CN101889111A - 织物处理方法 - Google Patents
织物处理方法 Download PDFInfo
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- CN101889111A CN101889111A CN2008801197927A CN200880119792A CN101889111A CN 101889111 A CN101889111 A CN 101889111A CN 2008801197927 A CN2008801197927 A CN 2008801197927A CN 200880119792 A CN200880119792 A CN 200880119792A CN 101889111 A CN101889111 A CN 101889111A
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- polymer
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- 239000004744 fabric Substances 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 144
- 239000012736 aqueous medium Substances 0.000 claims abstract description 55
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 229920001519 homopolymer Polymers 0.000 claims abstract description 33
- 229920001577 copolymer Polymers 0.000 claims abstract description 32
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 20
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims abstract description 14
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920002125 Sokalan® Polymers 0.000 claims description 24
- 239000004584 polyacrylic acid Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 11
- 239000004615 ingredient Substances 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 8
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 238000003672 processing method Methods 0.000 claims description 3
- 239000002609 medium Substances 0.000 claims 1
- -1 alkylene glycol Chemical compound 0.000 abstract description 8
- 150000001720 carbohydrates Chemical class 0.000 abstract 2
- 125000002947 alkylene group Chemical group 0.000 abstract 1
- 229920000742 Cotton Polymers 0.000 description 29
- 229920000728 polyester Polymers 0.000 description 26
- 230000008021 deposition Effects 0.000 description 21
- 239000002202 Polyethylene glycol Substances 0.000 description 19
- 238000004140 cleaning Methods 0.000 description 17
- 229920002451 polyvinyl alcohol Polymers 0.000 description 17
- 229920001223 polyethylene glycol Polymers 0.000 description 16
- 239000004753 textile Substances 0.000 description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000003599 detergent Substances 0.000 description 7
