CN106029790B - 染料聚合物 - Google Patents
染料聚合物 Download PDFInfo
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- CN106029790B CN106029790B CN201580005437.7A CN201580005437A CN106029790B CN 106029790 B CN106029790 B CN 106029790B CN 201580005437 A CN201580005437 A CN 201580005437A CN 106029790 B CN106029790 B CN 106029790B
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- reactive blue
- reactive
- dye
- blue
- group
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
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- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
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- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 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
- VZPXDCIISFTYOM-UHFFFAOYSA-K trisodium;1-amino-4-[4-[[4-chloro-6-(3-sulfonatoanilino)-1,3,5-triazin-2-yl]amino]-3-sulfonatoanilino]-9,10-dioxoanthracene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(N)=C(S([O-])(=O)=O)C=C1NC(C=C1S([O-])(=O)=O)=CC=C1NC(N=1)=NC(Cl)=NC=1NC1=CC=CC(S([O-])(=O)=O)=C1 VZPXDCIISFTYOM-UHFFFAOYSA-K 0.000 description 1
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Classifications
-
- 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
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/101—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an anthracene dye
-
- 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
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/106—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an azo dye
-
- 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
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/109—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing other specific dyes
-
- 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
- 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
- C11D3/42—Brightening agents ; Blueing agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
本发明提供染料聚合物。
Description
发明领域
本发明涉及染料聚合物及所述染料聚合物在洗衣组合物中的使用。
发明背景
WO2011/047987公开了用于洗衣洗涤剂配制品中以使织物变白的共价键合至聚乙烯亚胺聚合物的活性染料。
