CN108138083B - 粉末洗衣洗涤剂组合物 - Google Patents
粉末洗衣洗涤剂组合物 Download PDFInfo
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- CN108138083B CN108138083B CN201680057136.3A CN201680057136A CN108138083B CN 108138083 B CN108138083 B CN 108138083B CN 201680057136 A CN201680057136 A CN 201680057136A CN 108138083 B CN108138083 B CN 108138083B
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- detergent composition
- powder detergent
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- carbonate
- built powder
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
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- 125000000623 heterocyclic group Chemical group 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
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- 229930007744 linalool Natural products 0.000 description 1
- UWKAYLJWKGQEPM-UHFFFAOYSA-N linalool acetate Natural products CC(C)=CCCC(C)(C=C)OC(C)=O UWKAYLJWKGQEPM-UHFFFAOYSA-N 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 108010020132 microbial serine proteinases Proteins 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
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- 210000004080 milk Anatomy 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- KJPHTXTWFHVJIG-UHFFFAOYSA-N n-ethyl-2-[(6-methoxypyridin-3-yl)-(2-methylphenyl)sulfonylamino]-n-(pyridin-3-ylmethyl)acetamide Chemical compound C=1C=C(OC)N=CC=1N(S(=O)(=O)C=1C(=CC=CC=1)C)CC(=O)N(CC)CC1=CC=CN=C1 KJPHTXTWFHVJIG-UHFFFAOYSA-N 0.000 description 1
- ZOCHHNOQQHDWHG-UHFFFAOYSA-N n-hexan-3-ol Natural products CCCC(O)CC ZOCHHNOQQHDWHG-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002988 phenazines Chemical class 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical class OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000196 poly(lauryl methacrylate) Polymers 0.000 description 1
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- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- ABHHITAVUODQNA-UHFFFAOYSA-M potassium;benzenesulfonate Chemical class [K+].[O-]S(=O)(=O)C1=CC=CC=C1 ABHHITAVUODQNA-UHFFFAOYSA-M 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 235000019833 protease Nutrition 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229930007790 rose oxide Natural products 0.000 description 1
- 102200131574 rs11556620 Human genes 0.000 description 1
- 102220036452 rs137882485 Human genes 0.000 description 1
- 102200065573 rs140660066 Human genes 0.000 description 1
- 102200118280 rs33918343 Human genes 0.000 description 1
