CN108138091A - 用于减少自动洗碗系统中的污渍的添加剂 - Google Patents
用于减少自动洗碗系统中的污渍的添加剂 Download PDFInfo
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- CN108138091A CN108138091A CN201680057910.0A CN201680057910A CN108138091A CN 108138091 A CN108138091 A CN 108138091A CN 201680057910 A CN201680057910 A CN 201680057910A CN 108138091 A CN108138091 A CN 108138091A
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- monoethylenically unsaturated
- carboxylic acid
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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
- 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
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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Abstract
一种包含2.5到8重量％的第一聚合物的无磷自动洗碗机洗涤剂组合物，所述第一聚合物包含以下的聚合单元：(i)55到85重量％的C3‑C6单烯属不饱和羧酸、(ii)2到30重量％的C3‑C6单烯属不饱和二羧酸和(iii)2到15重量％的C5‑C12单烯属不饱和叔胺；并且其Mw为2,000到100,000。
Description
背景技术
本发明大体上涉及适用于无磷(non-phosphate)自动洗碗系统的洗涤剂组合物。
自动洗碗机洗涤剂公认为与用于织品洗涤或水处理的那些不同的一类洗涤剂组合物。需要自动洗碗机洗涤剂以在彻底的清洁循环之后在洗涤过的物品上产生无斑的和无薄膜外观。无磷组合物依赖于无磷助洗剂，如柠檬酸盐、碳酸盐、硅酸盐、二硅酸盐、碳酸氢盐、氨基羧酸盐等以螯合来自硬水的钙和镁，并且在干燥之后留下不可溶的可见沉积物。由丙烯酸和2-(二甲基氨基)甲基丙烯酸乙酯(DMAEMA)制成的聚合物已知用于洗涤剂配制物以增加泡沫体积，参见例如，US6207631。然而，这个参考文献未公开本发明的组合物，本发明的组合物提供了改进的清洁性能。
发明内容
本发明是针对无磷自动洗碗机洗涤剂组合物，其包含2.5到8重量％的第一聚合物，所述第一聚合物包含以下的聚合单元：(i)55到85重量％的C3-C6单烯属不饱和羧酸，(ii)2到30重量％的C3-C6单烯属不饱和二羧酸和(iii)2到15重量％的C5-C12单烯属不饱和叔胺；并且其Mw为2,000到100,000。
具体实施方式
除非另外指明，否则所有百分比均是重量百分比(重量％)，并且所有温度均以℃为单位。通过凝胶渗透色谱法(gel permeation chromatography，GPC)使用聚丙烯酸标准物测量重均分子量Mw，如所属领域中已知。GPC的技术在《现代尺寸排阻色谱(Modern SizeExclusion Chromatography)》,W.W.Yau,J.J.Kirkland,D.D.Bly；威利跨学科出版社(Wiley-Interscience),1979和《材料特征和化学分析指南(A Guide to MaterialsCharacterization and Chemical Analysis)》,J.P.Sibilia；VCH,1988,第81到84页中详细论述。本文中所报告的分子量是以道尔顿(dalton)为单位。如羧酸或磺酸的所列出的单体单元可取决于环境的pH呈酸和/或盐形式。如本文所使用，术语“(甲基)丙烯酸”是指丙烯酸或甲基丙烯酸；术语“碳酸盐”是指碱金属或铵的碳酸盐、碳酸氢盐、过碳酸盐、倍半碳酸盐；术语“硅酸盐”是指碱金属或铵的硅酸盐、二硅酸盐、偏硅酸盐；并且术语“柠檬酸盐”是指碱金属柠檬酸盐。优选地，碳酸盐、硅酸盐或柠檬酸盐为钠盐、钾盐或锂盐；优选为钠盐或钾盐；优选为钠盐。碳酸盐或柠檬酸盐的重量百分比是按盐的实际重量计，包括金属离子。术语“无磷”是指含有小于0.5重量％磷(为元素磷)、优选小于0.2重量％、优选小于0.1重量％、优选为不可检测磷的组合物。在洗涤剂组合物中的重量百分比为干重的百分比，即，排除可存在于洗涤剂组合物中的任何水。在聚合物中单体单元的百分比为固体重量的百分比，即，排除存在于聚合物乳液中的任何水。
