CN107810260B - 洗衣洗涤剂组合物 - Google Patents
洗衣洗涤剂组合物 Download PDFInfo
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- CN107810260B CN107810260B CN201680036564.8A CN201680036564A CN107810260B CN 107810260 B CN107810260 B CN 107810260B CN 201680036564 A CN201680036564 A CN 201680036564A CN 107810260 B CN107810260 B CN 107810260B
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- Prior art keywords
- laundry detergent
- detergent composition
- composition according
- alkoxylated polyarylphenol
- polyarylphenol
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- 239000004367 Lipase Substances 0.000 claims abstract description 30
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- 239000004365 Protease Substances 0.000 claims abstract description 22
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
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- 239000004753 textile Substances 0.000 claims abstract description 6
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- 235000016788 valerian Nutrition 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- 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
- C11D3/16—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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
-
- 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
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
-
- 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
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- C11D2111/12—
Abstract
一种洗衣洗涤剂组合物，其包含：(i)4至50重量％的除烷氧基化多芳基苯酚以外的阴离子带电表面活性剂；(ii)0.5至20重量％的具有平均5至70个烷氧基的烷氧基化多芳基苯酚；(iii)0.0005至0.5重量％的脂肪酶；和(iv)0.0005至0.2重量％的蛋白酶。一种处理纺织品的家用方法，所述方法包括以下步骤：用所述洗衣洗涤剂组合物的0.5至20g/L的水性溶液处理纺织品。
Description
技术领域
本发明涉及烷氧基化多芳基苯酚与包含脂肪酶和蛋白酶的酶混合物在洗涤剂制剂中的用途。
背景技术
脂肪酶被用于家用洗涤剂制剂中以除去基于脂肪的污渍。
蛋白酶被用于洗衣洗涤剂制剂中以从织物除去含蛋白质的污渍。
在家庭洗衣中发现的许多污渍含有蛋白质和脂肪二者。
包含蛋白酶和脂肪酶的酶混合物被用于家用洗衣洗涤剂制剂。
需要改善蛋白酶与脂肪酶的酶混合物在家用洗衣洗涤剂制剂中的性能。
WO 98/45396公开了清洁组合物，其包含：(a)约1至约60重量％的基本上由以下组成的表面活性剂组分：(i)脂肪烷基醚硫酸盐；(ii)直链醇乙氧基化物；和(iii)非离子糖表面活性剂，其具有在约0.5-1.0:1.5-2.5:0.5-1.5的范围内的(i):(ii):(iii)的重量比；和(b)约0.1至约10重量％的选自蛋白酶、淀粉酶、脂肪酶、纤维素酶、过氧化物酶及其混合物的酶组分。
GB 2007692公开了可用于去污的抗染垢和抗再沉积组合物。
发明内容
我们已经发现脂肪酶-蛋白酶的酶混合物与烷氧基化多芳基苯酚分散剂的组合给出增强的清洁。
在一个方面，本发明提供洗衣洗涤剂组合物，其包含：
(i)4至50重量％的阴离子带电表面活性剂，优选地，带电表面活性剂的水平为6至30重量％，最优选8至20重量％；
