CN105164211A - 烷氧基化双偶氮染料 - Google Patents
烷氧基化双偶氮染料 Download PDFInfo
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- CN105164211A CN105164211A CN201480025023.6A CN201480025023A CN105164211A CN 105164211 A CN105164211 A CN 105164211A CN 201480025023 A CN201480025023 A CN 201480025023A CN 105164211 A CN105164211 A CN 105164211A
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- alkyl
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- alkoxylated
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- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 150000001982 diacylglycerols Chemical class 0.000 description 1
- XSNQECSCDATQEL-UHFFFAOYSA-N dihydromyrcenol Chemical compound C=CC(C)CCCC(C)(C)O XSNQECSCDATQEL-UHFFFAOYSA-N 0.000 description 1
- 229930008394 dihydromyrcenol Natural products 0.000 description 1
- 239000001177 diphosphate Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- PMPJQLCPEQFEJW-UHFFFAOYSA-L disodium;2-[2-[4-[4-[2-(2-sulfonatophenyl)ethenyl]phenyl]phenyl]ethenyl]benzenesulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC=CC=C1C=CC1=CC=C(C=2C=CC(C=CC=3C(=CC=CC=3)S([O-])(=O)=O)=CC=2)C=C1 PMPJQLCPEQFEJW-UHFFFAOYSA-L 0.000 description 1
- VUJGKADZTYCLIL-YHPRVSEPSA-L disodium;5-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-[(e)-2-[4-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-sulfonatophenyl]ethenyl]benzenesulfonate Chemical compound [Na+].[Na+].C=1C=C(\C=C\C=2C(=CC(NC=3N=C(N=C(NC=4C=CC=CC=4)N=3)N3CCOCC3)=CC=2)S([O-])(=O)=O)C(S(=O)(=O)[O-])=CC=1NC(N=C(N=1)N2CCOCC2)=NC=1NC1=CC=CC=C1 VUJGKADZTYCLIL-YHPRVSEPSA-L 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000001102 lavandula vera Substances 0.000 description 1
- 235000018219 lavender Nutrition 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
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- UWKAYLJWKGQEPM-UHFFFAOYSA-N linalool acetate Natural products CC(C)=CCCC(C)(C=C)OC(C)=O UWKAYLJWKGQEPM-UHFFFAOYSA-N 0.000 description 1
- 108010003855 mesentericopeptidase Proteins 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- 108010020132 microbial serine proteinases Proteins 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
