被1-5个羟基取代的或者既被所述氧原子隔断又被所述羟基取代的1-20个碳原子的亚烷基,
在式B和B*中,
m是1或2,
当m是1时,
R2是1-4个碳原子的烷基或者R2是CH2(OCH2CH2)nOCH3,其中n是1-12,或
R2是苯基,或被1-3个甲基取代的所述苯基,
R2是-NHR3,其中R3是1-4个碳原子的烷基或苯基、或被1或2个甲基取代的所述苯基,
当m是2时,
R2是1-8个碳原子的亚烷基,4-8个碳原子的亚烯基,或者R2是-CH2(OCH2CH2)nOCH2-,其中n是1-12,
R2是NHR4NH,其中R4是2-6个碳原子的亚烷基、8-15个碳原子的亚芳烷基或6-12个碳原子的亚芳基,
R2是-CO-或-NHCONH-,
在式C和C*中,
R10是氢,或1-3个碳原子的烷酰基,
x是1或2
当x是1时,
R11是氢,1-6个碳原子的烷基或缩水甘油基,
R11是被羧基或COOZ取代的1-4个碳原子的烷基,其中Z是氢或1-4个碳原子的烷基,
当x是2时,
R11是1-6个碳原子的亚烷基,
在式D和D*中,
R10是氢,
y是1或2,
R12如上述R2所定义的,
在式Y、Y*、Z和Z*中,
x是1或2,
当x是1时,
R1和R2独立地是1-4个碳原子的烷基,
或R1和R2一起为四亚甲基或五亚甲基,
R2是氢或1-4个碳原子的烷基、被羟基取代的所述烷基,
当x是2时,
R1是氢,1-4个碳原子的烷基,被羟基取代的所述烷基,
R2是2-6个碳原子的亚烷基,
R3如上所定义。
例如,组分(b)的化合物为式A、A*、B、B*、C、C*、D、D*、Q、Q*、R和R*的那些,
R是氢,
在式A和A*中
h是1,
R1是氢,1-4个碳原子的烷基,缩水甘油基,被1或2个氧原子隔断的2-4个碳原子的烷基,被1或2个羟基取代的所述烷基或者既被所述氧原子隔断又被所述羟基取代的所述烷基,或
R1是被-COOZ取代的1-4个碳原子的烷基,其中Z是氢或1-4个碳原子的烷基,
在式B和B*中,
m是1或2,
当m是1时,
R2是1-4个碳原子的烷基或者R2是CH2(OCH2CH2)nOCH3,其中n是1-4,
当m是2时,
R2是1-8个碳原子的亚烷基,
在式C和C*中,
R10是氢,或1或2个碳原子的烷酰基,
x是1或2
当x是1时,
R11是氢,1-4个碳原子的烷基或缩水甘油基,
R11是被COOZ取代的1-4个碳原子的烷基,其中Z是氢或1-4个碳原子的烷基,
当x是2时,
R11是1-6个碳原子的亚烷基,
在式D和D*中,
R10是氢,
y是1或2,
R12如上述R2所定义的。
例如,组分(b)的受阻硝酰基化合物、受阻羟胺化合物和受阻羟胺盐化合物选自二(1-氧基-2,2-6-6-四甲基哌啶-4-基)癸二酸盐;二(1-羟基-2,2-6-6-四甲基哌啶-4-基)癸二酸盐;1-羟基-2,2-6-6-四甲基-4-乙酰氧基哌啶鎓柠檬酸盐;1-氧基-2,2,6,6-四甲基-4-乙酰氨基哌啶;1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶;1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓硫酸氢盐;1-氧基-2,2,6,6-四甲基-4-氧代-哌啶;1-羟基-2,2,6,6-四甲基-4-氧代-哌啶;1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓乙酸盐;1-氧基-2,2,6,6-四甲基-4-甲氧基-哌啶;1-羟基-2,2,6,6-四甲基-4-甲氧基-哌啶;1-羟基-2,2,6,6-四甲基-4-甲氧基-哌啶鎓乙酸盐;1-氧基-2,2,6,6-四甲基-4-乙酰氧基哌啶;1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶;1-氧基-2,2,6,6-四甲基-4-丙氧基-哌啶;1-羟基-2,2,6,6-四甲基-4-丙氧基-哌啶鎓乙酸盐;1-羟基-2,2,6,6-四甲基-4-丙氧基-哌啶;1-氧基-2,2,6,6-四甲基-4-(2-羟基-4-氧杂戊氧基)哌啶;1-羟基-2,2,6,6-四甲基-4-(2-羟基4-氧杂戊氧基)哌啶鎓乙酸盐;1-氧基-2,2,6,6-四甲基-4-羟基哌啶;1-羟基-2,2,6,6-四甲基-4-羟基哌啶;1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓氯化物;1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓乙酸盐;1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓硫酸氢盐;1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓柠檬酸盐;二(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)柠檬酸盐;三(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)柠檬酸盐;四(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)乙二胺四乙酸盐;四(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)乙二胺四乙酸盐;四(1-羟基-2,2,6,6-四甲基-4-氧代哌啶鎓)乙二胺四乙酸盐;五(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)二亚乙基三胺五乙酸盐;五(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)二亚乙基三胺五乙酸盐;五(1-羟基-2,2,6,6-四甲基-4-氧代哌啶鎓)二亚乙基三胺五乙酸盐;三(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)次氮基三乙酸盐;三(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)次氮基三乙酸盐;三(1-羟基-2,2,6,6-四甲基-4-氧代哌啶鎓)次氮基三乙酸盐;五(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)二亚乙基三胺五亚甲基膦酸盐;五(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)二亚乙基三胺五亚甲基膦酸盐;以及五(1-羟基-2,2,6,6-四甲基-4-氧代哌啶鎓)二亚乙基三胺五亚甲基膦酸盐。
例如,组分(b)的受阻硝酰基化合物、受阻羟胺化合物和受阻羟胺盐化合物选自1-氧基-2,2,6,6-四甲基-4-羟基哌啶;1-羟基-2,2,6,6-四甲基-4-羟基哌啶;1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓氯化物;1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓乙酸盐;1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓硫酸氢盐;1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓柠檬酸盐;二(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)柠檬酸盐;三(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)柠檬酸盐;四(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)乙二胺四乙酸盐;四(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)乙二胺四乙酸盐;四(1-羟基-2,2,6,6-四甲基-4-氧代哌啶鎓)乙二胺四乙酸盐;五(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)二亚乙基三胺五乙酸盐;五(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)二亚乙基三胺五乙酸盐;以及五(1-羟基-2,2,6,6-四甲基-4-氧代哌啶鎓)二亚乙基三胺五乙酸盐。
例如,组分(b)的化合物选自1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓柠檬酸盐;二(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)柠檬酸盐;三(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)柠檬酸盐;1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓DTPA;二(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)DTPA;三(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)DTPA;四(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)DTPA;五(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)DTPA;1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓EDTA;二(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)EDTA;三(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)EDTA;四(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)EDTA;1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓柠檬酸盐;二(1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓)柠檬酸盐;三(1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓)柠檬酸盐;1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓DTPA;二(1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓)DTPA;三(1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓)DTPA;四(1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓)DTPA;五(1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓)DTPA;1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓EDTA;二(1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓)EDTA;三(1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓)EDTA;四(1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓)EDTA;1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓柠檬酸盐;二(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)柠檬酸盐;三(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)柠檬酸盐;1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓DTPA;二(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)DTPA;三(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)DTPA;四(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)DTPA;五(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)DTPA;1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓EDTA;二(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)EDTA;三(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)EDTA;四(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)EDTA;1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶鎓柠檬酸盐;二(1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶鎓)柠檬酸盐;三(1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶鎓)柠檬酸盐;1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶鎓DTPA;二(1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶鎓)DTPA;三(1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶鎓)DTPA;四(1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶鎓)DTPA;五(1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶鎓)DTPA;1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶鎓EDTA;二(1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶鎓)EDTA;三(1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶鎓)EDTA以及四(1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶鎓)EDTA。