优选地，第一聚合物包含至少65重量％、优选是至少68重量％、优选是至少70重量％、优选是至少72重量％、优选是至少74重量％、优选是至少76重量％；优选不超过83重量％、优选不超过81重量％的C3-C6单烯属不饱和羧酸的聚合单元。优选地，C3-C6单烯属不饱和羧酸选自由以下组成的群组：(甲基)丙烯酸和丁烯酸；优选为(甲基)丙烯酸。优选地，C3-C6单烯属不饱和二羧酸单元是至少3重量％、优选是至少4重量％、优选是至少5重量％；优选不超过27重量％、优选不超过25重量％、优选不超过23重量％的第一聚合物。优选地，C3-C6单烯属不饱和二羧酸选自由以下组成的群组：马来酸(maleic acid)、富马酸(fumaricacid)、衣康酸(itaconic acid)、甲基反丁烯二酸和甲基顺丁烯二酸；优选为马来酸或衣康酸。
优选地，第一聚合物包含至少4重量％、优选至少8重量％、优选至少10重量％；优选不超过14重量％、优选不超过13重量％、优选不超过12重量％的C5-C12单烯属不饱和叔胺。优选地，C5-C12单烯属不饱和叔胺为(甲基)丙烯酸酯或(甲基)丙烯酰胺，其优选含有二烷基氨基，其中两种烷基碳数目的总和小于7，优选小于5。优选地，单烯属不饱和叔胺具有七到十二个、优选七到十个碳原子。优选地，单烯属不饱和叔胺仅含有碳、氢、氧和氮原子；优选地，其不具有羟基或羧基取代基。优选地，单烯属不饱和叔胺含有与乙基或丙基键合的二甲基氨基。尤其优选的单烯属不饱和三级胺包括2-(二甲基氨基)(甲基)丙烯酸乙酯、N-(3-二甲基氨基丙基)(甲基)丙烯酰胺、2-(二乙基氨基)(甲基)丙烯酸乙酯、2-(二异丙基氨基)(甲基)丙烯酸乙酯；优选为2-(二甲基氨基)甲基丙烯酸乙酯(DMAEMA)、2-(二乙基氨基)(甲基)丙烯酸乙酯(DEAEMA)和N-(3-二甲基氨基丙基)甲基丙烯酰胺(DMAPMA)；优选为DMAEMA、DMAPMA或DEAEMA。
优选地，第一聚合物的Mw为至少4,000，优选为至少5,000；优选不超过70,000，优选不超过50,000，优选不超过30,000，优选不超过25,000，优选不超过20,000，优选不超过16,000。
优选地，组合物包含至少2.8重量％、优选至少3重量％、优选至少3.2重量％、优选至少3.4重量％、优选至少3.6重量％、优选至少3.8重量％、优选至少3.9重量％；优选不超过7重量％、优选不超过6.5重量％、优选不超过6重量％、优选不超过5.5重量％的第一聚合物。
在一优选实施例中，组合物包含：(a)2.2到8重量％的第一聚合物，其包含以下的聚合单元：(i)55到85重量％的C3-C6单烯属不饱和羧酸、(ii)2到30重量％的C3-C6单烯属不饱和二羧酸和(iii)2到15重量％的C5-C12单烯属不饱和叔胺；并且其Mw为2,000到100,000；和(b)0.5到7重量％的第二聚合物，其包含以下的聚合单元：(i)60到95重量％的C3-C6单烯属不饱和羧酸，和(ii)5到40重量％的单烯属不饱和磺酸；并且其Mw为5,000到100,000。
优选第一聚合物和第二聚合物分别以9:1到1:3；优选9:1到1:2、优选6:1到1:3、优选6:1到1:2、优选6:1到1:1.5、优选6:1到1:1、优选6:1到1.5:1、优选4:1到1:1的重量比(第一:第二)存在。优选地，组合物中第一聚合物和第二聚合物的总量是3到12重量％、优选是至少3.3重量％、优选是至少3.6重量％；优选不超过10重量％、优选不超过8重量％、优选不超过6重量％、优选不超过5重量％。优选地，组合物包含至少2.2重量％、优选至少2.3重量％、优选至少2.4重量％、优选至少2.5重量％、优选至少2.6重量％、优选至少2.7重量％、优选至少2.8重量％；优选不超过7重量％、优选不超过6.5重量％、优选不超过6重量％、优选不超过5.5重量％、优选不超过5重量％的第一聚合物。优选地，包含第一聚合物和第二聚合物的组合物包含至少0.7重量％、优选至少0.9重量％、优选至少1.2重量％、优选至少1.5重量％、优选至少1.8重量％；优选不超过6重量％、优选不超过5.5重量％、优选不超过5重量％、优选不超过4.5重量％、优选不超过4重量％的第二聚合物。
对于第一聚合物和第二聚合物这两者，在单烯属不饱和二羧酸采用酐的形式可用的情况下，聚合物由聚合酐而制得，在聚合处理期间所述酐水解为酸，得到单烯属不饱和二羧酸的聚合单元。对在聚合物中的聚合二羧酸单元的全部引用包括酸的金属盐，其将在接近羧酸基pKa或更高pKa的pH值下存在。优选地，单烯属不饱和二羧酸具有四到六个碳原子，优选为四个或五个碳原子。优选地，单烯属不饱和二羧酸选自由以下组成的群组：马来酸、富马酸、衣康酸、甲基反丁烯二酸和甲基顺丁烯二酸；优选为马来酸或衣康酸；优选为马来酸。
优选地，单烯属不饱和磺酸具有五到十二个碳原子；优选其含有丙烯酰氨基或甲基丙烯酰氨基。尤其优选的单烯属不饱和磺酸包括2-丙烯酰氨基-2-甲基丙磺酸(AMPS)、(甲基)丙烯酸磺丙酯、磺甲基化丙烯酰胺、烯丙基磺酸、苯乙烯磺酸和乙烯基磺酸；优选为AMPS。这些单体可以其酸形式或以其单价金属离子盐形式使用。
