CN103168097B - 包含上蓝剂和粘土污垢移除/抗再沉积剂的洗涤剂组合物 - Google Patents
包含上蓝剂和粘土污垢移除/抗再沉积剂的洗涤剂组合物 Download PDFInfo
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- CN103168097B CN103168097B CN201180051018.9A CN201180051018A CN103168097B CN 103168097 B CN103168097 B CN 103168097B CN 201180051018 A CN201180051018 A CN 201180051018A CN 103168097 B CN103168097 B CN 103168097B
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- 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
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- 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
- C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
- C09B31/02—Disazo dyes
- C09B31/06—Disazo dyes from a coupling component "C" containing a directive hydroxyl group
- C09B31/068—Naphthols
- C09B31/072—Naphthols containing acid groups, e.g. —CO2H, —SO3H, —PO3H2, —OSO3H, —OPO2H2; Salts thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
- C09B31/02—Disazo dyes
- C09B31/08—Disazo dyes from a coupling component "C" containing directive hydroxyl and amino groups
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
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Abstract
衣物洗涤剂组合物，包含：（a）去污表面活性剂；（b）上蓝剂，和（c）粘土和污垢移除/抗再沉积剂；以及（d）任选的一种或多种附加的衣物洗涤剂成分。
Description
技术领域
本发明涉及包含上蓝剂和聚合物的洗涤剂组合物。本发明的组合物在棉织物上提供良好的清洁性能。
背景技术
在纺织物基底变旧时，由于暴露于光、空气、污垢以及构成基底的纤维的天然降解，它们的颜色趋于褪色或发黄。为抵消这种不期望的效应，衣物洗涤剂制造商将调色剂掺入到他们的产品中。因此，调色剂的目的通常是在视觉上加亮这些纺织品基底，并且抵消纺织品基底的褪色和泛黄。
通常将调色剂配制到固体衣物洗涤剂组合物中，尤其是自由流动颗粒衣物洗涤剂组合物中，所述组合物包含聚合物如粘土和污垢移除/抗再沉积剂。此类聚合物虽然有助于在多种织物类型上提供良好的清洁效果，但是遗憾的是，其可能不利地影响调色剂的性能，尤其是在棉织物上。
本发明人已发现，通过使用如本发明所述的特定调色剂（本文称为上蓝剂）与特定粘土和污垢移除/抗再沉积剂的组合，可提供在棉织物上具有优异增白性能的衣物洗涤剂组合物。
发明内容
本发明提供了衣物洗涤剂组合物，所述组合物包含：
(a)去污表面活性剂；
(b)上蓝剂，其中所述上蓝剂具有以下结构：
其中：
R1和R2独立地选自：H；烷基；烷氧基；亚烷基氧基；烷基封端的亚烷基氧基；脲；和酰氨基；
R3为取代的芳基；
X为包含磺酰胺部分和任选的烷基和/或芳基部分的取代基，并且其中所述取代基包含至少一个包含至少四个亚烷基氧基部分的亚烷基氧基链；和
(c)粘土和污垢移除/抗再沉积剂，其选自：
(I)共聚物，所述共聚物包含：
(i)50至小于98重量%的结构单元，所述结构单元衍生自一种或多种包含羧基的单体；
(ii)1至小于49重量%的结构单元，所述结构单元衍生自一种或多种包含磺酸根部分的单体；和
(iii)1至49重量%的结构单元，所述结构单元衍生自一种或多种类型的单体，所述单体选自由式（I）和（II）表示的含醚键的单体：
式（I）：
其中在式（I）中，R0代表氢原子或CH3基团，R代表CH2基团、CH2CH2基团或单键，X代表数字0-5，当R为单键时X代表数字1-5，并且R1为氢原子或C1至C20有机基团；
式（II）
在式（II）中，R0表示氢原子或CH3基团，R表示CH2基团、CH2CH2基团或单键，X表示数字0-5，并且R1为氢原子或C1-C20有机基团；
(II)它们的组合；以及
(d)任选的一种或多种附加的衣物洗涤剂成分。
具体实施方式
衣物洗涤剂组合物：通常，所述组合物为全配方衣物洗涤剂组合物，而不是其一部分，如仅形成衣物洗涤剂组合物一部分的喷雾干燥颗粒或附聚颗粒。然而，本发明方法中还可使附加的漂洗添加剂组合物（例如织物调理剂或增强剂）或主要的洗涤添加剂组合物（例如漂白添加剂）与所述衣物洗涤剂组合物组合使用，这是在本发明范畴内的。然而，本发明方法中漂白添加剂组合物与所述衣物洗涤剂组合物组合使用，可能是优选的。所述组合物可为固体衣物洗涤剂组合物。
通常，所述组合物包含多个化学上不同的颗粒，如喷雾干燥的基础洗涤剂颗粒和/或附聚的基础洗涤剂颗粒和/或压制的基础洗涤剂颗粒与一个或多个、通常两个或更多个、或三个或更多个、或四个或更多个、或五个或更多个、或六个或更多个、或甚至十个或更多个颗粒的组合，所述颗粒选自：表面活性剂颗粒，包括表面活性剂附聚物、表面活性剂挤出物、表面活性剂针粒、表面活性剂条粒、表面活性剂薄片；聚合物颗粒如纤维素聚合物颗粒、聚酯颗粒、聚胺颗粒、对苯二甲酸聚合物颗粒、聚乙二醇聚合物颗粒；助洗剂颗粒，如碳酸钠和硅酸钠共助洗剂颗粒、磷酸盐颗粒、沸石颗粒、硅酸盐颗粒、碳酸盐颗粒；填料颗粒，例如硫酸盐颗粒；染料转移抑制剂颗粒；染料固定剂颗粒；漂白剂颗粒，如过碳酸盐颗粒，特别是包被的过碳酸盐颗粒，如碳酸盐、硫酸盐、硅酸盐、硼硅酸盐、过碳酸盐、或它们的任何组合包被的过碳酸盐；过硼酸盐颗粒；漂白催化剂颗粒，如过渡金属漂白催化剂颗粒、或基于过氧亚胺正离子的漂白催化剂颗粒；预生的过酸颗粒，特别是包被的预生的过酸颗粒；和漂白活性剂的共漂白颗粒；过氧化氢源和任选的漂白催化剂；漂白活性剂颗粒如氧苯磺酸钠漂白活性剂颗粒和四乙酰基乙二胺漂白活性剂颗粒；螯合剂颗粒例如螯合剂附聚物；调色染料颗粒；增白剂颗粒；酶颗粒如蛋白酶粒、脂肪酶粒、纤维素酶粒、淀粉酶粒、甘露聚糖酶粒、果胶酸裂合酶粒、木葡聚糖酶粒、漂白酶粒、角质酶粒和其中任何酶的共同造粒；粘土颗粒，例如蒙脱石颗粒或粘土和硅酮的颗粒；絮凝剂颗粒如聚环氧乙烷颗粒；蜡颗粒如蜡质附聚物；香料颗粒如香料微胶囊，特别是基于三聚氰胺甲醛的香料微胶囊，淀粉包封的香料谐香剂颗粒，和前香料颗粒如席夫碱反应产物颗粒；美化颗粒如彩色条状或针状或薄片状颗粒，和皂环（包括彩色皂环）；以及它们的任何组合。
