CN1901876A - 稳定的身体护理品,家用制品,纺织品和织物 - Google Patents
稳定的身体护理品,家用制品,纺织品和织物 Download PDFInfo
- Publication number
- CN1901876A CN1901876A CNA2004800395960A CN200480039596A CN1901876A CN 1901876 A CN1901876 A CN 1901876A CN A2004800395960 A CNA2004800395960 A CN A2004800395960A CN 200480039596 A CN200480039596 A CN 200480039596A CN 1901876 A CN1901876 A CN 1901876A
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- China
- Prior art keywords
- azanol
- group
- alkyl
- agent
- described compositions
- 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
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- 239000004744 fabric Substances 0.000 title claims abstract description 46
- 239000004753 textile Substances 0.000 title claims abstract description 22
- 239000000047 product Substances 0.000 title abstract description 25
- 239000003381 stabilizer Substances 0.000 claims abstract description 123
- 150000001412 amines Chemical class 0.000 claims abstract description 27
- 239000003599 detergent Substances 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 26
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002979 fabric softener Substances 0.000 claims abstract description 8
- 239000002537 cosmetic Substances 0.000 claims abstract description 6
- 239000000551 dentifrice Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 115
- -1 methoxyl group Chemical group 0.000 claims description 107
- 238000002360 preparation method Methods 0.000 claims description 77
- 150000001875 compounds Chemical class 0.000 claims description 71
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 60
- 125000000217 alkyl group Chemical group 0.000 claims description 57
- 229910052757 nitrogen Inorganic materials 0.000 claims description 52
- 229910052799 carbon Inorganic materials 0.000 claims description 40
- 239000003795 chemical substances by application Substances 0.000 claims description 38
- 239000000975 dye Substances 0.000 claims description 38
- 150000001721 carbon Chemical group 0.000 claims description 36
- 239000002453 shampoo Substances 0.000 claims description 26
- 239000002250 absorbent Substances 0.000 claims description 25
- 230000002745 absorbent Effects 0.000 claims description 25
- 238000009472 formulation Methods 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 239000012459 cleaning agent Substances 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 239000003921 oil Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 235000006708 antioxidants Nutrition 0.000 claims description 16
- 230000003078 antioxidant effect Effects 0.000 claims description 15
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 15
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 14
- 239000006071 cream Substances 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 10
- 239000010985 leather Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- GXELTROTKVKZBQ-UHFFFAOYSA-N n,n-dibenzylhydroxylamine Chemical compound C=1C=CC=CC=1CN(O)CC1=CC=CC=C1 GXELTROTKVKZBQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 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 9
- 125000000623 heterocyclic group Chemical group 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 230000000474 nursing effect Effects 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 239000003760 tallow Substances 0.000 claims description 9
- 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 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 229960003330 pentetic acid Drugs 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims description 7
- 125000001252 propanoic acid ester group Chemical group 0.000 claims description 7
- 235000013599 spices Nutrition 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- FNYQXXQLQSNLEI-UHFFFAOYSA-N 1-(hydroxyamino)propan-2-ol Chemical compound CC(O)CNO FNYQXXQLQSNLEI-UHFFFAOYSA-N 0.000 claims description 6
- SZMBYKBVFJKLQB-UHFFFAOYSA-N 3-(hydroxyamino)propan-1-ol Chemical compound OCCCNO SZMBYKBVFJKLQB-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 6
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical group CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 6
- 238000004043 dyeing Methods 0.000 claims description 6
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002304 perfume Substances 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 239000003205 fragrance Substances 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 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 4
- 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 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-M benzoate Chemical compound [O-]C(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-M 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 4
- 239000000118 hair dye Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- FHDIEOHZERBGBK-UHFFFAOYSA-N 3-(hydroxyamino)propanoic acid Chemical compound ONCCC(O)=O FHDIEOHZERBGBK-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 3
