CN106459844A - 自动餐具洗涤用组合物 - Google Patents
自动餐具洗涤用组合物 Download PDFInfo
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- CN106459844A CN106459844A CN201580028509.XA CN201580028509A CN106459844A CN 106459844 A CN106459844 A CN 106459844A CN 201580028509 A CN201580028509 A CN 201580028509A CN 106459844 A CN106459844 A CN 106459844A
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
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- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
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- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
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- 230000002829 reductive effect Effects 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical class OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- BHTRKEVKTKCXOH-LBSADWJPSA-N tauroursodeoxycholic acid Chemical compound C([C@H]1C[C@@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCCS(O)(=O)=O)C)[C@@]2(C)CC1 BHTRKEVKTKCXOH-LBSADWJPSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UZVUJVFQFNHRSY-OUTKXMMCSA-J tetrasodium;(2s)-2-[bis(carboxylatomethyl)amino]pentanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC[C@@H](C([O-])=O)N(CC([O-])=O)CC([O-])=O UZVUJVFQFNHRSY-OUTKXMMCSA-J 0.000 description 1
- DTXLBRAVKYTGFE-UHFFFAOYSA-J tetrasodium;2-(1,2-dicarboxylatoethylamino)-3-hydroxybutanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)C(O)C(C([O-])=O)NC(C([O-])=O)CC([O-])=O DTXLBRAVKYTGFE-UHFFFAOYSA-J 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- PCHQDTOLHOFHHK-UHFFFAOYSA-L zinc;hydrogen carbonate Chemical compound [Zn+2].OC([O-])=O.OC([O-])=O PCHQDTOLHOFHHK-UHFFFAOYSA-L 0.000 description 1
- LKCUKVWRIAZXDU-UHFFFAOYSA-L zinc;hydron;phosphate Chemical compound [Zn+2].OP([O-])([O-])=O LKCUKVWRIAZXDU-UHFFFAOYSA-L 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
-
- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion 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
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3723—Polyamines or polyalkyleneimines