(ii)0.5至20重量％，优选2至14重量％，最优选2.5至8重量％的具有5至70个烷氧基，最优选10至30个烷氧基的烷氧基化多芳基苯酚分散剂；
(iii)0.0005至0.5重量％，优选0.01至0.2重量％的脂肪酶；和(iv)0.0005至0.2重量％，优选0.002至0.02重量％的蛋白酶。
在本发明的上下文中，烷氧基化多芳基苯酚不被认为是表面活性剂，并且在数量上不构成本文所定义的表面活性剂的部分。
所有的酶水平都是指纯蛋白质。
在另一个方面，本发明提供处理纺织品的家用方法，所述方法包括以下步骤：用本文限定的洗衣洗涤剂组合物的0.5至20g/L的水性溶液处理纺织品。
所述家用方法优选地在283至313K的温度下进行。
具体实施方式
烷氧基化多芳基苯酚分散剂
烷氧基化多芳基苯酚分散剂是芳基与其共价连接的苯酚，并且该分子优选被乙氧基烷氧基化。烷氧基化多芳基苯酚可以带电荷或不带电荷，优选带负电荷或不带电荷，最优选不带电荷(中性的)。
优选地，烷氧基化多芳基苯酚是烷氧基化三苯乙烯基苯酚。
烷氧基化多芳基苯酚含有平均5至70个烷氧基，优选10至30个烷氧基。优选地，烷氧基化是乙氧基化。
优选地，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。烷氧基化物可以被带电荷的基团(如磷酸酯或硫酸酯)封端。优选地，烷氧基化物被氢原子封端。
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，最优选是苯乙烯基。
最优选地，烷氧基化多芳基苯酚是具有以下结构的聚乙二醇单(2,4,6-三(1-苯基乙基)苯基)醚(CAS-No：70559-25-0)：
其中n选自5至70，优选地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，最优选地n选自：10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30。
标示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，例如以商品名Soprophor从Rhodia获得、以商品名Emulsogen从Clariant获得、以商品名Blaunon从Aoki Oil Industrial Co获得、以商品名Makon从Stepan获得和以商品名Sorpol从TOHO Chemical Industry Co获得。
在本发明的上下文中，烷氧基化多芳基苯酚不被认为是表面活性剂，并且在数量上不构成本文所定义的表面活性剂的部分。
脂肪酶
清洁性脂肪酶在Jan H.Van Ee，Onno Misset和Erik J.Baas编辑的Enzymes inDetergency(1997Marcel Dekker，New York)中论述。
清洁性脂肪酶优选在7至11范围内的碱性pH下具有活性，最优选它们在8至10.5的pH范围内具有最大活性。
脂肪酶可以选自E.C.类别3.1或3.2或其组合的脂肪酶。
优选地，清洁性脂肪酶选择为三酰基甘油脂肪酶(E.C.3.1.1.3)。
适合的三酰基甘油脂肪酶可以选自绵毛状腐质霉(Humicola lanuginosa)(疏棉状嗜热丝孢菌(Thermomyces lanuginosus))脂肪酶的变体。其它适合的三酰基甘油脂肪酶可以选自假单胞菌脂肪酶的变体，例如来自产碱假单胞菌(P.alcaligenes)或假产碱假单胞菌(P.pseudoalcaligenes)(EP218272)、洋葱假单胞菌(P.cepacia)(EP331376)、施氏假单胞菌(P.stutzeri)(GB1,372,034)、荧光假单胞菌(P.fluorescens)、假单胞菌菌株SD705(WO95/06720和WO96/27002)、威州假单胞菌(P.wisconsinensis)(WO96/12012)；芽孢杆菌脂肪酶的变体，例如来自枯草芽孢杆菌(B.subtilis)(Dartois等(1993)，Biochemica etBiophysica Acta，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)。
EC 3.1.1.3脂肪酶的另外的实例包括WIPO公布WO00/60063，WO99/42566，WO02/062973，WO97/04078，WO97/04079和US5,869,438中描述的那些。优选的脂肪酶由反射犁头霉(Absidia reflexa)，伞枝犁头霉(Absidia corymbefera)，米赫根毛霉(Rhizmucormiehei)，Rhizopus deleman，黑曲霉，塔宾曲霉(Aspergillus tubigensis)，尖孢镰刀菌(
oxysporum)，异孢镰刀菌(Fusarium heterosporum)，米曲霉(Aspergillusoryzea)，卡门柏青霉(Penicilium camembertii)，臭曲霉(Aspergillus foetidus)，黑曲霉，疏棉状嗜热丝孢菌(Thermomyces lanoginosus)(同义词：绵毛状腐质霉(Humicolalanuginosa))和Landerina penisapora产生，特别是疏棉状嗜热丝孢菌。某些优选的脂肪酶由Novozymes以商品名