优选地，第二聚合物包含至少63重量％、优选至少66重量％、优选至少69重量％；优选不超过85重量％、优选不超过80重量％、优选不超过77重量％的(甲基)丙烯酸的聚合单元，。优选地，第二聚合物包含至少15重量％、优选至少20重量％、优选至少23重量％；优选不超过37重量％、优选不超过34重量％、优选不超过31重量％的单烯属不饱和磺酸残余物(包括金属盐或铵盐)的聚合单元。
优选地，聚合物不含有超过8重量％、优选不超过5重量％、优选不超过3重量％、优选不超过1重量％的丙烯酸酯或甲基丙烯酸酯的聚合单元。
优选地，第二聚合物的Mw为至少10,000；优选不超过70,000、优选不超过50,000、优选不超过30,000、优选不超过25,000、优选不超过20,000。
聚合物可与其它聚合物组合使用，所述其它聚合物适用于控制在自动洗碗机中的不可溶沉积物，包括例如包含以下各项组合的聚合物：丙烯酸、甲基丙烯酸、马来酸或其它二酸单体的残余物，丙烯酸或甲基丙烯酸的酯(包括聚乙二醇酯)、苯乙烯单体、AMPS和其它磺化的单体，以及经取代的丙烯酰胺或甲基丙烯酰胺。
优选地，洗涤剂组合物以5到45重量％；优选至少6重量％、优选至少8重量％、优选至少10重量％、优选至少12重量％；优选不超过40重量％、优选不超过35重量％、优选不超过30重量％、优选不超过25重量％、优选不超过20重量％、优选不超过18重量％的量包含柠檬酸盐。优选地，洗涤剂组合物以15到50重量％；优选至少20重量％、优选至少22重量％、优选至少24重量％；优选不超过45重量％、优选不超过40重量％、优选不超过36重量％、优选不超过33重量％的量包含碳酸盐。优选地，洗涤剂组合物以5到45重量％的量包含过碳酸盐和/或过硼酸盐(优选为过碳酸盐)。优选地，过碳酸盐和/或过硼酸盐的量为至少6重量％、优选至少8重量％、优选至少10重量％、优选至少12重量％；优选不超过40重量％、优选不超过35重量％、优选不超过30重量％、优选不超过25重量％、优选不超过20重量％、优选不超过18重量％。
优选地，洗涤剂组合物优选以1到35重量％；优选至少1.5重量％、优选至少2重量％、优选至少5重量％、优选至少10重量％；优选不超过30重量％、优选不超过25重量％、优选不超过20重量％的量包含氨基羧酸盐助洗剂。优选的氨基羧酸盐助洗剂为甲基甘氨酸二乙酸(MGDA)。
本发明的聚合物可以经由用于聚合丙烯酸单体的任何已知技术生产。优选地，引发剂不含磷。优选地，聚合物包含小于1重量％、优选小于0.5重量％、优选小于0.1重量％的磷，优选地聚合物不含磷。优选地，聚合利用过硫酸盐引发，并且在聚合物上的端基为硫酸根或磺酸根。聚合物可呈水溶性溶液聚合物、浆液、干燥粉末或颗粒的形式或其它固体形式。
自动洗碗机洗涤剂组合物的其它组分可包括例如，表面活性剂、氧漂白剂和/或氯漂白剂、漂白活化剂、酶、发泡抑制剂、色料、芳香剂、抗菌剂和填充剂。典型表面活性剂含量取决于使用的特定表面活性剂；优选地，表面活性剂的总量为0.5重量％到15重量％、优选至少0.7重量％、优选至少0.9重量％；优选不超过10重量％、优选不超过7重量％、优选不超过4重量％、优选不超过2重量％、优选不超过1重量％。优选地，表面活性剂包含非离子表面活性剂。优选地，非离子表面活性剂具有化学式RO-(M)x-(N)y-OH或R-O-(M)x-(N)y-O-R'，其中M和N为衍生自环氧烷(其中一个为环氧乙烷)的单元，R表示C6-C22直链或支链烷基，并且R'表示衍生自醇前体与C6-C22直链或支链烷基卤化物、环氧烷烃或缩水甘油醚反应的基团。呈片剂或粉末形式的填充剂为惰性水溶性物质，通常为钠盐或钾盐，例如硫酸钠或硫酸钾和/或氯化钠或氯化钾，并且通常以0重量％到70重量％、优选10到50重量％、优选15到35重量％范围内的量存在。凝胶配制物中的填充剂可包括上文所提及的填充剂并且还可包括水。芳香剂、染料、发泡抑制剂、酶和抗菌剂通常总计不超过组合物的5重量％。
优选地，组合物的pH(在水中在1重量％下)为至少10，优选是至少11.5；在一些实施例中pH不超过13。
组合物可以任何典型形式配制，例如，以片剂、粉末、单剂、小袋、糊剂、液体或凝胶形式。在典型操作条件下组合物可用于任何典型自动洗碗机。在洗涤处理期间典型水温度优选为20℃到85℃，优选为30℃到70℃。按在洗碗机中总液体的百分比计，组合物的典型浓度优选为0.1到1重量％，优选为0.2到0.7重量％。在选择适当的产品形态和添加时间的情况下，组合物可以存在于预洗、主洗、倒数第二次冲洗、最后一次冲洗或这些循环的任何组合中。
这些实例中所用的缩写：
AA 丙烯酸
ADW 自动洗碗
AMPS 2-丙烯酰氨基-2-甲基-1-丙磺酸钠盐
DEAEMA 2-(二乙基氨基)甲基丙烯酸乙酯
DMAEMA 2-(二甲基氨基)甲基丙烯酸乙酯
DMAPMA N-[3-(二甲基氨基)丙基]甲基丙烯酰胺
IA 衣康酸
MAA 甲基丙烯酸
Mal 马来酸
MGDA 甲基甘氨酸二乙酸钠盐
Mn 数均分子量
Mw 重均分子量
SMBS 焦亚硫酸钠