- 239000002386 air freshener Substances 0.000 claims description 3
- LUFPJJNWMYZRQE-UHFFFAOYSA-N benzylsulfanylmethylbenzene Chemical compound C=1C=CC=CC=1CSCC1=CC=CC=C1 LUFPJJNWMYZRQE-UHFFFAOYSA-N 0.000 claims description 3
- 230000003115 biocidal effect Effects 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 238000005034 decoration Methods 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
- 239000000686 essence Substances 0.000 claims description 3
- 239000004611 light stabiliser Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- DHXOCDLHWYUUAG-UHFFFAOYSA-N n,n-didodecylhydroxylamine Chemical compound CCCCCCCCCCCCN(O)CCCCCCCCCCCC DHXOCDLHWYUUAG-UHFFFAOYSA-N 0.000 claims description 3
- WQAJFRSBFZAUPB-UHFFFAOYSA-N n,n-dioctylhydroxylamine Chemical compound CCCCCCCCN(O)CCCCCCCC WQAJFRSBFZAUPB-UHFFFAOYSA-N 0.000 claims description 3
- UBINNYMQZVKNFF-UHFFFAOYSA-N n-benzyl-1-phenylmethanimine oxide Chemical compound C=1C=CC=CC=1C=[N+]([O-])CC1=CC=CC=C1 UBINNYMQZVKNFF-UHFFFAOYSA-N 0.000 claims description 3
- GBMIPYGHTZRCRH-UHFFFAOYSA-N n-ethylethanimine oxide Chemical compound CC[N+]([O-])=CC GBMIPYGHTZRCRH-UHFFFAOYSA-N 0.000 claims description 3
- JQARHBQLKPQLRB-UHFFFAOYSA-N n-heptadecyl-n-hexadecylhydroxylamine Chemical compound CCCCCCCCCCCCCCCCCN(O)CCCCCCCCCCCCCCCC JQARHBQLKPQLRB-UHFFFAOYSA-N 0.000 claims description 3
- ZRPOKHXBOZQSOX-UHFFFAOYSA-N n-heptadecyl-n-octadecylhydroxylamine Chemical compound CCCCCCCCCCCCCCCCCCN(O)CCCCCCCCCCCCCCCCC ZRPOKHXBOZQSOX-UHFFFAOYSA-N 0.000 claims description 3
- WGCBLWIBXXQTAW-UHFFFAOYSA-N n-hexadecyl-n-octadecylhydroxylamine Chemical compound CCCCCCCCCCCCCCCCCCN(O)CCCCCCCCCCCCCCCC WGCBLWIBXXQTAW-UHFFFAOYSA-N 0.000 claims description 3
- IUMKEVRMAYGUGZ-UHFFFAOYSA-N n-hexadecyl-n-tetradecylhydroxylamine Chemical compound CCCCCCCCCCCCCCCCN(O)CCCCCCCCCCCCCC IUMKEVRMAYGUGZ-UHFFFAOYSA-N 0.000 claims description 3
- VNPWYJMHLZEKFZ-UHFFFAOYSA-N n-methyl-n-octadecylhydroxylamine Chemical compound CCCCCCCCCCCCCCCCCCN(C)O VNPWYJMHLZEKFZ-UHFFFAOYSA-N 0.000 claims description 3
- HORBOHJHQGXXOR-UHFFFAOYSA-N n-octadecyloctadecan-1-imine oxide Chemical compound CCCCCCCCCCCCCCCCCC[N+]([O-])=CCCCCCCCCCCCCCCCCC HORBOHJHQGXXOR-UHFFFAOYSA-N 0.000 claims description 3
- 238000005201 scrubbing Methods 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 claims description 3
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims description 2
- UIERETOOQGIECD-ARJAWSKDSA-M 2-Methyl-2-butenoic acid Natural products C\C=C(\C)C([O-])=O UIERETOOQGIECD-ARJAWSKDSA-M 0.000 claims description 2
- HQQTZCPKNZVLFF-UHFFFAOYSA-N 4h-1,2-benzoxazin-3-one Chemical class C1=CC=C2ONC(=O)CC2=C1 HQQTZCPKNZVLFF-UHFFFAOYSA-N 0.000 claims description 2
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
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- 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 2
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- 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 2
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- 150000002431 hydrogen Chemical class 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
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- 229940049920 malate Drugs 0.000 claims description 2
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- IWYDHOAUDWTVEP-UHFFFAOYSA-N mandelic acid Chemical group OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 claims description 2
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- LRUUZFQPCUFYPV-UHFFFAOYSA-N n-dodecyldodecan-1-imine oxide Chemical compound CCCCCCCCCCCC[N+]([O-])=CCCCCCCCCCCC LRUUZFQPCUFYPV-UHFFFAOYSA-N 0.000 claims description 2
- DBCWENWKZARTGU-UHFFFAOYSA-N n-heptadecyloctadecan-1-imine oxide Chemical compound CCCCCCCCCCCCCCCCCC=[N+]([O-])CCCCCCCCCCCCCCCCC DBCWENWKZARTGU-UHFFFAOYSA-N 0.000 claims description 2
- GCDJFNYVSDFWDB-UHFFFAOYSA-N n-hexadecylhexadecan-1-imine oxide Chemical compound CCCCCCCCCCCCCCCC[N+]([O-])=CCCCCCCCCCCCCCCC GCDJFNYVSDFWDB-UHFFFAOYSA-N 0.000 claims description 2
- FHAFFFSIDLDWQA-UHFFFAOYSA-N n-hexadecyloctadecan-1-imine oxide Chemical compound CCCCCCCCCCCCCCCCCC=[N+]([O-])CCCCCCCCCCCCCCCC FHAFFFSIDLDWQA-UHFFFAOYSA-N 0.000 claims description 2
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- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Abstract
本发明披露了稳定的身体护理品,家用制品,纺织品和织物,其包括某种二烷基羟胺稳定剂,二烷基羟胺稳定剂盐,硝酮稳定剂或氧化胺稳定剂。染色的产品和制品对变色是有效稳定的。例如,所述产品为护肤品、毛发护理品、洁齿剂、化妆品、洗衣用洗涤剂和织物柔软剂,基于非清洁剂的织物护理用品,家用清洁剂和纺织品护理用品。
Description
按照35 USC 119(e),本申请要求享有2003年10月30日申请的美国临时申请60/515,889的优先权。
本发明涉及选择的二烷基羟胺稳定剂,二烷基羟胺稳定剂盐,硝酮稳定剂(nitrone stabilizers)或氧化胺(amine oxide)稳定剂的用途,其用于保护身体护理品,家用制品,纺织品(textile)和织物(fabrics)免受光、热和氧的有害影响。
例如,该经稳定的组合物包含防止变色的稳定的染料。
WO00/25730和WO00/25731目的在于稳定身体护理品和家用制品。
WO01/07550教导用受阻胺稳定剂处理织物。
美国专利6,599,326教导用二烷基羟胺或取代的二烷基羟胺或它们的盐稳定纸浆或纸。