WO2012/119859公开了包含内核聚胺(core polyamine)的染料聚合物,其中所述内核聚胺的60-100摩尔%的伯胺和仲胺被烷氧基化,且所述内核聚胺的0.1-30摩尔%的伯胺和仲胺共价键合至活性染料。
US5565145公开了不存在染料的烷氧基化的环乙亚胺聚合物;该烷氧基化的环乙亚胺聚合物作为污垢分散剂(soil dispersing agent)公开。
需要改进家用洗衣条件下共价键合至聚乙烯亚胺的活性染料至织物上的沉积。
发明概述
我们已经发现,本发明的染料聚合物表现出改进的至纺织品上的沉积。
在一个方面,本发明提供了染料聚合物,最优选蓝色或紫色染料聚合物,其包含共价键合至活性染料的聚乙烯亚胺,所述聚乙烯亚胺具有6至1000000、优选6至50000、更优选10至200、最优选15至45个胺氮原子,其中,未取代的聚乙烯亚胺的伯胺和仲胺氮原子的质子的总数的20至98摩尔%、更优选57至95摩尔%、最优选57至91摩尔%被乙醇基团替代。
在另一方面,本发明提供了洗衣组合物,其包含0.001至2.0重量%,优选0.01至0.2重量%的染料聚合物和2至70重量%的表面活性剂。
在又一方面,本发明提供了处理待洗衣物纺织品(laundry textile)的家用方法,该方法包括以下步骤:
(i)用权利要求1至10中任一项所述的染料聚合物的水溶液处理纺织品,所述水溶液包含10ppb至5000ppm、优选100ppb至2ppm的染料聚合物;和0.0克/升至6克/升、优选0.2至4克/升的表面活性剂;和,
(ii)任选地漂洗并干燥所述纺织品。
在还另一方面,本发明提供染料聚合物,其可通过使聚乙烯亚胺与环氧乙烷反应,随后与活性染料反应获得。
在还另一方面,本发明提供染料聚合物,其可通过使聚乙烯亚胺与活性染料反应,随后与环氧乙烷反应获得。
发明详述
染料
活性染料优选为蓝色或紫色。蓝色或紫色染料的沉积增强了白色织物的白度。
许多活性染料列于Colour Index(Society of Dyers and Colourists/AmericanAssociation of Textile Chemists and Colorists)中。在Industrial Dyes(由K.Hunger编辑)中论述了活性染料。
活性染料包含共价连接一个或多个活性基团的发色团。所述活性基团与聚合物的NH或OH基团、优选NH反应以使染料共价键合至染料聚合物。胺远比羟基更亲核并将优先与活性染料反应。例如,对于NH2基团,如下所示:
发色团可选自蒽醌、吩嗪、三苯并二噁嗪(triphenodioxazine)、单偶氮、双偶氮、多偶氮、甲和酞菁。
活性基团优选选自杂环活性基团;2-溴丙-2-烯酰胺基;2,3-二溴丙酰胺基;2-氯乙酰胺基;和磺基氧基乙基磺酰基活性基团(-SO2CH2CH2OSO3Na)。
2-溴丙-2-烯酰胺基活性基团具有结构:
2,3-二溴丙酰胺基活性基团具有结构:
2-氯乙酰胺基具有结构:
所述杂环活性基团优选为与卤素或铵基团键合的含氮芳环,其与聚合物的NH2或NH基团反应以形成共价键。卤素是优选的。更优选的杂环活性基团是二氯三嗪基、二氟氯嘧啶(difluorochloropyrimidine)、单氟三嗪基(monofluorotrazinyl)、单氟氯三嗪基(monofluorochlorotrazinyl)、二氯喹喔啉、二氟三嗪、单氯三嗪基和三氯嘧啶。
所述活性基团可以经由烷基间隔基团(spacer)连接到染料发色团,例如:染料-NH-CH2-CH2-活性基团。
尤其优选的杂环活性基团是:
其中,R1选自H或烷基,优选H。
X选自F或Cl。
当X=Cl时,Z1选自-Cl、-NR2R3、-OR2、-SO3Na。
当X=F时,Z1选自-NR2R3。
R2和R3独立地选自H、烷基和芳基基团。芳基基团优选为苯基并优选被-SO3Na或-SO2CH2CH2OSO3Na取代。烷基基团优选为甲基或乙基。
活性染料的优选实例为:
所述活性染料优选选自单偶氮、双偶氮和蒽醌染料,最优选蒽醌染料。
所述活性蒽醌染料包括共价连接活性基团的蒽醌染料。活性基团与聚合物的NH反应以使染料共价键合至聚合物。
优选的蒽醌染料是
其中A环被活性基团取代。优选A环被选自以下的活性基团取代:二氯三嗪基;二氟氯嘧啶;单氟三嗪基;单氟氯三嗪基;二氯喹喔啉;二氟三嗪;单氯三嗪基;三氯嘧啶;2-溴丙-2-烯酰胺基;2,3-二溴丙酰胺基;以及磺基氧基乙基磺酰基活性基团(-SO2CH2CH2OSO3Na)。
A环可进一步被优选选自烷基和SO3Na的有机基团取代。所述烷基优选C1-C8-烷基,最优选甲基。
