CN109844083B - 增白组合物 - Google Patents
增白组合物 Download PDFInfo
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- CN109844083B CN109844083B CN201780064275.3A CN201780064275A CN109844083B CN 109844083 B CN109844083 B CN 109844083B CN 201780064275 A CN201780064275 A CN 201780064275A CN 109844083 B CN109844083 B CN 109844083B
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- laundry detergent
- detergent composition
- surfactant
- composition according
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- 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
- 235000016788 valerian Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- RGVQNSFGUOIKFF-UHFFFAOYSA-N verdyl acetate Chemical compound C12CC=CC2C2CC(OC(=O)C)C1C2 RGVQNSFGUOIKFF-UHFFFAOYSA-N 0.000 description 1
- YEIGUXGHHKAURB-UHFFFAOYSA-N viridine Natural products O=C1C2=C3CCC(=O)C3=CC=C2C2(C)C(O)C(OC)C(=O)C3=COC1=C23 YEIGUXGHHKAURB-UHFFFAOYSA-N 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Abstract
一种洗衣洗涤剂组合物，其包含：(i)0.5至20重量％的烷氧基化取代间苯二酚分散剂(I)
X独立地是：乙氧基、乙氧基和丙氧基的混合物，其中EO的数量>PO的数量，其中a+b＝n且n＝5‑40；R2、R3独立地是：H；C1‑C3直链或支链烷基芳基和芳基；和其中R2和/或R3选自C1‑C3直链或支链烷基芳基的芳基和芳基；T是：H、CH3、SO3 ‑、CH2COO‑、PO3 2‑、C2H5、正丙基、异丙基、正丁基、叔丁基、磺基琥珀酸根；(ii)0至50重量％的表面活性剂；(iii)0.001至3重量％的香料、0.0001至0.5重量％的荧光剂和/或0.0001至0.1重量％的调色染料。用水溶液处理纺织品的方法，所述水溶液包含10至5000ppm的(i)；0至6g/L的表面活性剂(ii)；0.1至100ppm的香料、1ppb至5ppm的荧光剂、和/或1ppb至1ppm的调色染料。
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
在家庭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除去的污垢再沉积到另一件衣服上。人体皮脂在衣服上和洗涤液中的存在加剧了污垢在洗涤中的再沉积。该过程导致白度和清洁在整个洗涤负荷中的总体损失。需要重量有效的洗衣有益剂，其减少污垢的再沉积，同时还增加污渍去除。这样的成分优选是可生物降解的。
发明内容
需要在家用洗衣产品中减少再沉积并增强清洁的技术。
我们已经发现，当掺入洗衣洗涤剂中时，所选择的烷氧基化取代间苯二酚(ASR)分散剂在家庭洗衣过程中增强了衣服的白度和亮度。
在一个方面，本发明提供一种洗衣洗涤剂组合物，其包含：
(i)0.5至20重量％，优选1至10重量％，最优选2至6重量％的具有以下结构的烷氧基化取代间苯二酚分散剂：
其中，
X独立地选自：乙氧基、以及乙氧基和丙氧基的混合物，其中乙氧基的数量大于丙氧基的数量，并且其中a+b＝n且n为5至40，优选6至34、最优选n选自6、7、8、9、10、11、12、13、14、15、16、17、18、19和20；
优选X是乙氧基；
R2和R3独立地选自：H、C1-C3直链或支链烷基芳基和芳基；其中R2和R3中的至少一个选自C1-C3直链或支链烷基芳基和芳基；优选R2和R3选自H、苯乙烯基和枯基，最优选苯乙烯基，优选R2和R3两者位于-O-[X]n-T基团的邻位、
T选自：H、CH3、SO3 -、CH2COO-、PO3 2-、C2H5、正丙基，异丙基、正丁基、叔丁基和磺基琥珀酸根，T优选为H、
(ii)0至50重量％的除所述烷氧基化取代间苯二酚分散剂以外的表面活性剂；优选表面活性剂选自：阴离子和非离子表面活性剂，优选表面活性剂的含量为4至40重量％，更优选6至30重量％，最优选8至20重量％；优选非离子表面活性剂/阴离子表面活性剂的重量分数为0至0.3，优选0至0.15，最优选0.05至0.12；和
(iii)选自以下的一种或多种的活性物质：0.001至3重量％的香料、0.0001至0.5重量％的荧光剂和/或0.0001重量％至0.1重量％的调色染料(shading dye)。
