CN108291175A - 洗衣洗涤剂组合物 - Google Patents
洗衣洗涤剂组合物 Download PDFInfo
- Publication number
- CN108291175A CN108291175A CN201680028285.7A CN201680028285A CN108291175A CN 108291175 A CN108291175 A CN 108291175A CN 201680028285 A CN201680028285 A CN 201680028285A CN 108291175 A CN108291175 A CN 108291175A
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- Prior art keywords
- laundry detergent
- detergent composition
- weight
- alkoxylate
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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- SXHLENDCVBIJFO-UHFFFAOYSA-M sodium;2-[2-(2-dodecoxyethoxy)ethoxy]ethyl sulfate Chemical compound [Na+].CCCCCCCCCCCCOCCOCCOCCOS([O-])(=O)=O SXHLENDCVBIJFO-UHFFFAOYSA-M 0.000 description 1
- RBYJOOWYRXEJAM-UHFFFAOYSA-M sodium;5,9-dianilino-7-phenylbenzo[a]phenazin-7-ium-4,10-disulfonate Chemical compound [Na+].C=1C=CC=CC=1[N+]1=C2C=C(NC=3C=CC=CC=3)C(S(=O)(=O)[O-])=CC2=NC(C2=CC=CC(=C22)S([O-])(=O)=O)=C1C=C2NC1=CC=CC=C1 RBYJOOWYRXEJAM-UHFFFAOYSA-M 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 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
- ZUCXUTRTSQLRCV-UHFFFAOYSA-K trisodium;1-amino-4-[3-[[4-chloro-6-(3-sulfonatoanilino)-1,3,5-triazin-2-yl]amino]-2,4,6-trimethyl-5-sulfonatoanilino]-9,10-dioxoanthracene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].CC1=C(S([O-])(=O)=O)C(C)=C(NC=2C=3C(=O)C4=CC=CC=C4C(=O)C=3C(N)=C(C=2)S([O-])(=O)=O)C(C)=C1NC(N=1)=NC(Cl)=NC=1NC1=CC=CC(S([O-])(=O)=O)=C1 ZUCXUTRTSQLRCV-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
- 241001446247 uncultured actinomycete Species 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
- 108010014498 vimelysin Proteins 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
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
- 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
- C11D1/37—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
- C11D3/16—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
- 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
-
- 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
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- 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
- C11D1/34—Derivatives of acids of phosphorus
- C11D1/345—Phosphates or phosphites
-
- 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
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/12—Soft surfaces, e.g. textile