优选的活性蒽醌染料为:活性蓝1;活性蓝2;活性蓝4;活性蓝5;活性蓝6;活性蓝12;活性蓝16;活性蓝19;活性蓝24;活性蓝27;活性蓝29;活性蓝36;活性蓝44;活性蓝46;活性蓝47;活性蓝49;活性蓝50;活性蓝53;活性蓝55;活性蓝61;活性蓝66;活性蓝68;活性蓝69;活性蓝74;活性蓝86;活性蓝93;活性蓝94;活性蓝101;活性蓝103;活性蓝114;活性蓝117;活性蓝125;活性蓝141;活性蓝142;活性蓝145;活性蓝149;活性蓝155;活性蓝164;活性蓝166;活性蓝177;活性蓝181;活性蓝185;活性蓝188;活性蓝189;活性蓝206;活性蓝208;活性蓝246;活性蓝247;活性蓝258;活性蓝261;活性蓝262;活性蓝263;活性蓝172;活性紫22;活性紫31;以及活性紫34。
根据Colour Index(Society of Dyers and Colourists/American Associationof Textile Chemists and Colortists)分类列出染料。
活性红染料
也可使活性红染料键合至聚合物,优选以1∶100至1∶4的与蒽醌活性染料的摩尔比。这为聚合物提供更为紫红色的色调。活性红染料优选单偶氮染料。
PEI聚合物
聚乙烯亚胺(PEI)通过环乙亚胺的开环聚合形成。
PEI通常是高度支化的聚胺,以分子量为43.07(作为重复单元)的经验式(C2H5N)n为特征。其在商业上通过酸催化的环乙亚胺(也称为吖丙啶)的开环制备。(后者,环乙亚胺,通过对乙醇胺的硫酸酯化制备)。
本发明的全部聚乙烯亚胺(PEI)均含有伯胺和仲胺。优选PEI中存在叔胺。
染料聚合物的氮可进一步被其它基团,例如烷基基团、或烷基硫酸酯基团、或烷基芳基基团或烷基芳基硫酸酯基团取代。
染料聚合物
未取代的聚乙烯亚胺是与活性染料反应之前或取代以得到乙醇基团之前的聚乙烯亚胺。由未取代的聚乙烯亚胺形成被乙醇基团取代的聚乙烯亚胺,该被乙醇基团取代的聚乙烯亚胺然后与活性染料反应。或者,未取代的聚乙烯亚胺与活性染料反应,其随后被乙醇基团取代。
被乙醇基团取代优选通过聚合物与环氧乙烷的反应实现,例如:
染料聚合物的实例合成示于下文:
含有29个氮原子(其中9个为伯氮原子(即NH2),13个为仲氮原子(即NH)及7个为叔氮原子)的未取代的PEI(结构1)与26摩尔当量的环氧乙烷反应得到下文的结构(结构2)。
未取代的PEI(结构1)含有(2×9)+(1×13)=31个伯氮和仲氮原子的质子。当与26摩尔当量的环氧乙烷反应时,26/31×100=83.9摩尔%的伯氮和仲氮的质子被乙醇基团替代(结构2)。
乙醇取代的PEI(结构式2)然后与1摩尔当量的染料活性蓝49反应,以产生本发明的染料聚合物(结构3)。
活性染料的活性基团优选与乙醇取代的PEI的NH基团反应。
优选地,染料聚合物含有1至30重量%的染料。在结构3中染料聚合物的分子量为3214.0,其中846.7为染料,染料聚合物上染料的重量%为846.7/3214.0×100=26.34重量%。
当聚乙烯亚胺具有10至200、最优选15至45个胺氮原子时,活性染料与聚合物的摩尔比为0.2∶1至1∶1。
具有两个活性基团的活性染料可使聚合物交联,如此其连接到两个聚合物链。优选地,活性染料仅连接到一个聚合物。
表面活性剂
洗衣组合物包含2至70重量%、最优选10至30重量%的表面活性剂。通常,表面活性剂体系的非离子和阴离子表面活性剂可选自在″Surface Active Agents″第1卷,Schwartz&Perry,Interscience 1949,第2卷,Schwartz,Perry&Berch,Interscience1958,由Manufacturing Confectioners Company出版的″McCutcheon′s Emulsifiers andDetergents″的现行版中或在″Tenside-Taschenbuch″,H.Stache,第二版,Carl HauserVerlag,1981中描述的表面活性剂。优选所使用的表面活性剂是饱和的。
可以使用的合适的非离子洗涤剂化合物特别包括具有疏水基团的化合物与活性氢原子的反应产物,例如,脂族醇、酸、酰胺或烷基酚与环氧烷,尤其是环氧乙烷(单独或与环氧乙烷一起)的反应产物。特定的非离子洗涤剂化合物是C6至C22烷基酚-环氧乙烷缩合物,其通常为5至25EO,即每分子5至25个环氧乙烷单元,以及脂族C8至C18伯或仲直链或支链醇与环氧乙烷的缩合产物,其通常为5至40EO,优选7EO至9EO。
