CN117736810A - 洗涤剂组合物 - Google Patents
洗涤剂组合物 Download PDFInfo
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- CN117736810A CN117736810A CN202311611720.7A CN202311611720A CN117736810A CN 117736810 A CN117736810 A CN 117736810A CN 202311611720 A CN202311611720 A CN 202311611720A CN 117736810 A CN117736810 A CN 117736810A
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- surfactant
- enzyme
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- alkyl
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- LGZQSRCLLIPAEE-UHFFFAOYSA-M sodium 1-[(4-sulfonaphthalen-1-yl)diazenyl]naphthalen-2-olate Chemical compound [Na+].C1=CC=C2C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C(S([O-])(=O)=O)C2=C1 LGZQSRCLLIPAEE-UHFFFAOYSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 229940101011 sodium hydroxymethylglycinate Drugs 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- CITBNDNUEPMTFC-UHFFFAOYSA-M sodium;2-(hydroxymethylamino)acetate Chemical compound [Na+].OCNCC([O-])=O CITBNDNUEPMTFC-UHFFFAOYSA-M 0.000 description 1
- FJBHGWADYLMEJG-UHFFFAOYSA-M sodium;3-[[4-[[4-(diethylamino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]cyclohexa-2,5-dien-1-ylidene]methyl]-n-ethylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC=1C=C(C=CC=1)S([O-])(=O)=O)=C(C=C1)C=CC1=[N+](CC)CC1=CC=CC(S([O-])(=O)=O)=C1 FJBHGWADYLMEJG-UHFFFAOYSA-M 0.000 description 1
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- LJFWQNJLLOFIJK-UHFFFAOYSA-N solvent violet 13 Chemical compound C1=CC(C)=CC=C1NC1=CC=C(O)C2=C1C(=O)C1=CC=CC=C1C2=O LJFWQNJLLOFIJK-UHFFFAOYSA-N 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000001629 stilbenes Chemical class 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 150000003900 succinic acid esters Chemical class 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 108010038851 tannase Proteins 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- QTTDXDAWQMDLOF-UHFFFAOYSA-J tetrasodium 3-[[4-[[4-[(6-amino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-6-sulfonatonaphthalen-1-yl]diazenyl]naphthalen-1-yl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].Nc1ccc2c(O)c(N=Nc3ccc(N=Nc4ccc(N=Nc5cc(c6cccc(c6c5)S([O-])(=O)=O)S([O-])(=O)=O)c5ccccc45)c4ccc(cc34)S([O-])(=O)=O)c(cc2c1)S([O-])(=O)=O QTTDXDAWQMDLOF-UHFFFAOYSA-J 0.000 description 1
- LKHDXIBHVSGUHN-UHFFFAOYSA-N thiadiazole 1,1-dioxide Chemical compound O=S1(=O)C=CN=N1 LKHDXIBHVSGUHN-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- JADVWWSKYZXRGX-UHFFFAOYSA-M thioflavine T Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C1=[N+](C)C2=CC=C(C)C=C2S1 JADVWWSKYZXRGX-UHFFFAOYSA-M 0.000 description 1
- 150000003573 thiols Chemical group 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 239000001585 thymus vulgaris Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 125000005208 trialkylammonium group Chemical group 0.000 description 1
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical class N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 1
- 229960003500 triclosan Drugs 0.000 description 1
- VRVDFJOCCWSFLI-UHFFFAOYSA-K trisodium 3-[[4-[(6-anilino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-5-methoxy-2-methylphenyl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].COc1cc(N=Nc2cc(c3cccc(c3c2)S([O-])(=O)=O)S([O-])(=O)=O)c(C)cc1N=Nc1c(O)c2ccc(Nc3ccccc3)cc2cc1S([O-])(=O)=O VRVDFJOCCWSFLI-UHFFFAOYSA-K 0.000 description 1
- 239000012588 trypsin Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 150000003732 xanthenes Chemical class 0.000 description 1
- 108010083879 xyloglucan endo(1-4)-beta-D-glucanase Proteins 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- GAWWVVGZMLGEIW-GNNYBVKZSA-L zinc ricinoleate Chemical compound [Zn+2].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O.CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O GAWWVVGZMLGEIW-GNNYBVKZSA-L 0.000 description 1
- 229940100530 zinc ricinoleate Drugs 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 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
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- C11D3/38636—Preparations containing enzymes, e.g. protease or amylase containing enzymes other than protease, amylase, lipase, cellulase, oxidase or reductase
-
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- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/044—Hydroxides or bases
-
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- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/16—Organic compounds
- C11D3/166—Organic compounds containing borium
-
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- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
- C11D3/201—Monohydric alcohols linear
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- C11D3/2003—Alcohols; Phenols
- C11D3/2041—Dihydric alcohols
- C11D3/2044—Dihydric alcohols linear
-
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- C11D3/2079—Monocarboxylic acids-salts thereof
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- C11D3/2086—Hydroxy carboxylic acids-salts thereof
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- C11D3/16—Organic compounds
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- C11D3/30—Amines; Substituted amines ; Quaternized amines
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- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
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- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
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- C11D3/40—Dyes ; Pigments
- C11D3/42—Brightening agents ; Blueing agents
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- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/50—Perfumes
- C11D3/502—Protected perfumes
- C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
-
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- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/008—Polymeric surface-active agents
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- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
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- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
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- C11D1/66—Non-ionic compounds