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
本文公开了洗衣洗涤组合物,其包含:(i)5至50重量%的除烷氧基化二或三芳基苯酚分散剂以外的表面活性剂,所述表面活性剂选自:阴离子表面活性剂和非离子表面活性剂;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;(ii)0.5至20重量%的烷氧基化二或三芳基苯酚分散剂;和(iii)0.0005至0.2重量%的金属蛋白酶。本文还公开了处理纺织品的家用方法,所述方法包括以下步骤:(i)用所述洗衣洗涤剂组合物的1g/L以上的水性溶液处理纺织品;和(ii)使所述洗衣洗涤剂水性溶液与所述纺织品保持接触10分钟至2天,然后漂洗和干燥所述纺织品。
Description
技术领域
本发明提供了用于家用洗衣的酶和分散剂制剂。
背景技术
含有相对于非离子表面活性剂而言高分数(fraction)的阴离子表面活性剂的洗衣洗涤剂制剂是普遍存在的。
金属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。
WO02/36727公开了包含去污表面活性剂、金属蛋白酶和钙离子的洗涤剂组合物。
US2005/107281公开了基于烷氧基化苯乙烯基苯酚的醚羧酸、其制备及其作为表面活性添加剂的用途。
US2004/087458公开了可用于从聚酯纤维和聚酯加工设备除去低聚物沉积物的包含非离子和阴离子表面活性剂的表面活性剂共混物的组合物。该发明的组合物包含乙氧基化脱水山梨醇酯和至少一种另外的非离子或阴离子表面活性剂的表面活性剂共混物。
GB2007692公开了可用于去污的抗污化和抗再沉积组合物。
需要提高含有相对于非离子表面活性剂而言高分数的阴离子表面活性剂的洗衣制剂的去污性。
发明内容
出人意料地,金属蛋白酶与特定烷氧基化二或三芳基苯酚分散剂的组合提供增强的去污性。
在一个方面,本发明提供洗衣洗涤剂组合物,其包含:
(i)5至50重量%,优选6至30重量%,更优选8至20重量%的除烷氧基化二或三芳基苯酚分散剂以外的表面活性剂,所述表面活性剂选自阴离子表面活性剂和非离子表面活性剂,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,优选0至0.15,最优选0.05至0.12;
(ii)0.5至20重量%,优选1.5至10重量%,最优选2.5至5重量%的烷氧基化二或三芳基苯酚,
优选地,所述烷氧基化二或三芳基苯酚是不带电荷的;优选地,所述烷氧基化是乙氧基化;优选地,具有以下结构:
其中R1选自H和芳基,X选自乙氧基或丙氧基,n为6至70,T选自H、SO3 -、COO-和PO3 2-,最优选H。最优选地,R1是苯乙烯基,且n为12至20;和
(iii)0.0005至0.2重量%,优选0.002至0.02重量%的金属蛋白酶。
阴离子表面活性剂的重量%以钠盐计算。带电荷的烷氧基化二或三芳基苯酚的重量%以钠盐计算。
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:
(i)用前述权利要求中任一项所限定的洗衣洗涤剂组合物的1g/L以上的水性溶液处理纺织品;和,
(ii)使所述洗衣洗涤剂水性溶液与所述纺织品保持接触10分钟至2天,然后漂洗和干燥所述纺织品。
具体实施方式
洗涤剂形式
优选地,洗衣洗涤剂制剂是非磷酸盐协助的洗衣洗涤剂制剂,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。
最优选地,洗衣洗涤剂是水性的液体洗衣洗涤剂,优选具有7至9的pH。
蛋白酶
金属蛋白酶(E.C 3.4.24)水解肽和蛋白质内的键,在洗衣环境中,这导致对含有蛋白质或肽的污渍的去除增强。金属蛋白酶(金属肽酶或金属蛋白质酶)是一类水解酶,其通过水分子的作用切割肽键,该类蛋白酶通过与属于锌、锰、钴、镍或铜离子的组的至少一种二价金属离子(优选锌)复合而激活。
根据在MEROPS数据库(http://merops.sanger.ac.uk/cgi-bin/family_index?type=P)中实施的基于蛋白质结构和同源性的蛋白酶的分类,金属蛋白酶存在于14个不同家族中。
优选地,蛋白酶选自M4、M7或M35家族,更优选是M4金属蛋白酶,最优选是中性金属蛋白酶。
可用于本发明的金属蛋白酶包括可用于家居护理应用的那些中的任一种。这些金属蛋白酶例如源自选自解淀粉芽孢杆菌,枯草芽孢杆菌,嗜热脂肪芽孢杆菌和热蛋白水解芽孢杆菌(Bacillus thermoproteolyticus)的细菌,以及选自米曲霉和黑曲霉的真菌。
本文所用术语“M4金属蛋白酶家族”或“M4金属蛋白酶”或“M4”是指落入根据Rawlings等,Biochem.J.,290,205-218(1993)且在MEROPS-(Rawlings等,MEROPS:thepeptidase database,Nucl Acids Res,34Database issue,D270-272,2006)中进一步描述的M4金属蛋白酶家族中的多肽。M4金属蛋白酶是主要含有内肽酶的中性金属蛋白酶。该家族中的所有肽酶结合单一催化锌离子。M4金属蛋白酶家族成员包括共同的HEXXH基序,其中组氨酸残基充当锌配体,而谷氨酸是活性位点残基。M4金属蛋白酶具有主要在中性pH下的最适pH。