-
- 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
- A47L15/0002—Washing processes, i.e. machine working principles characterised by phases or operational steps
- A47L15/0007—Washing phases
-
- 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
- C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
-
- 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
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
- C11D17/043—Liquid or thixotropic (gel) 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
- C11D17/045—Multi-compartment
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/395—Bleaching agents
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/18—Glass; Plastics
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)
Abstract
本发明涉及用于在自动器皿清洗机中保护如玻璃器皿等非金属无机材料的改良洗涤剂组合物。
Description
技术领域
本发明涉及一种用于在自动餐具洗涤(ADW)过程中保护如玻璃器皿等非金属无机材料的改良组合物。
背景技术
在本领域中已广泛意识到如玻璃器皿、陶瓷和釉质材料等非金属无机物品在经历自动餐具洗涤过程时受到腐蚀的问题。例如,已提出玻璃器皿腐蚀问题是两种单独的现象的结果。首先,已表明腐蚀是由于矿物质从玻璃网络结构中渗漏所致的,伴随着硅酸盐网络的水解。其次,已提出硅酸盐材料随后从玻璃中释出。
这些现象可导致玻璃器皿在多次单独的洗涤循环后受到损伤。损伤可能包括晦暗、刮擦、条纹和其它变色/有害效果。损伤通常是不可逆的,且随时间推移可以被检测为玻璃器皿的质量损失。这与玻璃漆面表面上的物质沉积所导致的晦暗、条纹或斑点(其可能在单次洗涤循环后出现,并且通常是可除去的)相反。
已提出硅酸盐材料作为可有效防止材料从玻璃组合物中释出的试剂。然而,使用硅酸盐化合物具有有害的副作用,例如增加硅酸盐材料在玻璃表面处的分离的倾向。
另一种解决方案是使用处于金属形式(如美国专利3,677,820号所述)或化合物形式的金属(例如锌)。可溶性锌化合物在防止餐具洗涤机中的玻璃器皿腐蚀方面的应用在例如美国专利3,255,117号中进行了描述。
欧洲专利EP-A-0 383 480、EP-A-0 383 482和EP-A-0 387 997描述了出于上述目的的非水溶性化合物(包括硅酸锌、碳酸锌、碱式碳酸锌(Zn2(OH)2CO3)、氢氧化锌、草酸锌、单磷酸锌(Zn3(PO4)2)和焦磷酸锌(Zn2P2O7))的使用。
然而,已发现在某些情形中使用重金属化合物会降低餐具洗涤用组合物对诸如茶渍等可漂白污渍的漂白性能。此外,出于环境原因,越来越希望限制(尤其是避免)在洗涤剂(detergent)配方中使用重金属。
WO2010/020765为玻璃和餐具腐蚀问题提出了一种不需要使用重金属的解决方案。该文献(通过援引并入本文)公开:诸如聚亚乙基亚胺(PEI)等聚亚烷基亚胺是防止非金属无机物品在自动洗涤机中受腐蚀的极为有效的添加剂。WO2012/153143也公开了含有PEI的用于抑制玻璃器皿腐蚀的ADW组合物。
WO 99/07815讨论了出于除去污渍目的而使用PEI作为洗涤剂中的螯合剂,优选用在基本不含漂白剂的洗衣洗涤剂中。所公开的组合物中有水性液体洗衣洗涤剂。
申请人越来越多地发现,可以向ADW洗涤剂组合物中添加越来越少量的PEI,且同时维持对抗玻璃器皿腐蚀的保护作用。PEI可以以等同于每个洗涤循环1mg~10mg的剂量添加,同时仍维持完全的玻璃器皿保护性能。
取决于其结构,聚亚乙基亚胺在室温下可以为固体或液体化合物。对于自动餐具洗涤领域,许多液体PEI特别受关注。然而,将液体形式的PEI以极低水平均匀地配制到自动餐具洗涤用洗涤剂中是极大的挑战。
申请人已发现,将低水平的PEI施用于固体粉末或颗粒很难,且可能导致材料在整个固体中的分布不一致。PEI是强表面活性和粘合性材料。这意味着在不同的洗涤之间PEI水平在粉末洗涤剂和其它固体单一剂型中可能有显著不同,从而导致在以工业规模配置此类产品时不一致的结果。