洗涤剂成分：所述组合物通常包含洗涤剂成分。适合的洗涤剂成分包括：上蓝剂；去污表面活性剂，包括阴离子去污表面活性剂、非离子去污表面活性剂、阳离子去污表面活性剂、两性离子去污表面活性剂、两性去污表面活性剂、以及它们的任何组合；聚合物，包括羧酸盐聚合物、聚乙二醇聚合物、去垢聚酯聚合物如对苯二甲酸乙二醇酯聚合物、聚胺、纤维素聚合物、染料转移抑制剂聚合物、染料封闭聚合物如由咪唑和环氧氯丙烷缩合产生的缩合低聚物，任选的比率是1:4:1、1,6-己二胺衍生物聚合物、以及它们的任何组合；助洗剂，包括沸石、磷酸盐、柠檬酸盐、以及它们的任何组合；缓冲剂和碱度来源，包括碳酸盐和/或硅酸盐；填料，包括硫酸盐和生物填料物质；漂白剂，包括漂白活性剂、可用氧源、预生的过酸、漂白催化剂、还原漂白剂，以及它们的任何组合；螯合剂；光漂白剂；调色剂；增白剂；酶，包括蛋白酶、淀粉酶、纤维素酶、脂肪酶、木葡聚糖酶、果胶酸裂合酶、甘露聚糖酶、漂白酶、角质酶、以及它们的任何组合；织物柔软剂，包括粘土、有机硅、季铵盐织物柔软剂、以及它们的任何组合；絮凝剂如聚环氧乙烷；香料，包括淀粉包封的香料谐香剂、香料微胶囊、载有香料的沸石、酮类香料原料和多胺的席夫碱反应产物、起霜香料、以及它们的任何组合；美化剂，包括皂环、层状美化颗粒、明胶小珠、碳酸盐和/或硫酸盐斑点、有色粘土、以及它们的任何组合；以及它们的任何组合。
上蓝剂：所述组合物包含具有下列结构的上蓝剂：
其中：R1和R2独立地选自：H；烷基；烷氧基；亚烷基氧基；烷基封端的亚烷基氧基；脲；和酰氨基；R3为取代的芳基；X为包含磺酰胺部分和任选的烷基和/或芳基部分的取代基，并且其中所述取代基包含至少一个包含至少四个亚烷基氧基部分的亚烷基氧基链。
适宜的上蓝剂具有以下结构：
结构式BA1
结构式BA2
结构式BA3
结构式BA6
结构式BA10
结构式BA11
结构式BA12
结构式BA15
结构式BA19
结构式BA20
结构式BA21
结构式BA24
结构式BA28
结构式BA29
结构式BA30
结构式BA33
结构式BA37
结构式BA38
结构式BA39
结构式BA42
结构式BA46
结构式BA47
结构式BA48
结构式BA51
结构式BA55
结构式BA56
结构式BA57
结构式BA60
结构式BA64
结构式BA65
结构式BA66
结构式BA69
结构式BA73
结构式BA74
结构式BA75
结构式BA78
粘土和污垢移除/抗再沉积剂：适宜的粘土和污垢移除/抗再沉积剂为共聚物，包含：
（i）50至小于98重量%的结构单元，所述结构单元衍生自一种或多种包含羧基的单体；（ii）1至小于49重量%的结构单元，所述结构单元衍生自一种或多种包含磺酸根部分的单体；和（iii）1至49重量%的结构单元，所述结构单元衍生自一类或多类单体，所述单体选自由式（I）和（II）表示的包含醚键的单体：
式（I）：
其中在式（I）中，R0代表氢原子或CH3基团，R代表CH2基团、CH2CH2基团或单键，X代表数字0-5，当R为单键时X代表数字1-5，并且R1为氢原子或C1至C20有机基团；
式（II）
在式（II）中，R0代表氢原子或CH3基团，R代表CH2基团、CH2CH2基团或单键，X代表数字0-5，并且R1为氢原子或C1至C20有机基团。
C.I.荧光增白剂260.所述组合物可包含具有下列结构的C.I.荧光增白剂260：
其中所述C.I.荧光增白剂260或者：（i）主要为α-晶体形式；或者（ii）主要为β-晶体形式，并且具有3至30微米的重均原生粒度。主要通常是指占至少50重量%，或占至少60重量%，或至少70重量%，或至少80重量%，或至少90重量%，至100重量%，或占100重量%。
去污表面活性剂：所述组合物包含去污表面活性剂。适宜的去污表面活性剂包括阴离子去污表面活性剂、非离子去污表面活性剂、阳离子去污表面活性剂、两性离子清洁表面活性剂、两性去污表面活性剂、以及它们的任何组合。
阴离子去污表面活性剂：适宜的阴离子去污表面活性剂包括硫酸盐和磺酸盐去污表面活性剂。
适宜的磺酸盐去污表面活性剂包括烷基苯磺酸盐，如C10-13烷基苯磺酸盐。适宜的烷基苯磺酸盐（LAS）可得自或甚至得自可商购获得的直链烷基苯（LAB）的磺化；适宜的LAB包括低级2-苯基LAB，如以商品名由Sasol供应的那些，或以商品名由Petresa供应的那些，其它适宜的LAB包括高级2-苯基LAB，如以商品名由Sasol供应的那些。另一种适宜的阴离子去污表面活性剂是烷基苯磺酸盐，其通过DETAL催化方法获得，然而其它合成途径如HF也是适宜的。
适宜的硫酸盐去污表面活性剂包括烷基硫酸盐如C8-18烷基硫酸盐，或主要地为C12烷基硫酸盐。烷基硫酸盐可来源于天然来源，如椰油和/或牛油。作为另外一种选择，烷基硫酸盐可来源于合成来源，如C12-15烷基硫酸盐。
另一种适宜的硫酸盐去污表面活性剂是烷基烷氧基化硫酸盐，如烷基乙氧基化硫酸盐，或C8-18烷基烷氧基化硫酸盐，或C8-18烷基乙氧基化硫酸盐。烷基烷氧基化硫酸盐可具有0.5至20，或0.5至10的平均烷氧基化度。烷基烷氧基化硫酸盐可为C8-18烷基乙氧基化硫酸盐，其通常具有0.5至10，或0.5至7，或0.5至5，或0.5至3的平均乙氧基化度。
所述烷基硫酸盐、烷基烷氧基化硫酸盐和烷基苯磺酸盐可为直链或支化的，取代的或未取代的。
阴离子去污表面活性剂可为中链支化的阴离子去污表面活性剂，如中链支化的烷基硫酸盐和/或中链支化的烷基苯磺酸盐。中链支链通常为C1-4烷基，如甲基和/或乙基。
另一种适宜的阴离子去污表面活性剂为烷基乙氧基羧酸盐。
所述阴离子去污表面活性剂通常以它们的盐形式存在，通常与适宜的阳离子复合。适宜的抗衡离子包括Na+和K+、适宜的铵如C1-C6链烷醇铵，如单乙醇胺（MEA）、三乙醇胺（TEA）、二乙醇胺（DEA）、以及它们的任何混合物。
非离子去污表面活性剂：适宜的非离子去污表面活性剂选自：C8-C18烷基乙氧基化物，如得自Shell的非离子表面活性剂；C6-C12烷基酚烷氧基化物，其中所述烷氧基化单元任选为乙烯氧基单元、丙烯氧基单元、或它们的混合物；C12-C18醇和C6-C12烷基酚与环氧乙烷/环氧丙烷嵌段聚合物的缩合物，如得自BASF的C14-C22中链支化的醇；C14-C22中链支化的烷基烷氧基化物，通常具有1至30的平均烷氧基化度；烷基多醣，如烷基多苷；多羟基脂肪酸酰胺；醚封端的聚(烷氧基化)醇表面活性剂；以及它们的混合物。
适宜的非离子去污表面活性剂为烷基多葡糖苷和/或烷基烷氧基化醇。
适宜的非离子去污表面活性剂包括烷基烷氧基化醇，如C8-18烷基烷氧基化醇，或C8-18烷基乙氧基化醇。烷基烷氧基化醇可具有0.5至50，或1至30，或1至20，或1至10的平均烷氧基化度。烷基烷氧基化醇可为C8-18烷基乙氧基化醇，其通常具有1至10，或1至7，或1至5，或3至7的平均乙氧基化度。所述烷基烷氧基化醇可以是直链或支化的，并且是取代的或未取代的。
适宜的非离子去污表面活性剂包括具有下式的基于仲醇的去污表面活性剂：
其中R1=直链或支化的、取代或未取代的、饱和或不饱和的C2-8烷基；
其中R2=直链或支化的、取代或未取代的、饱和或不饱和的C2-8烷基，
其中R1+R2部分中存在的碳原子总数在7至13范围内；
其中EO/PO为烷氧基部分，选自乙氧基、丙氧基、或它们的混合物，所述EO/PO烷氧基部分任选为无规或嵌段构型；
其中n为平均烷氧基化度，并且在4至10范围内。
其它适宜的非离子去污表面活性剂包括EO/PO嵌段共聚物表面活性剂，如得自BASF的系列表面活性剂，和糖衍生的表面活性剂如烷基N-甲基葡萄糖酰胺。
阳离子去污表面活性剂：适宜的阳离子去污表面活性剂包括烷基吡啶化合物、烷基季铵化合物、烷基季化合物、烷基三元锍化合物、以及它们的混合物。
适宜的阳离子去污表面活性剂为具有以下通式的季铵化合物：
(R)(R1)(R2)(R3)N+X-
其中，R为直链或支化的、取代或未取代的C6-18烷基或链烯基部分，R1和R2独立地选自甲基或乙基部分，R3为羟基、羟甲基或羟乙基部分，X为提供电中性的阴离子，适宜的阴离子包括：卤离子如氯离子；硫酸根；和磺酸根。适宜的阳离子去污表面活性剂为单C6-18烷基单羟乙基二甲基氯化铵。适宜的阳离子去污表面活性剂为单C8-10烷基单羟乙基二甲基氯化铵、单C10-12烷基单羟乙基二甲基氯化铵和单C10烷基单羟乙基二甲基氯化铵。