可以使用的合适的阴离子洗涤剂化合物通常是具有含约8至22个碳原子的烷基基团的有机硫酸盐和磺酸盐的水溶性碱金属盐,使用的术语烷基包括高级酰基基团的烷基部分。合适的合成阴离子洗涤剂化合物的实例是烷基硫酸钠和烷基硫酸钾,尤其通过硫酸盐化例如由牛油或椰子油制得的C8至C18高级醇来获得的那些,烷基(C9至C20)苯磺酸钠和烷基(C9至C20)苯磺酸钾,特别是直链仲烷基(C10至C15)苯磺酸钠;以及烷基甘油基醚硫酸钠,尤其是那些源自牛油或椰子油的高级醇和源自石油的合成醇的醚。优选的阴离子洗涤剂化合物是C11至C15烷基苯磺酸钠和C12至C18烷基硫酸钠。还可应用的表面活性剂例如为描述在EP-A-328 177(Unilever)中的那些(其显示出抗盐析性),在EP-A-070074中描述的烷基多糖苷表面活性剂,以及烷基单糖苷。
优选的表面活性剂体系是阴离子与非离子洗涤剂活性材料的混合物,特别是在EP-A-346 995(Unilever)中提出的阴离子和非离子表面活性剂的组和实例。尤其优选的表面活性剂体系是C16至C18伯醇硫酸盐的碱金属盐与C12至C15伯醇3至7EO乙氧基化物的混合物。
非离子洗涤剂的存在量优选小于表面活性剂体系的50重量%、最优选小于20重量%。阴离子表面活性剂的存在量可例如为表面活性剂体系的约50%至100重量%。
在另一方面,还优选表面活性剂可为阳离子表面活性剂,使得该配制品是织物调理剂。
阳离子化合物
当本发明用作织物调理剂时,其需要含有阳离子化合物。
最优选的是季铵化合物。
当所述季铵化合物为具有至少一个C12至C22烷基链的季铵化合物时是有利的。
当所述季铵化合物具有下式时是优选的:
其中R1是C12至C22烷基或烯基链;且R2、R3和R4独立地选自C1至C4烷基链,且X-为相容阴离子(compatible anion)。该类型的优选的化合物是季铵化合物十六烷基三甲基溴化铵(cetyl trimethyl quaternary ammonium bromide)。
与本发明一起使用的材料的第二类是具有上述结构的季铵,其中R1和R2独立地选自C12至C22烷基或烯基链;R3和R4独立地选自C1至C4烷基链且X-是相容阴离子。
根据权利要求1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率为至少2∶1。
其它合适的季铵化合物公开在EP0 239 910(Procter and Gamble)中。
当阳离子与非离子表面活性剂的比率为1∶100至50∶50时是优选的,更优选为1∶50至20∶50。
阳离子化合物可以组合物总重量的1.5重量%至50重量%存在。优选阳离子化合物可以2重量%至25重量%存在,更优选的组成范围是5重量%至20重量%。
软化材料的存在量优选为总组合物的2至60重量%、更优选2至40重量%、最优选3%至30重量%。
所述组合物任选地包含聚硅氧烷。
助洗剂或络合剂
助洗剂材料可选自1)钙螯合剂材料,2)沉淀用材料,3)钙离子交换材料和4)它们的混合物。
钙螯合剂助洗剂材料的实例包括碱金属多磷酸盐,例如三聚磷酸钠和有机螯合剂,如乙二胺四乙酸。
沉淀用助洗剂材料的实例包括正磷酸钠和碳酸钠。
钙离子交换助洗剂材料的实例包括各种类型的水不溶性的结晶或无定形硅铝酸盐,其中沸石是最著名的代表,例如沸石A、沸石B(也称为沸石P)、沸石C、沸石X、沸石Y以及沸石P-型,如在EP-A-0384070中所描述的。
所述组合物还可含有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、烷基或烯基琥珀酸、次氮基三乙酸或下面提及的其它助洗剂。许多助洗剂由于其络合金属离子的能力也是漂白稳定剂(bleach-stabilising agent)。
沸石和碳酸盐(碳酸盐(包括碳酸氢盐和倍半碳酸盐)是优选的助洗剂。
所述组合物可含有结晶硅铝酸盐、优选碱金属硅铝酸盐、更优选硅铝酸钠作为助洗剂。其通常以小于15重量%的水平存在。硅铝酸盐是具有以下通式的材料:
0.8-1.5 M2O.Al2O3.0.8-6 SiO2
其中,M是一价阳离子,优选钠。这些材料含有一些结合水且需要具有至少50毫克CaO/克的钙离子交换能力。优选的硅铝酸钠在上式中含有1.5至3.5个SiO2单元。其可通过硅酸钠与铝酸钠之间的反应容易地制备,如文献中充分描述的。表面活性剂与硅铝酸盐(当存在时)的比率优选大于5∶2,更优选大于3∶1。
作为替代或除硅铝酸盐助洗剂以外,也可以使用磷酸盐助洗剂。在本领域中术语“磷酸盐”包括二磷酸盐、三磷酸盐和膦酸盐种类。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)。
优选地,洗衣洗涤剂配制品是非磷酸盐助洗的洗衣洗涤剂配制品,即,含有小于1重量%的磷酸盐。优选地,所述洗衣洗涤剂配制品是碳酸盐助洗的。
荧光剂