- 239000003205 fragrance Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 230000002708 enhancing effect Effects 0.000 description 6
- 239000006081 fluorescent whitening agent Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
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- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- 238000002310 reflectometry Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010186 staining Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
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- 125000001033 ether group Chemical group 0.000 description 2
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- 239000002002 slurry Substances 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
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- D—TEXTILES; PAPER
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
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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
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
-
- 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
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- 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
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3753—Polyvinylalcohol; Ethers or esters thereof
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- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
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- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
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- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
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- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
- D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
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- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
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- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Detergent Compositions (AREA)
- Treatment Of Fiber Materials (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明提供织物的处理方法,该方法包括让织物与聚合物A和B在水性介质中接触的步骤,其中;(a)聚合物A选自乙烯醇、亚烷基二醇、糖和羧酸的均聚物或共聚物,和;(b)聚合物B选自乙烯基吡咯烷酮、氧化烯、糖和羧酸的均聚物或共聚物,和;其中聚合物A和B不是相同类型和该水性介质具有低于6的pH。本发明还提供了织物处理用的组合物和试剂盒。
Description
技术领域
本发明涉及织物处理方法。本发明进一步涉及织物处理用的组合物和试剂盒。本发明将在后面参考本申请进行描述。然而,可以认识到的是,本发明不局限于这一特殊应用领域。
背景和现有的技术
在整个说明书中现有技术的任何讨论决不认为承认该现有技术是广泛已知的或构成了本领域中一般公知常识的一部分。
US2006046950A(Penninger和Bastigkeit,2006)教导用于清洗纺织材料的洗涤剂组合物,它包括能够除去污垢的烷基或羟烷基纤维素衍生物和吸湿性聚合物的结合物,该吸湿性聚合物选自多肽,水凝胶,聚乙烯醇,聚(亚烷基)二醇,丙烯酸、甲基丙烯酸和马来酸的均聚物,丙烯酸、甲基丙烯酸和马来酸的共聚物以及这些均聚物和共聚物的混合物。吸湿性聚合物与纤维素衍生物的相结合使用被认为导致改进的清洗特性。
EP025696(Unilever,1988)教导,通过将乙烯基吡咯烷酮聚合物和非离子纤维素醚的混合物添加到洗涤剂组合物中而实现污垢悬浮的改进。
GB994353(Domestos,1965)教导某些聚合物材料的混合物,当被引入到以合成表面活性剂为基础的未复配洗涤剂组合物中时,提供了增强的抗再沉积作用,与当单独被添加到同一洗涤剂组合物中时单种聚合物单独的活性相比。
US3771951(Berni等人,1973)和GB133803(Gaf Corp,1973)教导,包含水溶性洗涤剂及由水溶性聚乙烯醇和水溶性聚乙烯基吡咯烷酮组成的混合物的洗涤剂组合物显示出增强的污垢悬浮程度。
以上方法据报道提供了污垢的改进的抗再沉积和织物的改进的清洗效果。然而,织物的后续的在洗涤后的结垢的减少却没有报导。此外,该清洗组合物主要由表面活性剂组成并且洗液的pH是碱性或中性的。
US4007305(Kakar等人,1977)解决了为纺织品提供令人满意的非耐久性整理剂的问题,赋予最佳的污垢松脱和污垢拒斥性能。根据D5,该纺织品必须用具有7.5-11的pH值并含有具有羧酸基团的水溶性亲水性污垢去除聚合物(soil release polymer)和分散的疏水性污垢拒斥性含氟化合物的碱性水性介质进行处理。
另一方面,织物改性的各种工业处理已知使得织物更容易玷污。这一类型的织物改性常常是在纺织品制造过程中进行的。除基材特定的外,这些处理在家庭中较难应用。
鉴于现有技术的缺点,本发明的目标中的一个是提供一种能够容易地在家庭中使用的减少织物玷污的方法。
本发明的另一个目的是提供减少织物玷污的织物处理方法。
本发明的又一个目的是提供改进后续清洗的效力的织物处理方法。
本发明的又一个目的是提供减少织物玷污的方法,该方法允许有益试剂如芳香剂和荧光增白剂的增强沉积。
本发明的又一个目的是提供织物的处理方法,它对于各种类型的织物如棉、聚酯和聚酯棉(polycotton)都有效果。
本发明的又一个目的是提供在家庭中较易实施的织物处理方法。
本发明人已令人吃惊地发现,让织物在具有酸性pH的水性介质中与两种不同聚合物(一种包括多个羟基和另一种包括多个的羰基或醚基团)接触可增加聚合物的沉积并且提供一些益处,如玷污的减少,后续清洗的容易性和有益试剂的增强沉积。
本发明的概述
根据本发明的第一方面,提供织物的处理方法,该方法包括让织物与聚合物A和B在水性介质中接触的步骤,其中;
(a)聚合物A选自乙烯醇、亚烷基二醇、糖和羧酸的均聚物或共聚物,和;
(b)聚合物B选自乙烯基吡咯烷酮、氧化烯、糖和羧酸的均聚物或共聚物,和;
其中聚合物A和B不是相同类型和该水性介质具有低于6的pH。
根据本发明的第二方面,提供一种用于织物的处理的组合物,该组合物包括1-99wt%的聚合物A,1-99wt%的聚合物B,和0-10wt%的酸性成分,其中:
(a)聚合物A选自乙烯醇、亚烷基二醇、糖和羧酸的均聚物或共聚物,和;
(b)聚合物B选自乙烯基吡咯烷酮、氧化烯、糖和羧酸的均聚物或共聚物,和;
其中聚合物A和B不是相同类型和组合物的1%水性溶液的pH低于6。
根据本发明的第三个方面,提供用于织物处理的试剂盒,该试剂盒包括第二方面的组合物和一套的使用说明书。
本发明的详细说明
织物
能够处理的织物包括合成和天然纺织品。织物可以由棉,聚酯棉,聚酯,蚕丝或尼龙组成。可以设想,本发明的方法能够用于处理衣服和其它服装和服饰材料,这些在家庭洗衣中形成了典型的洗涤负荷。能够根据本发明的方法处理的家庭用材料包括,但不限于,床罩,毛毯,地毯,窗帘和室内装饰材料。虽然本发明的方法主要被描述用于织物的处理,但是可以设想,本发明的方法能够有利地用于处理其它材料如黄麻,皮革,粗斜纹棉布和帆布。可以想到本发明的方法能够用于处理制品如鞋,雨衣和夹克。
聚合物A
根据本发明,聚合物A具有多个的羟基或羧基。聚合物A具有优选300到109的分子量。聚合物A选自乙烯醇、亚烷基二醇、糖和羧酸的均聚物或共聚物。
