CN102753671B - 共聚物在具有较低泛灰倾向的液体洗涤剂中作为增稠剂的用途 - Google Patents
共聚物在具有较低泛灰倾向的液体洗涤剂中作为增稠剂的用途 Download PDFInfo
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- 239000003208 petroleum Substances 0.000 description 1
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- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
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- 239000004033 plastic Substances 0.000 description 1
- 229960000502 poloxamer Drugs 0.000 description 1
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- 229920000193 polymethacrylate Polymers 0.000 description 1
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- 229910052573 porcelain Inorganic materials 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
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- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
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- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
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- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical class [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 229940102541 sodium trideceth sulfate Drugs 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- KLYDBHUQNXKACI-UHFFFAOYSA-M sodium;2-[2-(2-tridecoxyethoxy)ethoxy]ethyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCOCCOCCOCCOS([O-])(=O)=O KLYDBHUQNXKACI-UHFFFAOYSA-M 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
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- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical class [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- CMWCOKOTCLFJOP-UHFFFAOYSA-N titanium(3+) Chemical class [Ti+3] CMWCOKOTCLFJOP-UHFFFAOYSA-N 0.000 description 1
- LOIYMIARKYCTBW-OWOJBTEDSA-N trans-urocanic acid Chemical compound OC(=O)\C=C\C1=CNC=N1 LOIYMIARKYCTBW-OWOJBTEDSA-N 0.000 description 1
- LOIYMIARKYCTBW-UHFFFAOYSA-N trans-urocanic acid Natural products OC(=O)C=CC1=CNC=N1 LOIYMIARKYCTBW-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- OHOTVSOGTVKXEL-UHFFFAOYSA-K trisodium;2-[bis(carboxylatomethyl)amino]propanoate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C(C)N(CC([O-])=O)CC([O-])=O OHOTVSOGTVKXEL-UHFFFAOYSA-K 0.000 description 1
- ORHBXUUXSCNDEV-UHFFFAOYSA-N umbelliferone Chemical compound C1=CC(=O)OC2=CC(O)=CC=C21 ORHBXUUXSCNDEV-UHFFFAOYSA-N 0.000 description 1
- HFTAFOQKODTIJY-UHFFFAOYSA-N umbelliferone Natural products Cc1cc2C=CC(=O)Oc2cc1OCC=CC(C)(C)O HFTAFOQKODTIJY-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 235000013343 vitamin Nutrition 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
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229960003487 xylose Drugs 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
-
- 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
-
- 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
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Detergent Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明涉及共聚物,所述共聚物含有a)至少15重量%烯属不饱和羧酸单元,b)至少15重量%丙烯酸C4-C8烷基酯单元,c)小于5重量%甲基丙烯酸甲酯单元,且在液体织物洗涤剂中用作增稠剂。该共聚物还可含有通过聚合掺入的非离子烯属不饱和表面活性剂单体单元。该增稠剂的特征在于高增稠作用、高剪切稀化和在洗涤过程以后的低衣物泛灰。