- C11D1/75—Amino oxides
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- C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
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- C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
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- C11D2111/12—
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- C12Y—ENZYMES
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- C12Y301/21001—Deoxyribonuclease I (3.1.21.1)
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- C12Y301/30002—Serratia marcescens nuclease (3.1.30.2)
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- C12Y302/01052—Beta-N-acetylhexosaminidase (3.2.1.52)
Abstract
本发明公开了一种清洁组合物,其包含核酸酶,优选脱氧核糖核酸酶和/或核糖核酸酶和包含阴离子表面活性剂和非离子表面活性剂的表面活性剂体系,其中阴离子表面活性剂与非离子表面活性剂的重量比为1.5:1至1:10。
Description
本申请是申请日为2016年4月27日、发明名称为“洗涤剂组合物”的中国专利申请No.201680024500.6的分案申请。
技术领域
本发明涉及包含核酸酶的清洁组合物。
背景技术
织物美白对衣物洗涤剂制造商来说是一个不断的挑战。具体的问题可能是污垢随着时间的积累。这对于彩色织物和白色织物都是有问题的,但是在白色织物或浅色织物上可能特别明显,例如在不完全清洁发生的衬圈和袖带周围。因为它可能会导致恶臭,所以这也可能是问题所在。衣物洗涤剂制造商可基于可用的不同清洁技术诸如表面活性剂、漂白剂和酶考虑许多方案。许多不同类型的酶可用于洗涤剂配制人员用于清洁不同类型的污垢,例如脂肪酶、蛋白酶、淀粉酶、纤维素酶、过氧化酶、芳基酯酶、角质酶、果胶酶、甘露聚糖酶和脱氧核糖核酸酶。脱氧核糖核酸酶在清洁这种类型的污垢中可能特别有效,然而,为了提供清洁,酶需要沉积在纺织物表面上。某些表面活性剂可减少该沉积,因此仍然需要一种包含能够沉积酶的表面活性剂的清洁或处理组合物。
发明内容
本发明涉及清洁组合物,该清洁组合物包含核酸酶,优选脱氧核糖核酸酶或核糖核酸酶和包含阴离子表面活性剂和非离子表面活性剂的表面活性剂体系,其中阴离子表面活性剂与非离子表面活性剂的重量比为1.5:1至1:10。
包含核酸酶的清洁组合物为水的水溶性单位剂量小袋,优选地为多隔室单位剂量产品的形式。
本发明包括清洁纺织物的方法,该方法包括使纺织物与包含清洁组合物的含水液体接触。
根据本发明的另一方面,提供了一种清洁组合物,其包含如本文所定义的核酸酶和来自家族GH20的糖基水解酶,优选地来自E.C.3.2.1.52的β-N-乙酰基葡萄糖胺苷酶。
具体实施方式
定义
如本文所用,术语“烷氧基”旨在包括C1-C8烷氧基和多元醇的C1-C8烷氧基衍生物,该多元醇具有重复单元诸如环氧丁烷、缩水甘油氧化物、环氧乙烷或环氧丙烷。
如本文所用,除非另外指明,术语“烷基”和“烷基封端的”旨在包括C1-C18烷基基团,或甚至C1-C6烷基基团。
如本文所用,除非另外指明,术语“芳基”旨在包括C3-12芳基基团。
如本文所用,除非另外指明,术语“芳基烷基”和“烷芳基”是等同的,并且各自旨在包括包含烷基部分的基团,该烷基部分键合至芳族部分,通常具有C1-C18烷基基团以及在一个方面C1-C6烷基基团。
术语“环氧乙烷”、“环氧丙烷”和“环氧丁烷”在本文中可分别由它们的典型标记“EO”、“PO”和“BO”示出。
如本文所用,除非另外指明,术语“清洁和/或处理组合物”包括颗粒状、粉末状、液体状、凝胶状、糊剂状、单位剂量、条块形式和/或薄片类型的洗涤剂和/或织物处理组合物,包括但不限于用于洗涤织物的产品、织物软化组合物、织物增强组合物、织物清新组合物和用于织物护理和保持的其它产品,以及它们的组合。此类组合物可为洗涤步骤之前使用的预处理组合物,或可为漂洗添加组合物以及清洁辅剂,诸如漂白添加剂和/或“去污棒”或预处理组合物,或负载于基底的产品诸如干衣机纸。
如本文所用,“纤维素基质”旨在包括包含纤维素的任意基质,其为100重量%纤维素或至少20重量%,或至少30重量%,或至少40重量%,或至少50重量%,或甚至至少60重量%的纤维素。纤维素可存在于木、棉、亚麻、黄麻和大麻中。纤维素基质可为粉末、纤维、纸浆以及由粉末、纤维和纸浆形成的制品的形式。纤维素纤维包括但不限于棉、人造丝(再生纤维素)、乙酸酯类(乙酸纤维素)、三乙酸酯类(三乙酸纤维素)、以及它们的混合物。通常,纤维素基质包括棉花。由纤维素纤维形成的制品包括诸如织物的纺织物制品。由纸浆形成的制品包括纸。
如本文所用,术语“最大消光系数”旨在描述400纳米至750纳米范围内的最大吸收波长(本文还称为最大波长)处的摩尔消光系数。
如本文所用,“平均分子量”报告为通过其分子量分布所测定的平均分子量:因为其制造工艺,本文所公开的聚合物可在其聚合物部分中包含重复单元的分布。
如本文所用,术语“变体”是指含有不同于野生型序列或参考序列的氨基酸序列的多肽。由于相对于所述参考核苷酸序列或野生型核苷酸序列的核苷酸的去除、插入或取代,变体多肽可能与野生型序列或参考序列不同。参考序列或野生型序列可以是全长天然多肽序列或全长多肽序列的任意其它片段。多肽变体通常与参考序列具有至少约70%的氨基酸序列同一性,但可包括75%与参考序列的氨基酸序列同一性,80%与参考序列的氨基酸序列同一性,85%与参考序列的氨基酸序列同一性,86%与参考序列的氨基酸序列同一性,87%与参考序列的氨基酸序列同一性,88%与参考序列的氨基酸序列同一性,89%与参考序列的氨基酸序列同一性,90%与参考序列的氨基酸序列同一性,91%与参考序列的氨基酸序列同一性,92%与参考序列的氨基酸序列同一性,93%与参考序列的氨基酸序列同一性,94%与参考序列的氨基酸序列同一性,95%与参考序列的氨基酸序列同一性,96%与参考序列的氨基酸序列同一性,97%与参考序列的氨基酸序列同一性,98%与参考序列的氨基酸序列同一性,98.5%与参考序列的氨基酸序列同一性,或99%与参考序列的氨基酸序列同一性。
如本文所用,当用于权利要求中时,冠词诸如“一种”和“一个”被理解为是指一个或多个受权利要求保护或描述的物质。
如本文所用,术语“包括”和“包含”旨在是非限制性的。
如本文所用,术语“固体”包括颗粒、粉末、条和片剂产品形式。
如本文所用,术语“流体”包括液体、凝胶、糊剂和气体产品形式。
除非另有说明,否则所有组分或组合物含量均是就该组分或组合物的活性物质部分而言,不包括可能存在于这些组分或组合物的市售来源中的杂质,例如残余溶剂或副产物。
除非另外指明,否则所有百分比和比率均按重量计算。除非另外指明,否则所有百分比和比率均基于总组合物计算。
除了核酸酶之外,清洁和/或处理组合物还将包含来自此类清洁和/或处理组合物的任意附加辅助材料,如下所述。
核酸酶
核酸酶是能够裂解核酸的核苷酸亚单元之间的磷酸二酯键的酶。本文中的核酸酶优选地为脱氧核糖核酸酶或核糖核酸酶或其官能的片段。所谓的官能的片段或部分是指核酸酶的催化在DNA主链中磷酸二酯键的裂解的部分,因此是所述核酸酶蛋白的保留催化活性的区域。因此,其包括截短但官能的型式的酶和/或变体和/或衍生物和/或保持其官能度的同系物。
优选地,核酸酶是脱氧核糖核酸酶,优选选自以下类别的任一种:E.C.3.1.21.x,其中x=1,2,3,4,5,6,7,8或9,E.C.3.1.22.y,其中y=1,2,4或5,E.C.3.1.30.z,其中z=1或2,E.C.3.1.31.1以及它们的混合物。
在类别E.C.3.1.21.x中的核酸酶在3’羟基处裂解以释放5’磷酸单酯如下:
来自类别E.C.3.1.21.x的核酸酶,并且尤其其中x=1是特别优选的。
在类别E.C.3.1.22.y中的核酸酶在5’羟基处裂解以释放3’磷酸单酯。在类别E.C.3.1.30.z中的酶可能是优选的,因为它们作用于DNA和RNA两者并释放5’-磷酸单酯。来自类别E.C.3.1.31.2的合适的示例在US2012/0135498A中描述,诸如其中的SEQ ID NO:3。此类酶可从c-LECTA作为酶商购获得。
来自类别E.C.3.1.31.1的核酸酶产生3’-磷酸单酯。
优选地,核酸酶包含微生物酶。核酸酶可能是真菌或细菌源。细菌核酸酶可能是最优选的。真菌核酸酶可能是最优选的。
微生物核酸酶可从芽孢杆菌属(Bacillus)获得,诸如地衣芽孢杆菌(Bacilluslicheniformis)或枯草芽孢杆菌(Bacillus subtilis)细菌核酸酶。优选的核酸酶可从地衣芽孢杆菌获得,优选地来自菌株EI-34-6。优选的脱氧核糖核酸酶是来自本文SEQ ID NO:1中定义的菌株EI-34-6nucB脱氧核糖核酸酶或其变体例如与其具有至少70%、或75%、或80%、或85%、或90%、或95%、96%、97%、98%、99%或100%同一性的地衣芽孢杆菌的变体。
其它合适的核酸酶在本文SEQ ID NO:2中定义或其变体例如与其具有至少70%、或75%、或80%、或85%、或90%、或95%、96%、97%、98%、99%或100%同一性。其它合适的核酸酶在本文SEQ ID NO:3中定义或其变体例如与其具有至少70%、或75%、或80%、或85%、或90%、或95%、96%、97%、98%、99%或100%同一性。
真菌核酸酶可从曲霉属(Aspergillus)例如米曲霉(Aspergillus oryzae)获得。优选的核酸酶可从本文SEQ ID NO:5中定义的米曲霉或其变体例如与其具有至少60%、或70%、或75%、或80%、或85%、或90%、或95%、96%、97%、98%、99%或100%同一性中获得。
另一种合适的真菌核酸酶可从木霉属(Trichoderma)例如哈茨木霉(Trichodermaharzianum)获得。优选的核酸酶可从本文SEQ ID NO:6中定义的哈茨木霉或其变体例如与其具有至少60%、或70%、或75%、或80%、或85%、或90%、或95%、96%、97%、98%、99%或100%同一性中获得。
其它真菌核酸酶包括由以下的DNA序列编码的那些:米曲霉RIB40,米曲霉3.042,黄曲霉NRRL3357,寄生曲霉SU-1,曲霉菌NRRL13137,里氏木霉QM6a,绿木霉Gv29-8,双树粉孢Zn,贵州杜鹃绿僵菌ARSEF 977,金边草绿僵菌ARSEF 297,Metarhizium robertsiiARSEF 23,Metarhizium acridum CQMa 102,褐紫乌头绿僵菌ARSEF 3297,金龟子绿僵菌,围盾介壳虫炭疽菌PJ7,Colletotrichum sublineola,深绿楼梯草木霉IMI 206040,大团囊草弯颈霉CBS100239,球孢白僵菌ARSEF 2860,炭疽菌,明尼苏达被毛孢3608,尖端赛多孢子菌,Phaeomoniella chlamydospora,轮状镰孢7600,香蕉枯萎病拮抗4,高粱炭疽菌M1.001,尖孢镰孢FOSC 3-a,燕麦镰孢,Fusarium langsethiae,蓝菌属真菌kw1407,紫色麦角菌20.1,轮枝菌,香蕉枯萎病拮抗1,稻瘟病菌70-15,球孢白僵菌D1-5,小麦冠腐病菌CS3096,Neonectria ditissima,早熟禾夏季斑枯病菌ATCC 64411,冬虫夏草CM01,Marssoninabrunnea f.sp.′multigermtubi′MB_m1,Diaporthe ampelina,Metarhizium album ARSEF1941,炭疽菌奈良gc5,如马杜拉足肿菌,褐紫乌头绿僵菌ARSEF 3297,轮枝孢苜蓿VaMs.102,小麦全蚀病菌R3-111a-1,球丛赤壳mpVI 77-13-4,轮枝菌,棉花黄萎病菌VdLs.17,Torrubiella hemipterigena,轮枝菌,棉花黄萎病菌VdLs.17,灰葡萄孢B05.10,球壳藻CBS148.51,金龟子绿僵菌,蕃茄匍柄霉,北方贝核盘霉F-4157,Metarhiziumrobertsii ARSEF 23,嗜热毁丝菌ATCC 42464,颖枯壳针孢SN15,Phialophora attae,稻曲病菌,Diplodia seriata,Ophiostoma piceae UAMH 11346,Pseudogymnoascus pannorumVKM F-4515(FW-2607),稻平脐蠕孢ATCC 44560,贵州杜鹃绿僵菌ARSEF 977,嗜热毛细菌嗜热DSM 1495,拟盘多毛孢W106-1,玉米生离蠕孢26-R-13,玉米大斑病菌Et28A,Arthrodermaotae CBS113480和Pyrenophora tritici-repentis Pt-1C-BFP。
优选地,核酸酶为分离的核酸酶。
优选地核酸酶以0.01ppm至1000ppm的核酸酶,或从0.05或从0.1ppm至750或500ppm的量存在于衣物洗涤水性溶液中。
核酸酶也可能产生生物膜破坏作用。
在优选的组合物中,组合物另外地包含来自E.C.3.2.1.52的β-N-乙酰基葡萄糖胺苷酶,优选地与SEQ ID NO:4具有至少70%,或至少75%,或至少80%,或至少85%,或至少90%,或至少95%,或至少96%,或至少97%,或至少98%,或至少99%,或至少100%或100%的同一性的酶。
表面活性剂体系
表面活性剂体系包含阴离子表面活性剂和非离子表面活性剂,其中阴离子表面活性剂与非离子表面活性剂的重量比为1.5:1至1:10,优选1.2:1至1:5,更优选1:1至1:4。
清洁组合物中的总表面活性剂含量优选为5重量%至80重量%,或10重量%至50重量%,更优选为15重量%至45重量%。
阴离子表面活性剂