根据本发明的聚合物A的一些非限制性例子包括:
(a)乙烯醇或聚乙烯醇的均聚物。
(b)乙二醇或丙二醇的均聚物,即聚乙二醇和聚丙二醇。
(c)羧酸的均聚物,即聚羧酸如聚丙烯酸、聚马来酸或丙烯酸和马来酸的共聚物。
(d)多糖如淀粉,纤维素,海藻酸钠,天然树胶,以及它们的改性材料如羧甲基纤维素钠盐,羟乙基纤维素。
乙烯醇的均聚物或共聚物具有优选10,000到1,000,000,更优选50,000到500,000和最优选50,000到200,000的分子量。能够使用的商购聚乙烯醇包括GOHSENOL(Nippon Synthetic Chemical Industry),MOWIOL(Clariant)和POVAL(Kuraray)。
亚烷基二醇的均聚物或共聚物具有优选4,000到20,000,更优选5,000到15,000和最优选5,000到10,000的分子量。能够使用商购的聚亚烷基二醇。商购聚亚烷基二醇的一些例子包括POLYGLYKOL(Clariant)和CARBOWAX(Union Carbide)。
羧酸的均聚物或共聚物具有优选2,000到10,000,000,更优选50,000到1,000,000和最优选90,000到500,000的分子量。
糖的均聚物或共聚物具有优选1000到109,更优选10000到109和最优选100,000到109的分子量。
聚合物A可以是合成的或天然的。然而,合成聚合物比天然聚合物优选。
根据优选的方面,聚合物A是水溶性的。
优选的是聚合物A选自乙烯醇或羧酸的均聚物或共聚物。
聚合物A的量优选是0.005到2,更优选0.02到1,和最优选0.05到0.5mg/每cm2面积的该织物。在这里使用的术语“织物面积”是指织物的一个侧面的表面积。
聚合物B
根据本发明,聚合物B具有包括醚或羰基的单体单元。聚合物B具有优选1000到109的分子量。聚合物B选自乙烯基吡咯烷酮、氧化烯、糖和羧酸的均聚物或共聚物。
羧酸和/或糖和/或聚亚烷基二醇/醚的聚合物和均聚物有资格被选择为聚合物A或聚合物B,因为它们都包括羟基或羧基和羰基或醚基团。然而,根据主要的方面,聚合物A和聚合物B不是相同的类型。特别优选的是,聚合物A和B选自不同种类的聚合物。不希望受理论限制,可以相信,两种聚合物A和B,当溶于水中时,形成了溶解度比聚合物A和B中的每一种都低的复合物,这有助于增强沉积和其它益处。
乙烯基吡咯烷酮的均聚物或共聚物具有优选1000到10000000,更优选10,000到1,000,000和最优选30,000到500,000的分子量。能够使用商购的聚乙烯基吡咯烷酮,它的一个例子是LUVISKOL(BASF)。
聚氧化烯的均聚物或共聚物具有大于20,000的分子量。该分子量优选是从20,000到1,000,000,更优选30,000到500,000和最优选从50,000到200,000。
糖的均聚物或共聚物具有优选从1000到109,更优选10,000到109和最优选从100,000到109的分子量。根据本发明能够使用任何商购的聚氧化烯,例如POLYOX(Dow Chemical Co)。
聚合物B可以是合成的或天然的。然而,合成聚合物比天然聚合物优选。
根据优选的方面,聚合物B是水溶性的。
特别优选的是,聚合物B选自乙烯基吡咯烷酮或氧化烯的均聚物或共聚物。
聚合物B的量优选是0.005到2,更优选0.02到1,和最优选0.05到0.5mg/每cm2面积的该织物。
聚合物A和聚合物B的结合物的特别优选的一些例子在下面给出。
表1:聚合物的优选组合
聚合物A | 聚合物B |
聚丙烯酸(PAA) | 聚乙烯基吡咯烷酮(PVP) |
聚丙烯酸(PAA) | 聚氧化乙烯(PEO) |
聚乙二醇(PEG) | 聚丙烯酸(PAA) |
聚乙烯醇(PVA) | 聚丙烯酸(PAA) |
聚乙烯醇(PVA) | 聚氧化乙烯(PEO) |
羧甲基纤维素钠(SCMC) | 聚氧化乙烯(PEO) |
羟乙基纤维素 | 聚丙烯酸(PAA) |
聚合物的最优选组合是在以上表1中首先三行中的结合,即PAA-PVP,PAA-PEO和PEG-PAA。
水性介质
根据本发明,这两种聚合物与织物在pH低于6的水性介质中接触。该水性介质具有优选低于5和更优选低于4的pH。水性介质具有优选大于1和更优选大于2的pH。
该聚合物可以进行选择,要求当聚合物被添加到水性介质中时,该水性介质的pH低于6。优选,酸性成分被添加到水性介质中以确保水性介质的pH低于6。将所得水性介质的pH降低至低于6的酸性成分是所属技术领域的专业人员已知的并且任何合适的酸性成分都可以选择。
水性介质可以包括聚合物A,或聚合物B,或这两种聚合物。另外地,在本发明的方法中一种或两种的该聚合物可以被添加到水性介质中。
当与水性介质混合时,聚合物A按重量是水性介质的0.005-10%,更优选0.05-5%,和最优选0.05-2%。
当与水性介质混合时,聚合物B按重量是水性介质的0.005-10%,更优选0.01-5%,和最优选0.01-2%。
水性介质优选包括电解质。电解质优选按重量是水性介质的0.001-5%,更优选0.01-1%,和最优选0.04-0.2%。