该组合物优选包含荧光剂(荧光增白剂)。荧光剂是公知的,并且许多此类荧光剂是市售的。通常,这些荧光剂以其碱金属盐例如钠盐的形式供应和使用。在组合物中使用的一种或多种荧光剂的总量通常为0.005至2重量%、更优选0.01至0.1重量%。优选的荧光剂种类是:二-苯乙烯基联苯化合物,例如Tinopal(商标)CBS-X,二胺茋二磺酸化合物,例如Tinopal DMS pure Xtra和Blankophor(商标)HRH,以及吡唑啉化合物,例如BlankophorSN。优选的荧光剂是:2(4-苯乙烯基-3-磺苯基)-2H-萘酚(napthol)[1,2-d]三唑钠,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}茋-2-2′-二磺酸二钠,4,4′-双{[(4-苯胺基-6-吗啉代-1,3,5-三嗪-2-基)]氨基}茋-2-2′-二磺酸二钠和4,4′-双(2-磺基苯乙烯基)联苯二钠。
优选的是在该方法中使用的水溶液有荧光剂存在。当该方法中使用的水溶液中存在荧光剂时,其优选为0.0001克/升至0.1克/升、优选0.001至0.02克/升。
香料
优选地,该组合物包含香料。香料优选为0.001至3重量%、最优选0.1至1重量%。在由CFTA Publications出版的CTFA(Cosmetic,Toiletry and Fragrance Association)1992International Buyers Guide和由Schnell Publishing Co.出版的OPD1993Chemicals Buyers Directory 80th Annual Edition中提供了香料的许多合适的实例。
在配制品中存在多种香料组分是普遍的。在本发明的组合物中设想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、或甚至七种或更多种不同的香料组分。
在香料混合物中,优选15至25重量%是头香。头香是由Poucher(Journal of theSociety of Cosmetic Chemists 6(2):80[1955])定义的。优选的头香选自柑桔油、芳樟醇、乙酸芳樟酯、薰衣草、二氢月桂烯醇、玫瑰醚和顺式-3-己醇。
香料和头香可以用于提示本发明的增白益处。
优选该洗衣处理组合物不含过氧漂白剂,例如,过碳酸钠、过硼酸钠和过酸。
聚合物
该组合物可包含一种或多种其它的聚合物。实例为羧甲基纤维素、聚(乙二醇)、聚(乙烯醇)、聚羧酸盐如聚丙烯酸酯、马来酸/丙烯酸共聚物和甲基丙烯酸月桂酯/丙烯酸共聚物。
存在时阻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)优选不存在于该配制品中。
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种或多种酶。
优选地,每种酶在本发明的洗衣组合物中的水平为0.0001重量%至0.1重量%的蛋白质。
尤其涉及的酶包括蛋白酶、α-淀粉酶、纤维素酶、脂肪酶、过氧化物酶/氧化酶、果胶酸裂解酶和甘露聚糖酶或它们的混合物。
合适的脂肪酶包括具有细菌或真菌来源的那些。包括化学改性或蛋白质工程改造的突变体。可用的脂肪酶的实例包括来自腐质霉属(同义词,嗜热真菌属)的脂肪酶,例如,来自如EP258068和EP305216中所述的绵毛状腐质菌(H.lanuginosa)(疏棉状嗜热丝孢菌(T.lanuginosus))或来自如WO96/13580中所述的特异腐质霉(H.insolens)的脂肪酶,假单胞菌属脂肪酶,例如来自假产碱杆菌(P.alcaligenes)或类产碱假单胞菌(P.pseudoalcaligenes)(EP218272)、洋葱假单胞菌(P.cepacia)(EP331376)、司徒茨氏假单胞菌(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)、威州假单胞菌(P.wisconsinensis)(WO96/12012),芽孢杆菌脂肪酶,例如来自枯草芽孢杆菌(B.subtilis)(Dartois等(1993),Biochemica etBiophysicaActa,1131,253-360)、嗜热脂肪芽孢杆菌(B.stearothermophilus)(JP 64/744992)或短小芽孢杆菌(B.pumilus)(WO 91/16422)。
其它实例是脂肪酶变体,例如描述在WO 92/05249、WO 94/01541、EP 407 225、EP260 105、WO 95/35381、WO 96/00292、WO 95/30744、WO 94/25578、WO 95/14783、WO 95/22615、WO 97/04079和WO 97/07202、WO 00/60063中的那些。
优选的市售脂肪酶包括LipolaseTM和Lipolase UltraTM,LipexTM和lipocleanTM(NovozymesA/S)。
