CN103517976A - 改进的组合物 - Google Patents

改进的组合物 Download PDF

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CN103517976A
CN103517976A CN201280022668.5A CN201280022668A CN103517976A CN 103517976 A CN103517976 A CN 103517976A CN 201280022668 A CN201280022668 A CN 201280022668A CN 103517976 A CN103517976 A CN 103517976A
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polyalkyleneimine
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N·格拉夫
卡尔海因茨·乌尔里希·格哈德·哈恩
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Abstract

本发明提供包含聚亚烷基亚胺和/或其盐或衍生物以及两性聚合物的组合物在防止洗涤或漂洗过程中、特别是自动洗碗过程中的非金属无机制品的腐蚀中的用途。

Description

改进的组合物
技术领域
本发明涉及一种改进的组合物，所述组合物用于保护自动器皿洗涤机中(优选在洗碗过程中)的玻璃器皿等非金属无机材料。
背景技术
非金属无机制品(例如玻璃器皿、陶瓷和搪瓷材料)在自动洗碗过程中遇到的腐蚀问题在本领域中是公认的。例如，已经提出，两个独立的现象导致了玻璃器皿的腐蚀问题。首先，已提出腐蚀是因为矿物质从玻璃网络结构中泄露，且伴随着硅酸盐网络结构的水解。其次，提出了硅酸盐材料随后从玻璃中释放。
在多次单独的洗涤循环后，这些现象可能会使玻璃器皿受到损害。损害可以包括混浊、划痕、条纹和其他的变色/有害的影响。
已经提出，硅酸盐材料是防止材料从玻璃组合物中释放出的有效试剂。然而，使用硅酸盐化合物可能具有有害的副作用，例如，增大硅酸盐材料在表面分离的倾向。
另一方案是使用锌等金属，其使用形式或者为其金属形式(如美国专利3,677,820中所述)，或者为化合物形式。例如，在美国专利3,255,117中描述了使用可溶性锌化合物来防止洗碗机中玻璃器皿的腐蚀。
欧洲专利EP-A-0383480、EP-A-0383482和EP-A-0387997描述了为该目而使用水不溶性化合物，包括硅酸锌、碳酸锌、碱性碳酸锌(Zn2(OH)2CO3)、氢氧化锌、草酸锌、一磷酸锌(Zn3(PO4)2)和焦磷酸锌(Zn2P2O7)。
铋已经用作帮助防止上釉的玻璃器皿腐蚀的添加剂。例如，BE860180描述了使用铋来避免带饰纹的上釉物品的损坏。
因为使用铋化合物对洗涤过程或洗涤剂组合物中的其他成分具有有害效果，因此铋在该用途中的价值在减小。不溶性铋化合物可以在与这些化合物接触的厨房用具(例如玻璃器皿和刀叉餐具)上形成污渍。鉴于此，已不再单独使用铋作为釉层保护剂，但是已经发现组合使用锌和铋能够解决该问题(参见WO-A-04/106476)。
不过，已经发现，在某些环境下使用重金属化合物会降低洗碗用组合物对可漂白污渍(例如茶渍)的漂白性能。此外，出于环境原因，越来越需要限制(尤其是避免)在洗涤剂制剂中使用重金属。
WO2010/020765提出了不需要使用重金属来解决玻璃和餐具腐蚀问题的方案。该文献(以引用的方式并入本文中)中披露：聚亚烷基亚胺对于防止自动洗涤机中的非金属无机制品的腐蚀而言是高度有效的添加剂。
然而，除此之外还发现，尽管聚亚烷基亚胺确实改进了腐蚀保护，但却意外地发现使用该物质会造成漂洗性能不良。这导致在玻璃器皿上留下了不美观的垢点(spotting)。
本发明的目的是克服在使用聚亚烷基亚胺制剂时带来的漂洗性能不良问题。
发明内容
在本发明的第一方面中，提供一种组合物，所述组合物包含聚亚烷基亚胺和至少一种两性(amphoteric)聚合物。
根据一个实施方式，所述聚亚烷基亚胺优选包括聚乙烯亚胺，最优选是聚乙烯亚胺。
根据一个实施方式，所述聚亚烷基亚胺和/或其盐或衍生物的数量平均分子量为100～5,000,000。
根据一个实施方式，所述至少一种两性聚合物是亲水性聚合物。
根据另一个实施方式，至少一种两性聚合物是水性丙烯酸胺官能性聚合物。
根据另一个实施方式，至少一种两性聚合物是季铵化铵丙烯酰胺-丙烯酸共聚物。
根据另一个实施方式，至少一种两性聚合物由Rhodia制造，并以商品名MirapolSurf S无磷粉末销售。
根据本发明的一个实施方式，使用的组合物是自动洗碗用组合物，其包含占所述组合物的0.0001重量%～50重量%的量的聚亚烷基亚胺和/或其盐或衍生物。
根据本发明的另一个实施方式，使用的组合物是自动洗碗用漂洗助剂，其包含占所述组合物的0.0005重量%～70重量%的量的聚亚烷基亚胺和/或其盐或衍生物.