两性离子和/或两性去污表面活性剂：适宜的两性离子和/或两性去污表面活性剂包括氧化胺如十二烷基二甲基氧化胺、链烷醇胺磺酸甜菜碱、椰油酰胺基丙基甜菜碱、基于HN+-R-CO2 -的表面活性剂，其中R可能是任何桥接基团，如烷基、烷氧基、芳基或氨基酸。
聚合物：适宜的聚合物包括羧酸盐聚合物、聚乙二醇聚合物、聚酯去垢性聚合物如对苯二甲酸聚合物、胺聚合物、纤维素聚合物、染料转移抑制剂聚合物、染料固定聚合物如通过咪唑和表氯醇任选的以1:4:1比率缩合生成的缩合低聚物、1,6-己二胺衍生物聚合物、以及它们的任何组合。
无规的接枝共聚物：适宜的无规接枝共聚物包括：（i）包含聚乙二醇的亲水性主链；和（ii）一个或多个疏水性侧链，所述侧链选自：C4-C25烷基、聚丙烯、聚丁烯、饱和C1-C6一元羧酸的乙烯基酯、丙烯酸或甲基丙烯酸的C1-C6烷基酯、以及它们的混合物。适宜的聚乙二醇聚合物具有聚乙二醇主链和无规接枝聚乙酸乙烯酯侧链。聚乙二醇主链的平均分子量可在2,000Da至20,000Da，或4,000Da至8,000Da范围内。聚乙二醇主链与聚乙酸乙烯酯侧链的分子量比率可在1:1至1:5，或1:1.2至1:2范围内。每个环氧乙烷单元的接枝位点平均数可小于1，或小于0.8，每个环氧乙烷单元的接枝位点平均数可在0.5至0.9范围内，或每个环氧乙烷单元的接枝位点平均数可在0.1至0.5，或0.2至0.4范围内。适宜的聚乙二醇聚合物为SokalanHP22。
聚酯去垢性聚合物：适宜的聚酯去垢性聚合物包括具有由下列结构（I）、（II）或（III）之一限定的聚酯去垢性聚合物：
(I)-[(OCHR1-CHR2)a-O-OC-Ar-CO-]d
(II)-[(OCHR3-CHR4)b-O-OC-sAr-CO-]e
(III)-[(OCHR5-CHR6)c-OR7]f
其中：
a、b和c为1至200；
d、e和f为1至50；
Ar为1,4-取代的亚苯基；
sAr为在5位被SO3Me取代的1,3-取代的亚苯基；
Me为H、Na、Li、K、Mg/2、Ca/2、Al/3、铵、单烷基铵、二烷基铵、三烷基铵或四烷基铵，其中所述烷基为C1-C18烷基、或C2-C10羟烷基、或它们的任何混合；
R1、R2、R3、R4、R5和R6独立地选自H或C1-C18正烷基或异烷基；并且
R7为直链或支化的C1-C18烷基，或直链或支化的C2-C30烯基，或具有5个至9个碳原子的环烷基，或C8-C30芳基，或C6-C30芳烷基。适宜的聚酯去垢性聚合物为具有上式(I)或(II)结构的对苯二甲酸酯聚合物。
适宜的聚酯去垢性聚合物包括Repel-o-tex系列聚合物如Repel-o-texSF2（Rhodia），和/或Texcare系列聚合物如TexcareSRA300（Clariant）。
取代的纤维素：适宜的取代的纤维素包括纤维素聚合物，所述纤维素聚合物具有0.01至0.99的取代度（DS）和一定的嵌段度（DB），使得DS+DB为至少1.00，或DB+2DS-DS2为至少1.20。
如本文所用，术语“纤维素”包括天然纤维素和合成纤维素。纤维素可从植物中提取或由微生物制得。
所述取代的纤维素包含基本上由葡萄糖单元组成的纤维素主链。
取代的纤维素的取代度DS为0.01至0.99。取代的纤维素的取代度和嵌段度之和DS+DB可为至少1。取代的纤维素的DB+2DS-DS2可为至少1.10。
取代的纤维素可被相同或不同的取代基取代。
本发明的组合物可包含至少0.001重量%，或甚至至少0.01重量%的取代的纤维素。具体地讲，所述组合物可包含0.03重量%至20重量%，尤其是0.1重量%至10重量%，或甚至0.3重量%至3重量%，例如1重量%至1.5重量%的取代的纤维素。
取代的纤维素包含未取代的葡萄糖单元。未取代的葡萄糖单元是它们所有的羟基保持未取代的葡萄糖单元。在取代的纤维素中，未取代葡萄糖单元与葡萄糖单元总数的重量比可介于0.01至0.99之间。
取代的纤维素包含取代的葡萄糖单元。取代的葡萄糖单元是它们羟基中有至少一个被取代的葡萄糖单元。在取代的纤维素中，取代葡萄糖单元与葡萄糖单元总数的重量比可介于0.01至0.99之间。
纤维素主链基本上是直链。应当了解，基本上是直链是指所述聚合物中至少97%，例如至少99%（按重量计）或所有的葡萄糖单元位于纤维素骨架的主链中。
纤维素具有基本上β-1,4连接的主链。应当了解，基本上β-1,4连接的主链是指所述聚合物中至少97%，例如至少99%（按重量计）或所有的葡萄糖单元由β-1,4连接键合。当存在剩余葡萄糖单元时，它们在纤维素主链中可以多种方式键合，如α-或β-以及1-2、1-3、1-4、1-6或2-3连接、以及它们的混合。
纤维素主链基本上由葡萄糖单元组成。应当了解，基本上由葡萄糖单元组成是指包含大于95重量%或97重量%，例如大于99重量%，或甚至包含100重量%的葡萄糖单元。
通过β-1,4连接与其它纤维素单体连接的纤维素单体示于下图（I）中。
图（I）
R1、R2和R3示出纤维素单体中供取代基取代的氢原子位置。
取代的纤维素在其主链上包含至少一个被取代的葡萄糖单元。适宜的取代基可选自：支链、直链或环状的、取代或未取代的、饱和或不饱和的烷基、胺（伯胺、仲胺、叔胺）、铵盐、酰胺、脲、醇、羧酸、甲苯磺酸根、磺酸根、硫酸根、硝酸根、磷酸根、硅氧烷、以及它们的混合物。
取代可发生在葡萄糖单元的任何羟基上。例如，就如图（I）中所示的通过β-1,4连接的葡萄糖单元而言，取代能够发生在葡萄糖单元的2位、3位和/或6位上。葡萄糖的羟基–OH可被–O–R或–O–C(=O)–R基团取代。
R可为阴离子、阳离子或非离子基团。R可选自：R1、N(R2)(R3)、硅氧烷部分、SO3 -、PO3 -，其中R2和R3彼此独立地为氢原子或C1-6烷基，并且R1为直链或支化（通常为直链）的饱和或不饱和（通常为饱和）的取代或未取代（通常为取代）的环状或无环（通常为无环）的脂族或芳族（通常为脂族）的C1-C300（通常为C1-C30、C1-C12、或C1-C6）烃基，其烃主链可间插杂原子，所述杂原子选自O、S、N和P。R1可被一个或多个基团取代，所述基团选自胺基（伯胺、仲胺或叔胺）、酰胺、-OH、-CO-OR4、-SO3 -、R4、-CN、和-CO-R4，其中R4代表氢原子或碱金属离子，优选钠或钾离子。
R可为下列一种其酸或盐形式的阴离子基团，优选钠（此处示出）或钾盐形式：
-T-CO2Na
-T-SO3Na
-PO3Na
-SO3Na
其中T为C1-6烷基，更优选C1-4烷基。
R取代基可为下列阳离子基团：
其中T为C1-6烷基或CH2CH(OH)CH2，A、B和C各自为C1-6烷基或羟基-C1-6烷基，X为抗衡离子如卤离子或甲苯磺酸根。
R可为下列一种非离子基团：
-A
-T-OH
-T-CN
-C(=O)A
-C(=O)NH2
-C(=O)NHA
-C(=O)N(A)B
-C(=O)OA
-(CH2CH2CH2O)nZ
-(CH2CH2O)nZ
-(CH2CH(CH3)O)nZ
-(CH2O)nZ
其中：A和B为C1-30烷基；T为C1-6烷基；n=1至100；Z为H或C1-6烷基。
R可为羟烷基、羧烷基、或磺烷基、或它们的盐。R可代表羟基C1-4烷基如5-羟甲基，羧基C1-6烷基如羧基C1-4烷基，或磺基-C2-4烷基如磺乙基，C1-C30烷酰基、或它们的盐（例如钠盐）。
在示例性实施例中，-O-R代表选自下列的基团：-O-CH2OH、-O-CH2CH2SO3H、-O-CH2-CO2H、-O-CO-CH2CH2CO2H、以及它们的盐（例如钠盐）。所述取代基优选为羧甲基。
取代基可为有益基团，适宜的有益基团包括香料、香料颗粒、酶、荧光增白剂、拒油剂、拒水剂、去垢剂、拒垢剂、染料（包括织物整新染料、调色染料）、染料中间体、染料固定剂、润滑剂、织物软化剂、光褪色抑制剂、抗皱/熨烫剂、形状保持剂、紫外线吸收剂、防晒剂、抗氧化剂、防皱剂、抗微生物剂、皮肤有益剂、抗真菌剂、驱虫剂、光漂白剂、光引发剂、感觉物质、酶抑制剂、漂白催化剂、气味中和剂、信息素、以及它们的混合物。