本发明的方法可以在分类为EC 3.1.1.4和/或EC 3.1.1.32的磷脂酶的存在下进行。本文使用的术语磷脂酶是指对磷脂有活性的酶。
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;磷酸进而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,其将一个脂肪酰基水解(分别在sn-1和sn-2位置)以形成溶血磷脂;以及包括可以水解溶血磷脂中的剩余脂防酰基的溶血磷脂酶(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。
酶和调色染料(shading dye)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/或其它隔离方式来避免。
合适的蛋白酶包括具有动物、植物或微生物来源的那些。优选微生物来源。包括化学改性或蛋白质工程改造的突变体。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。优选的市售蛋白酶包括AlcalaseTM、SavinaseTM、PrimaseTM、DuralaseTM、DyrazymTM、EsperaseTM、EverlaseTM、PolarzymeTM和KannaseTM(Novozymes A/S),MaxataseTM、MaxacalTM、MaxapemTM、ProperaseTM、PurafectTM、PurafectOxPTM、FN2TM和FN3TM(Genencor International Inc.)。本发明的方法可以在分类于EC3.1.1.74.的角质酶的存在下进行。根据本发明使用的角质酶可具有任何来源。优选角质酶具有微生物来源,特别是具有细菌、真菌或酵母菌来源。
合适的淀粉酶(α和/或β)包括具有细菌或真菌来源的那些。包括化学改性或蛋白质工程改造的突变体。淀粉酶包括例如获自芽孢杆菌,例如在GB1,296,839中更为详细描述的地衣形芽孢杆菌(B.licheniformis)的特定菌株,或在WO95/026397或WO00/060060中公开的芽孢杆菌物种菌株的α-淀粉酶。市售的淀粉酶为DuramylTM、TermamylTM、TermamylUltraTM、NatalaseTM、StainzymeTM、FungamylTM和BANTM(Novozymes A/S),RapidaseTM和PurastarTM(来自Genencor International Inc.)。
合适的纤维素酶包括具有细菌或真菌来源的那些。包括化学改性或蛋白质工程改造的突变体。合适的纤维素酶包括来自芽孢杆菌属、假单胞菌属、腐质霉属、镰刀菌属、草根霉属、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中公开的由特异腐质菌、太瑞斯梭抱壳霉(Thielavia terrestris)、嗜热毁丝霉和尖孢镰刀菌制造的真菌纤维素酶。市售的纤维素酶包括CelluzymeTM、CarezymeTM、CellucleanTM、EndolaseTM、RenozymeTM(Novozymes A/S)、ClazinaseTM和Puradax HATM(Genencor International Inc.),以及KAC-500(B)TM(KaoCorporation)。
合适的过氧化酶/氧化酶包括具有植物、细菌或真菌来源的那些。包括化学改性或蛋白质工程改造的突变体。可用的过氧化酶的实例包括来自鬼伞属(Coprinus)(例如来自灰盖鬼伞菌(C.cinereus))的过氧化酶及其变体,如WO93/24618、WO95/10602和WO98/15257中描述的那些。市售的过氧化酶包括GuardzymeTM和NovozymTM 51004(Novozymes A/S)。
适用的其它酶在WO2009/087524、WO2009/090576、WO2009/107091、WO2009/111258和WO2009/148983中得到论述。
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(如乙二醇或丙三醇)、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),且所述组合物可以按例如WO92/19709和WO92/19708中所述来配制。
烷基基团足够长以形成支链或环状链时,所述烷基基团包括支链、环状和直链的烷基链。所述烷基基团优选为直链或支链的,最优选为直链的。
除非另有规定,本发明所用的不定冠词“a”或“an”和其相应的定冠词“the”是指至少一个,或一个或多个。
