CN107075412B - 增白组合物 - Google Patents
增白组合物 Download PDFInfo
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- CN107075412B CN107075412B CN201580049509.8A CN201580049509A CN107075412B CN 107075412 B CN107075412 B CN 107075412B CN 201580049509 A CN201580049509 A CN 201580049509A CN 107075412 B CN107075412 B CN 107075412B
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- detergent composition
- laundry detergent
- composition according
- negatively charged
- acetate
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Classifications
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- 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
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/37—Mixtures of compounds all of which are anionic
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3707—Polyethers, e.g. polyalkyleneoxides
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/06—Ether- or thioether carboxylic acids
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- C11D1/02—Anionic compounds
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- C11D1/146—Sulfuric acid esters
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Abstract
本发明提供了一种家用洗衣增白和增亮组合物，其包含带电荷的表面活性剂、带负电荷的烷氧基化多芳基苯酚和香料。
Description
技术领域
本发明涉及增白和增亮洗衣组合物的使用。
背景技术
在家用洗衣期间保持和改善纺织品的白度和亮度是期望的。问题是从一件衣服上去除的污垢再沉积到另一件衣服上。衣服上和洗涤中人油(皮脂)的存在，其用于增强洗涤中污垢的沉积，加剧了该问题。这个过程导致整个洗涤负荷中白度和清洁的整体损失。为了改善这个问题，分散聚合物如烷氧基化聚乙烯亚胺已广泛加入到洗涤剂中。乙氧基化PEI(PEI＝聚乙烯亚胺)被称为来自CA 121 0009的抗再沉积聚合物。某些纤维素酶也已用于通过改变棉织物的表面性质而防止再沉积。诺维信在WO02/099091和WO04/053039中描述了用于家用洗衣的纤维素酶。
EP1321510(Shipley)描述了一种含有烷氧基化多芳基苯酚的工业清洁组合物，其用于从用于制造半导体和其他电子设备和电路的光致抗蚀剂中剥离有机化学残留物。有机化学残留物是生产过程剩下的材料，且包括光引发剂、热引发剂、丙烯酸和甲基丙烯酸单体。
发明内容
需要进一步的技术以减少家用洗衣产品中的再沉积并增强清洁。
我们已经发现，带负电荷的烷氧基化多芳基苯酚在家用洗衣期间增强衣服的白度和亮度。
一方面，本发明提供了一种洗衣洗涤剂组合物，其包含：
(i)带电的表面活性剂，优选带电荷的表面活性剂的含量为4至50wt％，更优选6至30wt％，最优选8至20wt％；
(ii)带负电荷的烷氧基化多芳基苯酚，优选含量为0.1至20wt％，更优选0.5至10wt％，最优选2至9wt％；和
(iii)香料，优选0.05至0.5wt％香料。
另一方面，本发明提供了一种洗衣洗涤剂组合物，其包含：