申请人已发现一种可靠的配制含低水平PEI的ADW组合物的方式是将PEI配制于组合物的凝胶相或液相中。以此方式,PEI可能均匀地分布,且在洗涤条件下可用于保护玻璃器皿。
发明内容
在本发明的第一方面,提供了一种包含小于1重量%的聚亚乙基亚胺(PEI)的自动餐具洗涤机(ADW)洗涤剂组合物,其中所述PEI包含在所述ADW洗涤剂组合物的凝胶相或液相中。
在本发明的第二方面,提供了一种如权利要求1所述的组合物。
在本发明的第三方面,提供了一种包含本发明第一方面或第二方面所述的组合物的产品,其容纳于水溶性或水分散性膜或容器内。
在本发明的第四方面,提供了一种自动餐具洗涤方法,该方法包括:向自动餐具洗涤机中供给本发明第一方面或第二方面所述的组合物或本发明第三方面所述的产品,并且将所述组合物或产品释放至自动餐具洗涤机的洗涤循环中。
在本发明的第五方面,提供了本发明第一方面或第二方面所述的组合物或本发明第三方面所述的产品在清洁玻璃器皿的同时抑制所述玻璃器皿在自动餐具洗涤期间受腐蚀中的应用。
具体实施方式
在以下章节中,除非上下文另外明确规定,所讨论的实施方式同等地适用于本发明的所有方面。除非另外说明,所引用的量以重量计(重量%)。
本文中,术语“相”优选不以严格热力学意义来解读。例如,液“相”也可以包含悬浮的固体,即,其可以为悬浮体或糊体。优选地,其在宏观规模上是均匀的,并且/或者与存在的任何其它“相”在空间上分离。
出于本发明的目的,优选凝胶形式。本文中术语“凝胶”不限于严格为胶体的组合物。出于本发明的目的,凝胶可以认为是稠化的液体。
当为便于加工而使用粘度更低的凝胶前体材料时,优选其在静置后变得更为粘稠,且优选固化成具有稳定形状。
在本实施方式中,凝胶前体优选其自身已经是凝胶,适当地为粘性材料,但在重力作用下或在泵送时具有流动性。优选地,在其引入时,凝胶前体的粘度为至少1,000mPa.s.,优选至少5,000mPa.s.,优选至少10,000mPa.s.,该粘度在25℃以Brookfield粘度计RVDV-II+(27号转子,速度2.5rpm)测得。
产品形式
整体ADW组合物无需为液体或凝胶形式,但也可以是此形式。ADW组合物可以包含几个不同的相,其中至少一个相可以为液体或凝胶形式,条件是该液体或凝胶形式含有PEI。现有技术中的洗涤剂相包括片剂、粉末、凝胶、糊体和液体。本发明的洗涤剂组合物可以包含两个以上的相的混合物,只要至少一个相为凝胶相或液相即可。例如,所述组合物可以包含凝胶或液体成分和游离粉末成分。PEI可以完全包含在凝胶或液体部分内,或可以同时包含在这两个部分内。
在一个实施方式中,ADW洗涤剂组合物是具有至少两个以上的分离的相、优选至少三个以上的分离的相的多相组合物。在一个实施方式中,组合物包含一个或多个不同的相,其包括粉末、颗粒和压制固体。
优选地,本发明的ADW组合物是单剂量组合物,即,以单次洗涤循环所需的量预提供的组合物。
单剂量组合物可以包括具有凝胶部分或凝胶层的片剂。如果压制的片剂形成ADW洗涤剂组合物的一部分,则它们可以是均质的或者由多个层构成。如果所述片剂是多层的,则不同的层可以包含洗涤剂组合物的不同部分。这样做可以提高稳定性和/或提高性能。
在一个实施方式中,组合物包含在水溶性膜或容器、优选聚乙烯醇膜或容器内。ADW洗涤剂组合物可以容纳在PVOH硬胶囊或膜泡罩中。这些PVOH胶囊或泡罩可以是单区室或可以为多区室。
多区室泡罩或胶囊可以在每个区室中具有组合物的不同部分,或在每个区室中具有相同的组合物。不同的区域/区室可以根据需要含有成分总量的任意比例。
在本发明的范围内,PVOH胶囊或膜泡罩可以填充有片剂、粉末、凝胶、糊体或液体或者这些的组合。
单剂量可以包含具有多区室的注塑成型PVOH胶囊。每个区室可以包含不同的组合物。至少一个区室将含有凝胶或液体组合物,而至少一部分PEI将处于该组合物中且优选所有PEI均处于该组合物中。
聚亚乙基亚胺
聚亚乙基亚胺(PEI)包含在组合物的凝胶相或液相中,且聚亚乙基亚胺的量少于组合物的1重量%。优选地,当组合物为多相时,聚亚乙基亚胺仅存在于凝胶相或液相中。
优选地,将使用可实现有效结果的最低PEI量。在一个实施方式中,PEI占组合物的不足0.5重量%,优选占组合物的不足0.25重量%,最优选不足0.05重量%。优选地,PEI占组合物的不足0.005重量%,且优选占组合物的不足0.0025重量%。在一个实施方式中,PEI载量小于0.0005重量%。
优选地,每次洗涤中PEI的用量为0.5mg~100mg,更优选为1mg~50mg,更优选为2mg~25mg,最优选为4mg~10mg。
在一个实施方式中,组合物包含至少0.0001重量%的PEI,和/或小于0.5重量%、小于0.25重量%、小于0.05重量%、小于0.04重量%、小于0.03重量%、小于0.01重量%、小于0.005重量%或小于0.0025重量%的PEI。