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- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- WTJKGGKOPKCXLL-RRHRGVEJSA-N phosphatidylcholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCCC=CCCCCCCCC WTJKGGKOPKCXLL-RRHRGVEJSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 229920000196 poly(lauryl methacrylate) Polymers 0.000 description 1
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- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
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- 150000003219 pyrazolines Chemical class 0.000 description 1
- 229930007790 rose oxide Natural products 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- RYMZZMVNJRMUDD-HGQWONQESA-N simvastatin Chemical compound C([C@H]1[C@@H](C)C=CC2=C[C@H](C)C[C@@H]([C@H]12)OC(=O)C(C)(C)CC)C[C@@H]1C[C@@H](O)CC(=O)O1 RYMZZMVNJRMUDD-HGQWONQESA-N 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- AXMCIYLNKNGNOT-UHFFFAOYSA-N sodium;3-[[4-[(4-dimethylazaniumylidenecyclohexa-2,5-dien-1-ylidene)-[4-[ethyl-[(3-sulfophenyl)methyl]amino]phenyl]methyl]-n-ethylanilino]methyl]benzenesulfonate Chemical compound [Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](C)C)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S(O)(=O)=O)=C1 AXMCIYLNKNGNOT-UHFFFAOYSA-N 0.000 description 1
- RBYJOOWYRXEJAM-UHFFFAOYSA-M sodium;5,9-dianilino-7-phenylbenzo[a]phenazin-7-ium-4,10-disulfonate Chemical compound [Na+].C=1C=CC=CC=1[N+]1=C2C=C(NC=3C=CC=CC=3)C(S(=O)(=O)[O-])=CC2=NC(C2=CC=CC(=C22)S([O-])(=O)=O)=C1C=C2NC1=CC=CC=C1 RBYJOOWYRXEJAM-UHFFFAOYSA-M 0.000 description 1
- PCNRQYHSJVEIGH-UHFFFAOYSA-M sodium;5-benzo[e]benzotriazol-2-yl-2-(2-phenylethenyl)benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC(N2N=C3C4=CC=CC=C4C=CC3=N2)=CC=C1C=CC1=CC=CC=C1 PCNRQYHSJVEIGH-UHFFFAOYSA-M 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000000992 solvent dye Substances 0.000 description 1
- LJFWQNJLLOFIJK-UHFFFAOYSA-N solvent violet 13 Chemical compound C1=CC(C)=CC=C1NC1=CC=C(O)C2=C1C(=O)C1=CC=CC=C1C2=O LJFWQNJLLOFIJK-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- 125000002264 triphosphate group Chemical class [H]OP(=O)(O[H])OP(=O)(O[H])OP(=O)(O[H])O* 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
- C09B33/02—Disazo dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Detergent Compositions (AREA)
- Coloring (AREA)
- Accessory Of Washing/Drying Machine, Commercial Washing/Drying Machine, Other Washing/Drying Machine (AREA)
Abstract
本发明提供包含0.0001-1.0wt%的烷氧基化双偶氮染料和2-70wt%的表面活性剂的洗衣组合物。