洗衣洗涤剂组合物优选选自颗粒状洗涤剂粉末；和水性洗衣液体洗涤剂；最优选地，洗衣洗涤剂组合物是水性洗衣液体洗涤剂组合物。
另一方面，本发明提供一种处理纺织品的家用方法，所述方法包括以下步骤：
(i)用烷氧基化取代间苯二酚分散剂的水溶液处理纺织品，所述水溶液包含10ppm至5000ppm的本文定义的烷氧基化取代间苯二酚分散剂，优选100ppm至1000ppm；和0至6g/L的除所述烷氧基化取代间苯二酚分散剂以外的表面活性剂，优选0.2至1g/L；
(ii)任选地漂洗和干燥所述纺织品。
在该方法中，表面活性剂是本文优选的类型。
在该方法中，在水溶液中存在活性物质。活性物质选自：0.1ppm至100ppm，1ppb至5ppm的荧光剂和1ppb至1ppm的调色染料。水溶液中香料的含量优选为1至10ppm。
在本发明方法的方面中，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。
家用方法优选在家用洗衣机中进行或通过手洗进行。洗涤温度优选为285至335K。
纺织品优选是衣服、床上用品或桌布的物品。优选的衣服物品是含棉衬衫、裤子、内衣和套头衫。
具体实施方式
烷氧基化取代间苯二酚
在本发明的上下文中，烷氧基化取代间苯二酚(ASR)不被认为是表面活性剂，并且不在数量上贡献于如本文所定义的表面活性剂。
最优选的芳基是苯基和取代的苯基。
C1至C3直链或支链烷基芳基是被芳族基团取代的C1至C3直链或支链烷基，例如：苯乙烯基、枯基、苄基。
苯乙烯基是-CH(CH3)Ph；枯基是-C(CH3)2Ph；苄基是CH2Ph，其中Ph是苯基。
值n是烷氧基的摩尔平均数。n的值可以使用NMR测量。
磺基琥珀酸根(sulfoccinate)具有以下结构，描绘为Na盐：
本发明的ASR的结构实例是：
表面活性剂
洗衣组合物可包含阴离子和非离子表面活性剂(其包括它们的混合物)。
表面活性剂体系的非离子和阴离子表面活性剂可以选自“Surface ActiveAgents”，卷1，Schwartz&Perry，Interscience 1949；卷2，Schwartz,Perry&Berch，Interscience 1958；Manufacturing Confectioners Company出版的“McCutcheon'sEmulsifiers and Detergents”的当前版本，或“Tenside-Taschenbuch”，H.Stache，第2版，Carl Hauser Verlag，1981，或Helmut W.Stache编辑的Anionic Surfactants:OrganicChemistry(Marcel Dekker 1996)中描述的表面活性剂。
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至约22个碳原子的烷基的有机硫酸和磺酸的水溶性碱金属盐，术语烷基用于包括较高级烷基的烷基部分。
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，特别是通过使例如由牛油或椰油制得的较高级C8至C18醇硫酸化而获得的那些；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，特别是衍生自牛油或椰油的较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；烷基醚羧酸盐；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(SLES)是特别优选的。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(SDS，也称为伯烷基硫酸盐)是特别优选的。
洗衣组合物中阴离子表面活性剂的含量优选为4至40重量％，更优选6至30重量％，最优选8至20重量％。
优选地，存在两种或更多种阴离子表面活性剂，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。
可以使用的合适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(例如脂族醇、酸或酰胺)与尤其是环氧乙烷(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直链或支链伯或仲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。
优选地，所用的表面活性剂是饱和的。
同样适用的是表面活性剂，如EP-A-328 177(Unilever)中描述的表现出耐盐析性的那些，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，带电表面活性剂可以是阳离子的，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，其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，这是有利的。
优选的是季铵化合物具有下式：
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。这种类型的优选的化合物是季铵化合物鲸蜡基三甲基溴化季铵。