阴离子表面活性剂可包含一种表面活性剂或通常一种以上表面活性剂的混合物。优选的阴离子去污表面活性剂是烷基苯磺酸盐、烷氧基化阴离子表面活性剂或它们的组合。合适的阴离子去污表面活性剂包括硫酸盐和磺酸盐去污表面活性剂。
特别优选的烷基苯磺酸盐是直链烷基苯磺酸盐,特别是具有C8-15的碳链长度的烷基苯磺酸盐或C10-13烷基苯磺酸盐。合适的烷基苯磺酸盐(LAS)是可购得的,或甚至由可商购获得的直链烷基苯(LAB)磺化获得;合适的LAB包括低级2-苯基LAB,如由Sasol以商品名提供的那些或由Petresa以商品名/>提供的那些,其它适宜的LAB包括高级2-苯基LAB,如由Sasol以商品名/>提供的那些。另一种合适的阴离子去污表面活性剂是由DETAL催化方法获得的烷基苯磺酸盐,优选地具有8至15个碳原子。其它合成途径诸如HF也可是合适的。
适宜的硫酸盐去污表面活性剂包括烷基硫酸盐如C8-18烷基硫酸盐,或主要地为C12烷基硫酸盐。烷基硫酸盐可来源于天然来源,如椰油和/或牛油。可供选择地,所述烷基硫酸盐可来源于合成来源,如C12-15烷基硫酸盐。
表面活性剂组合物优选还可包含另外的阴离子表面活性剂,烷基烷氧基化硫酸盐,诸如烷基乙氧基化硫酸盐,或C8-18烷基烷氧基化硫酸盐,或C8-18烷基乙氧基化硫酸盐。优选地烷基链长可为12至16个碳原子。烷基烷氧基化硫酸盐可具有0.5至20,或0.5至10,或0.5至7,或0.5至5,或0.5至3的平均烷氧基化度。示例包括主要利用每摩尔平均3摩尔环氧乙烷乙氧基化的C12月桂基醚硫酸钠。
烷基硫酸盐、烷基烷氧基化硫酸盐和烷基苯磺酸盐可为直链或支链的、取代或未取代的。
阴离子去污表面活性剂可为中链支化的阴离子去污表面活性剂,如中链支化的烷基硫酸盐和/或中链支化的烷基苯磺酸盐。中链支化通常为C1-4烷基基团,如甲基和/或乙基基团。
另一种适宜的阴离子去污表面活性剂为烷基乙氧基羧酸盐。
阴离子表面活性剂通常以它们的盐形式存在,通常与适宜的阳离子配合。适宜的抗衡离子包括Na+和K+,取代的铵如C1-C6链烷醇铵,如单乙醇胺(MEA)、三乙醇胺(TEA)、二乙醇胺(DEA)、以及它们的任何混合物。
在清洁组合物中,当存在烷基(任选乙氧基化)硫酸盐时,优选直链烷基苯磺酸盐与烷基硫酸盐和/或烷基烷氧基化硫酸盐的重量比为20:1至1:2,更优选5:1至1:1。通常,阴离子表面活性剂以5重量%至30重量%的阴离子表面活性剂或至少8重量%或至少10重量%的阴离子表面活性剂的量存在于清洁组合物中。
本文,脂肪酸不被认为是表面活性剂。
非离子表面活性剂
适宜的非离子表面活性剂选自:C8-C18烷基乙氧基化物,诸如得自Shell的非离子表面活性剂;C6-C12烷基酚烷氧基化物,其中所述烷氧基化物单元可以为亚乙基氧单元、亚丙基氧单元或它们的混合物;与亚乙基氧/亚丙基氧嵌段聚合物缩合的C12-C18醇和C6-C12烷基酚,诸如得自BASF的/>C14-C22中链支化醇;C14-C22中链支化烷基烷氧基化物,通常具有1至30的平均烷氧基化度;烷基多糖,在一个方面,烷基多葡糖苷;多羟基脂肪酸酰胺;醚封端的聚(烷氧基化)醇表面活性剂;以及它们的混合物。
适宜的非离子去污表面活性剂包括烷基多葡糖苷和/或烷基烷氧基化醇。
当存在烷基烷氧基化醇时,优选地它们选自C8-18烷基烷氧基化醇,例如C8-18烷基乙氧基化醇。优选地,烷基烷氧基化醇具有1至80,优选1至50,最优选1至30,1至20,或1至10的平均烷氧基化度。优选的非离子表面活性剂可以是C8-18烷基烷氧基化的,优选具有1至10,1至7,更优选1至5或3至7,或甚至低于3或2的平均烷氧基化度优选平均乙氧基化度的乙氧基化醇。所述烷基烷氧基化醇可为直链或支链的,以及取代的或未取代的。
合适的非离子表面活性剂包括具有商品名(巴斯夫公司(BASF))的那些。
通常,非离子表面活性剂以4重量%至40重量%的阴离子表面活性剂,或至少8重量%或至少10重量%,或12 10重量%的非离子表面活性剂的量存在于清洁组合物中。
本发明的优选组合物是液体或单位剂量形式。对于外部结构化的各向同性含水液体衣物洗涤剂组合物,液体可能是优选的。
清洁和/或处理辅助材料
除了核酸酶和表面活性剂体系外,本发明的清洁组合物还将包含任选的清洁和/或处理辅助材料。优选地,该组合物还将另外地包含来自E.C.3.2.1.52的β-N-乙酰基葡萄糖胺苷酶,优选地与SEQ ID NO:4具有至少70%,或至少75%,或至少80%,或至少85%,或至少90%,或至少95%,或至少96%,或至少97%,或至少98%,或至少99%,或至少100%或100%的同一性的酶。当存在时,β-N-乙酰基葡萄糖胺苷酶通常将以按组合物的重量计0.00001%至约2%,约0.0001%至约1%,或甚至约0.001%至约0.5%的酶蛋白的量存在。
另外合适的助剂可例如有助于或增强清洁性能,通过例如软化或清新处理待清洁的基底,或在使用香料、着色剂、非织物着色染料等情况下改善洗涤剂组合物的美观性。适合的辅助材料包括但不限于:表面活性剂、助洗剂、螯合剂、分散剂、酶和酶稳定剂、催化物质、漂白活化剂、过氧化氢、过氧化氢源、预成形的过酸、聚合物分散剂、粘土污垢去除/抗再沉淀剂、附加的增白剂、抑泡剂、染料、调色染料、香料、香料递送体系、结构弹性化剂、织物软化剂、载体、水溶助长剂、加工助剂、溶剂、附加的染料和/或颜料,其中一些更详细论述于下文中。除了以下公开内容外,这些其它助剂的合适示例和用量还存在于美国专利5,576,282、6,306,812 B1和6,326,348 B1中,所述文献引入以供参考。
特别优选的附加的辅助材料可以是另外的酶。
酶:优选地,组合物包含一种或多种附加的酶。优选的酶提供清洁性能和/或织物护理有益效果。合适的酶的示例包括但不限于:半纤维素酶、过氧化物酶、蛋白酶、纤维素酶、木聚糖酶、脂肪酶、磷脂酶、酯酶、角质酶、果胶酶、甘露聚糖酶、果胶酸裂解酶、角蛋白酶、还原酶、氧化酶、酚氧化酶、脂氧合酶、木质酶、支链淀粉酶、鞣酸酶、戊聚糖酶、麦拉宁酶、β-葡聚糖酶、阿拉伯糖酶、透明质酸酶、软骨素酶、漆酶和淀粉酶、或它们的混合物。附加的酶的优选组合包括蛋白酶和脂肪酶,优选与淀粉酶结合。当存在于组合物中时,前述附加酶可以各自按组合物的重量计约0.00001%至约2%,约0.0001%至约1%,或甚至约0.001%至约0.5%的酶蛋白的含量存在。
蛋白酶:优选地,组合物包含一种或多种蛋白酶。合适的蛋白酶包括金属蛋白酶和丝氨酸蛋白酶,丝氨酸蛋白酶包括中性或碱性微生物丝氨酸蛋白酶,诸如枯草杆菌蛋白酶(EC 3.4.21.62)。合适的蛋白酶包括动物源、植物源或微生物源的那些。在一个方面,此类合适的蛋白酶可为微生物源的。合适的蛋白酶包括经化学修饰或基因修饰的上述合适的蛋白酶的突变体。在一个方面,合适的蛋白酶可为丝氨酸蛋白酶,诸如碱性微生物蛋白酶和/或胰蛋白酶型蛋白酶。合适的中性蛋白酶或碱性蛋白酶的示例包括:
(a)枯草杆菌蛋白酶(EC 3.4.21.62),包括来源于芽孢杆菌属(Bacillus)的那些,诸如US 6,312,936 B1、US 5,679,630、US 4,760,025、US7,262,042和WO09/021867中所述的迟缓芽孢杆菌(Bacillus lentus)、嗜碱芽孢杆菌(B.alkalophilus)、枯草芽孢杆菌(B.subtilis)、解淀粉芽孢杆菌(B.amyloliquefaciens)、短小芽孢杆菌(Bacilluspumilus)和吉氏芽孢杆菌(Bacillus gibsonii)。
(b)胰蛋白酶型或胰凝乳蛋白酶型蛋白酶,如胰蛋白酶(例如源自猪或牛),包括WO89/06270中所述的镰孢属(Fusarium)蛋白酶,以及WO 05/052161和WO 05/052146中所述的来源于纤维单胞菌属(Cellumonas)的胰凝乳蛋白酶。
(c)金属蛋白酶,包括WO 07/044993A2中所述的来源于解淀粉芽孢杆菌(Bacillusamyloliquefaciens)的那些。
优选的蛋白酶包括来源于吉氏芽孢杆菌(Bacillus gibsonii)或迟缓芽孢杆菌(Bacillus Lentus)的那些。
合适的可商购获得的蛋白酶包括以商品名 LiquanaseSavinase/>和/>由Novozymes A/S(Denmark)出售的那些;以商品名/> Purafect/>Purafect/> 和Purafect/>由Genencor International出售的那些;以商品名和/>由Solvay Enzymes出售的那些;得自Henkel/Kemira的那些即BLAP(序列示于US 5,352,604的图29中,具有下列突变S99D+S101 R+S103A+V104I+G159S,下文称为BLAP);均得自Henkel/Kemira的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);以及得自Kao的KAP(具有突变A230V+S256G+S259N的嗜碱芽孢杆菌枯草杆菌蛋白酶),或者如WO2009/149144,WO2009/149145,WO2010/56653,WO2010/56640,WO2011/072117,US2011/0237487,WO2011/140316,WO2012/151480,EP2510092,EP2566960或EP2705145中公开。
淀粉酶:优选地,组合物可包含淀粉酶。合适的α-淀粉酶包括源自细菌或真菌的那些。包括经化学修饰或基因修饰的突变体(变体)。优选的碱性α-淀粉酶来源于芽孢杆菌属的菌株,诸如地衣芽孢杆菌(Bacillus licheniformis)、解淀粉芽孢杆菌(Bacillusamyloliquefaciens)、嗜热脂肪芽胞杆菌(Bacillus stearothermophilus)、枯草芽孢杆菌(Bacillus subtilis)或其它芽孢杆菌属(Bacillus sp.),诸如芽孢杆菌属NCIB 12289、NCIB 12512、NCIB 12513、DSM 9375(USP 7,153,818)DSM 12368、DSMZ号12649、KSM AP1378(WO 97/00324)、KSM K36或KSM K38(EP 1,022,334)。优选的淀粉酶包括:
(a)WO 94/02597、WO 94/18314、WO96/23874和WO 97/43424中所述的变体,尤其是相对于WO 96/23874中SEQ ID NO.2所列的酶,在下列位置中的一个或多个中具有取代的变体:15、23、105,106、124、128、133、154、156、181、188、190、197、202、208、209、243、264、304、305、391、408和444。
(b)描述于USP 5,856,164以及WO99/23211、WO 96/23873、WO00/60060和WO 06/002643中的变体,尤其是相对于WO 06/002643中SEQ ID No.12所列的AA560酶,在下列位置具有一个或多个取代的变体:
26、30、33、82、37、106、118、128、133、149、150、160、178、182、186、193、203、214、231、256、257、258、269、270、272、283、295、296、298、299、303、304、305、311、314、315、318、319、339、345、361、378、383、419、421、437、441、444、445、446、447、450、461、471、482、484,优选还包含D183*和G184*缺失的变体。
(c)表现出与WO06/002643中的SEQ ID No.4至少90%同一性的变体,来自芽孢杆菌属SP722的野生型酶,尤其是在183和184位具有缺失的变体,以及WO 00/60060中描述的变体,将所述文献以引用方式并入本文。
(d)表现出与来自芽孢杆菌属707的野生型酶(US 6,093,562中的SEQ ID NO:7)至少95%同一性的变体,尤其是包含下列突变中的一个或多个的那些:M202、M208、S255、R172和/或M261。优选地,所述淀粉酶包含M202L、M202V、M202S、M202T、M202I、M202Q、M202W、S255N和/或R172Q中的一个或多个。尤其优选的是包含M202L或M202T突变的那些。
(e)WO 09/149130中所述的变体,优选表现出与WO 09/149130中的SEQ ID NO:1或SEQ ID NO:2(来自嗜热脂肪芽孢杆菌(Geobacillus Stearophermophilus)或其截短型式的野生型酶)至少90%同一性的那些;
(f)如EP2540825和EP2357220、EP2534233中所述的变体;(g)如WO2009100102和WO2010115028中所述的变体。
合适的可商购获得的α-淀粉酶包括 TERMAMYL/> STAINZYME/>和/>(Novozymes A/S,Bagsvaerd,Denmark)、/>AT 9000Biozym Biotech Trading GmbHWehlistrasse 27b A-1200Wien Austria、/> OPTISIZE HT/>和PURASTAR/>(Genencor International Inc.,Palo Alto,California)和/>(Kao,14-10Nihonbashi Kayabacho,1-chome,Chuo-ku Tokyo 103-8210,Japan)。在一个方面,合适的淀粉酶包括/>和STAINZYME/>以及它们的混合物。
脂肪酶:优选地,组合物包含一种或多种脂肪酶,包括“第一循环脂肪酶”,诸如美国专利6,939,702B1和US PA 2009/0217464中所述的那些。优选的脂肪酶为第一洗涤脂肪酶。在本发明的一个实施方案中,组合物包含第一洗涤脂肪酶。第一洗涤脂肪酶包括为具有氨基酸序列的多肽的脂肪酶,该氨基酸序列:(a)与来源于Humicola lanuginosa菌株DSM4109的野生型脂肪酶具有至少90%的同一性;(b)与所述野生型脂肪酶相比,包括在三维结构表面距E1或Q249 15A之内电中性或带负电的氨基酸被带正电的氨基酸取代;以及(c)包含在C-末端添加的肽;和/或(d)包含在N-末端添加的肽;和/或(e)满足以下限制:i)在所述野生型脂肪酶的E210位包含带负电的氨基酸;ii)在对应于所述野生型脂肪酶的90-101位的区域中包含带负电的氨基酸;以及iii)在对应于所述野生型脂肪酶的N94位包含中性或带负电的氨基酸和/或在对应于所述野生型脂肪酶的90-101位的区域内具有负的或中性的净电荷。优选得自包含一个或多个T231R和N233R突变的疏棉状嗜热丝孢菌的野生型脂肪酶的变体。野生型序列是Swissprot登录号为Swiss-Prot O59952(来源于疏棉状嗜热丝孢菌(柔毛腐质霉(Humicola lanuginosa)))的269个氨基酸(氨基酸23-291)。优选的脂肪酶将包括以商品名和/>以及/>出售的那些。其它合适的脂肪酶包括在欧洲专利申请12001034.3或EP2623586中描述的那些。
