CN103897817A - 含吡咯烷酮的洗涤剂组合物 - Google Patents
含吡咯烷酮的洗涤剂组合物 Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 80
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- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 1
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- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
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- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-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
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
- A47L15/00—Washing or rinsing machines for crockery or tableware
- A47L15/42—Details
- A47L15/44—Devices for adding cleaning agents; Devices for dispensing cleaning agents, rinsing aids or deodorants
-
- 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
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
- C11D17/0091—Dishwashing tablets
-
- 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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- 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
-
- 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
- C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
本发明提供了一种含吡咯烷酮的洗涤剂组合物,所述洗涤剂组合物包含疏水性聚合物、磺化聚丙烯酸酯、吡咯烷酮衍生物和阴离子表面活性剂。发现所述组合物可特别用于餐具洗涤应用中,并且表现出在待清洁物品上留斑的倾向减小。
Description
本申请是分案申请,其原申请的申请号为200880106322.7,申请日为2008年9月12日,发明名称为“含吡咯烷酮的洗涤剂组合物”。
技术领域
本发明涉及洗涤剂组合物。
背景技术
家用洗涤剂被广泛用于包括洗衣服务的许多应用并用于硬表面清洁,例如,用于自动餐具洗涤机中。洗涤剂通常可以以包括液体、粉末和固体的许多产品形式得到。
已认识到普通家用洗涤剂通常由数种不同组分构成。一种通常存在于自动餐具洗涤机洗涤剂中的组分是助洗剂(builder)。
可以将助洗剂用作螯合剂以帮助去除/捕获溶液中的金属离子。通过使用助洗剂,减少了自动餐具洗涤机内的金属离子类沉积物(如水垢)的沉积并且增强了清洁过程(某些污渍包含金属离子组分,例如,包含钙/单宁复合物的茶垢)。
事实上,在没有合适的助洗剂时,往往观察到较差的洗涤结果。经较差助洗的餐具洗涤操作的一个高度可见的、不理想的特征是在如玻璃器皿等受清洁物品上出现“留斑”。留斑是在物品上出现小的水垢斑点,据信这是在洗涤操作的清洗循环中出现的。由于大多数餐具器皿通常颜色较浅/透明,因而通常斑点高度可见。然而,除了这一较差的审美效果以外,还有较差的洗涤操作的顾虑。
过去直到近来,一直使用基于磷酸盐的助洗剂。这些助洗剂的优点是廉价、与其它洗涤剂组分(固体和液体洗涤剂配方)和洗涤机相容并且可广泛利用。然而,使用磷酸盐类助洗剂的一个问题是环境污染问题:水道中过量的磷酸盐与如富营养化(eutrification)和过度藻类生长等有害环境影响相关,从而导致如鱼群减少等其它问题。
因此,在某些管辖范围内已经立法禁止使用磷酸盐,而在其它管辖范围内正在立法禁止使用磷酸盐。
WO02/20708已经考虑了减少留斑和使磷酸盐垢的形成最小化,其中提出使用经疏水性修饰的聚羧酸和水溶性聚合物的组合。
然而,仍然需要替代性的助洗剂/螯合剂或性能良好且含有较低水平的磷酸盐或不含磷酸盐的组合物。特别是,在本领域中需要提供具有良好的抵抗在受清洁物品上“留斑”的抗性的洗涤剂组合物。
发明内容
本发明的目的是解决至少一个上文所概述的问题。
因此,根据本发明的第一方面,提供了一种洗涤剂组合物,所述洗涤剂组合物包含:
(a)疏水性聚合物,
(b)磺化聚丙烯酸酯,
(c)吡咯烷酮衍生物,和
(d)阴离子表面活性剂。
所述组合物优选不含磷。
除非另外说明,本文中的所有量是指基于组合物的总重的重量活性浓度(固体含量)。
已发现本发明的组合物表现优异,特别是当用在自动餐具洗涤操作中时。在这些操作中,极为有利的效果是显著减少了餐具洗涤机中受洗涤的物品上留斑的出现以及对于其它污渍的良好表现。对于无磷组合物,这些效果尤为令人惊讶。