(i)4至50wt％，更优选6至30wt％，最优选8至20wt％的阴离子表面活性剂，其选自：直链烷基苯磺酸盐；烷基硫酸盐；和烷基醚硫酸盐；及其混合物；
(ii)0.5至10wt％，更优选2至9wt％的带负电荷的烷氧基化多芳基苯酚，其具有以下结构：
其中R选自：SO3、COO-和PO3 2-，更优选选自：SO3 -和COO-，其中n选自：10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、38、39、40、41、42、43、44、45、46、47、48、49、50、51、52、53和54；和
香料，优选0.05至0.5wt％香料。
又一方面，本发明提供了一种处理纺织品的家用方法，该方法包括以下步骤：
(i)用带负电荷的烷氧基化多芳基苯酚的水溶液处理纺织品，所述水溶液包含10ppm至5000ppm的带负电荷的烷氧基化多芳基苯酚；和至多6g/L，优选0.2至4g/L的表面活性剂；和
(ii)任选地漂洗和干燥纺织品。
在该方法中，水溶液中香料的含量优选为0.1至100ppm，更优选为1至10ppm。
在本发明的方法方面，所用表面活性剂优选为对于本发明的组合物方面所优选的。
纺织品优选为衣服、床上用品或桌布中的项目。衣服的优选项目是含棉的衬衫、裤子、内衣和套衫。
具体实施方式
烷氧基化多芳基苯酚
优选地，带负电荷的烷氧基化多芳基苯酚是烷氧基化三苯乙烯基苯酚。
优选地，带负电荷的烷氧基化三苯乙烯基苯酚是聚乙二醇单(2,4,6-三(1-苯基乙基)苯基)醚衍生物。优选地，烷氧基化多芳基苯酚含有平均2-70个烷氧基，最优选10至54个烷氧基。
优选地，烷氧基化是乙氧基化。
优选地，带负电荷的烷氧基化多芳基苯酚具有2个或3个与苯酚连接的芳基。优选地，它们在苯酚的2、4或2、4、6位上。烷氧基化物连接到1位。优选地，烷氧基化物被带负电的基团封端。
优选地，带电荷的基团具有钠或钾作为抗衡离子。
带负电荷的烷氧基化多芳基苯酚中的芳基优选地选自：苯基、甲苯基、萘基、四氢萘基、茚满基、茚基、苯乙烯基、吡啶基、喹啉基及其混合物。
最优选地，带负电荷的烷氧基化多芳基苯酚是具有以下结构的：
其中R选自：SO3、COO-和PO3 2-，优选选自SO3 -和COO-。
优选n＝2至70，更优选n＝4至54，最优选n＝10至n＝54。
名称n是聚烷氧基链中烷氧基单元的平均摩尔数。
化合物可以从工业供应商获得，例如Rhodia、Clariant、Aoki Oil IndustrialCo、Stepan和TOHO Chemical Industry Co。
在本发明的上下文中，带负电荷的烷氧基化多芳基苯酚不认为是表面活性剂，并且对于本文所定义的表面活性剂在数字上没有贡献。
“带负”电荷的是指在水中pH＝8时的电荷。
表面活性剂
洗衣组合物包含带电荷的表面活性剂，并且最优选带电荷的表面活性剂是阴离子表面活性剂(包括其混合物)。
可以使用的适合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烷基的烷基部分。
适合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，特别是通过硫酸化例如由牛油或椰油制得的高级C8至C18醇而获得的那些，烷基C9至C20苯磺酸钠和钾，特别是直链仲烷基C10至C15苯磺酸钠；以及烷基甘油醚硫酸钠，特别是那些衍生自牛油或椰油的高级醇和衍生自石油的合成醇的那些醚。
阴离子表面活性剂优选选自：直链烷基苯磺酸盐；烷基硫酸盐；烷基醚硫酸盐；皂；烷基(优选甲基)酯磺酸盐及其混合物。
最优选的阴离子表面活性剂选自：直链烷基苯磺酸盐；烷基硫酸盐；烷基醚硫酸盐及其混合物。优选地，烷基醚硫酸盐是具有平均1至3个EO(乙氧基化物)单元的C12-C14正烷基醚硫酸盐。月桂基醚硫酸钠是特别优选的(SLES)。优选地，直链烷基苯磺酸盐是C11至C15烷基苯磺酸钠。优选地，烷基硫酸盐是直链或支链C12至C18烷基硫酸钠。十二烷基硫酸钠是特别优选的，(SDS，也称为伯烷基硫酸盐)。
洗衣组合物中的阴离子表面活性剂的含量优选为4至50wt％，更优选为6至30wt％，最优选为8至20wt％。
优选地，存在两种或更多阴离子表面活性剂，例如直链烷基苯磺酸盐与烷基醚硫酸盐一起。
优选地，除了阴离子表面活性剂以外，洗衣组合物还包含烷基乙氧基化非离子表面活性剂，优选2至8wt％的烷基烷氧基化(优选乙氧基化)非离子表面活性剂。