上述的抗衡离子是乙二胺四乙酸(EDTA)、二亚乙基三胺五乙酸(DTPA)、羟乙基乙二胺三乙酸(HEDTA)、次氮基三乙酸(NTA)或二亚乙基三胺五亚甲基膦酸(DTPMPA)。
所述有机UV吸收剂组分(c1)优选选自丁基甲氧基二苯甲酰甲烷、乙基己基甲氧基二苯甲酰甲烷和异丙基二苯甲酰甲烷。
组分(c1)最优选选自4-叔丁基-4’-甲氧基二苯甲酰甲烷和4-乙基己基-4’-甲氧基二苯甲酰甲烷。最优选的是1-(4-叔丁基苯基)-3-(4-甲氧基苯基)丙烷-1,3-二酮。
组分(c2)优选选自甲氧基肉桂酸辛基酯(4-甲氧基肉桂酸2-乙基己基酯),甲氧基肉桂酸二乙醇胺盐(4-甲氧基肉桂酸的二乙醇胺盐),对-甲氧基肉桂酸异戊基酯(4-甲氧基肉桂酸2-异戊基酯),肉桂酸2,5-二异丙基甲基酯和肉桂酸酰胺衍生物,以及最优选甲氧基肉桂酸辛基酯。
组分(c3)优选选自4-甲基-苯亚甲基樟脑(3-(4’-甲基)-苯亚甲基-莰-2-酮),3-苯亚甲基樟脑(3-苯亚甲基-莰-2-酮),聚丙烯酰胺基甲基苯亚甲基樟脑{N-[2(和4)-2-氧-冰片-3-基亚基-甲基)苄基]-丙烯酰胺聚合物(N-[2(and4)-2-oxyborn-3-ylidene-methyl)benzyl]acrylamide polymer)},三甲铵-苯亚甲基樟脑硫酸盐(trimonium-benzylidene camphor sulfate)[3-(4’-三甲基铵)-苯亚甲基-莰-2-酮甲基硫酸盐],对苯二亚甲基二樟脑磺酸(terephthalydenedicamphorsulfonic acid){3,3’-(1,4-亚苯基二次甲基)-二(7,7-二甲基-2-氧代-二环[2.2.1]庚烷-1-甲磺酸}或其盐,以及苯亚甲基樟脑磺酸[3-(4’-磺基)苯亚甲基莰-2-酮]或其盐,以及最优选选自4-甲基-苯亚甲基樟脑。
组分(c4)优选选自二乙基己基丁酰氨基三嗪酮和乙基己基三嗪酮。最优选使用乙基己基三嗪酮。
可以将组分(c)的有机UV滤光材料以与其他市场上可购得的UV滤光材料混合使用。可以使用的合适UV吸收剂列于下表中:
表1:其它UV吸收剂 |
对-氨基苯甲酸衍生物,如4-二甲基氨基苯甲酸2-乙基己基酯 |
水杨酸衍生物,如水杨酸2-乙基己基酯 |
二苯甲酮衍生物,如2-羟基-4-甲氧基二苯甲酮及其5-磺酸衍生物 |
二苯基丙烯酸酯,如2-氰基-3,3-二苯基丙烯酸2-乙基己基酯,和3-(苯并呋喃基)2-氰基丙烯酸酯 |
3-咪唑-4-基丙烯酸及其酯 |
苯并呋喃衍生物,尤其是2-(对-氨基苯基)苯并呋喃衍生物,在EP-A-582189、US-A-5 338 539、US-A-5 518 713和EP-A-613 893中得到描述 |
聚合物UV吸收剂,如在EP-A-709 080中描述的丙二酸亚苄酯衍生物 |
羟基苯基三嗪化合物,如2-(4’-甲氧基苯基)-4,6-二(2’-羟基-4’-正辛基氧苯基)-1,3,5-三嗪;2,4-二{[4-(3-(2-丙基氧)-2-羟基-丙基氧)-2-羟基]-苯基}-6-(4-甲氧基苯基)-1,3,5-三嗪;2,4-二{[4-(三(三甲基甲硅烷基氧-甲硅烷基丙基氧)-2-羟基]-苯基}-6-(4-甲氧基苯基)-1,3,5-三嗪;2,4-二{[4-(2”-甲基丙烯基氧)-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’,-七甲基三甲硅烷基-2”-甲基-丙基氧)-2-羟基]-苯基}-6-(4-甲氧基苯基)-1,3,5-三嗪 |
苯并三唑化合物,如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 |
2-苯基苯并咪唑-5-磺酸及其盐 |
邻氨基苯甲酸甲酯 |
优选使用下列的混合物
-二苯甲酰甲烷衍生物(组分c1)与二苯基丙烯酸酯;
-二苯甲酰甲烷衍生物(组分c1)与肉桂酸酯(组分c2)。
本发明组合物可以包含其他的常规添加剂,如抗氧化剂。
因此,本发明进一步涉及一种经稳定的组合物,其包含
(a)身体护理品、家用制品、公共设施与工业用制品(institutional &industrial products)、纺织品或织物,
(b)有效稳定量的至少一种化合物,其选自:
(i)式(I)的受阻硝酰基化合物,
(ii)式(II)的受阻羟胺化合物和
(iii)式(III)的受阻羟胺盐化合物,
(c)选自下列物质的有机UV滤光材料
(c1)二苯甲酰甲烷衍生物;
(c2)肉桂酸衍生物;
(c3)樟脑衍生物;和
(c4)三苯胺基-s-三嗪衍生物;以及
选自抗氧化剂、维生素E、醋酸维生素E、受阻胺光稳定剂、络合物形成剂(complex former)、荧光增白剂、表面活性剂和聚有机硅氧烷中的至少一种化合物。
其它合适抗氧化剂例如选自受阻酚和苯并呋喃酮稳定剂。
适合的抗氧化剂例如选自下列物质
组分(d)的受阻胺光稳定剂(hindered amine light stabilizers,HALS)例如是已知的商业性化合物。其例如选自癸二酸二(2,2,6,6-四甲基哌啶-4-基)酯,琥珀酸二(2,2,6,6-四甲基哌啶-4-基)酯,癸二酸二(1,2,2,6,6-五甲基哌啶-4-基)酯,正丁基-3,5-二叔丁基-4-羟基苄基丙二酸-二(1,2,2,6,6-五甲基哌啶基)酯,1-羟基乙基-2,2,6,6-四甲基-4-羟基哌啶与琥珀酸的缩合物,N,N′-二(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺与4-叔辛基氨基-2,6-二氯-1,3,5-s-三嗪的缩合物,三(2,2,6,6-四甲基-4-哌啶基)次氮基三乙酸酯,四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁四酸,1,1′-(1,2-乙烷二基)-二(3,3,5,5-四甲基哌嗪酮),4-苯甲酰-2,2,6,6-四甲基哌啶,4-十八烷氧基-2,2,6,6-四甲基哌啶,二(1,2,2,6,6-五甲基哌啶基)-2-正丁基-2-(2-羟基-3,5-二叔丁基苄基)丙二酸酯,3-正辛基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮,N,N-二(2,2,6,6-四甲基4-哌啶基)六亚甲基二胺与4-吗啉代-2,6-二氯-1,3,5-三嗪的缩合物,2-氯-4,6-二(4-正丁基氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪与1,2-二(3-氨基丙基氨基)乙烷的缩合物,2-氯-4,6-二(4-正丁基氨基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪与1,2-二(3-氨基丙基氨基)乙烷的缩合物,8-乙酰基-3-十二烷基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮,3-十二烷基-1-(2,2,6,6-四甲基-4-哌啶基)吡咯烷-2,5-二酮,3-十二烷基-1-(1,2,2,6,6-五甲基-4-哌啶基)-吡咯烷-2,5-二酮,4-十六烷氧基-2,2,6,6-四甲基哌啶和4-十八烷氧基-2,2,6,6-四甲基哌啶的混合物,N,N′-二(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺与4-环己基氨基-2,6-二氯-1,3,5-三嗪的缩合物,1,2-二(3-氨基丙基氨基)乙烷与2,4,6-三氯-1,3,5-三嗪和4-丁基氨基-2,2,6,6-四甲基哌啶的缩合物(CAS reg.No.[136504-96-6]);(2,2,6,6-四甲基-4-哌啶基)-正十二烷基琥珀酰亚胺,(1,2,2,6,6-五甲基-4-哌啶基)-正十二烷基琥珀酰亚胺,2-十一烷基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代-螺[4,5]癸烷,7,7,9,9-四甲基-2-环十一烷基-1-氧杂-3,8-二氮杂-4-氧代螺[4,5]癸烷与表氯醇的反应产物,四(2,2,6,6-四甲基哌啶-4-基)-丁烷-1,2,3,4-四羧酸酯,四(1,2,2,6,6-五甲基哌啶-4-基)-丁烷-1,2,3,4-四羧酸酯,2,2,4,4-四甲基-7-氧杂-3,20-二氮杂-21-氧代-二螺[5.1.11.2]-二十一烷,8-乙酰基-3-十二烷基-1,3,8-三氮杂-7,7,9,9-四甲基螺[4,5]-癸烷-2,4-二酮,
其中m是5-50,
其中R=H或CH3
组分(d)的络合物形成剂例如是含氮的络合物形成剂或多阴离子衍生的天然多糖,例如含有磷酸根、膦酸根或甲基膦酸根的那些,诸如壳多糖衍生物,如磺基壳多糖、羧甲基壳多糖、磷酸壳多糖,或壳聚糖衍生物,如磺基壳聚糖、羧甲基壳聚糖或磷酸壳聚糖。
的胺三亚甲基磷酸(ATMP),符合式
的丝氨酸二乙酸(SDA),
的甲基甘氨酸二乙酸(MGDA)。
本发明的稳定剂体系特别适合于稳定身体护理品,尤其适用于护肤品,如沐浴和淋浴用品,含香料和香味物质的制剂,护发品,洁齿剂,除臭和止汗剂,美饰剂(decorative preparations),光防护制剂和含活性成分的制剂。
适合的护肤品具体为洁身油(body oil)、爽身水(body lotion)、洁身胶(body gels)、护理霜(treatment cream)、护肤膏(skin protection ointment)、剃须用制剂如剃须泡沫或剃须胶,爽身粉(skin powders)如婴儿爽身粉(babypowder,保湿胶,保湿喷雾剂,清新护体喷雾剂(revitalising body sprays),去皮肤角质胶(cellulite gels)和磨肤剂(peeling preparations)。
含香料和香味物质的制剂具体有香水,香精,盥洗用香水(toilet waters)和剃须液(剃须后用制剂)。
适合的护发品为例如人用和动物(特别是狗)用香波,头发调理剂,造型和调理头发的产品(product for styling and treating hair),烫发剂,发胶和发蜡,发用凝胶(hair gels),发型固定剂(hair fixative)和染发剂或漂白剂。
适合的洁齿剂具体有牙霜(tooth creams),牙膏(toothpaste),漱口水,口腔清洗剂(mouse rinses),防牙菌斑剂(anti-plaque preparations)和假牙清洁剂。
适合的美饰剂具体有唇膏,指甲油,眼影膏,睫毛油(膏),干和湿化妆品(dry and mosit make-up),胭脂,底粉,脱毛剂和晒黑液(suntan lotion)。
适合的含活性成分的化妆品组合物尤其是激素制剂,维生素制剂,像维生素E、抗坏血酸、维生素Q、D和K,类胡萝卜素如视黄醇、视黄醛、视黄酸和licopen,植物提取物制剂,抗菌制剂,含不稳定的氨基酸的制剂,所述氨基酸包括二肽、寡肽和多肽如蛋氨酸(methionen)、半胱氨酸(cyctein)、胱氨酸、色氨酸、苯丙氨酸、酪氨酸,含酚、多酚或类黄酮的制剂。
本发明的另一方面在于选自维生素、类胡萝卜素、植物提取物、抗菌物、酚、多酚或类黄酮的活性成分的稳定,其包括将组分(b)的至少一种化合物和组分(c)的至少一种化合物施用于所述活性成分。
本发明的身体护理用品可以是霜膏、软膏、糊剂、泡沫体、凝胶、洗剂、粉剂、美容品(make-ups)、喷雾剂、棒或气溶胶或擦拭物(wipes)形式。本发明的稳定剂体系可以存在于油相中或在水相或水/醇相中。
组分(b)和(c)的添加剂例如基于整个组合物以约5-约10000ppm的浓度存在于身体护理和家用制品中,优选约10-约5000ppm,以及最优选约100-约1000ppm。
例如组分(b)和(c)的添加剂基于整个组合物以约5、10、15、20、25、35、40、45或50ppm的浓度存在于身体护理和家用制品中。
例如,组分(b)和(c)的添加剂在本发明的组合物(制剂)中为约5-约1000ppm。
组分(b)与组分(c)在本发明组合物中的比例是1∶1000至1000∶1,优选1∶100至100∶1,最优选1∶10-10∶1。
另外,所述化妆品或药物制剂可以包含如下所述的其他助剂。
作为含水和含油的乳液(如W/O、O/W、O/W/O和W/O/W乳液或微乳液),所述制剂例如包含以组合物总重计0.1-30重量%、优选0.1-15重量%以及特别是0.5-10重量%的一种或多种UV吸收剂;以组合物总重计1-60重量%、特别是5-50重量%以及优选10-35重量%的至少一种油组分;以组合物的总重计0-30重量%、特别是1-30重量%以及优选4-20重量%的至少一种乳化剂;以组合物的总重计10-90重量%、特别是30-90重量%的水;以及0-88.9重量%、特别是1-50重量%的其他化妆品可接受的助剂。
本发明的化妆品或药物组合物/制剂还可以包含一种或多种如下所述的其它化合物。
脂肪醇
基于具有6-18、优选8-10个碳原子的脂肪醇的格尔伯特醇(Guerbetalcohol),其包括鲸蜡醇、硬脂醇、鲸蜡硬脂醇、油醇、辛基十二烷醇,C12-C15醇的苯甲酸酯,乙酰化羊毛脂醇等。
脂肪酸酯
直链C6-C24脂肪酸与直链C3-C24醇的酯,支化C6-C13羧酸与直链C6-C24脂肪醇的酯,直链C6-C24脂肪酸与支化醇尤其是2-乙基己醇的酯,羟基羧酸与直链或支化C6-C22脂肪醇的酯,特别是苹果酸二辛酯,直链和/或支化脂肪酸与多元醇(如丙二醇、二聚物二醇或三聚物三醇)和/或格尔伯特醇的酯,如己酸、辛酸、2-乙基己酸、癸酸、月桂酸、异十三烷酸、肉豆蔻酸、棕榈酸、棕榈油酸、硬脂酸、异硬脂酸、油酸、反油酸、洋芜荽子酸(petroselinicacid)、亚油酸、亚麻酸、桐酸、花生酸、二十碳-9-烯酸(gadoleic acid)、山嵛酸和芥子酸及其工业级混合物(例如在天然脂肪和油的压力脱除pressureremoval中、在来自Roelen氧化合成的醛的还原中或在不饱和脂肪酸的二聚中得到),与醇如异丙醇、己醇、辛醇、2-乙基己醇、癸醇、月桂醇、异十三烷醇、肉豆蔻醇、鲸蜡醇、棕榈油醇(palmoleyl alcohol)、硬脂醇、异硬脂醇、油醇、反油醇(elaidyl alcohol)、洋芜荽子醇(petroselinyl alcohol)、亚油醇、亚麻醇、桐醇、花生醇、二十碳-9-烯醇(gadoleic acid)、山嵛醇、瓢儿菜醇和巴惟醇(brassidyl alcohol)及其工业级混合物(例如在基于脂肪和油的工业级甲基酯或来自Roelen氧化合成的醛的高压氢化中得到以及作为不饱和脂肪醇二聚中的单体馏分得到)的酯。
上述酯油的实例是肉豆蔻酸异丙酯、棕榈酸异丙酯、硬脂酸异丙酯、异硬脂酸异丙酯、油酸异丙酯、硬脂酸正丁酯、月桂酸正己酯、油酸正癸酯、硬脂酸异辛酯、硬脂酸异壬酯、异壬酸异壬酯、棕榈酸2-乙基己基酯、月桂酸2-己酯、硬脂酸2-己基癸基酯、棕榈酸2-辛基十二烷基酯、油酸油基酯、芥酸油基酯、油酸芥酯(erucyloleate)、芥酸芥酯、辛酸鲸蜡硬脂基酯、棕榈酸鲸蜡酯、硬脂酸鲸蜡酯、油酸鲸蜡酯、山嵛酸鲸蜡酯、乙酸鲸蜡酯、肉豆蔻酸肉豆蔻酯、山嵛酸肉豆蔻酯、油酸肉豆蔻酯、硬脂酸肉豆蔻酯、棕榈酸肉豆蔻酯、乳酸肉豆蔻酯、丙二醇二辛酸酯/癸酸酯、庚酸硬脂酯、苹果酸二异硬脂酯、羟基硬脂酸辛酯等。
其他助剂