除非另有说明,染料重量针对钠盐或氯盐。
优选地,该洗衣处理组合物在塑料袋、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至5kg包装存在。
所述组合物优选是液体洗涤剂。可在单位剂量(unit dose)内容纳该液体洗涤剂,例如20毫升液体容纳在聚乙烯醇膜内。在液体洗涤剂内,染料聚合物具有在未经稀释的液体与织物接触时显示出对织物的低染色的另外的优点。优选地,以2克/升溶解在水中时所述组合物的pH为7至9。
家用洗涤条件包括,在温度为278至335K、优选283K至305K的水中手洗衣物,及在前装式或顶装式洗衣机中在278至368K、优选283至335K的水温下机洗。
实施例
实施例1
制备以下液体组合物。
使用该组合物在室温下在Linitest中以10∶1的液体与衣物比率洗涤白色织物的混合物:织造棉(woven cotton)、微纤维聚酯和针织尼龙氨纶(elastane)。织物具有相等面积。使用26°(法国)硬水且每次洗涤持续30分钟并然后进行漂洗。所述组合物均以1.4克/升使用。将实施例1的聚合物加入到洗涤液体(wash liquor)中以提供在洗液(wash)中10ppm的浓度。将白色衣物洗涤三次。测试的染料聚合物和结果总结于下表中。PEI被乙氧基化然后连接染料(dyed)。
活性蓝171为双偶氮染料;活性蓝269为三苯并二噁嗪染料;活性蓝49为蒽醌染料。
如通过Δb值的增加所示,对于全部染料,乙醇基团的存在增加至织物上的沉积。
Claims (14)
1.一种包含聚乙烯亚胺共价键和活性染料的染料聚合物,所述聚乙烯亚胺具有6至1000000个胺氮原子,其中,20至98摩尔%未取代的聚乙烯亚胺的一级和二级胺氮原子的质子被乙醇基团取代。
2.根据权利要求1所述的染料聚合物,其中染料聚合物是蓝色或紫色染料的聚合物。
3.根据权利要求1或2所述的染料聚合物,其中所述聚乙烯亚胺包含15至45个胺氮原子。
4.根据权利要求1或2所述的染料聚合物,其中57至80摩尔%的一级和二级胺氮原子的质子被乙醇基团取代。
5.根据权利要求1或2所述的染料聚合物,其中活性染料的活性基团选自杂环活性基团;2-溴丙-2-烯酰胺;2,3-二溴丙酰胺;2-氯乙酰胺;磺基乙氧基磺酰基活性基团;和-SO2CH2CH2OSO3Na。
6.根据权利要求1或2所述的染料聚合物,其中活性染料的发色团选自:单偶氮;双偶氮;和蒽醌。
7.根据权利要求6的染料聚合物,其中活性染料为蒽醌。
8.根据权利要求7的染料聚合物,其中活性染料为具有以下结构的蒽醌染料:
其中A环被选自以下的活性基团取代:二氯三嗪;二氟氯嘧啶;氟曲唑;氟氯曲唑;二氯喹恶啉;二氟三嗪;氯三嗪;
三氯嘧啶;2-溴丙-2-烯酰胺;2,3-二溴丙酰胺;2-氯乙酰胺;磺基乙氧基磺酰基活性基团;和-SO2CH2CH2OSO3Na。
9.根据权利要求8所述的染料聚合物,其中A环被选自C1-C8-烷基;和SO3Na的一个或多个有机基团取代。
10.根据权利要求7所述的染料聚合物,其中蒽醌染料选自:活性蓝1;活性蓝2;活性蓝4;活性蓝5;活性蓝6;活性蓝12;活性蓝16;活性蓝19;活性蓝24;活性蓝27;活性蓝29;活性蓝36;活性蓝44;活性蓝46;活性蓝47;活性蓝49;活性蓝50;活性蓝53;活性蓝55;性蓝61;活性蓝66;活性蓝68;活性蓝69;活性蓝74;活性蓝86;活性蓝93;活性蓝94;活性蓝101;活性蓝103;活性蓝114;活性蓝117;活性蓝125;活性蓝141;活性蓝142;活性蓝145;活性蓝149;活性蓝155;活性蓝164;活性蓝166;活性蓝177;活性蓝181;活性蓝185;活性蓝188;活性蓝189;活性蓝206;活性蓝208;活性蓝246;活性蓝247;活性蓝258;活性蓝261;活性蓝262;活性蓝263;活性蓝172;活性紫22;活性紫31;和活性紫34。
11.一种洗衣组合物,其包含0.001至2.0重量%的前述任一项权利要求的染料聚合物和2至70重量%的表面活性剂。
12.一种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至10的任一项的染料聚合物的水溶液处理织物,所述水溶液包含10ppb至5000ppm的染料聚合物;及0.0克/升至6克/升的表面活性剂;和
(ⅱ)任选地漂洗并干燥所述织物。
13.根据权利要求12所述的处理织物的家用方法,其中所述水溶液包含0.2至4克/升的表面活性剂。
14.根据权利要求12或13的处理织物的家用方法,其中所述水溶液包含0.0001克/升至0.1克/升的荧光增白剂。
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