美国专利4,898,901公开了硝酮稳定剂。
美国专利5,081,300、5,844,029和5,922,794公开了氧化胺稳定剂。
发明详述
本发明涉及经稳定的组合物(stabilized composition),其包括
(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)二烷基羟胺稳定剂,
(ii)二烷基羟胺稳定剂盐,
(iii)硝酮稳定剂,和
(iv)氧化胺稳定剂。
二烷基羟胺稳定剂,例如N,N-二烷基羟胺和N,N-二苄基-羟胺,作为各种聚合基材的有用稳定剂是公知的,如在美国专利4,590,231、4,668,721、4,782,105、4,876,300和5,013,510中所教导的那样,其相关部分在此一并引入作为参考。
美国专利4,649,221和4,703,073教导将多羟胺化合物和烷基化的N,N-二苄基羟胺衍生物分别用于稳定聚烯烃。这些美国专利所公开的内容在此一并引入作为参考。
酯、酰胺或硫取代的N,N-二烷基羟胺(thio substituted N,N-dialkylhydroxyl amines)在美国专利4,612,393,4,720,517和5,019,285中公开,其相关公开内容在此一般引入作为参考。
例如,本发明的二烷基羟胺稳定剂是在上述美国专利中公开的那些,且优选具有下式
R1R2N-OH
其中
R1是1至36个碳原子的烷基,5至12个碳原子的环烷基或7至9个碳原子的芳烷基;或R1是被1至6个下列基团取代的所述烷基,环烷基或芳烷基:1至12个碳原子的烷基、卤素、氰基、E1O-、E1CO-、E1OCO-、E1COO-、E1S-、E1SO-、E1SO2-、-NH2、-NHE1、-NE1E2、-PO(OE1)(OE2)或-OPO(OE1)(OE2);
R2是氢或独立地具有与R1相同定义,其中R1和R2中至少一个含有与-NOH部分α位连接的氢原子;或
R1和R2一起形成C2-12杂环,其含有至少一个与-NOH部分α位连接的碳取代的氢原子(at least one carbon substituted hydrogen alpha to the-NOHmoiety),其中所述C2-12杂环是未被取代的或由1至3个下列基团取代:1至12个碳原子的烷基、卤素、氰基、E1O-、E1CO-、E1OCO-、E1COO-、E1S-、E1SO-、E1SO2-、-NH2、-NHE1、-NE1E2、-PO(OE1)(OE2)或-OPO(OE1)(OE2);或其中所述C2-12杂环被1至3个下述基团隔断:-O-、-NE1-、-CO-、-CONE1-、-S-、-SO-、-SO2-、-COO-、-PO3-或-PO4E1基团;或者,其中所述杂环被所述基团取代和隔断;和
E1和E2独立地是氢,1至4个碳原子的烷基或被1至3个羟基取代的1至4个碳原子的烷基;或E1和E2独立地是由羟基、甲氧基、乙酸酯基或丙酸酯基封端的聚(乙二醇)或聚(丙二醇)的低聚物,其中所述低聚物具有高达约500的分子量。
该措辞“其中R1和R2中至少一个含有与-NOH部分α位连接的氢原子”意指本发明的二烷基羟胺不是二-叔烷基羟胺。
本发明的二烷基羟胺稳定剂是,例如,N,N-二烃基羟胺,其中R1和R2独立地是苄基、甲基、乙基、辛基、月桂基(lauryl)、十二烷基(dodecyl)、十四烷基、十六烷基、十七烷基或十八烷基,或其中R1和R2各自是氢化牛脂胺(hydrogenated tallow amine)中发现的烷基混合物。
本发明的二烷基羟胺稳定剂例如,是N,N-二烃基羟胺,其选自:N,N-二苄基羟胺、N,N-二甲基羟胺、N,N-二乙基羟胺、N,N-二(2-羟丙基)羟胺、N,N-二(3-羟丙基)羟胺、N,N-二(2-羧乙基)羟胺、N,N-二(苄基硫-甲基)-羟胺、N,N-二辛基羟胺、N,N-二月桂基羟胺、N,N-二-十二烷基羟胺、N,N-二-十四烷基羟胺、N,N-二-十六烷基羟胺、N,N-二-十八烷基羟胺、N-十六烷基-N-十四烷基羟胺、N-十六烷基-N-十七烷基羟胺、N-十六烷基-N-十八烷基羟胺、N-十七烷基-N-十八烷基羟胺、N-甲基-N-十八烷基羟胺、N,N-二(氢化牛脂)羟胺、
例如,本发明的二烷基羟胺稳定剂是N,N-二乙基羟胺,N,N-二(2-羟丙基)羟胺,N,N-二(3-羟丙基)羟胺或N,N-二苄基羟胺或直接氧化N,N-二(氢化牛脂)胺而生成的N,N-二(烷基)羟胺。最后定义的二烷基羟胺,也就是说N,N-二(氢化牛脂)羟胺,其可以由美国专利5,013,510中的制备实施例(workingExamples)制备。
二烷基羟胺稳定剂盐是本发明二烷基羟胺稳定剂的无机或有机酸盐。例如,二烷基羟胺稳定剂盐的分子式为
(R1R2N-OH)·(HY)
其中
R1和R2如二烷基羟胺稳定剂所定义,而HY是无机或有机酸。
例如,Y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、羟乙酸根、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、次氮基三乙酸(NTA)的羧酸根、二亚乙基三胺五亚甲基膦酸(DTPMPA)的羧酸根、羟乙基乙二胺三乙酸(HEDTA)的羧酸根、乙二胺四乙酸(EDTA)的羧酸根、二亚乙基三胺五乙酸(DTPA)的羧酸根、二亚乙基二胺四乙酸或二亚乙基三胺五乙酸的羧酸根、烷基磺酸根或芳基磺酸根。
例如,当HY是氢氯酸时,Y是氯离子,二烷基羟胺盐是氯化二烷基羟基铵盐(dialkylhydroxylammonium chloride salt)。
例如,Y是氯离子、硫酸氢根、硫酸根、磷酸根、硝酸根、抗坏血酸根、甲酸根、乙酸根、苯甲酸根、草酸根、柠檬酸根、乙二胺四乙酸或二亚乙基三胺五乙酸的羧酸根或聚丙烯酸根;例如Y是氯离子、硫酸氢根或柠檬酸根。
例如,本发明的二烷基羟胺稳定剂盐是上述公开的具体二烷基羟胺稳定剂盐。
例如,本发明的二烷基羟胺稳定剂盐是柠檬酸-三(N,N-二乙基羟铵)盐或柠檬酸-三(N,N-二苄基羟基铵)盐。
硝酮稳定剂可以是例如美国专利4,898,901中公开的那些,其在此一并引入作为参考。
例如,硝酮稳定剂具有下式
其中
R1是1至36个碳原子的烷基,5至12个碳原子的环烷基或7至9个碳原子的芳烷基;或R1是被1至6个下列基团取代的所述烷基,环烷基或芳烷基:1至12个碳原子的烷基、卤素、氰基、E1O-、E1CO-、E1OCO-、E1COO-、E1S-、E1SO-、E1SO2-、-NH2、-NHE1、-NE1E2、-PO(OE1)(OE2)或-OPO(OE1)(OE2);
R2是氢或独立地具有与R1相同定义;或
R1和R2一起形成C2-12杂环,所述C2-12杂环是未被取代的或由1至3个下列基团取代:1至12个碳原子的烷基、卤素、氰基、E1O-、E1CO-、E1OCO-、E1COO-、E1S-、E1SO-、E1SO2-、-NH2、-NHE1、-NE1E2、-PO(OE1)(OE2)或-OPO(OE1)(OE2);或其中所述C2-12杂环被1至3个下述基团隔断:-O-、-NE1-、-CO-、-CONE1-、-S-、-SO-、-SO2-、-COO-、-PO3-或-PO4E1基团;或者,其中所述杂环被所述基团取代和隔断;
E1和E2独立地是氢,1至4个碳原子的烷基或被1至3个羟基取代的1至4个碳原子的烷基;或E1和E2独立地是由羟基、甲氧基、乙酸酯基或丙酸酯基封端的聚(乙二醇)或聚(丙二醇)的低聚物,其中所述低聚物具有高达约500的分子量;和R3独立地具有与R1相同的定义。
该硝酮稳定剂可以是二烷基羟胺稳定剂的相应氧化产物。也就是,该硝酮稳定剂可以是本发明的二烷基羟胺稳定剂的硝酮类似物。该硝酮稳定剂例如是N-苄基-α-苯基硝酮,N-乙基-α-甲基硝酮,N-辛基-α-庚基硝酮,N-月桂基-α-十一烷基硝酮,N-十四烷基-α-十三烷基硝酮,N-十六烷基-α-十五烷基硝酮,N-十八烷基-α-十七烷基硝酮,N-十六烷基-α-十七烷基硝酮,N-十八烷基-α-十五烷基硝酮,N-十七烷基-α-十七烷基硝酮,N-十八烷基-α-十六烷基硝酮,N-甲基-α-十七烷基硝酮和衍生自N,N-二(氢化牛脂)羟胺的硝酮。
该氧化胺稳定剂例如是美国专利5,081,300,5,162,408,5,844,029,5,880,191和5,922,794中公开的那些,其相关部分在此一并引入作为参考。
氧化胺稳定剂例如是由下式表示的饱和叔胺氧化物类:
其中
R1是1至36个碳原子的烷基,5至12个碳原子的环烷基或7至9个碳原子的芳烷基;或R1是被1至6个下列基团取代的所述烷基,环烷基或芳烷基:1至12个碳原子的烷基、卤素、氰基、E1O-、E1CO-、E1OCO-、E1COO-、E1S-、E1SO-、E1SO2-、-NH2、-NHE1、-NE1E2、-PO(OE1)(OE2)或-OPO(OE1)(OE2);
R2是氢或独立地具有与R1相同的定义;或
R1和R2一起形成C2-12杂环,所述C2-12杂环是未被取代的或由1至3个下列基团取代:1至12个碳原子的烷基、卤素、氰基、E1O-、E1CO-、E1OCO-、E1COO-、E1S-、E1SO-、E1SO2-、-NH2、-NHE1、-NE1E2、-PO(OE1)(OE2)或-OPO(OE1)(OE2);或其中所述C2-12杂环被1至3个下述基团隔断:-O-、-NE1-、-CO-、-CONE1-、-S-、-SO-、-SO2-、-COO-、-PO3-或-PO4E1基团;或者,其中所述杂环被所述基团取代和隔断;
E1和E2独立地是氢,1至4个碳原子的烷基或被1至3个羟基取代的1至4个碳原子的烷基;或E1和E2独立地是由羟基、甲氧基、乙酸酯基或丙酸酯基封端的聚(乙二醇)或聚(丙二醇)的低聚物,其中所述低聚物具有高达约500的分子量;和R3独立地具有与R1相同的定义。
其中R1、R2和R3至少一个包含β碳-氢键。
氧化胺稳定剂的实例是其中R1和R2独立地是苄基或取代的苄基的氧化胺。每个R1、R2和R3均可以具有相同的残基。
R1和R2独立地也可以是8至26个碳原子的烷基,例如10至26个碳原子的烷基。R3可以是1至22个碳原子的烷基,例如甲基或取代的甲基。此外,本发明的氧化胺包含其中R1、R2、和R3是6至36个碳原子的相同烷基的那些化合物。
氧化胺稳定剂例如是GenoxTM EP,二(C16-C18)烷基甲胺氧化物,CAS#204933-93-7。
烷基,包括具有各种取代基的直链或支链的烷基。
烷基例如是甲基,乙基,丙基如正-或异丙基;丁基如正-、异-、仲-和叔丁基;戊基,己基,庚基,辛基,壬基,癸基,十一基,十二烷基,十三烷基,十四烷基,十五基,十六烷基,十七烷基或十八烷基。
芳基是C6-C12芳基,例如苯基或萘基。
环烷基例如是环戊基,环己基,环庚基,环辛基,环壬基,环癸基,环十一烷基或环十二烷基。
芳烷基例如是苯烷基,其为被苯基取代的烷基。实例为苄基、α-甲苄基和α-枯基(cumyl)。
烯基是烯属不饱和烷基,例如烯丙基,乙烯基,丙烯基,丁烯基。
由羟基取代的烷基例如是羟乙基,二-羟乙基,羟丙基,二-羟丙基,羟丁基,羟戊基或羟己基。
卤素例如是氯、氟或溴。
C2-12杂环例如是5-或6-元环,例如
本发明的组合物可以进一步包含常规的添加剂,例如紫外(UV)吸收剂和抗氧化剂。
因此,本发明还涉及经稳定的组合物,其包括:
(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:
(i)二烷基羟胺稳定剂,