内切葡聚糖酶:其它优选的酶包括微生物来源的内切葡聚糖酶,表现出内切-β-1,4-葡聚糖酶活性(E.C.3.2.1.4),包括芽孢杆菌属成员内源性的细菌多肽(其具有与US7,141,403B2中氨基酸序列SEQ ID NO:2有至少90%、94%、97%和甚至99%的同一性的序列)以及它们的混合物。合适的内切葡聚糖酶以商品名和/>(Novozymes A/S,Bagsvaerd,Denmark)商购获得。
果胶酸裂解酶:其它优选的酶包括以商品名 出售的果胶酸裂解酶和以商品名/>出售的甘露聚糖酶(均得自Novozymes A/S,Bagsvaerd,Denmark),和以商品名/>出售的甘露聚糖酶(GenencorInternational Inc.,Palo Alto,California)。
抗微生物剂:此外,组合物还可优选地包含可引起抗微生物作用的一种化合物或多于一种化合物的混合物。这些可以是被添加用于清洁或恶臭有益效果的处理组合物的标准成分如漂白剂,但是具有一些抗微生物作用,或者它们可特别加入以提供抗微生物作用。合适的示例可包括但不限于醛(甲醛、戊二醛、邻苯二甲醛),二氧化硫,亚硫酸盐,亚硫酸氢盐,香草酸酯,氯和氧基氧化剂(次氯酸钠和次氯酸钙,或次溴酸钠和次溴酸钙,氯胺和氯胺T,二氧化氯,过氧化氢,碘,臭氧,过乙酸,过甲酸,高锰酸钾,过氧化单硫酸钾盐),酚醛树脂(苯酚,邻苯基苯酚,氯二甲苯酚,六氯酚,百里酚,戊间甲酚,2,4-二氯苄醇,policresylen,硫双氯酚,4-烯丙基儿茶酚,对羟基苯甲酸酯(包括对羟基苯甲酸苄酯、对羟基苯甲酸丁酯、对羟基苯甲酸乙酯、对羟基苯甲酸甲酯和对羟基苯甲酸丙酯)丁基化羟基茴香醚,丁基化羟基甲苯,辣椒素,香芹酚,甲氧甲酚,丁子香酚,愈创木酚),卤代(羟基)二苯醚(双氯酚,三氯生,六氯酚和溴氯酚,4-己基间苯二酚,8-羟基喹啉及其盐),季铵化合物(苯扎氯铵衍生物,苄索氯铵衍生物,十六烷基三甲基氯化铵/十六烷基三甲基溴化铵,十六烷基吡啶鎓,溴棕三甲铵,氯苄羟乙铵,二癸基二甲基氯化铵),吖啶衍生物(乳酸依沙吖啶,9-氨基吖啶,吖啶黄),双胍(包括聚合双胍),以及脒(聚氨基丙基双胍,二溴丙脒,氯己定,阿来西定,丙脒,己脒,聚已缩胍),硝基呋喃衍生物(呋喃西林),喹啉衍生物(地喹氯铵,氯喹那多,羟基喹啉,氯碘喹啉),碘产品,精油(月桂,肉桂,丁香,百里香,桉树,薄荷,柠檬,茶树,木兰提取物,薄荷醇,香叶醇),阳离子,苯胺类(水杨酸苯胺,二苯脲),水杨酸酯(包括水杨酸薄荷酯、水杨酸甲酯和水杨酸苯酯),邻苯二酚,邻苯二甲酸及其盐,海克替啶,奥替尼啶,血根碱,溴化度米芬,烷基吡啶鎓氯化物诸如氯化十六烷基吡啶,氯化十四烷基吡啶鎓和N-十四烷基-4-乙基吡啶鎓氯化物,碘,磺酰胺,哌啶子基衍生物如地米诺酚和辛苯醇,以及它们的混合物,各种防腐剂(1,3-二氧六环的衍生物,咪唑衍生物,异噻唑酮,六胺衍生物,三嗪,噁唑并-噁唑,羟甲基甘氨酸钠,二硫氰基甲烷,克菌丹)。
优选的抗菌体系是卤代苄醇衍生物,如氯二甲苯酚(PCMX),卤代羟基二苯醚优选地双氯酚,季铵盐优选烷基苯扎氯铵和烷基苄索氯铵及其衍生物,精油,漂白剂体系优选过氧化物漂白剂以及它们的混合物。最优选的抗菌体系是苯扎氯铵、双氯酚和PCMX。
包封物:组合物可包含包封物,例如包含芯、具有内表面和外表面的壳的包封物,所述壳包封所述芯。该芯可包含任何衣物洗涤护理助剂,但通常所述芯可包含选自下列的材料:香料;增白剂;染料;驱虫剂;硅氧烷;蜡;调味剂;维生素;织物软化剂;护肤剂,在一个方面,石蜡;酶;抗菌剂;漂白剂;感觉剂;以及它们的混合物;并且所述外壳可包含选自下列的材料:聚乙烯;聚酰胺;聚乙烯醇,任选地包含其它共聚单体;聚苯乙烯;聚异戊二烯;聚碳酸酯;聚酯;聚丙烯酸酯;氨基塑料,在一个方面所述氨基塑料可包含聚脲、聚氨酯和/或聚脲氨酯,在一个方面所述聚脲可包含聚甲醛脲(polyoxymethyleneurea)和/或三聚氰胺甲醛;聚烯烃;多糖,在一个方面所述多糖可包含海藻酸盐和/或脱乙酰壳多糖;明胶;虫胶;环氧树脂;乙烯基聚合物;水不溶的无机物;硅氧烷;以及它们的混合物。优选的包封物包含香料。优选的包封物包括壳,所述壳可包含三聚氰胺甲醛和/或交联的三聚氰胺甲醛。优选的包封物包括芯材料和壳,公开了至少部分包围所述芯材料的所述壳。至少75%、85%或甚至90%的所述包封物可具有0.2MPa至10MPa的破裂强度,以及基于初始包封的总有益剂计0%至20%,或甚至小于10%或5%的有益剂渗漏。优选下列那些:其中至少75%、85%或甚至90%的所述包封物可具有(i)1微米至80微米,5微米至60微米,10微米至50微米,或甚至15微米至40微米的粒度,和/或(ii)至少75%、85%或甚至90%的所述包封物可具有30nm至250nm,80nm至180nm,或甚至100nm至160nm的颗粒壁厚。甲醛清除剂可与包封物一起用于例如胶囊浆液中,和/或在包封物被添加到组合物中之前、期间或之后添加到此类组合物中。合适的胶囊能够按照USPA 2008/0305982 A1和/或USPA 2009/0247449 A1的教导制得。另选地,合适的胶囊可购自Appleton Papers Inc.(Appleton,Wisconsin,USA)。
在一个优选的方面,优选地除了包封物以外,组合物还可包含沉积助剂。优选的沉积助剂选自阳离子聚合物和非离子聚合物。适宜的聚合物包括阳离子淀粉、阳离子羟乙基纤维素、聚乙烯基甲醛、刺槐豆胶、甘露聚糖、木葡聚糖、罗望子胶、聚对苯二甲酸乙二醇酯、以及包含甲基丙烯酸二甲氨基乙酯任选地与一种或多种单体的聚合物,所述单体选自丙烯酸和丙烯酰胺。
香料:优选的本发明的组合物包含香料。通常,组合物包含香料,该香料包含一种或多种香料原料,其选自WO08/87497中所述那些。然而,可使用可用于洗涤剂中的任何香料。将香料掺入本发明组合物中的优选方法是经由包封的香料颗粒,所述颗粒包含水溶性羟基化合物或三聚氰胺-甲醛或改性的聚乙烯醇。在一个方面,包封物包含(a)包含一种或多种水溶性羟基化合物的至少部分水溶性的固体基质,优选淀粉;和(b)被固体基质所包封的香料油。在另一个方面,所述香料可与聚胺(优选聚乙烯亚胺)预复合,以便形成席夫碱。
聚合物:除可以是聚合物的DTI之外,洗涤剂组合物还可包含一种或多种聚合物。示例为任选地改性的羧甲基纤维素、聚(乙二醇)、聚(乙烯醇)、聚羧酸酯诸如聚丙烯酸酯、马来酸/丙烯酸共聚物、和甲基丙烯酸月桂酯/丙烯酸共聚物以及羧酸酯聚合物。
合适的羧酸酯聚合物包括马来酸酯/丙烯酸酯无规共聚物或聚丙烯酸酯均聚物。羧酸酯聚合物可为具有4,000Da至9,000Da,或6,000Da至9,000Da分子量的聚丙烯酸酯均聚物。其他适宜的羧酸酯聚合物为马来酸和丙烯酸的共聚物,并且可具有4,000Da至90,000Da范围内的分子量。
其他适宜的羧酸酯聚合物为共聚物,所述共聚物包含:(i)50重量%至小于98重量%的结构单元,所述结构单元衍生自一种或多种包含羧基基团的单体;(ii)1重量%至小于49重量%的结构单元,所述结构单元衍生自一种或多种包含磺酸根部分的单体;和(iii)1重量%至49重量%的结构单元,所述结构单元衍生自一种或多种类型的单体,所述单体选自由式(I)和(II)表示的包含醚键的单体:
式(I):
其中在式(I)中,R0表示氢原子或CH3基团,R表示CH2基团、CH2CH2基团、或单键,X表示0-5的数,前提条件是当R为单键时,X表示1-5的数,并且R1为氢原子或C1至C20有机基团;
式(II)
在式(II)中,R0表示氢原子或CH3基团,R表示CH2基团、CH2CH2基团或单键,X代表0-5的数,并且R1为氢原子或C1至C20有机基团。
组合物可包含一种或多种两亲性清洁聚合物,诸如具有以下通式结构的化合物:双((C2H5O)(C2H4O)n)(CH3)-N+-CxH2x-N+-(CH3)-双((C2H5O)(C2H4O)n),其中n=20至30,并且x=3至8,或其硫酸化或磺化变体。在一个方面,将该聚合物硫酸化或磺化,以提供两性离子污垢悬浮聚合物。
组合物优选地包含两亲性烷氧基化油脂清洁聚合物,该聚合物具有平衡的亲水和疏水性能,这使得它们从织物和表面去除油脂颗粒。优选的两亲性烷氧基化油脂清洁聚合物包括芯结构和连接到该芯结构的多个烷氧基化物基团。这些可包含烷氧基化的聚亚烷基亚胺,优选具有内部聚亚乙基氧嵌段和外部聚亚丙基氧嵌段。通常,可将这些以0.005重量%至10重量%,一般来讲0.5重量%至8重量%的量掺入本发明的组合物中。
烷氧基化聚羧酸酯诸如由聚丙烯酸酯制备的那些可用于本文中,以提供附加的油脂去除性能。此类材料描述于WO 91/08281和PCT 90/01815中。化学上,这些材料包含聚丙烯酸酯,其每隔7-8个丙烯酸酯单元具有一个乙氧基侧链。侧链具有式-(CH2CH2O)m(CH2)nCH3,其中m为2-3,并且n为6-12。侧链通过酯连接到聚丙烯酸酯“主链”,以提供“梳型”聚合物结构。分子量可变化,但是通常介于约2000至约50,000的范围内。此类烷氧基化聚羧酸酯可占本文组合物的约0.05重量%至约10重量%。
所述组合物可包含聚乙二醇聚合物,并且这些聚合物在包含混合表面活性剂体系的组合物中可为特别优选的。合适的聚乙二醇聚合物包括无规接枝共聚物,所述无规接枝共聚物包含:(i)包含聚乙二醇的亲水性主链;和(ii)一个或多个侧链,所述侧链选自:C4-C25烷基、聚亚丙基、聚亚丁基、饱和的C1-C6一元羧酸的乙烯基酯、丙烯酸或甲基丙烯酸的C1-C6烷基酯、以及它们的混合物。合适的聚乙二醇聚合物具有聚乙二醇主链,该聚乙二醇主链带有无规接枝的聚乙酸乙烯酯侧链。聚乙二醇主链的平均分子量可在2,000Da至20,000Da,或4,000Da至8,000Da的范围内。聚乙二醇主链与聚乙酸乙烯酯侧链的分子量比率可为1:1至1:5,或1:1.2至1:2。每个亚乙基氧单元的平均接枝位点数可小于1,或小于0.8,每个亚乙基氧单元的平均接枝位点数可在0.5至0.9的范围内,或者每个亚乙基氧单元的平均接枝位点数可在0.1至0.5,或0.2至0.4的范围内。合适的聚乙二醇聚合物为Sokalan HP22。
通常,可将这些以0.005重量%至10重量%,更通常0.05重量%至8重量%的量掺入本发明的组合物中。
优选地,组合物包含一种或多种羧酸酯聚合物,诸如马来酸酯/丙烯酸酯无规共聚物或聚丙烯酸酯均聚物。在一个方面,羧酸酯聚合物为聚丙烯酸酯均聚物,其具有4,000Da至9,000Da,或6,000Da至9,000Da的分子量。通常,可将这些以0.005重量%至10重量%、或0.05重量%至8重量%的量掺入本发明的组合物中。
优选地,组合物包含一种或多种去垢性聚合物。示例包括具有由下式(VI)、(VII)或(VIII)中的一者所定义的结构的去垢性聚合物:
(VI)-[(OCHR1-CHR2)a-O-OC-Ar-CO-]d
(VII)-[(OCHR3-CHR4)b-O-OC-sAr-CO-]e
(VIII)-[(OCHR5-CHR6)c-OR7]f
其中:
a、b和c为1至200;
d、e和f为1至50;
Ar为1,4-取代的亚苯基;
sAr为在5位被SO3Me取代的1,3-取代的亚苯基;
Me为Li、K、Mg/2、Ca/2、Al/3、铵、单烷基铵、二烷基铵、三烷基铵或四烷基铵,其中烷基基团为C1-C18烷基或C2-C10羟烷基、或它们的混合物;
R1、R2、R3、R4、R5和R6独立地选自H或C1-C18正烷基或C1-C18异烷基;并且
R7为直链或支链的C1-C18烷基,或者直链或支链的C2-C30烯基,或者具有5至9个碳原子的环烷基基团,或者C8-C30芳基基团,或者C6-C30芳烷基基团。
合适的去垢性聚合物为聚酯去垢性聚合物,诸如Repel-o-tex聚合物,包括由Rhodia提供的Repel-o-tex SF、SF-2和SRP6。其它合适的去垢性聚合物包括Texcare聚合物,包括由Clariant提供的Texcare SRA100、SRA300、SRN100、SRN170、SRN240、SRN300和SRN325。其它合适的去垢性聚合物为Marloquest聚合物,诸如由Sasol提供的MarloquestSL。
优选地,组合物包含一种或多种纤维素聚合物,包括选自下列的那些:烷基纤维素、烷基烷氧基烷基纤维素、羧烷基纤维素、烷基羧烷基纤维素。优选的纤维素聚合物选自羧甲基纤维素、甲基纤维素、甲基羟乙基纤维素、甲基羧甲基纤维素、以及它们的混合物。在一个方面,所述羧甲基纤维素具有0.5至0.9的羧甲基取代度和100,000Da至300,000Da的分子量。
漂白剂:组合物可优选包含一种或多种漂白剂。除了漂白催化剂之外的合适漂白剂包括光漂白剂、漂白活化剂、过氧化氢、过氧化氢源、预成形过酸以及它们的混合物。一般来讲,当使用漂白剂时,本发明的组合物可包含按本主题组合物的重量计约0.1%至约50%,或甚至约0.1%至约25%的漂白剂或漂白剂的混合物。合适漂白剂的示例包括:
(1)光漂白剂,例如磺化酞菁锌、磺化酞菁铝、呫吨类染料以及它们的混合物;
(2)预成形过酸:合适的预成形过酸包括但不限于选自下列的化合物:
预成形过氧酸或其盐,通常为过羧酸及盐、过碳酸及盐、过亚胺酸及盐、过一硫酸及盐(例如)、以及它们的混合物。合适的示例包括过氧羧酸或其盐,或过氧磺酸或其盐。适用于本文的典型过氧羧酸盐具有对应于下列化学式的化学结构:/>
其中:R14选自烷基、芳烷基、环烷基、芳基或杂环基团;R14基团可为直链或支链的,取代或未取代的;当过酸为疏水性时,其具有6至14个碳原子或8至12个碳原子,并且当过酸为亲水性时,其具有少于6个碳原子或甚至少于4个碳原子,并且Y为任何合适的抗衡离子,用以达到电中性,优选Y选自氢、钠或钾。
R14优选为直链或支链的、取代或未取代的C6-9烷基。优选地,过氧酸或其盐选自过氧己酸、过氧庚酸、过氧辛酸、过氧壬酸、过氧癸酸、它们的任何盐,或它们的任何组合。尤其优选的过氧酸为苯二甲酰亚氨基过氧链烷酸,特别是ε-苯二甲酰亚氨基过氧己酸(PAP)。优选地,过氧酸或其盐具有30℃至60℃范围内的熔点。
预成形的过氧酸或其盐也可为过氧磺酸或其盐,通常具有对应于下列化学式的化学结构:
其中:R15选自烷基、芳烷基、环烷基、芳基或杂环基团;R15基团可为直链或支链的、取代或未取代的;并且Z为任何合适的抗衡离子,用以达到电中性,Z优选选自氢、钠或钾。R15优选为直链或支链的、取代或未取代的C4-14优选C6-14烷基。优选地,此类漂白剂组分可以0.01至50%,最优选0.1%至20%的量存在于本发明的组合物中。
(3)过氧化氢源,例如无机过氧化氢合物盐,包括以下碱金属盐如过硼酸盐(通常为一水合物或四水合物)、过碳酸盐、过硫酸盐、过磷酸盐、过硅酸盐的钠盐以及它们的混合物。在本发明的一个方面,无机过氧化氢合物盐选自过硼酸钠盐、过碳酸钠盐以及它们的混合物。当使用无机过氧化氢合物盐时,无机过氧化氢合物盐通常以总的织物和家居护理产品的0.05重量%至40重量%或1重量%至30重量%的量存在,并且通常以可被涂覆的结晶固体形式被掺入此类织物和家居护理产品中。合适的涂层包含无机盐(诸如碱金属硅酸盐、碳酸盐或硼酸盐或它们的混合物)或有机材料(诸如水溶性或水分散性聚合物、蜡、油或脂肪皂);以及
(4)具有R-(C=O)-L的漂白活化剂,其中R为烷基基团,任选地为支链的;当漂白活化剂为疏水性时,其具有6至14个碳原子或者8至12个碳原子,并且当漂白活化剂为亲水性时,其具有少于6个碳原子或甚至少于4个碳原子;并且L为离去基团。适宜的离去基团的示例为苯甲酸及其衍生物,尤其是苯磺酸根。合适的漂白活化剂包括十二烷酰基羟基苯磺酸盐、癸酰基羟基苯磺酸盐、癸酰基羟苯甲酸或其盐、3,5,5-三甲基己酰基羟基苯磺酸盐、四乙酰基乙二胺(TAED)和壬酰基羟基苯磺酸盐(NOBS)。合适的漂白活化剂还公开于WO 98/17767中。虽然可采用任何适宜的漂白活化剂,但是在本发明的一个方面中,本主题组合物可包含NOBS、TAED、或它们的混合物。
(5)漂白催化剂:本发明的组合物还可包含一种或多种漂白催化剂,漂白催化剂能够接纳来自过氧酸和/或其盐的氧原子,并且将所述氧原子传递至可氧化基质。适宜的漂白催化剂包括但不限于:亚胺阳离子和聚离子;亚胺两性离子;改性胺;改性氧化胺;N-磺酰基亚胺;N-膦酰基亚胺;N-酰基亚胺;噻二唑二氧化物;全氟亚胺;环状糖酮和α-氨基酮以及它们的混合物。适宜的α-氨基酮如例如WO 2012/000846 A1、WO 2008/015443 A1和WO 2008/014965A1中所述。适宜的混合物如USPA 2007/0173430 A1中所述。
在一个方面,漂白催化剂具有对应于下列通式的结构:
其中R13选自:2-乙基己基、2-丙基庚基、2-丁基辛基、2-戊基壬基、2-己基癸基、正十二烷基、正十四烷基、正十六烷基、正十八烷基、异壬基、异癸基、异十三烷基和异十五烷基。
(6)组合物可优选地包含催化金属配合物。一类优选的包含金属的漂白催化剂是包含下列的催化剂体系:具有限定的漂白催化活性的过渡金属阳离子,如铜阳离子、铁阳离子、钛阳离子、钌阳离子、钨阳离子、钼阳离子或锰阳离子;具有很低或无漂白催化活性的辅助金属阳离子,如锌阳离子或铝阳离子;以及对于催化和辅助金属阳离子有限定的稳定性常数的螯合剂,尤其是乙二胺四乙酸、乙二胺四(亚甲基膦酸)以及它们的水溶性盐。这种催化剂公开于U.S.4,430,243中。
如果需要,本文组合物可借助锰化合物来催化。这些化合物和用量是本领域熟知的,并且包括例如公开于U.S.5,576,282中的锰基催化剂。
可用于本文的钴漂白催化剂是已知的,并且描述于例如U.S.5,597,936、U.S.5,595,967中。此类钴催化剂易于通过已知的方法制备,诸如例如U.S.5,597,936和U.S.5,595,967中教导的。
本文的组合物还可适宜地包含配体诸如戊二酮(WO 05/042532A1)和/或大多环刚性配体-缩写为“MRL”的过渡金属配合物。作为实施项而不是作为限制,可调节本文的组合物和方法,以在含水洗涤介质中提供大约至少一亿分之一的活性MRL物质,并且在洗涤液体中将通常提供约0.005ppm至约25ppm,约0.05ppm至约10ppm,或甚至约0.1ppm至约5ppm的MRL。
本发明过渡金属漂白催化剂中合适的过渡金属包括例如锰、铁和铬。合适的MRL包括5,12-二乙基-1,5,8,12-四氮杂双环[6.6.2]十六烷。
通过已知方法易于制备合适的过渡金属MRL,例如在WO 00/32601和U.S.6,225,464中教导的。
当存在时,过氧化氢源/过酸和/或漂白活化剂一般以基于织物和家居护理产品的重量计约0.1重量%至约60重量%,约0.5重量%至约40重量%,或甚至约0.6重量%至约10重量%的量存在于所述组合物中。一种或多种疏水过酸或其前体可与一种或多种亲水过酸或其前体结合使用。
通常,过氧化氢源和漂白活化剂将被一起掺入。可选择过氧化氢源和过酸或漂白活化剂的量,使得可用氧(来自过氧化物源)与过酸的摩尔比为1:1至35:1,或甚至2:1至10:1。
表面活性剂:除了阴离子和非离子表面活性剂体系外,本发明的组合物还可包含另外的表面活性剂,例如选自阳离子表面活性剂、两性表面活性剂、两性电解质表面活性剂、两亲性表面活性剂和两性离子表面活性剂以及它们的混合物的表面活性剂。优选地,这些另外的表面活性剂包含总表面活性剂体系的小于50重量%,更优选总表面活性剂体系的小于30重量%,更优选小于10重量%。
合适的阳离子去污表面活性剂包括烷基吡啶鎓化合物、烷基季铵化合物、烷基季鏻化合物、烷基三元锍化合物以及它们的混合物。
合适的阳离子去污表面活性剂为由以下通式表示的季铵化合物:
(R)(R1)(R2)(R3)N+X-
其中,R为直链或支链的、取代或未取代的C6-18烷基或烯基部分,R1和R2独立地选自甲基或乙基部分,R3为羟基、羟甲基或羟乙基部分,X为提供电中性的阴离子,合适的阴离子包括:卤离子例如氯离子;硫酸根;和磺酸根。合适的阳离子去污表面活性剂为单C6-18烷基单羟乙基二甲基季铵氯化物。高度合适的阳离子去污表面活性剂是单-C8-10烷基单-羟乙基双-甲基季铵氯化物,单-C10-12烷基单-羟乙基双-甲基季铵氯化物和单-C10烷基单-羟乙基双-甲基季铵氯化物。
适宜的两性/两性离子表面活性剂包括氧化胺和甜菜碱。
胺中和的阴离子表面活性剂-本发明的阴离子表面活性剂和辅助阴离子辅助表面活性剂可以酸形式存在,并且所述酸形式可被中和以形成适用于本发明洗涤剂组合物中的表面活性剂盐。用于中和的典型试剂包括碱性金属抗衡离子如氢氧根,例如NaOH或KOH。用于中和酸形式的本发明阴离子表面活性剂和辅助阴离子表面活性剂或辅助表面活性剂的其它优选试剂包括氨、胺或链烷醇胺。链烷醇胺是优选的。合适的非限制性示例包括单乙醇胺、二乙醇胺、三乙醇胺、和本领域中已知的其它直链或支链的链烷醇胺,例如,高度优选的链烷醇胺包括2-氨基-1-丙醇、1-氨基丙醇、单异丙醇胺、或1-氨基-3-丙醇。可完全或在部分程度上完成胺中和,例如可用钠或钾中和阴离子表面活性剂混合物的一部分并且可用胺或链烷醇胺中和阴离子表面活性剂混合物的一部分。
助洗剂:优选地,组合物包含一种或多种助洗剂或助洗剂体系。当使用助洗剂时,本发明的组合物将通常包含至少1%,或至少2%至60%的助洗剂。合适的助洗剂包括例如沸石、磷酸盐、柠檬酸盐等。可优选的是所述组合物包含低含量的磷酸盐和/或沸石,例如1重量%至10重量%或5重量%。所述组合物可甚至基本上不含强效助洗剂;基本上不含强效助洗剂是指“无有意添加的”沸石和/或磷酸盐。典型的沸石助洗剂包括沸石A、沸石P和沸石MAP。典型的磷酸盐助洗剂为三聚磷酸钠。
螯合剂:优选地,组合物包含螯合剂和/或晶体生长抑制剂。合适的分子包括铜、铁和/或锰螯合剂、以及它们的混合物。合适的分子包括氨基羧酸酯、氨基膦酸酯、琥珀酸酯、它们的盐、以及它们的混合物。用于本文的适宜螯合剂的非限制性示例包括乙二胺四乙酸盐、N-(羟乙基)乙二胺三乙酸盐、次氮基三乙酸盐、乙二胺四丙酸盐、三亚乙基四胺六乙酸盐、二亚乙基三胺五乙酸盐、乙醇二甘氨酸、乙二胺四(亚甲基膦酸盐)、二亚乙基三胺五(亚甲基膦酸)(DTPMP)、乙二胺二琥珀酸盐(EDDS)、羟基乙烷二亚甲基膦酸(HEDP)、甲基甘氨酸双乙酸(MGDA)、二亚乙基三胺五乙酸(DTPA)、它们的盐、以及它们的混合物。用于本发明的螯合剂的其它非限制性示例存在于美国专利7445644、7585376和2009/0176684A1中。其他用于本文的合适螯合剂是市售的DEQUEST系列,以及来自Monsanto,DuPont和Nalco,Inc的螯合剂。
pH调节剂:可掺入pH调节剂以产生所需的pH。可添加洗涤剂制造领域的技术人员已知的任何碱或酸,例如氢氧化钠或氢氧化钾、碳酸钠或碳酸钾或者硅酸钠或硅酸钾、柠檬酸或更强的酸诸如盐酸。那些增加缓冲能力的pH调节剂可为特别优选的。
硅酸盐:组合物还可优选地含有硅酸盐,诸如硅酸钠或硅酸钾。组合物可包含0重量%至小于10重量%的硅酸盐,至9重量%,或至8重量%,或至7重量%,或至6重量%,或至5重量%,或至4重量%,或至3重量%,或甚至至2重量%,并且优选地高于0重量%,或0.5重量%,或甚至1重量%的硅酸盐。合适的硅酸盐为硅酸钠。
分散剂:所述组合物还可优选地包含分散剂。合适的水溶性有机材料包括均聚或共聚酸或它们的盐,其中多元羧酸包含彼此间隔不超过两个碳原子的至少两个羧基。
酶稳定剂:组合物可优选地包含酶稳定剂。由于例如最终的织物和家居护理产品中存在钙和/或镁离子的水溶性源,因此可使用任何常规的酶稳定剂,所述水溶性源向所述酶提供此类离子。在含水组合物包含蛋白酶的情况下,可加入可逆蛋白酶抑制剂,诸如硼化合物(包括硼酸酯),或优选地加入4-甲酰基苯基硼酸、苯基硼酸以及它们的衍生物,或化合物诸如甲酸钙、甲酸钠和1,2-丙二醇、二甘醇,以进一步改善稳定性。
织物着色染料:
组合物可包含织物着色染料。合适的织物着色染料(有时称为调色剂、上蓝剂或美白剂)通常为织物提供蓝色或紫色色调。织物着色染料能够单独使用或组合使用,以产生特定的调色色调并/或对不同的织物类型调色。这可通过例如将红色和蓝绿色染料混合以产生蓝色或紫色色调来提供。织物着色染料可选自任何已知化学类别的染料,包括但不限于吖啶、蒽醌类(包括多环醌类)、吖嗪、偶氮(例如,单偶氮、双偶氮、三偶氮、四偶氮、多偶氮)、包括预金属化偶氮、苯并二呋喃和苯并二呋喃酮、类胡萝卜素、香豆素、花菁、二氮杂半花菁、二苯甲烷、甲臜、半花菁、靛蓝类、甲烷、萘酰亚胺、萘醌、硝基和亚硝基、噁嗪、酞菁、吡唑类、二苯乙烯、苯乙烯基、三芳基甲烷、三苯甲烷、氧杂蒽以及它们的混合物。
合适的织物着色染料包括染料以及染料-粘土缀合物。优选的织物着色染料选自小分子染料和聚合物染料。合适的小分子染料包括选自以下的小分子染料:属于酸性、直接、碱性、活性、溶剂或分散染料的颜色索引(C.I.)分类的染料,所述染料例如被分类为蓝、紫、红、绿或黑,并且单独地或与其它染料组合地或与其它助剂成分组合地提供所期望的色调。也可包括被描述为EP-A-1794274中所述的水解活性染料的染料。在另一方面,合适的小分子染料包括选自色素索引(Society of Dyers and Colourists,Bradford,UK)的下列编号的小分子染料:直接紫染料诸如5、7、9、11、31、35、48、51、66和99,直接蓝染料诸如1、71、80和279,酸性红染料诸如17、73、52、88和150,酸性紫染料诸如15、17、24、43、49和50,酸性蓝染料诸如15、17、25、29、40、45、48、75、80、83、90和113,酸性黑染料诸如1,碱性紫染料诸如1、3、4、10和35,碱性蓝染料诸如3、16、22、47、66、75和159,分散染料或溶剂染料诸如US2008/034511 A1或US 8,268,016 B2中描述的那些,或如US 7,208,459 B2中所公开的染料诸如溶剂紫罗兰13,以及它们的混合物。在另一方面,合适的小分子染料包括选自以下的小分子染料:C.I.编号酸性紫17、酸性蓝80、酸性紫50、直接蓝71、直接紫51、直接蓝1、酸性红88、酸性红150、酸性蓝29、酸性蓝113、或它们的混合物。
合适的聚合物染料包括选自下列的聚合物染料:包含共价键合(有时称为缀合)的色原体的聚合物(染料-聚合物缀合物)(例如具有共聚至该聚合物主链中的色原体的聚合物)以及它们的混合物。聚合物染料包括描述于WO2011/98355、US2012/225803 A1、US2012/090102 A1、WO2012/166768、US 7,686,892 B2和WO2010/142503中的那些。
其它合适的聚合物染料包括选自下列的聚合物染料:以商品名(美国南卡罗来纳州斯帕坦堡的美利肯公司(Milliken,Spartanburg,South Carolina,USA))销售的织物-实体着色剂,由至少一种活性染料形成的染料-聚合物缀合物,以及选自包含一定部分的聚合物的聚合物,所述部分选自:羟基部分、伯胺部分、仲胺部分、硫醇部分以及它们的混合物。在另一方面,合适的聚合物染料包括选自下列的聚合物染料:/>Violet CT,与一种或多种活性蓝、活性紫或活性红染料共价结合的羧甲基纤维素(CMC)诸如与C.I.活性蓝19缀合的CMC(由爱尔兰威克洛的Megazyme公司(Megazyme,Wicklow,Ireland)以产品名AZO-CM-CELLULOSE、产品代码S-ACMC销售),烷氧基化三苯基-甲烷聚合物着色剂,烷氧基化噻吩聚合物着色剂,烷氧基化碳环和烷氧基化杂环偶氮着色剂,以及它们的混合物。优选的聚合物染料包括任选取代的烷氧基化染料,诸如烷氧基化三苯基-甲烷聚合物着色剂、烷氧基化噻吩聚合物着色剂、烷氧基化碳环和烷氧基化杂环偶氮着色剂,以及它们的混合物,诸如Liquitint染料。
优选的调色染料包括存在于WO 08/8749|A1、WO2011/011799和US 2012/12975|A1中的美白剂。用于本发明中的优选的调色剂可以是这些参考文献中公开的优选的染料,包括选自WO2011/011799的表5中的实施例1-42的那些。其它优选的染料公开于US 8,138,222中。其它优选的染料公开于US 7,909,890 B2中。