可以使用的适合的非离子洗涤剂化合物包括，特别地，具有脂肪族疏水基团和反应性氢原子的化合物(例如脂肪醇、酸或酰胺，特别是环氧乙烷单独或与环氧丙烷一起)的反应产物。具体的非离子洗涤剂化合物是脂肪族C8至C18伯或仲直链或支链醇与环氧乙烷的缩合产物。
优选地，烷基乙氧基化非离子表面活性剂是具有7EO至9EO单元的平均乙氧基化的C8至C18伯醇。
表面活性剂体系的非离子和阴离子表面活性剂可以选自描述于Schwartz&Perry的"Surface Active Agents"第1卷，Interscience 1949，Schwartz,Perry&Berch的第2卷，Interscience 1958，Manufacturing Confectioners Company发布的"McCutcheon'sEmulsifiers and Detergents"的当前版本或在"Tenside-Taschenbuch"中，H.Stache，第2版，Carl Hauser Verlag，1981的表面活性剂。
优选地，所用表面活性剂是饱和的。
还可应用的是表面活性剂，例如EP-A-328 177(Unilever)中描述的那些，其表现出抗盐析性，EP-A-070 074中描述的烷基多糖苷表面活性剂，和烷基单糖苷。
在另一方面，带电荷的表面活性剂可以是阳离子，使得制剂是织物调理剂。然而，基于阴离子或阴离子/非离子表面活性剂的洗涤剂组合物是更优选的实施方式。
阳离子化合物
当本发明用作织物调理剂时，它需要含有阳离子化合物。
最优选的是季铵化合物。
如果季铵化合物是具有至少一个C12至C22烷基链的季铵化合物，则是有利的。
如果季铵化合物具有下式，则是优选的：
其中R1是C12至C22烷基或烯基链；R2、R3和R4独立地选自C1至C4烷基链，并且X-是相容的阴离子。这种类型的优选化合物是季铵化合物：十六烷基三甲基溴化季铵。
用于本发明的第二类材料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，并且X-是相容的阴离子。
组合物任选地包含硅氧烷。
助洗剂或络合剂
助洗剂材料可以选自1)钙螯合剂材料、2)沉淀材料、3)钙离子交换材料及4)其混合物。
钙螯合剂助洗剂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，例如乙二胺四乙酸。
沉淀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晶体或无定形铝硅酸盐，其中沸石是众所周知的代表，例如沸石A、沸石B(也称为沸石P)、沸石C、沸石X、沸石Y以及如EP-A-0,384,070中所述的沸石P型。
组合物还可以含有0-65％的助洗剂或络合剂，例如乙二胺四乙酸、二乙三胺五乙酸、烷基或烯基琥珀酸、次氮基三乙酸或下文提及的其他助洗剂。许多助洗剂借助其络合金属离子的能力同样是漂白稳定剂。
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，其中碳酸盐是特别优选的。
组合物可以含有作为助洗剂的晶体铝硅酸盐，优选碱金属铝硅酸盐，更优选铝硅酸钠。这通常是以小于15％w的水平存在。铝硅酸盐是具有以下通式的材料：
0.8-1.5M2O.Al2O3.0.8-6SiO2
其中M是一价阳离子，优选钠。这些材料含有一些结合水并且需要具有至少50mgCaO/g的钙离子交换能力。优选的铝硅酸钠在上式中含有1.5-3.5个SiO2单元。它们可以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。表面活性剂与铝硅酸盐(当存在时)的比例优选大于5:2，更优选大于3:1。
或者，或除了硅铝酸盐助洗剂之外，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、三磷酸盐和膦酸盐物质。其他形式的助洗剂包括硅酸盐，例如可溶性硅酸盐、偏硅酸盐、层状硅酸盐(例如来自Hoechst的SKS-6)。
优选地，洗衣洗涤剂制剂是非磷酸盐助洗剂洗衣洗涤剂制剂，即含有小于1wt％的磷酸盐。优选地，粉末洗衣洗涤剂制剂主要是碳酸盐助洗剂。粉末应优选在使用中给出pH为9.5-11。
最优选地，洗衣洗涤剂是水性液体洗衣洗涤剂，优选具有7至9的pH。
在水性液体洗衣洗涤剂中，优选单丙二醇以1至30wt％，最优选2至18wt％的含量存在，以提供具有适当的可倾倒粘度的制剂。
荧光剂
组合物优选地包含荧光剂(光亮剂)。荧光剂是众所周知的，并且许多这样的荧光是市售的。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。