不希望受理论限制,可以相信电解质的添加使得本发明的方法可以在有较低量的聚合物A和B的情况下进行。
根据本发明能够使用的电解质包括水溶性离子盐。盐的阳离子包括碱金属,碱土金属或三价金属阳离子。盐的阴离子包括氯化物,硫酸根,硝酸根和磷酸根。电解质的一些例子包括钠、钾、镁或钙的氯化物,硫酸盐或硝酸盐。钙盐是特别优选的。
根据优选的方面,水性介质包括不高于200ppm的阴离子表面活性剂。水性介质包括不高于100ppm,更优选低于50ppm的阴离子表面活性剂。特别优选的是,水性介质基本上不含阴离子表面活性剂。
该水性介质优选包括至少一种的有益试剂。能够包含在水性介质中的有益试剂包括但不限于诸如芳香剂,荧光增白剂,除臭剂,抗菌剂,色调染料和上蓝剂之类的成分。本发明的诸多优点中的一个是有益试剂的沉积得到增强。
工艺程序
可以设想到,织物与聚合物A和B按照任何顺序来顺序地或同时地接触。因此该织物可以与聚合物A接触,然后与聚合物B接触。另外,该织物可以与聚合物B接触,然后与聚合物A接触。该织物可以同时与聚合物A和B接触。虽然该织物可以同时与两种聚合物接触,但是优选的是该织物按照任何顺序与聚合物顺序地接触。
接触的过程
织物与聚合物A和B接触的步骤能够按照任何合适的方式来进行。
聚合物A或聚合物B或两者,与水性介质混合,之后与织物接触。另外地,聚合物A也可与包含溶剂如醇和丙酮的非水性介质混合,然后与织物接触。然而,优选的是,聚合物或这些聚合物与水性介质混合,然后与织物接触。该织物可以浸入到包含一种或多种聚合物的水性介质中。另外地,包含一种或两种聚合物的水性介质可以被喷雾到织物上。
也可设想的是,聚合物A和B中的任何一种能够以可磨蚀棒的形式使用,它能够在所要处理的织物的面积上摩擦,然后与水性介质接触。
组合物
根据本发明的第二方面,提供用于织物的处理的组合物,该组合物包括1-99wt%的聚合物A,1-99wt%的聚合物B,和0-10wt%的酸性成分,其中:
(a)聚合物A选自乙烯醇、亚烷基二醇、糖和羧酸的均聚物或共聚物,和;
(b)聚合物B选自乙烯基吡咯烷酮、氧化烯、糖和羧酸的均聚物或共聚物,和;
其中聚合物A和B不是相同类型和组合物的1%水性溶液的pH低于6。
组合物包括优选5-95%,更优选10-90%和最优选20-80wt%的聚合物A。组合物包括优选5-95%,更优选10-90%和最优选20-80wt%的聚合物B。
该聚合物可以进行选择,要求组合物的1%水性溶液的pH低于6。优选,酸性成分以组合物的0.1-10wt%的量存在于组合物中以确保组合物的1%水性溶液的pH低于6。将水性介质的pH降低至低于6的酸性成分是所属技术领域的专业人员已知的并且任何合适的酸性成分都可以选择。
试剂盒
根据本发明的第三个方面,提供用于织物处理的试剂盒,该试剂盒包括第二方面的组合物和一套使用说明书。
特别优选的是,聚合物A和B单独地包装,即聚合物A和B各自包装在单独的包装材料中或包装在双腔室包装材料的单独腔室中。
实施例
本发明现在用实施例来说明。实施例仅仅是举例而已并且无论如何都不限制本发明的范围。
材料和方法
下列材料用于实施例中。
表2:用于实施例中的材料
材料 | 来源/供应商 |
水 | 去离子水 |
聚乙烯基吡咯烷酮,分子量90000和1,300,000 | Aldrich |
聚丙烯酸,分子量2000 | Aldrich |
聚丙烯酸,钠盐,分子量8000 | Aldrich |
聚丙烯酸,分子量450000 | Aldrich |
聚乙烯醇,分子量124,000 | Aldrich |
聚乙二醇,分子量17500 | Fluka |
聚氧化乙烯,分子量100000 | Aldrich |
聚酯织物 | Bombay Dyeing |
聚酯棉织物 | Bombay Dyeing 67/33 |
炭黑 | Cabot India N220 |
沉积
在实施例1和2和对比实施例1-A到2-B中聚合物A是分子量450000的聚丙烯酸。在实施例1和对比实施例A和B中聚合物B是分子量90000的聚乙烯基吡咯烷酮。在实施例2和对比实施例C,D和2A中聚合物B是分子量100,000的聚氧化乙烯。
对于沉积研究,约10g的织物用聚合物在溶液中处理,然后在处理织物的干燥之后以重量分析法测定重量增加。
表3:聚合物在棉、聚酯棉和聚酯织物上的沉积
Ex.No | 聚合物A(在水性介质中的wt%) | 聚合物B(在水性介质中的wt%) | pH | 沉积的总聚合物(g/100g织物)棉 | 沉积的总聚合物(g/100g织物)聚酯棉 | 沉积的总聚合物(g/100g织物)聚酯 |
1 | 1 | 1 | 2.8 | 4.41 | 2.67 | 3.41 |
Ex.No | 聚合物A(在水性介质中的wt%) | 聚合物B(在水性介质中的wt%) | pH | 沉积的总聚合物(g/100g织物)棉 | 沉积的总聚合物(g/100g织物)聚酯棉 | 沉积的总聚合物(g/100g织物)聚酯 |
A | 2 | - | 2.5 | 0.90 | 0.96 | 0.96 |