2,6-萘二甲酸二乙基己基酯,己二酸二正丁酯,己二酸二(2-乙基己基酯),琥珀酸二(2-乙基己基酯)和二异十三烷基acelaat(diisotridecyl acelaat),以及二元醇酯,如乙二醇二油酸酯,乙二醇二异十三烷酸酯,丙二醇二(2-乙基己酸酯),丙二醇二异硬脂酸酯,丙二醇二壬酸酯,丁二醇二异硬脂酸酯和新戊二醇二辛酸酯。C6-C27脂肪醇和/或格尔伯特醇与饱和的和/或不饱和的芳族羧酸、尤其是苯甲酸的酯,C2-C12二羧酸与具有1-22个碳原子的直链或支化醇或具有2-10个碳原子以及2-6个羟基的多元醇的酯,或亚氨基二琥珀酸和亚氨基二琥珀酸盐[CAS 7408-20-0]或胶乳颗粒。
包括甘油酯和衍生物的天然或合成的甘油三酯
通过与其他醇的反应改性的基于C6-C18脂肪酸的甘油二酯或甘油三酯(辛酸/癸酸甘油三酯,麦芽甘油酯等)。聚甘油(聚甘油基-n)的脂肪酸酯如聚甘油基-4癸酸酯,聚甘油基-2异硬脂酸酯等,或蓖麻油、氢化植物油、甜杏仁油、麦芽油(wheat germ oil)、芝麻油、氢化棉籽油、椰子油、鳄梨油、玉米油、氢化蓖麻油、牛油树脂(shea butter)、可可油、豆油、貂油(mink oil)、向日葵油、红花油、澳洲坚果油、橄榄油、氢化牛油、杏仁油、榛子油、琉璃苣油(borago oil)等。
包括长链酸和醇的酯以及具有似蜡性质的化合物的蜡,如巴西棕榈蜡、蜂蜡(白蜡或黄蜡)、羊毛脂蜡、小烛树蜡、地蜡、日本蜡、石蜡、微晶蜡、纯白地蜡、鲸蜡硬脂基酯蜡(cetearyl esters wax)、合成蜂蜡等。此外,亲水的蜡如鲸蜡硬脂醇或偏甘油酯。
珠光蜡(pearlescent wax)
亚烷基二醇酯,尤其是乙二醇二硬脂酸酯;脂肪酸链烷醇酰胺,尤其是椰油脂肪酸二乙醇酰胺;偏甘油酯,尤其是硬脂酸单酸甘油酯;多价的、不饱和的或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;脂肪物质,例如脂肪醇、脂肪酮、脂肪醛、脂肪酯和脂肪碳酸酯,其总共具有至少24个碳原子,尤其是月桂酮和二硬脂基醚;脂肪酸,如硬脂酸、羟基硬脂酸或山嵛酸,具有12-22个碳原子的烯烃环氧化物与具有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,以及其混合物。
烃油
矿物油(轻质或重质),凡士林(黄凡士林或白凡士林),微晶蜡,链烷化合物和异构链烷化合物,氢化的异构链烷分子如聚癸烯和聚丁烯,氢化聚异丁烯,角鲨烷,异十六烷,异十二烷以及其他来自植物和动物界的其他化合物。
硅树脂或硅氧烷(有机取代的聚硅氧烷)
二甲基聚硅氧烷,甲基苯基聚硅氧烷,环状硅氧烷,以及氨基-、脂肪酸-、醇-、聚醚-、环氧-、氟-、苷-和/或烷基改性的硅氧烷化合物,其在室温下可以呈液体或树脂形式。线性聚硅氧烷,二甲基聚硅氧烷(Dow Corning200fluid,Rhodia Mirasil DM),二甲基聚硅氧烷醇,环状硅氧烷流体,环五硅氧烷(cyclopentasiloxanes)挥发物(Dow Corning 345fluid),苯基三甲基聚硅氧烷(Dow Corning 556fluid)。同样合适的是二甲基硅油,其是具有平均链长200-300个二甲基硅氧烷单元的二甲基聚硅氧烷与氢化硅酸盐的混合物。Todd等人对合适的挥发性硅氧烷的详细研究可以另外在Cosm.Toil.91,27(1976)中找到。
氟化的或全氟化的油
全氟己烷,二甲基环己烷,乙基环戊烷,聚全氟代甲基异丙基醚。
乳化剂
可以将任何常用的乳化剂用于所述组合物中。乳化剂体系例如可以包含:碳环酸(carbocyclic acid)及其盐:钠、钾和铵的碱性皂,钙或镁的金属皂,有机基皂如月桂酸、棕榈酸、硬脂酸和油酸等。烷基磷酸盐或磷酸酯,酸式磷酸盐,磷酸二乙醇胺,鲸蜡基磷酸钾。乙氧基化的羧酸或聚乙二醇酯,PEG-n丙烯酸酯。具有8-22个碳原子的直链脂肪醇,其由2-30mol氧化乙烯和/或由0-5mol氧化丙烯与具有12-22个碳原子的脂肪酸和烷基中具有8-15个碳原子的烷基酚所支化。脂肪醇聚二醇醚如月桂基聚氧乙烯醚-n、鲸蜡硬脂基聚氧乙烯醚-n、硬脂基聚氧乙烯醚-n、油基聚氧乙烯醚-n。脂肪酸聚二醇醚如PEG-n硬脂酸酯、PEG-n油酸酯、PEG-n椰油酸酯。单酸甘油酯和多元醇酯。1-30mol氧化乙烯与多元醇的加成产物的C12-C22脂肪酸单酯或二酯。脂肪酸与聚甘油酯如单硬脂酸甘油酯,二异硬脂酰基聚甘油基-3-二异硬脂酸酯,聚甘油基-3-二异硬脂酸酯,三甘油基二异硬脂酸酯,聚甘油基-2-倍半异硬脂酸酯或聚甘油基二聚体化物(polyglyceryl dimerates)。来自多个上述物质种类的化合物的混合物也是适合的。脂肪酸聚二元醇酯如单硬脂酸二甘醇酯,脂肪酸与聚乙二醇酯,脂肪酸与蔗糖酯如蔗糖酯(sucro esters),甘油与蔗糖酯如蔗糖甘油酯。山梨糖醇和脱水山梨糖醇,具有6-22个碳原子的饱和的和不饱和的脂肪酸及其氧化乙烯加成产物的脱水山梨糖醇单酯和二酯。聚山梨酸酯-n系列,脱水山梨糖醇酯如倍半异硬脂酸脱水山梨糖醇酯,PEG-(6)-异硬脂酸脱水山梨糖醇酯,PEG-(10)-脱水山梨糖醇月桂酸酯,PEG-17-二油酸脱水山梨糖醇酯。葡萄糖衍生物,C8-C22烷基单苷和低聚苷以及乙氧基化的类似物,其中优选作为糖成分的葡萄糖。O/W乳化剂如甲基葡萄糖聚氧乙烯醚-20倍半硬脂酸酯(methyl gluceth-20sesquistearate),脱水山梨糖醇硬脂酸酯/蔗糖椰油酸酯,甲基葡萄糖倍半硬脂酸酯,鲸蜡硬脂醇/鲸蜡硬脂葡糖苷。W/O乳化剂如甲基葡萄糖二油酸酯/甲基葡萄糖异硬脂酸酯。硫酸酯和磺化衍生物,二烷基磺基琥珀酸酯,二辛基琥珀酸酯,烷基月桂基磺酸酯,直链磺化链烷烃,磺化四聚丙烯磺酸酯(sulfonated tetraproplyne sulfonate),月桂基硫酸钠,月桂基硫酸铵和月桂基乙醇胺,月桂基醚硫酸盐,月桂基聚氧乙烯醚硫酸钠,磺基琥珀酸盐,酰基异硫代硫酸盐(acyl isothionate),链烷醇酰胺硫酸盐,牛磺酸盐,甲基牛磺酸盐,咪唑硫酸盐。胺衍生物,胺盐,乙氧基化的胺,具有含杂环的链的氧化物胺,如烷基咪唑啉,吡啶衍生物,异喹啉(isoquinoteines),鲸蜡基吡啶鎓氯化物,鲸蜡基吡啶鎓溴化物,季铵化合物如鲸蜡基三甲基溴化铵(CTBA),硬脂基烷铵(stearyl alkonium)。酰胺衍生物,链烷醇酰胺如酰胺DEA,乙氧基化的酰胺如PEG-n酰胺,oxydeamide。聚硅氧烷/聚烷基/聚醚共聚物及其衍生物,二甲基聚硅氧烷,共聚醇,硅氧烷聚氧乙烯共聚物,硅氧烷二醇共聚物。丙氧基化的或POE-n醚(Meroxapols),Polaxamers或聚(氧乙烯)m-嵌段-聚(氧丙烯)n-嵌段(氧乙烯)。两性离子表面活性剂分子中带有至少一个季铵基团和至少一个羧酸根和/或磺酸根。特别适合的两性离子表面活性剂是甜菜碱,如N-烷基-N,N-二甲基铵甘氨酸盐,椰油烷基二甲基铵甘氨酸盐,N-酰基氨基丙基-N,N-二甲基铵甘氨酸盐,椰油酰氨基丙基二甲基铵甘氨酸盐和2-烷基-3-羧基甲基-3-羟基乙基咪唑啉,其各自在烷基或酰基中具有8-18个碳原子,以及椰油酰基氨基乙基羟基乙基羧基甲基甘氨酸盐,N-烷基甜菜碱,N-烷基氨基甜菜碱。烷基咪唑啉,烷基肽(alkylopeptides),脂氨基酸(lipoaminoacides),自乳化的碱以及在K.F.DePolo,A short textbook ofcosmetology,第8章,表8-7,第250-251页中描述的化合物。
非离子乳化剂如PEG-6蜂蜡(和)PEG-6硬脂酸酯(和)聚甘油基-2-异硬脂酸酯[Apifac],硬脂酸甘油酯(和)PEG-100硬脂酸酯。[Arlacel 165],PEG-5硬脂酸甘油酯[arlatone 983 S],脱水山梨糖醇油酸酯(和)聚甘油基-3蓖麻醇酸酯。[Arlacel 1689],脱水山梨糖醇硬脂酸酯和蔗糖椰油酸酯[arlatone 2121],硬脂酸甘油酯和月桂基聚氧乙烯醚-23[Cerasynth 945],鲸蜡硬脂醇和鲸蜡基聚氧乙烯醚-20[Cetomacrogol Wax],鲸蜡硬脂醇和colysorbate 60和PEG-150和硬脂酸酯-20[Polawax GP 200,Polawax NF],鲸蜡硬脂醇和鲸蜡硬脂基聚葡糖苷[Emulgade PL 1618],鲸蜡硬脂醇和鲸蜡硬脂基聚氧乙烯醚-20[Emulgade 1000NI,Cosmowax],鲸蜡硬脂醇和PEG-40蓖麻油[EmulgadeF Special],鲸蜡硬脂醇和PEG-40蓖麻油和鲸蜡硬脂基硫酸钠[Emulgade F],硬脂醇和硬脂基聚氧乙烯醚-7和硬脂基聚氧乙烯醚-10[Emulgator E 2155],鲸蜡硬脂醇和硬脂基聚氧乙烯醚-7和硬脂基聚氧乙烯醚-10[Emulsifying waxU.S.N.F.],硬脂酸甘油酯和PEG-75硬脂酸酯[Gelot 64],丙二醇鲸蜡基聚氧乙烯醚-3乙酸酯[Hetester PCS],丙二醇异鲸蜡基聚氧乙烯醚-3乙酸酯[Hetester PHA],鲸蜡硬脂醇和鲸蜡基聚氧乙烯醚-12和油基聚氧乙烯醚-12[Lanbritol Wax N 21],PEG-6硬脂酸酯和PEG-32硬脂酸酯[Tefose 1500],PEG-6硬脂酸酯和鲸蜡基聚氧乙烯醚-20和硬脂基聚氧乙烯醚-20[Tefose2000],PEG-6硬脂酸酯和鲸蜡基聚氧乙烯醚-20和硬脂酸甘油酯和硬脂基聚氧乙烯醚-20[Tefose 2561],硬脂酸甘油酯和鲸蜡硬脂基聚氧乙烯醚-20[Teginacid H,C,X]。
阴离子乳化剂如PEG-2硬脂酸酯SE,硬脂酸甘油酯SE[Monelgine,Cutina KD],丙二醇硬脂酸盐[Tegin P],鲸蜡硬脂醇和鲸蜡硬脂基硫酸钠[Lanette N,Cutina LE,Crodacol GP],鲸蜡硬脂醇和月桂基硫酸钠[LanetteW],trilaneth-4磷酸盐和乙二醇硬脂酸酯和PEG-2硬脂酸酯[Sedefos 75],硬脂酸甘油酯和月桂基硫酸钠[Teginacid Special]。阳离子酸碱(cationic acidbases)如鲸蜡硬脂醇和溴化鲸蜡基三甲铵。
乳化剂的用量基于所述组合物的总重量可以是1-30重量%,特别是4-20重量%以及优选5-10重量%。
当配制成O/W乳液时,上述乳化剂体系的优选用量可以占油相的5%-20%。
助剂和添加剂
所述化妆品/药物组合物,例如霜,凝胶,洗剂,醇和水/醇溶液,乳液,蜡/脂肪组合物,棒状制剂,粉末或软膏,可以另外包含温和表面活性剂、超富脂剂、稠度调节剂、增稠剂、聚合物、稳定剂、生物活性成分、除臭活性成分、抗头皮屑剂、成膜剂、溶胀剂、进一步的UV光防护剂、抗氧化剂、水溶助剂(hydrotropic agent)、防腐剂、驱虫剂、自晒黑剂、增溶剂、芳香油、着色剂、抗微生物剂等作为进一步的助剂和添加剂。
超富脂剂(super-fatting agents)
适于用作超富脂剂的物质例如是羊毛脂和卵磷脂,以及聚乙氧基化的或丙烯酸酯化羊毛脂和卵磷脂衍生物,多元醇脂肪酸酯,单甘油酯和脂肪酸链烷醇酰胺,后者同时充当泡沫稳定剂。
表面活性剂
适合的温和表面活性剂,也就是说特别好地为皮肤所接受的表面活性剂,其实例包括脂肪醇聚二醇醚硫酸盐、单甘油酯硫酸盐、单烷基和/或二烷基磺基琥珀酸盐、脂肪酸羟乙基磺酸盐、脂肪酸肌氨酸盐、脂肪酸牛磺酰胺、脂肪酸谷氨酸盐、α-烯烃磺酸盐、醚羧酸、烷基低聚葡糖苷、脂肪酸葡糖酰胺、烷基酰氨基甜菜碱和/或蛋白质脂肪酸缩合产物,后者优选基于小麦蛋白质。
稠度调节剂/增稠剂和流变学改性剂
二氧化硅,硅酸镁,硅酸铝,多糖或其衍生物如透明质酸、黄原胶、瓜尔胶、琼脂、藻酸盐、角叉菜胶(carraghenan)、胶凝糖(gellan)、果胶,或改性纤维素如羟基纤维素、羟丙基甲基纤维素。此外聚丙烯酸酯或网状丙烯酸(reticulated acrylic acid)的均聚物和聚丙烯酰胺,卡波姆(carbomer)(carbopol types 980、981、1382、ETD2001、ETD2020、Ultrez10)或Salcare系列如Salcare SC80(硬脂基聚氧乙烯醚-10烯丙基醚/丙烯酸酯共聚物),Salcare SC81(丙烯酸酯共聚物),Salcare SC91和Salcare AST(丙烯酸钠共聚物/PPG-1十三烷基聚氧乙烯醚-6),sepigel 305(聚丙烯酰胺/月桂基聚氧乙烯醚-7),Simulgel NS和Simulgel EG(丙烯酸羟基乙酯/丙烯酰基二甲基牛磺酸钠共聚物),Stabilen 30(丙烯酸酯/异癸酸乙烯基酯交联聚合物),Pemulen TR-1(丙烯酸酯/丙烯酸C10-30烷基酯交联聚合物),Luvigel EM(丙烯酸钠共聚物),Aculyn 28(丙烯酸酯/山嵛醇聚氧乙烯醚-25甲基丙烯酸酯共聚物)等。
聚合物
适合的阳离子聚合物例如是阳离子纤维素衍生物,如以名称Polymer JR400可从Amerchol得到的季铵化羟甲基纤维素,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,例如Luviquat(BASF),聚二醇和胺的缩合产物,季铵化胶原多肽,如月桂基二甲基铵羟基丙基水解胶原(LamequatL/Grünau),季铵化小麦多肽,聚乙烯亚胺,阳离子硅氧烷聚合物,如酰氨基甲基聚硅氧烷,己二酸和二甲基氨基羟基丙基二亚乙基三胺的共聚物(Cartaretin/Sandoz),丙烯酸与二甲基二烯丙基氯化铵的共聚物(Merquat 550/Chemviron),聚氨基聚酰胺,如在FR-A-2252840中描述的,及其交联水溶性聚合物,阳离子壳多糖衍生物,如季铵化的壳聚糖,其任选地作为微晶分布;二卤代烷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,如来自Celanese的Jaguar C-17、Jaguar C-16,季铵盐聚合物,如来自Miranol的Mirapol A-15、Mirapol AD-1、Mirapol AZ-1。至于阴离子、两性离子、两性和非离子聚合物,例如考虑乙酸乙烯酯/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、未交联的聚丙烯酸和用多元醇交联的聚丙烯酸、丙烯酰氨基丙基-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-羟基丙基酯共聚物、聚乙烯基吡咯烷酮、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基酯/乙烯基己内酰胺三元共聚物以及任选衍生的纤维素醚和硅氧烷。此外可以使用在EP 1093796(第3-8页,第17-68段)中所述的聚合物。
生物活性成分
生物活性成分应理解为例如指的是维生素E、醋酸维生素E、棕榈酸维生素E、抗坏血酸、脱氧核糖核酸、视黄醇、没药醇(bisabolol)、尿囊素、植烷三醇、泛酰醇、AHA酸、氨基酸、神经酰胺、假神经酰胺、精油、植物提取物和维生素配合物。
除臭活性成分