(ii)二烷基羟胺稳定剂盐,
(iii)硝酮稳定剂,和
(iv)氧化胺稳定剂和
(c)选自:紫外线吸收剂、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 formers)、荧光增白剂、表面活性剂和聚硅氧烷中的至少一种化合物。
例如,成分(c)其他的添加剂是共同未决的美国申请09/830,788和09/830,787中所公开的那些,其中09/830,788是于2001年5月1日申请的,09/830,787是于2001年5月1日申请的。这些共同未决申请所公开的内容在此一并引入作为参考。这些申请已经以WO00/25730和WO00/25731公开。
UV(紫外线)吸收剂例如选自:2H-苯并三唑类、均三嗪类(s-triazine)、二苯甲酮类、α-氰基丙烯酸酯类、草酰替苯胺类、苯并噁嗪酮类、苯甲酸酯类和α-烷基肉桂酸酯类。
例如,紫外线吸收剂是:2,4,6-三(2-羟基-4-辛氧基苯基)-1,3,5-三嗪;2-(2,4-二羟苯基)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪;2,4-二(2-羟基-4-丙氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三嗪;2-(2-羟基-4-辛氧基苯基)-4,6-二(4-甲苯基)-1,3,5-三嗪;2-(2-羟基-4-十二烷氧基苯基)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪;2-[2-羟基-4-(2-羟基-3-丁氧基丙氧基)苯基]-4,6-二[2,4-二甲基苯基]-1,3,5-三嗪;2-[2-羟基-4-(2-羟基-3-辛氧基丙氧基)苯基]-4,6-二[2,4-二甲基苯基]-1,3,5-三嗪;2-[2-羟基-4-(2-羟基-3-十三烷氧基丙氧基)苯基]-4,6-二[2,4-二甲基苯基]-1,3,5-三嗪;5-氯-2-(2-羟基-3,5-二-叔丁基苯基)-2H-苯并三唑;2-(2-羟基-3-十二烷基-5-甲基苯基)-2H-苯并三唑;5-氯-2-(2-羟基-3-叔丁基-5-甲基苯基)-2H-苯并三唑;二-(3-(2H-苯并三唑-2-基)-2-羟基-5-叔辛基)甲烷;2-(2-羟基-3,5-二-叔丁基苯基)-2H-苯并三唑;2-(2-羟基-3,5-二-叔-戊基苯基)-2H-苯并三唑;2-(2-羟基-3,5-二-α-枯基苯基)-2H-苯并三唑;2-(2-羟基-3-α枯基-5-叔辛基苯基)-2H-苯并三唑;2-(2-羟基-5-叔辛基苯基)-2H-苯并三唑;3-(2H-苯并三唑-2-基)-4-羟基-5-(1-甲基丙基)-苯磺酸一钠盐;3-叔丁基-4-羟基-5-(2H-苯并三唑-2-基)-氢化肉桂酸和钠盐;12-羟基-3,6,9-三氧杂十二烷3-叔丁基-4-羟基-5-(2H-苯并三唑-2-基)-氢化肉桂酸酯;3-叔丁基-4-羟基-5-(2H-苯并三唑-2-基)-氢化肉桂酸辛酯;4,6-二(2,4-二甲基苯基)-2-(4-(3-十二烷氧基*-2-羟基丙基)-2-羟苯基)-均三嗪(*是C12-14氧基异构体的混合物);4,6-二(2,4-二甲基苯基)-2-(4-辛氧基-2-羟苯基)-均三嗪;2,4-二羟基二苯甲酮;2,2′-二羟基-4,4′-二甲氧基-5,5′-二磺基-二苯甲酮,二钠盐;2-羟基-4-辛氧基二苯甲酮;2-羟基-4-十二烷氧基-二苯甲酮;2,4-二羟基二苯甲酮;2,2′,4,4′-四羟基二苯甲酮;4-氨基苯甲酸;2,3-二羟丙基-4-氨基苯甲酸;3-(4-咪唑基)丙烯酸;2-苯基-5-苯并咪唑磺酸;N,N,N-三甲基-α-(2-氧代-3-亚冰片基)-对甲苯铵甲基硫酸盐(N,N,N-trimethyl-α-(2-oxo-3-bomylidene)-p-toluidinium methyl sulfate);5-苯甲酰基-4-羟基-2-甲氧基苯磺酸,钠盐;氯化3-(4-苯甲酰基-3羟基苯氧基)-2-羟基-N,N,N-三甲基-1-丙铵;氯化3-[4-(2H-苯并三唑-2-基)-3-羟基苯氧基]-2-羟基-N,N,N-三甲基-1-丙铵;2-(2-羟基-5-甲基苯基)-2H-苯并三唑;和2,2′-二羟基-4,4′-二甲氧基二苯甲酮((Uvinul3049)。
优选,适宜的紫外线吸收剂选自:
3-(2H-苯并三唑-2-基)-4-羟基-5-(1-甲基丙基)-苯磺酸一钠盐;3-叔丁基-4-羟基-5-(2H-苯并三唑-2-基)-氢化肉桂酸和钠盐;2-(2-羟基-3,5-二-叔丁基苯基)-2H-苯并三唑;2-(2-羟基-3,5-二-叔戊基苯基)-2H-苯并三唑;4,6-二(2,4-二甲基苯基)-2-(4-(3-十二烷氧基*-2-羟基丙基)-2-羟基苯基)-均三嗪(*是C12-14氧基异构体的混合物);12-羟基-3,6,9-三氧杂十二烷基3-叔丁基-4-羟基-5-(2H-苯并三唑-2-基)-氢化肉桂酸酯;2,4-二羟基二苯甲酮;2,2′-二羟基-4,4′-二甲氧基-5,5′-二磺基二苯甲酮,二钠盐;2,2′,4,4′-四羟基二苯甲酮;氯化3-(4-苯甲酰基-3-羟基苯氧基)-2-羟基-N,N,N-三甲基-1-丙铵;氯化3-[4-(2H-苯并三唑-2-基)-3-羟基苯氧基]-2-羟基-N,N,N-三甲基-1-丙铵;5-苯甲酰基-4-羟基-2-甲氧基-苯磺酸,钠盐;和2-(2-羟基-3-α-枯基-5-叔辛基苯基)-2H-苯并三唑。
其他适宜的抗氧化剂例如选自:受阻酚和苯并呋喃酮的稳定剂。
适宜的抗氧化剂例如选自:
成分(c)中受阻胺光稳定剂(HALS)例如是公知的市售化合物。它们例如选自:
二(2,2,6,6-四甲基哌啶-4-基)癸二酸酯、二(2,2,6,6-四甲基哌啶-4-基)琥珀酸酯、二(1,2,2,6,6-五甲基哌啶-4-基)癸二酸酯、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-羟乙基-2,2,6,6-四甲基-4-羟基哌啶和琥珀酸的缩合物、N,N′-二(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-叔辛基氨基-2,6-二氯-1,3,5-均三嗪的缩合物、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-苯甲酰基-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-叔丁基苯甲基)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)六亚甲基二胺和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)-1,3,5-三嗪和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)-1,3,5-三嗪和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)六亚甲基二胺和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)乙烷和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(CAS reg.[136504-96-6])的缩合物;(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]和表氯醇的反应产物、四(2,2,6,6-四甲基哌啶基-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,
成分(c)中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,如含有磷酸根,膦酸根或甲基膦酸根的那些,比如壳多糖衍生物,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。
络合物形成剂优选选自:乙二胺四乙酸(EDTA),次氮基三乙酸(NTA),
β-丙氨酸二乙酸(EDETA)或乙二胺二琥珀酸(EDDS)、
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,爽身粉如婴儿爽身粉,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,头发造型和调理产品(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(mouth washer),口腔清洗剂(mouse rinse),防牙菌斑剂(anti-plaquepreparations)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制剂具体有激素制剂,维生素制剂,植物提取物制剂和抗菌制剂。
所述的身体护理品可以是霜膏(cream),软膏(ointment),糊剂(paste),泡沫体,凝胶,洗剂,粉,化妆品(make-up),喷雾剂,棒剂或气溶胶剂的形式。本发明的稳定剂体系能以油相或水相或水/醇相的形式存在。
身体护理和家用制品中的成分(b)的添加剂例如以大约5至10000ppm的浓度存在,优选大约10至5000ppm,更优选大约100-1000ppm,基于总的制剂。优选身体护理和家用制品中成分(b)的添加剂以大约5,10,15,20,25,35,40,45或50ppm的浓度存在,基于总的制剂。例如,在本发明的制剂(组合物)中成分(b)的添加剂以大约5至1000ppm的浓度存在。这些ppm浓度是重量份。
本发明的家用制品应认为是洗衣用洗涤剂、织物柔软剂或其他产品,来自于这些产品的成分(b)的添加剂用于沉积在使用的织物上,并且上述浓度水平也对其适用。本发明的成分(b)的添加剂能有效稳定洗衣用洗涤剂和织物柔软剂和以此处理的织物。
霜膏是含50%以上水的水包油型乳液。此中所用的含油基质通常主要为脂肪醇如月桂醇,鲸蜡醇或硬脂醇,脂肪酸如棕榈酸或硬脂酸,液态至固态蜡如肉豆蔻酸异丙酯或蜂蜡和/或烃化合物如石蜡油。适合的乳化剂主要为亲水性的表面活性剂,诸如相应的非离子乳化剂,如多元醇脂肪酸酯的环氧乙烷加成物,如聚甘油脂肪酸酯或聚氧乙烯脱水山梨醇脂肪酸醚(商标为Tween);聚氧乙烯脂肪醇醚或其酯或相应的离子乳化剂,诸如脂肪醇磺酸的碱金属盐,十六烷基硫酸钠或硬脂基硫酸钠,其通常与脂肪醇如鲸蜡醇或硬脂醇一起使用。此外,霜膏包含降低蒸发时失水量的试剂如多元醇象甘油,山梨醇,丙二醇和/或聚乙二醇。
软膏为含高至70%,优选不超过20-50%的水或水相的油包水乳液。所述含油相主要包含烃类诸如优选含羟基化合物的石蜡油和/或固态石蜡,例如脂肪醇或其酯诸如鲸蜡醇或羊毛蜡,用以改善吸水性。乳化剂为相应的亲脂物质诸如脱水山梨醇脂肪酸酯。此外,所述软膏包含润湿剂诸如多元醇如甘油,丙二醇,山梨醇和/或聚乙二醇以及保存剂。
浓乳油(rich cream)为无水制剂并且在烃化合物的基础上制备,所述烃化合物的实例有石蜡,天然或部分合成的脂肪,例如椰油脂肪酸三甘油酯或例如硬化油和甘油偏脂肪酸酯。
糊剂为含有用于吸收分泌物的粉末成分如金属氧化物象二氧化钛或氧化锌以及用于结合水分或吸收的分泌物的牛脂和/或硅酸铝的霜膏和软膏。