虽然发现使用的PEI出于有效性可以具有任何分子量,但优选PEI具有较低的分子量。优选地,本发明中所用的PEI的分子量为100~50000,更优选为400~25000,更优选为800~10000,且最优选为1000~3000。在一个实施方式中,PEI的分子量为100~2500,优选200~1500,且最优选400~1200。在一个实施方式中,PEI分子量为700~900。最优选的PEI的分子量为800。分子量通过光散射来适当地测定。
可以使用任何PEI。PEI可以为支化或直链的。优选地,PEI是支化的。优选地,其含有伯胺基团、仲胺基团和叔胺基团,且伯胺与仲胺之比优选为1:0.5~1:1,优选为1:0.7~1:0.9。
优选地,PEI在室温下为液体。
优选地,PEI不含烷氧基化基团,或为均聚物。
特别优选的PEI是由BASF供应的FG。
溶剂
在ADW洗涤剂组合物中可以包含水。但是,优选地,包含PEI的凝胶相或液相是非水性的。在一个实施方式中,凝胶相或液相含有不超过该凝胶相或液相的10重量%、不超过5重量%、不超过3重量%、不超过1重量%的水或者不含水。
凝胶相或液相可以含有有机溶剂,优选与水混溶的溶剂。
表面活性剂
ADW洗涤剂组合物中也可以包含表面活性剂,并且可以使用任何非离子型、阴离子型、阳离子型、酸碱兼性型(amphoteric)或两性离子型(zwitterionic)表面活性剂及其合适的混合物。许多这些合适的表面活性剂在Kirk Othmer的Encyclopedia of ChemicalTechnology,第3版,第22卷,第360-379页,"Surfactants and Detersive Systems"中有所描述,本文通过援引将其并入。通常,本发明优选耐漂白表面活性剂。
在ADW组合物的情形中,优选将阴离子型表面活性剂的量最小化。优选地,组合物包含不多于2重量%、不多于1重量%的阴离子型表面活性剂或者不含阴离子型表面活性剂。优选地,组合物包含不多于2重量%、不多于1重量%的任何类型的离子型表面活性剂或者不含离子型表面活性剂。相反,非离子型表面活性剂对于自动餐具洗涤组合物是尤为优选的。
优选的一类非离子型表面活性剂是通过使具有6~20个碳原子的单羟基烷醇或烷基酚反应而制备的乙氧基化非离子型表面活性剂。优选地,表面活性剂的每摩尔醇或烷基酚具有至少12摩尔、特别优选至少16摩尔、进而更优选至少20摩尔(例如至少25摩尔)的氧化乙烯。
特别优选的非离子型表面活性剂是源于具有16~20个碳原子且每摩尔醇具有至少12摩尔、特别优选至少16摩尔、进而更优选至少20摩尔氧化乙烯的直链脂肪醇的非离子型表面活性剂。
根据本发明的一个实施方式,非离子型表面活性剂可以在分子中额外包含氧化丙烯单元。优选地,这些PO单元构成非离子型表面活性剂的整个分子量的至多25重量%、优选至多20重量%、进而更优选至多15重量%。
可以使用额外包含聚氧乙烯-聚氧丙烯嵌段共聚物单元的作为乙氧基化的单羟基烷醇或烷基酚的表面活性剂。这些表面活性剂的醇或烷基酚部分构成非离子型表面活性剂的整个分子量的多于30重量%、优选多于50重量%、更优选多于70重量%。
另一类合适的非离子型表面活性剂包括聚氧乙烯和聚氧丙烯的反嵌段共聚物以及由三羟甲基丙烷引发的聚氧乙烯和聚氧丙烯的嵌段共聚物。
另一类优选的非离子型表面活性剂可以由下式表示:
R1O[CH2CH(CH3)O]x[CH2CH2O]y[CH2CH(OH)R2]
其中,R1表示具有4~18个碳原子的直链或支化链脂肪族烃基或其混合物,R2表示具有2~26个碳原子的直链或支化链脂肪族烃残基或其混合物,x为0.5~1.5的值,且y为至少15的值。
另一组优选的非离子型表面活性剂是下式的封端聚氧烷基化非离子型表面活性剂:
R1O[CH2CH(R3)O]x[CH2]kCH(OH)[CH2]jOR2
其中,R1和R2表示具有1~30个碳原子的直链或支化链、饱和或不饱和、脂肪族或芳香族烃基,R3表示氢原子或甲基、乙基、正丙基、异丙基、正丁基、2-丁基或2-甲基-2-丁基,x是1~30的值,且k和j为1~12、优选1~5的值。当x的值>2时,上式中的各个R3可以不同。R1和R2优选为具有6~22个碳原子的直链或支化链、饱和或不饱和、脂肪族或芳香族烃基,其中特别优选具有8~18个碳原子的基团。对于基团R3,特别优选H、甲基或乙基。特别优选的x值为1~20,优选6~15。
如上所述,在x>2的情况下,式中各个R3可以不同。例如,当x=3时,基团R3可以经选择来构建氧化乙烯(R3=H)或氧化丙烯(R3=甲基)单元,所述单元可以以每一种顺序使用,例如(PO)(EO)(EO)、(EO)(PO)(EO)、(EO)(EO)(PO)、(EO)(EO)(EO)、(PO)(EO)(PO)、(PO)(PO)(EO)和(PO)(PO)(PO)。x值为3仅为举例,且可以选择更大的值,由此将产生更多数量的(EO)或(PO)单元的变化形式。