Description
本发明涉及碱溶性共聚物在液体织物洗涤剂中作为增稠剂的用途和液体洗涤剂或清洁剂组合物。
透明粘性液体洗涤剂和清洁剂组合物日益普及。因此需要在溶解,即中和状态下具有高透明度,且当掺入含表面活性剂的配制剂中时不显示任何类型的浑浊的增稠剂。此外,赋予静止状态下的增稠介质非常高的粘度且当高剪切力作用时低粘度的增稠剂是理想的。
具体形式的碱溶性增稠剂为缔合增稠剂。
缔合增稠剂为水溶性聚合物且具有表面活性剂类疏水组分,其在亲水性,特别是含水介质中能缔合,即与其本身以及与其它疏水物质相互作用。介质通过由其产生的缔合网络增稠或胶凝。
EP-A 0013836公开了乳液共聚物,其包含(i)20-69.5重量%(甲基)丙烯酸,(ii)0.5-25重量%式CH2=C(R)-C(O)-O-(CH2CH2O)n-R0单体,其中R为H或CH3,n为至少2且R0为C8-C30烷基,和(iii)至少30重量%(甲基)丙烯酸C1-C4烷基酯。在用碱中和以后,共聚物用作油漆、洗涤剂等的增稠剂。
WO 99/65958描述了碱溶性增稠剂,其包含不饱和羧酸、单烯属不饱和单体和疏水性烷基化大单体的反应产物。单烯属不饱和单体包含甲基;它优选为丙烯酸甲酯。这些聚合物在pH4.5-6.0下应变得可溶,因此适于化妆品。
WO 2006/016035涉及水溶性丙烯酸聚合物在着色含水制剂中作为增稠剂的用途。丙烯酸聚合物由具有羧基官能的烯属不饱和单体、烯属不饱和非离子单体和用具有10-24个碳原子的疏水性非芳族支链封住的烯属不饱和氧基烷基化单体组成。一个实施方案涉及其中烯属不饱和非离子单体由丙烯酸乙酯和丙烯酸丁酯组成的聚合物(实施例7)。
WO 2009/019225公开了具有至少一种烯属不饱和羧酸、至少一种非离子烯属不饱和表面活性剂单体、至少一种甲基丙烯酸C1-C2烷基酯和至少一种丙烯酸C2-C4烷基酯的共聚单元的缔合增稠剂,其中丙烯酸烷基酯中烷基数上的平均烷基链长为2.1-4.0。缔合增稠剂的溶液或其具有高表面活性剂含量的配制剂是高度透明的且具有与同时高剪切稀化结合的高增稠效果。
术语“泛灰”应当理解意指洗涤期间织物的灰色着色,这尤其通过已分离的污物以更细的分布重附着于织物上而产生。重附着可能通过静电力触发。重附着的程度尤其取决于织物和污物的类型、织物的沾污度、洗涤过程中的水量和洗涤罐中机械搅拌的程度。洗涤剂的组成本身可通过例如它们沉积于织物上或支持污物重附着而导致泛灰。因此理想的是液体洗涤剂中所用增稠剂在洗涤过程以后导致尽可能低的泛灰。
本发明的目的是提供与高增稠效果和同时高剪切稀化联合,导致洗涤过程以后衣物尽可能低的泛灰的增稠剂,特别是缔合增稠剂。
该目的根据本发明通过使用共聚物在液体织物洗涤剂中作为增稠剂而实现,其中共聚物包含:
a)至少15重量%烯属不饱和羧酸单元,
b)至少15重量%丙烯酸C4-C8烷基酯单元,
c)小于5重量%甲基丙烯酸甲酯单元。
此外,本发明涉及包含以上定义的共聚物的液体洗涤剂或清洁剂组合物。
令人惊讶的是,发现甲基丙烯酸C1-C2烷基酯单元,例如特别是甲基丙烯酸甲酯单元含量高的增稠剂可削弱洗涤衣物的光反射比。降低的光反射比感知为泛灰。表面活性剂单体通常作为在甲基丙烯酸甲酯中的溶液市售。使用这些溶液得到的共聚物总是包含甲基丙烯酸甲酯的共聚单体。
根据本发明使用的共聚物包含小于5重量%,优选小于2重量%甲基丙烯酸甲酯单元,特别优选基本不含甲基丙烯酸甲酯单元。优选共聚物包含小于5重量%,优选小于2重量%甲基丙烯酸C1-C2烷基酯单元,特别优选基本不含甲基丙烯酸C1-C2烷基酯单元。
典型地,共聚物包含:
a)15-50重量%,特别优选28-35重量%烯属不饱和羧酸单元,
b)20-85重量%,特别优选25-60重量%丙烯酸C4-C8烷基酯单元。
此外,共聚物可包含例如5-40重量%,优选25-35重量%的丙烯酸C1-C3烷基酯的共聚单元。
此外,共聚物可包含例如0.1-5重量%,优选0.5-3重量%的非离子烯属不饱和表面活性剂单体的共聚单元。
烯属不饱和羧酸一般为具有3-8个碳原子的单烯属不饱和单-或二羧酸。合适的烯属不饱和羧酸例如选自丙烯酸、甲基丙烯酸、衣康酸和马来酸。在这些中,甲基丙烯酸是特别优选的。
合适的丙烯酸C4-C8烷基酯为丙烯酸正丁酯、丙烯酸正戊酯、丙烯酸正己酯、丙烯酸正庚酯和丙烯酸正辛酯,优选丙烯酸正丁酯。
合适的丙烯酸C1-C3烷基酯为丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯和丙烯酸异丙酯,优选丙烯酸乙酯。
合适的非离子烯属不饱和表面活性剂单体是本身已知的。这些例如为:
(a)单烯属不饱和异氰酸酯和非离子表面活性剂的含氨基甲酸酯基团的反应产物,
(b)烯属不饱和羧酸和非离子表面活性剂的酯,
(c)非离子表面活性剂的乙烯基或烯丙基醚。
合适的非离子表面活性剂优选为烷氧基化C6-C30醇,例如脂肪醇烷氧基化物或羰基合成醇烷氧基化物。每摩尔醇使用至少2摩尔,例如2-100摩尔,优选3-20摩尔的至少一种C2-C4氧化烯。不同的氧化烯单元可以以嵌段方式排列或可以以无规分布存在。优选所用氧化烯为氧化乙烯和/或氧化丙烯。
另一类合适的非离子表面活性剂为具有C6-C14烷基链和5-30摩尔氧化乙烯单元的烷基酚乙氧基化物。
在优选实施方案中,非离子烯属不饱和表面活性剂单体具有如下通式:
R-O-(CH2-CHR′-O)n-CO-CR″=CH2
其中R为C6-C30烷基,优选C8-C22烷基,
R′为氢或甲基,优选氢,
R″为氢或甲基,优选甲基,且
n为2-100,优选3-50的整数。
括号中重复单元衍生自氧化乙烯或氧化丙烯。R'的含义在各重复单元中与其它重复单元无关。不同的氧化烯重复单元可以以嵌段方式排列或以无规分布存在。
水分散体一般包含阴离子和/或非离子乳化剂。
典型的乳化剂为阴离子乳化剂,例如月桂基硫酸钠、十三烷基醚硫酸钠、二辛基磺基琥珀酸钠盐和烷基芳基聚醚磺酸钠盐;和非离子乳化剂,例如烷基芳基聚醚醇和氧化乙烯-氧化丙烯共聚物。
优选的乳化剂具有如下通式:
R-O-(CH2-CHR′-O)n-X
其中R为C6-C30烷基,
R′为氢或甲基,
X为氢或SO3M,
M为氢或碱金属,且
n为2-100的整数。
共聚物可以以各种方式,优选乳液聚合制备。
就聚合而言,使用合适的聚合引发剂。可热活化的自由基聚合引发剂是优选的。
合适的可热活化自由基引发剂主要为过氧和偶氮类型的那些。这些尤其包括过氧化氢、过乙酸、氢过氧化叔丁基、过氧化叔丁基、过氧化二苯甲酰、氢过氧化苯甲酰、过氧化2,4-二氯苯甲酰、2,5-二甲基-2,5-双(氢过氧)己烷、过苯甲酸、过氧新戊酸叔丁酯、过乙酸叔丁酯、过氧化二月桂酰、过氧化二辛酰、过氧化二硬脂酰、过氧化二苯甲酰、过氧化二碳酸二异丙酯、过氧化二碳酸二癸酯、过氧化二碳酸二-二十烷基酯、过苯甲酸二-叔丁酯、偶氮双异丁腈、2,2'-偶氮双-2,4-二甲基戊腈、过硫酸铵、过硫酸钾、过硫酸钠和过磷酸钠。
过硫酸盐(过氧二硫酸盐),特别是过硫酸钠是最优选的。