B | - | 2 | 5.2 | 0.87 | 0.70 | 0.78 |
2 | 0.5 | 0.5 | 3.2 | 2.67 | 2.68 | 4.37 |
C | 1 | - | 2.6 | 1.40 | 1.72 | 1.30 |
D | - | 1 | 5.5 | 1.68 | 0.80 | 1.19 |
2A | 0.5 | 0.5 | 8.0 | 1.49 | 1.52 | 1.27 |
从上述结果能够看出,与仅仅用一种的聚合物处理的织物相比,当根据本发明的方法一起使用时两种聚合物的沉积是明显更高的。
玷污
玷污规程
织物用聚合物处理并干燥。干燥的织物被浸入到炭黑水分散体(150ppm)中,该分散体通过烷基苯磺酸钠(50ppm)的添加来稳定化。该织物从炭黑溶液中取出,然后立即在水中漂洗,然后干燥。反射率的变化(ΔR),即在玷污之前和之后织物反射率的差异,是织物的玷污的量度,其中ΔR的负值表明该织物被玷污。
在下表中,使用下列缩写:
PEG 17500-聚乙二醇,分子量17,500。
PAA 8000-聚丙烯酸,分子量8,000。
PVA 124000-聚乙烯醇,分子量125,000。
PVP 90000-聚乙烯基吡咯烷酮,分子量90,000。
表4:棉织物被炭黑的玷污
实施例No | 聚合物A(在水性介质中的wt%) | 聚合物B(在水性介质中的wt%) | pH | ΔR460*(最终-初始)在棉织物浸入炭黑中后 |
3 | PEG 17500(0.05%) | PAA 8000(0.05%) | 3.2 | -1.7 |
实施例No | 聚合物A(在水性介质中的wt%) | 聚合物B(在水性介质中的wt%) | pH | ΔR460*(最终-初始)在棉织物浸入炭黑中后 |
4 | PVA 124000(0.05%) | PAA 8000(0.05%) | 3.4 | -4.7 |
5 | PAA(0.05%) | PVP 90000(0.05%) | 4.3 | -0.1 |
E | PEG 17500(0.1%) | - | 5.5 | -31.7 |
F | - | PAA-8000(0.1%) | 3.3 | -14.7 |
G | PVA 124000(0.1%) | - | 5.9 | -22.7 |
H | PVP 90000(0.1%) | 6.9 | -27.7 | |
I | - | - | 7.0 | -37.7 |
从上述结果能够看出,被本发明的方法处理的织物的玷污显著地低于未处理的织物(对比实施例1)或低于仅仅用一种聚合物处理的织物(对比实施例F、G和H)。
清洗
清洗规程
织物用聚合物处理并干燥。干燥的织物被浸入到炭黑水分散体(150ppm)中,该分散体通过烷基苯磺酸钠(50ppm)的添加来稳定化。织物然后干燥。干燥织物然后用水、碳酸钠水溶液(0.15wt%)、和商购洗涤剂水溶液(SURF EXCEL0.3wt%)清洗。反射率的变化(ΔR)是织物的清洗的量度。较高的ΔR值表明更好的清洗作用。
聚合物A是分子量2000的聚丙烯酸和聚合物B是分子量90000的聚乙烯基吡咯烷酮。在实施例6中,两种聚合物都以水性介质的0.2wt%的量使用。水性介质的pH是3.0。在对比实施例J和K中,聚合物A和B分别地各自以水性介质的0.4wt%的量(分别地pH 2.7和7.0)单独使用。
对比实施例L用于未处理的织物(pH 7)。该织物(棉纱,聚酯棉和聚酯)根据以上给出的规程进行清洗,然后结果在下面的表中列出。
表5:被碳黑玷污的织物的清洗
C*-棉
PC**-聚酯棉
PE***-聚酯
从结果可以清楚地看出,对于在本发明的范围内的实施例6的清洗效力高于在本发明范围之外的对比实施例J、K和L中获得的清洗效力。尤其,对于用碳酸钠或水清洗的情况,清洗效力是更好的。此外,结果表明,当用商购表面活性剂洗涤时,清洗效力对于聚酯棉和聚酯织物特别地得到增强。
电解质的效果
聚合物A是分子量450,000的聚丙烯酸和聚合物B是分子量1,300,000的聚乙烯基吡咯烷酮。在全部的实施例中,两种聚合物是以水性介质的0.1wt%的量使用。电解质添加的效果是通过将各种电解质以总水性介质的0.1wt%的量添加来研究的。水性介质的pH是在2.7到3.0范围内。该织物(棉,聚酯棉和聚酯)是通过使用碳酸钠(0.15wt%)水溶液来清洗的。结果根据清洗效力列于下表中。
表6:电解质添加的效果
从该结果可以清楚地看出,电解质的添加会导致清洗效力的进一步增强,尤其对于聚酯棉和聚酯织物。此外,对于棉织物,氯化钙尤其获得了在清洗效力的增强。
芳香剂沉积
规程
烯丙基戊基乙醇酸酯取作代表性的香料成分。聚合物A是具有450,000分子量的聚丙烯酸和聚合物B是具有90000的分子量的聚乙烯基吡咯烷酮。该芳香剂与聚合物A和B两者(各自以水性介质的0.1wt%的量)(实施例11-pH 2.8),聚合物A和聚合物B单独(各自以水性介质的0.2wt%的量)(对比实施例M-pH 3和N-pH 7,分别地)一起添加,而对比实施例O(pH 7)是用于未处理的织物。对于各种类型的织物评价芳香剂保留性。该织物由受训练的香水调配者按照0至5的标度来测试芳香剂保留性,其中0的标度表示没有芳香冲击和5的标度有最高芳香冲击。细节在下表中列出。