取代的纤维素具有0.01至0.99的DS。
如纤维质聚合物化学领域技术人员认识到的，术语“取代度”（或DS）是指纤维素主链中的纤维素单元上的平均官能团取代度。因此，由于纤维素主链的每个葡萄糖单元包含三个羟基，取代的纤维素的最大取代度为3。DS值一般不涉及沿纤维素主链的化学基团的取代一致性，并且不涉及纤维素主链的分子量。取代的纤维素的取代度可为至少0.02或0.05，具体地为至少0.10或0.20或甚至0.30。通常，纤维素主链的取代度为0.50至0.95，具体地为0.55至0.90，或0.60至0.85，或甚至0.70至0.80。
测定DS的方法可根据取代基而变化。技术人员知道或可确定如何测定指定取代的纤维素的取代度。例如，测定羧甲基纤维素DS的方法公开于下文中。
测试方法1:CMC聚合物取代度（DS）的评定
如下测定DS：在高温（650℃）下将CMC燃烧45分钟灰化以去除所有有机物质。将剩余的无机灰分溶于蒸馏水中，并且加入甲基红。用0.1M盐酸滴定样本直至溶液变成粉红色。采用下列公式，由滴定的酸量（bmL）和CMC量（Gg）计算DS。
DS=0.162*{(0.1*b/G)/[1-(0.08*0.1*(b/G)]}
作为另外一种选择，取代的纤维素的DS可由电导分析法或13CNMR测得。两种方法的实验方案在D.Capitani等人的“CarbohydratePolymers”（2000，v42，第283-286页）中给出。
嵌段度（DB）：本发明的取代的纤维素具有使得DB+DS为至少1或DB+2DS-DS2为至少1.20的DB。
纤维质聚合物化学领域技术人员认识到，术语“嵌段度”（DB）是指取代（或未取代）葡萄糖单元在纤维素主链上的簇集程度。具有较低DB的取代的纤维素的特征在于，沿着纤维素主链，具有更均匀分布的未取代葡萄糖单元。具有较高DB的取代的纤维素的特征在于，沿着纤维素主链，具有更簇集的未取代葡萄糖单元。
更具体地，在包含取代和未取代的葡萄糖单元的取代的纤维素中，取代的纤维素的DB等于B/(A+B)，其中A是指直接连接至少一个取代的葡萄糖单元的未取代的葡萄糖单元数，而B是指未直接连接取代的葡萄糖单元的未取代的葡萄糖单元数（即仅直接连接未取代的葡萄糖单元）。
通常，取代的纤维素具有至少0.35，或甚至0.40至0.90，0.45至0.80，或甚至0.50至0.70的DB。
取代的纤维素可具有至少为1的DB+DS。通常，取代的纤维素具有1.05至2.00，或1.10至1.80，或1.15至1.60，或1.20至1.50，或甚至1.25至1.40的DB+DS。
DS介于0.01至0.20之间或介于0.80至0.99之间的取代的纤维素可具有至少为1，通常为1.05至2.00，或1.10至1.80，或1.15至1.60，或1.20至1.50，或甚至1.25至1.40的DB+DS。
DS介于0.20至0.80之间的取代的纤维素可具有至少0.85，通常0.90至1.80，或1.00至1.60，或1.10至1.50，或1.20至1.40的DB+DS。
取代的纤维素可具有至少为1.20的DB+2DS-DS2。通常，取代的纤维素具有1.22至2.00，或1.24至1.90，或1.27至1.80，或1.30至1.70，或甚至1.35至1.60的DB+2DS-DS2。
DS介于0.01和0.20之间的取代的纤维素可具有1.02或1.05至1.20的DB+2DS-DS2。
DS介于0.20和0.40之间的取代的纤维素可具有1.05或1.10至1.40的DB+2DS-DS2。
DS介于0.40至1.00之间或介于0.60至1.00之间或介于0.80至1.00之间的取代的纤维素可具有1.10至2.00，或1.20至1.90，或1.25至1.80，或1.20至1.70，或甚至1.35至1.60的DB+2DS-DS2。
测定DB的方法可随取代基官能团的变化而变化。技术人员知道或可确定如何测定指定取代的纤维素的取代度。例如，测定取代的纤维素DB的方法公开于下文中。
测试方法2：取代的纤维素嵌段度（DB）的评定
就取代的纤维素而言，DB可对应于用商购内葡聚糖酶酶（EconaseCE，ABEnzymes，Darmstadt，Germany）专一性酶水解后释放出的未取代葡萄糖单元量（A）除以酸水解后释放出的未取代葡萄糖单元总量（A+B）。酶活性对聚合物链中与另一个未取代葡萄糖单元直接键合的未取代葡萄糖单元是专一性的。V.Stigsson等人的“Cellulose”（2006，13，第705-712页）详细提供了取代的纤维素的嵌段度和测量的进一步说明。
在pH4.8的缓冲液中，在50℃下使用酶（EconaseCE）进行酶促降解3天。向25mL取代的纤维素样本，使用250μL酶。通过将样品加热至90℃并使它们保持加热15分钟来停止降解。测定取代形式和嵌段度的酸水解在高氯酸中进行（室温下在70%HClO4中进行15分钟，在120℃下6.4%HClO4中进行3小时）。采用阴离子交换色谱法和脉冲安培检测来分析样本（PAD检测器：BioLC50（Dionex，Sunnyvale，California，USA））。用C13NMR校正HPAEC/PAD体系。在35℃下，采用0.2ml/min的流量，在PA-1分析柱上使用乙酸钠渐增（在30分钟内乙酸钠从0增至1M）的100mMNaOH作为洗脱液，来分离单糖。将每个样本分析三至五次，并且计算平均值。推导出与至少一个取代葡萄糖直接连接的未取代葡萄糖数（A）和不与取代葡萄糖直接连接的未取代葡萄糖数（B），并且计算取代的纤维素样本的DB：DB=B/(A+B)。
取代的纤维素的粘度：当以2重量%溶于水中时，取代的纤维素在25℃下通常具有至少100mPa.s的粘度，例如250至5000，或500至4000，1000至3000，或1500至2000mPa.s的粘度。可根据下列测试方法，测定纤维素的粘度。
测试方法3：取代的纤维素粘度的评定
通过将纤维素溶于水中，配制2重量%的纤维素溶液。使用HaakeVT500粘度计，以5s-1的剪切速率在25℃下测定溶液的粘度。每次测定进行1分钟，收集20个测量点并且取平均。
取代的纤维素的分子量：通常，本发明的纤维素具有10000至10000000，例如20000至1000000，通常50000至500000，或甚至60000至150000g/mol范围内的分子量。
取代的纤维素的聚合度（DP）：取代的纤维素可具有10至7000，或至少20的葡萄糖单元总数。可用于本发明的适宜取代的纤维素包括聚合度（DP）超过40，优选约50至约100,000，更优选约500至约50,000的纤维素。
取代的纤维素的葡萄糖单元总数为例如10至10000，或20至7500，例如50至5000，并且通常为100至3000，或150至2000。
合成：用于本发明中的取代的纤维素可由聚合物化学领域技术人员熟知的多种途径合成。例如，与羧烷基醚连接的纤维素可通过纤维素与适宜卤代链烷酸的反应制得，与羧烷基酯连接的纤维素可通过纤维素与适宜酸酐如琥珀酸酐的反应制得，而与磺烷基醚连接的纤维素可通过纤维素与适宜烯基磺酸的反应制得。
技术人员可通过例如选择反应溶剂、反应物的加入速率、以及取代的纤维素合成期间介质的碱度，获得具有较高嵌段度的取代的纤维素。可使合成方法最优化以控制DB，如V.Stigsson等人的“Cellulose”（2006，13，第705-712页）；N.Olaru等人的“MacromolecularChemistry&Physics”（2001，202，第207-211页）；J.Koetz等人的“Papier（Heidelburg）”（1998，52，第704-712页）；G.Mann等人的“Polymer”（1998，39，第3155-3165页）中所述。制备具有嵌段特征的羧甲基纤维素和羟乙基纤维素的方法还公开于WO2004/048418（Hercules）和WO06/088953（Hercules）中。