当进行乳液聚合时,引发剂以足够的量使用以引发聚合反应。引发剂通常以基于所用单体的总重量约0.01-3重量%的量使用。引发剂的量基于所用单体的总重量优选为约0.05-2重量%,特别是0.1-1重量%。
乳液聚合通常在35-130℃下进行。它可以作为分批方法或以进料方法的形式进行。优选进料程序:其中首先引入至少一些聚合引发剂和任选一些单体,并加热至聚合温度,然后通常借助多种单独进料连续或逐步地引入聚合混合物的其余部分,其中一种或多种包含纯或乳化形式的单体,同时保持聚合。优选,单体进料以单体乳液的形式进行。与单体进料并行,可计量加入另一聚合引发剂。
在优选实施方案中,首先引入总量的引发剂,即没有另外的引发剂计量加入与单体进料并行发生。令人惊讶地发现该程序导致特别高透明度的缔合增稠剂。
因此,在优选实施方案中,首先将可热活化自由基聚合引发剂全部引入,并将单体混合物优选以单体乳液的形式插入。在开始单体混合物进料以前,使初始进料达到可热活化自由基聚合引发剂的活化温度或更高的温度。活化温度被认为是在1小时以后至少一半引发剂分解时的温度。
根据另一优选类型的制备,共聚物通过单体混合物在氧化还原引发剂体系的存在下聚合而得到。氧化还原引发剂体系包含至少一种氧化剂组分和至少一种还原剂组分,其中在反应介质中,优选重金属离子另外作为催化剂存在,例如铈盐、锰盐或铁(II)盐。
合适的氧化剂组分例如为过氧化物和/或氢过氧化物,例如过氧化氢、氢过氧化叔丁基、氢过氧化异丙基苯、氢过氧化蒎烷、氢过氧化二异丙基苯基、过碳酸二环己基酯、过氧化二苯甲酰、过氧化二月桂酰和过氧化二乙酰。过氧化氢和氢过氧化叔丁基是优选的。
合适的还原剂组分为碱金属亚硫酸盐、碱金属连二硫酸盐、碱金属连二亚硫酸盐、亚硫酸氢钠、Rongalit C(甲醛合次硫酸钠)、单-和二羟基丙酮、糖(例如葡萄糖或右旋糖)、抗坏血酸及其盐、丙酮亚硫酸氢盐加合物和/或羟基甲烷亚磺酸的碱金属盐。抗坏血酸是优选的。
适用作还原剂组分或催化剂的还有铁(II)盐如硫酸铁(II)、锡(II)盐如氯化锡(II)、钛(III)盐如硫酸钛(III)。
氧化剂的用量为0.001-5.0重量%,优选0.005-1.0重量%,特别优选0.01-0.5重量%,基于所用单体的总重量。还原剂以基于所用单体的总重量0.001-2.0重量%,优选0.005-1.0重量%,特别优选0.01-0.5重量%的量使用。
特别优选的氧化还原引发剂体系为体系过氧化硫酸氢钠/抗坏血酸,例如0.001-5.0重量%过氧化硫酸氢钠和0.001-2.0重量%抗坏血酸,特别是0.005-1.0重量%过氧化硫酸氢钠和0.005-1.0重量%抗坏血酸,特别优选0.01-0.5重量%过氧化硫酸氢钠和0.01-0.5重量%抗坏血酸。
进一步特别的氧化还原引发剂体系为体系氢过氧化叔丁基/过氧化氢/抗坏血酸,例如0.001-5.0重量%氢过氧化叔丁基,0.001-5.0重量%过氧化氢和0.001-2.0重量%抗坏血酸,特别是0.005-1.0重量%氢过氧化叔丁基,0.005-1.0重量%过氧化氢和0.005-1.0重量%抗坏血酸,特别优选0.01-0.5重量%氢过氧化叔丁基,0.01-0.5重量%过氧化氢和0.01-0.5重量%抗坏血酸。
在优选实施方案中,单体混合物优选以单体乳液的形式插入含水初始进料中。与单体进料并行,至少此时插入氧化还原引发剂体系的氧化剂组分和还原剂组分。优选首先引入氧化还原引发剂体系的一些氧化剂组分。任选可首先引入一些单体。
共聚物分散体可经受化学除臭。在化学除臭期间,在实际乳液聚合结束以后加入另一引发剂如氧化还原引发剂。适于化学除臭的氧化还原引发剂包含,例如至少一种有机过氧化物和/或氢过氧化物,例如过氧化氢、氢过氧化叔丁基、氢过氧化异丙基苯、氢过氧化蒎烷、氢过氧化二异丙基苯基、过氧化二苯甲酰、过氧化二月桂酰和过氧化二乙酰作为氧化组分,和铁(II)盐、碱金属亚硫酸盐、抗坏血酸、丙酮亚硫酸氢盐加合物和/或羟基甲烷亚磺酸的碱金属盐作为还原组分。
共聚物分散体一般具有25-60重量%,特别是约30-50重量%的固体含量。
共聚物分散体以未中和形式,具有相对低的粘度。因此它容易处理并可毫无问题地通过泵计量加入或循环。由于中和例如至大于5.5,优选大于6,特别是8-9的pH,共聚物变得可溶且含水介质的粘度相当地提高。合适的中和剂例如为氢氧化钠、氢氧化钾、氢氧化铵、胺如三乙胺、三乙醇胺、单乙醇胺和其它碱性材料。
除增稠剂外,液体洗涤剂或清洁剂包含表面活性剂,其中可使用阴离子、非离子、阳离子和/或两性表面活性剂。从应用观点来看,优选使用阴离子和非离子表面活性剂的混合物。液体洗涤剂或清洁剂的总表面活性剂含量基于总液体洗涤剂或清洁剂优选为5-60重量%,特别优选15-40重量%。
所用非离子表面活性剂优选为优选具有8-18个碳原子和平均1-12摩尔氧化乙烯(EO)/每摩尔醇的烷氧基化,有利地乙氧基化伯醇,其中醇基团可以为线性或优选在2位上甲基支化的,或在混合物中可包含线性或甲基支化的基团,如羰基合成醇基团中通常存在的。然而,特别优选具有来自具有12-18个碳原子的天然来源的醇,例如来自椰子醇、棕榈醇、牛油脂肪醇或油醇的线性基团和平均2-8个EO/摩尔醇的醇乙氧基化物。优选的乙氧基化醇包括例如具有3个EO、4个EO或7个EO的C12-C14醇,具有7个EO的C9-C11醇,具有3个EO、5个EO、7EO或8个EO的C13-C15醇,具有3个EO、5EO或7个EO的C12-C18醇,和这些的混合物,例如具有3个EO的C12-C14醇和具有7个EO的C12-C18醇的混合物。所述乙氧基化度为统计平均值,其可以为关于具体产物的整数或分数。优选的醇乙氧基化物具有窄同系物分布(窄范围乙氧基化物,NRE)。除这些非离子表面活性剂外,也可使用具有多于12个EO的脂肪醇。其实例为具有14个EO、25个EO、30个EO或40个EO的牛油脂肪醇。也可使用在分子中一起包含EO和PO的非离子表面活性剂。就这点而言,可使用具有EO-PO嵌段单元或PO-EO嵌段单元的嵌段共聚物,以及EO-PO-EO共聚物或PO-EO-PO共聚物。当然也可使用混合烷氧基化非离子表面活性剂,其中EO和PO单元不是嵌段方式,而是无规分布。这类产物可通过氧化乙烯和氧化丙烯同时作用于脂肪醇上而得到。
此外,可使用的其它非离子表面活性剂还有通式(I)的烷基糖苷:
R1O(G)x (1)
其中R1为具有8-22个,优选12-18个碳原子的直链伯脂族基团或甲基支化,特别是2-甲基支化的脂族基团,且g为具有5或6个碳原子的糖苷单元,优选葡萄糖。低聚度x表示单糖苷和寡糖苷的分布,为1-10之间的任何所需数;优选x为1.2-1.4。
可作为唯一非离子表面活性剂或与其它非离子表面活性剂组合使用的另一类优选使用的非离子表面活性剂为烷基链中优选具有1-4个碳原子的烷氧基化,优选乙氧基化或乙氧基化和丙氧基化脂肪酸烷基酯,特别是脂肪酸甲酯,例如如日本专利申请JP 58/217598所述,或优选通过国际专利申请WO-A-90/13533所述方法制备。
氧化胺类非离子表面活性剂如N-椰油烷基-N,N-二甲基氧化胺和N-牛脂烷基-N,N-二羟乙基氧化胺,和脂肪酸链烷醇胺类型的也可以是合适的。这些非离子表面活性剂的量优选不多于乙氧基化脂肪醇的,特别是不多于其一半。