- 102220243297 rs374524755 Human genes 0.000 description 1
- 102200034374 rs6092 Human genes 0.000 description 1
- 102220289974 rs757282628 Human genes 0.000 description 1
- 102200025035 rs786203989 Human genes 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000003001 serine protease inhibitor Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- AXMCIYLNKNGNOT-UHFFFAOYSA-N sodium;3-[[4-[(4-dimethylazaniumylidenecyclohexa-2,5-dien-1-ylidene)-[4-[ethyl-[(3-sulfophenyl)methyl]amino]phenyl]methyl]-n-ethylanilino]methyl]benzenesulfonate Chemical compound [Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](C)C)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S(O)(=O)=O)=C1 AXMCIYLNKNGNOT-UHFFFAOYSA-N 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
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003852 triazoles Chemical class 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
- 230000002087 whitening effect Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2089—Ether acids-salts thereof
-
- 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
- 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
- C11D1/831—Mixtures of non-ionic with anionic compounds of sulfonates with ethers of polyoxyalkylenes without phosphates
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- 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
- C11D3/38609—Protease or amylase in solid compositions only
-
- 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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- 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
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- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
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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
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- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
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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
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- C11D2111/12—
Abstract
本发明提供了用于家庭洗衣的无磷酸盐的碳酸盐协助粉末洗涤剂制剂，其包含阴离子表面活性剂、烷基醚羧酸、枯草杆菌蛋白酶型蛋白酶、碳酸钠和任选的非离子表面活性剂。
Description
技术领域
本发明提供了用于家庭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碳酸盐协助粉末洗涤剂制剂是普遍存在的。
蛋白酶被用于碳酸盐协助粉末洗涤剂制剂以从织物除去含蛋白质的污渍。
WO2013/087286(Unilever)公开了含有烷基醚羧酸、甜菜碱、阴离子表面活性剂、非离子表面活性剂的液体制剂，用于提供软化益处。
US5269960(Clorox)公开了含有酶、非离子表面活性剂、脂肪酸和烷基醚羧酸的液体水性酶洗涤剂，其具有增强的物理和酶稳定性。