荧光剂的优选类别是：二苯乙烯基联苯化合物，如Tinopal(商标)CBS-X，二胺芪二磺酸化合物，如Tinopal DMS pure Xtra和Blankophor(商标)HRH，以及吡唑啉化合物，如Blankophor SN。
优选的荧光剂是：2-(4-苯乙烯基-3-磺基苯基)-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'-二磺酸二钠以及4,4'-双(2-磺基苯乙烯基)联苯二钠。
香料
组合物包含香料。香料优选在0.001至3wt％，更优选0.05至0.5wt％，最优选0.1至1wt％的范围内。许多适合的香料的实例提供于由CFTA Publications and OPD1993Chemicals Buyers Directory 80th Annual Edition出版、由Schnell PublishingCo.出版的CTFA(Cosmetic,Toiletry and Fragrance Association)1992InternationalBuyers Guide。
优选地，香料包含至少一种香型(note)(化合物)：α-异甲基紫罗酮；水杨酸苄酯；香茅醇；香豆素；己基肉桂醛(hexyl cinnamal)；芳樟醇；2-甲基戊酸乙基酯(Pentanoicacid,2-methyl-,ethyl ester)；辛醛；乙酸苄酯；3,7-二甲基-1,6-辛二烯-3-醇乙酸酯(1,6-octadien-3-ol,3,7-dimethyl-,3-acetate)；2-(1,1-二甲基乙基)-环己醇乙酸酯(cyclohexanol,2-(1,1-dimethylethyl)-,1-acetate)；δ-大马酮(damascone)；β-紫罗酮；乙酸三环癸烯酯(verdyl acetate)；十二醛；己基肉桂醛(hexyl cinnamic aldehyde)；环十五内酯；苯乙酸2-苯基乙基酯；水杨酸戊酯；β-石竹烯；十一碳烯酸乙酯；邻氨基苯甲酸香叶酯；α-鸢尾酮；β-苯基乙基苯甲酸酯；α-檀香醇；雪松醇；乙酸柏木酯；甲酸柏木酯(cedryformate)；水杨酸环己酯；γ-十二内酯(gamma-dodecalactone)，和β-苯乙基苯基乙酸酯。
香料的有用组分包括天然和合成来源两者的材料。它们包括单一化合物和混合物。这样的组分的具体实例可见于现有文献，例如Fenaroli's Handbook of FlavorIngredients,1975,CRC Press；Synthetic Food Adjuncts,1947,M.B.Jacobs,VanNostrand编辑；或Perfume and Flavor Chemicals,S.Arctander,1969,Montclair,N.J.(USA)。多种香料组分存在于一个制剂中是常见事物。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25wt％的是头香(top note)。头香由Poucher(Journalof the Society of Cosmetic Chemists 6(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、玫瑰氧化物和顺-3-己醇。
国际香氛协会已在2011年发布了香氛成分(香料)清单。(http:// www.ifraorg.org/en-us/ingredients#.U7Z4hPldWzk)。
香氛材料研究所提供了具有安全信息的香料(香氛)数据库。
香料头香可用于提示本发明的白度和亮度益处。
一些或所有香料可以被包封，有利于包封的典型香料组分包括具有相对低沸点的那些，优选沸点小于300℃，优选100-250℃的那些。包封具有低Clog P(即，将具有更大的被分配到水中的倾向的那些)，优选具有小于3.0的CLog P的香料组分也是有利的。这些具有相对低沸点和相对低CLog P的材料已被称为“延迟释香”的香料成分，并且包含以下材料中的一种或多种：