SPS 过硫酸钠
TAED 四乙酰基乙二胺
实例
聚合物C的合成
向配备有氮气鼓泡器、回流冷凝器、加热套、热电偶和顶置式混合器(overheadmixer)的圆底玻璃烧瓶中添加马来酸酐(35g)、去离子水(275g)和3.32g的0.15重量％的硫酸亚铁水溶液。将反应混合物的温度升高到78℃。保持这一温度直到下文指出。在达到这一温度后，装入SMBS溶液(在7g去离子水中2.7g)。同时开始进料(A)AA(320g)和DMAEMA(39g)的混合物；(B)SMBS溶液(57.3g在100g去离子水中)；和(C)SPS溶液(2.95g在30g去离子水中)。进料溶液A以使得其将在90分钟之后耗尽。进料溶液B以使得其将在80分钟之后耗尽。进料溶液C以使得其将在85分钟之后耗尽。停止进料溶液A十分钟后，进料SPS第一追加溶液(0.53g在15g去离子水中)开始并且在10分钟后完成。完成第一次追加二十分钟后，在另10分钟的时间内添加相同溶液。完成第二次追加二十分钟后，使温度降到60℃并且添加100g氢氧化钠的第一中和剂溶液(50％)，随后添加1.5g过氧化氢溶液(35％)和180g氢氧化钠的第二中和剂溶液(50％)。最终添加50g去离子水。含有44.4重量％固体含量(在150℃的强制空气烘箱中干燥之后残留的残余物)的溶液的pH为6.33，黏度(布鲁克菲尔德，Brookfield)为370，并且通过GPC，Mw＝5,743，Mn＝1,166。通过液相色谱检测到残余AA为481ppm并且残余Mal为0ppm。
其它聚合物使用相同方法制备但视需要调整链转移剂(SMBS)和单体的含量。
食物类污垢的制备：
1.将水煮沸。
2.在16盎司(473mL)纸杯中混合：速食肉汁、苯甲酸和淀粉；将这一混合物添加到沸腾水中。
3.添加牛奶和人造奶油。
4.使混合物冷却到大约40℃。
5.将混合物填充到厨房机器(Kitchen Machine，宝创(POLYTRON))的碗中。
6.在16盎司纸杯中，使用勺子混合蛋黄、番茄酱和芥末。
7.连续搅拌下将冷却的混合物添加到碗中。
8.使混合物搅拌5分钟。
9.冷冻混合物。
10.在开始方案之前，将冻结的污物放置到洗碗机中。
洗碗测试的情况：
当洗涤剂装入洗涤液体(20分钟标记)时装入食物类污垢。
在露天干燥之后，通过两种经过训练的观测器根据污垢和污渍从1(干净)到5(大量污垢)评定两种玻璃。(参见ASTM-D 3556-85.)
表1.用于自动洗碗实例的聚合物
表2.ADW实例1：聚合物组成研究。
注意：成膜和污渍评估在10次循环之后进行。
aStepan Co.；bBRITESIL H 20,PQ Corp.
表3.ADW实例2：掺合物比率研究
注意：成膜和污渍评估在10次循环之后进行。
aStepan Co.；bBRITESIL H 20,PQ Corp.
表4.ADW实例3：组成和MW变化。
注意：成膜和污渍评估在15次循环b之后进行。
aBritesilTM H 20，PQ Corp.
b来自这一表格的数据不能直接与在10次循环后所得的表格2和3中的数据进行比较。
表5.ADW实例4：基于柠檬酸盐配制物的性能(比较与对照)。
注意：成膜和污渍评估在10次循环之后进行。
一分开组的评估显示第一聚合物在不存在第二聚合物下使用时导致玻璃上略微蓝色的膜。在本发明工作中，蓝色膜在一起使用第一聚合物和第二聚合物时不可见。
Claims (10)
1.一种包含2.5到8重量％的第一聚合物的无磷自动洗碗机洗涤剂组合物，所述第一聚合物包含以下的聚合单元：(i)55到85重量％的C3-C6单烯属不饱和羧酸、(ii)2到30重量％的C3-C6单烯属不饱和二羧酸和(iii)2到15重量％的C5-C12单烯属不饱和叔胺；并且其Mw为2,000到100,000。
2.根据权利要求1所述的组合物，其中所述第一聚合物的Mw为2,000到25,000。
3.根据权利要求2所述的组合物，其中所述第一聚合物包含以下的聚合单元：(i)65到85重量％的C3-C6单烯属不饱和羧酸、(ii)4到25重量％的C3-C6单烯属不饱和二羧酸和(iii)6到15重量％的C5-C12单烯属不饱和叔胺。
4.一种无磷自动洗碗机清洁剂组合物，包含：
(a)2到8重量％的第一聚合物，所述第一聚合物包含以下的聚合单元：(i)55到85重量％的C3-C6单烯属不饱和羧酸、(ii)2到30重量％的C3-C6单烯属不饱和二羧酸和(iii)2到15重量％的C5-C12单烯属不饱和叔胺；并且其Mw为2,000到100,000；和
(b)0.5到7重量％的第二聚合物，所述第二聚合物包含以下的聚合单元：(i)60到95重量％的C3-C6单烯属不饱和羧酸，和(ii)5到40重量％的单烯属不饱和磺酸；并且其Mw为5,000到100,000。
5.根据权利要求4所述的组合物，其中所述第一聚合物的Mw为2,000到25,000。