其它合适的表面活性剂为式(2)的多羟基脂肪酰胺:
其中R2C(=O)为具有6-22个碳原子的脂族酰基,R3为氢、具有1-4个碳原子的烷基或羟烷基,且[Z]为具有3-10个碳原子和3-10个羟基的线性或支化多羟烷基。多羟基脂肪酰胺是已知物质,其通常可通过还原糖与氨、烷基胺或链烷醇胺的还原胺化并随后用脂肪酸、脂肪酸烷基酯或脂肪酰氯酰化而得到。
多羟基脂肪酰胺组还包括式(3)化合物:
其中R4为具有7-12个碳原子的线性或支化烷基或链烯基,R5为具有2-8个碳原子的线性、支化或环状链烯基或具有6-8个碳原子的亚芳基,且R6为具有1-8个碳原子的线性、支化或环状烷基或芳基或氧基烷基,其中C1-C4烷基或苯基是优选的,且[Z]1为其烷基链被至少两个羟基取代的线性多羟基烷基,或该基团的烷氧基化,优选乙氧基化或丙氧基化衍生物。[Z]1优选通过糖如葡萄糖、果糖、麦芽糖、乳糖、半乳糖、甘露糖或木糖的还原胺化而得到。然后可将N-烷氧基-或N-芳氧基取代的化合物例如根据WO-A-95/07331,通过与脂肪酸甲基酯在醇盐作为催化剂的存在下反应而转化成所需多羟基脂肪胺。
液体洗涤剂或清洁剂中非离子表面活性剂的含量每种情况下基于总组合物优选为1-30重量%,优选7-20重量%,特别是9-15重量%。
所用阴离子表面活性剂例如为磺酸盐和硫酸盐类的那些。合适的磺酸盐类表面活性剂优选为C9-C13烷基苯磺酸盐、烯烃磺酸盐,即链烯烃-和羟基链烷磺酸盐的混合物,以及二磺酸盐,如例如通过用气体三氧化硫磺化,随后将磺化产物碱或酸水解而由具有末端或内部双键的C12-C18单烯烃得到。合适的还有例如通过氯磺化或磺化氧化,随后水解或中和而由C12-C18链烷烃得到的链烷磺酸盐。同样,α-磺基脂肪酸的酯(磺酸酯)如氢化椰油、棕榈仁或牛油脂肪酸的α-磺化甲基酯。
其它合适的阴离子表面活性剂为硫酸化脂肪酸甘油酯。脂肪酸甘油酯应当理解意指单酯、二酯和三酯及其混合物,如在通过将单甘油用1-3摩尔脂肪酸酯化而制备中或在甘油三酯与0.3-2摩尔甘油酯交换期间得到。此处优选的硫酸化脂肪酸甘油酯为具有6-22个碳原子的饱和脂肪酸如己酸、辛酸、癸酸、肉豆蔻酸、月桂酸、棕榈酸、硬脂酸或山萮酸的硫酸化产物。
烷(链烯)基硫酸盐优选为C12-C18脂肪醇如椰油脂肪醇、牛油脂肪醇、月桂醇、肉豆蔻醇、鲸蜡醇或硬脂醇,或C10-C20羰基合成醇的硫酸半酯和具有这些链长的仲胺的那些半酯的碱金属,特别是钠盐。此外,优选包含合成、石油化学基直链烷基的具有所述链长的烷(链烯)基硫酸盐,其具有与基于脂肪化学原料的等价化合物类似的降解行为。从洗涤观点来看C12-C16烷基硫酸盐和C12-C15烷基硫酸盐以及C14-C15烷基硫酸盐是优选的。2,3-烷基硫酸盐也是合适的阴离子表面活性剂,其例如根据美国专利说明书3,234,258或5,075,041制备并可作为商品以名由Shell Oil Company得到。
用1-6摩尔氧化乙烯乙氧基化的的直链或支化C7-C21醇如具有平均3.5摩尔氧化乙烯(EO)的2-甲基支化的C9-C11醇或具有1-4个EO的C12-C18脂肪醇的硫酸单酯也是合适的。由于它们的高起泡行为,它们仅以相对少量,例如以1-5重量%的量用于清洁剂中。
其它合适的阴离子表面活性剂还有烷基磺基琥珀酸的盐,其也称为磺基琥珀酸盐或磺基琥珀酸酯,并与醇,优选脂肪醇,特别是乙氧基化脂肪醇构成磺基琥珀酸的单酯和/或二酯。优选的磺基琥珀酸酯包含C8-C18脂肪醇基团或其混合物。特别优选的磺基琥珀酸酯包含衍生自乙氧基化脂肪醇的脂肪醇基团。就这点而言,又特别优选其脂肪醇基团衍生自具有窄同系物分布的乙氧基化脂肪醇的磺基琥珀酸酯。同样还可使用在烷(链烯)基链中具有优选8-18个碳原子的烷(链烯)基琥珀酸或其盐。
特别优选的阴离子表面活性剂为皂。饱和和不饱和脂肪酸皂,例如月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、(氢化)芥酸和山萮酸的盐,以及特别衍生自天然脂肪酸如椰油、棕榈仁、橄榄油或牛油脂肪酸的皂混合物是合适的。
包括皂在内的阴离子表面活性剂可以以其钠、钾或铵盐的形式以及作为有机碱的可溶性盐如单-、二-或三乙醇胺存在。优选阴离子表面活性剂以其钠或钾盐的形式,特别是钠盐的形式存在。
优选液体洗涤剂或清洁剂中阴离子表面活性剂的含量每种情况下基于总组合物为2-30重量%,优选2-40重量%,特别是5-22重量%。特别优选脂肪酸皂的量为至少2重量%,特别优选至少4重量%,特别优选至少6重量%。
液体洗涤剂或清洁剂的粘度可通过常规标准方法(例如布氏粘度计LVT-II,在20rpm和20℃下,心轴3)测量,优选为100-5000mPas。优选的组合物具有300-4000mPas的粘度,1000-3000mPas的值是特别优选的。
除增稠剂和表面活性剂外,液体洗涤剂或清洁剂可包含进一步改进液体洗涤剂或清洁剂的应用和/或审美性能的其它成分。通常,除缔合增稠剂和表面活性剂外,优选的组合物包含一种或多种选自如下的物质:增洁剂、漂白剂、漂白活化剂、酶、电解质、非水溶剂、pH增长剂、芳香剂、香料载体、荧光剂、燃料、水溶助长剂、抑泡剂、硅油、防再沉积剂、荧光增白剂、泛灰抑制剂、抗缩剂、抗皱剂、色转移抑制剂、抗菌活性成分、杀菌剂、杀真菌剂、抗氧化剂、腐蚀抑制剂、抗静电剂、熨平助剂、疏水和浸渍剂、溶胀和防滑剂以及UV吸收剂。
可存在于液体洗涤剂或清洁剂中的增洁剂特别是硅酸盐、铝硅酸盐(特别是沸石)、碳酸盐、有机二-和多羧酸的盐,和这些物质的混合物。
适用作有机增洁剂的低分子量聚羧酸酯例如为:
C4-C20二-、三-和四羧酸,例如琥珀酸、丙烷三羧酸、丁烷四羧酸、环戊烷四羧酸和具有C2-C16烷基或亚烷基的烷基-和亚烷基琥珀酸;
C4-C20羟基羧酸,例如苹果酸、酒石酸、葡糖酸、戊二酸、柠檬酸、乳糖酸和蔗糖单-、二-和三羧酸;
氨基聚羧酸酯,例如次氮基三乙酸、甲基甘氨酸二乙酸、丙氨酸二乙酸、乙二胺四乙酸和丝氨酸二乙酸;
膦酸如羟基乙烷二膦酸、乙二胺四(亚甲基膦酸酯)和二亚乙基三胺五(亚甲基磷酸酯)的盐。
适用作有机增洁剂的低聚或聚合聚羧酸酯例如为:
低聚马来酸,例如如EP-A 0 451 508和EP-A 0 396 303所述;
不饱和C4-C8二羧酸的共聚物和三聚物,其中:
至多95重量%的量的来自组(i),
至多60重量%的量的来自组(ii),
至多20重量%的量的来自组(iii)
的单烯属不饱和单体可以作为共聚单体以共聚形式存在。
此处合适的不饱和C4-C8二羧酸例如为马来酸、富马酸、衣康酸和柠康酸(甲基马来酸)。优选马来酸。
组(i)包括单烯属不饱和C3-C8单羧酸如丙烯酸、甲基丙烯酸、巴豆酸和乙烯基乙酸。从组(i)中优选使用丙烯酸和甲基丙烯酸。
组(ii)包括单烯属不饱和C2-C22烯烃、具有C1-C8烷基的乙烯基烷基醚、苯乙烯、C1-C8羧酸的乙烯酯、(甲基)丙烯酰胺和乙烯基吡咯烷酮。从组(ii)中优选使用C2-C6烯烃、具有C1-C4烷基的乙烯基烷基醚、乙酸乙烯酯和丙酸乙烯酯。
组(iii)包括C1-C8醇的(甲基)丙烯酸酯、(甲基)丙烯酰胺、C1-C8胺的(甲基)丙烯酰胺、N-乙烯基甲酰胺和乙烯基咪唑。