Description
发明领域
本发明涉及染料在洗衣组合物中的用途。
发明背景
WO2006/045375(Unilever)、WO2008/087497(P&G)、WO2012/166768(P&G)和WO2011/011799(P&G)公开了用于从家用洗衣洗涤剂产品调色(shading)织物的烷氧基化单偶氮化合物。该染料不具有直接连接到染料的芳环上的磺化基团。
WO2011/098356(Unilever)和WO2012/054835(P&G)公开了具有直接连接到染料的芳环上的磺酸根基团的烷氧基化双偶氮染料。
聚酯纤维在现代衣物中是普遍存在的。
需要在聚酯上的相对沉积高于棉的偶氮烷氧基化调色染料,以使得针对聚酯纤维。
发明概述
在一个方面,本发明提供一种洗衣组合物,其包含0.0001-1.0wt%、优选0.0005-0.2wt%的烷氧基化双偶氮染料和2-70wt%的表面活性剂,其中所述烷氧基化双偶氮染料具有以下形式:
,
其中,
仅R1和R2可以带有(bare)带电基团;
Ar1和Ar2为选自苯基和杂芳基的芳香族基团;
R1和R2各自独立地选自:H;烷基;烷基-芳基;和芳基;具有2-20个重复单元、优选2-10个重复单元的聚氧化烯链,其中所述聚氧化烯链与选自SO3 -、CO2 -、季铵、OH、-OC1-C20-烷基、-OC1-C20-烯烃、酰胺和酯中的至少一个基团共价键合;其中R1和R2中的至少一个为所述聚氧化烯链。
当带电基团共价连接到R1和/或R2时,其优选选自SO3 -和CO2 -。
在另一个方面,本发明提供一种处理织物的家用方法,该方法包括以下步骤:
(i)用所述烷氧基化双偶氮染料的水溶液处理织物,所述水溶液包含1ppb-5000ppm、更优选10ppb-10ppm、最优选100ppb-5ppm的所述烷氧基化双偶氮染料,和0.0g/L-3g/L、优选0.2-3g/L的表面活性剂;和(ii)任选地漂洗和干燥该织物。
在又一个方面,本发明提供所述烷氧基化双偶氮染料本身。
发明详述
不带电基团为在pH为7-11的水溶液中不带电的基团。在本发明的烷氧基化双偶氮染料中,仅R1和R2可以带有带电基团。该带电基团例如为羧酸根、磺酸根和季铵基团。硝基在本发明的上下文中不被认为是带电的基团。羟基在本发明的上下文中不被认为是带电的基团。
当指定芳基时,在所有情况下,优选的芳基为苯基。优选的烷基-芳基为-CH2-苯基。
当对于R1和R2指定烷基时,其优选为C1-C10-正烷基,最优选为甲基或乙基。
当对于R1和R2指定季铵时,其优选为–N+(Me)3或–N+(Et)3。
当对于R1和R2指定OC1-C20-烷基时,其优选为OC1-C10-正烷基,最优选为OMe。
当对于R1和R2指定-OC1-C20-烯烃时,其优选为OC1-C10-正烯烃。
当对于R1和R2指定酯时,其优选为-OCOCH2CH(COOH)CH2CH=CHR5,其中R5为烷基,优选R5为C3-C10直链烷基链。
当对于R1和R2指定酰胺时,其优选为-NCOCH2CH(COOH)CH2CH=CHR5,其中R5为烷基,优选R5为C3-C10直链烷基链。
优选地,Ar1和Ar2中的一个或多个被选自胺、酰胺、烷基、卤素(halide)、NO2、CN、烷基磺酰基、-O烷基和酯的一个或多个基团取代。更优选地,Ar1和Ar2中的一个或多个被选自CN、F、Cl、Br、NO2、CH3、C2H5、OCH3、OC2H5、NHCOCH3、COOCH3、COOC2H5、OCOCH3、OCOC2H5和CH3SO2的一个或多个基团取代。
优选地,所述聚氧化烯链选自氧化乙烯、氧化丙烯、氧化缩水甘油(glycidoloxide)、氧化丁烯、以及它们的混合物。最优选地,所述聚氧化烯链为氧化乙烯。
所述B环可以进一步被取代。优选地,所述B环被选自酰胺、O烷基和烷基的一个或多个基团取代。更优选地,所述B环被选自NHCOCH3、CH3和C2H5的一个或多个基团取代。
优选地,Ar1和Ar2中的至少一个为杂芳基。
优选地,Ar1和Ar2相同。
所述杂芳基的杂原子优选为N、O和S,最优选为N和S。优选地,所述杂芳基的一个或多个杂原子为五元环或六元环中的一部分。优选地,所述杂芳基为单环六元或五元杂环芳香族基团。优选地,所述杂芳基选自噻吩、噻唑、异噻唑、噻二唑和吡啶基。最优选地,所述杂芳基为噻吩。
优选的芳香族基团选自:
优选的结构为:
;
;
;
其中R3和R4为烷基,优选C3-C10直链烷基链。
所述染料的另外的例子为:
,
最优选为:
。
优选地,所述染料为蓝色或紫色。最优选地,所述染料向聚酯和65/35涤棉(polycotton)提供蓝色或紫色色光。最优选地,所述染料在65/35白色机织涤棉织物上提供240-340的色相角(hueangle)、更优选260-320的色相角。
其它染料
在本发明的一个优选实施方案中,可以存在其它调色着色剂。所述调色着色剂优选选自疏水染料,更优选为溶剂染料和分散染料例如溶剂紫13、分散紫27、分散紫28和烷氧基化噻吩染料。
疏水染料是不带电荷的,pH=8。
还更优选存在如WO2008/017570中所述的酸性吖嗪染料,所述酸性吖嗪染料的水平应为0.0001-0.1重量%。所述酸性吖嗪染料主要对纯棉衣物有益,而阳离子吩嗪染料主要对涤棉衣物有益。优选的酸性吖嗪染料为酸性紫50、酸性蓝59和酸性蓝98。如WO2009/141172和WO2009/141173中所述,也可以存在蓝色和紫色阳离子吩嗪染料。
可以存在光漂白剂,例如磺化Zn/Al酞菁。
表面活性剂