优选的取代的纤维素：取代的纤维素可选自硫酸纤维素、乙酸纤维素、磺乙基纤维素、氰乙基纤维素、甲基纤维素、乙基纤维素、羧甲基纤维素、羟乙基纤维素、和羟丙基纤维素。具体地讲，取代的纤维素为羧甲基纤维素。
适宜的取代的纤维素衍生物的非限制性例子是以下物质的钠盐或钾盐：羧甲基纤维素、羧乙基纤维素、磺乙基纤维素、磺丙基纤维素、纤维素硫酸盐、磷酸化纤维素、羧甲基羟乙基纤维素、羧甲基羟丙基纤维素、磺乙基羟乙基纤维素、磺乙基羟丙基纤维素、羧甲基甲基羟乙基纤维素、羧甲基甲基纤维素、磺乙基甲基羟乙基纤维素、磺乙基甲基纤维素、羧甲基乙基羟乙基纤维素、羧甲基乙基纤维素、磺乙基乙基羟乙基纤维素、磺乙基乙基纤维素、羧甲基甲基羟丙基纤维素、磺乙基甲基羟丙基纤维素、羧甲基十二烷基纤维素、羧甲基十二烷酰基纤维素、羧甲基氰乙基纤维素和磺乙基氰乙基纤维素。
所述纤维素可以是被2个或更多个不同取代基取代的纤维素，如甲基和羟乙基纤维素。
羧酸盐聚合物：适宜的羧酸盐聚合物包括马来酸盐/丙烯酸盐无规共聚物或聚丙烯酸盐均聚物。羧酸酯聚合物可为具有4,000Da至9,000Da，或6,000Da至9,000Da分子量的聚丙烯酸酯均聚物。其它适宜的羧酸酯聚合物为马来酸和丙烯酸的共聚物，并且可具有在4,000Da至90,000Da范围内的分子量。
胺聚合物：适宜的胺聚合物包括任选地包含聚环氧乙烷和/或聚环氧丙烷嵌段的聚乙烯亚胺聚合物，如烷氧基化聚亚烷基亚胺。
纤维素聚合物：所述组合物可包含纤维素聚合物，如选自烷基纤维素、烷基烷氧基烷基纤维素、羧烷基纤维素、烷基羧烷基纤维素、以及它们任何组合的聚合物。适宜的纤维素聚合物选自羧甲基纤维素、甲基纤维素、甲基羟乙基纤维素、甲基羧甲基纤维素、以及它们的混合物。羧甲基纤维素可具有0.5至0.9的羧甲基取代度和100,000Da至300,000Da的分子量。另一种适宜的纤维素聚合物为疏水改性的羧甲基纤维素，如FinnfixSH-1（CPKelco）。适宜的取代的纤维素聚合物为羧甲基纤维素。另一种适宜的纤维素聚合物为阳离子改性的羟乙基纤维素。
染料转移抑制剂聚合物：适宜的染料转移抑制剂（DTI）聚合物包括聚乙烯吡咯烷酮（PVP）、乙烯基吡咯烷酮和咪唑啉共聚物（PVPVI）、聚乙烯-N-氧化物（PVNO）、以及它们的任何混合物。
1,6-己二胺衍生物聚合物：适宜的聚合物包括1,6-己二胺衍生物聚合物，所述1,6-己二胺衍生物聚合物通常具有下式：
R2（CH3）N+（CH2）6N+（CH3）R2.2X-
其中X-为适宜的抗衡离子例如氯离子，并且R为具有20至30平均乙氧基化度的聚(乙二醇)链。所述聚(乙二醇)链优选可独立地被硫酸根和/或磺酸根基团封端，通常具有通过减少X-抗衡离子数目，或（在每分子平均硫酸化度大于二的情况下）引入Y+抗衡离子例如钠阳离子来平衡的电荷。
助洗剂：适宜的助洗剂包括沸石、磷酸盐、柠檬酸盐、以及它们的任何组合。
沸石助洗剂：所述组合物可基本上不含沸石助洗剂。基本上不含沸石助洗剂通常是指包含0重量%至10重量%的沸石助洗剂，或至8重量%，或至6重量%，或至4重量%，或至3重量%，或至2重量%，或甚至至1重量%的沸石助洗剂。基本上不含沸石助洗剂优选是指“无有意添加的”沸石助洗剂。典型的沸石助洗剂包括沸石A、沸石P、沸石MAP、沸石X和沸石Y。
磷酸盐助洗剂：所述组合物可基本上不含磷酸盐助洗剂。基本上不含磷酸盐助洗剂通常是指包含0重量%至10重量%的磷酸盐助洗剂，或至8重量%，或至6重量%，或至4重量%，或至3重量%，或至2重量%，或甚至至1重量%的磷酸盐助洗剂。基本上不含沸石助洗剂优选是指“无有意添加的”磷酸盐助洗剂。典型的磷酸盐助洗剂为三聚磷酸钠（STPP）。
柠檬酸盐：适宜的柠檬酸盐为柠檬酸钠。然而，也可将柠檬酸掺入到所述组合物中，其在洗涤液体中形成柠檬酸盐。
缓冲剂和碱度来源：适宜的缓冲剂和碱度来源包括碳酸盐和/或硅酸盐和/或复盐如碳酸钠矾。
碳酸盐：适宜的碳酸盐是碳酸钠和/或碳酸氢钠。所述组合物可包含碳酸氢盐。所述组合物适于包含低含量的碳酸盐，例如所述组合物适于包含0重量%至10重量%的碳酸盐，或至8重量%，或至6重量%，或至4重量%，或至3重量%，或至2重量%，或甚至至1重量%的碳酸盐。所述组合物可甚至基本上不含碳酸盐；基本上不含是指“无有意添加的”。
碳酸盐可具有100微米至500微米的重均平均粒度。作为另外一种选择，所述碳酸盐可具有10微米至25微米的重均平均粒度。
硅酸盐：所述组合物可包含0重量%至20重量%的硅酸盐，或至15重量%、或至10重量%、或至5重量%、或至4重量%、或甚至至2重量%的硅酸盐，并且可包含高于0重量%、或0.5重量%、或甚至1重量%的硅酸盐。所述硅酸盐可以是结晶的或无定形的。适宜的结晶硅酸盐包括结晶层状硅酸盐如SKS-6。其它适宜的硅酸盐包括1.6R硅酸盐和/或2.0R硅酸盐。适宜的硅酸盐为硅酸钠。另一种适宜的硅酸盐为偏硅酸钠。
填料：所述组合物可包含0重量%至70%的填料。适宜的填料包括硫酸盐和/或生物填充材料。
硫酸盐：适宜的硫酸盐是硫酸钠。硫酸盐可具有100微米至500微米的重均平均粒度，作为另外一种选择，硫酸盐可具有10微米至45微米的重均平均粒度。
生物填充材料：适宜的生物填充材料为碱和/或漂白剂处理过的农业废料。
漂白剂：所述组合物可包含漂白剂。作为另外一种选择，所述组合物可以基本上不含漂白剂；基本上不含是指“无有意添加的”。适宜的漂白剂包括漂白活性化剂、可用氧源、预生的过酸、漂白催化剂、还原漂白剂、以及它们的任何组合。如果存在，则漂白剂或其任何组分例如预生过酸可用例如脲或环糊精涂覆，如包封或包合。
漂白活化剂：适宜的漂白活性剂包括：四乙酰基乙二胺（TAED）；羟苯磺酸盐，如壬酰基羟苯磺酸盐（NOBS）、辛酰胺基壬酰基羟苯磺酸盐（NACA-OBS）、3,5,5-三甲基己酰基羟苯磺酸盐（Iso-NOBS）、十二烷基羟苯磺酸盐（LOBS）、以及它们的任何混合物；己内酰胺；五乙酰基葡萄糖（PAG）；腈季铵；酰亚胺漂白活性剂，如N-壬酰基-N-甲基乙酰胺；以及它们的任何混合物。
可用氧源：适宜的可用氧源（AvOx）是指过氧化氢源，如过碳酸盐和/或过硼酸盐，如过碳酸钠。过氧源可被涂层成分如碳酸盐、硫酸盐、硅酸盐、硼硅酸盐、或它们的任何混合物（包括它们的混合盐）至少部分涂覆，或甚至完全涂覆。适宜的过碳酸盐可由流化床方法或由结晶方法制得。适宜的过硼酸盐包括过硼酸钠一水合物（PB1）、过硼酸钠四水合物（PB4）和被称为泡沫过硼酸钠的无水过硼酸钠。其它适宜的AvOx源包括过硫酸盐如过硫酸氢钾。另一种适宜的AvOx源为过氧化氢。
预生的过酸：适宜的预生的过酸是N,N-邻苯二甲氨基己过氧酸（PAP）。
漂白催化剂：适宜的漂白催化剂包括基于过氧亚胺正离子的漂白催化剂、过渡金属漂白催化剂和漂白酶。
基于过氧亚胺正离子的漂白催化剂：适宜的基于过氧亚胺正离子的漂白催化剂具有下式：
其中：R1选自：H、包含3个至24个碳的支链烷基和包含1个至24个碳的直链烷基；R1可为包含6个至18个碳的支链烷基，或包含5个至18个碳的直链烷基，R1可选自：2-丙基庚基、2-丁基辛基、2-戊基壬基、2-己基癸基、正己基、正辛基、正癸基、正十二烷基、正十四烷基、正己基癸基、正十八烷基、异壬基、异癸基、异十三烷基和异十五烷基；R2独立地选自：H、包含3个至12个碳的支链烷基和包含1个至12个碳的直链烷基；R2任选独立地选自H和甲基；并且n为0至1的整数。
过渡金属漂白催化剂：所述组合物可包含过渡金属漂白催化剂，其通常包含铜、铁、钛、钌、钨、钼和/或锰阳离子。适宜的过渡金属漂白催化剂为基于锰的过渡金属漂白催化剂。
还原漂白剂：所述组合物可包含还原漂白剂。然而，所述组合物可以基本上不含还原漂白剂；基本上不含是指“无有意添加的”。适宜的还原漂白剂包括亚硫酸钠和/或二氧化硫脲（TDO）。
共漂白颗粒：所述组合物可包含共漂白颗粒。通常，所述助漂白剂颗粒包含漂白活性剂和过氧化物源。在助漂白剂颗粒中，相对于过氧化氢源存在大量的漂白活性剂，是高度适宜的。存在于助漂白剂颗粒状的漂白活性剂与过氧化氢源的重量比可为至少0.3:1，或至少0.6:1，或至少0.7:1，或至少0.8:1，或至少0.9:1，或至少1.0:1.0，或甚至至少1.2:1或更高。