M4金属蛋白酶家族包括例如NeutraseTM(Novozymes)(分类为MEROPS亚类M04.014),嗜热菌蛋白酶(Thermolysin),芽孢杆菌蛋白酶(Bacillolysin),弧菌蛋白酶(vibriolysin),假单胞菌蛋白酶(pseudolysin),Msp肽酶,球菌蛋白酶(coccolysin),金黄色葡萄球菌蛋白酶(aureolysin),比梅溶素(vimelysin),λ毒素中性肽酶B,PA肽酶(气单胞菌型),格里塞溶素(griselysin),硬脂溶素(stearolysin),MprIII(交替单胞菌物种菌株0-7),pap6肽酶,中性肽酶(高温放线菌型),ZmpA肽酶(伯克霍尔德氏菌物种),zpx肽酶,PrtS肽酶(发光杆菌(photohabdus luminescens)),多变溶素(protealysin),ZmpB肽酶(伯克霍尔德氏菌物种)。多肽的M4金属蛋白酶家族已被进一步表征,且根据MEROPS,目前包括至少二十二个亚类,已经对其分配不同MEROPS ID(即,式M04.xxx的标识符),以及非肽酶同源物和未分配的肽酶。
本文所用术语“嗜热菌蛋白酶样金属蛋白酶”是指(a)MEROPS亚类M04.001的M4金属蛋白酶;(b)MEROPS亚类M04.018的M4金属蛋白酶;(c)MEROPS亚类M04.021的M4金属蛋白酶;(d)具有活性裂隙基序:TG[TS][QS]DNGGVH[TI]的M4金属蛋白酶;(e)具有活性裂隙基序:DPDHSKRYTG[TS][QS]DNGGVH[TI]NSGI的M4金属蛋白酶;和(f)具有活性裂隙基序:NT[TS][QS]DNGGVH[TI]NSGI的M4金属蛋白酶。在这些基序中,使用公认的IUPAC单字母氨基酸缩写。同样在上述基序中,括号的使用表示在特定位置处的可选氨基酸选择。嗜热菌蛋白酶样金属蛋白酶描述于例如Barret等,(1998),Handbook of proteolytic enzymes,Academic Press,第350-369页。已经确定多种TLP的氨基酸序列,并且已经解析出多种TLP的三维结构。焦点一直以来在于提高TLP的热稳定性,并且大量出版物描述了芽孢杆菌TLP的热稳定性,例如Veltman等,(1998)Biochemistry 37(15):5312-9。TLP由α-螺旋C-末端结构域和主要由β-链组成的N-末端结构域组成。该结构域通过中心α-螺旋连接。该螺旋位于活性位点裂隙的底部,并且含有催化上重要的残基中的多个,例如四个底物结合袋S2、Si、Si'和S2'已经被识别(Hangauer等,(1984)Biochemistry 23:5730-5741)。
本文所用术语“M7金属蛋白酶家族”或“M7金属蛋白酶”或“M7”或“小中性蛋白酶(snapalysin)家族”是指落入根据Rawlings等,Biochem.J.,290,205-218(1993)的M7金属蛋白酶家族中且在MEROPS-(Rawlings等,MEROPS:the peptidase database,Nucl AcidsRes,34Database issue,D270-272,2006)中进一步描述的多肽。蛋白酶家族M7含有金属内肽酶,小中性蛋白酶。小中性蛋白酶在中性pH下具有活性。唯一已知的活性是切割脱脂乳的蛋白质以在生长的细菌菌落周围形成清晰的斑块。锌被HEXXHXXGXXD序列基序中的两个组氨酸和天冬氨酸结合;谷氨酸是催化残基。M7蛋白酶具有由SignalP预测程序识别的明确的信号肽。它们也都具有被切除的前肽。
本文所用术语“M35金属蛋白酶家族”或“M35金属蛋白酶”或“M35”或“deuterolysin家族”是指落入根据Proteolysis in Cell Function,第13-21页,IOSPress,Amsterdam(1997),Rawlings等,Biochem.J.,290,205-218(1993)的M35金属蛋白酶家族中且在MEROPS-(Rawlings等,MEROPS:the peptidase database,Nucl Acids Res,34Database issue,D270-272,2006)中进一步描述的多肽。M35家族成员含有HEXXH基序中的两个锌结合组氨酸和催化性谷氨酸。存在第三锌配体:Asp,其在相对于His锌配体的GTXDXXYG基序C末端中发现(参见比对)。由于这个原因,该家族中的肽酶有时被称为“aspzincins”,尽管其中锌的第三配体是Asp的肽酶也存在于家族M6、M7和M64中。
烷氧基化二或三芳基苯酚
在本发明的上下文中,烷氧基化二或三芳基苯酚分散剂不作为表面活性剂被包含。
烷氧基化二或三芳基苯酚优选是不带电荷的。优选地,烷氧基化是乙氧基化,最优选具有6至70个(CH2CH2O)单元。
优选地,其是三芳基苯酚乙氧基化物。
优选地,具有以下结构:
其中R1选自H和芳基,X选自乙氧基或丙氧基,n为6至70,T选自H、SO3 -、COO-和PO3 2-,最优选为H。最优选地,R1是苯乙烯基,且n为12至20。
最优选的结构是:
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;优选地选自12,13,14,15,16,17,18,19,20。
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)。
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盐和磺酸盐的水溶性碱金属盐,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水平优选为(i)5至50重量%带负电荷的表面活性剂,优选带负电荷的表面活性剂的水平为6至30重量%,更优选8至20重量%。
优选地,存在两种或更多种阴离子表面活性剂,优选地,直链烷基苯磺酸盐与烷基醚硫酸盐一起。