基于所述组合物的总重,所述疏水性聚合物优选以0.1重量%~10重量%、更优选以0.5重量%~5重量%的量存在,例如,1重量%~3重量%。
根据本发明可以使用任何合适的疏水性聚合物。
合适的疏水性聚合物包括作为CH2=CR1-CR2R3-O-C4H3R4-SO3X(其中R1、R2、R3、R4独立地为1~6碳烷基或氢,且X是氢或碱金属)与包括经修饰的丙烯酸、富马酸、马来酸、衣康酸、乌头酸、甲基富马酸、柠康酸和亚甲基丙二酸(methylenemalonicacid)或其盐、马来酸酐、丙烯酰胺、烷烯烃(alkylene)、乙烯基甲基醚、苯乙烯及其任何混合物的任何合适的其它单体单元的共聚物的磺化共聚物。可加入磺化聚合物(共聚物)的其它合适的磺化单体是2-丙烯酰氨基-2-甲基-1-丙磺酸、2-甲基丙烯酰氨基-2-甲基-1-丙磺酸、3-甲基丙烯酰氨基-2-羟基丙磺酸、烯丙基磺酸、甲基烯丙基磺酸、2-羟基-3-(2-丙烯氧基)丙磺酸、2-甲基-2-丙烯-1-磺酸、苯乙烯磺酸、乙烯基磺酸、丙烯酸3-磺基丙酯、甲基丙烯酸3-磺基丙酯、磺基甲基丙烯酰胺、磺基甲基甲基丙烯酰胺及其水溶性盐。用于本发明的合适的磺化疏水性聚合物也描述于US5308532和WO2005/090541中。
所述疏水性聚合物优选包含经疏水性修饰的羧酸类聚合物,最优选经疏水性修饰的马来酸类聚合物。所述经疏水性修饰的羧酸类聚合物的数均分子量优选为约8,000~15,000,更优选为约9,000~12,000,例如9,500~11,000。这类聚合物的一个优选实例是可获自Rohm&Haas的基于马来酸的Acusol 460 NDP。
磺化聚丙烯酸酯优选以0.1重量%~10重量%、更优选1重量%~7重量%的量存在,例如,1.5重量%~5重量%。
合适的磺化聚丙烯酸酯的数均分子量为约8,000~15,000,更优选为约10,000~14,000,例如11,000~13,000。这类聚合物的一个优选实例是可获自Rohm&Haas的Acusol588。
例如从WO2006/106332已知聚乙烯吡咯烷酮可用作洗涤剂片剂中的粘合剂。此外,已知N-烷基吡咯烷酮衍生物可用于水性酸性抗菌清洁组合物中(见WO2004/074417)。
所述吡咯烷酮衍生物优选以0.05重量%~10重量%、更优选以0.1重量%~1.5重量%的量存在,例如,0.12重量%~0.5重量%(如0.15重量%~0.4重量%)。
所述吡咯烷酮衍生物优选包含烷基吡咯烷酮化合物,最优选为N-烷基吡咯烷酮化合物。这类化合物的一个尤为优选的实例是N-正辛基-2-吡咯烷酮。
根据本发明已发现,当将吡咯烷酮衍生物与阴离子表面活性剂组合使用时,对于在餐具洗涤机中用所述组合物洗涤的物品上留斑的减少而言,获得了尤其好的结果。于是,所述组合物也包含阴离子表面活性剂。可以将吡咯烷酮衍生物和阴离子表面活性剂作为单独组分添加到所述组合物中或者可以将其作为预先混合的混合物添加。优选的阴离子表面活性剂是硫酸盐表面活性剂、特别是烷基硫酸酯盐,尤其是C8~C16硫酸酯盐且最尤其是C10~C14硫酸酯盐,例如,单十二烷基硫酸酯盐。优选使用这些表面活性剂的钠盐,然而也可以使用任何合适的盐。
这类吡咯烷酮衍生物/阴离子表面活性剂混合物的优选实例是可获自ISP的Easy-Wet(RTM)20,该混合物是15重量%~25重量%的N-正辛基-2-吡咯烷酮和1重量%~2重量%的硫酸单十二烷基酯的钠盐的水性混合物。
阴离子表面活性剂通常以0.005重量%~1.5重量%、更优选为0.01重量%~0.5重量%的量存在,如0.02重量%~0.2重量%。根据本发明,所述组合物优选包含0.005重量%~1.5重量%烷基硫酸酯盐。
所述洗涤剂组合物一般包含助洗剂。通常,助洗剂以0.1重量%~80重量%、更优选25重量%~35重量%的量存在。
助洗剂优选包含非磷类助洗剂。尤其优选的是,所述非磷类助洗剂以1重量%~80重量%、更优选25重量%~35重量%的量存在。
非磷类助洗剂的合适实例为氨基羧酸酯类助洗剂并且包括甲基甘氨酸乙酰乙酸(MGDA)和/或谷氨酸-N,N-乙酰乙酸(GLDA)和/或其盐。
所述洗涤剂组合物可以为粉末、压缩颗粒体、注射成型体或液体/凝胶的形式。所述组合物最优选为液体/凝胶的形式。通常,本发明的液体/凝胶组合物包含30重量%~70重量%、更优选40重量%~65重量%、最优选50重量%~60重量%的量的水。可以将所述洗涤剂组合物包装于如水溶性膜等水溶性材料(例如,聚乙烯醇)中。
所述组合物还可以并入如常用洗涤剂添加剂或填料等辅助材料,例如,一种或多种以下试剂:漂白剂、腐蚀抑制剂、香料、共助洗剂、表面活性剂、粘合剂、染料、酸性修饰剂、分散助剂或酶。
本发明的洗涤剂组合物优选被用作自动洗涤剂组合物/添加剂,且最优选被用作自动餐具洗涤组合物/添加剂。
根据本发明的第二方面,提供了一种包含以下物质的组合物在自动餐具洗涤过程中的应用:
(a)疏水性聚合物,
(b)磺化聚丙烯酸酯,
(c)吡咯烷酮衍生物,和
(d)非离子表面活性剂。
于是,发现本发明的组合物可特别用于餐具洗涤应用中。
具体实施方式
现在将参考实施例进一步描述本发明。处于本发明的范围内的其它实施例对本领域技术人员将是显而易见的。
实施例
实施例1
制备了具有以下组成的制剂。
*1获自德国BASF的脂肪醇烷氧基化非离子表面活性剂。
*2数均分子量约为10,000的经疏水性修饰的马来酸类聚合物,作为Acusol(RTM)460NDP获自Rohm&Haas。
*315重量%~25重量%的N-正辛基-2-吡咯烷酮与1重量%~2重量%的单十二烷基硫酸酯钠的混合物,作为Easy-Wet(RTM)20获自ISP。