与本发明一起使用的第二类物质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酮。
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。
钙螯合剂助洗剂材料的实例包括碱金属聚磷酸盐，如三聚磷酸钠，和有机螯合剂，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，其中沸石是公知的代表，例如沸石A、沸石B(也称为沸石P)、沸石C、沸石X、沸石Y以及在EP-A-0,384,070中描述的P型沸石。
组合物还可以含有0至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，或下文所述的其他助洗剂。许多助洗剂因其络合金属离子的能力而同样是漂白稳定剂。
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，碳酸盐是特别优选的。
组合物可以含有晶体铝硅酸盐，优选碱金属铝硅酸盐，更优选铝硅酸钠作为助洗剂。这通常以小于15重量％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需要具有至少50mgCaO/g的钙离子交换容量。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，如文献中所充分描述的。表面活性剂与铝硅酸盐(存在时)的比率优选大于5:2，更优选大于3:1。
替代性地，或除铝硅酸盐助洗剂外，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、三磷酸盐和膦酸盐种类。助洗剂的其他形式包括硅酸盐，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的洗衣洗涤剂制剂，即含有少于1重量％的磷酸盐。优选地，粉末洗衣洗涤剂制剂主要是碳酸盐助洗的。粉末应优选给出9.5至11的使用中pH。
最优选地，洗衣洗涤剂是水性液体洗衣洗涤剂，优选pH为7至9。
在水性液体洗衣洗涤剂中，优选单丙二醇以1至30重量％，最优选2至18重量％的水平存在，以提供具有适当的、可倾倒的粘度的制剂。
荧光剂
组合物优选地包含荧光剂(光学增亮剂)。荧光剂是众所周知的，并且许多这样的荧光剂是可商购的。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。
优选的荧光剂类别是：二苯乙烯基联苯化合物，如Tinopal(商标)CBS-X；二胺二苯乙烯二磺酸化合物，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-磺苯基)-2H-萘酚[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}二苯乙烯-2,2'二磺酸二钠、4,4'-双{[(4-苯胺基-6-吗啉基-1,3,5-三嗪-2-基)]氨基}二苯乙烯-2-2'二磺酸二钠，和4,4'-双(2-磺苯乙烯基)联苯二钠。
用于组合物中的一种或多种荧光剂的总量优选为0.0001至0.5重量％，更优选0.005至2重量％，最优选0.05至0.25重量％。
用于该方法的水溶液具有荧光剂存在。荧光剂存在于用于该方法的水溶液中，优选在0.0001g/l至0.1g/l，更优选0.001至0.02g/l的范围内。
香料
组合物优选包含香料。香料优选地在0.001至3重量％，更优选0.05至0.5重量％，最优选0.1至1重量％范围内。香料的许多合适的实例在由CFTA Publications出版的CTFA(Cosmetic,Toiletry and Fragrance Association)1992 International Buyers Guide和由Schnell Publishing Co.出版的OPD 1993 Chemicals Buyers Directory 80thAnnual Edition中提供。
优选地，香料包含以下的至少一种香型(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；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3-乙酸酯；2-(1,1-二甲基乙基)-环己醇1-乙酸酯；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(hexylcinnamic 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(cedry formate)；水杨酸环己酯；γ-十二内酯，和β-苯乙基苯基乙酸酯。
香料的可用组分包括天然和合成来源二者的材料。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著，VanNostrand编辑；或Perfume and Flavor Chemicals，S.Arctander著，1969，Montclair,N.J.(USA)中。
在制剂中存在多种香料组分是常见的。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])所定义的。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、氧化玫瑰和顺-3-己醇。