EP0154380公开了洗衣剂，其含有活性洗涤剂、助洗剂、作为螯合剂的多磷酸盐与沸石的组合，以及如果期望的话，另外的常用添加剂，其中多磷酸盐-沸石组合的螯合作用通过式RO-(C2H4O)x-CH2COOM或R-CO-NH-(C2H4O)x-CH2COOM的醚羧酸增强，其中R是具有至少8个碳原子的脂族或烷基芳族烃的残基，x是平均值为0.5-20的数字，并且M是氢或在洗衣剂中可允许的阳离子，所述聚醚羧酸基于整个组合物以0.3-10％，优选0.3-5％的量存在。
US3741911公开了使用常规助洗剂协助的洗涤剂组合物，优选不含磷酸盐，任选地包含有机螯合剂，并且含有作为活性15系统的含有烷基或烷基-芳基聚氧化烯羧酸和非离子洗涤剂的凝聚系统。该凝聚系统适用于洗涤织物和用于自动洗碗机。
US2011034367公开了将丝氨酸蛋白酶抑制剂例如RASI、BASI、WASI(水稻、大麦和小麦的双功能α-淀粉酶/枯草杆菌蛋白酶抑制剂)引入含有丝氨酸蛋白酶的液体洗涤剂中可以使丝氨酸蛋白酶和/或第二种酶稳定化。
需要增加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碳酸盐协助粉末洗涤剂制剂的去污。
发明内容
出人意料地，蛋白酶与特定烷基醚羧酸的组合在非磷酸盐的碳酸盐协助粉末洗涤剂制剂中提供增强的去污。
在一个方面，本发明提供了非磷酸盐的碳酸盐协助粉末洗涤剂制剂，其包含：
(i)10至40重量％的选自阴离子和非离子表面活性剂的表面活性剂，优选12至25重量％，更优选14至21重量％，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至0.12；
(ii)0.5至10重量％，优选2至10重量％，最优选3至8重量％，甚至最优选3至6重量％的具有以下结构的烷基醚羧酸分散剂
R-(OCH2CH2)n-OCH2-COOH,
其中：
R选自饱和的C8至C18直链烷基链，优选C12至C18直链烷基链，更优选C12或C18直链烷基链，最优选C12直链烷基链；
n是平均乙氧基化，并且n选自5至20，优选7至14，更优选8至12，最优选9至11；
(iii)0.002至0.2重量％的枯草杆菌蛋白酶(subtilisin)蛋白酶，优选0.005至0.05重量％；和，
(iv)5至40重量％，优选10至25重量％的碳酸钠。
枯草杆菌蛋白酶型蛋白酶是枯草杆菌酶(subtilase)型丝氨酸蛋白酶家族的成员。
阴离子表面活性剂的重量％以钠盐计算。烷基醚羧酸分散剂的重量％以COOH形式计算。蛋白酶的重量％是对于纯活性酶。
另一方面，本发明提供了处理纺织品的家用方法，所述方法包括以下步骤：用1.5至20g/L的如本文中限定的洗衣洗涤剂组合物的水溶液处理纺织品。
优选地，水性洗衣洗涤剂溶液与纺织品保持接触10分钟至2天，然后漂洗并干燥纺织品。
具体实施方式
洗涤剂形式
洗衣洗涤剂制剂是非磷酸盐洗衣洗涤剂制剂，即含有小于1重量％的磷酸盐。在本领域中，术语“磷酸盐”涵盖二磷酸盐、三磷酸盐和膦酸盐种类。粉末洗衣洗涤剂制剂主要是碳酸盐协助的，即碳酸钠的重量％大于存在的其它助洗剂成分的重量％总和，优选其它助洗剂材料的重量％水平小于碳酸钠的重量％水平的30％，更优选小于15重量％。粉末应优选提供从9.5到11的使用pH。
洗涤剂制剂可以存在于聚乙烯醇小袋中以易于分配。
蛋白酶
枯草杆菌蛋白酶型蛋白酶(EC 3.4.21.62)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。枯草杆菌蛋白酶型蛋白酶是枯草杆菌酶型丝氨酸蛋白酶家族的成员。丝氨酸蛋白酶家族在MEROPS肽酶数据库(http://merops.sanger.ac.uk/)中描述。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、其与底物形成共价加合物的蛋白酶的亚组。枯草杆菌酶可以分为6个亚分类，枯草杆菌蛋白酶家族是其中之一。
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，解淀粉芽解杆菌，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。另外的蛋白酶在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，特别是在使用BNP’编号方式的以下位置中的一个或多个进行替换的变体：3，4，9，15，27，36，57，68，76，87，95，96，97，98，99，100，101，102，103，104，106，1 18，120，123，128，129，130，160，167，170，194，195，199，205，206，217，218，222，224，232，235，236，245，248，252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,R S103A,V104I,Y,N,S106A,G1 18V,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’编号方式)。
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。
对于粉末包含，蛋白酶优选被制粒并且后投配(post-dosed)到粉末中。优选地，如使用分级筛测定的，酶颗粒具有小于2mm的粒度。最优选地，如使用分级筛测定的，酶颗粒具有0.2-1.5mm的粒度。
枯草杆菌蛋白酶可商购自例如NovozymesTM和GenencorTM。
烷基醚羧酸
在本发明的上下文中，烷基醚羧酸分散剂不作为阴离子表面活性剂被包含。烷基醚羧酸的重量计算为质子化形式R-(OCH2CH2)n-OCH2COOH。它们可作为盐形式使用，例如钠盐或胺盐。
烷基链是脂肪族的和直链的，并且可以选自CH3(CH2)7-；CH3(CH2)8-；CH3(CH2)9-；CH3(CH2)10-；CH3(CH2)11-；CH3(CH2)12-；CH3(CH2)13-；CH3(CH2)14-；CH3(CH2)15-；CH3(CH2)16-和CH3(CH2)17-。