所述洗衣组合物包含2-70wt%的表面活性剂,最优选10-30wt%。通常,可以从以下文献所记述的表面活性剂中选择表面活性剂体系中的非离子和阴离子表面活性剂:“SurfaceActiveAgents”第1卷(Schwartz&Perry,Interscience1949),第2卷(Schwartz、Perry&Berch,Interscience1958);ManufacturingConfectionersCompany出版的现行版“McCutcheon'sEmulsifiersandDetergents”;或“Tenside-Taschenbuch”,H.Stache,第二版,CarlHauserVerlag,1981。优选所用表面活性剂是饱和的。
可用的适合的非离子洗涤剂化合物包括,特别是,具有疏水基和活泼氢原子的化合物(例如脂族醇、酸、酰胺或烷基酚)与氧化烯特别是氧化乙烯(单独或者与氧化丙烯一起)的反应产物。具体的非离子洗涤剂化合物有C6-C22烷基酚-氧化乙烯缩合物(通常为5-25EO,即每个分子中含有5-25个氧化乙烯单元),以及脂肪族C8-C18直链或支链的伯醇或仲醇与氧化乙烯的缩合产物(通常为5-40EO)。
可用的适合的阴离子洗涤剂化合物通常为具有包含约8-约22个碳原子的烷基的水溶性碱金属有机硫酸盐和磺酸盐,所用术语“烷基”包括高级酰基的烷基部分。适合的合成阴离子洗涤剂化合物的例子有钠和钾的烷基硫酸盐(特别是通过例如由牛油或椰子油制备的高级C8-C18醇硫酸盐化得到的那些),钠和钾的烷基C9-C20苯磺酸盐,特别是直链仲烷基C10-C15苯磺酸钠;以及钠的烷基甘油醚硫酸盐,特别是来源于牛油或椰子油的高级醇和来源于石油的合成醇的那些醚。优选的阴离子洗涤剂化合物为C11-C15烷基苯磺酸钠和C12-C18烷基硫酸钠。也可采用EP-A-328177(Unilever)中记述的那些显示耐盐析性的表面活性剂,EP-A-070074中记述的烷基多糖苷(alkylpolyglycoside)表面活性剂,以及烷基单糖苷(alkylmonoglycosides)。
优选的表面活性剂体系是阴离子和非离子洗涤剂活性材料的混合物,特别是EP-A-346995(Unilever)中指出的阴离子和非离子表面活性剂的群组和实例。特别优选的表面活性剂体系是C16-C18伯醇硫酸的碱金属盐与C12-C15伯醇3-7EO乙氧基化物的混合物。
所述非离子洗涤剂的存在量优选为小于所述表面活性剂体系的50wt%,最优选小于20wt%。阴离子表面活性剂的存在量可以例如为所述表面活性剂体系的约50wt%-100wt%。
在另一个还优选的方面,所述表面活性剂可以是阳离子型的,从而所述配方为织物调理剂。
阳离子化合物
当本发明用作织物调理剂时,其需要包含阳离子化合物。
最优选的是季铵化合物。
有利的是所述季铵化合物为具有至少一个C12-C22烷基链的季铵化合物。
优选所述季铵化合物具有以下结构式:
其中R1为C12-C22烷基或烯基链;R2、R3和R4独立地选自C1-C4烷基链,X - 为相容的阴离子。优选的此类化合物为季铵化合物:十六烷基三甲基季铵溴化物。
可用于本发明的第二类材料是这类季铵:其具有上述结构,其中R1和R2独立地选自C12-C22烷基或烯基链;R3和R4独立地选自C1-C4烷基链且X-为相容的阴离子。
根据权利要求1所述的洗涤剂组合物,其中(ii)阳离子材料与(iv)阴离子表面活性剂的比为至少2:1。
其它适合的季铵化合物在EP0239910(ProcterandGamble)中公开。
优选阳离子与非离子表面活性剂的比为1:100到50:50,更优选1:50到20:50。
所述阳离子化合物可以以所述组合物总重量的1.5wt%-50wt%存在。优选所述阳离子化合物可以以2wt%-25wt%存在,更优选组成范围为5wt%-20wt%。
软化材料的存在量优选为总组合物的2-60wt%,更优选2-40wt%,最优选3-30wt%。
所述组合物任选地包含硅酮。
助洗剂或络合剂
助洗剂材料可以选自1)钙多价螯合剂材料,2)沉淀材料,3)钙离子交换材料和4)其混合物。
钙多价螯合剂助洗剂材料的例子包括碱金属多磷酸盐如三聚磷酸钠,和有机多价螯合剂如乙二胺四乙酸。
沉淀助洗剂材料的例子包括正磷酸钠和碳酸钠。
钙离子交换助洗剂材料的例子包括各种不溶于水的晶态或非晶态铝硅酸盐,其中最著名的代表就是沸石,例如沸石A、沸石B(又称为沸石P)、沸石C、沸石X、沸石Y以及如EP-A-0,384,070中所记述的P型沸石。
所述组合物还可包含0-65%的助洗剂或络合剂,如乙二胺四乙酸、二亚乙基三胺-五乙酸、烷基或烯基丁二酸、次氮基三乙酸或下面提及的其它助洗剂。许多助洗剂由于其具有与金属离子络合的能力,所以也是漂白稳定剂。
优选的助洗剂是沸石和碳酸盐(碳酸盐(包括碳酸氢盐和倍半碳酸盐)。
所述组合物中作为助洗剂可以包含晶态铝硅酸盐,优选碱金属铝硅酸盐,更优选铝硅酸钠。其一般以小于15%w的含量存在。铝硅酸盐是指具有以下通式的材料:
0.8-1.5M2O.Al2O3.0.8-6SiO2
其中M为一价阳离子,优选钠。这些材料包含一些结合水且要求钙离子交换容量为至少50mgCaO/g。优选的铝硅酸钠在上式中包含1.5-3.5个SiO2单元。如文献中所充分记述的,它们很容易通过硅酸钠与铝酸钠之间的反应制备。表面活性剂与铝硅酸盐(当存在时)之比优选大于5:2,更优选大于3:1。
作为所述铝硅酸盐助洗剂的替代,或者除其之外,还可使用磷酸盐助洗剂。在这里,术语"磷酸盐"包括二磷酸盐、三磷酸盐和膦酸盐类。其它形式的助洗剂包括硅酸盐(如可溶性硅酸盐)、偏硅酸盐、层状硅酸盐(例如来自Hoechst的SKS-6)。