根据本发明的又一个实施方式，使用的组合物是水软化盐组合物，其包含占所述组合物的0.0001重量%～90重量%的量的聚亚烷基亚胺和/或其盐或衍生物。
具体实施方式
已经发现，添加两性聚合物可以改善由于存在聚亚烷基亚胺而导致的组合物的漂洗问题。
任何两性聚合物都可用于获得该效果。优选的是，所述两性聚合物是亲水性聚合物。
WO2010/020765表明，将两性聚合物添加到含有聚亚烷基亚胺的洗涤剂制剂中未影响对玻璃器皿、陶瓷和搪瓷等非金属无机制品的保护。
优选的是，适合与聚亚烷基亚胺组合使用的两性聚合物优选至少包含(1)具有阴离子电荷或能够形成阴离子电荷的酸性单体和(2)具有持久的阳离子电荷或者能够在质子化时形成阳离子电荷的单体。
另外，所述聚合物优选是水性丙烯酸胺官能性聚合物。该聚合物的实例是季铵化铵丙烯酰胺-丙烯酸共聚物。适于包含在本发明的组合物中的亲水性聚合物在美国专利6,569,261、6,593,288、6,703,358和6,767,410中有所描述，其公开的内容以引用的方式并入本文中。
这些专利文献描述了水溶性或水分散性共聚物，其包含呈聚合的单元形式的(1)至少一种胺官能性单体、(2)至少一种具有酸性性质的亲水性单体和(3)可选的至少一种具有烯不饱和性和中性电荷的亲水性单体。所述共聚物包括季铵化铵丙烯酰胺-丙烯酸共聚物。应当理解，根据聚合物选择适宜的相关材料和结构时应当能够凭借这些专利文献中的教导而获得更详细地指导。以上类型的优选共聚物是Rhodia制造的以商品名Mirapol Surf S销售的共聚物，尤其是以商品名Mirapol Surf S无磷粉末销售的共聚物。
在自动洗碗机的洗涤或漂洗循环中，所述两性聚合物在每次洗涤或漂洗循环中的用量优选为0.01mg～10g，更优选为0.05mg～5g，更优选为0.1mg～1g，最优选0.5mg～100mg。
还可以在自动洗碗机的洗涤和漂洗循环中都使用两性聚合物。
本发明的组合物可包含0.001重量%～90重量%、优选0.005重量%～50重量%、更优选0.01重量%～10重量%的两性聚合物。
此处使用的术语聚亚烷基亚胺包括任何含有2个以上亚烷基亚胺重复单元的亚烷基亚胺，因此该术语也包括亚烷基亚胺低聚物，例如乙烯亚胺低聚物。通常，聚亚烷基亚胺将包括2～50,000个亚烷基亚胺重复单元，优选10～25,000个，例如50～10,0000个。
除非另作说明或者是上下文另有需要，否则本文中的所有百分比均是基于所述组合物总重量的重量百分比。本文中提到“聚亚烷基亚胺”时包括其盐和/或衍生物。提到“两性聚合物”时包括其盐和/或衍生物。
聚亚烷基亚胺和/或其盐或衍生物以能够在洗涤或漂洗循环中有效地提供前述腐蚀保护效果的量使用。在自动洗碗机的洗涤或漂洗循环中，聚亚烷基亚胺在每次洗涤或漂洗循环中的用量优选为0.01mg～10g以上、优选为0.05mg～5g、更优选为0.1mg～1g、最优选为0.5mg～100mg。
更优选的是，所述聚亚烷基亚胺和两性聚合物是洗涤剂制剂或漂洗制剂的一部分。所述洗涤剂制剂可以是自动洗碗机所通常采用的任何常用类型的洗涤剂制剂。所述制剂可以包括能够至少部分地包裹或填充在水溶性小袋内的液体制剂、凝胶制剂、粉末制剂或片剂制剂。类似地，可以使用包衣来包覆至少一部分所述制剂。单剂量的洗涤剂制剂可以进行再分，使得不同的部分彼此分隔开。
当所述制剂是液体/凝胶时，聚亚烷基亚胺和两性聚合物通常以溶液形式存在于该液体/凝胶中。不过，也可以使聚亚烷基亚胺和/或两性聚合物以不溶性固体盐/化合物的形式存在于该液体/凝胶中，以使聚亚烷基亚胺和/或两性聚合物可以包含悬浮颗粒(例如，常见于这些制剂中的“散斑”)。对于具有水溶性包衣或小袋的组合物，可以使聚亚烷基亚胺和/或两性聚合物作为包衣/小袋组合物的一部分。
洗涤剂制剂通常包含常见于洗碗机用洗涤剂制剂中的其他成分。关于该点，所述洗涤剂制剂通常包含一种或多种选自包括表面活性剂(非离子型、阴离子型、阳离子型和两性离子型)、增洁剂、酶、泡沫抑制剂、漂白剂、漂白活化剂、增稠剂、香料、染料、腐蚀抑制剂的组的成分。
所述聚亚烷基亚胺和两性聚合物可以存在于自动洗碗机(ADW)用洗涤剂组合物中。在该情况中，聚亚烷基亚胺优选占所述洗涤剂组合物的0.0001重量%～50重量%，更优选为所述洗碗机用洗涤剂组合物的0.0005重量%～5重量%、最优选0.001重量%～1重量%(例如，对于20g的片剂为10mg)。
ADW洗涤剂组合物的pH可以是6～12。洗涤剂组合物可以为中性，pH为6～8，或者为碱性制剂，pH为8～12，优选为9～11。
ADW洗涤剂组合物可以是不含磷酸盐的组合物。
聚亚烷基亚胺和两性聚合物也可以包含在漂洗助剂组合物中。在该情况中，所述漂洗助剂组合物优选包含0.0005重量%～70重量%、更优选0.001重量%～50重量%、最优选0.005重量%～25重量%的聚亚烷基亚胺，例如，占漂洗助剂组合物的0.01重量%～5重量%的聚亚烷基亚胺。所述漂洗助剂组合物优选包含0.0005重量%～70重量%、更优选0.001重量%～50重量%、最优选0.005重量%～25重量%的两性聚合物，例如，占漂洗助剂组合物的0.01重量%～5重量%的两性聚合物。
所述漂洗助剂组合物可以为酸性的，并且可包含柠檬酸。
聚亚烷基亚胺和两性聚合物还可以包含在水软化盐组合物中。这些组合物通常用于使存在于自动洗碗机中的离子交换剂再生。在该情况中，所述水软化盐组合物所含的活性物优选为所述水软化盐组合物的0.0001重量%～90重量%、更优选0.001重量%～50重量%、最优选0.005重量%～25重量%，例如，0.01重量%～10重量%。