非离子表面活性剂可以存在于表面活性剂混合物中。
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。
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。
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,其中沸石是最众所周知的代表,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))对于粉末洗涤剂是优选的助洗剂。
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)。
优选地,洗衣洗涤剂制剂是非磷酸盐协助的洗衣洗涤剂制剂,即含有小于1重量%的磷酸盐。优选地,粉末洗衣洗涤剂制剂是碳酸盐协助的。
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0.005至2重量%,更优选0.01至0.1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: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。
优选的是方法中使用的水性溶液具有荧光剂存在。当荧光剂存在于方法中使用的水性溶液中时,其优选在0.0001g/L至0.1g/L,优选0.001至0.02g/L的范围内。
香料
优选地,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)1992 International Buyers Guide和由Schnell Publishing Co.出版的OPD 1993Chemicals Buyers Directory 80th Annual Edition中提供了香料的许多适合实例。
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。
香料和头香可用于提示本发明的增白益处。
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。
用于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),优选不存在于制剂中。
另外的酶
在本发明的洗衣组合物中和当实施本发明的方法时优选存在一种或多种另外的酶。
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。
另外的酶优选选自:淀粉酶、脂肪酶和纤维素酶。
存在于组合物中的任何酶都可以使用常规稳定剂稳定,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(例如芳族硼酸酯)或苯基硼酸衍生物如4-甲酰基苯基硼酸,且组合物可以如例如WO92/19709和WO92/19708中所述配制。
调色染料
调色染料(shading dye)优选以0.002至0.2重量%的水平存在于制剂中。
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是不带电荷的。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),WO06/027086(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。在WO2012/054058和WO2010/151906中讨论了烷氧基化双偶氮染料。
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特定效力。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色蒽醌染料。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:
(结构I)。
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,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。
实验
实施例1
制备具有以下配方的水性的液体洗衣洗涤剂:
成分 | 重量% |
单丙二醇 | 2 |
三乙胺 | 1.5 |
具有7摩尔环氧乙烷的C12-C15醇乙氧基化物 | 2.1 |
直链烷基苯磺酸盐 | 8.4 |
具有3摩尔环氧乙烷的月桂醇聚醚硫酸钠 | 10.5 |
柠檬酸 | 0.5 |
香料 | 0.3 |
氢氧化钠 | 至pH=8.4 |
水 | 余量 |
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2.3g/L的制剂在35℃下在800ml 26°法国硬度水中进行20分钟洗涤。为了模拟油性污垢,将12.5g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。
测试了等同但加入8.7重量%烷氧基化三芳基苯酚的制剂,所述烷氧基化三芳基苯酚是具有不同乙氧基化水平(16和54个EO)的聚乙二醇单(2,4,6-三(1-苯基乙基)苯基)醚。
向洗涤液中加入和不加入M4家族蛋白酶(分类为MEROPS亚类M04.014)(来自Novozymes)的情况下重复实验。加入酶以对于制剂给予0.0043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给出95%置信限。