优选所述洗衣洗涤剂配方是无磷酸盐助洗(non-phosphatebuilt)的洗衣洗涤剂配方,即含有小于1wt%的磷酸盐。优选所述洗衣洗涤剂配方是碳酸盐助洗的(built)。
荧光剂
所述组合物中优选包含荧光剂(光学增白剂)。荧光剂是大家所熟知的且许多这类荧光剂可商购获得。通常,这些荧光剂以其碱金属盐例如钠盐的形式提供和使用。所述组合物中使用的一种或多种荧光剂的总量通常为0.005-2wt%,更优选0.01-0.1wt%。优选的荧光剂种类为:二苯乙烯基联苯化合物,例如Tinopal(商标)CBS-X;二胺-1,2-二苯乙烯二磺酸化合物,例如TinopalDMSpureXtra和Blankophor(商标)HRH;以及吡唑啉化合物,例如BlankophorSN。优选的荧光剂为:2-(4-苯乙烯基-3-磺基苯基)-2H-萘并[1,2-d]三唑钠盐、4,4'-双{[(4-苯胺基-6-(N-甲基-N-2羟乙基)氨基-1,3,5-三嗪-2-基)]氨基}-(1,2-二苯乙烯基)-2-2'二磺酸二钠盐、4,4'-双{[(4-苯胺基-6-吗啉基-1,3,5-三嗪-2-基)]氨基}-(1,2-二苯乙烯基)-2-2'二磺酸二钠盐和4,4'-双(2-磺基苯乙烯基)联苯二钠盐。
优选所述方法中使用的水溶液含有荧光剂。当所述方法中使用的水溶液中存在荧光剂时,荧光剂优选为0.0001g/l-0.1g/l,优选为0.001-0.02g/l。
香精
优选所述组合物包含香精。香精优选为0.001-3wt%,最优选0.1-1wt%。在CFTAPublications出版的CTFA(Cosmetic,ToiletryandFragranceAssociation)1992InternationalBuyersGuide,和SchnellPublishingCo.出版的OPD1993ChemicalsBuyersDirectory80thAnnualEdition中提供了许多适合的香精的例子。
通常在一个配方中会存在多种香精组分。在本发明的组合物中,预计将存在四种或更多种,优选五种或更多种,更优选六种或更多种,乃至七种或更多种不同的香精组分。
在香精混合物中,优选15-25wt%的是头香。头香由Poucher(JournaloftheSocietyofCosmeticChemists6(2):80[1955])定义。优选的头香选自柑橘油、芳樟醇、乙酸芳樟酯、薰衣草、二氢月桂烯醇、玫瑰醚和顺式3-已醇。
香精和头香可用于指示本发明在白度方面的益处。
优选所述洗衣处理组合物不包含过氧漂白剂,例如过碳酸钠、高硼酸钠和过酸。
聚合物
所述组合物可以包含一或多种其它的聚合物。实例有羧甲基纤维素、聚(乙二醇)、聚(乙烯醇)、聚羧酸酯如聚丙烯酸酯、马来酸/丙烯酸共聚物和甲基丙烯酸月桂酯/丙烯酸共聚物。
所述配方中优选不包含用于防止染料沉积的聚合物,例如聚(乙烯基吡咯烷酮)、聚(乙烯基吡啶-N-氧化物)和聚(乙烯基咪唑)。
酶
在本发明的组合物中和在实施本发明的方法时,优选存在一或多种酶。
优选每种酶的含量为0.0001wt%-0.1wt%蛋白质。
容易想到的酶包括蛋白酶、α-淀粉酶、纤维素酶、脂肪酶、过氧化酶/氧化酶、果胶裂解酶和甘露聚糖酶,或其混合物。
适合的脂肪酶包括来源于细菌或真菌的那些。包括化学改性或蛋白工程(proteinengineered)突变体。可用的脂肪酶的例子包括来源于腐质霉属(同义词,嗜热真菌属)的脂肪酶,例如,如EP258068和EP305216中所述来源于绵毛状腐质霉(H.lanuginosa)(疏棉状嗜热丝孢菌(T.lanuginosus))或如WO96/13580中所述来源于特异腐质霉(H.insolens)的脂肪酶;假单胞菌属脂肪酶,例如来源于产碱假单胞菌(P.alcaligenes)或类产碱假单胞菌(P.pseudoalcaligenes)(EP218272)、洋葱假单胞菌(P.cepacia)(EP331376)、斯氏假单胞菌(P.stutzeri)(GB1,372,034)、荧光假单胞菌(P.fluorescens)、假单胞菌属菌株SD705(WO95/06720和WO96/27002)、P.wisconsinensis(WO96/12012);芽孢杆菌脂肪酶,例如来源于枯草芽孢杆菌(B.subtilis)(Dartois等(1993),BiochemicaetBiophysicaActa,1131,253-360)、嗜热脂肪芽孢杆菌(B.stearothermophilus)(JP64/744992)或短小芽孢杆菌(B.pumilus)(WO91/16422)。
其它例子为脂肪酶变体,如在WO92/05249、WO94/01541、EP407225、EP260105、WO95/35381、WO96/00292、WO95/30744、WO94/25578、WO95/14783、WO95/22615、WO97/04079、WO97/07202和WO00/60063中记述的那些。
优选的可商购获得的脂肪酶包括Lipolase?、LipolaseUltra?和Lipex?(NovozymesA/S)。
本发明的方法可以在分类号为EC3.1.1.4和/或EC3.1.1.32的磷脂酶的存在下进行。在这里所用的术语磷脂酶指的是对磷脂具有活性的酶。