特别优选的上式的封端聚氧烷基化醇是k=1且j=1的那些,其产生以下简化式:
R1O[CH2CH(R3)O]xCH2CH(OH)CH2OR2
在本发明的背景下,使用不同的非离子型表面活性剂的混合物是合适的,例如烷氧基化醇和含羟基的烷氧基化醇的混合物。
其它合适的表面活性剂公开于WO 95/01416中,在此明确援引其内容。
优选地,基于洗涤剂组合物的总重量,非离子型表面活性剂以0.1重量%~20重量%、更优选1重量%~15重量%(例如2重量%~10重量%)的量存在于洗涤剂组合物中。
在一个实施方式中,包含PEI的凝胶相或液相还包含占所述凝胶相或液相至少10重量%、至少15重量%、至少20重量%或至少25重量%的表面活性剂,优选非离子型表面活性剂。
在一个实施方式中,凝胶组合物包含30%~80%的非离子型表面活性剂、5%~35%的溶剂、0.1~5%和0~10%的水。
助洗剂
洗涤剂组合物可以包含助洗剂(builder)(或共洗剂(co-builder))。在一个实施方式中,液相或凝胶相不含助洗剂。在组合物为多相的实施方式中,助洗剂包含在与PEI分离的相中。
根据需要,助洗剂/共洗剂可以为含磷助洗剂或无磷助洗剂。在许多管辖范围内,磷酸盐助洗剂被禁用。在一个实施方式中,组合物是无磷的。
如果使用含磷助洗剂,优选使用单磷酸盐、二磷酸盐、三磷酸盐或低聚磷酸盐。优选这些化合物的碱金属盐、特别是钠盐。尤为优选的助洗剂是三聚磷酸钠(STPP)。含磷助洗剂的常规使用量通常可以为15重量%~60重量%,例如20重量%~50重量%或25重量%~40重量%。
如果包含无磷助洗剂,其优选选自琥珀酸盐类化合物。术语“琥珀酸盐类化合物”和“琥珀酸类化合物”在本文可互换使用。琥珀酸盐类化合物的常规使用量通常可以为5重量%~80重量%,例如15重量%~70重量%或20重量%~60重量%。所述化合物可以单独使用或作为混合物使用。
其它合适的助洗剂如US 6,426,229中所述,本文通过援引将其并入。特别合适的助洗剂包括:例如,天冬氨酸-N-单乙酸(ASMA)、天冬氨酸-N,N-二乙酸(ASDA)、天冬氨酸-N-单丙酸(ASMP)、亚氨基二琥珀酸(IDA)、N-(2-磺基甲基)天冬氨酸(SMAS)、N-(2-磺基乙基)天冬氨酸(SEAS)、N-(2-磺基甲基)谷氨酸(SMGL)、N-(2-磺基乙基)谷氨酸(SEGL)、N-甲基亚氨基二乙酸(MIDA)、α-丙氨酸-N,N-二乙酸(α-ALDA)、β-丙氨酸-N,N-二乙酸(β-ALDA)、丝氨酸-N,N-二乙酸(SEDA)、异丝氨酸-N,N-二乙酸(ISDA)、苯丙氨酸-N,N-二乙酸(PHDA)、邻氨基苯甲酸-N,N-二乙酸(ANDA)、对氨基苯磺酸-N,N-二乙酸(SLDA)、牛磺酸-N,N-二乙酸(TUDA)和磺基甲基-N,N-二乙酸(SMDA)及其碱金属盐或铵盐。
其它优选的琥珀酸盐化合物如US-A-5,977,053中所述且具有下式:
其中,R、R1彼此独立地表示H或OH,R2、R3、R4、R5彼此独立地表示阳离子、氢、碱金属离子和铵离子、具有通式R6R7R8R9N+的铵离子,且R6、R7、R8、R9彼此独立地表示氢、具有1~12个碳原子的烷基或具有2~3个碳原子的具有羟基取代基的烷基。
优选实例包括亚氨基琥珀酸四钠。亚氨基二琥珀酸(IDS)和(羟基)亚氨基二琥珀酸(HIDS)及它们的碱金属盐或铵盐是尤其优选的琥珀酸盐类助洗剂盐。
无磷共洗剂可以额外包括或替代性地包括具有羧基的非聚合物有机分子。含有羧基的有机分子助洗剂化合物包括柠檬酸、富马酸、酒石酸、马来酸、乳酸及它们的盐。特别地,可以使用这些有机化合物的碱金属盐或碱土金属盐,尤其是钠盐。尤其优选的无磷助洗剂是柠檬酸钠。含有两个羧基的这类多羧酸盐包括例如丙二酸、(亚乙基二氧基)二乙酸、马来酸、二羟乙酸、酒石酸、丙醇二酸和富马酸的水溶性盐。含有三个羧基的这类多羧酸盐包括例如水溶性柠檬酸盐。相应地,合适的羟基羧酸为例如柠檬酸。
三种其它极为优选的助洗剂为MGDA、GLDA和丙二酰乳酸盐。
优选的次要助洗剂包括多羧酸及其部分或完全中和盐的均聚物和共聚物、单体多羧酸和羟基羧酸及其盐、磷酸盐和膦酸盐、以及这些物质的混合物。优选的上述化合物的盐是铵盐和/或碱金属盐,即锂盐、钠盐和钾盐,且特别优选的盐是钠盐。优选的是有机次要助洗剂。一种聚合物多羧酸是丙烯酸均聚物。其它合适的次要助洗剂公开于WO 95/01416,本文对其内容进行明确援引。
优选地,组合物中存在的助洗剂的总量为至少20重量%且最优选为至少25重量%,优选为至多70重量%、优选至多60重量%、更优选至多45重量%。组合物中所用的实际量将取决于所用的助洗剂的性质。如果需要,可以使用含磷助洗剂和无磷助洗剂的组合。