6.根据权利要求5所述的组合物，其中所述第一聚合物包含以下的聚合单元：(i)65到85重量％的C3-C6单烯属不饱和羧酸、(ii)4到25重量％的C3-C6单烯属不饱和二羧酸和(iii)6到15重量％的C5-C12单烯属不饱和叔胺，并且所述第二聚合物包含以下的聚合单元：(i)66到80重量％的C3-C6单烯属不饱和羧酸，和(ii)20到34重量％的单烯属不饱和磺酸。
7.根据权利要求6所述的组合物，其中所述组合物包含5到45重量％的柠檬酸盐、15到50重量％的碳酸盐、5到45重量％的过碳酸盐和过硼酸盐中的至少一种以及小于0.2重量％的磷。
8.根据权利要求1所述的组合物，其中所述第一聚合物以2.2到6.5重量％的量存在。
9.根据权利要求7所述的组合物，其中所述单烯属不饱和磺酸是2-丙烯酰氨基-2-甲基丙磺酸。
10.根据权利要求8所述的组合物，其中所述第一聚合物包含以下的聚合单元：(i)65到85重量％的C3-C6单烯属不饱和羧酸、(ii)5到25重量％的C3-C6单烯属不饱和二羧酸和(iii)6到15重量％的C5-C12单烯属不饱和叔胺，并且所述第二聚合物包含以下的聚合单元：(i)66到80重量％的C3-C6单烯属不饱和羧酸，和(ii)20到34重量％的单烯属不饱和磺酸。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP15290257.3A EP3153571A1 (en) | 2015-10-09 | 2015-10-09 | Additive for reducing spotting in automatic dishwashing systems |
| EP15290257.3 | 2015-10-09 | ||
| PCT/US2016/053862 WO2017062222A1 (en) | 2015-10-09 | 2016-09-27 | Additive for reducing spotting in automatic dishwashing systems |
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| CN108138091A true CN108138091A (zh) | 2018-06-08 |
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| CN201680057910.0A Pending CN108138091A (zh) | 2015-10-09 | 2016-09-27 | 用于减少自动洗碗系统中的污渍的添加剂 |
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| Country | Link |
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| US (1) | US10683469B2 (zh) |
| EP (2) | EP3153571A1 (zh) |
| JP (1) | JP6799059B2 (zh) |
| KR (1) | KR20180064421A (zh) |
| CN (1) | CN108138091A (zh) |
| AU (1) | AU2016335888B2 (zh) |
| BR (1) | BR112018006517A2 (zh) |
| MX (1) | MX2018004191A (zh) |
| WO (1) | WO2017062222A1 (zh) |
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| EP3790951B1 (en) * | 2018-05-09 | 2022-04-13 | Dow Global Technologies, LLC | Automatic dishwashing composition with dispersant polymer |
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| EP0560519A2 (en) * | 1992-03-10 | 1993-09-15 | Rohm And Haas Company | Use of water-soluble polymers in cleaning compositions, and water-soluble polymers for such use |
| CN1154375A (zh) * | 1995-10-27 | 1997-07-16 | 罗姆和哈斯公司 | 用于自动洗碗洗涤剂的聚羧酸盐 |
| US20030158064A1 (en) * | 2000-07-07 | 2003-08-21 | Arnd Kessler | Machine dishwasher rinsing agent |