磷脂,如卵磷脂或磷脂酰胆碱,由在外(sn-1)和中(sn-2)位置用两个脂肪酸酯化且在第三位置用磷酸酯化的丙三醇构成;其中所述磷酸接着可以被酯化成氨基醇。磷脂酶是参与磷脂水解的酶。可以区分几种类型的磷脂酶活性,包括磷脂酶A1和A2,其将一个脂酰基水解(分别在sn-1和sn-2位置)以形成溶血磷脂;还包括可以水解溶血磷脂中的剩余脂酰基的溶血磷脂酶(或磷脂酶B)。磷脂酶C和磷脂酶D(磷酸二酯酶)分别释放二酰基丙三醇或磷脂酸。
所述酶和调色染料可以显示某种相互作用,且应当加以选择以使该相互作用不是负面的。某些负面的相互作用可通过在产品中将酶或调色染料中的任意一个包封(encapsulation)和/或用其它隔离方式来避免。
适合的蛋白酶包括来源于动物、植物或微生物的那些。优选微生物源。包括化学改性或蛋白工程突变体。所述蛋白酶可以为丝氨酸蛋白酶或金属蛋白酶,优选为碱性微生物蛋白酶或类胰蛋白酶。优选的可商购获得的蛋白酶包括Alcalase?、Savinase?、Primase?、Duralase?、Dyrazym?、Esperase?、Everlase?、Polarzyme?和Kannase?(NovozymesA/S),Maxatase?、Maxacal?、Maxapem?、Properase?、Purafect?、PurafectOxP?、FN2?和FN3?(GenencorInternationalInc.)。
本发明的方法可以在分类号为EC3.1.1.74的角质酶的存在下进行。用于本发明的角质酶可以是任何来源的。优选角质酶是来源于微生物,特别是来源于细菌、真菌或酵母菌。
适合的淀粉酶(α和/或β)包括来源于细菌或真菌的那些。包括化学改性或蛋白工程突变体。淀粉酶例如包括从芽孢杆菌,例如在GB1,296,839中更详细描述的地衣芽孢杆菌(B.licheniformis)的特定菌株,或在WO95/026397或WO00/060060中公开的芽孢杆菌属菌株获得的α-淀粉酶。可商购获得的淀粉酶有Duramyl?、Termamyl?、TermamylUltra?、Natalase?、Stainzyme?、Fungamyl?和BAN?(NovozymesA/S),Rapidase?和Purastar?(来自GenencorInternationalInc.)。
适合的纤维素酶包括来源于细菌或真菌的那些。包括化学改性或蛋白工程突变体。适合的纤维素酶包括来源于芽孢杆菌属、假单胞菌属、腐质霉属、镰刀菌属、梭孢壳属、枝顶孢属的纤维素酶,例如US4,435,307、US5,648,263、US5,691,178、US5,776,757、WO89/09259、WO96/029397和WO98/012307中公开的由由特异腐质霉(Humicolainsolens)、太瑞斯梭孢壳霉(Thielaviaterrestris)、嗜热毁丝霉(Myceliophthorathermophila)和尖孢镰刀菌(Fusariumoxysporum)生产的真菌纤维素酶。可商购获得的纤维素酶包括Celluzyme?、Carezyme?、Endolase?、Renozyme?(NovozymesA/S)、Clazinase?和PuradaxHA?(GenencorInternationalInc.),以及KAC-500(B)?(KaoCorporation)。
适合的过氧化酶/氧化酶包括来源于植物、细菌或真菌的那些。包括化学改性或蛋白工程突变体。可用的过氧化酶的例子包括来源于鬼伞属(Coprinus)(例如来源于灰盖鬼伞(C.cinereus))的过氧化酶及其变体,如WO93/24618、WO95/10602和WO98/15257中记述的那些。可商购获得的过氧化酶包括Guardzyme?和Novozym?51004(NovozymesA/S)。
适用的其它酶在WO2009/087524、WO2009/090576、WO2009/107091、WO2009/111258和WO2009/148983中论述。
酶稳定剂
存在于所述组合物中的任何酶都可以使用常规的稳定剂来稳定,例如,多元醇(如丙二醇或丙三醇),糖或糖醇,乳酸,硼酸或硼酸衍生物(例如芳族硼酸酯,或苯基硼酸衍生物如4-甲酰基苯基硼酸),且所述组合物可以如例如WO92/19709和WO92/19708中所述来配制。
烷基足够长以形成支链或环状链时,所述烷基包含支链、环状和直链的烷基链。所述烷基优选为直链或支链的,最优选为直链的。
除非另外指出,在本文中所用的不定冠词“一(a或an)”及其相应的定冠词“该(the)”是指至少一个,或者是指一或多个。
除非另有说明,染料重量针对钠盐或氯化物盐。
优选所述洗衣处理组合物装在塑料袋、塑料盒或纸板盒中。
为便于使用,优选所述洗衣处理组合物以0.5-5kg的包装呈现。
实验
使用以下染料:
实施例1
将0.01wt%的染料溶于以下配方的液体洗涤剂中。
成分 | wt% |
丙二醇 | 15 |
NaOH | 至pH=6.5 |
三乙胺 | 2 |
醇乙氧基化物(具有7摩尔乙氧基单元(ethoxylate)(EO)的C12-C15伯醇) | 7.3 |
月桂基醚硫酸钠(3EO) | 2.4 |
直链烷基苯磺酸 | 4.9 |
氢化拔顶棕榈仁脂肪酸 | 0.9 |
碳代甜菜碱(carbobetaine) | 0.9 |
Proxel (防腐剂) | 0.02 |
香精 | 1.4 |
软化水 | 余量 |
在Tergotomete锅中将该配方以4g/L的剂量加入13oFH水中,并将10×10cm的机织棉、针织棉、65/35涤棉、聚酯超细纤维和80/20尼龙-氨纶加入水中,使得液体与布料的比例为100:1。将洗涤液在室温下以200rpm搅拌1小时,将该布料在13oFH水中漂洗,并干燥。然后使用反射计测量该布料的颜色,并表示为CIEL*a*b*。