Lipolase
和
(Novozymes的注册商标)提供；以及LIPASE P
可获自ArearioPharmaceutical Co.Ltd.，名古屋，日本；AMANO-
可商购自Toyo Jozo Co.，Tagata，日本；和另外的粘质色杆菌(Chromobacter viscosum)脂肪酶，来自AmershamPharmacia Biotech.，Piscataway，新泽西，美国，和Diosynth Co.，荷兰；和其它脂肪酶，例如唐菖蒲假单胞菌(Pseudomonas gladioli)。另外的有用脂肪酶描述于WIPO公布WO02062973，WO2004/101759，WO2004/101760和WO2004/101763中。在一个实施方式中，适合的脂肪酶包括WO00/60063和美国专利6,939,702B1中描述的“第一循环脂肪酶(firstcycle lipase)”，优选SEQ ID No.2的变体，更优选与SEQ ID No.2具有至少90％同源性的SEQ ID No.2的变体，其包含在位置3、224、229、231和233中的任一处电中性的或带负电荷的氨基酸被R或K的置换，最优选包含T231R和N233R突变的变体，这样的最优选的变体以商品名
(Novozymes)销售。
上述脂肪酶可以组合使用(可以使用脂肪酶的任何混合物)。适合的脂肪酶可购自Novozymes，Bagsvaerd，丹麦；Areario Pharmaceutical Co.Ltd.，名古屋，日本；Toyo JozoCo.，Tagata，日本；Amersham Pharmacia Biotech.，Piscataway，新泽西，美国；DiosynthCo.，Oss，荷兰；和/或根据本文包括的实施例制备。
如WO2007/087243中所述，具有降低的气味产生潜力和良好的相对性能的脂肪酶是特别优选的。这些包括
(Novozyme)。
蛋白酶
蛋白酶水解肽和蛋白质内的键，在洗衣环境中，这导致增强对含有蛋白质或肽的污渍的去除。适合的蛋白酶家族的实例包括天冬氨酸蛋白酶，半胱氨酸蛋白酶，谷氨酸蛋白酶，天冬酰胺(aspargine)肽裂解酶，丝氨酸蛋白酶和苏氨酸蛋白酶。这些蛋白酶家族在MEROPS肽酶数据库(http://merops.sanger.ac.uk/)中描述。丝氨酸蛋白酶是优选的。枯草杆菌酶(Subtilase)型丝氨酸蛋白酶是更优选的。术语“枯草杆菌酶”是指根据Siezen等，Protein Engng.4(1991)719-737和Siezen等，Protein Science 6(1997)501-523所述的丝氨酸蛋白酶的亚组。丝氨酸蛋白酶是特征在于在活性位点具有丝氨酸的蛋白酶亚组，该丝氨酸与底物形成共价加合物。枯草杆菌酶可以分为6个亚分类，即枯草杆菌蛋白酶(Subtilisin)家族，嗜热蛋白酶(Thermitase)家族，蛋白酶K家族，羊毛硫氨酸抗生素(Lantibiotic)肽酶家族，Kexin家族和Pyrolysin家族。
枯草杆菌酶的实例是源自芽孢杆菌例如在US7262042和WO09/021867中描述的迟缓芽孢杆菌，嗜碱芽孢杆菌，枯草芽孢杆菌，解淀粉芽孢杆菌，短小芽孢杆菌和吉氏芽孢杆菌的那些，以及在WO89/06279中描述的迟缓枯草杆菌蛋白酶(subtilisin lentus)，枯草杆菌蛋白酶Novo，枯草杆菌蛋白酶Carlsberg，地衣芽孢杆菌，枯草杆菌蛋白酶BPN’，枯草杆菌蛋白酶309，枯草杆菌蛋白酶147和枯草杆菌蛋白酶168，以及在WO93/18140中描述的蛋白酶PD138。其它有用的蛋白酶可以是WO92/175177，WO01/016285，WO02/026024和WO02/016547中描述的那些。胰蛋白酶样蛋白酶的实例是WO89/06270，WO94/25583和WO05/040372中描述的胰蛋白酶(例如，猪或牛来源的)和镰刀菌蛋白酶，以及在WO05/052161和WO05/052146中描述的源自纤维单胞菌属(Cellumonas)的糜蛋白酶。
有用的蛋白酶的另一些实例是在WO92/19729，WO96/034946，WO98/20115，WO98/20116，WO99/011768，WO01/44452，WO03/006602，WO04/03186，WO04/041979，WO07/006305，WO11/036263，WO11/036264中描述的变体，特别是具有在使用BNP’编号的以下位置的一个或多个中的置换的变体：3，4，9，15，27，36，57，68，76，87，95，96，97，98，99，100，101，102，103，104，106，118，120，123，128，129，130，160，167，170，194，195，199，205，206，217，218，222，224，232，235，236，245，248，252和274。更优选的枯草杆菌酶变体可以包含以下突变：S3T,V4I,S9R,A15T,K27R,*36D,V68A,N76D,N87S,R,*97E,A98S,S99G,D,A,S99AD,S101G,M,RS103A,V104I,Y,N,S106A,G118V,R,H120D,N,N123S,S128L,P129Q,S130A,G160D,Y167A,R170S,A194P,G195E,V199M,V205I,L217D,N218D,M222S,A232V,K235L,Q236H,Q245R,N252K,T274A(使用BNP’编号)。