助漂白剂颗粒可包含：(i)漂白活性剂如TAED；和(ii)过氧化氢源如过碳酸钠。所述漂白活性剂可至少部分，或甚至完全包封过氧化氢源。
助漂白剂颗粒可包含粘合剂。适宜的粘合剂为羧酸酯聚合物如聚丙烯酸酯聚合物，和/或表面活性剂，包括非离子去污表面活性剂和/或阴离子去污表面活性剂，如直链C11-C13烷基苯磺酸盐。
所述助漂白剂颗粒可包含漂白催化剂，如基于过氧亚胺正离子的漂白催化剂。
螯合剂：适宜的螯合剂选自：二亚乙基三胺五乙酸盐、二亚乙基三胺五(甲基膦酸)、乙二胺-N’N’-二琥珀酸、乙二胺四乙酸盐、乙二胺四(亚甲基膦酸)、羟乙烷二(亚甲基膦酸)、以及它们的任何组合。适宜的螯合剂为乙二胺-N’N’-二琥珀酸（EDDS）和/或羟基乙烷二膦酸（HEDP）。所述衣物洗涤剂组合物可包含乙二胺-N’N’-二琥珀酸或其盐。乙二胺-N’N’-二琥珀酸可为S,S对映体形式。所述组合物可包含4,5-二羟基间苯二磺酸二钠盐。适宜的螯合剂还可为钙晶体生长抑制剂。
碳酸钙晶体生长抑制剂：所述组合物可包含碳酸钙晶体生长抑制剂，如选自下列的一种：1-羟乙烷二膦酸（HEDP）及其盐；N,N-二羧甲基-2-氨基戊烷-1,5-二甲基及其盐；2-膦酰基丁烷-1,2,4-三甲酸及其盐；以及它们的任何组合。
光漂白剂：适宜的光漂白剂是磺化酞菁锌和/或磺化酞菁铝。
调色剂：通常配制调色剂（本文还定义为调色染料）以从洗涤液体中沉积到织物上以改善织物白色感。所述调色剂通常为蓝色或紫色。期望一种或多种调色染料具有550nm至650nm，或570nm至630nm的峰值吸收波长。所述调色剂可为染料的组合，其共同对人眼具有如同单一染料的视觉效应，其在聚酯上具有550nm至650nm，或570nm至630nm的峰值吸收波长。这可通过例如将红色和竹绿色染料混合以产生蓝色或紫色色调来提供。
染料通常为有色有机分子，其可溶于包含表面活性剂的含水介质中。染料可选自碱性染料、酸性染料、疏水性染料、直接染料和聚合物染料、以及染料缀合物类别。适宜的聚合物调色染料是可商购获得的，例如得自Milliken（Spartanburg，SouthCarolina，USA）。
适宜染料的例子为紫色DD、直接紫7、直接紫9、直接紫11、直接紫26、直接紫31、直接紫35、直接紫40、直接紫41、直接紫51、直接紫66、直接紫99、酸性紫50、酸性蓝9、酸性紫17、酸性黑1、酸性红17、酸性蓝29、溶剂紫13、分散紫27、分散紫26、分散紫28、分散紫63和分散紫77、碱性蓝16、碱性蓝65、碱性蓝66、碱性蓝67、碱性蓝71、碱性蓝159、碱性紫19、碱性紫35、碱性紫38、碱性紫48；碱性蓝3、碱性蓝75、碱性蓝95、碱性蓝122、碱性蓝124、碱性蓝141、噻唑染料、活性蓝19、活性蓝163、活性蓝182、活性蓝96、VioletCT（Milliken，Spartanburg，USA）和Azo-CM-Cellulose（Megazyme，Bray，RepublicofIreland）。其它适宜的调色剂为调色染料-光漂白剂缀合物，如磺化酞菁锌与直接紫99的缀合物。尤其适宜的调色剂为酸性红52和酸性蓝80的组合，或直接紫9和溶剂紫13的组合。
增白剂：适宜的增白剂为二苯乙烯，如增白剂15。其它适宜的增白剂为疏水性增白剂和增白剂49。所述增白剂可为微粉化颗粒形式，具有3微米至30微米，或3微米至20微米，或3微米至10微米范围内的重均粒度。所述增白剂可为α或β晶形。
酶：适宜的酶包括蛋白酶、淀粉酶、纤维素酶、脂肪酶、木葡聚糖酶、果胶酸裂合酶、甘露聚糖酶、漂白酶、角质酶、以及它们的混合物。
就酶而言，括弧中示出的登录号和ID是指数据库Genbank、EMBL和/或Swiss-Prot中的编目流水号。就任何突变而言，将标准的1-字母氨基酸编码与代表缺失的*一起使用。以DSM为前缀的登录号是指保存于DeutscheSammlungvonMikroorganismenundZellkulturenGmbH（MascheroderWeg1b，38124Brunswick（DSMZ））处的微生物体。
蛋白酶所述组合物可包含蛋白酶。适宜的蛋白酶包括金属蛋白酶和/或丝氨酸蛋白酶，包括中性或碱性微生物丝氨酸蛋白酶，如枯草杆菌蛋白酶（EC3.4.21.62）。适用的蛋白酶包括动物、植物或微生物起源的那些蛋白酶。在一个方面，此类适宜的蛋白酶可源自微生物。适宜的蛋白酶包括化学上或基因上改性的上述适宜蛋白酶的突变体。在一个方面，适宜的蛋白酶可为丝氨酸蛋白酶，如碱性微生物蛋白酶和/或胰蛋白酶型蛋白酶。适宜中性或碱性蛋白酶的例子包括：
(a)枯草杆菌蛋白酶（EC3.4.21.62），包括来源于芽孢杆菌属的那些，如迟缓芽孢杆菌、嗜碱芽孢杆菌（P27963，ELYA_BACAO）、枯草芽孢杆菌、解淀粉芽孢杆菌（P00782，SUBT_BACAM）、短小芽孢杆菌（P07518）和吉氏芽孢杆菌（DSM14391）。
(b)胰蛋白酶型或胰凝乳蛋白酶型蛋白酶，如胰蛋白酶（例如源自猪或牛的胰蛋白酶），包括来源于纤维单胞菌属（A2RQE2）的镰孢属蛋白酶和胰凝乳蛋白酶。
(c)金属蛋白酶，包括来源于解淀粉芽孢杆菌（P06832，NPRE_BACAM）的那些。
适宜的蛋白酶包括来源于吉氏芽孢杆菌或迟缓芽孢杆菌如枯草杆菌蛋白酶309（P29600）和/或DSM5483（P29599）的那些。
适宜的可商购获得的蛋白酶包括：以商品名 LiquanaseSavinase和由NovozymesA/S（Denmark）出售的那些；以商品名 PurafectPurafect 和Purafect由GenencorInternational出售的那些；以商品名和由SolvayEnzymes出售的那些；得自Henkel/Kemira的那些即BLAP（P29599，具有下列突变S99D+S101R+S103A+V104I+G159S）及其变体，包括BLAPR（BLAP，具有S3T+V4I+V199M+V205I+L217D）、BLAPX（BLAP，具有S3T+V4I+V205I）和BLAPF49（BLAP，具有S3T+V4I+A194P+V199M+V205I+L217D），均得自Henkel/Kemira；以及得自Kao的KAP（嗜碱芽孢杆菌枯草杆菌蛋白酶，具有突变A230V+S256G+S259N）。
淀粉酶：适宜的淀粉酶为α-淀粉酶，包括源自细菌或真菌的那些。包括化学或基因修饰的突变体（变体）。适宜的碱性α-淀粉酶来源于芽孢杆菌属菌株，如地衣芽孢杆菌、解淀粉芽孢杆菌、嗜热脂肪芽胞杆菌、枯草芽孢杆菌、或其它芽孢杆菌属，如芽孢杆菌属NCIB12289、NCIB12512、NCIB12513、sp707、DSM9375、DSM12368、DSMZno.12649、KSMAP1378、KSMK36或KSMK38。适宜的淀粉酶包括：
(a)来源于地衣芽孢杆菌（P06278，AMY_BACLI）的α-淀粉酶及其变体，尤其是在下列一个或多个位置具有取代基的变体：15、23、105、106、124、128、133、154、156、181、188、190、197、202、208、209、243、264、304、305、391、408和444。
(b)AA560淀粉酶（CBU30457，HD066534）及其变体，尤其是在下列一个或多个位置具有取代基的变体：26、30、33、82、37、106、118、128、133、149、150、160、178、182、186、193、203、214、231、256、257、258、269、270、272、283、295、296、298、299、303、304、305、311、314、315、318、319、339、345、361、378、383、419、421、437、441、444、445、446、447、450、461、471、482、484，任选地还包含D183*和G184*缺失的那些。