合适的染料粘土缀合物包括选自包含以下各项的组的染料粘土缀合物:至少一种阳离子/碱性染料和绿土粘土、以及它们的混合物。在另一方面,合适的染料粘土缀合物包括选自一种阳离子/碱性染料的染料粘土缀合物和选自蒙脱石粘土、锂蒙脱石粘土、皂石粘土、以及它们的混合物的粘土。合适的阳离子/碱性染料的示例包括C.I.碱性黄1至108,C.I.碱性橙1至69,C.I.碱性红1至118,C.I.碱性紫1至51,C.I.碱性蓝1至164,C.I.碱性绿1至14,C.I.碱性棕1至23,CI碱性黑1至11,在另一方面,合适的染料粘土缀合物包括选自下列的染料粘土缀合物:蒙脱石碱性蓝B7 C.I.42595缀合物、蒙脱石碱性蓝B9 C.I.52015缀合物,蒙脱石碱性紫V3 C.I.42555缀合物,蒙脱石碱性绿G1 C.I.42040缀合物,蒙脱石碱性红R1 C.I.45160缀合物,蒙脱石C.I.碱性黑2缀合物,锂蒙脱石碱性蓝B7 C.I.42595缀合物,锂蒙脱石碱性蓝B9 C.I.52015缀合物,锂蒙脱石碱性紫V3 C.I.42555缀合物,锂蒙脱石碱性绿G1 C.I.42040缀合物,锂蒙脱石碱性红R1 C.I.45160缀合物,锂蒙脱石C.I.碱性黑2缀合物、皂石碱性蓝B7 C.I.42595缀合物、皂石碱性蓝B9 C.I.52015缀合物,皂石碱性紫V3C.I.42555缀合物,皂石碱性绿G1 C.I.42040缀合物,皂石碱性红R1 C.I.45160缀合物,皂石C.I.碱性黑2缀合物、以及它们的混合物。
由有机合成途径制成的织物着色染料或甚至其它助剂诸如颜料、光学增白剂、聚合物可作为反应混合物的一部分掺入洗涤剂组合物中,该反应混合物是具有一个或多个任选纯化步骤的助剂的有机合成的结果。此类反应混合物一般包含助剂自身,并且此外还可包含未反应的原料和/或有机合成途径的副产物。
合适的聚合物织物着色染料如下所示。如所有此类烷氧基化化合物一样,有机合成可制备具有不同烷氧基化度的分子的混合物。此类混合物可直接用于提供织物着色染料,或可经历纯化步骤。
织物着色染料可具有以下结构:
其中:
R1和R2独立地选自:H、烷基、烷氧基、亚烷基氧基、烷基封端的亚烷基氧基、脲和酰胺基;
R3为取代的芳基基团;
X为包含磺酰胺部分和任选地烷基和/或芳基部分的取代基,并且其中所述取代基包含至少一个亚烷基氧基链。调色染料可为噻吩染料,诸如噻吩偶氮染料,优选地为烷氧基化的。任选地,染料可被选自磺酸根基团、羧基或季铵基团的至少一种增溶基团取代。特别优选的染料是来自Milliken公司的Liquitint染料,特别是Violet DD。
颜料:合适的颜料包括选自下列的颜料:黄烷士酮、靛蒽醌、包含1至4个氯原子的氯化靛蒽醌、皮蒽酮、二氯皮蒽酮、单溴二氯皮蒽酮、二溴二氯皮蒽酮、四溴皮蒽酮、二萘嵌苯-3,4,9,10-四羧酸二酰亚胺,其中酰亚胺基团可为未取代的或者被C1至C3烷基或苯基或杂环基取代,并且其中苯基和杂环基可另外带有不提供水中溶解度的取代基、蒽嘧啶羧酸酰胺、蒽酮紫、异蒽酮紫、二噁嗪颜料、每个分子可包含至多2个氯原子的铜酞菁、多氯铜酞菁或每个分子包含至多14个溴原子的多溴氯铜酞菁、以及它们的混合物。其它适宜的颜料如WO2008/090091中所述。在另一方面,适宜的颜料包括选自下列的颜料:群青蓝(C.I.颜料蓝29)、群青紫(C.I.颜料紫15)、单星蓝以及它们的混合物。尤其优选颜料蓝15至20,尤其是颜料蓝15和/或16。其它合适的颜料包括选自以下的那些:群青蓝(C.I.颜料蓝29)、群青紫(C.I.颜料紫15)、单星蓝以及它们的混合物。合适的调色剂更详细地描述于US 7,208,459B2中。
前述织物调色剂可用于调色剂的混合物中和/或用于与任何颜料的混合物中。
光学增白剂:光学增白剂的合适示例为例如二苯乙烯增白剂、香豆素增白剂、苯并噁唑增白剂以及它们的混合物。二氨基二苯乙烯二磺酸型增白剂(下文称为“DAS”)在WO-A-98/52907中被分类为亲水性的。DAS的商业示例为Tinopal DMS(出自汽巴公司(CIBA))。另一种类型的低ClogP增白剂为二苯乙烯基联苯增白剂(下文称为“DSBP”)。该类型的增白剂的商业示例为Tinopal CBS-X(也出自汽巴公司(CIBA))。可用于本发明的商业光学增白剂可分成亚类,它们包括但不限于二苯乙烯、吡唑啉、羧酸、次甲基花青、二苯并噻吩-5,5-二氧化物、唑、5-和6-元环杂环的衍生物,以及其它多种试剂。特别优选的增白剂选自:2(4-苯乙烯基-3-磺苯基)-2H-萘并[1,2-d]三唑钠、4,4′-双([4-苯胺基-6-(N-甲基-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′-二磺酸二钠以及4,4′-双(2-磺基苯乙烯基)联苯二钠。此类增白剂的其它示例公开于“The Production and Application of FluorescentBrightening Agents”(M.Zahradnik,由John Wiley&Sons公布,New York(1982)中。
优选的增白剂具有下列结构:
合适的增白剂含量为约0.01重量%、约0.05重量%、约0.1重量%或甚至约0.2重量%,至0.5重量%、0.75重量%或甚至1.0重量%的上限含量。
高度优选的光学增白剂包括C.I.荧光增白剂260,优选具有下列结构:
用于制备C.I荧光增白剂260的方法在BE680847中有所描述。
美观染料:所述组合物可包含美观染料和/或颜料。合适的染料包括用于使清洁和/或处理组合物着色的任何常规染料,通常为小分子或聚合物。这些染料一般为非织物着色染料。
溶剂体系:本发明的组合物可包含溶剂体系,例如单独包含水的溶剂体系,或者由不含水或含水的有机溶剂的混合物组成的溶剂体系。优选的有机溶剂包括1,2-丙二醇、乙醇、甘油、二丙二醇、甲基丙烷二醇以及它们的混合物。还可使用其它低级醇、C1-C4链烷醇胺诸如单乙醇胺和三乙醇胺。可不含溶剂体系,例如本发明的无水固体实施方案中可不含溶剂体系,但该溶剂体系的含量更通常在约0.1%至约98%,优选至少约1%至约50%,更通常约5%至约25%的范围内。此类溶剂体系可特别适用于在增白剂与洗涤剂组合物中的其它组分混合之前与增白剂预混合。另选地或除此之外,可将一种或多种表面活性剂与增白剂预混合。在这种优选的实施方案中,与增白剂预混合的表面活性剂包含至少25重量%或至少50重量%(基于表面活性剂的总重量计)的非离子表面活性剂。
在本发明的一些实施方案中,组合物为结构化液体的形式。此类结构化液体可为内部结构化的,由此结构由主要成分(例如表面活性剂物质)形成,和/或可为通过使用次级成分(例如聚合物、粘土和/或硅酸盐物质)用作例如增稠剂来提供三维基质结构而外部结构化的。组合物可包含结构剂,优选地0.01重量%至5重量%,0.1重量%至2.0重量%的结构剂。合适的结构剂的示例示于US2006/0205631A1、US2005/0203213A1、US7294611、US6855680中。结构剂通常选自甘油二酯和甘油三酯、二硬脂酸乙二醇酯、微晶纤维素、基于纤维素的材料、微纤维纤维素、疏水改性的碱溶胀性乳液如Polygel W30(3VSigma)、生物聚合物、黄原胶、结冷胶、氢化蓖麻油、氢化蓖麻油衍生物如它们的非乙氧基化衍生物以及它们的混合物,具体地,选自下列的那些:氢化蓖麻油、氢化蓖麻油衍生物、微纤维纤维素、羟基官能化结晶材料、长链脂肪醇、12-羟基硬脂酸、粘土、以及它们的混合物。优选的结构剂描述于美国专利6,855,680中,其详细定义了合适的羟基官能化结晶材料。优选氢化蓖麻油。有用的结构剂的非限制性示例包括:此类结构剂具有螺纹状结构化体系,所述螺纹状结构化体系具有一定范围的纵横比。其它适宜的结构剂和用于制备它们的方法描述于WO2010/034736中。
本发明的组合物可包含高熔点脂肪族化合物。可用于本文的高熔点脂肪族化合物具有25℃或更高的熔点,并且选自:脂肪醇、脂肪酸、脂肪醇衍生物、脂肪酸衍生物、以及它们的混合物。不旨在将此类低熔点化合物包括在此部分中。高熔点化合物的非限制性示例可见于“International Cosmetic Ingredient Dictionary”,第五版,1993;和“CTFACosmetic Ingredient Handbook”,第二版,1992中。当存在时,为了提供改善的调理有益效果,如向湿发施用期间的光滑感、柔软性和干发上的润湿感,高熔点脂肪族化合物优选以按所述组合物的重量计0.1%至40%,优选1%至30%,更优选1.5%至16%,1.5%至8%的含量被包含在所述组合物中。
阳离子聚合物:本发明组合物可包含阳离子聚合物。阳离子聚合物在组合物中的浓度通常在0.05%至3%,在另一个实施方案中0.075%至2.0%,在另一个实施方案中0.1%至1.0%的范围内。在组合物预期使用的pH值下(该pH一般在pH 3至pH 9范围内,在一个实施方案中介于pH 4和pH 8之间),适宜的阳离子聚合物具有至少0.5meq/gm,在另一个实施方案中至少0.9meq/gm,在另一个实施方案中至少1.2meq/gm,在另一个实施方案中至少1.5meq/gm,但在一个实施方案中还小于7meq/gm,并且在另一个实施方案中小于5meq/gm的阳离子电荷密度。本文中,聚合物的“阳离子电荷密度”是指聚合物上的正电荷数目与聚合物分子量的比率。此类适宜阳离子聚合物的平均分子量通常介于10,000和1千万之间,在一个实施方案中介于50,000和5百万之间,并且在另一个实施方案中介于100,000和3百万之间。
适用于本发明的组合物的阳离子聚合物,包含阳离子含氮部分(如季铵)或阳离子质子化氨基部分。任何阴离子抗衡离子可以与阳离子聚合物缔合使用,只要该聚合物在水中、在组合物中或在组合物的凝聚层相中保持可溶,并且只要该抗衡离子与组合物的基本组分在物理上和化学上是相容的,或换句话讲不会不适当地损害产品的性能、稳定性或美观性。这样的抗衡离子的非限制性示例包括卤素离子(例如氯离子、氟离子、溴离子、碘离子)、硫酸根和甲酯硫酸根。
上述聚合物的非限制性示例描述于Estrin、Crosley和Haynes编的CTFA CosmeticIngredient Dictionary,第3版,(The Cosmetic,Toiletry,and Fragrance Association,Inc.,Washington,D.C.(1982))。
用于所述组合物的其它适用的阳离子聚合物包括多糖聚合物、阳离子瓜耳胶衍生物、包含四价氮的纤维素醚、合成聚合物、醚化纤维素的共聚物、瓜尔胶和淀粉。当使用时,本文的阳离子聚合物可溶于组合物或者可溶于组合物中的复合凝聚层相,该凝聚层相是由本文上述的阳离子聚合物与阴离子表面活性剂、两性表面活性剂和/或两性离子表面活性剂组分形成的。阳离子聚合物的复合凝聚层也可以与组合物中的其它带电物质一起形成。
合适的阳离子聚合物描述于美国专利3,962,418、3,958,581、和美国专利公布2007/0207109A1中。
非离子聚合物:本发明的组合物可包含非离子聚合物作为调理剂。本文可用的是具有大于1000的分子量的聚亚烷基二醇。可用的是具有以下通式的那些:
其中R95选自H、甲基、以及它们的混合物。组合物中可包含调理剂,具体地硅氧烷。可用于本发明组合物中的调理剂通常包括水不溶性、水分散性、非挥发性、可形成乳化液体颗粒的液体。适用于组合物的调理剂是通常特征为硅氧烷(例如硅油、阳离子硅氧烷、硅橡胶纯胶料、高折射硅氧烷和硅氧烷树脂)、有机调理油(例如烃油、聚烯烃和脂肪酸酯)或它们的组合的那些调理剂,或在本文含水表面活性剂基质中形成液体分散颗粒的那些调理剂。上述调理剂应当在物理上和化学上与组合物的基本组分相容,并且换句话讲不应不适当地损害产品的稳定性、美观性或性能。
调理剂在组合物中的浓度应足以提供所需的调理有益效果。此类浓度可随调理剂、所需的调理性能、调理剂颗粒的平均尺寸、其它组分的类型和浓度以及其它类似因素而变化。
硅氧烷调理剂的浓度通常在约0.01%至约10%的范围内。合适的硅氧烷调理剂和硅氧烷的任选的悬浮剂的非限制性示例描述于美国重新公布的专利34,584;美国专利5,104,646、5,106,609、4,152,416、2,826,551、3,964,500、4,364,837、6,607,717、6,482,969、5,807,956、5,981,681、6,207,782、7,465,439、7,041,767、7,217,777,美国专利申请2007/0286837A1、2005/0048549A1、2007/0041929A1,英国专利849,433,德国专利DE10036533,其以引用方式全文并入本文;Chemistry and Technology of Silicones,NewYork:Academic Press(1968);General Electric Silicone Rubber Product DataSheets SE 30,SE 33,SE 54and SE 76;Silicon Compounds,Petrarch Systems,Inc.(1984);以及Encyclopedia of Polymer Science and Engineering,第15卷,第2版,第204-308页,John Wiley&Sons,Inc.(1989)。
染料转移抑制剂(DTI):清洁和/或处理组合物优选地包含一种染料转移抑制剂或多于一种染料转移抑制剂的混合物。合适的染料转移抑制剂选自:聚乙烯基吡咯烷酮聚合物、聚胺N-氧化物聚合物、N-乙烯基吡咯烷酮和N-乙烯基咪唑的共聚物、聚乙烯基噁唑烷酮、聚乙烯基咪唑以及它们的混合物。其它合适的DTI为如WO2012/095354中所述的三嗪、如WO2010/130624中所述的聚合苯并噁嗪、如DE 102009001144A中所述的聚乙烯基四唑、如WO2009/127587中所述的多孔聚酰胺颗粒以及如WO2009/124908中所述的不溶性聚合物颗粒。其它合适的DTI描述于WO2012/004134中,或选自如下的聚合物:(a)两亲性烷氧基化聚胺、两亲性接枝共聚物、两性离子污垢悬浮聚合物、酞菁锰、过氧化物酶以及它们的混合物。
优选的DTI类包括但不限于聚乙烯基吡咯烷酮聚合物、聚胺N-氧化物聚合物、N-乙烯基吡咯烷酮和N-乙烯基咪唑的共聚物、聚乙烯基噁唑烷酮、聚乙烯基咪唑、以及它们的混合物。更具体地讲,优选用于本文的聚胺N-氧化物聚合物包含具有以下结构式的单元:R-AX-P;其中P是可聚合单元,N-O基团可连接于其上,或者N-O基团可形成该可聚合单元的一部分,或者N-O基团可连接到两个单元;A为以下结构中的一种:-NC(O)-、-C(O)O-、-S-、-O-、-N=;x为0或1;并且R是脂族基团、乙氧基化脂族基团、芳族基团、杂环基团或脂环族基团,或它们的任意组合,N-O基团的氮可连接于其上,或者N-O基团是这些基团的一部分。优选的聚胺N-氧化物为其中R是杂环基团诸如吡啶、吡咯、咪唑、吡咯烷、哌啶以及它们的衍生物的那些。
所述N-O基团可用以下通用结构表示:
其中R1、R2、R3是脂族基团、芳族基团、杂环基团或脂环族基团,或它们的组合;x、y和z是0或1;并且N-O基团的氮可连接于其上,或可形成上述基团中任一个的一部分。聚胺N-氧化物的氧化胺单元具有的pKa<10,优选pKa<7,更优选pKa<6。