最优选地，蛋白酶是枯草杆菌蛋白酶(EC 3.4.21.62)。
枯草杆菌酶的实例是源自芽孢杆菌例如在US7262042和WO09/021867中描述的迟缓芽孢杆菌，嗜碱芽孢杆菌，枯草芽孢杆菌，解淀粉芽孢杆菌，短小芽孢杆菌和吉氏芽孢杆菌的那些，以及在WO89/06279中描述的迟缓枯草杆菌蛋白酶，枯草杆菌蛋白酶Novo，枯草杆菌蛋白酶Carlsberg，地衣芽孢杆菌，枯草杆菌蛋白酶BPN’，枯草杆菌蛋白酶309，枯草杆菌蛋白酶147和枯草杆菌蛋白酶168，以及在WO93/18140中描述的蛋白酶PD138。优选地，枯草杆菌蛋白酶源自芽孢杆菌，优选迟缓芽孢杆菌，嗜碱芽孢杆菌，枯草芽孢杆菌，解淀粉芽孢杆菌，短小芽孢杆菌和吉氏芽孢杆菌，如US 6,312,936B1，US 5,679,630，US 4,760,025，US7,262,042和WO09/021867中所述。最优选地，枯草杆菌蛋白酶源自吉氏芽孢杆菌或迟缓芽孢杆菌。
适合的可商购蛋白酶包括以商品名
DuralaseTM，DurazymTM，
和
销售的那些，所有都可作为
或
(Novozymes A/S)销售。
由Genencor International以商品名
和Purafect
销售的那些。
以商品名
Purafect
PreferenzTM，Purafect
Purafect
Purafect
EffectenzTM，
和
(Danisco/DuPont)，AxapemTM(Gist-Brocases N.V.)销售的那些。
可获自Henkel/Kemira的那些，即BLAP(在US 5,352,604附图29中示出的序列，具有以下突变：S99D+S101R+S103A+V104I+G159S；在下文中称为BLAP)，BLAP R(具有S3T+V4I+V199M+V205I+L217D的BLAP)，BLAP X(具有S3T+V4I+V205I的BLAP)和BLAP F49(具有S3T+V4I+A194P+V199M+V205I+L217D的BLAP)，所有都来自Henkel/Kemira；以及KAP(具有A230V+S256G+S259N突变的嗜碱芽孢杆菌枯草杆菌蛋白酶)，来自Kao。
还可以使用金属蛋白酶，最优选锌基蛋白酶。
表面活性剂
洗衣组合物包含阴离子带电表面活性剂(其包括阴离子带电表面活性剂的混合物)。组合物包含4至50重量％，优选6至30重量％，更优选8至20重量％的阴离子表面活性剂。
制剂可以含有非离子表面活性剂，优选地，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0.1。
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。
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；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)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。
在液体制剂中，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。
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。优选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。
最优选地，非离子洗涤剂化合物是烷基乙氧基化非离子表面活性剂，其是具有7EO至9EO单元的平均乙氧基化的C8至C18伯醇。
优选地，所使用的表面活性剂是饱和的。
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，其中沸石是其众所周知的代表，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P型沸石。
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，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，优选为钠。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而容易地制备，如文献中充分描述的。表面活性剂与铝硅酸盐(当存在时)的比率优选大于5:2，更优选大于3:1。
可选地或在铝硅酸盐助洗剂之外，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)。
最优选地，洗衣洗涤剂制剂是非磷酸盐协助的粉末洗衣洗涤剂制剂，即含有小于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协助的。粉末在使用中应优选给出9.5-11的pH。优选地，粉末洗衣洗涤剂具有大于存在的总阴离子表面活性剂的80重量％的直链烷基苯磺酸盐。
在水性的液体洗衣洗涤剂中，优选的是单丙二醇以1至30重量％，优选2至18重量％的水平存在，以对制剂提供适宜的、可倾倒的粘度。