烷基链优选选自CH3(CH2)11-和CH3(CH2)17-。
烷基醚羧酸最优选具有以下结构：
CH3(CH2)11(OCH2CH2)10OCH2COOH。
烷基醚羧酸可从Kao
Huntsman
和Clariant
获得。
烷基醚羧酸可以通过改良Williamson合成制备：
R-(OCH2CH2)n-OCH2COOH+NaOH+ClCH2COONa→
R-(OCH2CH2)n-OCH2COONa+NaCl+H2O
替代方案是通过如DE3135946、DE2816127和EP0304763中所述的使用Pt或Pd催化剂的氧化反应。
烷基醚羧酸分散剂优选在洗涤剂粉末的造粒之前加入到浆料中。或者，它可以被单独造粒并且后投配或喷洒到成品粉末上。
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个碳原子的烷基的脂肪酸(皂)、有机硫酸盐和磺酸盐的水溶性碱金属或胺盐，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；皂；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(LAS)。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)。皂优选是C12至C18饱和脂肪酸，优选它们以制剂的少于3重量％的水平存在。
洗衣组合物中阴离子表面活性剂的水平为(i)10至40重量％。优选在组合物中LAS是占主要地位的存在的阴离子表面活性剂。
在碳酸盐协助粉末洗涤剂中，优选存在的阴离子表面活性剂中>90重量％是LAS。
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(例如脂肪醇、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，非离子表面活性剂是烷基乙氧基化非离子表面活性剂并且是C8至C18伯醇，最优选C12至C16伯醇，具有7EO至9EO单元的平均乙氧基化。
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(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5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。
替代地，或在铝硅酸盐助洗剂之外，可以存在其他形式的助洗剂，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)。
粉末洗涤剂的喷雾干燥是优选的。
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，二胺茋二磺酸化合物，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}茋-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}茋-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，其优选为0.0001g/L至0.1g/L，优选0.001至0.02g/L。
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)1992International Buyers Guide和由Schnell Publishing Co.出版的OPD1993Chemicals 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普遍的。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清洁和增白益处。
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。
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，每种另外的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％蛋白质。
另外的酶优选选自：淀粉酶，甘露聚糖酶，脂肪酶，和纤维素酶，最优选淀粉酶和脂肪酶。合适的脂肪酶包括Novozymes,Bagsvaerd Denmark以商品名
和
销售的那些。
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5000Lmol-1cm-1，优选大于10000Lmol-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，为织物提供可见的色调。在这方面，染料向白色布料给予色调角为240至345、更优选250至320、最优选250至280的蓝色或紫色。该测试中使用的白色布料是经漂白的、未作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％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。
染料根据颜色指数(Society of Dyers and Colourists/American Associationof Textile Chemists and Colorists)分类列出。
为了容易使用，如果碳酸盐协助粉末洗涤剂制剂以0.5至5kg包装存在，则是优选的。
实施例
实施例1
碳酸盐协助粉末制剂的实例
NI(7EO)是具有9摩尔环氧乙烷的C12-C15醇乙氧基化物。
实施例2
磷酸盐协助的相比于非磷酸盐的碳酸盐协助的
制备基础洗衣洗涤剂粉末组合物，以在以2.0g/L投配时，在洗液中给出以下浓度的成分：