己酸烯丙酯、乙酸戊酯、丙酸戊酯、茴香醛、苯甲醚、苯甲醛、乙酸苄酯、苄基丙酮、苯甲醇、甲酸苄酯、异戊酸苄酯、丙酸苄酯、β-γ己烯醇、樟脑胶、左-香芹酮、d-香芹酮、肉桂醇、甲酸肉桂酯(cinamyl formate)、顺-茉莉酮、顺-3-己烯基乙酸酯，枯茗醇、cyclal c、二甲基苄基甲醇、二甲基苄基甲醇乙酸酯、乙酸乙酯、乙酰乙酸乙酯、乙基戊基酮、苯甲酸乙酯、丁酸乙酯、乙基己基酮、乙基苯基乙酸酯、桉树脑、丁香酚、乙酸葑酯(fenchylacetate)、flor acetate(乙酸三环癸烯基酯)、frutene(丙酸三环癸烯基酯)、香叶醇、己烯醇、乙酸己烯酯、乙酸己酯、甲酸己酯、龙葵醇(hydratropic alcohol)、羟基香茅醛、茚酮、异戊醇、异薄荷酮、异胡薄荷醇乙酸酯(isopulegyl acetate)、异喹啉酮、女贞醛、芳樟醇、芳樟醇氧化物、甲酸芳樟酯、薄荷酮、薄荷基苯乙酮(menthyl acetphenone)、甲基戊基酮、邻氨基苯甲酸甲酯、苯甲酸甲酯、甲基苯基乙酸酯、甲基丁香酚、甲基庚烯酮、甲基庚炔碳酸酯(methyl heptine carbonate)、甲基庚基酮、甲基己基酮、甲基苯基甲基乙酸酯、水杨酸甲酯、甲基-n-甲基邻氨基苯甲酸酯、橙花醇、辛内酯、辛醇、对甲酚、对甲酚甲基醚、对甲氧基苯乙酮、对甲基苯乙酮、苯氧乙醇、苯基乙醛、苯基乙基乙酸酯、苯基乙基醇、苯基乙基二甲基甲醇、乙酸异戊二烯酯、硼酸丙酯(propyl bornate)、胡薄荷酮、玫瑰氧化物、黄樟素、4-萜品烯醇(4-terpinenol)、α-萜品烯醇和/或苯乙醛二甲缩醛(viridine)。多种香料组分存在于一个制剂中是常见事物。在本发明的组合物中，设想将有四种或更多种，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上文给出的延迟释香香料的列表中给出的香料组分存在于香料中。
本发明可以应用的另一组香料是所谓的“芳香疗法”材料。这些包括也用于香水中的许多组分，包括精油如鼠尾草、桉树、天竺葵、薰衣草、肉豆蔻干皮(Mace)提取物、橙花油、肉豆蔻、留兰香、甜紫罗兰叶和缬草的组分。
优选的是洗衣处理组合物不含有过氧漂白剂，例如过碳酸钠、过硼酸钠和过酸。
聚合物
组合物也包含一种或多种另外的聚合物。实例是羧甲基纤维素、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。
存在以防止染料沉积的聚合物可以存在，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
一种或多种酶优选存在于本发明的洗衣组合物中以及当实施本发明的方法时。
优选地，本发明的洗衣组合物中每种酶的水平为0.0001wt％至0.1wt％蛋白质。
优选地，酶选自：蛋白酶；脂肪酶；和纤维素酶，优选蛋白酶。
特别考虑的酶包括蛋白酶、α-淀粉酶、纤维素酶、脂肪酶、过氧化物酶/氧化酶、果胶酸酯裂解酶和甘露聚糖酶或其混合物。
适合的脂肪酶包括具有细菌或真菌来源的那些。包括化学修饰或蛋白质工程化的突变体。有用的脂肪酶的实例包括来自腐质霉属(Humicola)(同义词嗜热真菌属(Thermomyces))，例如来自EP 258 068和EP 305 216中描述的H.lanuginosa(T.lanuginosus)或来自WO 96/13580中描述的H.insolens；假单胞菌脂肪酶，例如来自P.alcaligenes或P.pseudoalcaligenes(EP 218 272)、P.cepacia(EP 331 376)、P.stutzeri(GB 1,372,034)、P.fluorescens、假单胞菌属菌株SD 705(WO 95/06720和WO96/27002)、P.wisconsinensis(WO 96/12012)；芽孢杆菌脂肪酶，例如来自枯草芽孢杆菌(Dartois等，(1993),Biochemica et Biophysica Acta,1131,253-360)、嗜热脂肪芽孢杆菌(JP 64/744992)或短小芽孢杆菌(WO 91/16422)。
其他实例是脂肪酶的变体，如在WO 92/05249、WO 94/01541、EP 407 225、EP 260105、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中所述的那些。
优选的市售脂肪酶包括LipolaseTM和Lipolase UltraTM、LipexTM和LipocleanTM(Novozymes A/S)。
本发明的方法可以在归类为EC 3.1.1.4和/或EC 3.1.1.32的磷脂酶的存在下进行。如本文所用，术语磷脂酶是对磷脂具有活性的酶。