至于除臭活性成分,例如考虑止汗剂,如氯化铝水合物(参见J.Soc.Cosm.Chem.24,281(1973))。以Hoechst AG的商标Locron,例如可购得一种对应于式Al2(OH)5Cl×2.5H2O的氯化铝水合物,其使用是特别优选的(参见J.Pharm.Pharmacol.26,531(1975))。除了氯水合物(chlorohydrate)以外,也可以使用羟基乙酸铝和酸性铝/锆盐。酯酶抑制剂可以作为其他除臭活性成分加入。所述抑制剂优选是柠檬酸三烷基酯,如柠檬酸三甲基酯、柠檬酸三丙基酯、柠檬酸三异丙基酯、柠檬酸三丁基酯以及特别是柠檬酸三乙基酯(Hydagen CAT,Henkel),其抑制酶活性以及因此减少气味形成。考虑作为酯酶抑制剂的其他物质是甾醇硫酸盐或磷酸盐,例如羊毛甾醇、胆甾醇、菜油甾醇(campesterol)、豆甾醇(stigmasterol)和谷甾醇(sitosterol)的硫酸盐或磷酸盐,二羧酸及其酯,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以及羟基羧酸及其酯,例如柠檬酸、苹果酸、酒石酸或酒石酸二乙酯。影响微生物菌群和杀死汗分解细菌或抑制其生长的抗菌活性成分同样可以存在于所述制剂中(尤其是在棒状制剂中)。其实例包括壳聚糖、苯氧基乙醇和葡萄糖酸洗必太(chlorhexidine gluconate)。5-氯-2-(2,4-二氯苯氧基)-苯酚(Triclosan,Irgasan,Ciba Specialty Chemicals Inc.)也已经证实特别有效。
抗头皮屑剂
至于抗头皮屑剂,例如可以使用苯咪丁酮(climbazole),羟甲辛吡酮(octopirox)和巯氧吡啶锌(zinc pyrithione)。常规成膜剂例如包括壳聚糖、微晶壳聚糖、季铵化壳聚糖、聚乙烯基吡咯烷酮、乙烯基吡咯烷酮/乙酸乙烯酯共聚物、包含高比例丙烯酸的季铵化纤维素衍生物的聚合物、胶原、透明质酸及其盐以及类似化合物。
水溶助剂
为了提高流动性质,也可以采用水溶助剂,例如乙氧基化的或非乙氧基化的碳原子数较少的一元醇、二元醇或多元醇或者其醚(如乙醇、异丙醇、1,2-二丙烷二醇、丙二醇、甘油、乙二醇、乙二醇单乙基醚、乙二醇单丁基醚、丙二醇单甲基醚、丙二醇单乙基醚、丙二醇单丁基醚、二甘醇单甲基醚、二甘醇单乙基醚、二甘醇单丁基醚以及类似产品)。为此考虑到的多元醇优选具有2-15个碳原子和至少2个羟基。所述多元醇也可以含有其他官能团,尤其是氨基,和/或可以由氮改性。典型实例如下:甘油,亚烷基二醇,如乙二醇、二甘醇、丙二醇、丁二醇、己二醇以及具有100-1000道尔顿的平均分子量的聚乙二醇;具有1.5-10的本征缩合度(intrinsic degree ofcondensation)的工业级低聚甘油混合物,例如具有40-50重量%二甘油含量的工业级二甘油混合物;羟甲基化合物,例如尤其是三羟甲基乙烷、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-葡糖苷,尤其是在烷基部分中具有1-8个碳原子的那些,例如甲基和丁基葡糖苷;具有5-12个碳原子的糖醇,例如山梨糖醇或甘露糖醇;具有5-12个碳原子的糖,例如葡萄糖或蔗糖;氨基糖,如葡糖胺;二醇胺,如二乙醇胺或2-氨基-1,3-丙二醇。
防腐剂
适合的防腐剂例如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、对羟基苯甲酸丁酯,杀藻胺,2-溴-2-硝基丙烷-1,3-二醇,脱氢乙酸,二偶氮烷基脲(Diazolidinyl Urea),2-二氯-苄醇,DMDM乙内酰脲,甲醛溶液,甲基二溴戊二腈(Methyldibromoglutanitrile),苯氧基乙醇,羟甲基甘氨酸钠,咪唑烷基脲(Imidazolidinyl Urea),三氯生(Triclosan)以及列于以下参考文献中的其他物质类别:K.F.DePolo-A short textbook ofcosmetology,第7章,表7-2、7-3、7-4和7-5,第210-219页。
细菌抑制剂
细菌抑制剂的典型实例是对革兰氏阳性细菌具有特定作用的防腐剂,如2,4,4’-三氯-2’-羟基二苯基醚,洗必太(1,6-二(4-氯苯基-二胍基)己烷)或TCC(3,4,4’-三氯N-碳酰苯胺)。大量的芳族化合物和醚油也具有抗微生物性能。典型实例是丁香油、薄荷油和百里香油中的活性成分丁子香酚、薄荷醇和百里酚。关注的天然除臭剂是存在于莱檬花油中的萜烯醇金合欢醇(3,7,11-三甲基-2,6,10-十二烷三烯-1-醇(3,7,11-trimethyl-2,6,10-dodecatrien-1-ol))。甘油单月桂酸酯也被证实为一种抑菌剂。所存在的其他细菌抑制剂的用量通常基于所述制剂的固体含量是0.1-2重量%。
芳香油
作为芳香油,可以提及天然和/或合成的芳族物质的混合物。天然芳族物质例如是下列物质的提取物:花(百合(lilies)、熏衣草(lavender)、玫瑰(roses)、茉莉(jasmine)、橙花(neroli)、夷兰(ylang-ylang))、茎和叶(天竺葵(geranium)、绿叶刺蕊草(patchouli)、橙叶(petitgrain))、果实(茴芹(aniseed)、胡荽(coriander)、藏茴香(caraway)、桧柏(juniper))、果实皮(香柠檬(bergamot)、柠檬(lemons)、橙子(oranges))、根(肉豆蔻(mace)、当归(angelica)、芹菜(celery)、小豆蔻(cardamom)、木香(costus)、鸢尾根(iris)、菖蒲(calmus))、木材(松木(pine-wood)、檀木(sandalwood)、愈创木(guaiacum wood)、杉木(cedarwood)、玫瑰木(rosewood))、草本和禾草(龙蒿(tarragon)、香茅(lemon grass)、鼠尾草(sage)、百里香(thyme))、针叶和细枝(云杉(spruce)、松树(pine)、欧洲赤松(Scotspine)、高山陆均松(mountain pine))、树脂和香脂(古篷香脂(galbanum)、榄香脂(elemi)、安息香(benzoin)、没药树脂(myrrh)、乳香(olibanum)、合家欢(opo-ponax))。也可以考虑动物原料,如灵猫香和海狸香。典型的合成芳族物质例如是酯、醚、醛、酮、醇或烃类产物。酯类的芳族物质化合物例如是乙酸苄基酯、异丁酸苯氧基乙酯、乙酸对-叔丁基环己基酯、乙酸里哪酯、乙酸二甲基苄基甲基酯、乙酸苯基乙酯、苯甲酸里哪酯、甲酸苄基酯、甘氨酸乙基甲基苯基酯、丙酸烯丙基环己基酯、丙酸苏合香酯(styrallyl propionate)和水杨酸苄基酯。所述醚例如包括苄基乙基醚;所述醛例如包括具有8-18个烃原子的直链烷醛、柠檬醛、香茅醛、香茅基氧乙醛(citronellyloxyacetaldehyde)、仙客来醛(cyclamen aldehyde)、羟基香茅醛(hydroxycitronellal)、玲兰醛(lilial)和波旁醛(bourgeonal);所述酮例如包括紫罗兰酮、异甲基紫罗兰酮和甲基雪松酮(methyl cedryl ketone);所述醇例如包括茴香脑(anethol)、香茅醇、丁子香酚、异丁子香酚、香叶醇、里哪醇、苯基乙基醇和萜品醇(terpinol);以及所述烃主要包括萜烯和香脂。然而,优选使用共同产生有吸引人的香味的多种芳族物质的混合物。主要用作芳香组分的相对低挥发性的醚油也适于作为芳香油,如鼠尾草油、春黄菊油、丁香油、蜂花油、肉桂叶油、莱檬花油(lime blossom oil)、刺柏油、香根草油、乳香油、古篷香脂油、金莲花油和杂熏衣草油。优选使用单独或相互混合的香柠檬油、二氢月桂烯醇、玲兰醛、新玲兰醛(lyral)、香茅醇、苯基乙基醇、己基肉桂醛、香叶醇、苄基丙酮、仙客来醛、里哪醇、甲氧基甲基环十二基醚(boisambrene)forte、龙涎呋喃(ambroxan)、吲哚、二氢茉莉酮酸甲酯、sandelice、柠檬油、红橘油、橙油、烯丙基戊基乙醇酸酯、cyclovertal、杂熏衣草油、肉豆蔻酒洋苏叶油、突厥酮、波旁酒天竺葵油、水杨酸环己基酯、甲基柏木酮优级(vertofix coeur)、iso-E-Super、Fixolide NP、合成橡苔(evernyl)、甲基紫罗兰酮γ、苯基乙酸、乙酸香叶酯、乙酸苄酯、玫瑰氧化物、romillat、irotyl和floramat。
其他助剂
所述化妆品制剂另外可以包含作为助剂的消泡剂如硅氧烷,结构化剂(structurants)如马来酸,增溶剂如乙二醇、丙二醇、甘油或二甘醇,遮光剂如胶乳、苯乙烯/PVP或苯乙烯/丙烯酰胺共聚物,推进剂如丙烷/丁烷混合物、N2O、二甲醚、CO2、N2或空气,作为氧化染料前体的所谓偶联剂和显影剂组分,还原剂如硫代乙醇酸及其衍生物、硫代乳酸、半胱胺、硫代苹果酸或巯基乙烷磺酸,或氧化剂如过氧化氢、溴酸钾或溴酸钠。
适合的驱虫剂例如是N,N-二乙基-间-甲苯酰胺,1,2-戊二醇或驱虫剂3535;适合的自晒黑剂例如是二羟基丙酮和/或赤藓酮糖或二羟基丙酮和/或二羟基丙酮前体(如在WO 01/85124中描述的)和/或赤藓酮糖。
本发明的稳定剂体系特别适于稳定身体护理品,尤其是:
-护肤剂,如片剂形式或液体皂、无皂洗涤剂或洗涤糊剂形式(washingpaste)的皮肤洗涤和清洁制剂,
-沐浴制剂,如液体(泡沫浴、乳、淋浴制剂)或固体沐浴制剂,如浴块和浴盐;
-护肤剂,如护肤乳液(skin emulsion)、多重乳液或护肤油(skin oil);洁身油、爽身水、洁身胶;护肤膏;
-化妆用个人护理制剂,如以日霜或粉霜(powder cream)、扑面粉(松散的或压实的)、胭脂或乳膏化妆品形式的面部化妆品,眼部护理制剂,如眼影制剂、睫毛膏、眼线膏、眼霜或定眼乳膏(eye-fix cream);唇部护理制剂,如唇膏、润唇膏(lip contour pencil)、唇线笔,指甲护理制剂,如指甲油、指甲油去除剂、指甲硬化剂或角质层去除剂;
-足部护理制剂,如足浴、足粉、足霜或足用香脂(foot balsam),特殊防臭剂和止汗剂或老茧去除制剂(callus-removing preparation);
-光防护制剂,如防晒乳、洗剂、乳膏或油,防晒霜(sunblock)或热带粉(tropical),预晒黑制剂或晒后制剂;
-皮肤晒黑制剂,如自晒黑霜;
-褪色制剂(depigmenting preparation),如漂白皮肤用的制剂或皮肤光亮制剂;
-驱虫剂,如驱虫油、洗剂、喷雾剂或棒;
-除臭剂,如除臭喷雾、泵送喷雾剂、除臭凝胶、棒或走珠;
-止汗剂,如止汗剂棒、霜或走珠;
-用于清洁和护理被玷污皮肤的制剂,如合成洗涤剂(固体或液体),剥离或擦洗制剂或剥离掩模;
-化学品形式的脱毛剂(脱毛),如毛发去除粉,液体脱毛剂,乳膏或糊形式的脱毛剂,凝胶形式或气溶胶泡沫的脱毛剂;
-剃须制剂,如剃须皂、发泡剃须乳膏、非发泡剃须乳膏、泡沫和凝胶、用于干剃须的须前制剂,须后水或须后洗剂;
-香料制剂,如含香料和有香味物质的制剂(香水、科隆香水(eau deCologne)、化妆香水(eau de toilette)、香味香水(eau de parfum)、化妆香味(parfum de toilette)、香料),芳香油或香料乳膏;
-化妆品头发处理制剂,如洗发剂和调理剂形式的头发洗涤制剂,护发制剂,如预处理制剂、生发油(hair tonics)、造型乳膏(styling cream)、造型凝胶(styling gels)、润发脂(pomade)、发用漂洗剂、处理包、深入的头发处理剂,头发结构化制剂,如用于烫发(热烫、温烫、冷烫)的烫发制剂,头发拉直制剂,液体头发定型制剂,头发泡沫,头发喷雾,漂发剂,如过氧化氢溶液、光亮洗发剂、漂白乳膏、漂白粉末、漂白糊剂或油,暂时、半永久或永久头发着色剂,包含自氧化染料、或天然头发着色剂如指甲花染料或甘菊的制剂;
-洁齿剂,尤其是牙霜、牙膏、漱口水、口腔清洗剂、抗牙石制剂和假牙清洗剂;
-美饰剂,尤其是唇膏、指甲油、眼影、睫毛膏、干湿化妆品、胭脂、底粉、脱毛剂(depilatory agent)和晒黑液
-含活性成分的化妆品组合物,尤其是激素制剂、维生素制剂、植物提取物制剂和抗菌制剂。
适合的含活性成分的化妆品组合物尤其是激素制剂、维生素制剂、植物提取物制剂和抗菌制剂。
表现形式
所列举的最终组合物可以以许多种表现形式存在,例如:
液体制剂形式,如W/O、O/W、O/W/O、W/O/W、或PIT乳液以及所有种类的微乳液,
凝胶形式,
油、霜、乳或洗剂形式,
棒的形式,
喷雾剂(使用推进剂气体的喷雾剂或泵送喷雾剂)或气溶胶形式,
泡沫形式,或
糊剂形式。
作为皮肤用化妆品制剂,特别重要的是光防护制剂,如防晒乳、洗剂、乳膏、擦拭物、油,防晒霜或热带粉,预晒黑制剂或晒后制剂,以及皮肤晒黑制剂,如自晒黑霜。特别关注的是防晒保护霜、防晒保护洗剂、防晒保护乳和喷雾剂形式的防晒保护制剂。
作为头发用化妆品制剂,特别重要的是头发处理用的上述制剂,尤其是洗发剂形式的头发洗涤制剂,头发调理剂,头发调理剂如预处理制剂、生发油、造型乳膏、造型凝胶、润发脂、发用漂洗剂、处理包、加强型头发处理剂(intensive hair treatments),头发拉直制剂(hair-straighteningpreparation),液体头发定型制剂,摩丝(hair foam)和头发喷雾剂。特别关注的是洗发剂形式的头发洗涤制剂。
洗发剂例如具有下列组成:0.01-5重量%本发明的组分(b),12.0重量%月桂基聚氧乙烯醚-2-硫酸钠,4.0重量%椰油酰氨基丙基甜菜碱,3.0重量%氯化钠,以及加至100%的水。
例如,尤其可以使用以下的发用化妆品组合物:
a1)自发乳化原料组合物(stock formulation),由本发明的组分(b),表1-3中任选的UV吸收剂,PEG-6-C10氧代醇()和脱水山梨糖醇倍半油酸酯组成,向其中加入水和任何所需的季铵化合物,例如4%水貂酰氨基丙基二甲基-2-羟基乙基氯化铵(minkamidopropyl dimethyl-2-hydroxyethylammoniumchloride)或季铵(Quaternium)80;
a2)自发乳化原料组合物,由本发明的组分(b),表1-3中任选的UV吸收剂,柠檬酸三丁基酯和PEG-20-脱水山梨糖醇单油酸酯组成,向其中加入水和任何所需的季铵化合物,例如4%水貂酰氨基丙基二甲基-2-羟基乙基氯化铵或季铵80;
b)本发明的组分(b)在丁基三甘醇(butyl triglycol)和柠檬酸三丁基酯中的1/4掺杂(quat-doped)溶液;以及表1-3中任选的UV吸收剂;
c)本发明的组分(b)与n-烷基吡咯烷酮的混合物或溶液;以及表1-3中任选的UV吸收剂。
将洗衣用洗涤剂、洗衣用助剂、洗衣用预处理品、洗衣用增效剂(lanudarybooster)、织物处理剂(如喷雾上浆剂(spray starches)、织物翻新剂)、织物软化剂或其他制品视为本发明的家用制品,欲使组分(b)和(c)的添加剂在使用时从所述制品中沉积到织物上,以及上述浓度范围也是适用的。在稳定洗衣用洗涤剂和织物软化剂以及用其处理过的织物方面,本发明组分(b)和(c)的添加剂是有效的。
以下是本发明的身体护理品及其成分的实例的列表:
身体护理品 | 成分 |
保湿霜 | 植物油、乳化剂、增稠剂、香料、水、抗氧化剂、UV吸收剂 |
洗发剂 | 表面活性剂、乳化剂、防腐剂、香料、抗氧化剂、UV吸收剂 |
牙膏 | 清洁剂、增稠剂、增甜剂、食用香料、着色剂、抗氧化剂、水、UV吸收剂 |
护唇膏 | 植物油、蜡、TiO2、抗氧化剂、UV吸收剂 |
本发明的身体护理品、家用制品、纺织品和织物对于存在于这些制品中的成分的变色和化学降解具有高度的稳定性。例如,发现包含染料的本发明组合物具有极佳的颜色稳定性。
因此,本发明进一步涉及一种经稳定的组合物,其包含
(a)身体护理品、家用制品、纺织品或织物,
(b)有效稳定量的选自以下的至少一种化合物
(i)式(I)的受阻硝酰基化合物,