聚亚烷基亚胺和两性聚合物可以包含在机器清洁剂/机器添加剂组合物中。在任一种情况中，所述组合物包含0.0001重量%～90重量%的两性聚合物，更优选0.0005重量%～50重量%的两性聚合物，最优选0.001重量%～10重量%的两性聚合物。所述组合物还包含0.0001重量%～90重量%的聚亚烷基亚胺，更优选0.0005重量%～50重量%的聚亚烷基亚胺，最优选0.001重量%～10重量%的聚亚烷基亚胺。
聚亚烷基亚胺以例如LugalvanTM P(ex BASF)和LupasolTMBASF等各种商品名由不同的供应商在市面上销售。聚亚烷基亚胺已知具有极宽范围的平均分子量，约100至几百万，优选为约100～约5,000,000，最优选为约250～1,000,000，例如，约400～约100,000。其中亚烷基优选为直链或带支链的，也可以是例如环状的。所述亚烷基优选具有1～50个C原子，更优选为2～20个，例如2～5个，例如为亚乙基。这些聚合物可以是直链的、带支链的或封端的。合适的封端包括亚烷基二胺，如C2-C5亚烷基二胺，例如乙二胺。所述聚合物可以是通过例如质子化的烷氧基化、乙氧基化、丙氧基化而得到的衍生物，并且可具有或不具有反荷离子。
如果存在反荷离子，可以使用任何适宜的反荷离子。
如果使用已知在洗碗过程中具有负效应的反荷离子，例如氯阴离子，则氯阴离子反荷离子在洗碗过程中的存在浓度优选小于200mg/L洗碗液，更优选小于100mg/L洗碗液，最优选小于50mg/L洗碗液，这是为了避免在不锈钢(例如刀叉餐具)上出现生锈、点蚀或其他类型的腐蚀。
一般市售的聚亚烷基亚胺通常作为一种或多种以上物质的共混混合物存在。可以存在例如水等溶剂。这些物质中的任一种均适用于本发明。
本发明由以下非限制性实施例说明。
试验结果
在漂洗测试中使用以下基本组合物A来确定垢点水平。
组合物A的成分 重量%
三聚磷酸钠 45.0
碳酸钠 24.0
碳酸氢钠 3.0
柠檬酸 1.0
纤维素 1.0
乳糖 1.0
二硅酸钠 3.0
聚乙二醇(PEG) 7.0
过碳酸钠 10.0
TAED 2.0
蛋白酶 0.9
淀粉酶 0.4
非离子表面活性剂 1.0
苯并三唑 0.2
香料+染料 0.5
漂洗测试评估数据
Figure BDA0000411630370000061
测试针对以下物质进行：基本组合物A自身，其与聚亚烷基亚胺(LupasolTM)的组合，其同时与聚亚烷基亚胺(LupasolTM)和两性聚合物(Mirapol Surf S(无磷粉末)TM)的组合。
结果显示，添加两性聚合物改进了与聚亚烷基亚胺组合的洗涤剂组合物的垢点形成性能。
通过添加两性聚合物以维持对玻璃器皿的保护。
漂洗测试法的细节
测试方法：R206V1
机器：Bosch SGS058M02EU/36
程序：Eco50℃+各种速度(No3in1function)
水的硬度：21°GH
评估者：1位受过训练的人员
垢点评分
评分 结果
10 无条纹和垢点
9 很少的轻微的条纹和/或少许小垢点
8 一些轻微的条纹和/或一些小垢点
7 数个轻微的条纹和/或少许中等大小的垢点
6 一些中等的条纹和/或中等大小的垢点
5 中等的条纹和/或少许大垢点
4 一些很强的条纹和/或许多大垢点
3 很强的条纹和/或许多大垢点
2 极强的条纹和/或极多大垢点
1 整个表面均覆盖了极强的条纹和/或垢点

Claims (10)

1.一种组合物，所述组合物包含：聚亚烷基亚胺和/或其盐或衍生物；和至少一种两性聚合物。
2.如权利要求1所述的组合物，其中，所述聚亚烷基亚胺的数量平均分子量为100～5,000,000。
3.如权利要求1或2所述的组合物，其中，所述聚亚烷基亚胺包括聚乙烯亚胺。
4.如前述权利要求中任一项所述的组合物，其中，所述至少一种两性聚合物是亲水性聚合物。
5.如权利要求4所述的组合物，其中，所述亲水性聚合物是水性丙烯酸胺官能性聚合物。
6.如权利要求4或5所述的组合物，其中，所述亲水性聚合物是季铵化铵丙烯酰胺-丙烯酸共聚物。
7.如权利要求4～6中任一项所述的组合物，所述亲水性聚合物是Rhodia制造的Mirapol Surf STM。
8.如前述权利要求中任一项所述的组合物，其中，所述组合物是自动洗碗用洗涤剂，其包含占所述组合物的0.0001重量%～50重量%的量的所述聚亚烷基亚胺和占所述组合物的0.0001重量%～50重量%的量的所述两性聚合物。
9.如权利要求1～7中任一项所述的组合物，其中，所述组合物是自动洗碗用漂洗助剂，其包含占所述组合物的0.0005重量%～70重量%的量的所述聚亚烷基亚胺和占所述组合物的0.0005重量%～70重量%的量的所述两性聚合物。
10.如权利要求1～7中任一项所述的组合物，其中，所述组合物是水软化盐组合物，其包含占所述组合物的0.0001重量%～90重量%的量的所述聚亚烷基亚胺和占所述组合物的0.0001重量%～90重量%的量的所述两性聚合物。
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Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201107885D0 (en) 2011-05-12 2011-06-22 Reckitt Benckiser Nv Improved composition