国际日用香精香料协会已在2011年发布了香氛成分(香料)的清单。(http://www.ifraorg.org/en-us/ingredients#.U7Z4hPldWzk)。
国际日用香料研究所提供了具有安全性信息的香料(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的沸点的那些，优选沸点小于300℃，优选为100-250℃的那些。包封具有低Clog P(即，将具有被分配到水中的更高倾向的那些)，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的材料已经被称为“延迟释香(delayed blooming)”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、左旋-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(三环癸烯基乙酸酯)、frutene(三环癸烯基丙酸酯)、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、乙酸异胡薄荷酯(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、甲基苄基乙酸酯(methyl benyl acetate)、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、propyl bornate、胡薄荷酮、氧化玫瑰、黄樟素、4-萜品烯醇(4-terpinenol)、α-萜品烯醇和/或苯乙醛二甲醇缩醛(viridine)。多种香料组分存在于制剂中是常见的。在本发明的组合物中，设想将有来自上文给出的延迟释香香料的给定列表的四种或更多种，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存在于香料中。
可以与本发明一起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，包括精油的组分，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。
优选的是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
组合物可以含有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)、聚羧酸盐如聚丙烯酸盐、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)。
调色染料
染料在Color Chemistry Synthesis,Properties and Applications ofOrganic Dyes and Pigments(H Zollinger，Wiley VCH，Zürich，2003)和Industrial DyesChemistry,Properties Applications(K Hunger(ed)，Wiley-VCH Weinheim 2003)中描述。
用于洗衣洗涤剂的调色染料优选在可见光范围(400-700nm)中的最大吸收处具有大于5000L mol-1cm-1，优选大于10000L mol-1cm-1的消光系数。染料的颜色是蓝色或紫色。
优选的调色染料发色团是偶氮、吖嗪、蒽醌和三苯甲烷。
偶氮、蒽醌、酞菁和三苯甲烷染料优选带有净阴离子电荷或不带电荷。吖嗪优选带有净阴离子或阳离子电荷。在洗涤过程的洗涤或漂洗步骤期间，蓝色或紫色调色染料沉积到织物上，从而为织物提供可见的色调。在这方面，染料对白色布料赋予蓝色或紫色，色调角为240至345、更优选250至320、最优选250至280。该测试中使用的白色布料是经漂白的、非丝光处理的编织棉片。
调色染料在WO2005/003274，WO2006/032327(Unilever)，WO2006/032397(Unilever)，WO2006/045275(Unilever)，WO2006/027086(Unilever)，WO2008/017570(Unilever)，WO2008/141880(Unilever)，WO2009/132870(Unilever)，WO2009/141173(Unilever)，WO2010/099997(Unilever)，WO2010/102861(Unilever)，WO2010/148624(Unilever)，WO2008/087497(P&G)，WO2011/011799(P&G)，WO2012/054820(P&G)，WO2013/142495(P&G)和WO2013/151970(P&G)中讨论。
单偶氮染料优选含有杂环，并且最优选是噻吩染料。单偶氮染料优选是烷氧基化的，并且优选在pH＝7时不带电荷或带阴离子电荷。烷氧基化噻吩染料在WO/2013/142495和WO/2008/087497中讨论。噻吩染料的优选实例如下所示：
双偶氮染料优选为磺化双偶氮染料。磺化双偶氮化合物的优选实例是直接紫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及其烷氧基化形式。烷氧基化双偶氮染料在WO2012/054058和WO2010/151906中讨论。