将金属蛋白酶和烷氧基化芳基苯酚包含到制剂中增加了污渍去除,如通过更高的L*值所看到的。金属蛋白酶和烷氧基化三芳基苯酚分散剂的组合给出比从单独的蛋白酶和烷氧基化三芳基苯酚分散剂的效果预期的更大的L*增加。例如,对于蛋白酶,其自身使L*增加1.02个单位,因此对于16EO分散剂和蛋白酶会预期54.21+1.02=55.23的值,然而获得57.18的值。
Claims (12)
1.一种洗衣洗涤剂组合物,其包含:
(i)5至50重量%的除烷氧基化二或三芳基苯酚分散剂以外的表面活性剂,所述表面活性剂选自阴离子表面活性剂和非离子表面活性剂,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;
(ii)0.5至20重量%的烷氧基化二或三芳基苯酚分散剂;和
(iii)0.0005至0.2重量%的金属蛋白酶。
2.根据权利要求1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,且所述非离子表面活性剂选自:具有7至9个乙氧基基团的烷基醚。
3.根据权利要求1或2所述的洗衣洗涤剂组合物,其中所述金属蛋白酶是锌金属蛋白酶。
4.根据权利要求3所述的洗衣洗涤剂组合物,其中所述蛋白酶是M4,M7或M35家族。
5.根据权利要求3所述的洗衣洗涤剂组合物,其中所述蛋白酶是M4金属蛋白酶。
6.根据前述权利要求中任一项所述的洗衣洗涤剂组合物,其中所述组合物是水性的洗衣液体洗涤剂。
7.根据前述权利要求中任一项所述的洗衣洗涤剂组合物,其中烷氧基化二或三芳基苯酚分散剂是不带电荷的,且所述烷氧基化是乙氧基化。
8.根据前述权利要求中任一项所述的洗衣洗涤剂组合物,其中所述烷氧基化二或三芳基苯酚分散剂具有以下结构:
其中R1选自H和苯乙烯基,X选自乙氧基或丙氧基,n为6至70,T选自H、SO3 -、COO-和PO3 2-。
9.根据前述权利要求中任一项所述的洗衣洗涤剂组合物,其中所述阴离子表面活性剂和非离子表面活性剂以8至20重量%的范围存在。
10.根据前述权利要求中任一项所述的洗衣洗涤剂组合物,其中所述非离子表面活性剂/阴离子表面活性剂的重量分数为0.05至0.12。
11.根据前述权利要求中任一项所述的洗衣洗涤剂组合物,其中所述烷氧基化二或三芳基苯酚分散剂以1.5至10重量%的范围存在。
12.一种处理纺织品的家用方法,所述方法包括以下步骤:
(i)用前述权利要求中任一项所限定的洗衣洗涤剂组合物的1g/L以上的水性溶液处理纺织品;和
(ii)使所述洗衣洗涤剂水性溶液与所述纺织品保持接触10分钟至2天,然后漂洗和干燥所述纺织品。
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WO2012110563A1 (en) * | 2011-02-16 | 2012-08-23 | Novozymes A/S | Detergent compositions comprising metalloproteases |
WO2012110564A1 (en) * | 2011-02-16 | 2012-08-23 | Novozymes A/S | Detergent compositions comprising m7 or m35 metalloproteases |
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GB2007692A (en) * | 1977-11-02 | 1979-05-23 | Rhone Poulenc Ind | Anti-soiling and anti-redesposition compositions which can be used in detergency |
WO2002036727A1 (en) * | 2000-01-14 | 2002-05-10 | The Procter & Gamble Company | A detergent composition comprising a metallo protease and calcium ion |
US20040087458A1 (en) * | 2002-11-01 | 2004-05-06 | Nicca U.S.A., Inc. | Surfactant blends for removing oligomer deposits from polyester fibers and polyester processing equipment |
US20050107281A1 (en) * | 2003-11-17 | 2005-05-19 | Clariant Gmbh | Ether carboxylic acids based on alkoxylated styrylphenols |
WO2012110563A1 (en) * | 2011-02-16 | 2012-08-23 | Novozymes A/S | Detergent compositions comprising metalloproteases |
WO2012110564A1 (en) * | 2011-02-16 | 2012-08-23 | Novozymes A/S | Detergent compositions comprising m7 or m35 metalloproteases |
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