EP2961822B1 (de) 2013-02-28 2017-04-12 Basf Se Formulierungen, ihre verwendung als oder zur herstellung von geschirrspülmitteln und ihre herstellung
GB201409631D0 (en) * 2014-05-30 2014-07-16 Reckitt Benckiser Brands Ltd Improved PEI composition
GB201409632D0 (en) * 2014-05-30 2014-07-16 Reckitt Benckiser Brands Ltd Improved detergent composition
DE102014212728A1 (de) * 2014-07-01 2016-01-07 Henkel Ag & Co. Kgaa Geschirrspülmittel
EP3181670B1 (en) * 2015-12-17 2019-01-30 The Procter and Gamble Company Automatic dishwashing detergent composition
EP3181675B2 (en) * 2015-12-17 2022-12-07 The Procter & Gamble Company Automatic dishwashing detergent composition
EP3181671A1 (en) 2015-12-17 2017-06-21 The Procter and Gamble Company Automatic dishwashing detergent composition
EP3181676B1 (en) 2015-12-17 2019-03-13 The Procter and Gamble Company Automatic dishwashing detergent composition
EP3710569A1 (en) 2017-11-14 2020-09-23 Ecolab USA Inc. Solid controlled release caustic detergent compositions
CN114222808A (zh) 2019-09-27 2022-03-22 埃科莱布美国股份有限公司 浓缩二合一洗碗机洗涤剂和漂洗助剂
PL3835399T3 (pl) * 2019-12-12 2023-07-24 Henkel Ag & Co. Kgaa Środek czyszczący do twardych powierzchni
EP4001388A1 (en) * 2020-11-17 2022-05-25 The Procter & Gamble Company Automatic dishwashing method with amphiphilic graft polymer in the rinse
USD1008559S1 (en) 2023-08-14 2023-12-19 E. Mishan & Sons, Inc. Pedicure device

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999005248A1 (en) * 1997-07-23 1999-02-04 Unilever Plc Automatic dishwashing compositions containing water soluble cationic or amphoteric polymers
TW200810923A (en) * 2006-07-12 2008-03-01 Jsr Corp Optical film, and use and production method thereof
WO2010020765A1 (en) * 2008-08-16 2010-02-25 Reckitt Benckiser N.V. Composition
CN101821371A (zh) * 2007-08-14 2010-09-01 S.C.约翰逊父子公司 具有长期残留清洁益处的硬表面清洁剂

Family Cites Families (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2182306A (en) * 1935-05-10 1939-12-05 Ig Farbenindustrie Ag Polymerization of ethylene imines
BE615597A (zh) * 1958-06-19
US3255117A (en) 1963-10-08 1966-06-07 Fmc Corp Low-foaming dishwashing composition
US3677820A (en) 1970-05-28 1972-07-18 Whirlpool Co Method to prevent glassware etching in a dishwasher
GB1586067A (en) 1976-10-28 1981-03-18 Procter & Gamble Detergent composition