荧光剂
组合物优选包含荧光剂(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，例如钠盐的形式提供和使用。
组合物中使用的一种或多种荧光剂的总量通常为0.0001至0.5重量％，优选0.005至2重量％，更优选0.05至0.25重量％。
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CAS-No 3426-43-5；CAS-No 35632-99-6；CAS-No 24565-13-7；CAS-No 12224-16-7；CAS-No 13863-31-5；CAS-No 4193-55-9；CAS-No 16090-02-1；CAS-No133-66-4；CAS-No68444-86-0；CAS-No 27344-41-8的荧光剂。
最优选的荧光剂是：2-(4-苯乙烯基-3-磺基苯基)-2H-萘并(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}芪-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}芪-2-2'-二磺酸二钠以及4,4'-双(2-磺基苯乙烯基)联苯二钠。
方法中使用的水性溶液具有荧光剂存在。荧光剂存在于方法中使用的水性溶液中，优选以0.0001g/L至0.1g/L，更优选0.001至0.02g/L的范围存在。
香料
组合物优选包含香料。在由CFTA Publications出版的CTFA(Cosmetic，Toiletryand Fragrance Association)1992International Buyers Guide和由SchnellPublishing Co.出版的OPD 1993Chemicals Buyers Directory 80th Annual Edition中提供了香料的许多适合实例。
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(fenchyl acetate)、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(hydratropicalcohol)、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(menthylacetphenone)、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(methylbenyl acetate)、甲基丁香酚、甲基庚烯酮、甲基庚炔碳酸酯(methyl heptinecarbonate)、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(rose oxide)、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。
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
组合物可包含一种或多种另外的聚合物。实例为羧甲基纤维素、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。
在烷基足够长以形成支链或环状链的情况下，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，最优选是直链的。
除非另有规定，否则本文所用不定冠词“一个/种(‘a’或‘an’)”及其相应的定冠词“所述/该(the)”是指至少一个/种，或一个/种或多个/种。
除非另有说明，否则染料重量是指钠盐或氯化物盐。
实验实施例
制备具有以下配方的粉末洗衣洗涤剂：
该制剂用于在设定为200rpm的洗涤测试仪(Tergotometer)中洗涤8个5×5cm的EMPA 117污渍监测物(聚酯棉上的血液/牛奶/油墨污渍)。用1.5g/L制剂在35℃下在800ml26°法国硬度水中进行60分钟洗涤。为了模拟油性污垢，将7.4g的SBL2004污垢条(来自Warwick Equest)加入洗涤液。
一旦洗涤已经完成，将棉监测物在400ml清水中漂洗一次，取出干燥，在反射计上测量颜色并表示为CIE L*a*b*值。
污渍去除计算为ΔL*值：
ΔL*＝L*(处理)-L*(不存在酶或烷氧基化多芳基苯酚的对照)
更高的ΔL*值等同于更好的清洁。
测试了等同但加入13.3重量％的烷氧基化多芳基苯酚(其是聚乙二醇单(2,4,6-三(1-苯基乙基)苯基)醚(CAS-No：70559-25-0)，具有平均16和54个环氧乙烷基团)的制剂。
在加入和不加入脂肪酶-蛋白酶酶混合物：
作为脂肪酶且
作为蛋白酶(均来自Novozymes)的情况下重复实验。加入脂肪酶以对于制剂给予0.3重量％的纯活性蛋白，并且加入蛋白酶以对于制剂给予0.007重量％的纯活性蛋白。
还从8个监测物的测量值的标准偏差计算以给出95％置信限。
酶混合物和烷氧基化多芳基苯酚的组合增加污渍去除，如更大的ΔL*值所示。对于16EO烷氧基化多芳基苯酚，与酶混合物的组合比从单一组分的效果的组合预期的更多地增加污渍去除。对于组合，会预期ΔL*＝4.06+1.19＝5.25，但却获得10.25。