| US20100234264A1 (en) * | 2009-03-13 | 2010-09-16 | Marianne Patricia Creamer | Scale-reducing additive for automatic dishwashing systems |
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| US560519A (en) * | 1896-05-19 | Stop and waste cock | ||
| SE8100044L (sv) | 1981-01-07 | 1982-07-08 | Vitrum Ab | Pump |
| DE3233778A1 (de) | 1982-09-11 | 1984-03-15 | Basf Ag, 6700 Ludwigshafen | Verfahren einer kontinuierlichen herstellung von copolymerisaten aus monoethylenisch ungesaettigten mono- und dicarbonsaeuren |
| US5308532A (en) * | 1992-03-10 | 1994-05-03 | Rohm And Haas Company | Aminoacryloyl-containing terpolymers |
| CA2090933A1 (en) * | 1992-03-10 | 1993-09-11 | David E. Adler | Water-soluble polymers for use in automatic machine dishwashing detergent compositions |
| DE19621509A1 (de) * | 1996-05-29 | 1997-12-04 | Basf Ag | Verwendung von wasserlöslichen, N-Vinylimidazol-Einheiten enthaltenden Copolymerisaten als Farbübertragungsinhibitoren in Waschmitteln |
| DE69807519T2 (de) | 1997-11-21 | 2003-05-15 | The Procter & Gamble Company, Cincinnati | Washmittelzusammensetzungen enthaltend polymere schaumbilder und deren verwendung |
| MXPA01012190A (es) * | 1999-05-26 | 2002-06-21 | Procter & Gamble | Composiciones detergentes que comprenden incrementadores polimericos del volumen de espuma de jabon y de la duracion de espuma de jabon y metodos para el lavado con los mismos. |
| US20020137649A1 (en) * | 2000-06-12 | 2002-09-26 | Carnali Joseph Oreste | Mechanical warewashing compositions containing scale inhibiting polymers with targeted rinse cycle delivery |
| FR2894585B1 (fr) * | 2005-12-14 | 2012-04-27 | Rhodia Recherches Et Tech | Copolymere comprenant des unites zwitterioniques et d'autres unites, composition comprenant le copolymere, et utilisation |
| US9670435B2 (en) * | 2010-11-23 | 2017-06-06 | Basf Se | Copolymers comprising carboxylic acid groups, sulfo groups and polyalkylene oxide groups as a scale-inhibiting additive to washing and cleaning products |
| US9347027B2 (en) * | 2012-12-19 | 2016-05-24 | Rohm And Haas Company | Automatic dishwashing detergent |
-
2015
- 2015-10-09 EP EP15290257.3A patent/EP3153571A1/en not_active Withdrawn