US4933101A (en) 1989-02-13 1990-06-12 The Procter & Gamble Company Liquid automatic dishwashing compositions compounds providing glassware protection
US4917812A (en) 1989-02-13 1990-04-17 The Procter & Gamble Company Granular automatic dishwasher detergent composition providing glassware protection containing insoluble zinc compound
US4908148A (en) 1989-02-13 1990-03-13 The Procter & Gamble Company Rinse additive compositions providing glassware protection comprising insoluble zinc compounds
US5981456A (en) * 1997-07-23 1999-11-09 Lever Brothers Company Automatic dishwashing compositions containing water soluble cationic or amphoteric polymers
US5904735A (en) * 1997-08-04 1999-05-18 Lever Brothers Company Detergent compositions containing polyethyleneimines for enhanced stain removal
FR2796392B1 (fr) 1999-07-15 2003-09-19 Rhodia Chimie Sa Composition nettoyante comprenant un polymere hydrosoluble ou hydrodispersable
FR2796391B1 (fr) 1999-07-15 2003-09-19 Rhodia Chimie Sa Composition nettoyante pour surfaces dures
FR2796390B1 (fr) 1999-07-15 2001-10-26 Rhodia Chimie Sa Utilisation d'un polymere amphotere pour traiter une surface dure
DE10027634A1 (de) * 2000-06-06 2001-12-13 Basf Ag Verwendung von kationisch modifizierten, teilchenförmigen, hydrophoben Polymeren als Zusatz zu Spül- oder Pflegemitteln für Textilien und als Zusatz zu Waschmitteln
EP1290126B1 (en) * 2000-06-14 2007-08-08 The Procter & Gamble Company Process for cleaning a surface
US6703358B1 (en) 2000-07-13 2004-03-09 Rhodia Chimie Cleaning composition for hard surfaces
DE10141006A1 (de) 2001-08-21 2003-03-06 Basf Ag Verwendung von amphoteren Polymeren als schmutzablösungsfördernder Zusatz von Mitteln für die Behandlung von Oberflächen
FR2829383B1 (fr) 2001-09-11 2005-09-23 Oreal Compositions cosmetiques contenant un copolymere d'acide methacrylique, une silicone et un polymere cationique et leurs utilisations
US6750186B2 (en) * 2002-02-04 2004-06-15 Robert Black Composition and method for cleaning dishwashers
JP3963364B2 (ja) 2002-09-12 2007-08-22 ハイモ株式会社 紙力増強剤及び紙力増強方法
GB2402132B (en) 2003-05-28 2005-10-19 Reckitt Benckiser Nv Dishwasher anti-corrosion composition
RU2403898C2 (ru) * 2004-06-21 2010-11-20 Басф Акциенгезельшафт Водные композиции, содержащие, по меньшей мере, один растворимый или диспергируемый в воде сополимер с катионогенными группами