泡沫体为气溶胶形式的液体水包油乳液。对于含油相来说,尤其使用了烃化合物,例如石蜡油,脂肪醇如鲸蜡醇,脂肪酸酯如肉豆蔻酸异丙酯和/或蜡。特别适合的乳化剂有主要为亲水性的乳化剂如聚氧乙烯脱水山梨醇脂肪酸酯与主要为亲脂性的乳化剂如脱水山梨醇脂肪酸酯的混合物。通常另外还使用市售可得的添加剂如防腐剂。
凝胶具体为凝胶形成体分散或溶胀在其中的活性物质的水溶液或悬浮液,凝胶形成体的实例具体有纤维素醚诸如甲基纤维素,羟乙基纤维素,羧甲基纤维素或植物水胶体如藻酸钠,黄蓍胶或阿拉伯胶和聚丙烯酸酯增稠剂体系。该凝胶例如另外还包含作为加湿剂的多元醇如丙二醇或甘油和润湿剂如聚氧乙烯脱水山梨醇脂肪酸酯。该凝胶还包含市售可得的防腐剂如苯甲醇,苯乙醇,苯氧基乙醇等。
下表列出了本发明身体护理品的实例和其组分:
身体护理品 | 成分 |
保湿霜膏 | 植物油,乳化剂,增稠剂,香料,水,抗氧化剂,紫外线吸收剂 |
香波 | 表面活性剂,乳化剂,防腐剂,香料,抗氧化剂,紫外线吸收剂 |
牙膏 | 清洁剂,增稠剂,甜味剂,调味剂,着色剂,抗氧化剂,水,紫外线吸收剂 |
唇膏 | 植物油,蜡,TiO2,抗氧化剂,紫外线吸收剂 |
本发明的身体护理品,家用制品,纺织品和织物能够使这些产品中成分的变色和化学降解具有高稳定性。比如,含染料的本发明的组合物具有出色的颜色稳定性。
因此,本发明还涉及经稳定的组合物,其包括:
(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:
(i)二烷基羟胺稳定剂,
(ii)二烷基羟胺稳定剂盐,
(iii)硝酮稳定剂,和
(iv)氧化胺稳定剂,和
(d)染料。
该术语“有效稳定量的”例如指达到所需染料稳定性的必需的数量。
按照本发明的染料例如:
-无机颜料,优选氧化铁(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;
-可溶于溶剂的分散染料,诸如HC型直接毛发染料,如HC Red 3,HCBlue 2等以及其他毛发染料(登记在国际化妆品成分辞典和手册(International Cosmetic Ingredient Dictionary and Handbook),第7版,19997),或登记在染料索引国际(Color Index International)或英国染色工作者学会上的分散染料;
-染料清漆(color varnishes)(可溶性染料的不溶性盐,如许多阴离子染料的Ca-,Ba-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(阳离子的),直接染料,活性染料或溶剂染料。
通常,用于家用和身体护理品染色的所有材料是适宜的,其能够吸收电磁辐射的可见光(波长大约4000至700nm)。该吸收通常由下列发色团引起: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-,咕吨-,吖啶-,喹啉,次甲基-(也包括聚甲炔-),噻唑-,吲达胺-(indamin-),吲哚酚-,吖嗪-,噁嗪,噻嗪-,蒽醌-,靛青-,酞菁-和其它合成,天然和/或无机发色团。
本发明稳定剂体系也可以用于家用清洁剂和处理剂,例如用于洗涤品和织物柔软剂,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,例如用于洗涤剂,漂洗剂和器皿洗涤剂,厨房和炉灶清洁剂,透明漂洗剂(clear rinsing agent),洗碟机用洗涤剂,鞋油,上光蜡,地板洗涤剂和和抛光剂,金属清洁剂,玻璃洗涤剂和陶瓷清洁剂,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和皮革修饰剂和乙烯基修饰剂(皮革和乙烯基喷雾剂)和空气清新剂。
本发明也涉及家用护理和织物护理品,诸如排水管清洗剂,消毒剂溶液,室内装璜清洁剂,汽车护理品(例如,为清洗和/或抛光和保护涂料,轮胎,铬,乙烯树脂,皮革,织物,橡胶,塑料和织物),脱脂剂,抛光剂(玻璃,木材,皮革,塑料,大理石,花岗岩,和瓷砖,等),和金属抛光剂和清洁剂。抗氧化剂适合于保护上述产品和干燥剂片中的香味。本发明也涉及家用护理品诸如蜡烛,凝胶蜡烛,空气清新剂和香味油(家用)。
本发明的稳定剂能够用于织物使用之后进行的织物处理,称为织物护理。这种处理包括洗涤,其使用清洁剂和/或织物调节剂,和基于非清洁剂的织物护理品(比如喷涂产品(spray-on product))的应用。当应用于这种形式,本发明的稳定剂用于沉积在织物上并用于保护织物,和与所述这些织物相关的着色剂和香料免于损害环境。
家用清洗剂和处理剂的典型实例是:
家用清洁剂/家用处理剂 | 成分 |
清洁剂浓缩液 | 表面活性剂混合物、乙醇、抗氧化剂、水、紫外线吸收剂、抗氧化剂 |
鞋油 | 蜡、蜡乳化剂、抗氧化剂、水、防腐剂、紫外线吸收剂、抗氧化剂 |
含蜡地板洗涤剂 | 蜡、乳化剂、氯化钠、抗氧化剂、水、防腐剂、紫外线吸收剂、抗氧化剂 |
本发明的稳定剂例如通过溶解在油相或醇相或水相中而加入的,有时需要高温。
本发明也涉及稳定身体护理品、家用制品、纺织品或织物的方法,其包括向其中加入或施加至少一种化合物,其选自:
(i)二烷基羟胺稳定剂,
(ii)二烷基羟胺稳定剂盐,
(ii)硝酮稳定剂,和
(iv)氧化胺稳定剂。
就稳定织物,例如染色的织物而言,本发明的稳定剂是通过从如清洁剂,织物调理剂或基于非清洁剂的织物护理品沉积而施加到其上的。
本发明的织物是天然或合成织物,和可以是机织或非机织的。
本发明也涉及稳定身体护理品、家用制品、纺织品或织物的方法,其每一个均包含染料,该方法包括向其中加入或施加选自成分(i)-(iv)中的至少一种化合物。成分(i)-(iv)的本发明的稳定剂对于稳定本发明组合物内的染料非常有效。
本发明的纺织品例如是纺织品纤维材料,例如含氮或含羟基的纤维材料,如其选自:纤维素,丝,羊毛,合成的聚酰胺,皮革和聚氨酯。包括棉,亚麻和大麻,纸浆和再生纤维素。也包括纤维素混合物,例如棉花和聚酰胺的混合物或棉花/聚酯混合物。
本发明的添加剂例如以染色或印刷方法或以染整加工应用于纺织品。例如,该添加剂可以作为染料制剂的组分而应用。该添加剂例如可以用喷墨印刷方法应用到纺织品。该添加剂例如用作含水染料溶液或印染浆的一部分。它们可以用排气方法(exhaust method)或轧染机染色法染色而应用,其中纺织品用含水染料溶液浸渍,其可以含盐,和在碱处理之后或存在碱的情况下,将染料和添加剂附着到织物,适当的时候,可以加热或在室温下存储几个小时。附着之后,染色或印刷用冷水和热水彻底漂洗,适当的时候,加入具有分散作用和促进非附着部分扩散的制剂。
应用于纺织品的该染料或涂料制剂可以进一步包含通常的添加剂,例如表面活性剂,除泡剂,抗菌制剂等,如美国专利6,281,339,6,353,094和6,323,327中公开的那些,其公开据此一并引入作为参考。
下列实施例阐明了本发明。除非另外指明,百分比是重量百分比。
实施例1
该化合物由Aldrich Chemical Company获得。
实施例2
该化合物由Aldrich Chemical Company获得。
实施例3
该化合物由Aldrich Chemical Company获得。
实施例4
实施例3的化合物(3.2g,0.012摩尔)溶于50mL的无水异丙醇中。将1.5mL的无水异丙醇(7.60摩尔氢氯酸)在40℃下滴加入该搅拌溶液。三十分钟后,将混合物加热到50℃并持续30分钟。最终的清液冷却到5℃。过滤生成的白色沉淀物,然后用冷异丙醇洗涤,接着在真空烘箱中干燥至恒重。获得白色固体的标题化合物(3.4g,92%产率),其熔点161-169℃,其结构与HNMR一致。
实施例5
实施例2的化合物(8.9g,0.1摩尔)溶于100mL的无水二乙醚中。将59mL的无水乙醇(1.68摩尔氢氯酸)在室温下滴加入该搅拌溶液。三小时之后,蒸馏除去溶剂并用25mL的异丙醇/己烷(1∶2比率)置换。过滤生成的白色沉淀物,然后用冷异丙醇/己烷(1∶2比率)洗涤,接着在真空烘箱中干燥至恒重。获得白色固体的标题化合物(5.2g,43%产率),其熔点为70-72℃,其结构与HNMR一致。
实施例6
实施例1的化合物(10.7g,0.05摩尔)溶于35mL庚烷和35mL无水异丙醇中。将含0.05摩尔氢氯酸的9.38g的无水异丙醇在室温下滴加入该搅拌溶液。过滤生成的白色沉淀物,并将其从400g沸腾的异丙醇中重结晶,接着在真空烘箱中干燥至恒重。获得白色固体的标题化合物(8.5g,68%产率),其熔点为174℃,其结构与HNMR一致。
实施例7
该化合物按照J.E.Baldwin,Tetrahedron,1984,40(21),4363-70制备。
实施例8
该化合物按照J.E.Baldwin,Tetrahedron,1984,40(21),4363-70制备。
实施例9
该化合物按照J.E.Baldwin,Tetrahedron,1984,40(21),4363-70制备。
实施例10
该化合物按照美国专利4,898,901制备。
实施例11
该化合物按照美国专利4,898,901制备。
实施例12
该化合物按照美国专利4,972,009和美国专利5,202,441制备。
实施例13
该化合物按照美国专利4,898,901制备。
实施例14
该化合物按照美国专利4,898,901制备。
实施例16
该化合物按照美国专利4,898,901制备。
实施例17
该化合物按照美国专利5,081,300,5,162,408,5,844,029,5,880,191和5,922,794制备。
实施例18
将该化合物加入到市售香波制剂中,并评价当样品曝光于荧光照明下时其减少染料褪色量的能力。将该化合物(0.36g)溶于5mL甲醇中,然后在搅拌下将其加入120g香波(SuaveNatural Fresh Mountain StrawberryShampoo)中。将该稳定的香波制剂搅拌15分钟并将其加入20mL的玻璃闪烁管。在室温下使这些制剂荧光老化。曝光前后的CIEL*a*b色标系用X-Rite 938光密度计测定。色变可以表示为ΔE(DE)。由下面公式计算ΔE(DE)表示的色变:
DE=[(DL*)2+(Da*)2+(Db*)2]1/2
稳定剂(以0.30wt%加入) | 2周之后的DE |
无 | 8.49 |
实施例9 | 7.38 |
实施例2 | 7.26 |
实施例5 | 6.44 |
实施例7 | 5.13 |
实施例6 | 4.61 |
实施例8 | 4.46 |
本发明的化合物能明显地改善香波制剂的耐光性能(light fastness)。
实施例19
将该化合物加入到市售香波制剂中,并评价当样品曝光于荧光照明下时其减少染料褪色量的能力。将该化合物(0.36g)溶于5mL甲醇中,然后在搅拌下将其加入120g的香波(Clairol草本精华香波)中。将该稳定香波制剂搅拌15分钟并将其加入20mL的玻璃闪烁管。在室温下使这些制剂荧光老化。曝光前后的CIEL*a*b色标系用X-Rite 938光密度计测定。色变可以表示为ΔE(DE)。
稳定剂(以0.30wt%加入) | 2周之后的DE |
无 | 1.86 |
实施例8 | 1.40 |
实施例5 | 1.22 |
本发明的化合物能明显地改善香波制剂的耐光性能。
实施例20
将该化合物加入到市售漱口水制剂中,并评价当样品曝光于荧光照明下时其减少染料褪色量的能力。将该化合物(0.36g)溶于5mL甲醇中,然后在搅拌下将其加入120g漱口水(ScopeOriginal Mint)中。将该稳定漱口水制剂搅拌15分钟并将其加入20mL的玻璃闪烁管。在室温下使这些制剂荧光老化。曝光前后的CIEL*a*b色标系用X-Rite 938光密度计测定。色变可以表示为ΔE(DE)。