(ii)式(II)的受阻羟胺化合物,和
(iii)式(III)的受阻羟胺盐化合物,
(c)选自以下物质的有机UV滤光材料
(c1)二苯甲酰甲烷衍生物;
(c2)肉桂酸衍生物;
(c3)樟脑衍生物;
(c4)三苯胺基-2-三嗪衍生物;以及
(e)染料。
根据本发明的染料例如是:
-无机颜料,如氧化铁(氧化铁红、氧化铁黄、氧化铁黑等)、群青、氧化铬绿或炭黑;
-天然或合成有机颜料;
-可溶于溶剂中的分散染料,如HC型直接染发剂,如HC红No.3,HC蓝No.2以及所有其他列于1997年第7版的International CosmeticIngredient Dictionary and Handbook 中的染发剂或列于Color IndexInternational或Society of Dyes and Colourists中的分散染料;
-彩色清漆(可溶性染料的不溶性盐,如许多阴离子染料的Ca盐、Ba盐或Al盐);
-可溶性阴离子或阳离子染料,如酸性染料(阴离子)、碱性染料(阳离子)、直接染料、活性染料或溶剂染料;
-荧光染料;
-荧光素;和
-异硫氰酸盐。
一般而言,对于家用制品和身体护理品的着色,在电磁辐射的可见光(波长约为4000-700nm)中具有吸收作用的所有物质都是适宜的。所述吸收通常由以下发色团所致:偶氮-(一-、二-、三-或多-)均二苯乙烯-、类胡萝卜素-、二芳基甲烷-、三芳基甲烷-、呫吨-、吖啶-、喹啉、次甲基-(还有聚甲炔-)、噻唑-、吲达胺-、靛酚-、吖嗪-、噁嗪-、噻嗪-、蒽醌-、靛青类-、酞菁-以及其他合成的、天然的和/或无机发色团。
本发明的稳定剂体系也用于家用清洁剂和处理剂中,例如用于洗衣用制品和织物软化剂、液体清洁剂和擦洗剂、玻璃洗涤剂、中性清洁剂(多用途清洁剂)、酸性家用清洁剂(沐浴)、浴室清洁剂中,如用于洗涤剂、漂洗剂和餐具洗涤剂、厨房和炉灶清洁剂、透明漂洗剂、洗碗机用洗涤剂、鞋油、上光蜡、地板洗涤剂和抛光剂、金属、玻璃和陶瓷清洁剂、纺织品护理用品、毯类清洁剂和地毯洗涤剂、去锈,染色和着色用制剂(去污渍盐)、家具和多用途抛光剂以及皮革和乙烯基树脂修饰剂(皮革和乙烯基树脂喷雾剂)和空气清新剂。
本发明还涉及家庭护理和织物护理品如排水清洁剂、消毒液、室内装饰清洁剂、汽车护理用品(如清洁和/或抛光及保护油漆、轮胎、铬钢、乙烯树脂、皮革、织物、橡胶、塑料和纤维)、脱脂剂、抛光剂(玻璃、木材、皮革、塑料、大理石、花岗岩和瓷砖等)、以及金属抛光剂和清洁剂。抗氧化剂适于保护上述制品和干燥床单中的香味。本发明也涉及家用护理用品如蜡烛、凝胶蜡烛、空气清新剂和香精油(家用)。
本发明的稳定剂可以在进行织物使用后用于织物处理,称为织物护理。这种处理包括使用洗涤剂、洗衣用助剂和/或织物调理剂的浆洗,以及基于非洗涤剂的织物护理品如喷涂制品的应用。当以这种方式使用时,欲使本发明的稳定剂沉积在织物上以及用于保护所述织物、与这些织物相关的着色剂和香料免遭环境的侵害。
家用清洁剂和处理剂的典型实例是:
家用清洁剂/家用处理剂 | 成分 |
洗涤剂浓缩物 | 表面活性剂混合物、乙醇、抗氧化剂、水、UV吸收剂、抗氧化剂 |
鞋油 | 蜡、蜡乳化剂、抗氧化剂、水、防腐剂、UV吸收剂、抗氧化剂 |
含蜡的地板 | 乳化剂、蜡、氯化钠、抗氧化剂、水 |
清洁剂 | 防腐剂、UV吸收剂、抗氧化剂 |
本发明的稳定剂例如通过溶解结合到油相或醇或水相中,该过程需要在升高的温度下。
本发明还涉及一种稳定身体护理品、家用制品、纺织品或织物的方法,该方法包含将至少一种组分(b)的化合物和至少一种组分(c)的化合物(优选至少一种式A至EE和A*至EE*的化合物)结合于所述制品中或施用于所述制品上。
优选将二苯甲酰甲烷衍生物(=组分c1)、最优选将1-(4-叔丁基苯基)-3-(4-甲氧基苯基)丙烷-1,3-二酮用作组分(c)。
在经稳定的织物如染色过的织物的情况下,通过来自例如洗涤剂、织物调理剂或基于非洗涤剂的织物护理品的沉积作用,将本发明的稳定剂施用于其中。
本发明的织物是天然的或合成的,以及可以是织造织物或非织造织物。
本发明也涉及一种稳定各自含有染料的身体护理品、家用制品、纺织品或织物的方法,该方法包含将至少一种式(I)、(II)和(III)的化合物(=组分(b))和至少一种组分(c)的化合物(例如至少一种式A至EE和A*至EE*的化合物和至少一种组分(c)的化合物)结合于所述制品中或施用于所述制品上。
优选将二苯甲酰甲烷衍生物(=组分c1)以及最优选将1-(4-叔丁基苯基)-3-(4-甲氧基苯基)丙烷-1,3-二酮用作组分(c)。
式(I)、(II)和(III)的稳定剂(=组分(b))连同有机UV吸收剂(组分(c))一起对于本发明组合物中的染料的稳定非常有效。
本发明的纺织品例如是纺织纤维材料,如含氮或含羟基的纤维材料,例如选自纤维素、丝、羊毛、合成聚酰胺、皮革和聚氨酯的纺织纤维材料。包括棉、亚麻布和大麻、纸浆和再生纤维素。还包括纤维素掺合物,如棉与聚酰胺的混合物或棉/聚酯掺合物。
本发明的添加剂例如在染色或印刷工艺或在染整工艺中施用于纺织品。例如,所述添加剂可以作为染料组合物的组成部分而施用。添加剂可以例如在喷墨印刷工艺中使用于纺织品。添加剂例如作为染料水溶液或印刷浆料的组成部分而施用。其可以用吸尽法(exhaust method)施用,或通过轧染法染色,其中将织物用可以含有盐的染料水溶液浸渍,在碱处理之后或在碱的存在下,适当的话在热量作用下或者通过在室温下存储数小时,使染料和添加剂固定。固定之后,用冷水和热水彻底漂洗染色物或印刷物,适当的话加入具有分散作用以及促进未固定部分扩散的试剂。
施用于纺织品的染料或油墨组合物可以包含其他常用添加剂,例如表面活性剂、消泡剂、杀菌剂等,例如在美国专利6,281,339、6,353,094和6,323,327中所公开的,其公开内容通过引用并入本文。
本发明的另一方面在于组分(c)的UV滤光材料的光稳定化。
因此,本发明也涉及一种光稳定组分(c)的化合物的方法,所述方法包含对该化合物施用至少一种组分(b)的化合物。
下列实施例对本发明进行举例说明。除非另有说明,百分数为重量百分数。
实施例
在实施例中采用了下列稳定剂:
A.胺化合物(=组分(b)):
B.有机UV吸收剂(=组分(c)):
(B1) | 甲氧基肉桂酸乙基己基酯 |
(B2) | 丁基甲氧基二苯甲酰甲烷 |
(B3) | 4-甲基苯亚甲基樟脑 |
(B4) | 乙基己基三嗪酮 |
(B5) | 甲氧基肉桂酸乙基己基酯和丁基甲氧基二苯甲酰甲烷的混合物 |
(B6) | 丁基甲氧基二苯甲酰甲烷和氰双苯丙烯酸辛酯(Octocrylene) |
实施例1-6:盥洗用香水的制备 | ||||||
实施例 | ||||||
成分(w/w)% | 1 | 2 | 3 | 4 | 5 | 6 |
乙醇,96% | 60 | 60 | 60 | 60 | 60 | 60 |
d-柠檬烯 | 5 | 5 | 5 | 5 | 5 | 5 |
雪松烯 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
香茅醇 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
桧油savin | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
稳定剂(A1)、(A2)或(A3) | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 |
有机UV滤光材料(B1) | 0.1 | |||||
有机UV滤光材料(B2) | 0.1 | |||||
有机UV滤光材料(B3) | 0.1 | |||||
有机UV滤光材料(B4) | 0.1 | |||||
有机UV滤光材料(B5) | 0.1 | |||||
有机UV滤光材料(B6) | 0.1 | |||||
S,S-EDDS | 0.005 | 0.005 | 0.005 | 0.005 | 0.005 | 0.005 |
着色剂(D&C黄色No.5) | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 |
水 | 加至100 | 加至100 | 加至100 | 加至100 | 加至100 | 加至100 |
在50℃下将各组分按上述顺序充分混合,得到透明的均匀溶液。获得极佳的结果。
实施例7-12:头发造型喷雾剂(hair styling spray)的制备 | ||||||
实施例 | ||||||
成分(w/w)% | 7 | 8 | 9 | 10 | 11 | 12 |
乙醇,无水 | 96.21 | 96.21 | 96.21 | 96.21 | 96.21 | 96.21 |
辛基丙烯酰胺/丙烯酸酯/丁基氨基乙基甲基丙烯酸酯共聚物 | 2.52 | 2.52 | 2.52 | 2.52 | 2.52 | 2.52 |
羟丙基纤维素 | 0.51 | 0.51 | 0.51 | 0.51 | 0.51 | 0.51 |
氨基甲基丙醇(95%) | 0.46 | 0.46 | 0.46 | 0.46 | 0.46 | 0.46 |
稳定剂(A1)、(A2)或(A3) | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
有机UV滤光材料(B1) | 0.05 | |||||
有机UV滤光材料(B2) | 0.05 | |||||
有机UV滤光材料(B3) | 0.05 | |||||
有机UV滤光材料(B4) | 0.05 | |||||
有机UV滤光材料(B5) | 0.05 | |||||
有机UV滤光材料(B6) | 0.05 | |||||
芳香油 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 |
首先将羟丙基纤维素预先溶解于一半的醇中(Vortex混合器),并与氨基甲基丙醇一起进料。将除了丙烯酸酯树脂以外的其他组分溶解在醇中,在搅拌下将该溶液加入到羟丙基纤维素中。随后加入丙烯酸酯树脂并搅拌直至完全溶解为止。获得极佳的结果。
实施例13-18:油性头发用洗发剂的制备 | ||||||
实施例 | ||||||
成分(w/w)% | 13 | 14 | 15 | 16 | 17 | 18 |
豆蔻醇聚氧乙烯醚硫酸钠(sodium myreth sulphate) | 50.00 | 50.00 | 50.00 | 50.00 | 50.00 | 50.00 |
TEA松香胶原水解产物(TEA abietoyl collagen hydrolysate) | 3.50 | 3.50 | 3.50 | 3.50 | 3.50 | 3.50 |
月桂基聚氧乙烯醚-3 | 3.00 | 3.00 | 3.00 | 3.00 | 3.00 | 3.00 |
着色剂(D&C红色No.33) | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 |
稳定剂(A1)、(A2)或(A3) | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
有机UV滤光材料(B1) | 0.15 | |||||
有机UV滤光材料(B2) | 0.15 | |||||
有机UV滤光材料(B3) | 0.15 | |||||
有机UV滤光材料(B4) | 0.15 | |||||
有机UV滤光材料(B5) | 0.15 | |||||
有机UV滤光材料(B6) | 0.15 | |||||
膦酰基甲基壳聚糖,钠盐 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 |
芳香油 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 |
水 | 加至 | 加至 | 加至 | 加至 | 加至 | 加至 |
100 | 100 | 100 | 100 | 100 | 100 |
在室温和搅拌下,将各组分混合直至其完全溶解为止。pH为6.5。获得极佳的结果。
实施例19-24:婴儿洗发剂的制备 | ||||||
实施例 | ||||||
成分(w/w)% | 19 | 20 | 21 | 22 | 23 | 24 |
椰油酰氨基丙基甜菜碱 | 35.00 | 35.00 | 35.00 | 35.00 | 35.00 | 35.00 |
去离子水 | 加至100 | 加至100 | 加至100 | 加至100 | 加至100 | 加至100 |
柠檬酸 | 适量(pH) | 适量(pH) | 适量(pH) | 适量(pH) | 适量(pH) | 适量(pH) |
聚季铵-15(polyquaternium-15) | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 |
芳香油 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
叶绿素 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 |
稳定剂(A1)、(A2)或(A3) | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
有机UV滤光材料(B1) | 0.15 | |||||
有机UV滤光材料(B2) | 0.15 | |||||
有机UV滤光材料(B3) | 0.15 | |||||
有机UV滤光材料(B4) | 0.15 | |||||
有机UV滤光材料(B5) | 0.15 | |||||
有机UV滤光材料(B6) | 0.15 | |||||
式(102)的抗氧化剂 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
着色剂(D&C黄色No.5) | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 |
氯化钠 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
在室温和搅拌下将各组分混合直至其完全溶解为止。pH为6.5。获得极佳的结果。
实施例25-30:绿色玻璃洗涤剂的制备 | ||||||
实施例 | ||||||
成分(w/w)% | 25 | 26 | 27 | 28 | 29 | 30 |
阴离子/两性表面活性剂(Lumorol RK) | ||||||
丁二醇 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 |
异丙醇 | 20.0 | 20.0 | 20.0 | 20.0 | 20.0 | 20.0 |
d-柠檬烯 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 |
着色剂(D&C绿色No.2) | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
稳定剂(A1)、(A2)或(A3) | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
有机UV滤光材料(B1) | 0.05 | |||||
有机UV滤光材料(B2) | 0.05 | |||||