*4作为Acusol(RTM)588获自Rohm&Haas,分子量约为12,000。
针对商购含磷组合物,在自动餐具洗涤过程中测试了实施例1。使用含规定量(见表)的液体组合物的水溶性袋对两种组合物进行测试。
对于测试条件而言,使用GE GSD4800J01WW机器并在正常洗涤/加热干燥程序下进行操作。机器中所用水的硬度为160ppm~180ppm且温度为49℃。没有使用清洗辅助剂(rinse aid),并在5次洗涤循环后使用以下标准来评估结果:
成膜:评分1~5(5=严重成膜;1=未成膜)
留斑:评分1~5(5=完全覆盖;1=无斑点)
| 产品 | 商购含磷组合物(24.3g) | 实施例1(21.5g) |
| 留斑 | 3.8 | 3.0 |
| 成膜 | 1.7 | 1.8 |
本发明组合物相比商购含磷组合物显示出更好的留斑表现和相当的成膜表现。
实施例2
针对商购含磷组合物,在自动餐具洗涤过程中对根据本发明的制剂(实施例1)进行了测试。使用含一定量(见表)的液体组合物的水溶性袋对两种组合物进行测试。
对于测试条件而言,使用GE GSD4800J01WW机器并在正常洗涤/加热干燥程序下进行操作。机器中所用水的硬度为9°dH且温度为49℃。没有使用清洗辅助剂,并在4次洗涤循环后使用数字标准来评估结果。
当与商购含磷组合物相比时,本发明的组合物对于大范围的污渍显示出相当的性能。
Claims (20)
1.一种洗涤剂组合物,所述洗涤剂组合物包含:
(a)疏水性聚合物,
(b)磺化聚丙烯酸酯,
(c)吡咯烷酮衍生物,和
(d)阴离子表面活性剂。
2.如权利要求1所述的组合物,其中,所述组合物不含磷。
3.如权利要求1或2中任一项所述的组合物,其中,所述疏水性聚合物以0.1重量%~10重量%的量存在。
4.如权利要求1~3中任一项所述的组合物,其中,所述疏水性聚合物包含经疏水性修饰的羧酸类聚合物。
5.如权利要求4所述的组合物,其中,所述疏水性聚合物是经疏水性修饰的马来酸类聚合物。
6.如前述权利要求中任一项所述的组合物,其中,所述疏水性聚合物的数均分子量为8,000~15,000。
7.如前述权利要求中任一项所述的组合物,其中,所述磺化聚丙烯酸酯以0.1重量%~10重量%的量存在。
8.如前述权利要求中任一项所述的组合物,其中,所述磺化聚丙烯酸酯的数均分子量为约8,000~约15,000。
9.如前述权利要求中任一项所述的组合物,其中,所述吡咯烷酮衍生物以0.05重量%~10重量%的量存在。
10.如前述权利要求中任一项所述的组合物,其中,所述吡咯烷酮衍生物包含烷基吡咯烷酮化合物。
11.如权利要求10所述的组合物,其中,所述吡咯烷酮衍生物包含N-烷基吡咯烷酮化合物。
12.如权利要求11所述的组合物,其中,所述N-烷基吡咯烷酮化合物包含N-正辛基-2-吡咯烷酮。
13.如前述权利要求中任一项所述的组合物,其中,所述阴离子表面活性剂包含烷基硫酸酯盐。
14.如前述权利要求中任一项所述的组合物,其中,所述组合物包含0.005重量%~1.5重量%的阴离子表面活性剂。
15.如前述权利要求中任一项所述的组合物,其中,所述组合物包含N-烷基吡咯烷酮化合物和0.005重量%~1.5重量%的烷基硫酸酯盐。
16.如前述权利要求中任一项所述的组合物,其中,所述洗涤剂组合物包含非磷类助洗剂。
17.如权利要求16所述的组合物,其中,所述非磷类助洗剂以0.1重量%~80重量%的量存在。
18.如权利要求16或17中任一项所述的组合物,其中,所述助洗剂包含甲基甘氨酸乙酰乙酸和/或谷氨酸-N,N-乙酰乙酸和/或其盐。
19.如权利要求1~18中任一项所述的组合物,其中,所述组合物是餐具洗涤组合物。
20.如前述权利要求中任一项所述的组合物在自动餐具洗涤过程中的应用。
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| EP3050947A1 (en) * | 2015-02-02 | 2016-08-03 | The Procter and Gamble Company | Detergent pack |
| ES2714130T3 (es) | 2015-02-02 | 2019-05-27 | Procter & Gamble | Composición detergente |
| EP3561031B1 (en) | 2018-04-27 | 2025-06-04 | The Procter & Gamble Company | Alkaline hard surface cleaners comprising alkylpyrrolidones |
| EP3561033B1 (en) | 2018-04-27 | 2025-03-26 | The Procter & Gamble Company | Acidic hard surface cleaners comprising alkylpyrrolidones |
| EP3569683B1 (en) | 2018-05-15 | 2020-10-14 | The Procter & Gamble Company | Liquid acidic hard surface cleaning compositions providing improved maintenance of surface shine, and prevention of water marks and splash marks |