漂白剂
洗涤剂组合物可以包含漂白剂成分或材料。例如,漂白剂材料可以包含任何基于氧或氯的漂白剂。漂白剂材料可以选自已知用于洗涤剂组合物的任何常规漂白剂材料。所述材料可以包括活性漂白剂物质自身或该物质的前体。例如,漂白剂材料可以包含至少一种无机过氧化物或有机过酸或者基于氯的漂白剂,包括它们的衍生物和盐或它们的混合物。无机过氧化物包括过碳酸盐、过硼酸盐、过硫酸盐、过氧化氢以及它们的衍生物和盐。这些无机过氧化物的钠盐和钾盐是适合的,尤其是钠盐。过碳酸钠和过硼酸钠是最优选的,尤其是过碳酸钠。
洗涤剂组合物还可以包含漂白添加剂或漂白活化催化剂。取决于漂白性化合物的性质,组合物可以优选包含一种或多种漂白活化剂或漂白催化剂。如果是活化漂白剂材料所需的,可以包括任何合适的漂白活化剂,例如TAED。可以使用任何合适的漂白催化剂,例如乙酸锰或双核锰络合物,例如EP-A-1,741,774中所述的那些。诸如过苯甲酸和过氧羧酸(例如,PAP)等有机过酸不需要使用漂白活化剂或催化剂,因为这些漂白剂在相对低的温度(例如约30℃)下也有活性,这促使这些漂白剂材料在本发明中尤为优选。
在一个实施方式中,组合物在与PEI相同的液相或凝胶相中不含漂白剂(且优选也不含漂白活化剂或漂白催化剂)。
其他成分
本领域技术人员会知晓形成有效的ADW(自动餐具洗涤)洗涤剂组合物所需的成分的种类。洗涤剂组合物可以包括本领域已知的任何其它合适成分。
例如,洗涤剂组合物可以包含酶。优选的是,所述酶选自蛋白酶、脂酶、淀粉酶、纤维素酶和过氧化物酶,最优选蛋白酶和淀粉酶,尤其是蛋白酶。最优选的是,在本发明的组合物中包含蛋白酶和/或淀粉酶,因为这些酶在餐具洗涤用洗涤剂组合物中尤其有效。可以根据需要使用这些酶的任何合适的种类。可以使用多于一种种类。
ADW洗涤剂组合物可以包含一种或多种额外的抗腐蚀剂。这些抗腐蚀剂可以提供对抗玻璃和/或金属腐蚀的额外益处,并且该术语涵盖了旨在防止或减少非铁金属(特别是银和铜)的锈蚀(tarnishing)的试剂。
为了获得抗腐蚀益处,已知在洗涤剂组合物、特别是在自动餐具洗涤用组合物中包含多价离子源。例如,因为具备抑制这种腐蚀的能力,多价离子,尤其是锌、铋和/或锰离子已包含在内。WO 94/26860和WO 94/26859中提及了已知适合用作银/铜腐蚀抑制剂的有机和无机氧化还原活性物质。合适的无机氧化还原活性物质为,例如,选自由锌、铋、锰、钛、锆、铪、钒、钴和铈盐和/或络合物组成的组的金属盐和/或金属络合物,所述金属处于氧化态II、III、IV、V或VI中的一种。特别适合的金属盐和/或金属络合物选自由MnSO4、Mn(II)柠檬酸盐、Mn(II)硬脂酸盐、Mn(II)乙酰丙酮、Mn(II)[1-羟基乙烷-1,1-二膦酸盐]、V2O5、V2O4、VO2、TiOSO4、K2TiF6、K2ZrF6、CoSO4、Co(NO3)2、乙酸锌、硫酸锌和Ce(NO3)3组成的组。可以使用任何合适的多价离子来源,所述来源优选选自硫酸盐、碳酸盐、乙酸盐、葡糖酸盐和金属-蛋白化合物。锌盐是尤其优选的腐蚀抑制剂。
优选的银/铜抗腐蚀剂为苯并三唑(BTA)或二苯并三唑及其具有取代基的衍生物。其它合适的试剂是有机和/或无机氧化还原活性物质和石蜡油。苯并三唑衍生物是其芳香环上的可利用的取代位点被部分取代或完全取代的那些化合物。合适的取代基是直链或支化链C1-20烷基和羟基、巯基、苯基或卤素(例如氟、氯、溴和碘)。优选的具有取代基的苯并三唑为甲苯并三唑。
可以包含任何常规量的抗腐蚀剂。然而,优选的是,其以基于总重量为0.01重量%~5重量%、优选0.05重量%~3重量%、更优选0.1重量%~2.5重量%(例如,0.2重量%~2重量%)的总量存在。
还可以在洗涤剂组合物中包含旨在改善其清洁性能的聚合物。例如,可以使用磺酸化聚合物。优选的实例包括CH2=CR1-CR2R3-O-C4H3R4-SO3X的共聚物,其中,R1、R2、R3、R4独立地为1~6碳烷基或氢,且X为氢或具有任何合适的其它单体单元的碱,所述单体单元包括改性丙烯酸、富马酸、马来酸、衣康酸、乌头酸、中康酸、柠康酸和亚甲基丙二酸或其盐、马来酸酐、丙烯酰胺、烯、乙烯基甲基醚、苯乙烯及其任意混合物。其它合适的用于并入磺酸化聚合物(或共聚物)中的磺酸化单体为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以及它们的水溶性盐。适合的磺酸化聚合物也在US 5308532和WO 2005/090541中进行了描述。
当存在磺酸化聚合物时,其优选以至少0.1重量%、优选至少0.5重量%、更优选至少1重量%且最优选至少3重量%、至多40重量%、优选至多25重量%、更优选至多15重量%且最优选至多10重量%的量存在。
洗涤剂组合物还可以包含一种或多种泡沫控制剂。出于此目的的合适的泡沫控制剂都是本领域常规使用的那些泡沫控制剂,例如硅油及其衍生物以及石蜡油。泡沫控制剂优选以0.5重量%以下的量存在。