磷脂，例如卵磷脂或磷脂酰胆碱，由在外(sn-1)和中间(sn-2)位置用两个脂肪酸酯化并在第三个位置用磷酸酯化的甘油组成；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，其水解一个脂肪酰基(分别在sn-1和sn-2位置)以形成溶血磷脂；以及溶血磷脂酶(或磷脂酶B)，其可以水解溶血磷脂中剩余的脂肪酰基。磷脂酶C和磷脂酶D(磷酸二酯酶)分别释放二酰基甘油或磷脂酸。
适合的蛋白酶包括具有动物、植物或微生物来源的蛋白酶。微生物来源是优选的。包括化学修饰或蛋白质工程化的突变体。蛋白酶可以是丝氨酸蛋白酶或金属蛋白酶，优选碱性微生物蛋白酶或胰蛋白酶样蛋白酶。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以及FN3TM(Genencor International Inc.)。
本发明的方法可以在归类为EC 3.1.1.74的角质酶的存在下进行。根据本发明使用的角质酶可以具有任何来源。优选地，角质酶具有微生物来源，特别是具有细菌、真菌或酵母来源。
适合的淀粉酶(α和/或β)包括具有细菌或真菌来源的淀粉酶。包括化学修饰或蛋白质工程化的突变体。淀粉酶包括，例如，从芽孢杆菌获得的α-淀粉酶，如，更详细地描述在GB 1,296,839中的地衣芽孢杆菌的特定菌株，或在WO 95/026397或WO 00/060060中公开的芽孢杆菌属菌株。市售的淀粉酶是DuramylTM、TermamylTM、Termamyl UltraTM、NatalaseTM、StainzymeTM、FungamylTM和BANTM(Novozymes A/S)、RapidaseTM和PurastarTM(来自GenencorInternational Inc.)。
适合的纤维素酶包括具有细菌或真菌来源的纤维素酶。包括化学修饰或蛋白质工程化的突变体。适合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、梭孢壳属(Thielavia)、支顶孢属的纤维素酶，例如在US 4,435,307、US 5,648,263、US 5,691,178、US 5,776,757、WO 89/09259、WO 96/029397和WO 98/012307中公开的由特异腐质霉(Humicola insolens)、太瑞斯梭孢壳霉(Thielavia terrestris)、嗜热毁丝霉(Myceliophthora thermophila)和尖孢镰刀菌产生的真菌纤维素酶。市售的纤维素酶包括CelluzymeTM、CarezymeTM、CellucleanTM、EndolaseTM、RenozymeTM(Novozymes A/S)、ClazinaseTM和Puradax HATM(Genencor International Inc.)和KAC-500(B)TM(KaoCorporation)。CellucleanTM是优选的。
适合的过氧化物酶/氧化酶包括具有植物、细菌或真菌来源的那些。包括化学修饰或蛋白质工程化的突变体。有用的过氧化物酶的实例包括来自鬼伞属(例如来自灰盖鬼伞(C.cinereus))的过氧化物酶及其变体，如在WO 93/24618、WO 95/10602和WO 98/15257中所述的那些。市售的过氧化物酶包括GuardzymeTM和NovozymTM 51004(Novozymes A/S)。
适用的另外的酶在WO2009/087524、WO2009/090576、WO2009/107091、WO2009/111258和WO2009/148983中讨论。
酶稳定剂
组合物中存在的任何酶都可以使用常规的稳定剂稳定，例如多元醇，如丙二醇或甘油、糖或糖醇、乳酸、硼酸或硼酸衍生物，例如芳香族硼酸酯，或苯基硼酸衍生物，如4-甲酰基苯基硼酸，并且组合物可以如例如WO 92/19709和WO 92/19708所述配制。
当烷基足够长以形成支链或环状链时，烷基包括支链、环状或直链烷基链。烷基优选直链或直链，最优选直链。
除非另有说明，本文所用不定冠词“一”或“一个”及其相应的定冠词“该”是指至少一个，或一个或多个。
实施例
实验
实施例1
制备具有以下配方的水性液体洗衣洗涤剂：
该制剂用于在设定为200rpm的tergotometer中洗涤8个5x5cm的编织棉布片。在800ml的6°法国硬水中在20℃下用2.3g/L的制剂进行1小时的洗涤。为了模拟微粒污垢，将0.04g/L的100％压缩炭黑(来自Sigma-Aldrich)加入到洗涤液中。
一旦洗涤已经完成，则将棉检测物在500ml清水中漂洗两次，除去干燥的并在反射计上测量颜色并表示为CIE L*a*b*值。