如果组(ii)聚合物包含共聚形式的乙烯酯,则这些也可以以部分或完全水解的形式存在以得到乙烯醇结构单元。合适的共聚物和三聚物例如由US 3,887,806和SE-A 43 13 909已知。
适用作有机增洁剂的二羧酸共聚物优选为:
重量比为10:90-95:5的马来酸和丙烯酸的共聚物,特别优选重量比为30:70-90:10且摩尔质量为10000-150000的那些;
重量比为10(马来酸):90(丙烯酸+乙烯酯)-95(马来酸):10(丙烯酸+乙烯酯)的马来酸、丙烯酸和C1-C3羧酸乙烯酯的三聚物,其中丙烯酸与乙烯酯的重量比为20:80-80:20,特别优选:
重量比为20(马来酸):80(丙烯酸+乙烯酯)-90(马来酸):10(丙烯酸+乙烯酯)的马来酸、丙烯酸和乙酸乙烯酯或丙酸乙烯酯的三聚物,其中丙烯酸与乙烯酯的重量比为30:70-70:30;
摩尔比为40:60-80:20的马来酸与C2-C8烯烃的共聚物,其中摩尔比为50:50的马来酸与乙烯、丙烯或异丁烷的共聚物是特别优选的。
不饱和羧酸在低分子量碳水化合物或氢化碳水化合物上的接枝聚合物,参见US 5,227,446、DE-A 4415623、DE-A 43 13 909同样适用作有机增洁剂。
此处合适的不饱和羧酸例如为马来酸、富马酸、衣康酸、柠康酸、丙烯酸、甲基丙烯酸、巴豆酸和乙烯基乙酸,以及以基于待接枝组分40-95重量%的量接枝的丙烯酸和马来酸的混合物。
为改性,基于待接枝组分至多30重量%的另一单烯属不饱和单体也可以以共聚形式存在。合适的改性组分为上述组(ii)和(iii)中的单体。
合适的接枝基为降解多糖,例如酸或酶降解糖、菊粉或纤维素,还原(氢化或还原胺化)降解多糖,例如甘露糖醇、山梨糖醇、氨基山梨糖醇和葡糖胺,以及摩尔质量为至多Mw=5000的聚亚烷基二醇,例如聚乙二醇、氧化乙烯/氧化丙烯或氧化乙烯/氧化丁烯嵌段共聚物、无规氧化乙烯/氧化丙烯或氧化乙烯/氧化丁烯共聚物、烷氧基化单-或多元C1-C22醇,参见US 4,746,456。
从这组中,优选使用接枝降解或降解还原糖和接枝聚氧化乙烯,其中基于接枝组分20-80重量%单体用于接枝聚合中。就接枝而言,优选使用重量比为90:10-10:90的马来酸和丙烯酸的混合物。
作为有机增洁剂的聚乙醛酸例如描述于EP-B 0001004、US 5,399,286、DE-A 4106355和EP-A 0656914中。聚羟基乙酸的端基可具有不同的结构。
作为有机增洁剂的聚酰氨基羧酸和改性聚酰氨基羧酸例如由EP-A 0 454 126、EP-B 0 511 037、WO-A 94/01486和EP-A 0581452中已知。
优选所用有机增洁剂还有聚天冬氨酸或天冬氨酸与其它氨基、C4-C25单-或二羧酸和/或C4-C25单-或二胺的共缩合物。特别优选使用用C6-C22单-或二羧酸或用C6-C22单-或二胺改性并在含磷酸中制备的聚天冬氨酸。
作为有机增洁剂的柠檬酸与羟基羧酸或聚羟基化合物的缩合产物例如由WO-A 93/22362和WO-A 92/16493已知。这类含羧基缩合物通常具有至多10000,优选至多5000的摩尔质量。
在水中产生H2O2并可用作漂白剂的化合物中,过硼酸钠四水合物和过硼酸钠一水合物特别重要。可使用的其它漂白剂例如为过碳酸钠、过氧焦磷酸盐、柠檬酸过水合物和过酸性盐或产生H2O2的过酸,例如过苯甲酸盐、过氧邻苯二甲酸盐、二过壬二酸、邻苯二甲酰氨基过酸或二过十二烷二酸。
为实现在60℃及以下的温度下洗涤期间的改进漂白效果,可将漂白活化剂掺入洗涤剂或清洁剂中。可使用的漂白活化剂为在全水解条件下产生具有优选1-10个碳原子,特别是2-4个碳原子的脂族过氧羧酸和/或任选取代的过苯甲酸的化合物。带有指定碳原子数的O-和/或N-酰基和/或任选取代苯甲酰基的物质是合适的。优选聚酰化亚烷基二胺,特别是四乙酰乙二胺(TAED),酰化三嗪衍生物,特别是1,5-二乙酰基-2,4-二氧代六氢-1,3,5-三嗪(DADHT),酰化甘脲,特别是四乙酰基甘脲(TAGU)、N-酰基酰亚胺,特别是N-壬酰琥珀酰亚胺(NOSI),酰化苯酚磺酸盐,特别是正壬酰或异壬酰氧基苯磺酸盐(正-或异-NOBS),羧酸酐,特别是邻苯二甲酸酐,酰化多元醇,特别是三醋精,乙二醇二乙酸酯和2,5-二乙酰氧基-2,5-二氢呋喃。
除常规漂白活化剂外,或代替它们,也可将所谓的漂白催化剂掺入液体洗涤剂或清洁剂中。这些物质为助漂白过渡金属盐或过渡金属配合物,例如Mn-、Fe-、Co-、Ru-或Mo-salene配合物或-羰基配合物。也可使用具有含氮三角配体的Mn、Fe、Co、Ru、Mo、Ti、V和Cu配合物,以及Co-、Fe-、Cu-和Ru-胺配合物作为漂白催化剂。
合适的酶特别是水解酶类的那些,例如蛋白酶、酯酶、脂肪酶或脂肪分解酶、淀粉酶、纤维酶和其它糖基水解酶和所述酶的混合物。所有这些水解酶在洗涤期间有助于除去污点如含蛋白、脂肪或淀粉的污点和泛灰。此外,纤维酶和其它糖基水解酶可有助于通过除去球和微纤维而提高织物的柔软度。氧化还原酶也可用于漂白或色传递的抑制。由细菌菌株或真菌如枯草杆菌(Bacillus subtilis)、地衣芽孢杆菌(Bacillus licheniformis)、灰色链霉菌(Streptomyceus griseus)和特异腐质霉(Humicola insolens)得到的酶活性成分是非常特别合适的。优选使用枯草溶菌素类的蛋白酶,特别是由迟缓芽孢杆菌(bacillus lentus)得到的蛋白酶。此处,例如蛋白酶和淀粉酶或蛋白酶和脂肪酶或脂肪分解酶或蛋白酶和纤维素酶或纤维素酶和脂肪酶或脂肪分解酶或蛋白酶、淀粉酶和脂肪酶或脂肪分解酶或蛋白酶、脂肪酶或脂肪分解酶和纤维素酶的混合物,但特别是含有蛋白酶和/或脂肪酶的混合物或具有脂肪分解酶的混合物是特别有意义的。这类脂肪分解酶的实例为已知的角质酶。还证明过氧化物酶或氧化酶在一些情况下是合适的。合适的淀粉酶包括特别α-淀粉酶、异淀粉酶、支链淀粉酶和果胶酶。所用纤维素酶优选为纤维二糖水解酶、内切葡聚糖酶和β-葡糖苷酶,其也称为纤维二糖酶,或这些的混合物。由于不同类型的纤维素酶在其CMC酶和微晶纤维素酶活性方面不同,所需活性可通过目标纤维素酶混合物建立。
酶也可吸收于载体中以保护它们以防过早分解。酶、酶混合物或酶颗粒的含量可例如为约0.1-5重量%,优选0.12重量%至约2.5重量%。
许多高度不同的盐可用作来自无机盐的电解质。优选的阳离子为碱金属和碱土金属,优选的阴离子为卤素和硫酸根。从生产观点看,NaCl或MgCl2在组合物中的使用是优选的。组合物中电解质的含量通常为0.5-5重量%。
可用于液体洗涤剂或清洁剂中的非水溶剂例如源自单-或多元醇、链烷醇胺或乙二醇醚,条件是它们在指定浓度范围内与水溶混。优选溶剂选自乙醇、正-或异丙醇、丁醇、甘醇、丙二醇或丁二醇、甘油、二甘醇、丙二醇或丁二甘醇、己二醇、乙二醇甲基醚、乙二醇乙基醚、乙二醇丙基醚、乙二醇单-正丁基醚、二甘醇甲基醚、二甘醇乙基醚、丙二醇甲基、乙基或丙基醚、二丙二醇单甲基或-乙基醚、二异丙二醇单甲基或-乙基醚、甲氧基-、乙氧基-或丁氧基三甘醇、异丁氧基乙氧基-2-丙醇、3-甲基-3-甲氧基丁醇、丙二醇叔丁基醚和这些溶剂的混合物。非水溶剂可以以0.5-15重量%,但优选12重量%以下,特别是9重量%以下的量用于液体洗涤剂或清洁剂中。