洗涤剂组合物还可以包含少量、常规量的防腐剂、香料等。
pH
ADW洗涤剂组合物还可以包含酸性源或碱性源以便在溶解时获得所需pH,尤其是当组合物将用于自动餐具洗涤应用中时。酸性源可以适当地为任何合适的酸性化合物,例如多羧酸。例如,碱性源可以是碳酸盐或碳酸氢盐(例如,碱金属或碱土金属盐)。碱性源可以适当地为任何合适的碱性化合物,例如,强碱与弱酸的任何盐。当需要碱性组合物时,硅酸盐属于合适的碱性源。优选的硅酸盐是硅酸钠,例如二硅酸钠、偏硅酸钠和结晶页硅酸盐。在一个实施方式中,组合物不含硅酸盐。
在一个实施方式中,组合物的pH为6~13、6.5~12、7~11或8~10。
将参考下述非限制性实施例进一步描述本发明。本发明范围内的其它实例对于本领域技术人员将显而易见。
实施例
实施例1
制备了容纳于三区室PVOH胶囊中的三相单剂量组合物。
区室1中的粉末配方1,剂量11g:
MGDA | 25% |
碳酸钠 | 30% |
过碳酸钠 | 20% |
柠檬酸 | 10% |
固体表面活性剂 | 15% |
区室3中的粉末配方2,剂量1.3g:
漂白活化剂(TAED) | 25% |
碳酸钠 | 25% |
助洗剂(聚丙烯酸盐、膦酸盐) | 22% |
蛋白酶 | 23% |
淀粉酶 | 5% |
具有玻璃保护剂的凝胶,剂量1.8g:
总PEI含量:7.6mg/单位剂量。
实施例2
在三区室PVOH袋中的含磷酸盐的3部分组合物。
粉末配方1——16g
STPP | 48.70% |
碳酸钠 | 16.00% |
柠檬酸三钠 | 22.00% |
苯并三唑 | 0.40% |
HEDP | 0.30% |
蛋白酶 | 1.50% |
淀粉酶 | 1.00% |
1,2-二丙二醇(1,2propylenedigylcol) | 1.00% |
磺酸化聚合物 | 5.00% |
粉末2——1.3g
过碳酸钠 | 100% |
凝胶组合物——2.5g
总PEI含量:5mg/单位剂量。
根据WO 2010/020765第14-16页所描述的玻璃腐蚀测试方法对实施例组合物1和2均进行了测试。两者均给出至少与WO 2010/020765的表5a和表5b中实施例3(其为固体配方)的结果等同的结果。在以工业规模制造组合物时,本发明的组合物的结果一致且可靠。
Claims (15)
1.一种包含聚亚乙基亚胺的自动餐具洗涤机洗涤剂组合物,其中所述聚亚乙基亚胺包含在所述组合物的凝胶相或液相中,且所述聚亚乙基亚胺的量小于所述组合物的1重量%。
2.如权利要求1所述的组合物,其中所述组合物包含:
小于0.5重量%、小于0.25重量%、小于0.05重量%、小于0.04重量%、小于0.03重量%、小于0.01重量%、小于0.005重量%或小于0.0025重量%的聚亚乙基亚胺;和/或
至少0.0001重量%的聚亚乙基亚胺。
3.如权利要求1或2所述的组合物,其中,所述组合物由所述凝胶相或液相构成。
4.如权利要求1或2所述的组合物,其中,所述组合物包含至少两个分离的相或者至少三个分离的相。
5.如权利要求4所述的组合物,其中所述组合物包含处于粉末、颗粒或压制固体形式的至少一个固相。
6.如前述权利要求中任一项所述的组合物,其中,包含所述聚亚乙基亚胺的所述凝胶相或液相:
含有占所述凝胶相或液相不多于5重量%、不多于3重量%、不多于1重量%的水,或者不含水;和/或
包含占所述凝胶相或液相至少10重量%、至少15重量%、至少20重量%或至少10重量%的表面活性剂,优选为非离子型表面活性剂。
7.如前述权利要求中任一项所述的组合物,其中,所述组合物包含不多于4重量%、不多于3重量%、不多于2重量%或不多于1重量%的阴离子型表面活性剂,或其中所述组合物不含阴离子型表面活性剂,或其中所述组合物不含离子型表面活性剂。
8.如前述权利要求中任一项所述的组合物,其中,所述组合物包含至少10重量%的助洗剂。
9.如前述权利要求中任一项所述的组合物,其中,所述组合物包含蛋白酶和/或淀粉酶和/或漂白剂。
10.如前述权利要求中任一项所述的组合物,其中,所述聚亚乙基亚胺的分子量为100~2500,优选为200~1500,优选为400~1200,优选为700~900。
11.如前述权利要求中任一项所述的组合物,其中,所述聚亚乙基亚胺:
在室温下为液体成分;和/或
不含烷氧基化基团或为均聚物;和/或
含有伯胺基团、仲胺基团和叔胺基团,并且伯胺基团与仲胺基团之比优选为1:0.5~1:1,优选为1:0.7~1:0.9。
12.包含如前述权利要求中任一项所述的组合物的产品,所述产品:
为单位剂量形式;和/或
容纳于水溶性或水分散性膜或容器、优选聚乙烯醇膜或容器之内。
13.一种自动餐具洗涤方法,所述方法包括:向自动餐具洗涤机中供给权利要求1~11中任一项所述的组合物或权利要求12所述的产品,并且将所述组合物或产品释放至所述自动餐具洗涤机的洗涤循环中。