可以使用任何聚合物主链,只要形成的氧化胺聚合物是水溶性的并且具有染料转移抑制特性。合适的聚合物主链的示例是聚乙烯基、聚亚烷基、聚酯、聚醚、聚酰胺、聚酰亚胺、聚丙烯酸酯以及它们的混合物。这些聚合物包括无规共聚物或嵌段共聚物,其中一种单体类型是胺N-氧化物,而另一种单体类型是N-氧化物。胺N-氧化物聚合物通常具有10:1至1:1,000,000的胺与胺N-氧化物的比率。然而,聚氧化胺聚合物中存在的氧化胺基团数可通过适当的共聚作用或通过适当的N-氧化度来改变。所述聚氧化胺可以由几乎任何聚合度获得。
典型地,平均分子量在500至1,000,000;更优选1,000至500,000;最优选5,000至100,000的范围内。这种优选类型的物质被称为“PVNO”。
可用于本文洗涤剂组合物中的最优选的聚胺N-氧化物是平均分子量为约50,000并且胺与胺N-氧化物比率为约1:4的聚(4-乙烯基吡啶-N-氧化物)。
N-乙烯基吡咯烷酮和N-乙烯基咪唑聚合物的共聚物(被称为“PVPVI”类)也优选用于本文。优选地,PVPVI具有5,000至1,000,000,更优选5,000至200,000,并且最优选10,000至20,000的平均分子量范围。(可如Barth等人,Chemical Analysis,Vol 113.“ModemMethods of Polymer Characterization”
中所述的那样,通过光散射来测定平均分子量范围,该文献的公开内容以引用方式并入本文。)所述PVPVI共聚物通常具有1:1至0.2:1,更优选为0.8:1至0.3:1,最优选为0.6:1至0.4:1的N-乙烯基咪唑与N-乙烯基吡咯烷酮的摩尔比。
这些共聚物可以是直链的或支链的。
本发明组合物还可使用具有约5,000至约400,000,优选约5,000至约200,000,并且更优选约5,000至约50,000的平均分子量的聚乙烯吡咯烷酮(“PVP”)。PVP是洗涤剂领域技术人员所已知的;参见例如EP-A-262,897和EP-A-256,696所述文献引入本发明以供参考。
包含PVP的组合物还可包含具有约500至约100,000,优选约1,000至约10,000的平均分子量的聚乙二醇(“PEG”)。优选地,以ppm计,递送于洗涤溶液中的PEG与PVP的比率为约2:1至约50:1,并且更优选为约3:1至约10:1。
包含(a)N-乙烯基吡咯烷酮与N-乙烯基咪唑的共聚物和(b)聚胺N-氧化物聚合物、特别是聚4-乙烯基吡啶N-氧化物的混合聚合物体系是特别优选的DTI体系,特别优选的是(a):(b)的重量比为5:1至1:5。对于本发明必要的DTI的优选分子量为1000至250000道尔顿,更优选地2000至150000或甚至8000至100000道尔顿。
合适的示例包括得自Ashland Aqualon的PVP-K15、PVP-K30、ChromaBond S-400、ChromaBond S-403E和Chromabond S-100,以及得自BASF的HP165、/>HP50、/>HP53、/>HP59、/>HP 56K、/>HP 66。
本发明人已经发现,包含光学增白剂和DTI的组合物提供显著的白度增加,这是令人惊讶的,因为通常DTI降低光学增白剂的功效。
染料转移抑制剂可以按组合物的重量计的约0.0001%至约15%,约0.01%至约10%,优选地约0.01%至约5%的含量存在。
有机调理油:本发明的组合物还可包含约0.05%至约3%的至少一种作为调理剂的有机调理油,所述有机调理油可单独使用,或与其它调理剂诸如硅氧烷(本文所述)组合使用。合适的调理油包括烃油、聚烯烃和脂肪酸酯。还适用于本文组合物的是Procter&Gamble Company描述于美国专利5,674,478和5,750,122中的调理剂。还适用于本文的是描述于美国专利4,529,586、4,507,280、4,663,158、4,197,865、4,217,914、4,381,919、和4,422,853中的那些调理剂。
卫生剂:本发明的组合物还可包含组分以递送卫生和/或恶臭有益效果,诸如蓖麻油酸锌、百里酚、季铵盐(诸如)、聚乙烯亚胺(诸如得自巴斯夫公司(BASF)的)及其锌配合物、银和银化合物(尤其是设计用于缓慢释放Ag+或纳米银分散体的那些)中的一种或多种。
益生菌:组合物可包含益生菌,诸如描述于WO2009/043709中的那些。
促泡剂:如果期望高度起泡,组合物可优选地包含促泡剂。合适的示例为C10-C16链烷醇酰胺或C10-C14烷基硫酸盐,其优选以1%-10%的含量掺入。C10-C14单乙醇酰胺和二乙醇酰胺举例说明了典型的一类这种促泡剂。与高起泡辅助表面活性剂,诸如以上提到的氧化胺、甜菜碱和磺基甜菜碱一起使用这种促泡剂也是有利的。如果需要,可以通常为0.1%-2%的含量添加水溶性镁盐和/或钙盐诸如MgCl2、MgSO4、CaCl2、CaSO4等以提供附加的泡沫并增强油脂去除性能。
抑泡剂:可将用于减少或抑制泡沫形成的化合物掺入本发明的组合物中。泡沫抑制在如美国专利4,489,455和4,489,574中所述的所谓的“高浓度清洁过程”中以及在前加载式洗衣机中可以是尤其重要的。可使用各种各样的材料作为抑泡剂,并且抑泡剂是本领域的技术人员熟知的。参见例如Kirk Othmer Encyclopedia of Chemical Technology,第三版,第7卷,第430-447页(John Wiley&Sons,Inc.,1979)。抑泡剂的示例包括一元羧酸脂肪酸及其可溶性盐、高分子量烃如石蜡、脂肪酸酯(例如脂肪酸甘油三酯)、一元醇的脂肪酸酯、脂族C18-C40酮(例如硬脂酮)、N-烷基化氨基三嗪、优选具有低于约100℃的熔点的含蜡烃、硅氧烷抑泡剂和二级醇。抑泡剂描述于美国专利2,954,347;4,265,779;4,265,779;3,455,839;3,933,672;4,652,392;4,978,471;4,983,316;5,288,431;4,639,489;4,749,740;和4,798,679;4,075,118;欧洲专利申请89307851.9;EP 150,872;以及DOS 2,124,526中。
对于待用于自动衣物洗涤洗衣机中的任何洗涤剂组合物,泡沫不应形成至它们溢流出洗衣机的程度。当使用时,抑泡剂优选以“抑泡量”存在。所谓“抑泡量”是指所述组合物的配制人员能够选择将足以控制泡沫的这种泡沫控制剂的量,以得到用于自动衣物洗涤洗衣机中的低度起泡衣物洗涤剂。本文的组合物将一般包含0%至10%的抑泡剂。当用作抑泡剂时,一元羧酸脂肪酸及其盐通常以按洗涤剂组合物的重量计至多5%的量存在。优选采用0.5%至3%的脂肪族一元羧酸盐抑泡剂。硅氧烷抑泡剂通常以按所述洗涤剂组合物的重量计至多2.0%的量使用,但是可使用更高的量。磷酸单硬脂基酯抑泡剂一般以按所述组合物的重量计0.1%至2%的范围内的量使用。烃抑泡剂的量通常以0.01%至5.0%的范围内的量使用,但是可使用更高的含量。醇抑泡剂通常以按成品组合物的重量计0.2%-3%的量使用。
珠光剂:可将如WO2011/163457中所述的珠光剂掺入本发明的组合物中。
香料:优选地,组合物包含在优选地在0.001重量%至3重量%,最优选地0.1重量%至1重量%范围内的香料。许多适宜的香料示例提供于由CFTA Publications公布的CTFA(Cosmetic,Toiletry and Fragrance Association)1992International BuyersGuide和由Schnell Publishing Co.公布的OPD 1993Chemicals Buyers Directory 80thAnnual Edition中。本发明组合物中通常存在多种香料组分,例如四种、五种、六种、七种或更多种。在香料混合物中,优选15重量%至25重量%为顶香。顶香由Poucher(Journal ofthe Society of Cosmetic Chemists 6(2):80[1995])定义。优选的顶香包括玫瑰红氧化物、柑橘油、乙酸里哪酯、薰衣草、里哪醇、二氢月桂烯醇和顺式-3-己醇。
包装:可采用任何常规的包装,并且所述包装可为完全或部分透明的,使得消费者可看见产品的颜色,这可由对于本发明必要的染料的颜色提供或贡献。可在一些或所有包装中包含紫外吸收化合物。
制备组合物的方法
本发明的组合物可为固体(例如颗粒剂或片剂)或液体形式。优选地,所述组合物为液体形式。它们可通过由配方师选择的任何方法制备,其非限制性示例描述于示例以及U.S.4,990,280;U.S.20030087791A1;U.S.20030087790A1;U.S.20050003983A1;U.S.20040048764A1;U.S.4,762,636;U.S.6,291,412;U.S.20050227891A1;EP 1070115A2;U.S.5,879,584;U.S.5,691,297;U.S.5,574,005;U.S.5,569,645;U.S.5,565,422;U.S.5,516,448;U.S.5,489,392;U.S.5,486中。
当为液体形式时,本发明的组合物可为含水的(通常高于2重量%,或甚至高于5重量%或10重量%的总水,至多90重量%或至多80重量%或70重量%的总水)或非水的(通常低于2重量%的总水含量)。通常,本发明的组合物将为光学增白剂、DTI和任选附加辅助材料的水性溶液或均匀分散体或悬浮液形式,其中一些可通常为固体形式,这些固体形式与组合物中的通常为液体的组分组合,诸如非离子液体醇乙氧基化物、含水液体载体以及任何其它通常为液体的任选成分。上述溶液、分散体或悬浮液将为可接受的相稳定的。当为液体形式时,本发明的洗涤剂在20s-1和21℃下优选具有1至1500厘泊(1-1500mPa*s),更优选100至1000厘泊(100-1000mPa*s),并且最优选200至500厘泊(200-500mPa*s)的粘度。粘度可通过常规方法来测定。可使用得自TA Instruments的AR 550流变仪,采用40mm直径的钢板锭子和500μm间隙尺寸,来测量粘度。在20s-1的高剪切粘度和0.05-1的低剪切粘度可通过在21℃下在3分钟时间内由0.1-1至25-1的对数剪切速率扫描获得。其中本文所述的优选流变特性可使用内部现有的具有洗涤剂成分的结构或通过使用外部的流变改性剂获得。更优选地,所述洗涤剂诸如洗涤剂液体组合物具有约100厘泊至1500厘泊、更优选地100cps至1000cps的高剪切速率粘度。单位剂量洗涤剂诸如洗涤剂液体组合物具有400cps至1000cps的高剪切速率粘度。洗涤剂诸如衣物洗涤软化组合物通常具有10cps至1000cps、更优选地10cps至800cps、最优选地10cps至500cps的高剪切速率粘度。手洗餐具洗涤组合物具有300cps至4000cps,更优选地300cps至1000cps的高剪切速率粘度。
可通过将本文的液体形式的清洁和/或处理组合物的组分以任何方便的顺序组合,然后通过混合例如搅拌所得的组分组合以形成相稳定的液体洗涤剂组合物,来制备本文的液体形式的清洁和/或处理组合物。在用于制备此类组合物的方法中,形成了液体基质,其包含至少大部分或甚至基本上所有的液体组分,如非离子表面活性剂、无表面活性液体载体和其它任选液体组分,同时通过向该液体组合施加剪切搅拌来彻底混合液体组分。例如,使用机械搅拌器快速搅拌可有效地被采用。在保持剪切搅拌的同时,可添加基本上所有的任何阴离子表面活性剂和固体形式的成分。继续搅拌该混合物,并且如果需要,可在此时增强搅拌,以在液相中形成溶液或不溶固相颗粒的均匀分散体。在一些或所有固体形式物质都已加入此搅拌混合物中后,可掺入任何待包含的酶物质的颗粒如酶小球。作为上文所述的组合物制备过程的一种变化,一种或多种固体组分可作为与少部分的一种或多种液体组分预混的溶液或颗粒浆液加入搅拌混合物中。在加入所有组合物组分之后,继续搅拌该混合物充足的一段时间,以形成具有所需粘度和相稳定特性的组合物。通常,这将涉及约30至60分钟的一段搅拌时间。
小袋:在本发明的一个优选的实施方案中,组合物以组合剂量形式提供,为片剂形式或优选地为保留于水溶性膜内的液体/固体(任选地为颗粒)/凝胶/糊剂形式,所述水溶性膜被称为小袋或小囊。组合物可被包封于单隔室小袋或多隔室小袋中。多隔室小袋更详细地描述于EP-A-2133410中。着色染料或非着色染料或颜料或其它美观剂也可用于一个或多个隔室中。
适于形成小袋的膜可溶解或分散于水中,并且优选地具有至少50%,优选地至少75%,或甚至至少95%的水溶解度/分散度,如在使用具有20微米最大孔径的玻璃过滤器之后,由此处描述的方法测得:
将50克±0.1克的小袋材料加入预称重的400ml烧杯中,并加入245ml±1ml的蒸馏水。在设定为600rpm的磁力搅拌器上,将其剧烈搅拌30分钟。然后,将该混合物经由具有上述限定孔尺寸(最大20微米)的折叠式定性多孔玻璃过滤器过滤。通过任意常规方法将收集的滤液中的水分干燥,并测定剩余材料的重量(溶解或分散的那部分)。然后,可计算出溶解度或分散度的百分比。优选的膜材料为聚合物材料。如本领域所已知的,膜材料可通过例如将聚合物材料浇铸、吹塑、挤出或吹塑挤出而获得。适合用作小袋材料的优选的聚合物、共聚物或其衍生物选自聚乙烯醇、聚乙烯吡咯烷酮、聚环氧烷、丙烯酰胺、丙烯酸、纤维素、纤维素醚、纤维素酯、纤维素酰胺、聚乙酸乙烯酯、聚羧酸和聚羧酸盐、聚氨基酸或肽、聚酰胺、聚丙烯酰胺、马来酸/丙烯酸共聚物、多糖(包括淀粉和明胶)、天然树胶(诸如黄原胶和角叉菜胶)。更优选的聚合物选自聚丙烯酸酯和水溶性丙烯酸酯共聚物、甲基纤维素、羧甲基纤维素钠、糊精、乙基纤维素、羟乙基纤维素、羟丙基甲基纤维素、麦芽糖糊精、聚甲基丙烯酸酯,并且最优选地选自聚乙烯醇、聚乙烯醇共聚物和羟丙基甲基纤维素(HPMC)、以及它们的组合。优选地,小袋材料中的聚合物如PVA聚合物的含量为至少60%。所述聚合物可具有任何重均分子量,优选约1000至1,000,000,更优选约10,000至300,000,还更优选约20,000至150,000。聚合物的混合物也可用作小袋材料。这对于根据其应用和所需的要求来控制隔室或小袋的机械特性和/或溶解特性来讲可能是有益的。合适的混合物包括例如其中一种聚合物具有比另一种聚合物高的水溶解度,和/或一种聚合物具有比另一种聚合物高的机械强度的混合物。还合适的是具有不同重均分子量的聚合物的混合物,例如重均分子量为约10,000至40,000,优选约20,000的PVA或其共聚物与重均分子量为约100,000至300,000,优选约150,000的PVA或其共聚物的混合物。还适于本文的是聚合物共混物组合物,其例如包含水解可降解的和水溶性聚合物共混物如聚交酯和聚乙烯醇,可通过混合聚交酯和聚乙烯醇而获得,通常包含按重量计约1-35%的聚交酯和按重量计约65%至99%的聚乙烯醇。优选用于本文的是约60%至约98%水解,优选地约80%至约90%水解以改善材料的溶解特性的聚合物。