烷氧基化双偶氮染料的实例是：
吖嗪染料优选选自磺化吩嗪染料和阳离子吩嗪染料。优选的实例是酸性蓝98，酸性紫50，CAS号为72749-80-5的染料，酸性蓝59，以及选自以下的吩嗪染料：
其中：
X3选自：-H，-F，-CH3，-C2H5，-OCH3和-OC2H5；
X4选自：-H，-CH3，-C2H5，-OCH3和-OC2H5；
Y2选自：-OH，-OCH2CH2OH，-CH(OH)CH2OH，-OC(O)CH3和C(O)OCH3。
调色染料优选以0.0001至0.5重量％、优选0.001至0.1重量％的范围存在于组合物中。取决于调色染料的性质，存在取决于调色染料的效力的优选范围，所述调色染料的效力取决于类别和任何特定类别内的具体效力。如上所述，调色染料是蓝色或紫色调色染料。
可以使用调色染料的混合物。
调色染料最优选是与烷氧基化聚乙烯亚胺共价连接的活性蓝蒽醌染料。烷氧基化优选选自乙氧基化和丙氧基化，最优选丙氧基化。优选地，通过丙氧基化将聚乙烯亚胺中80至95摩尔％的N-H基团替换为异丙醇基团。优选地，在与染料反应和丙氧基化之前，聚乙烯亚胺的分子量为600至1800。
共价连接到丙氧基化聚乙烯亚胺的优选活性蒽醌的实例结构是：
优选的活性蒽醌染料是：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，反应性蓝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和活性蓝172。
染料根据颜色指数(Society of Dyers and Colourists/American Associationof Textile Chemists and Colorists)分类列出。
酶
一种或多种酶优选存在于本发明的洗衣组合物以及在实施本发明的方法时存在。
优选地，本发明的洗衣组合物中每种酶的水平为0.0001重量％至0.1重量％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、果胶酸裂解酶和甘露聚糖酶，或其混合物。
合适的脂肪酶包括具有细菌或真菌来源的那些。包括化学修饰的或蛋白质工程化的突变体。有用的脂肪酶的实例包括来自以下的脂肪酶：腐质霉(Humicola)(同义词嗜热真菌(Thermomyces))，例如来自EP 258 068和EP 305 216中所述的H.lanuginosa(T.lanuginosus)或来自WO 96/13580中所述的H.insolens；假单胞菌脂肪酶，例如来自产碱假单胞菌(P.alcaligenes)或假产碱假单胞菌(P.pseudoalcaligenes)(EP 218 272)、洋葱假单胞菌(P.cepacia)(EP 331 376)、施氏假单胞菌(P.stutzeri)(GB 1,372,034)、荧光假单胞菌(P.fluorescens)，假单胞菌菌株SD 705(WO 95/06720和WO 96/27002)、P.wisconsinensis(WO 96/12012)；芽孢杆菌脂肪酶，例如来自枯草芽孢杆菌(B.subtilis)(Dartois等(1993),Biochemica et Biophysica Acta,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)。
其他实例是脂肪酶变体，例如在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中描述的那些。
优选的可商购脂肪酶包括LipolaseTM和Lipolase UltraTM、LipexTM和LipocleanTM(Novozymes A/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的磷脂酶存在下进行。如在本文中所使用的，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，由在外部(sn-1)和中间(sn-2)位置被两个脂肪酸酯化，并在第三位置被磷酸酯化的甘油组成；磷酸反过来可以被酯化成氨基醇。磷脂酶是参与磷脂水解的酶。可以区分磷脂酶活性的多种类型，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；和溶血磷脂酶(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。
合适的蛋白酶包括动物、植物或微生物来源的那些。微生物来源是优选的。包括化学修饰的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，优选地是碱性微生物蛋白酶或胰蛋白酶样蛋白酶。优选的可商购蛋白酶包括AlcalaseTM、SavinaseTM、PrimaseTM、DuralaseTM、DyrazymTM、EsperaseTM、EverlaseTM、PolarzymeTM和KannaseTM(Novozymes A/S)、MaxataseTM、MaxacalTM、MaxapemTM、ProperaseTM、PurafectTM、Purafect OxPTM、FN2TM和FN3TM(Genencor International Inc.)。
本发明的方法可以在分类为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，特别是细菌、真菌或酵母来源。