该制剂用于在设定为200rpm的测试仪(Tergotometer)中洗涤8个5×5cm的EMPA117污渍监视物(聚酯棉上的血液/牛奶/油墨污渍)。用0.86g/L制剂在35℃下在800ml 26°法国硬水中进行60分钟洗涤。为了模拟油性污垢，将7.0g的SBL2004污垢条(来自WarwickEquest)加入洗液。
一旦洗涤已经完成，将棉监视物在400ml清水中漂洗一次，取出干燥，并在反射计(UVexcluded)上测量反射率，并且RTOT值计算为：
RTOT＝R(460nm)+R(550nm)+R(650nm)+R(740nm)
其中R(460nm)是460nm处的反射率％。RTOT是在织物上的染污的量度，值越高表示织物越干净、越少染污。干净的布的RTOT为344。
制备了等同但加入烷基醚羧酸的制剂，以在洗涤中得到0.14g/L的烷基醚羧酸盐。在烷基醚羧酸盐中，烷基为月桂基，乙氧基的摩尔平均数为11。
在向洗液(
16L，来自Novozymes)中添加和不添加枯草杆菌蛋白酶丝氨酸蛋白酶(EC no.232-752-2)的情况下重复实验。当制剂以0.86g/L投配时，加入酶以给洗液提供0.0002g/L的纯活性蛋白质。
还从8个监视物的测量值的标准偏差计算，给出95％置信限度。
包含蛋白酶给出RTOT(去污)的显著增加，其为248.6-170.1＝78.5。在烷基醚羧酸盐的存在下，这降低至254.6-191.9＝62.7。对于非磷酸盐的碳酸盐基础，蛋白酶给出RTOT的增加，为155.3-103.6＝51.7，其在烷基醚羧酸的存在下增加至168.8-114.4＝54.4。蛋白酶和烷基醚羧酸在非磷酸盐的碳酸盐基础中具有协同作用，但在磷酸盐基础中具有拮抗作用。
实施例3：非离子表面活性剂/阴离子表面活性剂的重量分数。
重复实施例2中制剂含有蛋白酶和烷基醚羧酸的实验，但采用不同重量分数的非离子表面活性剂/阴离子表面活性剂。使用的非离子表面活性剂是具有7摩尔环氧乙烷的C12-C15醇乙氧基化物，阴离子表面活性剂是重量比为1:1的LAS和油酸钠。结果显示在下表中。
如由更高的RTOT值所示，具有0.0和0.3的非离子表面活性剂/阴离子表面活性剂的重量分数的制剂提供最佳的清洁。
Claims (21)
1.一种非磷酸盐的碳酸盐协助粉末洗涤剂组合物，其包含
(i)10至40重量％的选自阴离子表面活性剂的表面活性剂；
(ii)0.5至10重量％的具有以下结构的烷基醚羧酸分散剂
R-(OCH2CH2)n-OCH2-COOH,
其中：
R选自饱和的C8至C18直链烷基链；
n是平均乙氧基化，并且n选自5至20；
(iii)0.002至0.2重量％的枯草杆菌蛋白酶型蛋白酶；和，
(iv)5至40重量％的碳酸钠。
2.根据权利要求1所述的碳酸盐协助粉末洗涤剂组合物，其中所述阴离子表面活性剂选自：C11-C15直链烷基苯磺酸盐；直链或支链C12-C18烷基硫酸盐；具有平均1至3EO的C12-C14正烷基醚硫酸盐；C12-C18饱和脂肪酸及其混合物。
3.根据权利要求1或2所述的碳酸盐协助粉末洗涤剂组合物，其中存在的所述阴离子表面活性剂中大于90重量％是LAS。
4.根据权利要求1或2所述的碳酸盐协助粉末洗涤剂组合物，其中R选自C12至C18直链烷基链。
5.根据权利要求1或2所述的碳酸盐协助粉末洗涤剂组合物，其中R选自CH3(CH2)11-和CH3(CH2)17-。
6.根据权利要求1或2所述的碳酸盐协助粉末洗涤剂组合物，其中R选自C12直链烷基链。
7.根据权利要求1或2所述的碳酸盐协助粉末洗涤剂组合物，其中所述组合物包含0.002至0.2重量％的调色染料。
8.根据权利要求1或2所述的碳酸盐协助粉末洗涤剂组合物，其中n选自7至14。
9.根据权利要求1或2所述的碳酸盐协助粉末洗涤剂组合物，其中n选自8至12。
10.根据权利要求1或2所述的碳酸盐协助粉末洗涤剂组合物，其中n选自9至11。
11.根据权利要求1或2所述的碳酸盐协助粉末洗涤剂组合物，其中所述烷基醚羧酸分散剂选自：
CH3(CH2)11(OCH2CH2)10OCH2COOH。
12.根据权利要求1或2所述的碳酸盐协助粉末洗涤剂组合物，其中所述阴离子表面活性剂以12至25重量％的范围存在。
13.根据权利要求1或2所述的碳酸盐协助粉末洗涤剂组合物，其中所述阴离子表面活性剂以14至21重量％的范围存在。
14.根据权利要求1或2所述的碳酸盐协助粉末洗涤剂组合物，其中所述烷基醚羧酸分散剂以2至10重量％的范围存在。
15.根据权利要求1或2所述的碳酸盐协助粉末洗涤剂组合物，其中所述烷基醚羧酸分散剂以3至8重量％的范围存在。
16.根据权利要求1或2所述的碳酸盐协助粉末洗涤剂组合物，其中所述烷基醚羧酸分散剂以3至6重量％的范围存在。
17.根据权利要求1或2所述的碳酸盐协助粉末洗涤剂组合物，其中所述枯草杆菌蛋白酶型蛋白酶以0.005至0.05重量％存在。
18.根据权利要求1或2所述的碳酸盐协助粉末洗涤剂组合物，其中碳酸钠的重量％大于存在的其他助洗剂成分的重量％总和。
19.根据权利要求18所述的碳酸盐协助粉末洗涤剂组合物，其中其他助洗剂材料的重量％水平小于碳酸钠的重量％水平的15重量％。
20.根据权利要求1或2所述的碳酸盐协助粉末洗涤剂组合物，其中所述组合物包含10至25重量％的碳酸钠。
21.一种处理纺织品的家用方法，所述方法包括以下步骤：用1.5至20g/L的权利要求1-20中任一项限定的碳酸盐协助粉末洗涤剂组合物的水溶液处理纺织品。
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| EP3750978A1 (en) | 2019-06-12 | 2020-12-16 | Unilever N.V. | Laundry detergent composition |
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