(c)表现出与来源于芽孢杆菌属SP722（CBU30453、HD066526）中野生型酶具有至少90%的同一性的变体，特别是在183和184位点发生缺失的变体。
适宜的可商购获得的α-淀粉酶为 TermamylStainzyme和（NovozymesA/S），及其变体（BioconIndiaLtd.），AT9000（BiozymGes.m.b.H，Austria），OptisizeHT 和Purastar（GenencorInternationalInc.），以及（KAO，Japan）。适宜的淀粉酶为和Stainzyme
纤维素酶：所述组合物可包含纤维素酶。适用的纤维素酶包括那些细菌或真菌起源的淀粉酶。包括化学改性的或蛋白工程化的突变体。适宜的纤维素酶包括来源于芽孢杆菌属、假单胞菌属、腐质霉属、镰孢属、草根霉菌属、枝顶孢霉属的纤维素酶，例如购自特异腐质霉、嗜热毁丝霉和尖孢镰孢菌的真菌纤维素酶。
可商购获得的纤维素酶包括和（NovozymesA/S），和PURADAX（GenencorInternationalInc.），以及（KaoCorporation）。
所述纤维素酶能包括微生物来源的内葡聚糖酶，具有内切-β-1,4-葡聚糖酶活性(E.C.3.2.1.4），包括一个芽孢杆菌属成员AA349的内源性细菌多肽以及它们的混合物。适宜的内切葡聚糖酶以商品名和（NovozymesA/S（Bagsvaerd，Denmark））出售。
所述组合物可包含属于糖基水解酶第45族的具有17kDa至30kDa分子量的清洁纤维素酶，例如以商品名NCD、DCC和DCL（ABEnzymes（Darmstadt，Germany）出售的内葡聚糖酶。
适宜的纤维素酶还可表现出木葡聚糖酶活性，如
脂肪酶。所述组合物可包含脂肪酶。适宜的脂肪酶包括细菌源或真菌源的那些。包括化学改性的或蛋白工程化的突变体。有用的脂肪酶例子包括来自腐质霉属（同义词嗜热）、例如来自柔毛腐质霉（疏绵状嗜热丝胞菌）、或来自特异腐质霉脂肪酶；假单胞菌脂肪酶，例如来自产碱假单胞菌或类产碱假单胞菌、洋葱假单胞菌、施氏假单胞菌、荧光假单胞菌、假单胞菌属株系名为SD705的菌种、威斯康辛假单胞菌；芽孢杆菌属脂肪酶，例如枯草芽孢杆菌、嗜热脂肪芽孢杆菌或短小芽孢杆菌。
所述脂肪酶可为“第一循环脂肪酶”，任选地为来源于包含T231R和N233R突变的疏绵状嗜热丝胞菌野生型脂肪酶的变体。野生型序列是Swissprot登录号为Swiss-ProtO59952（来源于疏棉状嗜热丝孢菌（柔毛腐质霉属））的269种氨基酸（氨基酸23-291）。适宜的脂肪酶将包括以商品名和由Novozymes（Bagsvaerd，Denmark）出售的那些。
所述组合物可包含与野生型氨基酸具有>90%同一性并且在T231和/或N233处，任选地在T231R和/或N233R处包含一个或多种取代基的疏棉状嗜热丝孢菌（O59952）脂肪酶的变体。
木葡聚糖酶：适宜的木葡聚糖酶对木葡聚糖和无定形纤维素底物均具有酶活性。所述酶可为选自GH第5、12、44或74家族的糖基水解酶（GH）。选自GH第44家族的糖基水解酶是尤其适宜的。来自GH第44家族的适宜糖基水解酶为来源于多粘类芽胞杆菌（ATCC832）XYG1006糖基水解酶及其变体。
果胶酸裂合酶：适宜的果胶酸裂合酶为野生型的或为来源于芽孢杆菌属果胶裂解酶（CAF05441、AAU25568）的变体，以商品名 和（购自NovozymesA/S、Bagsvaerd、Denmark）销售。
甘露聚糖酶：适宜的甘露聚糖酶以商品名（购自NovozymesA/S，Bagsvaerd，Denmark）和（GenencorInternationalInc.，PaloAlto，California）销售。
漂白酶：适宜的漂白酶包括氧化还原酶，例如氧化酶如葡萄糖、胆碱或碳水化合物氧化酶、加氧酶、过氧化氢酶、过氧化物酶如卤代、氯代、溴代、木质素、葡萄糖或锰过氧化物酶、双加氧酶或漆酶（酚氧化酶、多酚氧化酶）。适宜的商业产品以商品名和系列由Novozymes出售。使附加的有机化合物，尤其是芳族化合物，掺有漂白酶是尤其有利的；这些化合物与漂白酶相互作用，以提高氧化还原酶活性（增强剂）或通常在显著不同的氧化还原电势下有利于氧化酶与色斑之间的电子流动（调节剂）。
其它适宜的漂白酶包括过水解酶，其催化由酯底物和过氧源形成过酸。适宜的过水解酶包括耻垢分枝杆菌过水解酶变体、俗称CE-7的过水解酶变体、以及具有过水解酶活性的野生型枯草菌溶素变体。
角质酶：适宜的角质酶由E.C.Class3.1.1.73定义，任选地显示与来源于镧素对镰孢菌、门多萨假单胞菌或特异腐质霉之一的野生型具有至少90%，或95%，或最任选地至少98%的同一性。
同一性.两种氨基酸序列之间的关系由参数“同一性”描述。就本发明目的而言，两个氨基酸序列的比对通过来自EMBOSS软件包（http://emboss.org），版本2.8.0的Needle程序进行测定。Needle程序执行Needleman，S.B.和Wunsch，C.D.在（1970）J.Mol.（48，443-453）中描述的全序列对准算法。使用的取代矩阵是BLOSUM62，空位开放罚分是10，空位延伸罚分是0.5。
织物软化剂：适宜的织物软化剂包括粘土、有机硅和/或季铵化合物。适宜的粘土包括蒙脱石粘土、锂蒙脱石粘土和/或合成锂皂石粘土。适宜的粘土为蒙脱石粘土。适宜的硅氧烷包括氨基硅氧烷和/或聚二甲基硅氧烷（PDMS）。适宜的织物软化剂为包含粘土和硅氧烷的颗粒，如包含蒙脱石粘土和PDMS的颗粒。
絮凝剂：适宜的絮凝剂包括聚环氧乙烷；例如具有300,000Da至900,000Da平均分子量的聚环氧乙烷。
抑泡剂：适宜的抑泡剂包括硅氧烷和/或脂肪酸如硬脂酸。
香料：适宜的香料包括香料微胶囊、聚合物辅助释放的香料体系，包括席夫碱香料/聚合物复合物、淀粉包封的香料谐香剂、载有香料的沸石、起霜香料谐香剂、以及它们的任何组合。适宜的香料微胶囊是基于三聚氰胺甲醛的，通常包含被包含三聚氰胺甲醛的外壳包封的香料。此类香料微胶囊高度适于在外壳中包含阳离子和/或阳离子前体材料，如聚乙烯基甲酰胺（PVF）和/或阳离子改性的羟乙基纤维素（catHEC）。
美化剂：适宜的美化颗粒包括皂环、层状美化颗粒、明胶小珠、碳酸盐和/或硫酸盐斑粒、有色粘土颗粒、以及它们的任何组合。
洗涤织物的方法：洗涤织物的方法通常包括使所述组合物接触水以形成洗涤液体，并且在所述洗涤液体中洗涤织物的步骤，其中所述洗涤液体通常具有高于0℃至90℃，或至60℃，或至40℃，或至30℃，或至20℃，或至10℃，或甚至至8℃的温度。织物可在衣物洗涤剂组合物与水接触之前、或之后、或同时与水接触。所述组合物可用于预处理应用中。
通常，通过使洗涤剂与一定量的水接触来形成洗涤液体，使得洗涤液体中衣物洗涤剂组合物的浓度为0g/l以上至5g/l，或1g/l，并且至4.5g/l，或至4.0g/l，或至3.5g/l，或至3.0g/l，或至2.5g/l，或甚至至2.0g/l，或甚至至1.5g/l。
洗涤织物的方法可在顶部加载式或前加载式自动洗衣机中实施，或可用于手洗衣物洗涤应用中。在这些应用中，所形成的洗涤液体以及衣物洗涤剂组合物在所述洗涤液体中的浓度为主洗涤循环中的那些。在任何任选的一个或多个漂洗步骤期间，当确定所述洗涤液体的体积时，不包括任何加入的水。
所述洗涤液体可包含40升或更少的水，或30升或更少，或20升或更少，或10升或更少，或8升或更少，或甚至6升或更少的水。所述洗涤液体可包含0升以上至15升，或2升，并且至12升，或甚至至8升的水。
通常将每升洗涤液体0.01kg至2kg的织物加入到所述洗涤液体中。通常将每升洗涤液体0.01kg，或0.05kg，或0.07kg，或0.10kg，或0.15kg，或0.20kg，或0.25kg织物加入到所述洗涤液体中。
任选使50g或更少，或45g或更少，或40g或更少，或35g或更少，或30g或更少，或25g或更少，或20g或更少，或甚至15g或更少，或甚至10g或更少的组合物接触水以形成洗涤液体。