为使液体洗涤剂或清洁剂的pH达到所需范围内,pH增长剂的使用可能是合适的。此处可以使用所有已知的酸或碱,条件是由于应用相关或生态原因或由于消费者保护原因不排除它们的使用。通常,这些增长剂的量不超过总配制剂的7重量%。
为改进液体洗涤剂或清洁剂的审美印象,可将它们用合适的染料着色。优选的染料,其选择对本领域技术人员而言完全不难,具有高储存稳定性和对组合物的其它成分和光的不灵敏性,以及对织物纤维不具有显著直染性,以便不会沾污它们。
可用于液体洗涤剂或清洁剂中的合适抑泡剂例如为皂、石蜡或硅油,可任选将其应用于载体材料上。
合适的防再沉积剂,也称为防污剂例如为非离子纤维素醚,例如甲基纤维素和甲基羟丙基纤维素,其具有每种情况下基于非离子纤维素醚15-30重量%的甲氧基和1-15重量%的羟丙基含量。合适的去污聚合物例如为聚氧化乙烯与乙二醇和/或丙二醇和芳族二羧酸或芳族和脂族二羧酸的酯;在一端上用二-和/或多元醇封端的聚氧化乙烯和二羧酸的聚酯,特别是对苯二甲酸乙二醇酯和/或聚乙二醇对苯二甲酸酯的聚合物或这些的阴离子和/或非离子改性衍生物。在这些中,特别优选邻苯二甲酸聚合物和对苯二甲酸的磺酸化衍生物。这类聚酯例如由US 3,557,039、GB-A 1154730、EP-A0185427、EP-A 0241984、EP-A 0241985、EP-A 0272033和US-A5,142,020已知。其它合适的去污聚合物为乙烯基和/或丙烯酸酯在聚氧化烯(参见US 4,746,456、US 4,846,995、DE-A 3711299、US 4,904,408、US4,846,994和US 4,849,126)上的两亲接枝聚合物或共聚物,或改性纤维素如甲基纤维素、羟丙基纤维素或羧甲基纤维素。
可将荧光增白剂(所谓增白剂)加入液体洗涤剂或清洁剂中以消除处理织物的泛灰和变黄。这些物质附着于纤维上并通过将不可见的紫外线辐射转化成可见的较长波光而产生发亮和类似漂白效果,其中由日光吸收的紫外线作为浅蓝色荧光发射并以泛灰和/或泛黄衣物的黄色阴影产生纯白色。合适的化合物源自例如如下物质类:4,4'-二氨基-2,2'-芪二磺酸(黄酮酸)、4,4'-联苯乙烯联苯撑、甲基伞形酮、香豆素、二氢喹啉酮、1,3-二芳基吡唑啉、萘二甲酰亚胺、苯并唑、苯并异唑和苯并咪唑体系,和被杂环取代的芘衍生物。荧光增白剂通常以基于最终组合物0.03-0.3重量%的量使用。
泛灰抑制剂的任务是保持污物与悬浮于液体中的纤维分离,因此防止污物重附着。为此合适的主要具有有机性质的水溶性胶体,例如胶、明胶、淀粉或纤维素的醚磺酸盐或纤维素或淀粉的酸性硫酸酯的盐。包含酸性基团的水溶性聚酰胺也适于该目的。此外,可使用不同于上述那些的合适淀粉制剂和淀粉产品,例如降解淀粉、醛淀粉等。也可使用聚乙烯吡咯烷酮。然而,优选使用基于组合物0.1-5重量%的量的纤维素醚,例如羧甲基纤维素(Na盐)、甲基纤维素、羟烷基纤维素和混合醚,例如甲基羟乙基纤维素、甲基羟丙基纤维素、甲基羧甲基纤维素及其混合物。
由于织物,特别是由人造丝、粘胶人造丝、棉及其混合物构成的,可能具有褶皱的倾向,因为单独的纤维对与纤维方向成直角的弯曲、折叠、挤压和压榨敏感,组合物可包含合成抗皱试剂。这些包括例如基于脂肪酸、脂肪酸酯、脂肪酰胺、脂肪烷基醇酯、脂肪烷基醇酰胺或脂肪醇(其大部分与氧化乙烯反应)的合成产品,或基于卵磷脂或改性磷酸酯的产品。
为防治微生物,液体洗涤剂或清洁剂可包含抗菌活性成分。取决于抗菌谱和作用机理,此处的区别是抑菌剂和杀菌剂、抑真菌剂与杀真菌剂等。这些组的重要物质例如为苯扎氯铵、烷基芳基磺酸盐、卤代苯酚和苯酚乙酸汞化物。
为防止通过氧气和其它氧化方法导致的液体洗涤剂或清洁剂和/或处理织物中不想要的变换,组合物可包含抗氧化剂。这类化合物包括例如取代苯酚、氢醌、焦儿茶酚和芳族胺,以及有机硫化物、聚硫化物、二硫代氨基甲酸酯、亚磷酸酯和膦酸酯。
提高的穿着舒适性可产生于另外加入组合物中的抗静电剂的额外使用。抗静电剂提高表面导电率并因此容许所形成的电荷的改进放电。外部抗静电剂一般为具有至少一种亲水分子配体的物质并在表面上产生或多或少的吸湿膜。这些主要界面活性抗静电剂可分为含氮抗静电剂(胺、酰胺、季铵化合物)、含磷抗静电剂(磷酸酯)和含硫抗静电剂(烷基磺酸盐、烷基硫酸盐)。外部抗静电剂例如描述于专利申请FR 1,156,513、GB 873214和GB 839 407中。此处公开的月桂基(或硬脂基)二甲基苄基氯化铵适用作织物的抗静电剂和洗涤剂的添加剂,其中另外实现手动改进效果。
为改进处理织物的吸水能力和促进处理织物的熨平,硅酮衍生物例如可用于液体洗涤剂或清洁剂中。这些另外改进组合物通过它们的抑泡性能的洗出行为。优选的硅酮衍生物例如为聚二烷基-或烷基芳基硅氧烷,其中烷基具有1-5个碳原子且为部分或完全氟化的。优选的硅酮为可任选衍生,然后氨基官能化或季铵化或具有Si-OH、Si-H和/或Si-Cl键的聚二甲基硅氧烷。优选的硅酮在25℃下的粘度为100-100000mPas,可使用基于总组合物0.2-5重量%的量的硅酮。
最后,液体洗涤剂或清洁剂还可包含UV吸收剂,其附着于处理织物上并改进纤维的光稳定性。具有这些所需性能的化合物例如为在2和/或4位上具有取代基的二苯甲酮化合物和衍生物,其由于非辐射减活而有效。此外,取代的苯并三唑、任选在2位上具有氰基的在3位上苯基取代的丙烯酸酯(肉桂酸衍生物)、水杨酸酯、有机Ni配合物,和天然物质如伞形酮和内源尿刊酸也是合适的。
为避免某些洗涤剂成分通过重金属催化而分解,可使用配合重金属的物质。合适重金属配合剂例如为乙二胺四乙酸(EDTA)、次氮基三乙酸(NTA)或甲基甘氨酸二乙酸(MGDA)的碱金属盐,以及阴离子聚电解质如聚马来酸酯和聚磺酸酯的碱金属盐。
一类优选的配合剂为膦酸盐,其以0.01-2.5重量%,优选0.02-2重量%,特别是0.03-1.5重量%的量存在于优选的液体洗涤剂或清洁剂中。这些优选的化合物特别包括有机膦酸盐,例如1-羟基乙烷-1,1-二膦酸(HEDP)、氨基三(亚甲基膦酸)(ATMP)、二亚乙基三胺五(亚甲基膦酸)(DTPMP或DETPMP),以及2-膦基丁烷-1,2,4-三甲酸(PBS-AM),其主要以其铵或碱金属盐的形式使用。
所得含水液体洗涤剂或清洁剂不具有沉降;在优选实施方案中,它们是透明或至少半透明的。优选含水液体洗涤剂或清洁剂具有至少30%,优选50%,特别优选75%,最优选90%的可见光透射。作为选择,本发明增稠剂可掺入不透明洗涤剂或清洁剂中。
除这些组分外,含水洗涤剂或清洁剂可包含分散颗粒,沿着其最大空间膨胀,其直径为0.01-10000μm。
颗粒可以为微胶囊以及微粒、化合物和香珠,其中微胶囊是优选的。