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| WO2002020708A1 (en) * | 2000-09-08 | 2002-03-14 | Unilever Plc | Polycarboxylic acid containing three-in-one dishwashing composition |
| WO2007052004A1 (en) * | 2005-11-07 | 2007-05-10 | Reckitt Benckiser N.V. | Delivery cartridge |
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| US5399284A (en) * | 1991-04-03 | 1995-03-21 | Chemische Fabrik Dr. Weigert (Gmbh & Co.) | Process for removing starch-containing contamination from dishes and surfactant concentrates suitable for this process |
| US5308532A (en) * | 1992-03-10 | 1994-05-03 | Rohm And Haas Company | Aminoacryloyl-containing terpolymers |
| DE19618725A1 (de) * | 1996-05-09 | 1997-11-13 | Weigert Chem Fab | Verfahren und Kit zum Reinigen von Geschirr |
| US6210600B1 (en) * | 1996-12-23 | 2001-04-03 | Lever Brothers Company, Division Of Conopco, Inc. | Rinse aid compositions containing scale inhibiting polymers |
| DE10050622A1 (de) | 2000-07-07 | 2002-05-02 | Henkel Kgaa | Klarspülmittel II a |
| ATE435272T1 (de) | 2001-11-14 | 2009-07-15 | Procter & Gamble | Maschinelle geschirrspülmittel in form einer einmaldosis enthaltend ein verkrustung inhibierendes polymer |
| WO2004074417A1 (en) | 2003-02-24 | 2004-09-02 | Unilever Plc | Antimicrobial cleaning compositions |
| GB0507069D0 (en) | 2005-04-07 | 2005-05-11 | Reckitt Benckiser Nv | Detergent body |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2259096A (en) * | 1991-08-28 | 1993-03-03 | Unilever Plc | Liquid cleaning products |
| WO2002020708A1 (en) * | 2000-09-08 | 2002-03-14 | Unilever Plc | Polycarboxylic acid containing three-in-one dishwashing composition |
| WO2007052004A1 (en) * | 2005-11-07 | 2007-05-10 | Reckitt Benckiser N.V. | Delivery cartridge |
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| EP2190963B1 (en) | 2013-11-20 |
| US8598104B2 (en) | 2013-12-03 |
| CN101802160A (zh) | 2010-08-11 |
| PL2190963T3 (pl) | 2014-04-30 |
| US20140048105A1 (en) | 2014-02-20 |
| EP2190963A1 (en) | 2010-06-02 |
| BRPI0816716A2 (pt) | 2015-02-24 |
| AU2008299653A1 (en) | 2009-03-19 |
| CA2710414A1 (en) | 2009-03-19 |
| CN101802160B (zh) | 2014-06-18 |
| WO2009034355A1 (en) | 2009-03-19 |
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| AU2008299653B2 (en) | 2013-07-25 |
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Application publication date: 20140702 |