有机UV滤光材料(B3) | 0.05 | |||||
有机UV滤光材料(B4) | 0.05 | |||||
有机UV滤光材料(B5) | 0.05 | |||||
有机UV滤光材料(B6) | 0.05 | |||||
软化水 | 加至100 | 加至100 | 加至100 | 加至100 | 加至100 | 加至100 |
制备:将各组分按上述顺序溶解直至获得透明的均匀混合物为止。
实施例31-36:地板蜡的制备 | ||||||
实施例 | ||||||
成分(w/w)% | 31 | 32 | 33 | 34 | 35 | 36 |
蜡混合物 | 12 | 12 | 12 | 12 | 12 | 12 |
松香水(white spirit) | 加至100 | 加至100 | 加至100 | 加至100 | 加至100 | 加至100 |
d-柠檬烯 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 |
稳定剂(A1)、(A2)或(A3) | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
有机UV滤光材料(B1) | 0.2 | |||||
有机UV滤光材料(B2) | 0.2 | |||||
有机UV滤光材料(B3) | 0.2 | |||||
有机UV滤光材料(B4) | 0.2 | |||||
有机UV滤光材料(B5) | 0.2 | |||||
有机UV滤光材料(B6) | 0.2 |
制备:将各组分按上述顺序搅拌直至获得透明的均匀混合物为止。
实施例37-42:眼线膏的制备
实施例 | ||||||
成分(w/w)% | 37 | 38 | 39 | 40 | 41 | 42 |
多糖树脂(Kama KM 13,Kama) | 8.00 | 8.00 | 8.00 | 8.00 | 8.00 | 8.00 |
氧化铁黑 | 6.50 | 6.50 | 6.50 | 6.50 | 6.50 | 6.50 |
巴西棕榈蜡 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
三乙醇胺,99% | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
氢化聚异丁烯 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
氢化聚癸烯 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
脱水山梨糖醇倍半油酸酯 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
黄蓍胶(Xanthum gum) | 0.50 | 0.50 | 0.50 | 0.50 | 0.50 | 0.50 |
羧甲基纤维素 | 0.40 | 0.40 | 0.40 | 0.40 | 0.40 | 0.40 |
硅酸镁铝 | 0.40 | 0.40 | 0.40 | 0.40 | 0.40 | 0.40 |
对羟基苯甲酸甲酯 | 0.35 | 0.35 | 0.35 | 0.35 | 0.35 | 0.35 |
硬脂酸 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 |
卵磷脂 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 |
咪唑烷基脲 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 |
稳定剂(A1)、(A2)或(A3) | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
有机UV滤光材料(B1) | 0.1 | |||||
有机UV滤光材料(B2) | 0.1 | |||||
有机UV滤光材料(B3) | 0.1 | |||||
有机UV滤光材料(B4) | 0.1 | |||||
有机UV滤光材料(B5) | 0.1 | |||||
有机UV滤光材料(B6) | 0.1 | |||||
式(100)的抗氧化剂 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
水 | 加至100 | 加至100 | 加至100 | 加至100 | 加至100 | 加至100 |
实施例43-48:指甲油的制备 | ||||||
实施例 | ||||||
成分(w/w)% | 43 | 44 | 45 | 46 | 47 | 48 |
聚(1-三甲基甲硅烷基丙烯) | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
硝基纤维素 | 12.00 | 12.00 | 12.00 | 12.00 | 12.00 | 12.00 |
醇酸树脂 | 10.00 | 10.00 | 10.00 | 10.00 | 10.00 | 10.00 |
邻苯二甲酸二丁酯 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 |
樟脑 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 |
乙酸丁酯 | 49.50 | 49.50 | 49.50 | 49.50 | 49.50 | 49.50 |
甲苯 | 20.00 | 20.00 | 20.00 | 20.00 | 20.00 | 20.00 |
颜料红57.1 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
季化膨润土(Quaternary bentonite) | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
稳定剂(A1)、(A2)或(A3) | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
有机UV滤光材料(B1) | 0.02 | |||||
有机UV滤光材料(B2) | 0.02 | |||||
有机UV滤光材料(B3) | 0.02 | |||||
有机UV滤光材料(B4) | 0.02 | |||||
有机UV滤光材料(B5) | 0.02 | |||||
有机UV滤光材料(B6) | 0.02 | |||||
式(103)的抗氧化剂 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 |
Claims (40)
1.一种经稳定的组合物,其包含:
(a)身体护理品、家用制品、纺织品或织物,
(b)有效稳定量的至少一种化合物,其选自:
(ii)式(II)的受阻羟胺化合物
和
(iii)式(III)的受阻羟胺盐化合物
其中
G1和G2独立地是1-4个碳原子的烷基,或一起为五亚甲基,
Z1和Z2各自为甲基,或Z1和Z2一起形成可以另外地被酯、醚、羟基、氧代、氰醇、酰胺、氨基、羧基或氨基甲酸酯基团取代的连接部分,
X是无机或有机阴离子,如磷酸根,膦酸根,碳酸根,碳酸氢根,硝酸根,氯离子,溴离子,亚硫酸氢根,亚硫酸根,硫酸氢根,硫酸根,硼酸根,甲酸根,乙酸根,苯甲酸根,柠檬酸根,草酸根,酒石酸根,丙烯酸根,聚丙烯酸根,富马酸根,马来酸根,衣康酸根,乙醇酸根,葡糖酸根,苹果酸根,扁桃酸根,惕各酸根,抗坏血酸根,聚甲基丙烯酸根,次氮基三乙酸的羧酸根、羟乙基乙二胺三乙酸的羧酸根、乙二胺四乙酸的羧酸根或二亚乙基三胺五乙酸的羧酸根,二亚乙基三胺五亚甲基膦酸根、烷基磺酸根或芳基磺酸根,以及
其中阳离子的总电荷h等于阴离子的总电荷j;和
(c)选自下列物质的有机UV滤光材料:
(c1)二苯甲酰甲烷衍生物;
(c2)肉桂酸酯;
(c3)樟脑衍生物;和
(c4)三苯胺基-s-三嗪衍生物。
2.根据权利要求1的组合物,其中X是磷酸根,膦酸根,碳酸根,碳酸氢根,硝酸根,氯离子,溴离子,亚硫酸氢根,亚硫酸根,硫酸氢根,硫酸根,硼酸根,甲酸根,乙酸根,苯甲酸根,柠檬酸根,草酸根,酒石酸根,丙烯酸根,聚丙烯酸根,富马酸根,马来酸根,衣康酸根,乙醇酸根,葡糖酸根,苹果酸根,扁桃酸根,惕各酸根,抗坏血酸根,聚甲基丙烯酸根,次氮基三乙酸的羧酸根、羟乙基乙二胺三乙酸的羧酸根、乙二胺四乙酸的羧酸根或二亚乙基三胺五乙酸的羧酸根,二亚乙基三胺五亚甲基膦酸根、烷基磺酸根或芳基磺酸根。
3.权利要求1的组合物,其中所述组分(b)的化合物具有式A至EE和A*至EE*
其中
E是氧基或羟基,
R是氢或甲基,
在式A和A*中,
n是1或2,
当n是1时,
R1是氢,1-18个碳原子的烷基,2-18个碳原子的烯基,炔丙基,缩水甘油基,被1-20个氧原子隔断的2-50个碳原子的烷基、被1-10个羟基取代的所述烷基或者既被所述氧原子隔断又被所述羟基取代的所述烷基,或
R1是被羧基或-COOZ取代的1-4个碳原子的烷基,其中Z是氢、1-4个碳原子的烷基或苯基,或者其中Z是被-(COO-)nMn+取代的所述烷基,其中n是1-3以及M是周期表中第一、第二或第三族的金属离子或Zn、Cu、Ni或Co,或者M是基团Nn+(R2)4,其中R2是1-8个碳原子的烷基或苄基,
当n是2时,
R1是1-12个碳原子的亚烷基,4-12个碳原子的亚烯基,亚二甲苯基或被1-20个氧原子隔断的、被1-10个羟基取代的或者既被所述氧原子隔断又被所述羟基取代的1-50个碳原子的亚烷基,
在式B和B*中,
m是1-4,
当m是1时,
R2是1-18个碳原子的烷基,被-COO-隔断的3-18个碳原子的烷基,或者R2是-CH2(OCH2CH2)nOCH3,其中n是1-12,或
R2是5-12个碳原子的环烷基,6-12个碳原子的芳基,或被1-4个具有1-4个碳原子的烷基取代的所述芳基,或
R2是-NHR3,其中R3是1-18个碳原子的烷基、5-12个碳原子的环烷基、6-12个碳原子的芳基,或被1-4个具有1-4个碳原子的烷基取代的所述芳基,或
R2是-N(R3)2,其中R3如上所定义,
当m是2时,
R2是1-12个碳原子的亚烷基,4-12个碳原子的亚烯基,亚二甲苯基,被-COO-隔断的2-12个碳原子的亚烷基,或者R2是-CH2(OCH2CH2)nOCH2-,其中n是1-12,或
R2是5-12个碳原子的亚环烷基,7-15个碳原子的亚芳烷基,或6-12个碳原子的亚芳基,或
R2是-NHR4NH-,其中R4是2-18个碳原子的亚烷基、5-12个碳原子的亚环烷基、8-15个碳原子的亚芳烷基或6-12个碳原子的亚芳基,或
R2是-N(R3)R4N(R3)-,其中R3和R4如上所定义,或
R2是-CO-或-NH-CO-NH-,
当m是3时,
R2是3-8个碳原子的烷三基或苯三基,或
当m是4时,
R2是5-8个碳原子的烷四基或苯四基,
在式C和C*中,
R10是氢,1-18个碳原子的烷基,5-12个碳原子的环烷基,7-15个碳原子的芳烷基,2-18个碳原子的烷酰基,3-5个碳原子的烯酰基或苯甲酰基,
x是1或2
当x是1时,
R11是氢,1-18个碳原子的烷基,2-18个碳原子的烯基,炔丙基,缩水甘油基,被1-20个氧原子隔断的2-50个碳原子的烷基、被1-10个羟基取代的所述烷基或者既被所述氧原子隔断又被所述羟基取代的所述烷基,或
R11是被羧基或-COOZ取代的1-4个碳原子的烷基,其中Z是氢、1-4个碳原子的烷基或苯基,或者其中Z是被-(COO-)nMn+取代的所述烷基,其中n是1-3以及M是周期表中第一、第二或第三族的金属离子或Zn、Cu、Ni或Co,或者M是基团Nn+(R2)4,其中R2是氢、1-8个碳原子的烷基或苄基,
当x是2时,
R11是1-12个碳原子的亚烷基,4-12个碳原子的亚烯基,亚二甲苯基或被1-20个氧原子隔断的、被1-10个羟基取代的或者既被所述氧原子隔断又被所述羟基取代的1-50个碳原子的亚烷基,
在式D和D*中,
R10如上所定义,
y是1-4,和
R12如上述R2所定义的,
在式E和E*中,
k是1或2
当k是1时,
R20和R21独立地是1-12个碳原子的烷基,2-12个碳原子的烯基或7-15个碳原子的芳烷基,或R20还可以是氢,或
R20和R21一起为2-8个碳原子的亚烷基或被羟基取代的所述亚烷基,或为4-22个碳原子的酰氧基-亚烷基,或
当k是2时,
R20和R21一起为(-CH2)2C(CH2-)2,
在式F和F*中,
R30是氢,1-18个碳原子的烷基,苄基,缩水甘油基,或2-6个碳原子的烷氧基烷基,
g是1或2,
当g是1时,R31如上述n为1时R1所定义,
当g是2时,R31如上述n为2时R1所定义,
在式G和G*中,
Q1是-NR41-或-O-,
E1是1-3个碳原子的亚烷基,或E1是-CH2-CH(R42)-O-,其中R42是氢、甲基或苯基,或E1是-(CH2)3-NH-或E1是直键,
R40是氢或1-18个碳原子的烷基,
R41是氢,1-18个碳原子的烷基,5-12个碳原子的环烷基,7-15个碳原子的芳烷基,6-10个碳原子的芳基,或R41是-CH2-CH(R42)-OH,其中R42如上所定义,
在式H和H*中,
p是1或2
T4如x是1或2时对R11所定义的,
M和Y独立地是亚甲基或羰基,例如M是亚甲基和Y是羰基,
在式I和I*中,
该式表示聚合物的重复结构单元,其中T1是乙烯或1,2-丙烯或是衍生自α-烯烃与丙烯酸烷基酯或甲基丙烯酸烷基酯的共聚物的重复结构单元,以及其中,
q是2-100,
Q1是-N(R41)-或-O-,其中R41如上所定义,
在式J和J*中,
r是1或2
T7如式A中当n是1或2时对R1所定义的,
例如当r是2时T7是八亚甲基,
在式L和L*中,
u是1或2,
T13如式A中n是1或2时对R1所定义的,条件是当u是1时T13不是氢,
在式M和M*中,
E1和E2不同,且各自为-CO-或-N(E5)-,其中E5是氢、1-12个碳原子的烷基或4-22个碳原子的烷氧羰基烷基,例如E1是-CO-和E2是-N(E5)-,
E3是氢,1-30个碳原子的烷基,苯基,萘基,被氯或1-4个碳原子的烷基取代的所述苯基或所述萘基,或7-12个碳原子的苯基烷基,或被1-4个碳原子的烷基取代的所述苯基烷基,
E4是氢,1-30个碳原子的烷基,苯基,萘基或7-12个碳原子的苯基烷基,或
E3和E4一起为4-17个碳原子的聚亚甲基,或被1-4个具有1-4个碳原子的烷基如甲基所取代的所述聚亚甲基,
在式N中,
R1如式A中n是1时对R1所定义的,
G3是直键,1-12个碳原子的亚烷基,亚苯基或-NH-G1-NH-,其中G1是1-12个碳原子的亚烷基,
在式O和O*中,
R10如式C中对R10所定义的,
在式P和P*中,
E6是脂族或芳族四价基团,例如新戊四基或苯四基,
在式T和T*中,
R51是氢,1-18个碳原子的烷基,5-12个碳原子的环烷基,或6-10个碳原子的芳基,
R52是氢或1-18个碳原子的烷基,或
R51和R52一起为4-8个碳原子的亚烷基,
f是1或2,
当f是1时,
R50如式C中x是1时对R11所定义的,或R50是-(CH2)zCOOR54,其中z是1-4以及R54是氢或1-18个碳原子的烷基,或R54是周期表第一、第二或第三族的金属离子或基团-N(R55)4,其中R55是氢、1-12个碳原子的烷基或苄基,
当f是2时,R50如式C中x是2时对R11所定义的,
在式U和U*中,