加入淀粉酶、甘露聚糖酶和果胶酶(
Novozyme，
Novozymes，
Novozymes)的混合物，再制备制剂。
Claims (13)
1.一种洗衣洗涤剂组合物，其包含：
(i)4至50重量％的除烷氧基化多芳基苯酚以外的阴离子带电表面活性剂；
(ii)0.5至20重量％的具有平均5至70个烷氧基的烷氧基化多芳基苯酚；
(iii)0.0005至0.5重量％的脂肪酶；和
(iv)0.0005至0.2重量％的蛋白酶，
其中所述烷氧基化多芳基苯酚分散剂是：
2.根据权利要求1所述的洗衣洗涤剂组合物，其中所述脂肪酶选自三酰基甘油脂肪酶(E.C.3.1.1.3)。
3.根据权利要求1或2所述的洗衣洗涤剂组合物，其中所述蛋白酶是枯草杆菌蛋白酶型丝氨酸蛋白酶(EC 3.4.21.62)。
4.根据权利要求1或2所述的洗衣洗涤剂组合物，其中所述烷氧基化多芳基苯酚具有10至30个烷氧基。
5.根据权利要求1或2所述的洗衣洗涤剂组合物，其中所述组合物是非磷酸盐协助的粉末洗衣洗涤剂制剂。
6.根据权利要求1或2所述的洗衣洗涤剂组合物，其中所述烷氧基化多芳基苯酚以2至14重量％的水平存在，所述脂肪酶以0.05至0.25重量％的水平存在，且所述蛋白酶以0.002至0.02重量％的水平存在。
7.根据权利要求1或2所述的洗衣洗涤剂组合物，其中所述阴离子带电表面活性剂选自：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。
8.根据权利要求1或2所述的洗衣洗涤剂组合物，其中阴离子表面活性剂的水平为8至20重量％。
9.根据权利要求1或2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0.1。
10.根据权利要求1或2所述的洗衣洗涤剂组合物，其中所述烷氧基化多芳基苯酚不带电荷。
11.根据权利要求1或2所述的洗衣洗涤剂组合物，其中所述烷氧基化多芳基苯酚具有由氢原子封端的烷氧基化物。
12.根据权利要求1或2所述的洗衣洗涤剂组合物，其中所述烷氧基化多芳基苯酚是乙氧基化多芳基苯酚。
13.一种处理纺织品的家用方法，所述方法包括以下步骤：用根据前述权利要求中任一项所述的洗衣洗涤剂组合物的0.5至20g/L的水性溶液处理纺织品。
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| EP15174012.3 | 2015-06-26 | ||
| EP15174012 | 2015-06-26 | ||
| PCT/EP2016/059424 WO2016206837A1 (en) | 2015-06-26 | 2016-04-27 | Laundry detergent composition |
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| CN107810260B true CN107810260B (zh) | 2020-07-17 |
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| EP (1) | EP3313966B1 (zh) |
| CN (1) | CN107810260B (zh) |
| AR (1) | AR105100A1 (zh) |
| BR (1) | BR112017027402B1 (zh) |
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| BR112021025430A2 (pt) * | 2019-06-28 | 2022-02-01 | Unilever Ip Holdings B V | Composição de tensoativos, composição detergente para uso de cuidado doméstico e pessoal e método doméstico para tratar um tecido |
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Also Published As
| Publication number | Publication date |
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| EP3313966A1 (en) | 2018-05-02 |
| CN107810260A (zh) | 2018-03-16 |
| WO2016206837A1 (en) | 2016-12-29 |
| ZA201707559B (en) | 2019-06-26 |
| EP3313966B1 (en) | 2020-07-29 |
| AR105100A1 (es) | 2017-09-06 |
| BR112017027402B1 (pt) | 2022-05-10 |
| BR112017027402A2 (pt) | 2018-08-28 |
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