术语“微胶囊”应当理解意指包含至少一种被至少一种连续外壳,特别是由聚合物构成的外壳包围的固体或液体芯的聚集体。通常,这些为由成膜聚合物包围的细分散液相或固相,在其生产期间聚合物在乳化并凝聚或界面聚合以后沉淀至待包封材料上。纤维小胶囊可以为干燥的,如同粉末。除单芯微胶囊外,多芯聚集体也是已知的,也称为微球,其包含分布于连续涂料中的两个或更多芯。单芯或多芯微胶囊还可被另外的第二、第三等外壳包围。优选具有连续外壳的单芯微胶囊。外壳可由天然、半合成或合成材料组成。天然外壳材料例如为阿拉伯树胶、琼脂、琼脂糖、麦芽糖糊精、藻酸及其盐如藻酸钠或藻酸钙、脂肪和脂肪酸、鲸蜡醇、胶原壳聚糖、卵磷脂、明胶、白蛋白、虫胶、多糖如淀粉或葡聚糖、蔗糖和蜡。半合成涂料尤其是化学改性纤维素,特别是纤维素酯和醚,例如乙酸纤维素、乙基纤维素、羟丙基纤维素、羟丙基甲基纤维素和羧甲基纤维素,以及淀粉衍生物,特别是淀粉醚和酯。合成涂料例如为聚合物如聚丙烯酸酯、聚酰胺、聚乙烯醇或聚乙烯吡咯烷酮。含水液体洗涤剂或清洁剂的敏感、化学或物理不相容以及挥发性组分(=活性成分)可以以储存稳定且运输稳定的方式包封在微胶囊内部。例如荧光增白剂、表面活性剂、配合剂、漂白剂、漂白活化剂、染料和芳香剂、抗氧化剂、增洁剂、酶、酶稳定剂、抗菌活性成分、泛灰抑制剂、防再沉积剂、pH增长剂、电解质、抑泡剂和UV吸收剂可以存在于微胶囊中。
微胶囊还可包含阳离子表面活性剂、维生素、蛋白质、防腐剂、去污助剂或珠光剂。微胶囊的填料可以为固体或溶液或乳液或悬浮液形式的液体。
微胶囊可具有生产范围内的任何所需形式,但优选为近似球形。它们沿着其最大空间膨胀的直径取决于其内部存在的组分和应用可以为0.01μm(视觉上不认为是胶囊)-10000μm。优选直径为100-7000μm,特别是400-5000μm的可见微胶囊。微胶囊可通过已知方法达到,其中凝聚和界面聚合贡献最大的重要性。可使用的微胶囊为市场上供应的所有表面活性剂稳定的微胶囊,例如商品(涂料在各括号中给出)Hallcrest Microcapsules(明胶、阿拉伯树胶)、Coletica Thalaspheres(海洋胶原)、Lipotec Millicapseln(藻酸、瓜尔胶)、Induchem Unispheres(乳糖、微晶纤维素、羟丙基甲基纤维素);Unicerin C30(乳糖、微晶纤维素、羟丙基甲基纤维素)、KoboGlycospheres(改性淀粉、脂肪酸酯、磷脂)、Softspheres(改性琼脂)和KuhsProbiol Nanospheres(磷脂)。
作为选择,也可使用不具有芯-壳结构的颗粒,但其中活性成分分布于基体形成材料的基体中。这类颗粒也称为“斑点”。
优选基体形成材料为藻酸盐。为生产藻酸盐基斑点,将还包含一种或多种待包封活性成分的藻酸盐水溶液滴落,然后在包含Ca2+离子或Al3+离子的沉淀浴中硬化。
作为选择,代替藻酸盐,可使用其它基体形成材料。基体形成材料的实例包括聚乙二醇、聚乙烯吡咯烷酮、聚甲基丙烯酸酯、多溶素、泊洛沙姆、聚乙烯醇、聚丙烯酸、聚氧化乙烯、聚乙氧基唑啉、白蛋白、明胶、阿拉伯树胶、壳聚糖、纤维素、葡聚糖、淀粉、羟乙基纤维素、羟丙基纤维素、羟丙基甲基纤维素、透明质酸、羧甲基纤维素、羧甲基纤维素、脱乙酰壳聚糖、葡聚糖硫酸盐和这些材料的衍生物。基体形成就这些材料而言例如借助胶凝、聚阴离子-聚阳离子相互作用或聚电解质-金属离子相互作用而进行。具有这些基体形成材料的颗粒的制备本身是已知的。
颗粒可稳定地分散于含水液体洗涤剂或清洁剂中。稳定意指组合物在室温下和在40℃下经至少4星期,优选至少6星期期间稳定,同时组合物不会乳油化或沉降。本发明增稠剂通过浓度提高而产生颗粒沉降的运动减缓和因此它们在悬浮状态下的稳定。
活性成分从微胶囊或斑点中的释放通常在包含它们的组合物的应用期间通过外壳或基体由于机械、热、化学或酶作用分解而发生。
本发明洗涤剂或清洁剂可用于清洁织物和/或硬表面。本发明清洁剂可以为如下形式:手动或机械洗碗洗涤剂、用于非织物表面如由金属、上漆木或塑料构成的表面的通用清洁剂、用于陶瓷产品如瓷器、瓷砖的清洁剂。洗涤剂或清洁剂可配制成液体或糊。
为制备液体洗涤剂或清洁剂,可将表面活性剂、增稠剂和任选组分以任何所需顺序相互组合。例如可首先引入酸性组分如线性烷基磺酸盐、柠檬酸、硼酸、膦酸、脂肪醇醚硫酸酯等,然后将非离子表面活性剂加入其中。然后加入碱如NaOH、KOH、三乙醇胺或单乙醇胺,其后如果存在的话加入脂肪酸。随后将含水液体洗涤剂或清洁剂的其余成分和溶剂加入混合物中。然后加入本发明缔合增稠剂并任选将pH校正至例如8-9.5。
根据本发明使用的增稠剂的具体优点是它们适于随后掺入洗涤剂或清洁剂预配制剂中(后加入)。增稠剂分散体的随后掺入简化了生产运行,且为有利的,因为洗涤剂或清洁剂仅在其制备的稍后阶段实现高粘度。它容许精确的粘度调整。由于低粘度液体的处理,例如通过泵送、混合或均化更快速且更容易地进行,低粘度预配制剂可以用更短的批处理时间和更低的能量消耗制备。
通常,增稠剂的随后掺入可产生于洗涤剂或清洁剂的其它组分的提高的不相容性,这可导致不令人满意的粘度建立和/或削弱的透明度。令人惊讶地,用本发明所用的增稠剂不会产生这类不相容性。
任选,最后可加入待分散颗粒并通过混合,均匀地分散于含水液体洗涤剂或清洁剂中。
通过以下实施例更详细地阐述本发明。
对比例1
在由具有锚式搅拌器(150rpm)、回流冷凝器、内热敏元件和计量站的4L HWS容器组成的搅拌设备中,将631.99g软化水(软化水)和10.71g乳化剂Texapon NSO-在水中28%浓度混合作为初始进料。
在75℃下,将16.29g 7%浓度的过氧化硫酸氢钠水溶液加入该溶液中并将混合物在75℃下搅拌5分钟。然后在75℃下随着进一步搅拌,将由560.75g完全软化水(软化水)、单体(183.67g甲基丙烯酸、180g丙烯酸乙酯、180g丙烯酸正丁酯、60g来自EvonikGmbH的Plex 6877-O[由15gLutensolAT 25甲基丙烯酸酯[=(EO)25-甲基丙烯酸(C16-18)烷基酯]、45g甲基丙烯酸甲酯]组成)和10.71g乳化剂Texapon NSO-在水中28%浓度组成的乳液经2小时均匀地计量加入。然后将反应混合物在75℃下搅拌另外1小时,然后使其达到室温。在室温下,加入0.3g 4%浓度Dissolvine E-FE-6溶液(铁(II)盐溶液)和12g 5%浓度过氧化氢溶液,并经30分钟过程计量加入90g 1%浓度抗坏血酸溶液。这得到具有31%固体含量的聚合物水分散体。
实施例1-8和对比例2和3
类似地制备表1所列其它分散体。Lutencryl 250为(EO)25-甲基丙烯酸(C16-C18)烷基酯与50重量%甲基丙烯酸的混合物。进料材料的数据以份/100反应性单体份(份/100单体;pphm)给出。
为表征分散体,测量如下值:
固体含量:将分散体在140℃下干燥30分钟,并作为干残余物与初始重量之比的百分数测定固体含量。
粒度:将分散体稀释至0.01%并在来自Malvern Instruments的高性能粒度仪5001(HPPS)中通过光散射测量粒度。
LT值:将分散体稀释至0.01%并与纯水相比在Hach DR/2010中作为粒度的尺度光学测量分散体的光透射(LT)。
液体洗涤剂的制备
制备如下备料配制剂(重量%,基于最终配制剂):
配制剂类型A | 配制剂类型B | |
C10-C13线性烷基苯磺酸 | 17.9g | 13g |
CH3-(CH2)11-(O-CH2CH2)7-OH | 20g | 7.5g |
椰油脂肪酸Edenor K8-18 | 8.5g | 8.5g |