将相对于不含染料洗涤的对照品的颜色变化表示为?b值:?b=b(对照)–b(染料)。
计算相对于涤棉织物的在织物上的相对沉积。将机织棉和针织棉的值取平均值而得到棉的单一值。
在下表中给出结果。
棉 | 涤棉 | 聚酯 | 尼龙-氨纶 | |
参比染料1 | 98 | 100 | 63 | 264 |
本发明染料 | 12 | 100 | 86 | 160 |
BA1在聚酯和涤棉上的相对沉积高于棉。另外的优点是表现出在尼龙-氨纶上较低的相对沉积,从而防止该织物的过度发蓝。
Claims (19)
1.洗衣组合物,其包含0.0001-1.0wt%的烷氧基化双偶氮染料和2-70wt%的表面活性剂,其中所述烷氧基化双偶氮染料具有以下形式:
,
其中:
仅R1和R2可以带有带电基团;
Ar1和Ar2为选自苯基和杂芳基的芳香族基团;
R1和R2独立地选自:H;烷基;烷基-芳基;和芳基;具有2-20个重复单元的聚氧化烯链,其中所述聚氧化烯链与选自SO3 -、CO2 -、季铵、OH、-OC1-C20-烷基、-OC1-C20-烯烃、酰胺和酯的至少一个基团共价键合,其中R1和R2中的至少一个为所述聚氧化烯链。
2.根据权利要求1所述的洗衣组合物,其中Ar1和Ar2中的一个或多个被选自胺、酰胺、烷基、卤素、NO2、CN、烷基磺酰基、-O烷基和酯的一个或多个基团取代。
3.根据权利要求2所述的洗衣组合物,其中Ar1和Ar2中的一个或多个被选自CN、F、Cl、Br、NO2、CH3、C2H5、OCH3、OC2H5、NHCOCH3、COOCH3、COOC2H5、OCOCH3、OCOC2H5和CH3SO2的一个或多个基团取代。
4.根据前述权利要求中任一项所述的洗衣组合物,其中所述聚氧化烯链选自氧化乙烯、氧化丙烯、氧化缩水甘油、氧化丁烯、以及它们的混合物。
5.根据前述权利要求中任一项所述的洗衣组合物,其中所述B环被选自酰胺、O烷基和烷基的一个或多个基团取代。
6.根据权利要求5所述的洗衣组合物,其中所述B环被选自NHCOCH3、CH3和C2H5的一个或多个基团取代。
7.根据前述权利要求中任一项所述的洗衣组合物,其中所述聚氧化烯链具有2-10个重复单元。
8.根据前述权利要求中任一项所述的洗衣组合物,其中Ar1和Ar2中的至少一个为杂芳基。
9.根据前述权利要求中任一项所述的洗衣组合物,其中Ar1和Ar2相同。
10.根据前述权利要求中任一项所述的洗衣组合物,其中所述杂芳基选自噻吩、噻唑、异噻唑、噻二唑和吡啶基。
11.根据前述权利要求中任一项所述的洗衣组合物,其中所述芳香族基团选自:
。
12.根据前述权利要求中任一项所述的洗衣组合物,其中所述烷氧基化双偶氮染料选自:
、
和
,
其中R3和R4为烷基。
13.根据权利要求12所述的洗衣组合物,其中R3和R4为C3-C10直链烷基链。
14.根据权利要求12或13所述的洗衣组合物,其中Ar1和Ar2为:
。
15.前述权利要求中任一项所述的烷氧基化双偶氮染料。
16.权利要求12-14中任一项所述的烷氧基化双偶氮染料。
17.处理织物的家用方法,所述方法包括以下步骤:
(i)用权利要求1-14中任一项所述的烷氧基化双偶氮染料的水溶液处理织物,所述水溶液包含1ppb-5000ppm的所述烷氧基化双偶氮染料和0.0g/L-3g/L的表面活性剂;和
(ii)任选地漂洗和干燥所述织物。
18.根据权利要求17所述的处理织物的家用方法,其中所述水溶液包含0.2-3g/L的表面活性剂。
19.根据权利要求17或18所述的处理织物的家用方法,其中所述水溶液包含0.0001g/l-0.1g/l的荧光剂。
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EP13166374 | 2013-05-03 | ||
EP13166374.2 | 2013-05-03 | ||
PCT/EP2014/057420 WO2014177369A1 (en) | 2013-05-03 | 2014-04-11 | Alkoxylated bis azo dyes |
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AR (1) | AR096154A1 (zh) |
BR (1) | BR112015026098A2 (zh) |
CL (1) | CL2015003203A1 (zh) |
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US9745544B2 (en) | 2015-10-13 | 2017-08-29 | The Procter & Gamble Company | Whitening agents for cellulosic substrates |
US10597614B2 (en) | 2015-10-13 | 2020-03-24 | The Procter & Gamble Company | Whitening agents for cellulosic substrates |
US9902923B2 (en) | 2015-10-13 | 2018-02-27 | The Procter & Gamble Company | Polyglycerol dye whitening agents for cellulosic substrates |