当然,可在制备本发明的隔室中采用不同的膜材料和/或不同厚度的膜。选择不同膜的益处是所得到的隔室可能表现出不同的溶解度或释放特性。
最优选的膜材料是由MonoSol贸易参考M8630、M8900、H8779获知的PVA膜(如申请人共同未决的专利申请参考44528和11599中所述)和描述于US 6 166 117和US 6 787 512中的那些,以及具有对应溶解度和可塑性特征的PVA膜。
本文的膜材料还可包含一种或多种添加剂成分。例如,可能有利的是添加增塑剂,例如甘油、乙二醇、二甘醇、丙二醇、山梨醇以及它们的混合物。其他添加剂包括待递送至洗涤水的功能性洗涤剂添加剂,例如有机聚合物分散剂等。
可通过将苦味剂掺入小袋内的组合物中和/或涂布到膜上,来将苦味剂掺入到小袋或小囊中。
使用方法:通常如上文所述制备的本发明的组合物可用于形成洗涤/处理织物中使用的含水洗涤/处理溶液。一般来讲,将有效量的此类组合物添加到水中,例如常规的织物自动洗衣机中,以形成此类含水衣物洗涤溶液。接着通常在搅拌下使由此形成的含水洗涤溶液与待用其洗涤/处理的织物接触。加入水中形成含水衣物洗涤溶液的有效量的本文洗涤剂组合物可包含足够的量,以形成约500ppm至25,000ppm或500ppm至15,000ppm组合物的含水洗涤溶液,或将以含水洗涤溶液形式提供约1,000ppm至3,000ppm的本文洗涤剂组合物。
通常,通过使洗涤剂以一定量与洗涤水接触来形成洗涤液体,该量使得洗涤液体中洗涤剂的浓度为高于0g/l至5g/l、或1g/l、以及至4.5g/l、或至4.0g/l、或至3.5g/l、或至3.0g/l、或至2.5g/l、或甚至至2.0g/l、或甚至至1.5g/l。洗涤织物或纺织物的方法可在顶部加载式或前加载式自动洗衣机中进行,或可用于手洗衣物洗涤应用中。在这些应用中,所形成的洗涤液体以及衣物洗涤剂组合物在所述洗涤液体中的浓度为主洗涤循环中的那些。在任何任选的一个或多个漂洗步骤期间,当确定所述洗涤液体的体积时,不包括任何加入的水。
洗涤液体可包含40升或更少的水,或30升或更少、或20升或更少、或10升或更少、或8升或更少、或甚至6升或更少的水。洗涤液体可包含0升以上至15升,或2升,并且至12升,或甚至至8升的水。通常将每升洗涤液体0.01kg至2kg织物定量投配到所述洗涤液体中。通常将每升洗涤液体0.01kg、或0.05kg、或0.07kg、或0.10kg、或0.15kg、或0.20kg、或0.25kg织物定量投配到所述洗涤液体中。任选地,使50g或更少、或45g或更少、或40g或更少、或35g或更少、或30g或更少、或25g或更少、或20g或更少、或甚至15g或更少、或甚至10g或更少的组合物与水接触以形成洗涤液体。此类组合物通常在溶液中以约500ppm至约15,000ppm的浓度使用。当洗涤溶剂为水时,水温通常在约5℃至约90℃的范围内,并且当区域包含织物时,水与织物的比率通常为约1:1至约30:1。通常,包含本发明洗涤剂的洗涤液体具有3至11.5的pH。
在一个方面,所公开的此类方法包括以下步骤:任选地洗涤和/或漂洗所述表面或织物,使所述表面或织物与本说明书中公开的任何组合物接触,然后任选地洗涤和/或漂洗所述表面或织物,以及任选的干燥步骤。
此类表面或织物的干燥可通过家庭或工业环境中采用的普通方法中的任一种(机器干燥或室外干燥)而实现。所述织物可包括能够在正常消费者或机构使用条件下被洗涤的任何织物,并且本发明尤其适用于合成纺织物诸如聚酯和尼龙,并且尤其适于处理混合织物和/或包含合成织物和纤维素织物和/或纤维的织物。合成织物的示例为聚酯、尼龙,这些可存在于与纤维素纤维的混合物中,例如涤棉布织物。溶液通常具有7至11,更通常8至10.5的pH。组合物通常在溶液中以500ppm至5,000ppm的浓度使用。水温通常在约5℃至约90℃范围内。水与织物的比率通常为约1:1至约30:1。
可在具有或没有中间纯化步骤的情况下,将本发明组合物中的助剂成分作为生成此类组分的合成的产物掺入组合物中。在没有纯化步骤的情况下,通常所使用的混合物将包含所需的组分或其混合物(并且除非另外指明,否则本文给出的百分比涉及组分本身的重量百分比),此外还包含未反应的原料以及由副反应和/或不完全反应形成的杂质。例如,对于乙氧基化或取代的组分而言,混合物将可能包含不同程度的乙氧基化/取代。
实施例
以下是本发明的清洁组合物的实施例:
实施例1-7重垢型液体衣物洗涤剂组合物
基于总清洁和/或处理组合物重量计。酶含量报告为原料。
实施例8至16单位剂量组合物
这些实施例提供了用于单位剂量衣物洗涤剂的多种制剂。组合物8至12包含单个单位剂量隔室。该膜用于将组合物包封在PVA中。
基于总清洁和/或处理组合物重量计。酶含量报告为原料。
在以下实施例中,单位剂量具有三个隔室,但类似的组合物能够制备有两个、四个或五个隔室。用于包封所述隔室的膜是聚乙烯醇。
基于总清洁和/或处理组合物重量计,酶含量报告为原料。
实施例19至24:用于手洗或洗衣机(通常为顶部加载式洗衣机)的颗粒状衣物洗涤剂组合物。
实施例25-37
通常用于前加载式自动洗衣机的颗粒状衣物洗涤剂组合物。
AE1.8S 为C12-15烷基乙氧基(1.8)硫酸盐。
AE3S 为C12-15烷基乙氧基(3)硫酸盐。
AE7 为C12-13醇乙氧基化物,平均乙氧基化度为7
AE8 为C12-13醇乙氧基化物,平均乙氧基化度为8。
AE9 为C12-13醇乙氧基化物,平均乙氧基化度为9。
淀粉酶1 为15mg活性物质/g
淀粉酶2 为29mg活性物质/g
淀粉酶3 为Stainzyme20mg活性物质/g
AS 为C12-14烷基硫酸盐
纤维素酶2 为CellucleanTM,15.6mg活性物质/g
木葡聚糖酶 为20mg活性物质/g
螯合剂1 为二亚乙基三胺五乙酸
螯合剂2 为1-羟乙烷1,1-二膦酸
螯合剂3 为乙二胺-N,N′-二琥珀酸的钠盐,(S,S)异构体(EDDS)
分散体B 为糖苷酶水解酶,报告为1000mg活性物质/g
DTI 1 为聚(4-乙烯基吡啶-1-氧化物)(诸如Chromabond),
DTI 2 为聚(1-乙烯基吡咯烷酮-共-1-乙烯基咪唑)(诸如Sokalan)。
HSAS 是中间支化的烷基硫酸盐,公开于US 6,020,303和US 6,060,443中。
LAS 是具有C9-C15平均脂族碳链长度的直链烷基苯磺酸盐(HLAS为酸形式)。
脂肪酶 为18mg活性物质/g
甘露聚糖酶 为25mg活性物质/g
核酸酶 为磷酸二酯酶SEQ ID NO 1,报告为1000mg活性物质/g
光学增白剂1 为4,4′-双{[4-苯氨基-6-吗啉基-均-三嗪-2-基]-氨基}-2,2′-二苯乙烯二磺酸二钠
光学增白剂2 为4,4′-双-(2-磺基苯乙烯基)联苯二钠(钠盐)
光学增白剂3 为得自3V Sigma的Optiblanc
香料包封物 是核壳三聚氰胺甲醛香料微胶囊。
光漂白剂 为磺化酞菁锌
抛光酶 为Paranitrobenzyl酯酶,报告为1000mg活性物质/g
聚合物1 为双((C2H5O)(C2H4O)n)(CH3)-N+-CxH2x-N+-(CH3)-双
((C2H5O)(C2H4O)n),其中n=20-30,x=3至8,或其硫酸化或磺化变体
聚合物2 为乙氧基化(EO15)四亚乙基五胺
聚合物3 为乙氧基化聚乙烯亚胺
聚合物4 为乙氧基化六亚甲基二胺
聚合物5 为由Rohm&Haas提供的Acusol 305,
聚合物6 为由BASF提供的用乙酸乙烯酯侧链接枝的聚乙二醇聚合物。
蛋白酶 为Purafect40.6mg活性物质/g
蛋白酶2 为32.89mg活性物质/g
蛋白酶3 为84mg活性物质/g
季铵 为C12-14二甲基羟乙基氯化铵。
S-ACMC 为由Megazyme提供的活性蓝19偶氮-CM-纤维素
去垢剂 为/>
结构剂 为氢化蓖麻油
紫罗兰DD 是由Milliken提供的噻吩偶氮染料
本文所公开的量纲和值不应理解为严格限于所引用的精确数值。相反,除非另外指明,否则每个这样的量纲旨在表示所述值以及围绕该值功能上等同的范围。例如,公开为“40mm”的量纲旨在表示“约40mm”。
Claims (14)
1.一种清洁组合物,包含核酸酶,优选脱氧核糖核酸酶和/或核糖核酸酶和包含阴离子表面活性剂和非离子表面活性剂的表面活性剂体系,其中所述阴离子表面活性剂与非离子表面活性剂的重量比为1.5:1至1:10。
2.根据权利要求1所述的清洁组合物,包含5重量%至80重量%,或10重量%至50重量%,更优选地15重量%至45重量%的总表面活性剂含量。
3.根据权利要求1或权利要求2所述的清洁组合物,其中所述阴离子表面活性剂与非离子表面活性剂的重量比为1.2:1至1:4,或甚至1:1至1:2。
4.根据前述权利要求中任一项所述的清洁组合物,其中所述阴离子表面活性剂包括烷基烷氧基化硫酸盐表面活性剂,其优选地为乙氧基化的并且优选地具有0.5至2.5的平均烷氧基化度。
5.根据前述权利要求中任一项所述的清洁组合物,其中所述表面活性剂体系包含选自阳离子表面活性剂、两性离子表面活性剂和两性表面活性剂的另外的表面活性剂,优选地所述另外的表面活性剂占所述总表面活性剂体系的小于20重量%。
6.根据前述权利要求中任一项所述的清洁组合物,其中所述核酸酶选自以下E.C.类别中的任一种:E.C.3.1.21.x(其中x=1,2,3,4,5,6,7,8,9),
3.1.22.y(其中y=1,2,4,5),E.C.3.1.30.z(其中z=1,2)或E.C.3.1.31.1,或它们的混合物,优选地来自E.C.3.1.21,优选E.C.3.1.21.1。
7.根据前述权利要求中任一项所述的清洁组合物,其中所述核酸酶包括脱氧核糖核酸酶。
8.根据权利要求6所述的清洁组合物,其中所述酶包括具有RNA酶和DNA酶活性两者,优选地来自E.C.3.1.30.2的酶。
9.根据前述权利要求中任一项所述的清洁组合物,其中所述酶为微生物的,优选地细菌酶。
10.根据前述权利要求中任一项所述的清洁组合物,其中所述酶具有氨基酸序列,所述氨基酸序列与SEQ ID NO:1,SEQ ID NO:2或SEQ ID NO:3所示的氨基酸序列具有至少85%,或至少90%,或至少95%,或甚至100%的同一性。
11.根据前述权利要求中任一项所述的方法,其中所述纺织物包含来自E.C.3.2.1.52的β-N-乙酰基葡萄糖胺苷酶,优选与SEQ ID NO:4具有至少70%的同一性的酶。
12.根据前述权利要求中任一项所述的清洁组合物,其中所述组合物另外包含织物着色染料和/或选自脂肪酶,诸如第一洗涤脂肪酶、淀粉酶、蛋白酶、甘露聚糖酶、果胶酸裂解酶、纤维素酶和角质酶的另外的酶。
13.一种清洁纺织物的方法,包括将根据前述权利要求中任一项所述的清洁组合物与水混合以形成含水液体,并且在衣物洗涤步骤中使纺织物与所述含水液体接触。
14.包含阴离子表面活性剂和非离子表面活性剂的表面活性剂体系促进利用核酸酶进行的纺织物的清洁的用途,其中所述阴离子表面活性剂与非离子表面活性剂的重量比为1.5:1至1:10。
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-
2016
- 2016-04-27 CN CN202311611720.7A patent/CN117736810A/zh active Pending
- 2016-04-27 WO PCT/US2016/029427 patent/WO2016176241A1/en active Application Filing
- 2016-04-27 EP EP16167262.1A patent/EP3088506B1/en active Active
- 2016-04-27 JP JP2017556542A patent/JP2018521149A/ja active Pending
- 2016-04-27 CN CN201680024500.6A patent/CN107820515A/zh active Pending
- 2016-04-27 DK DK16167262.1T patent/DK3088506T3/en active
- 2016-04-27 US US15/139,373 patent/US20160319228A1/en not_active Abandoned
- 2016-04-27 HU HUE16167262A patent/HUE039245T2/hu unknown
- 2016-04-27 ES ES16167262.1T patent/ES2682178T3/es active Active
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2017
- 2017-10-04 ZA ZA2017/06666A patent/ZA201706666B/en unknown
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2019
- 2019-09-27 JP JP2019177533A patent/JP2020023704A/ja active Pending
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DK3088506T3 (en) | 2018-08-13 |
ES2682178T3 (es) | 2018-09-19 |
JP2018521149A (ja) | 2018-08-02 |
WO2016176241A1 (en) | 2016-11-03 |
JP2022017378A (ja) | 2022-01-25 |
CN107820515A (zh) | 2018-03-20 |
HUE039245T2 (hu) | 2018-12-28 |
EP3088506A1 (en) | 2016-11-02 |
ZA201706666B (en) | 2019-05-29 |
EP3088506B1 (en) | 2018-05-23 |
US20160319228A1 (en) | 2016-11-03 |
JP2020023704A (ja) | 2020-02-13 |
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