合适的淀粉酶(α和/或β)包括具有细菌或真菌来源的那些。包括化学修饰的或蛋白质工程化的突变体。淀粉酶包括例如获自芽孢杆菌，如在GB 1,296,839中更详细描述的地衣芽孢杆菌的特殊菌株，或在WO 95/026397或WO 00/060060中公开的芽孢杆菌菌株的α-淀粉酶。可商购的淀粉酶是DuramylTM、TermamylTM、Termamyl UltraTM、NatalaseTM、StainzymeTM、FungamylTM和BANTM(Novozymes A/S)、RapidaseTM和PurastarTM(来自GenencorInternational Inc.)。
合适的纤维素酶包括具有细菌或真菌来源的那些。包括化学修饰的或蛋白质工程化的突变体。合适的纤维素酶包括来自以下的纤维素酶：芽孢杆菌属、假单胞菌属、腐质霉属、镰刀菌属、梭孢壳属、支顶孢属，例如从公开于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的特异腐质霉、太瑞斯梭孢壳霉、嗜热毁丝霉和尖孢镰刀菌产生的真菌纤维素酶。可商购的纤维素酶包括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。
合适的过氧化物酶/氧化酶包括具有植物、细菌或真菌来源的那些。包括化学修饰的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。可商购的过氧化物酶包括GuardzymeTM和NovozymTM 51004(Novozymes A/S)
另外的适用的酶在WO2009/087524、WO2009/090576、WO2009/107091、WO2009/111258和WO2009/148983中讨论。
酶稳定剂
存在于组合物中的任何酶可以使用常规的稳定剂稳定化，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，例如芳族硼酸酯，或苯基硼酸衍生物，如4-甲酰基苯基硼酸，以及可以如例如WO 92/19709和WO 92/19708中所述配制的组合物。
当烷基足够长以形成支链或环状链时，烷基包括支链、环状和直链烷基链。烷基优选是直链或支链的，更优选直链的。
除非另有规定，如本文中所用不定冠词“一个/种(a或an)”及其对应的定冠词“所述/该(the)”指的是至少一个/种，或一个/种或多个/种。
试验
实施例1：合成
将1.25摩尔间苯二酚在氮气下，在500ml三颈圆底烧瓶中，与6.88mmol对甲苯磺酸一起加热至393K。在393K下，在1.5小时内逐滴加入所需摩尔数的苯乙烯，然后将反应混合物在403K下搅拌6小时。冷却产生固体，GC-MS分析显示其为苯乙烯化间苯二酚。将该材料置于清洁且干燥的高压釜中，然后在搅拌下加入甲醇钠甲醇溶液，并用氮气吹扫高压釜。在施加完全真空之前进行压力测试，并将反应混合物加热至373K 2小时以除去甲醇。用氮气补偿真空，然后将反应混合物加热至433K。在该温度下，加入安全量的环氧乙烷(EO)并观察压力直至反应开始(压力降低)。在接下来的7至20小时内，在433K(4-5巴)下加入其余环氧乙烷并继续搅拌1-2小时以完成反应。然后将反应混合物冷却至373K并施加真空30分钟以除去残留环氧乙烷。之后，用氮气补偿真空，将反应混合物冷却至353K并装入烧瓶中。
实施例2：再沉积益处
制备具有以下配方的水性液体洗衣洗涤剂：
| 成分 | 重量％ |
| 单丙二醇 | 2.2 |
| 三乙胺 | 1.5 |
| 具有7摩尔环氧乙烷的C<sub>12</sub>-C<sub>15</sub>醇乙氧基化物 | 1.2 |
| 直链烷基苯磺酸盐 | 4.6 |
| 具有1摩尔环氧乙烷的月桂基聚醚硫酸酯钠 | 5.8 |
| 柠檬酸 | 2.0 |
| CaCl<sub>2</sub>二水合物 | 0.2 |
| NaCl | 0.2 |
| Tinopal CBS-X(荧光剂BASF) | 0.3 |
| 氢氧化钠 | 至pH＝8.4 |
| ASR分散剂 | 参见文本 |
| 水 | 余量 |
该制剂用于在设定为200rpm的测试仪(tergotometer)中洗涤八块5×5cm针织棉布片。在20℃下在800ml的26°法国硬度的水中进行一小时洗涤，具有2.3g/L的该制剂。为了模拟可能再沉积的污垢，将0.04g/L的100％压缩炭黑(来自Alfa Aesur)加入洗涤液中。为了模拟油性皮脂污垢，将7.2g的SBL2004污垢条带(来自Warwick Equest)加入洗涤液中。
一旦洗涤完成，将棉监视物在400ml清水中漂洗一次，取出干燥并在反射计上测量颜色，并表示为CIE L*a*b*值。清洁抗再沉积益处表示为ΔL值：
ΔL＝L(分散剂)-L(对照)
ΔL值越大，对炭黑污垢沉积的阻止越多。计算基于8个独立棉监视物的95％置信限。在添加和不添加8.7重量％ASR分散剂的情况下制备制剂：
结果如下所示。
| n | ΔL | 95％ |
| 单苯乙烯基间苯二酚，n＝8 | 2.8 | 0.4 |
| 二苯乙烯基间苯二酚，n＝8 | 5.9 | 0.5 |
| 二苯乙烯基间苯二酚，n＝17 | 3.5 | 0.5 |
| 二苯乙烯基间苯二酚，n＝28 | 1.8 | 0.6 |
分散剂阻止炭黑污垢沉积至棉布。
Claims (12)