稳定剂(以0.30wt%加入) | 2周之后的DE |
无 | 5.30 |
实施例8 | 5.02 |
实施例5 | 2.28 |
本发明的化合物能明显地改善漱口水制剂的耐光性能。
实施例21
将该化合物加入到市售漱口水制剂中,并评价当样品曝光于荧光照明下时其减少染料褪色量的能力。该化合物(0.36g)溶于5mL甲醇,然后在搅拌下将其加入120g的漱口水(ListerineCool Mint)。该稳定漱口水制剂搅拌15分钟并将其加入20mL的玻璃闪烁管。在室温下使这些制剂荧光老化。曝光前后的CIEL*a*b色标系用X-Rite 938光密度计测定。色变可以表示为ΔE(DE)。
稳定剂(以0.30wt%加入) | 2周之后的DE |
无 | 2.70 |
实施例9 | 2.64 |
实施例8实施例5 | 2.040.91 |
实施例2 | 0.64 |
本发明的化合物能明显地改善漱口水制剂的耐光性能。
实施例22
将该化合物加入到市售香波制剂中,并评价当样品曝光于荧光照明下时其减少染料褪色量的能力。该化合物搅拌溶于香波制剂。将3-(2H-苯并三唑-2-基)-4-羟基-5-(1-甲基丙基)-苯磺酸一钠盐,苯并三唑紫外线吸收剂加入到香波制剂。在室温下使这些制剂荧光老化。测定曝光前后的CIEL*a*b色标系。色变用ΔE(DE)表示。本发明的化合物在改善香波制剂的耐光性能方面非常有效。
实施例23
将该化合物加入到市售香波制剂中,并评价当样品曝光于荧光照明下时其减少染料褪色量的能力。该化合物搅拌溶于香波制剂。将均三嗪UV吸收剂加入到香波制剂。在室温下使这些制剂荧光老化。测定曝光前后的CIEL*a*b色标系。色变用ΔE(DE)表示。本发明的化合物在改善香波制剂的耐光性能方面非常有效。
实施例24
将该化合物加入到市售香波制剂中,并评价当样品曝光于荧光照明下时其减少染料褪色量的能力。该化合物搅拌溶于香波制剂。将二苯甲酮UV吸收剂加入到香波制剂。在室温下荧光照射这些制剂。测定曝光前后的CIEL*a*b色标系。色变用ΔE(DE)表示。本发明的化合物在改善香波制剂的耐光性能方面非常有效。
实施例25
将该化合物加入到市售漱口水制剂中中,并评价当样品曝光于荧光照明下时其减少染料褪色量的能力。将该化合物搅拌加入到漱口水制剂。将3-(2H-苯并三唑-2-基)-4-羟基-5-(1-甲基丙基)-苯磺酸一钠盐,苯并三唑紫外线吸收剂加入到漱口水制剂。在室温下使这些制剂荧光老化。测定曝光前后的CIEL*a*b色标系。色变(color change)可以表示为ΔE(DE)。本发明的化合物在改善漱口水制剂的耐光性能方面非常有效。
实施例26
将该化合物加入到市售漱口水制剂中,并评价当样品曝光于荧光照明下时其减少染料褪色量的能力。将该化合物搅拌加入到漱口水制剂将均三嗪UV吸收剂加入到漱口水制剂。在室温下使这些制剂荧光老化。测定曝光前后的CIEL*a*b色标系。色变可以表示为ΔE(DE)。本发明的化合物在改善漱口水制剂的耐光性能方面非常有效。
实施例27
将该化合物加入到市售漱口水制剂中,并评价当样品曝光于荧光照明下时其减少染料褪色量的能力。将该化合物搅拌加入到漱口水制剂。将二苯甲酮UV吸收剂加入到漱口水制剂。在室温下使这些制剂荧光老化。测定曝光前后的CIEL*a*b色标系。色变可以表示为ΔE(DE)。本发明的化合物在改善漱口水制剂的耐光性能方面非常有效。
实施例28
水基试验制剂制备如下:
月桂醇聚氧乙烯醚硫酸钠(30%,TEXAPON NSO,Cognis) | 30% |
椰油酰氨基甜菜碱(30%,DEHYTON K,Cognis) | 10% |
着色剂* | 0.001% |
本发明的稳定剂 | 0.05% |
柠檬酸(10%水溶液) | 至pH6 |
去离子水 | 至100% |
*着色剂是PURICOLOR BLUE ABL9(FD & C Blue 1)
将约20mL的每一含水试验制剂放入硼硅酸盐玻璃瓶。将玻璃瓶暴露于Atlas Ci-65氙弧老化试验机,用AATCC试验方法16(AATCC Test Method16)。在Hunter Ultrascan XE分光光度计上测定颜色。ΔL、a和b的值为初始值与各时间间隔值的差值。可以发现本发明的稳定剂能赋予个人护理品出色的颜色稳定性。
实施例29
水基试验制剂制备如下:
月桂醇聚氧乙烯醚硫酸钠(30%,TEXAPON NSO,Cognis) | 30% |
椰油酰氨基甜菜碱(30%,DEHYTON K,Cognis) | 10% |
着色剂* | 0.001% |
本发明的稳定剂 | 0.05% |
柠檬酸(10%水溶液) | 至pH6 |
去离子水 | 至100% |
*着色剂是PURICOLOR BLUE ABL9(FD & C Blue 1)
将约20mL的每一含水试验制剂放入硼硅酸盐玻璃瓶。将玻璃瓶暴露于Atlas Ci-65氙弧老化试验机,用AATCC试验方法16,选项E。在HunterUltrascan XE分光光度计上测定颜色。ΔL、a和b的值为初始值与各时间间隔值的差值。可以发现本发明的稳定剂能赋予个人护理品出色的颜色稳定性。
实施例30
水基试验制剂制备如下:
月桂醇聚氧乙烯醚硫酸钠(30%,TEXAPON NSO,Cognis) | 30% |
椰油酰氨基甜菜碱(30%,DEHYTON K,Cognis) | 10% |
着色剂* | 0.001% |
本发明的稳定剂 | 0.05% |
柠檬酸(10%水溶液) | 至pH6 |
去离子水 | 至100% |
*着色剂是FD & C Red 40
将约20mL的每一含水试验制剂放入硼硅酸盐玻璃瓶。将玻璃瓶暴露于Atlas Ci-65氙弧老化试验机,用AATCC试验方法16。在Hunter UltrascanXE分光光度计上测定颜色。ΔL、a和b的值为初始值与各时间间隔值的差值。可以发现本发明的稳定剂赋予个人护理品出色的颜色稳定性。
实施例31
水基试验制剂制备如下:
月桂醇聚氧乙烯醚硫酸钠(30%,TEXAPON NSO,Cognis) | 30% |
椰油酰氨基甜菜碱(30%,DEHYTON K,Cognis) | 10% |
着色剂* | 0.001% |
本发明的稳定剂 | 0.05% |
柠檬酸(10%水溶液) | 至pH6 |
去离子水 | 至100% |
*着色剂是PURICOLOR BLUE ABL9(FD & C Blue 1)
将约20mL的每一含水试验制剂放入硼硅酸盐玻璃瓶。玻璃瓶也曝光于加速荧光照明中,灯型号:Philips,40瓦,Daylight Deluxe(D65),全光照。在Hunter Ultrascan XE分光光度计上测定颜色。ΔL、a和b的值为初始值与各时间间隔值的差值。可以发现本发明的稳定剂能赋予个人护理品出色的颜色稳定性。
实施例32
水基试验制剂制备如下:
月桂醇聚氧乙烯醚硫酸钠(30%,TEXAPON NSO,Cognis) | 30% |
椰油酰氨基甜菜碱(30%,DEHYTON K,Cognis) | 10% |
着色剂* | 0.001% |
本发明的稳定剂 | 0.05% |
柠檬酸(10%水溶液) | 至pH6 |
去离子水 | 至100% |
*着色剂是PURICOLOR RED ARE33(FD & C Red 33)
将约20mL的每一含水试验制剂放入硼硅酸盐玻璃瓶。玻璃瓶也曝光于加速荧光照明中,灯型号:Philips,40瓦,Daylight Deluxe(D65),全光照。在Hunter Ultrascan XE分光光度计上测定颜色。ΔL、a和b的值为初始值与各时间间隔值的差值。可以发现本发明的稳定剂能赋予个人护理品出色的颜色稳定性。
实施例33
水基试验制剂制备如下:
月桂醇聚氧乙烯醚硫酸钠(30%,TEXAPON NSO,Cognis) | 30% |
椰油酰氨基甜菜碱(30%,DEHYTON K,Cognis) | 10% |
着色剂* | 0.001% |
本发明的稳定剂 | 0.05% |
柠檬酸(10%水溶液) | 至pH6 |
去离子水 | 至100% |
*着色剂是FD & C Red 40
将约20mL的每一含水试验制剂放入硼硅酸盐玻璃瓶。玻璃瓶也曝光于加速荧光照明中,灯型号:Philips,40 Watt,Daylight Deluxe(D65),全光照。在Hunter Ultrascan XE分光光度计上测定颜色。ΔL、a和b的值为初始值与各时间间隔值的差值。可以发现本发明的稳定剂能赋予个人护理品出色的颜色稳定性。
实施例34 保湿霜
于75-80℃,在均质器内充分混合相A成分约10分钟。水相B,同样的预先加热到75-80℃,然后慢慢将其加入到均质器并将混合物均化1分钟。在搅拌下,将混合物冷却到40℃,然后加入相C和E,接着将混合物均化1分钟。然后,加入相D并将混合物均化0.5分钟,接着在搅拌下冷却到室温。
相 | 成分 | (w/w)% |
A | 西番莲油(passionflower oil) | 8 |
二油酸甘油酯 | 4 | |
二辛基醚 | 4 | |
异硬脂肪酸异丙酯 | 4 | |
本发明的稳定剂 | 0.05 | |
B | 去离子水 | 至100 |
EDTA | 0.1 | |
C | 卡波姆(Carbomer) | 0.15 |
D | 氢氧化钠 | 10% |
E | 香料,防腐剂 | 适量 |
可以发现本发明的稳定剂能赋予个人护理品出色的颜色稳定性。
实施例35 盥洗用香水
下面成分以所列举的顺序在50℃充分混合,获得澄清的均质溶液。紫外线吸收剂是例如3-(2H-苯并三唑-2-基)-4-羟基-5-(1-甲基丙基)-苯磺酸一钠盐。
成分 | (w/w)% |
乙醇,96% | 60 |
d-柠檬烯 | 5 |
雪松烯 | 1.5 |
香茅醇 | 0.5 |
Savin | 0.5 |
本发明的稳定剂 | 0.08 |
紫外线吸收剂 | 0.1 |
S,S-EDDS | 0.005 |
着色剂(D&C Yellow 5) | 0.02 |
水 | 至100 |
该实施例的盥洗用香水制剂,获得极佳的效果。
实施例36头发造型喷雾剂(Hair Styling Spray)
羟丙基纤维素首先预溶解到一半的乙醇中(旋涡混合器),并用氨基甲基丙醇稀释。不含丙烯酸酯树脂的其它成分溶于乙醇,然后在搅拌下,将这个溶液加至羟丙基纤维素中。接着,加入丙烯酸酯树脂并且搅拌直到完全溶解。所用的紫外线吸收剂例如是二苯甲酮-4,5-苯甲酰基-4-羟基-2-甲氧基苯磺酸钠盐。
成分 | (w/w)% |
无水乙醇 | 96.21 |
辛基丙烯酰胺/丙烯酸酯/甲基丙烯酸(丁基氨基乙基)酯共聚物 | 2.52 |
羟丙基纤维素 | 0.51 |
氨基甲基丙醇(95%) | 0.46 |
本发明的稳定剂 | 0.05 |
紫外线吸收剂 | 0.05 |
芳香油 | 0.20 |
对于该实施例的头发造型喷雾剂制剂,获得极好的效果。
实施例37 油性毛发用香波
所列成分在室温下搅拌混合,直到它们完全地溶解。pH是6.5。紫外线吸收剂例如是2-(2-羟基-3-十二烷基-5-甲基苯基)-2H-苯并三唑。
成分 | (w/w)% |
豆蔻醇聚氧乙烯醚硫酸钠(sodium myreth sulphate) | 50.00 |