R53、R54、R55和R56独立地是1-4个碳原子的烷基或一起为五亚甲基,
在式V和V*中,
R57、R58、R59和R60独立地是1-4个碳原子的烷基或一起为五亚甲基,
在式W和W*中,
R61、R62、R63和R64独立地是1-4个碳原子的烷基或一起为五亚甲基,
R65是1-5个碳原子的烷基,
M是氢或氧,
其中在式X至CC和X*至CC*中,
n是2-3,
G1是氢、甲基、乙基、丁基或苄基,
m是1-4,
x是1-4,
当x是1时,
R1和R2独立地是1-18个碳原子的烷基,被1-5个氧原子隔断的所述烷基,被1-5个羟基取代的所述烷基,或者既被所述氧原子隔断又被所述羟基取代的所述烷基;5-12个碳原子的环烷基,7-15个碳原子的芳烷基,6-10个碳原子的芳基或被1-3个具有1-8个碳原子的烷基取代的所述芳基,或R1还可以是氢,
或R1和R2一起为四亚甲基、五亚甲基、六亚甲基或3-氧杂五亚甲基基,
当x是2时,
R1是氢,1-8个碳原子的烷基,被1或2个氧原子隔断的所述烷基,被羟基取代的所述烷基,或者既被1或2个氧原子隔断又被羟基取代的所述烷基,
R2是2-18个碳原子的亚烷基,被1-5个氧原子隔断的所述亚烷基,被1-5个羟基取代的所述亚烷基,或者既被所述氧原子隔断又被所述羟基取代的所述亚烷基;邻-、间-或对-亚苯基,或被1或2个具有1-4个碳原子的烷基取代的所述亚苯基,或
R2是-(CH2)kO[(CH2)kO]h(CH2)k-,其中k是2-4以及h是1-40,或
R1和R2与连接至其上的两个N原子一起为哌嗪-1,4-二基,
当x是3时,
R1是氢,
R2是被1个氮原子隔断的4-8个碳原子的亚烷基,
当x是4时,
R1是氢,
R2是被2个氮原子隔断的6-12个碳原子的亚烷基,
R3是氢,1-8个碳原子的烷基,被1或2个氧原子隔断的所述烷基,被羟基取代的所述烷基,或者既被1或2个氧原子隔断又被羟基取代的所述烷基,
P是2或3,以及
Q是碱金属盐、铵或N+(G1)4,
在式DD和DD*中,
m是2或3,
当m是2时,
G是-(CH2CHR-O)rCH2CHR-,其中r是0-3,以及R是氢或甲基,和
当m是3时,
G是甘油基,
在式EE和EE*中,
G2是-CN、-CONH2或-COOG3,其中G3是氢、1-18个碳原子的烷基或苯基,
X是无机或有机阴离子,如磷酸根,膦酸根,碳酸根,碳酸氢根,硝酸根,氯离子,溴离子,亚硫酸氢根,亚硫酸根,硫酸氢根,硫酸根,硼酸根,甲酸根,乙酸根,苯甲酸根,柠檬酸根,草酸根,酒石酸根,丙烯酸根,聚丙烯酸根,富马酸根,马来酸根,衣康酸根,乙醇酸根,葡糖酸根,苹果酸根,扁桃酸根,惕各酸根,抗坏血酸根,聚甲基丙烯酸根,次氮基三乙酸的羧酸根、羟乙基乙二胺三乙酸的羧酸根、乙二胺四乙酸的羧酸根或二亚乙基三胺五乙酸的羧酸根,二亚乙基三胺五亚甲基膦酸根、烷基磺酸根或芳基磺酸根,以及
其中阳离子的总电荷h等于阴离子的总电荷j。
4.权利要求1-3中任一项的组合物,其中
X是磷酸根,膦酸根,碳酸根,碳酸氢根,硝酸根,氯离子,溴离子,亚硫酸氢根,亚硫酸根,硫酸氢根,硫酸根,硼酸根,甲酸根,乙酸根,苯甲酸根,柠檬酸根,草酸根,酒石酸根,丙烯酸根,聚丙烯酸根,富马酸根,马来酸根,衣康酸根,乙醇酸根,葡糖酸根,苹果酸根,扁桃酸根,惕各酸根,抗坏血酸根,聚甲基丙烯酸根,次氮基三乙酸的羧酸根、羟乙基乙二胺三乙酸的羧酸根、乙二胺四乙酸的羧酸根或二亚乙基三胺五乙酸的羧酸根,二亚乙基三胺五亚甲基膦酸根、烷基磺酸根或芳基磺酸根。
5.权利要求1-3中任一项的组合物,其中所述组分(b)的化合物是式A、A*、B、B*、C、C*、D、D*、Q、Q*、R、R*、S、S*、X、X*、Y、Y*、Z和Z*的那些,
其中
R是氢,
在式A和A*中,
n是1或2,
当n是1时,
R1是氢,1-6个碳原子的烷基,2-6个碳原子的烯基,炔丙基,缩水甘油基,被1-10个氧原子隔断的2-20个碳原子的烷基,被1-5个羟基取代的所述烷基或者既被所述氧原子隔断又被所述羟基取代的所述烷基,或
R1是被羧基或-COOZ取代的1-4个碳原子的烷基,其中Z是氢、1-4个碳原子的烷基,
当n是2时,
R1是1-8个碳原子的亚烷基,4-8个碳原子的亚烯基,被1-10个氧原子隔断的、被1-5个羟基取代的或者既被所述氧原子隔断又被所述羟基取代的1-20个碳原子的亚烷基,
在式B和B*中,
m是1或2,
当m是1时,
R2是1-4个碳原子的烷基或者R2是CH2(OCH2CH2)nOCH3,其中n是1-12,或
R2是苯基,或被1-3个甲基取代的所述苯基,
R2是-NHR3,其中R3是1-4个碳原子的烷基或苯基、或被1或2个甲基取代的所述苯基,
当m是2时,
R2是1-8个碳原子的亚烷基,4-8个碳原子的亚烯基,或者R2是-CH2(OCH2CH2)nOCH2-,其中n是1-12,
R2是NHR4NH,其中R4是2-6个碳原子的亚烷基、8-15个碳原子的亚芳烷基或6-12个碳原子的亚芳基,
R2是-CO-或-NHCONH-,
在式C和C*中,
R10是氢,或1-3个碳原子的烷酰基,
x是1或2
当x是1时,
R11是氢,1-6个碳原子的烷基或缩水甘油基,
R11是被羧基或COOZ取代的1-4个碳原子的烷基,其中Z是氢或1-4个碳原子的烷基,
当x是2时,
R11是1-6个碳原子的亚烷基,
在式D和D*中,
R10是氢,
y是1或2,
R12如上述R2所定义的,
在式Y、Y*、Z和Z*中,
x是1或2,
当x是1时,
R1和R2独立地是1-4个碳原子的烷基,
或R1和R2一起为四亚甲基或五亚甲基,
R2是氢或1-4个碳原子的烷基、被羟基取代的所述烷基,
当x是2时,
R1是氢,1-4个碳原子的烷基,被羟基取代的所述烷基,
R2是2-6个碳原子的亚烷基,
R3如上所定义。
6.权利要求5的组合物,其中所述组分(b)的化合物为式A、A*、B、B*、C、C*、D、D*、Q、Q*、R和R*的那些,
其中
R是氢,
在式A和A*中
h是1
R1是氢,1-4个碳原子的烷基,缩水甘油基,被1或2个氧原子隔断的2-4个碳原子的烷基,被1或2个羟基取代的所述烷基或者既被所述氧原子隔断又被所述羟基取代的所述烷基,或
R1是被-COOZ取代的1-4个碳原子的烷基,其中Z是氢或1-4个碳原子的烷基,
在式B和B*中,
m是1或2,
当m是1时,
R2是1-4个碳原子的烷基或者R2是CH2(OCH2CH2)nOCH3,其中n是1-4,
当m是2时,
R2是1-8个碳原子的亚烷基,
在式C和C*中,
R10是氢或1或2个碳原子的烷酰基,
x是1或2,
当x是1时,
R11是氢,1-4个碳原子的烷基或缩水甘油基,
R11是被COOZ取代的1-4个碳原子的烷基,其中Z是氢或1-4个碳原子的烷基,
当x是2时,
R11是1-6个碳原子的亚烷基,
在式D和D*中,
R10是氢,
y是1或2,
R12如上述R2所定义的。
7.权利要求1-3中任一项的组合物,其中所述组分(b)的化合物选自:
二(1-氧基-2,2-6-6-四甲基哌啶-4-基)癸二酸盐;二(1-羟基-2,2-6-6-四甲基哌啶-4-基)癸二酸盐;1-羟基-2,2-6-6-四甲基-4-乙酰氧基哌啶鎓柠檬酸盐;1-氧基-2,2,6,6-四甲基-4-乙酰氨基哌啶;1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶;1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓硫酸氢盐;1-氧基-2,2,6,6-四甲基-4-氧代-哌啶;1-羟基-2,2,6,6-四甲基-4-氧代-哌啶;1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓乙酸盐;1-氧基-2,2,6,6-四甲基-4-甲氧基-哌啶;1-羟基-2,2,6,6-四甲基-4-甲氧基-哌啶;1-羟基-2,2,6,6-四甲基-4-甲氧基-哌啶鎓乙酸盐;1-氧基-2,2,6,6-四甲基-4-乙酰氧基哌啶;1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶;1-氧基-2,2,6,6-四甲基-4-丙氧基-哌啶;1-羟基-2,2,6,6-四甲基-4-丙氧基-哌啶鎓乙酸盐;1-羟基-2,2,6,6-四甲基-4-丙氧基-哌啶;1-氧基-2,2,6,6-四甲基-4-(2-羟基-4-氧杂戊氧基)哌啶;1-羟基-2,2,6,6-四甲基-4-(2-羟基-4-氧杂戊氧基)哌啶鎓乙酸盐;1-氧基-2,2,6,6-四甲基-4-羟基哌啶;1-羟基-2,2,6,6-四甲基-4-羟基哌啶;1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓氯化物;1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓乙酸盐;1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓硫酸氢盐;1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓柠檬酸盐;二(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)柠檬酸盐;三(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)柠檬酸盐;四(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)乙二胺四乙酸盐;四(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)乙二胺四乙酸盐;四(1-羟基-2,2,6,6-四甲基-4-氧代哌啶鎓)乙二胺四乙酸盐;五(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)二亚乙基三胺五乙酸盐;五(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)二亚乙基三胺五乙酸盐;五(1-羟基-2,2,6,6-四甲基-4-氧代哌啶鎓)二亚乙基三胺五乙酸盐;三(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)次氮基三乙酸盐;三(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)次氮基三乙酸盐;三(1-羟基-2,2,6,6-四甲基-4-氧代哌啶鎓)次氮基三乙酸盐;五(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)二亚乙基三胺五亚甲基膦酸盐;五(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)二亚乙基三胺五亚甲基膦酸盐;以及五(1-羟基-2,2,6,6-四甲基-4-氧代哌啶鎓)二亚乙基三胺五亚甲基膦酸盐。
8.权利要求1-3中任一项的组合物,其中所述组分(b)的化合物选自:1-氧基-2,2,6,6-四甲基-4-羟基哌啶;1-羟基-2,2,6,6-四甲基-4-羟基哌啶;1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓氯化物;1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓乙酸盐;1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓硫酸氢盐;1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓柠檬酸盐;二(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)柠檬酸盐;三(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)柠檬酸盐;四(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)乙二胺四乙酸盐;四(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)乙二胺四乙酸盐;四(1-羟基-2,2,6,6-四甲基-4-氧代哌啶鎓)乙二胺四乙酸盐;五(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)二亚乙基三胺五乙酸盐;五(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)二亚乙基三胺五乙酸盐;以及五(1-羟基-2,2,6,6-四甲基-4-氧代哌啶鎓)二亚乙基三胺五乙酸盐。
9.权利要求1-3中任一项的组合物,其中所述组分(b)的化合物选自:1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓柠檬酸盐;二(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)柠檬酸盐;三(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)柠檬酸盐;1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓DTPA;二(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)DTPA;三(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)DTPA;四(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)DTPA;五(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)DTPA;1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓EDTA;二(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)EDTA;三(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)EDTA;四(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)EDTA;1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓柠檬酸盐;二(1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓)柠檬酸盐;三(1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓)柠檬酸盐;1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓DTPA;二(1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓)DTPA;三(1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓)DTPA;四(1