表7:芳香剂在织物上的沉积
Ex No | 芳香冲击标度(棉) | 芳香冲击标度(聚酯棉) | 芳香冲击标度(聚酯) |
11 | 2.5 | 1.5 | 2.5 |
M | 0.5 | 0.5 | 0.75 |
N | 0.5 | 0.5 | 0.75 |
O | 0.5 | 0.5 | 0.5 |
从上表中的结果可以清楚地看出,对于根据本发明的方法处理过的织物,在60分钟下的芳香冲击是显著更高的。
荧光增白剂沉积
表8:荧光增白剂在织物上的沉积
Ex No | 聚合物A | 聚合物B | R460(棉) |
12 | PAA(2.5%) | PEG(2.5%) | 95.9 |
P | PAA(5%) | - | 94.7 |
Q | - | PEG(5%) | 89.9 |
R | - | - | 85.7 |
从结果可以清楚地看出,与未处理的织物(对比实施例R)或仅仅用一种的聚合物处理的织物(对比实施例P和Q)相比,当根据本发明的方法用聚合物A和B两者处理织物(实施例12)时由白度标度显示的荧光增白剂沉积作用得到增强。
可以理解的是,以上实施例清楚地和足够地描述了本发明的方法能够实施的方式。进一步认识到,本发明的方法能够符合了提供减少织物玷污的织物处理方法的目标,提高后续清洗的效力,允许有益试剂的增强沉积并且对于包括棉、聚酯棉和聚酯在内的各种类型的织物是有效的。
Claims (11)
1.织物的处理方法,该方法包括让织物与聚合物A和B在水性介质中接触的步骤,其中;
(a)聚合物A选自乙烯醇、亚烷基二醇、糖和羧酸的均聚物或共聚物,和;
(b)聚合物B选自乙烯基吡咯烷酮、氧化烯、糖和羧酸的均聚物或共聚物,和;
其中聚合物A和B不是相同类型和该水性介质具有低于6的pH。
2.根据权利要求1所要求的方法,其中水性介质包括不超过200ppm的阴离子表面活性剂。
3.根据前述权利要求中任何一项的方法,其中该聚合物A选自乙烯醇或羧酸的均聚物或共聚物。
4.根据前述权利要求中任何一项的方法,其中该聚合物B选自乙烯基吡咯烷酮或氧化烯的均聚物或共聚物。
5.根据前述权利要求中任何一项的方法,其中该羧酸的均聚物或共聚物是聚丙烯酸或其共聚物。
6.根据前述权利要求中任何一项的方法,其中该水性介质包括电解质。
7.根据权利要求6所要求的方法,其中该电解质是该介质的0.001-5wt%。
8.根据前述权利要求中任何一项的方法,其中该水性介质的pH是1-10。
9.根据前述权利要求中任何一项的方法,其中织物与聚合物A和B按照任何顺序来顺序地接触或同时地接触。
10.用于织物的处理的组合物,该组合物包括1-99wt%的聚合物A,1-99wt%的聚合物B,和0-10wt%的酸性成分,其中:
(a)聚合物A选自乙烯醇、亚烷基二醇、糖和羧酸的均聚物或共聚物,和;
(b)聚合物B选自乙烯基吡咯烷酮、氧化烯、糖和羧酸的均聚物或共聚物,和;
其中聚合物A和B不是相同类型和组合物的1%水性溶液的pH低于6。
11.织物处理用的试剂盒,它包括权利要求10的组合物和使用说明。
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PCT/EP2008/064764 WO2009077255A1 (en) | 2007-12-14 | 2008-10-31 | Process for treatment of a fabric |
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MX2012002747A (es) * | 2009-09-02 | 2012-04-19 | Unilever Nv | Composicion y proceso para tratamiento de un genero. |
BR112014017891A8 (pt) | 2012-01-31 | 2017-07-11 | Unilever Nv | Composição, método de tratamento de um substrato, método de preparação da composição e agente condicionador |
EP4108752A1 (en) * | 2021-06-25 | 2022-12-28 | The Procter & Gamble Company | Detergent compositions |
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GB994353A (en) * | 1960-06-13 | 1965-06-02 | Domestos Ltd | Improvements in detergent compositions |
GB1340517A (en) * | 1969-12-01 | 1973-12-12 | Burton Parsons Chemicals Inc | Ophthalmic solution |