实例
实例1：适宜的颗粒状衣物洗涤剂组合物
实例2：上蓝剂与共聚物组合的有益效果
测试方法
织物的洗涤：在96孔板模拟洗涤体系中测试每个样本，所述体系采用磁化轴承以模拟典型全尺寸洗衣机的搅拌，使用棉织物和下列条件：1826ppm洗涤剂浓度，25℃，2.05mM（2:1Ca2+:Mg2+摩尔比）水硬度，和作为污垢应力的3000ppmArizona测试粉尘（PTI提供，PowderTechnologyInc）。将棉织物洗涤60分钟，并且在环境条件下避光干燥。就每个洗涤条件而言，每个96孔板进行八次内部平行测定，每个洗涤条件4块板共32次平行测定。
干燥时，用ImageAnalysisStation对每个96孔板点进行L*、a*和b*的测定。“L”为样本中白色或黑色量的量度；较高“L”表示较浅着色样本。样本中红色或绿色的量的测定由“a*”值确定。样本中蓝色或黄色的量的测定由“b*”值确定；较低的（更负）b*值表示样本上有更多蓝色。
通过下列转换，可由L*、a*和b*值计算CIEWI：
CIEWI=(100*((L*+16)/116)^3)+800*(0.313776034-((94.825*(((a*/500)+(((100*((L*+a*)/116)^3)/100)^0.3333))^3))/((100*((L*+a*)/116)^3)+(94.825*(((I9/500)+(((100*((L*+a*)/116)^3)/100)^0.3333))^3))+(107.381*(((((100*((L*+a*)/116)^3)/100)^0.3333)-b*/200)^3)))))+1700*((0.330900114-((100*((L*+a*)/)/116)^3)/((100*((L*+a*)/)/116)^3)+(94.825*(((I9/500)+(((100*((L*+a*)/)/116)^3)/100)^0.3333))^3))+(107.381*(((((100*((L*+a*)/)/116)^3)/100)^0.3333)-b*/200)^3))))))
衣物洗涤剂样本
制备下列衣物洗涤剂组合物以供测试：
当存在染料时，其以在洗涤溶液中提供0.05AU的染料强度的水平被掺入。所述染料为具有如本发明所述结构的上蓝剂或紫罗兰DV9染料（比较例）。所述聚合物为MW4500的聚丙烯酸酯聚合物（PA，比较例）、聚合物1（NP1，根据本发明磺化、乙氧基化、羧化）和聚合物2（NP2，根据本发明磺化、乙氧基化、羧化）。
结果
结论
DV9（对比物）与任何聚合物（PA、NP1、NP2）的组合表明增白性能无显著提高。相比之下，如本发明所述的上蓝剂与聚合物NP1或NP2（如本发明所述）的组合致使增白性能显著提高。+2CIEWI单位的差值是人眼可显著注意到的。
本文所公开的尺寸和数值不应被理解为严格限于所述确切数值。相反，除非另外指明，每个上述尺寸旨在表示所述值以及围绕该值功能上等同的范围。例如，公开为“40mm”的量纲旨在表示“约40mm”。
除非明确地不包括在内或另外限制，本文所引用的每篇文献，包括任何交叉引用的或相关的专利或专利申请，均特此以引用方式全文并入本文。任何文献的引用不是对其作为本文所公开或受权利要求书保护的任何发明的现有技术的认可，或者对其自身，或者与任何其它的参考文献的任意组合，或者参考、指导、建议或公开任何此类发明的认可。此外，当本文件中术语的任何含义或定义与以引用方式并入的文件中相同术语的任何含义或定义矛盾时，应当服从在本发明中赋予该术语的含义或定义。
Claims (10)
1.一种衣物洗涤剂组合物，包含：
(a)去污表面活性剂；
(b)上蓝剂，其中所述上蓝剂具有以下结构：
其中：
R1、R2独立地选自：H；烷基；烷氧基；亚烷基氧基；烷基封端的亚烷基氧基；脲；酰氨基；
R3为取代的芳基；
X为包含磺酰胺部分和任选的烷基和/或芳基部分的取代基，并且其中所述取代基包含至少一个亚烷基氧基链，所述亚烷基氧基链包含至少四个亚烷基氧基部分；
(c)粘土和污垢移除/抗再沉积剂，其选自共聚物，其包含：
(i)50至小于98重量％的结构单元，所述结构单元衍生自一种或多种包含羧基的单体；
(ii)1至小于49重量％的结构单元，所述结构单元衍生自一种或多种包含磺酸根部分的单体；以及
(iii)1至49重量％的结构单元，所述结构单元衍生自一种或多种类型的单体，所述单体选自由式(I)和(II)表示的含醚键的单体：
式(I)：
其中在式(I)中，R0代表氢原子或CH3基团，R代表CH2基团、CH2CH2基团或单键，X代表数字0-5，当R为单键时X代表数字1-5，并且R1为氢原子或C1至C20有机基团；
式(II)：
在式(II)中，R0表示氢原子或CH3基团，R表示CH2基团、CH2CH2基团或单键，X表示数字0-5，并且R1为氢原子或C1-C20有机基团；以及
(d)任选的一种或多种附加的衣物洗涤剂成分。
2.根据权利要求1所述的组合物，其中所述上蓝剂具有以下结构：
其中：
R1、R2独立地选自：H；烷基；烷氧基；亚烷基氧基；烷基封端的亚烷基氧基；脲；酰氨基；
U为氢、取代或未取代的氨基；
W为包含氨基部分和任选的烷基和/或芳基部分的取代基，并且其中所述取代基包含至少一个包含至少四个亚烷基氧基部分的亚烷基氧基链；
Y为氢或磺酸部分；并且
Z为磺酸部分或被芳基取代的氨基。
3.根据权利要求2所述的组合物，其中R1为烷氧基，并且R2为烷基。
4.根据权利要求1所述的组合物，其中所述组合物包含具有下列结构的C.I.荧光增白剂260：
其中所述C.I.荧光增白剂260或者：
(i)主要为α-晶体形式；或者
(ii)主要为β-晶体形式，并且具有3至30微米的重均原生粒度。
5.根据权利要求1所述的组合物，其中所述去污表面活性剂包含：
(i)烷氧基化烷基硫酸盐阴离子去污表面活性剂，所述表面活性剂具有0.5至5的平均烷氧基化度；和/或
(ii)主要为C12烷基硫酸盐阴离子去污表面活性剂。
6.根据权利要求1所述的组合物，其中所述组合物不含沸石助洗剂，并且其中所述组合物不含磷酸盐助洗剂。
7.根据权利要求1所述的组合物，其中所述组合物包含酶，所述酶选自：
(a)绵毛嗜热丝孢菌脂肪酶的变体，所述绵毛嗜热丝孢菌脂肪酶与野生型氨基酸具有>90％的同一性并且在T231和/或N233处包含一个或多个取代基；
(b)属于糖基水解酶第45族的清洁纤维素酶；
(c)内源于芽孢杆菌属DSM12649的AA560α-淀粉酶的变体，其具有：
(i)在一个或多个下列位点处的突变：9、26、149、182、186、202、257、295、299、323、339和345；和
(ii)在下列所述位点处的一个或多个取代和/或缺失：118、183、184、195、320和458；以及
(d)它们的任何组合。
8.根据权利要求1所述的组合物，其中所述组合物包含基于过氧亚胺正离子的漂白催化剂，所述漂白催化剂具有下式：
其中：R1选自：H、包含3至24个碳的支链烷基、以及包含1至24碳的直链烷基；R2独立地选自：H、包含3至12个碳的支链烷基、以及包含1至12个碳的直链烷基；并且n为0至1的整数。
9.根据权利要求1所述的组合物，其中所述组合物包含香料微胶囊。
10.根据权利要求1所述的组合物，其中所述组合物为固体形式。
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| BR (5) | BR112013009793A2 (zh) |
| CA (1) | CA2815479C (zh) |
| ES (1) | ES2699751T3 (zh) |
| MX (5) | MX357388B (zh) |
| PL (1) | PL2630229T3 (zh) |
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