DE102004044605A1 (de) * 2004-09-13 2006-03-30 Basf Ag Verwendung von Polymeren zur Modifizierung von Oberflächen in Reinigeranwendungen
EP1856183B1 (en) * 2005-02-08 2014-06-25 Basf Se Method of making an alkoxylated polyethylenimine product
US8669221B2 (en) * 2005-04-15 2014-03-11 The Procter & Gamble Company Cleaning compositions with alkoxylated polyalkylenimines
GT200600375A (es) 2005-08-17 2007-03-14 Composición limpiadora ácida que contiene un polímero de hidrofilización
US8093195B2 (en) 2005-11-09 2012-01-10 Ecolab Usa Inc. Composition with surface modifying properties
ES2376125T3 (es) * 2006-03-22 2012-03-09 The Procter & Gamble Company Composición de tratamiento l�?quida.
WO2008007590A1 (fr) * 2006-07-12 2008-01-17 Jsr Corporation Pellicule optique, et son procédé de production et d'utilisation
BRPI0913980A2 (pt) * 2008-06-30 2015-10-27 Basf Se composição de limpeza de superfície dura, filme preventivo de turvação, e, método para limpar uma superfície dura
US8542650B2 (en) * 2008-07-28 2013-09-24 Qualcomm Incorporated Methods and systems for concurrent data and signaling methodology for WiMAX handover
US8852353B2 (en) * 2008-12-10 2014-10-07 Michael Oberlander Solid dishmachine detergent not requiring a separate rinse additive
ES2663702T5 (es) 2009-06-16 2021-12-16 Basf Se Procedimiento para el aumento de la resistencia en seco de papel, cartulina y cartón
CA2764102A1 (en) * 2009-06-30 2011-01-06 The Procter & Gamble Company Fabric care compositions comprising cationic polymers and amphoteric
GB201107885D0 (en) 2011-05-12 2011-06-22 Reckitt Benckiser Nv Improved composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999005248A1 (en) * 1997-07-23 1999-02-04 Unilever Plc Automatic dishwashing compositions containing water soluble cationic or amphoteric polymers
TW200810923A (en) * 2006-07-12 2008-03-01 Jsr Corp Optical film, and use and production method thereof
CN101821371A (zh) * 2007-08-14 2010-09-01 S.C.约翰逊父子公司 具有长期残留清洁益处的硬表面清洁剂
WO2010020765A1 (en) * 2008-08-16 2010-02-25 Reckitt Benckiser N.V. Composition
EP2733195A1 (en) * 2008-08-16 2014-05-21 Reckitt Benckiser N.V. Polyalkyleneimine as corrosion inhibitor in dishwashing or rinsing processes

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