测试含有Sokalan HP20(BASF)——乙氧基化聚乙烯亚胺聚合物PEI(600)20EO，作为针对抗再沉积益处的比较聚合物——的制剂。
测试含有带负电荷的烷氧基化多芳基苯酚——Dispersogen LFH，来自Clariant(三苯乙烯基苯酚聚氧乙烯磷酸酯(阴离子))——的制剂。
结果总结在下表中。还给出从对于8个检测物的测量值的标准偏差计算的95％置信限。L*值是来自8个检测物的测量值的平均值。
带负电荷的烷氧基化多芳基苯酚增加了检测物的L*。高L*值等于更清洁的更白的织物。带负电荷的烷氧基化多芳基苯酚提供了比乙氧基化聚乙烯亚胺显著更好的益处。
实施例2
制备具有以下配方的水性液体洗衣洗涤剂：
该制剂用于在设定为200rpm的tergotometer中洗涤8个5x5cm的编织棉布片。在800ml的26°法国硬水中在20℃下用2.3g/L的制剂进行1小时的洗涤。为了模拟微粒污垢，将0.04g/L的100％压缩炭黑(来自Sigma-Aldrich)加入到洗涤液中。为了模拟油性污垢，将(6.3g)的SBL2004污垢带(soil strip)(来自Warwick Equest)加入到洗涤液中。
一旦洗涤已经完成，将棉检测物在500ml清水中漂洗两次，除去干燥的并在反射计上测量颜色并表示为CIE L*a*b*值。
测试含有
NN7718(BASF)——萘磺酸与甲醛的缩聚产物——和木质素磺酸盐作为针对抗再沉积益处的比较磺化芳族聚合物的制剂。
测试含有带负电荷的烷氧基化多芳基苯酚——Dispersogen LFH，来自Clariant(三苯乙烯基苯酚聚氧乙烯磷酸酯(阴离子))——的制剂。
结果总结在下表中。还给出从8个检测物的测量值的标准偏差计算的95％置信限。L*值是来自8个监视物的测量值的平均值。
带负电荷的烷氧基化多芳基苯酚增加了检测物的L*。高L*值等于更清洁的更白的织物。带负电荷的烷氧基化多芳基苯酚提供了比萘磺酸与甲醛的缩合物或木质素磺酸盐显著更好的益处。
Claims (20)
1.一种洗衣洗涤剂组合物，其包含：
(i)4至50wt％的带电荷的表面活性剂；
(ii)0.1至20wt％的带负电荷的烷氧基化多芳基苯酚；和，
(iii)0.001至3wt％的香料；
其中所述带负电荷的烷氧基化多芳基苯酚是带负电荷的烷氧基化三苯乙烯基苯酚。
2.根据权利要求1所述的洗衣洗涤剂组合物，其中所述带负电荷的烷氧基化多芳基苯酚是带负电荷的乙氧基化多芳基苯酚。
3.根据权利要求1所述的洗衣洗涤剂组合物，其中所述带负电荷的烷氧基化三苯乙烯基苯酚是带负电荷的聚乙二醇单(2,4,6-三(1-苯基乙基)苯基)醚。
4.根据权利要求1至3中任一项所述的洗衣洗涤剂组合物，其中所述带负电荷的烷氧基化多芳基苯酚含有平均2至70个烷氧基。
5.根据权利要求4所述的洗衣洗涤剂组合物，其中所述带负电荷的烷氧基化多芳基苯酚含有平均10至54个烷氧基。
6.根据权利要求1至3中任一项所述的洗衣洗涤剂组合物，其中所述带负电荷的烷氧基化多芳基苯酚以0.5至10wt％的含量存在。
7.根据权利要求1至3中任一项所述的洗衣洗涤剂组合物，其中所述带负电荷的烷氧基化多芳基苯酚以2至9wt％的含量存在。
8.根据权利要求1至3中任一项所述的洗衣洗涤剂组合物，其中所述带电荷的表面活性剂是阴离子表面活性剂。
9.根据权利要求8所述的洗衣洗涤剂组合物，其中所述阴离子表面活性剂选自：直链烷基苯磺酸盐、烷基硫酸盐、烷基醚硫酸盐、皂、甲基酯磺酸盐及其混合物。
10.根据权利要求9所述的洗衣洗涤剂组合物，其中所述阴离子表面活性剂选自：直链烷基苯磺酸盐、烷基硫酸盐、烷基醚硫酸盐及其混合物。
11.根据权利要求8所述的洗衣洗涤剂组合物，其中阴离子表面活性剂的含量为4至50wt％。
12.根据权利要求1至3中任一项所述的洗衣洗涤剂组合物，其中所述组合物包含2至8wt％的烷基乙氧基化非离子表面活性剂。
13.根据权利要求1至3中任一项所述的洗衣洗涤剂组合物，其中香料以0.001至3wt％存在并且包含来自以下的一种或多种香型化合物：α-异甲基紫罗酮；水杨酸苄酯；香茅醇；香豆素；己基肉桂醛；芳樟醇；2-甲基戊酸乙基酯；辛醛；乙酸苄酯；3,7-二甲基-1,6-辛二烯-3-醇乙酸酯；2-(1,1-二甲基乙基)-环己醇乙酸酯；δ-大马酮；β-紫罗酮；乙酸三环癸烯酯；十二醛；己基肉桂醛；环十五内酯；苯乙酸2-苯基乙基酯；水杨酸戊酯；β-石竹烯；十一碳烯酸乙酯；邻氨基苯甲酸香叶酯；α-鸢尾酮；β-苯基乙基苯甲酸酯；α-檀香醇；雪松醇；乙酸柏木酯；甲酸柏木酯；水杨酸环己酯；γ-十二内酯，和β-苯乙基苯基乙酸酯。