KOH | 5g | 4.4g |
柠檬酸钠二水合物 | 3g | 3g |
1,2-丙二醇 | 8g | 8g |
乙醇 | 2g | 2g |
水 | 适量 | 适量 |
将以上组分混合并用水补充至90重量%,即保留10重量%的配制余地。将备料配制剂用KOH调整至pH8.6。
就(未增稠)参比配制剂而言,将备料配制剂用水补充至100重量%。就增稠的测试配制剂而言,将备料配制剂用增稠剂分散体和水补充,使得考虑分散体的固体含量,建立基于最终配制剂1.5重量%的增稠剂浓度。在粘度测量以前,使配制剂静止至少5小时。
低剪切粘度考虑使用说明根据DIN 51550、DIN 53018、DIN 53019使用布氏粘度计型号RV-03在20℃下以20rpm的转速使用心轴No.63测量。
洗涤实验使用已描述的洗涤剂配制剂(类型A和B)进行。洗涤条件为:
仪器 Atlas,Chicago,美国的耐洗试验机
洗涤液 250ml
洗涤时间 在40℃下30分钟
洗涤剂剂量 5g/l
水硬度 2.5毫摩尔,Ca:Mg:HCO34:1:8
洗涤周期 3
试验织物 5.0g棉织物221(单位面积重量132g/m2),5.0g混纺织物
768(65:35聚酯:棉,单位面积重量155g/m2)
沾污织物 10g被1:1:1比的三类粘土(Niederahr红色烧制粘土
178/RI、Hessian褐色烧制锰粘土262、黄色烧制粘土
158/G,Hilgert,德国的CarlKG)的混合物沾污的
混纺织物768(65:35聚酯:棉;单位面积重量155g/m2)
为测定二次去污力,通过在洗涤以前和以后使用光度计测定白度而测定白色测试织物的泛灰。白度的降低越大,织物的泛灰越大,反之亦然。
结果汇总于表2和3中。
可以看出包含高含量甲基丙烯酸甲酯的增稠剂分散体具有降低的反射比值。实施例显示增稠剂分散体中甲基丙烯酸甲酯的量与反射比值之间的关系;甲基丙烯酸甲酯含量越高,反射比越低。
Claims (10)
1.共聚物在液体织物洗涤剂中作为增稠剂的用途,该增稠剂导致衣物洗涤后的泛灰降低,其中所述共聚物包含:
a)至少15重量%烯属不饱和羧酸单元,
b)至少15重量%丙烯酸C4-C8烷基酯单元,
c)小于5重量%甲基丙烯酸甲酯单元,
d)非离子烯属不饱和表面活性剂单体单元。
2.根据权利要求1的用途,其中所述共聚物包含0.1-5重量%非离子烯属不饱和表面活性剂单体单元。
3.根据权利要求1的用途,其中所述非离子烯属不饱和表面活性剂单体具有如下通式:
R-O-(CH2-CHR′-O)n-CO-CR″=CH2
其中R为C6-C30烷基,
R′为氢或甲基,
R″为氢或甲基,且
n为2-100的整数。
4.根据权利要求2的用途,其中所述非离子烯属不饱和表面活性剂单体具有如下通式:
R-O-(CH2-CHR′-O)n-CO-CR″=CH2
其中R为C6-C30烷基,
R′为氢或甲基,
R″为氢或甲基,且
n为2-100的整数。
5.根据权利要求1-4中任一项的用途,其中所述共聚物可任选包含丙烯酸C1-C3烷基酯共聚单元。
6.根据权利要求5的用途,其中所述共聚物包含5-40重量%丙烯酸C1-C3烷基酯单元。
7.根据权利要求1-4中任一项的用途,其中所述烯属不饱和羧酸选自丙烯酸、甲基丙烯酸、衣康酸和马来酸。
8.根据权利要求1-4中任一项的用途,其中所述丙烯酸C4-C8烷基酯包含丙烯酸正丁酯。
9.根据权利要求1-4中任一项的用途,其中所述共聚物包含小于2重量%甲基丙烯酸甲酯单元。
10.根据权利要求1-4中任一项的用途,其中所述共聚物基本不含甲基丙烯酸甲酯单元。
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-
2011
- 2011-02-11 CA CA2788046A patent/CA2788046A1/en not_active Abandoned
- 2011-02-11 JP JP2012552415A patent/JP5788414B2/ja not_active Expired - Fee Related
- 2011-02-11 ES ES11702844.9T patent/ES2534766T3/es active Active
- 2011-02-11 EP EP11702844.9A patent/EP2534234B1/de active Active
- 2011-02-11 US US13/578,469 patent/US8865639B2/en not_active Expired - Fee Related
- 2011-02-11 KR KR1020127023695A patent/KR101794368B1/ko active Search and Examination
- 2011-02-11 PL PL11702844T patent/PL2534234T3/pl unknown
- 2011-02-11 WO PCT/EP2011/052051 patent/WO2011098571A1/de active Application Filing
- 2011-02-11 CN CN201180008565.9A patent/CN102753671B/zh not_active Expired - Fee Related
- 2011-02-11 MX MX2012008970A patent/MX341054B/es active IP Right Grant
- 2011-02-11 BR BR112012020157A patent/BR112012020157A2/pt not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
EP2534234A1 (de) | 2012-12-19 |
US8865639B2 (en) | 2014-10-21 |
KR20130010115A (ko) | 2013-01-25 |
US20130040870A1 (en) | 2013-02-14 |
PL2534234T3 (pl) | 2015-06-30 |
BR112012020157A2 (pt) | 2017-12-05 |
JP5788414B2 (ja) | 2015-09-30 |
KR101794368B1 (ko) | 2017-11-06 |
ES2534766T3 (es) | 2015-04-28 |
MX341054B (es) | 2016-08-05 |
EP2534234B1 (de) | 2015-01-14 |
WO2011098571A1 (de) | 2011-08-18 |
MX2012008970A (es) | 2012-08-23 |
CN102753671A (zh) | 2012-10-24 |
JP2013519748A (ja) | 2013-05-30 |
CA2788046A1 (en) | 2011-08-18 |
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