US3689435A (en) * | 1970-07-27 | 1972-09-05 | Gaf Corp | Detergency compositions containing a synergistic mixture of pvp and pva |
US4007305A (en) * | 1974-12-23 | 1977-02-08 | Basf Wyandotte Corporation | Method of imparting nondurable soil release and soil repellency properties to textile materials |
JPS5945038B2 (ja) * | 1977-07-19 | 1984-11-02 | ライオン株式会社 | 洗浄剤組成物 |
SU836262A1 (ru) * | 1979-08-01 | 1981-06-07 | Латвийский Научно-Исследовательскийинститут Легкой Промышленности | Состав дл гр зеотталкивающей отделкицЕллюлОзНыХ ТЕКСТильНыХ МАТЕРиАлОВ |
DE3163112D1 (en) * | 1980-12-17 | 1984-05-17 | Unilever Nv | Detergent composition with reduced soil-redeposition effect |
SU1141127A1 (ru) * | 1983-01-06 | 1985-02-23 | Украинский Научно-Исследовательский И Конструкторско-Технологический Институт Бытового Обслуживания | Состав дл гр зеотталкивающей отделки текстильных изделий |
GB8618635D0 (en) * | 1986-07-30 | 1986-09-10 | Unilever Plc | Detergent composition |
JPS6392700A (ja) * | 1986-10-08 | 1988-04-23 | 花王株式会社 | 洗浄剤組成物 |
ES2238845T3 (es) * | 1998-08-25 | 2005-09-01 | Clariant Finance (Bvi) Limited | Composiciones acuosas de agentes activos frente a la luz uv, su produccion y uso. |
US6785989B2 (en) * | 2000-03-31 | 2004-09-07 | The Procter & Gamble Company | Methods and apparatus for removal of wrinkles from fabrics |
US7026278B2 (en) * | 2000-06-22 | 2006-04-11 | The Procter & Gamble Company | Rinse-added fabric treatment composition, kit containing such, and method of use therefor |
JP3965518B2 (ja) * | 2002-04-26 | 2007-08-29 | 第一工業製薬株式会社 | 中性洗浄剤 |
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WO2009077255A1 (en) | 2009-06-25 |
JP5080652B2 (ja) | 2012-11-21 |
CA2707805A1 (en) | 2009-06-25 |
EP2220288A1 (en) | 2010-08-25 |
AU2008337741A1 (en) | 2009-06-25 |
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EP2220288B1 (en) | 2012-02-08 |
AU2008337741B2 (en) | 2011-11-24 |
US20100297359A1 (en) | 2010-11-25 |
ATE544901T1 (de) | 2012-02-15 |
RU2010129064A (ru) | 2012-01-20 |
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ZA201002991B (en) | 2011-07-27 |
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