14.如权利要求13所述的方法,所述方法包括:洗涤所述自动餐具洗涤机中的玻璃器皿。
15.权利要求1~11中任一项所述的组合物或权利要求12所述的产品在清洁玻璃器皿并同时抑制所述玻璃器皿在自动餐具洗涤期间受腐蚀中的应用。
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- 2014-05-30 GB GBGB1409631.7A patent/GB201409631D0/en not_active Ceased
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2015
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- 2015-06-01 CN CN201580028509.XA patent/CN106459844A/zh active Pending
- 2015-06-01 BR BR112016028134A patent/BR112016028134A2/pt not_active Application Discontinuation
- 2015-06-01 PL PL15726279T patent/PL3149142T3/pl unknown
- 2015-06-01 US US15/314,656 patent/US10815451B2/en active Active
- 2015-06-01 MX MX2016015525A patent/MX2016015525A/es unknown
- 2015-06-01 EP EP15726279.1A patent/EP3149142B1/en active Active
- 2015-06-01 CA CA2950044A patent/CA2950044A1/en not_active Abandoned
- 2015-06-01 WO PCT/GB2015/051596 patent/WO2015181571A1/en active Application Filing
- 2015-06-01 RU RU2016151725A patent/RU2672557C2/ru active
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2016
- 2016-12-08 ZA ZA2016/08493A patent/ZA201608493B/en unknown
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CN110382678A (zh) * | 2017-03-30 | 2019-10-25 | 陶氏环球技术有限责任公司 | 用于自动餐具洗涤制剂的分散剂系统 |
CN110382678B (zh) * | 2017-03-30 | 2021-06-18 | 陶氏环球技术有限责任公司 | 用于自动餐具洗涤制剂的分散剂系统 |
Also Published As
Publication number | Publication date |
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BR112016028134A2 (pt) | 2017-08-22 |
RU2672557C2 (ru) | 2018-11-16 |
AU2015265650A1 (en) | 2017-01-05 |
ZA201608493B (en) | 2018-05-30 |
RU2016151725A (ru) | 2018-07-02 |
RU2016151725A3 (zh) | 2018-07-02 |
CA2950044A1 (en) | 2015-12-03 |
EP3149142B1 (en) | 2020-06-17 |
GB201409631D0 (en) | 2014-07-16 |
EP3149142A1 (en) | 2017-04-05 |
MX2016015525A (es) | 2017-04-25 |
AU2015265650B2 (en) | 2019-05-16 |
WO2015181571A1 (en) | 2015-12-03 |
US10815451B2 (en) | 2020-10-27 |
PL3149142T3 (pl) | 2020-11-30 |
US20170191004A1 (en) | 2017-07-06 |
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