CN109403095A (zh) * | 2018-09-29 | 2019-03-01 | 濮阳宏业环保新材料股份有限公司 | 一种聚酯纤维材质衣物家用洗涤、染色剂及其应用 |
US12031113B2 (en) | 2020-03-02 | 2024-07-09 | Milliken & Company | Composition comprising hueing agent |
US11718814B2 (en) | 2020-03-02 | 2023-08-08 | Milliken & Company | Composition comprising hueing agent |
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WO2010151906A2 (en) * | 2010-10-22 | 2010-12-29 | Milliken & Company | Bis-azo colorants for use as bluing agents |
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CA2817718C (en) | 2010-11-12 | 2016-02-09 | The Procter & Gamble Company | Laundry care compositions comprising charged thiophene azo dyes |
CN103582696B (zh) | 2011-06-03 | 2015-11-25 | 宝洁公司 | 包含染料的衣物洗涤护理组合物 |
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2014
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- 2014-04-11 EP EP14717138.3A patent/EP2992054B1/en not_active Revoked
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- 2014-04-11 BR BR112015026098A patent/BR112015026098A2/pt not_active Application Discontinuation
- 2014-04-11 CN CN201480025023.6A patent/CN105164211B/zh active Active
- 2014-04-30 AR ARP140101785A patent/AR096154A1/es active IP Right Grant
-
2015
- 2015-10-28 ZA ZA2015/08009A patent/ZA201508009B/en unknown
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Patent Citations (4)
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GB1393393A (en) * | 1971-06-18 | 1975-05-07 | Colgate Palmolive Co | Coloured detergent compositions |
WO1999024659A1 (en) * | 1997-11-07 | 1999-05-20 | Milliken Research Corporation | Polyoxyalkylenated disazo colored thermoplastic resins |
CN101583704A (zh) * | 2007-01-19 | 2009-11-18 | 宝洁公司 | 包含用于纤维质基底的增白剂的衣物洗涤护理组合物 |
WO2010151906A2 (en) * | 2010-10-22 | 2010-12-29 | Milliken & Company | Bis-azo colorants for use as bluing agents |
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CN112543801A (zh) * | 2018-07-27 | 2021-03-23 | 荷兰联合利华有限公司 | 洗衣洗涤剂 |
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BR112015026098A2 (pt) | 2017-07-25 |
EP2992054A1 (en) | 2016-03-09 |
ES2620122T3 (es) | 2017-06-27 |
WO2014177369A1 (en) | 2014-11-06 |
EP2992054B1 (en) | 2017-01-04 |
AR096154A1 (es) | 2015-12-09 |
CN105164211B (zh) | 2017-05-24 |
ZA201508009B (en) | 2017-01-25 |
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