TEA松香胶原水解产物(TEA abietoyl collagen hydrolysate) | 3.50 |
月桂醇聚氧乙烯醚-3 | 3.00 |
着色剂(D&C Red 33) | 0.20 |
本发明的稳定剂 | 0.05 |
紫外线吸收剂 | 0.15 |
膦酰基甲基壳聚糖(phosphonomethylchitosan),钠盐 | 0.01 |
芳香油 | 0.10 |
水 | 至100 |
该实施例的油性毛发用香波混合物,获得极好的效果。
实施例38皮革修整剂和清洁剂(Leather Dressing and Cleaning Agent)
将稳定剂预溶解于萜烯中。这些成分然后以所列举的顺序在约65℃下搅拌直到均匀。混合物然后冷却到室温。
成分 | (w/w)% |
合成皂(Zetesap 813) | 7.85 |
甘油 | 6.00 |
阴离子表面活性剂(Lumorol 4192;Mulsifan RT 13) | 22.00 |
凡士林 | 11.00 |
石蜡52/54 | 20.00 |
滑石 | 2.00 |
橙萜烯(orange terpene) | 4.00 |
本发明的稳定剂 | 0.02 |
水 | 27.13 |
该实施例的皮革修整剂和清洁剂混合物,获得极好的效果。
实施例39 玻璃洗涤剂
下列成分以所列举的顺序溶解直到获得澄清的均匀混合物。
成分 | (w/w)% |
阴离子/两性表面活性剂(Lumorol RK) | 0.7 |
丁二醇 | 5.0 |
异丙醇 | 20.00 |
d-柠檬烯 | 4.00 |
本发明的稳定剂 | 0.02 |
去离子水 | 至100 |
该实施例的玻璃洗涤剂制剂,获得极好的效果。
实施例40 织物中染料的保护
分别将本发明的稳定剂沉积在染色过的棉织物上,稳定剂的浓度为0.05,0.1,0.2,0.5和1.0重量份,基于棉织物的重量。染色过的织物包含下列染料,染料的含量为0.05,0.1,0.2和0.5重量份,该重量份基于棉织物。对于每个所列的染料,这将获得60个不同制剂:
猩红HE-3G | 深红)HE-XL | 黄HE-6G | 红HE-XL |
蓝HE-XL | 绿松石色H-A | 藏青色HE-XL | Remazol |
红RB | 亮红RBS | 橙FR | 藏青色CG |
绿松石色G | 黑B |
用Atlas Ci-65氙弧老化试验机,使棉织物承受光暴晒或加速荧光照明。本发明的稳定剂对染色过的织物提供突出的色保护。该实验通过例如含稳定剂的洗衣用洗涤剂或织物调理剂处理织物,使稳定剂沉积在织物上,模拟了可获得的染料保护。
实施例41 织物中染料的保护
本发明的稳定剂和紫外线吸收剂,例如3-(2H-苯并三唑-2-基)-4-羟基-5-(1-甲基丙基)-苯磺酸一钠盐,每个均(从水)沉积到染色棉织物,其含量为0.05,0.1,0.2,0.5和1.0重量份,该重量份基于棉花的重量。染色的织物包含下列染料,染料的含量为0.05,0.1,0.2和0.5重量份,该重量份基于棉花。对于每个所列的染料,这将获得60个不同制剂:
猩红HE-3G | 深红HE-XL | 黄HE-6G | 红HE-XL |
蓝HE-XL | 绿松石色H-A | 藏青色HE-XL | Remazol |
红RB | 亮红RBS | 橙FR | 藏青色CG |
绿松石色G | 黑B |
用Atlas Ci-65氙弧老化试验机,使棉织物承受光暴晒或加速荧光照明。本发明的稳定剂对染色织物提供突出的色保护。该实验通过例如含稳定剂的洗衣用洗涤剂或织物调理剂处理织物,使稳定剂沉积在织物上,模拟了可获得的染料保护。
Claims (38)
1.一种经稳定的组合物,其包括:
(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)二烷基羟胺稳定剂,
(ii)二烷基羟胺稳定剂盐,
(iii)硝酮稳定剂,和
(iv)氧化胺稳定剂。
2.权利要求1所述的组合物,其包含有效稳定量的选自二烷基羟胺稳定剂的至少一种化合物。
3.权利要求2所述的组合物,其中二烷基羟胺稳定剂具有分子式:
R1R2N-OH,其中
R1是1至36个碳原子的烷基,5至12个碳原子的环烷基或7至9个碳原子的芳烷基;或R1是被1至6个下列基团取代的所述烷基,环烷基或芳烷基:1至12个碳原子的烷基、卤素、氰基、E1O-、E1CO-、E1OCO-、E1COO-、E1S-、E1SO-、E1SO2-、-NH2、-NHE1、-NE1E2、-PO(OE1)(OE2)或-OPO(OE1)(OE2)基团;
R2是氢或独立地具有与R1相同的定义,其中R1和R2中至少一个含有与-NOH部分α位连接的氢原子;或
R1和R2一起形成C2-12杂环,所述杂环含有至少一个与-NOH部分α位连接的碳取代的氢,其中所述C2-12杂环是未被取代的或由1至3个下列基团取代:1至12个碳原子的烷基、卤素、氰基、E1O-、E1CO-、E1OCO-、E1COO-、E1S-、E1SO-、E1SO2-、-NH2、-NHE1、-NE1E2、-PO(OE1)(OE2)或-OPO(OE1)(OE2);或其中所述C2-12杂环被1至3个下述基团隔断:-O-、-NE1-、-CO-、-CONE1-、-S-、-SO-、-SO2-、-COO-、-PO3-或-PO4E1基团;或者,其中所述杂环被所述基团取代和隔断;和
E1和E2独立地是氢,1至4个碳原子的烷基或被1至3个羟基取代的1至4个碳原子的烷基;或E1和E2独立地是由羟基、甲氧基、乙酸酯基或丙酸酯基封端的聚(乙二醇)或聚(丙二醇)的低聚物,其中所述低聚物具有高达约500的分子量。
5.权利要求2所述的组合物,其中二烷基羟胺稳定剂是N,N-二乙基羟胺、N,N-二(2-羟丙基)羟胺、N,N-二(3-羟丙基)羟胺或N,N-二苄基羟胺或N,N-二(氢化牛脂)羟胺。
6.权利要求2所述的组合物,其中二烷基羟胺稳定剂是N,N-二乙基羟胺或N,N-二苄基羟胺。
7.权利要求1所述的组合物,其包括有效稳定量的选自二烷基羟胺稳定剂盐的至少一种化合物。
8.权利要求7所述的组合物,其中二烷基羟胺稳定剂盐具有分子式:
(R1R2N-OH)·(HY),其中
R1是1至36个碳原子的烷基,5至12个碳原子的环烷基或7至9个碳原子的芳烷基;或R1是被1至6个下列基团取代的所述烷基,环烷基或芳烷基:1至12个碳原子的烷基、卤素、氰基、E1O-、E1CO-、E1OCO-、E1COO-、E1S-、E1SO-、E1SO2-、-NH2、-NHE1、-NE1E2、-PO(OE1)(OE2)或-OPO(OE1)(OE2)基团;
R2是氢或独立地具有与R1相同定义,其中R1和R2中至少一个包含氢原子,该氢原子与-NOH部分α位连接;或
R1和R2一起形成C2-12杂环,所述杂环含有至少一个与-NOH部分α位连接的碳取代的氢,所述C2-12杂环是未被取代的或由1至3个下列基团取代:1至12个碳原子的烷基、卤素、氰基、E1O-、E1CO-、E1OCO-、E1COO-、E1S-、E1SO-、E1SO2-、-NH2、-NHE1、-NE1E2、-PO(OE1)(OE2)或-OPO(OE1)(OE2);或其中所述C2-12杂环被1至3个下述基团隔断:-O-、-NE1-、-CO-、-CONE1-、-S-、-SO-、-SO2-、-COO-、-PO3-或-PO4E1基团;或者,其中所述杂环被所述基团取代和隔断;
E1和E2独立地是氢,1至4个碳原子的烷基或被1至3个羟基取代的1至4个碳原子的烷基;或E1和E2独立地是由羟基、甲氧基、乙酸酯基或丙酸酯基封端的聚(乙二醇)或聚(丙二醇)的低聚物,其中所述低聚物具有高达约500的分子量;和
HY是无机或有机酸。
9.权利要求8所述的组合物,其中Y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、羟乙酸根、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(NTA)的羧酸根、二亚乙基三胺五亚甲基膦酸(DTPMPA)的羧酸根、羟乙基乙二胺三乙酸(HEDTA)的羧酸根、乙二胺四乙酸(EDTA)的羧酸根、二亚乙基三胺五乙酸(DTPA)的羧酸根、二亚乙基二胺四乙酸或二亚乙基三胺五乙酸的羧酸根、烷基磺酸根或芳基磺酸根。
10.权利要求8所述的组合物,其中Y是氯离子、硫酸氢根、硫酸根、磷酸根、硝酸根、抗坏血酸根、甲酸根、乙酸根、苯甲酸根、草酸根、柠檬酸根、乙二胺四乙酸或二亚乙基三胺五乙酸的羧酸根或聚丙烯酸根。
11.权利要求8所述的组合物,其中Y是氯离子,硫酸氢根或柠檬酸根。
12.权利要求8所述的组合物,其中二烷基羟胺稳定剂盐选自下列化合物的HY盐:N,N-二苄基羟胺、N,N-二甲基羟胺、N,N-二乙基羟胺、N,N-二(2-羟丙基)羟胺、N,N-二(3-羟丙基)羟胺、N,N-二(2-羧乙基)羟胺、N,N-二(苄基硫甲基)羟胺、N,N-二辛基羟胺、N,N-二月桂基羟胺、N,N-二-十二烷基羟胺、N,N-二-十四烷基羟胺、N,N-二-十六烷基羟胺、N,N-二-十八烷基羟胺、N-十六烷基-N-十四烷基羟胺、N-十六烷基-N-十七烷基羟胺、N-十六烷基-N-十八烷基羟胺、N-十七烷基-N-十八烷基羟胺、N-甲基-N-十八烷基羟胺、N,N-二(氢化牛脂)羟胺、
13.权利要求8所述的组合物,其中二烷基羟胺稳定剂盐是N,N-二乙基-羟胺,N,N-二(2-羟丙基)羟胺,N,N-二(3-羟丙基)羟胺或N,N-二苄基羟胺或N,N-二(氢化牛脂)羟胺的HY盐。
14.权利要求8所述的组合物,其中二烷基羟胺稳定剂盐是N,N-二乙基羟胺或N,N-二苄基羟胺的HY盐。
15.权利要求1所述的组合物,其包含有效稳定量的选自包含硝酮稳定剂的至少一种化合物。
16.权利要求15所述的组合物,其中硝酮稳定剂具有分子式,
R1是1至36个碳原子的烷基,5至12个碳原子的环烷基或7至9个碳原子的芳烷基;或R1是被1至6个下列基团取代的所述烷基,环烷基或芳烷基:1至12个碳原子的烷基、卤素、氰基、E1O-、E1CO-、E1OCO-、E1COO-、E1S-、E1SO-、E1SO2-、-NH2、-NHE1、-NE1E2、-PO(OE1)(OE2)或-OPO(OE1)(OE2)基团;
R2是氢或独立地具有与R1相同的定义;或
R1和R2一起形成C2-12杂环,所述C2-12杂环是未被取代的或由1至3个下列基团取代:1至12个碳原子的烷基、卤素、氰基、E1O-、E1CO-、E1OCO-、E1COO-、E1S-、E1SO-、E1SO2-、-NH2、-NHE1、-NE1E2、-PO(OE1)(OE2)或-OPO(OE1)(OE2);或其中所述C2-12杂环被1至3个下述基团隔断:-O-、-NE1-、-CO-、-CONE1-、-S-、-SO-、-SO2-、-COO-、-PO3-或-PO4E1基团;或者,其中所述杂环被所述基团取代和隔断;
E1和E2独立地是氢,1至4个碳原子的烷基或被1至3个羟基取代的1至4个碳原子的烷基;或E1和E2独立地是由羟基、甲氧基、乙酸酯基或丙酸酯基封端的聚(乙二醇)或聚(丙二醇)的低聚物,其中所述低聚物具有高达约500的分子量;
和R3独立地具有与R1相同的定义。
17.权利要求15所述的组合物,其中硝酮稳定剂选自:N-苄基-α-苯基硝酮、N-乙基-α-甲基硝酮、N-辛基-α-庚基硝酮、N-月桂基-α-十一烷基硝酮、N-十四烷基-α-十三烷基硝酮、N-十六烷基-α-十五烷基硝酮、N-十八烷基-α-十七烷基硝酮、N-十六烷基-α-十七烷基硝酮、N-十八烷基-α-十五烷基硝酮、N-十七烷基-α-十七烷基硝酮、N-十八烷基-α-十六烷基硝酮、N-甲基-α-十七烷基硝酮和衍生自N,N-二(氢化牛脂)羟胺的硝酮。