14.根据权利要求1所述的洗衣洗涤剂组合物，其包含：
(i)4至50wt％的阴离子表面活性剂，其选自：直链烷基苯磺酸盐；烷基硫酸盐；烷基醚硫酸盐及其混合物；
(ii)0.5至10wt％的具有以下结构的带负电荷的烷氧基化多芳基苯酚：
其中R选自：SO3 -和PO3 2-；其中n选自10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、38、39、40、41、42、43、44、45、46、47、48、49、50、51、52、53和54；和，
(iii)0.001至3wt％的香料。
15.根据权利要求14所述的洗衣洗涤剂组合物，其中R是SO3 -。
16.根据权利要求1至3中任一项所述的洗衣洗涤剂组合物，其中所述组合物包含0.0001wt％至0.1wt％的酶，所述酶选自：蛋白酶、脂肪酶、纤维素酶及其混合物。
17.根据权利要求16所述的洗衣洗涤剂组合物，其中所述酶包含蛋白酶。
18.根据权利要求1至3中任一项所述的洗衣洗涤剂组合物，其中所述洗衣洗涤剂组合物是洗衣水性液体洗涤剂组合物。
19.一种处理纺织品的家用方法，所述方法包括以下步骤：
(i)用根据权利要求1至18中任一项所限定的洗衣洗涤剂组合物的水溶液处理所述纺织品，所述水溶液包含10ppm至5000ppm的所述带负电荷的烷氧基化多芳基苯酚，和至多6g/L的表面活性剂；和，
(ii)任选地漂洗和干燥所述纺织品。
20.根据权利要求19所述的处理纺织品的家用方法，其中所述水溶液包含0.2至4g/L的表面活性剂。
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| CA1210009A (en) * | 1982-12-23 | 1986-08-19 | Eugene P. Gosselink | Ethoxylated amine polymers having clay soil removal/anti-redeposition properties useful in detergent compositions |
| CN102202639A (zh) * | 2008-09-02 | 2011-09-28 | 巴斯夫欧洲公司 | 用作流变改性剂和家庭和个人护理组合物的共聚物 |
| CN103781893A (zh) * | 2011-08-31 | 2014-05-07 | 阿克佐诺贝尔化学国际公司 | 包含去污剂的洗衣剂组合物 |
| CN103857781A (zh) * | 2011-07-21 | 2014-06-11 | 荷兰联合利华有限公司 | 液体洗衣组合物 |
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| DE10353603B4 (de) * | 2003-11-17 | 2006-01-19 | Clariant Gmbh | Verwendung von Ethercarbonsäuren auf Basis alkoxylierter Mono-, Di- und/oder Tri(1-phenylethyl)phenole in Kühlschmiermitteln |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CA1210009A (en) * | 1982-12-23 | 1986-08-19 | Eugene P. Gosselink | Ethoxylated amine polymers having clay soil removal/anti-redeposition properties useful in detergent compositions |
| CN102202639A (zh) * | 2008-09-02 | 2011-09-28 | 巴斯夫欧洲公司 | 用作流变改性剂和家庭和个人护理组合物的共聚物 |
| CN103857781A (zh) * | 2011-07-21 | 2014-06-11 | 荷兰联合利华有限公司 | 液体洗衣组合物 |
| CN103781893A (zh) * | 2011-08-31 | 2014-05-07 | 阿克佐诺贝尔化学国际公司 | 包含去污剂的洗衣剂组合物 |
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