1.一种洗衣洗涤剂组合物，其包含：
(i)0.5至20重量％的具有以下结构的烷氧基化取代间苯二酚分散剂：
其中，
X独立地选自：乙氧基、以及乙氧基和丙氧基的混合物，其中乙氧基的数量大于丙氧基的数量，并且其中a+b＝n且n为5至40；
R2和R3独立地选自：H；C1-C3直链或支链烷基芳基和芳基；其中R2和R3中的至少一个选自C1-C3直链或支链烷基芳基和芳基；
T为H；
(ii)0至50重量％的除所述烷氧基化取代间苯二酚分散剂以外的表面活性剂；
(iii)选自以下的一种或多种的活性物质：0.001至3重量％的香料、0.0001至0.5重量％的荧光剂和/或0.0001重量％至0.1重量％的调色染料；
其中所述组合物包含0.001至3重量％范围内的香料。
2.根据权利要求1所述的洗衣洗涤剂组合物，其中R2和R3选自：H、-CH(CH3)Ph和枯基。
3.根据权利要求1所述的洗衣洗涤剂组合物，其中R2和R3是-CH(CH3)Ph，并且R2和R3两者分别在-O-[X]a-T和-O-[X]b-T基团的邻位。
4.根据权利要求1、2或3所述的洗衣洗涤剂组合物，其中X是乙氧基。
5.根据权利要求1-3中任一项所述的洗衣洗涤剂组合物，其中n为6至34。
6.根据权利要求1-3中任一项所述的洗衣洗涤剂组合物，其中除所述烷氧基化取代间苯二酚分散剂以外的所述表面活性剂选自：阴离子和非离子表面活性剂，并且表面活性剂的含量为4至40重量％。
7.根据权利要求6所述的洗衣洗涤剂组合物，其中非离子表面活性剂/阴离子表面活性剂的重量分数为0至0.3。
8.根据权利要求7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、烷基硫酸盐和烷基醚硫酸盐，及其混合物。
9.根据权利要求1-3中任一项所述的洗衣洗涤剂组合物，其中所述烷氧基化取代间苯二酚分散剂的含量为1至10重量％。
10.根据权利要求1-3中任一项所述的洗衣洗涤剂组合物，其中n选自：6、7、8、9、10、11、12、13、14、15、16、17、18、19和20。
11.一种处理纺织品的家用方法，所述方法包括以下步骤：
(i)用烷氧基化取代间苯二酚分散剂的水溶液处理纺织品，所述水溶液包含10ppm至5000ppm的权利要求1-10中任一项所定义的烷氧基化取代间苯二酚分散剂；和0至6g/L的除所述烷氧基化取代间苯二酚分散剂以外的表面活性剂；和选自0.1ppm至100ppm的香料、1ppb至5ppm的荧光剂和1ppb至1ppm的调色染料的活性物质，
(ii)任选地漂洗和干燥所述纺织品。
12.根据权利要求11所述的处理纺织品的家用方法，其中所述方法中所述水溶液中的所述香料的含量为1至10ppm。
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2017
- 2017-09-27 EP EP17777871.9A patent/EP3529342B1/en active Active
- 2017-09-27 CN CN201780064275.3A patent/CN109844083B/zh active Active
- 2017-09-27 BR BR112019007851-7A patent/BR112019007851B1/pt active IP Right Grant
- 2017-09-27 WO PCT/EP2017/074562 patent/WO2018072979A1/en unknown
- 2017-10-17 AR ARP170102879A patent/AR109959A1/es active IP Right Grant
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2019
- 2019-04-17 ZA ZA2019/02463A patent/ZA201902463B/en unknown
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| WO2016041679A1 (en) * | 2014-09-18 | 2016-03-24 | Unilever Plc | Whitening composition |
| EP3208293A1 (en) * | 2016-02-17 | 2017-08-23 | Clariant International Ltd | Alkoxylated phenol derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3529342B1 (en) | 2020-03-18 |
| ZA201902463B (en) | 2020-08-26 |
| EP3529342A1 (en) | 2019-08-28 |
| BR112019007851B1 (pt) | 2022-10-18 |
| WO2018072979A1 (en) | 2018-04-26 |
| AR109959A1 (es) | 2019-02-06 |
| CN109844083A (zh) | 2019-06-04 |
| BR112019007851A2 (pt) | 2019-07-16 |
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