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓)DTPA;五(1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓)DTPA;1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓EDTA;二(1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓)EDTA;三(1-羟基-2,2,6,6-四甲基4-氧代-哌啶鎓)EDTA;四(1-羟基-2,2,6,6-四甲基-4-氧代-哌啶鎓)EDTA;1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓柠檬酸盐;二(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)柠檬酸盐;三(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)柠檬酸盐;1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓DTPA;二(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)DTPA;三(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)DTPA;四(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)DTPA;五(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)DTPA;1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓EDTA;二(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)EDTA;三(1-羟基-2,2,6,6-四甲基-4-乙酰氨基哌啶鎓)EDTA;四(1-羟基-2,2,6,6-四甲基-4-羟基哌啶鎓)EDTA;1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶鎓柠檬酸盐;二(1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶鎓)柠檬酸盐;三(1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶鎓)柠檬酸盐;1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶鎓DTPA;二(1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶鎓)DTPA;三(1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶鎓)DTPA;四(1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶鎓)DTPA;五(1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶鎓)DTPA;1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶鎓EDTA;二(1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶鎓)EDTA;三(1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶鎓)EDTA以及四(1-羟基-2,2,6,6-四甲基-4-乙酰氧基哌啶鎓)EDTA。
10.权利要求1-9中任一项的组合物,其中
(c1)选自丁基甲氧基二苯甲酰甲烷、乙基己基甲氧基二苯甲酰甲烷和异丙基二苯甲酰甲烷。
11.权利要求10的组合物,其中
(c1)选自4-叔丁基-4’-甲氧基二苯甲酰甲烷和4-乙基己基-4’-甲氧基二苯甲酰甲烷。
12.权利要求11的组合物,其中
(c1)是1-(4-叔丁基苯基)-3-(4-甲氧基苯基)丙烷-1,3-二酮。
13.权利要求1-9中任一项的组合物,其中
(c2)选自甲氧基肉桂酸辛基酯(4-甲氧基肉桂酸2-乙基己基酯)、甲氧基肉桂酸二乙醇胺盐(4-甲氧基肉桂酸二乙醇胺盐)、对-甲氧基肉桂酸异戊基酯(4-乙氧基肉桂酸2-异戊基酯)、肉桂酸2,5-二异丙基甲基酯和肉桂酸酰胺衍生物。
14.权利要求13的组合物,其中
(c2)是甲氧基肉桂酸辛基酯。
15.权利要求1-9中任一项的组合物,其中
(c3)选自4-甲基-苯亚甲基樟脑(3-(4’-甲基)苯亚甲基-莰-2-酮)、3-苯亚甲基樟脑(3-苯亚甲基-莰-2-酮)、聚丙烯酰胺基甲基苯亚甲基樟脑{N-[2(和4)-2-氧-冰片-3-基亚基-甲基)苄基]-丙烯酰胺聚合物}、三甲铵-苯亚甲基樟脑硫酸盐[3-(4’-三甲基铵)-苯亚甲基-莰-2-酮甲基硫酸盐]、对苯二亚甲基二樟脑磺酸{3,3’-(1,4-亚苯基二次甲基)-二(7,7-二甲基-2-氧代-二环[2.2.1]庚烷-1-甲磺酸}或其盐、以及苯亚甲基樟脑磺酸[3-(4’-磺基)苯亚甲基莰-2-酮]或其盐。
16.权利要求15的组合物,其中
(c3)是4-甲基-苯亚甲基樟脑。
17.权利要求1-9中任一项的组合物,其中
(c4)选自二乙基己基丁酰氨基三嗪酮和乙基己基三嗪酮。
18.权利要求17的组合物,其中
(c4)是乙基己基三嗪酮。
19.权利要求1-18中任一项的组合物,其进一步包含
(d)选自抗氧化剂、维生素E、醋酸维生素E、受阻胺光稳定剂、络合物形成剂、荧光增白剂、表面活性剂和聚有机硅氧烷中的至少一种化合物。
20.权利要求1-19中任一项的组合物,其中所述组分(b)和(c)的化合物基于整个组合物以大约5-约10000ppm的浓度存在于所述身体护理品或家用制品中。
21.权利要求1-20中任一项的组合物,其中组分(b)与组分(c)的比例是1∶1000至1000∶1。
22.权利要求21的组合物,其中组分(b)与组分(c)的比例是1∶100至100∶1。
23.权利要求1-22中任一项的组合物,其中所述身体护理品选自护肤品、沐浴和淋浴用品、液体皂、条皂、含香料或香味物质的制剂、护发品、洁齿剂、除臭和止汗制剂、美饰剂、光防护制剂和含有活性成分的制剂。
24.权利要求23的组合物,其中所述身体护理品选自洁身油、爽身水、洁身胶、护理霜、护肤膏、剃须用制剂和爽身粉。
25.权利要求23的组合物,其中所述含有香料和有香味物质的制剂选自香料、香水、盥洗用香水和剃须液。
26.权利要求23的组合物,其中所述护发品选自洗发剂、头发调理剂、2合1调理剂、保留型和洗脱型调理剂(leave in and rinse off conditioners)、毛发造型和处理剂、烫发剂、蓬松剂、发胶和发蜡、染发体系、永久性、部分永久性、半永久性或暂时性染发体系、以及漂发剂。
27.权利要求23的组合物,其中所述美饰剂选自唇膏、指甲油、眼影、睫毛膏、干湿化妆品、胭脂、底粉、脱毛剂、防晒和晒后用品。
28.权利要求23的组合物,其中所述含活性成分的制剂选自激素制剂、维生素制剂、植物提取物制剂和抗菌制剂。
29.权利要求1-22中任一项的组合物,其中所述家用制品选自家用清洁剂和处理剂。
30.权利要求28的组合物,其中所述家用清洁剂和处理剂选自洗衣用洗涤剂和织物软化剂、基于非洗涤剂的纤维护理用品、液体清洁剂和擦洗剂、玻璃洗涤剂、中性清洁剂(多用途清洁剂)、酸性家用清洁剂(沐浴)、浴室清洁剂、洗涤剂、漂洗剂和餐具洗涤剂、厨房和炉灶清洁剂、透明漂洗剂、洗碗机用洗涤剂、鞋油、上光蜡、地板洗涤剂和抛光剂、金属、玻璃和陶瓷清洁剂、纺织品护理用品、毯类清洁剂和地毯洗涤剂、去锈,染色和着色用制剂(去污渍盐)、家具和多用途抛光剂以及皮革和乙烯基树脂修饰剂(皮革和乙烯基树脂喷雾剂)以及固体和液体空气清新剂。
31.一种稳定身体护理品、家用制品、纺织品或织物的方法,该方法包含将权利要求1的至少一种组分(b)的化合物和至少一种组分(c)的化合物结合于所述制品中或施用于所述制品上。
32.权利要求31的方法,其中采用权利要求3的至少一种式A至EE和A*至EE*的化合物(=组分(b))以及至少一种组分(c)的化合物。
33.权利要求32的方法,其中将二苯甲酰甲烷衍生物(=组分c1)用作组分(c)。
34.权利要求33的方法,其中将1-(4-叔丁基苯基)-3-(4-甲氧基苯基)丙烷-1,3-二酮用作组分(c1)。
35.一种稳定各自含有染料的身体护理品、家用制品、纺织品或织物的方法,该方法包含将权利要求1的至少一种式(I)、(II)和(III)的化合物(=组分(b))和至少一种组分(c)的化合物结合于所述制品中或施用于所述制品上。
36.一种稳定各自含有染料的身体护理品、家用制品、纺织品或织物的方法,该方法包含将权利要求3的至少一种式A至EE和A*至EE*的化合物以及至少一种组分(c)的化合物结合于所述制品中或施用于所述制品上。
37.权利要求36的方法,其中将二苯甲酰甲烷衍生物(=组分c1)用作组分(c)。
38.权利要求37的方法,其中将1-(4-叔丁基苯基)-3-(4-甲氧基苯基)丙烷-1,3-二酮用作组分(c1)。
39.一种选自维生素、类胡萝卜素、植物提取物、抗菌物、酚、多酚或类黄酮的活性成分的稳定方法,该方法包含将至少一种组分(b)的化合物和至少一种组分(c)的化合物施用于所述活性成分。
40.一种组分(c)的化合物的稳定方法,所述方法包含对该化合物施用权利要求1的至少一种组分(b)的化合物。
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CN2004800397449A Active CN1902353B (zh) | 2003-11-03 | 2004-10-25 | 经稳定的身体护理品、家用制品、纺织品和织物 |
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US (1) | US7678381B2 (zh) |
EP (1) | EP1680541B1 (zh) |
JP (1) | JP5384791B2 (zh) |
KR (1) | KR101158266B1 (zh) |
CN (1) | CN1902353B (zh) |
BR (1) | BRPI0415684B1 (zh) |
ES (1) | ES2401436T3 (zh) |
TW (1) | TWI392785B (zh) |
WO (1) | WO2005042828A2 (zh) |
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2004
- 2004-10-25 BR BRPI0415684A patent/BRPI0415684B1/pt active IP Right Grant
- 2004-10-25 EP EP04804504A patent/EP1680541B1/en active Active
- 2004-10-25 ES ES04804504T patent/ES2401436T3/es active Active
- 2004-10-25 CN CN2004800397449A patent/CN1902353B/zh active Active
- 2004-10-25 JP JP2006538835A patent/JP5384791B2/ja active Active
- 2004-10-25 US US10/576,915 patent/US7678381B2/en not_active Expired - Fee Related
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103502528A (zh) * | 2011-04-20 | 2014-01-08 | 亨斯迈先进材料(瑞士)有限公司 | 聚酯染色方法 |
CN103502528B (zh) * | 2011-04-20 | 2017-10-20 | 亨斯迈先进材料(瑞士)有限公司 | 聚酯染色方法 |
CN106479381A (zh) * | 2016-10-14 | 2017-03-08 | 柳州立洁科技有限公司 | 一种黑色皮鞋油 |
CN106479377A (zh) * | 2016-10-14 | 2017-03-08 | 柳州立洁科技有限公司 | 一种鞋油及其制备方法 |
CN106479379A (zh) * | 2016-10-14 | 2017-03-08 | 柳州立洁科技有限公司 | 一种环保鞋油及其制备方法 |
CN106479378A (zh) * | 2016-10-14 | 2017-03-08 | 柳州立洁科技有限公司 | 一种鞋油 |
CN106905857A (zh) * | 2017-02-24 | 2017-06-30 | 青岛海之星生物科技有限公司 | 一种高耐久性地板蜡及其制备方法 |
CN107556923A (zh) * | 2017-08-01 | 2018-01-09 | 德施普科技发展温州有限公司 | 一种鞋油及其制备方法 |
CN113789128A (zh) * | 2021-10-12 | 2021-12-14 | 安徽威廉维尔科技有限公司 | 天然环保木质护理上光蜡及其制备方法 |
TWI805177B (zh) * | 2022-01-07 | 2023-06-11 | 中日合成化學股份有限公司 | 多支化界面活性劑及其製作方法 |
Also Published As
Publication number | Publication date |
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WO2005042828A3 (en) | 2005-07-14 |
BRPI0415684B1 (pt) | 2015-12-08 |
TWI392785B (zh) | 2013-04-11 |
WO2005042828A2 (en) | 2005-05-12 |
KR101158266B1 (ko) | 2012-06-19 |
US20070079446A1 (en) | 2007-04-12 |
TW200530460A (en) | 2005-09-16 |
JP2007515396A (ja) | 2007-06-14 |
CN1902353B (zh) | 2012-08-15 |
EP1680541A2 (en) | 2006-07-19 |
ES2401436T3 (es) | 2013-04-19 |
KR20060095759A (ko) | 2006-09-01 |
US7678381B2 (en) | 2010-03-16 |
EP1680541B1 (en) | 2012-12-19 |
BRPI0415684A (pt) | 2006-12-19 |
JP5384791B2 (ja) | 2014-01-08 |
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