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2016
- 2016-09-27 BR BR112018006517-0A patent/BR112018006517A2/pt not_active Application Discontinuation
- 2016-09-27 MX MX2018004191A patent/MX2018004191A/es unknown
- 2016-09-27 US US15/766,068 patent/US10683469B2/en active Active
- 2016-09-27 EP EP16778616.9A patent/EP3359633A1/en not_active Withdrawn
- 2016-09-27 KR KR1020187011101A patent/KR20180064421A/ko unknown
- 2016-09-27 WO PCT/US2016/053862 patent/WO2017062222A1/en active Application Filing
- 2016-09-27 CN CN201680057910.0A patent/CN108138091A/zh active Pending
- 2016-09-27 AU AU2016335888A patent/AU2016335888B2/en not_active Ceased
- 2016-09-27 JP JP2018516807A patent/JP6799059B2/ja active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0560519A2 (en) * | 1992-03-10 | 1993-09-15 | Rohm And Haas Company | Use of water-soluble polymers in cleaning compositions, and water-soluble polymers for such use |
| CN1154375A (zh) * | 1995-10-27 | 1997-07-16 | 罗姆和哈斯公司 | 用于自动洗碗洗涤剂的聚羧酸盐 |
| US20030158064A1 (en) * | 2000-07-07 | 2003-08-21 | Arnd Kessler | Machine dishwasher rinsing agent |
| US20100234264A1 (en) * | 2009-03-13 | 2010-09-16 | Marianne Patricia Creamer | Scale-reducing additive for automatic dishwashing systems |
Also Published As
| Publication number | Publication date |
|---|---|
| MX2018004191A (es) | 2018-05-17 |
| JP6799059B2 (ja) | 2020-12-09 |
| US10683469B2 (en) | 2020-06-16 |
| US20180291313A1 (en) | 2018-10-11 |
| JP2018531309A (ja) | 2018-10-25 |
| AU2016335888B2 (en) | 2020-07-16 |
| KR20180064421A (ko) | 2018-06-14 |
| BR112018006517A2 (pt) | 2018-10-09 |
| EP3359633A1 (en) | 2018-08-15 |
| WO2017062222A1 (en) | 2017-04-13 |
| AU2016335888A1 (en) | 2018-05-10 |
| EP3153571A1 (en) | 2017-04-12 |
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Effective date of registration: 20200618 Address after: Pennsylvania, USA Applicant after: Rohm and Haas Co. Applicant after: Union Carbide Corp. Address before: Pennsylvania, USA Applicant before: Rohm and Haas Co. Applicant before: Union Carbide Chemicals & Plastics Technology LLC |
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