18.权利要求15所述的组合物,其中硝酮稳定剂是N-苄基-α-苯基硝酮,N-乙基-α-甲基硝酮或N-十八烷基-α-十七烷基硝酮。
19.权利要求1所述的组合物,其包含有效稳定量的选自氧化胺稳定剂的至少一种化合物。
20.权利要求19所述的组合物,其中氧化胺稳定剂具有分子式,
其中
R1是1至36个碳原子的烷基,5至12个碳原子的环烷基或7至9个碳原子的芳烷基;或R1是被1至6个下列基团取代的所述烷基,环烷基或芳烷基:1至12个碳原子的烷基、卤素、氰基、E1O-、E1CO-、E1OCO-、E1COO-、E1S-、E1SO-、E1SO2-、-NH2、-NHE1、-NE1E2、-PO(OE1)(OE2)或-OPO(OE1)(OE2);
R2是氢或独立地具有与R1相同定义;或
R1和R2一起形成C2-12杂环,所述C2-12杂环是未被取代的或由1至3个下列基团取代:1至12个碳原子的烷基、卤素、氰基、E1O-、E1CO-、E1OCO-、E1COO-、E1S-、E1SO-、E1SO2-、-NH2、-NHE1、-NE1E2、-PO(OE1)(OE2)或-OPO(OE1)(OE2);或其中所述C2-12杂环被1至3个下述基团隔断:-O-、-NE1-、-CO-、-CONE1-、-S-、-SO-、-SO2-、-COO-、-PO3-或-PO4E1基团;或者,其中所述杂环被所述基团取代和隔断;
E1和E2独立地是氢,1至4个碳原子的烷基或被1至3个羟基取代的1至4个碳原子的烷基;或E1和E2独立地是由羟基、甲氧基、乙酸酯基或丙酸酯基封端的聚(乙二醇)或聚(丙二醇)的低聚物,其中所述低聚物具有高达约500的分子量;和
R3独立地具有与R1相同的定义。
其中R1、R2和R3中的至少一个包含β碳-氢键。
21.权利要求20所述的组合物,其中R1和R2独立地是8至26个碳原子的烷基和R3是甲基。
22.权利要求20所述的组合物,其中R1,R2和R3独立地是6至36个碳原子的烷基。
23.权利要求20所述的组合物,其中氧化胺稳定剂是二(C16-C18)烷基甲基氧化胺,CAS#204933-93-7。
24.权利要求1所述的组合物,其进一步包括:
(c)选自紫外线吸收剂,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。
25.权利要求24所述的组合物,其中紫外线吸收剂选自:2H-苯并三唑类,均三嗪类,二苯甲酮类,α-氰基丙烯酸酯类,草酰替苯胺类,苯并噁嗪酮类,苯甲酸酯类和α-烷基肉桂酸酯类。
26.权利要求1所述的组合物,进一步包括:
(d)染料。
27.权利要求1所述的组合物,其中身体护理或家用制品中成分(b)的化合物以基于总组合物的约5至10000ppm的浓度存在。
28.权利要求1所述的组合物,其中成分(b)的化合物以基于总组合物的约10至5000ppm的浓度存在。
29.权利要求1所述的组合物,其中身体护理品选自:护肤品、沐浴和淋浴用品、液体皂、条皂、含香料和香味物质的制剂、护发品、洁齿剂、除臭和止汗剂、美饰剂、光防护制剂和含活性成分的制剂。
30.权利要求29所述的组合物,其中所述护肤品选自洁身油、爽身水、洁身胶、护理霜、护肤膏、剃须用制剂和爽身粉。
31.权利要求29所述的组合物,其中含香料和香味物质的制剂选自香水、香精、盥洗用香水和剃须液。
32.权利要求29所述的组合物,其中护发品选自:香波、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(relaxant)、发胶和发蜡、染发剂体系、永久性烫发,部分永久性、半永久性和临时染发剂体系、和毛发漂白剂。
33.权利要求29所述的组合物,其中美饰剂选自:唇膏、指甲油、眼影膏、睫毛油、干和湿化妆品、胭脂、底粉、脱毛剂和防晒和晒后用品。
34.权利要求29所述的组合物,其中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。
35.权利要求1所述的组合物,其中家用制品选自家用清洁剂和处理剂。
36.权利要求35所述的组合物,其中该家用清洁剂和处理剂选自:洗衣用洗涤剂和织物柔软剂,基于非洗涤剂的织物护理用品,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,用于洗涤、漂洗和器皿洗涤的试剂,厨房和炉灶清洁剂,透明漂洗剂,洗碟机用洗涤剂,鞋油,上光蜡,地板洗涤剂和和抛光剂,金属清洁剂,玻璃洗涤剂和陶瓷清洁剂,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和皮革修饰剂和乙烯基修饰剂(皮革和乙烯基喷雾剂)和固体以及液体空气清新剂。
37.稳定身体护理品、家用制品、纺织品或织物的方法,其包括将至少一种下述化合物结合于所述制品中或施用于所述制品上,所述化合物选自:
(i)二烷基羟胺稳定剂,
(ii)二烷基羟胺稳定剂盐,
(iii)硝酮稳定剂,和
(iv)氧化胺稳定剂。
38.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,该方法包括将至少一种下述化合物结合于所述制品中或施用于所述制品上,所述化合物选自:
(i)二烷基羟胺稳定剂,
(ii)二烷基羟胺稳定剂盐,
(iii)硝酮稳定剂,和
(iv)氧化胺稳定剂。
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EP1094106A1 (en) * | 1999-10-19 | 2001-04-25 | The Procter & Gamble Company | Cleaning composition |
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-
2004
- 2004-10-20 US US12/291,742 patent/US7618644B2/en not_active Expired - Fee Related
- 2004-10-20 CN CN2004800395960A patent/CN1901876B/zh not_active Expired - Fee Related
- 2004-10-20 MX MXPA06004618A patent/MXPA06004618A/es active IP Right Grant
- 2004-10-20 WO PCT/EP2004/052584 patent/WO2005041905A2/en active Application Filing
- 2004-10-20 JP JP2006537279A patent/JP2007513875A/ja not_active Ceased
- 2004-10-20 EP EP20040816323 patent/EP1718271B1/en not_active Expired - Lifetime
- 2004-10-20 BR BRPI0416075-4A patent/BRPI0416075B1/pt not_active IP Right Cessation
- 2004-10-20 KR KR1020067007718A patent/KR101279899B1/ko active IP Right Grant
- 2004-10-21 US US10/970,112 patent/US7309682B2/en not_active Expired - Fee Related
- 2004-10-28 TW TW93132717A patent/TWI411456B/zh not_active IP Right Cessation
-
2007
- 2007-09-07 US US11/899,692 patent/US7429545B2/en not_active Expired - Fee Related
- 2007-09-17 US US11/901,423 patent/US7618618B2/en not_active Expired - Fee Related
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN106061941B (zh) * | 2014-03-07 | 2018-05-08 | 陶氏环球技术有限责任公司 | 硝酮化合物及其在个人护理中的使用 |
CN106458871A (zh) * | 2014-05-12 | 2017-02-22 | 陶氏环球技术有限责任公司 | 硝酮化合物和其在个人护理中的用途 |
CN106458871B (zh) * | 2014-05-12 | 2018-12-28 | 陶氏环球技术有限责任公司 | 硝酮化合物和其在个人护理中的用途 |
CN108024933A (zh) * | 2015-03-20 | 2018-05-11 | 陶氏环球技术有限责任公司 | 硝酮抑制不饱和脂肪的氧化 |
CN108024933B (zh) * | 2015-03-20 | 2021-04-13 | 陶氏环球技术有限责任公司 | 硝酮抑制不饱和脂肪的氧化 |
CN115449952A (zh) * | 2022-09-29 | 2022-12-09 | 董健 | 一种抑菌透气吸湿型纺织面料 |
Also Published As
Publication number | Publication date |
---|---|
BRPI0416075A (pt) | 2007-01-02 |
TW200528129A (en) | 2005-09-01 |
KR20060101472A (ko) | 2006-09-25 |
CN1901876B (zh) | 2013-04-10 |
WO2005041905A2 (en) | 2005-05-12 |
BRPI0416075B1 (pt) | 2015-07-07 |
EP1718271A2 (en) | 2006-11-08 |
WO2005041905A3 (en) | 2005-09-01 |
US7618618B2 (en) | 2009-11-17 |
US20050186170A1 (en) | 2005-08-25 |
TWI411456B (zh) | 2013-10-11 |
JP2007513875A (ja) | 2007-05-31 |
KR101279899B1 (ko) | 2013-06-28 |
US20080009550A1 (en) | 2008-01-10 |
US7618644B2 (en) | 2009-11-17 |
EP1718271B1 (en) | 2014-10-08 |
US7309682B2 (en) | 2007-12-18 |
US20070294837A1 (en) | 2007-12-27 |
US20090074681A1 (en) | 2009-03-19 |
MXPA06004618A (es) | 2006-06-27 |
US7429545B2 (en) | 2008-09-30 |
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