CN114026212A - 自动盘碟洗涤剂组合物 - Google Patents
自动盘碟洗涤剂组合物 Download PDFInfo
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- CN114026212A CN114026212A CN202080046325.7A CN202080046325A CN114026212A CN 114026212 A CN114026212 A CN 114026212A CN 202080046325 A CN202080046325 A CN 202080046325A CN 114026212 A CN114026212 A CN 114026212A
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000011962 puddings Nutrition 0.000 description 1
- 238000001303 quality assessment method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 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
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- 108010075550 termamyl Proteins 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
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000004711 α-olefin Substances 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
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- C11D1/66—Non-ionic compounds
- C11D1/835—Mixtures of non-ionic with cationic 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
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- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
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- 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
- C11D1/66—Non-ionic compounds
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
-
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- C11D17/0065—Solid detergents containing builders
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
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- C11D17/043—Liquid or thixotropic (gel) compositions
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- C11D17/045—Multi-compartment
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-salts thereof
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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
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- C11D3/2086—Hydroxy carboxylic acids-salts thereof
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- C11D3/32—Amides; Substituted amides
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- C11D3/361—Phosphonates, phosphinates or phosphonites
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- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
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- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
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- 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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- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38609—Protease or amylase in solid compositions only
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- C11D3/3905—Bleach activators or bleach catalysts
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- C11D1/02—Anionic compounds
- C11D1/34—Derivatives of acids of phosphorus
- C11D1/342—Phosphonates; Phosphinates or phosphonites
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- C11D2111/14—
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Abstract
本发明公开了一种自动盘碟洗涤清洁组合物,其包含:·a)混合助洗剂体系,该混合助洗剂体系包含可溶性助洗剂和结晶硅酸盐,其中所述可溶性助洗剂包含络合剂、膦酸盐和聚合物分散剂,并且其中该组合物中每种可溶性助洗剂的水平为:·a1)按组合物的重量计15%至40%的络合剂;·a2)按组合物的重量计2%至7%的膦酸盐;和·a 3)按组合物的重量计1%至7%的聚合物分散剂,其中可溶性助洗剂和结晶硅酸盐的重量比为8:1至15:1;·b)漂白体系,所述漂白体系包含漂白剂、漂白催化剂和漂白活化剂;以及·c)按组合物的重量计0%至20%的碳酸盐。
Description
技术领域
本发明涉及自动盘碟洗涤领域。特别地,其涉及能够提供有效清洁、光泽和护理的组合物。即使在具有高水平碳酸氢盐的硬水中使用时,组合物也可提供良好的茶渍去除。本发明还涉及一种使用所述组合物的方法和所述组合物用以提供茶渍去除的用途。
背景技术
预期自动盘碟洗涤使物品清洁和光泽,即不含污垢残留物、成膜和斑染。茶渍似乎是在自动盘碟洗涤中从餐具去除的最顽固的污渍之一。
WO2015/124384A1提供了单位剂量形式的零磷酸盐机器盘碟洗涤组合物,其包含相对低量的非磷酸盐助洗剂、碱金属过碳酸盐、锰漂白催化剂以及一种或多种聚羧酸酯聚合物。所述助洗剂包含以下中的一种或多种:甲基甘氨酸-N,N-二乙酸和/或其一种或多种盐、柠檬酸和/或其一种或多种盐、以及谷氨酸-N、N-二乙酸和/或其一种或多种盐。聚羧酸酯聚合物的重均分子量介于1000与100,000之间,所述聚合物包含至少20mol%的丙烯酸酯单体和0mol%至40mol%的马来酸酯单体。据说组合物在使用时提供改善的茶渍去除。
WO2015/0700976 A1提供了一种组合物,其包含a)10重量%至90重量%的一种或多种助洗剂,其中相对于所述一种或多种助洗剂的总量,至少10重量%由式(1)Na2SixO2x+1-y H2O的结晶页硅酸钠组成,其中x为1.9至4的数字并且y为0至20的数字,b)0.0025%至2.0000%的一种或多种漂白催化剂,c)0.1重量%至20重量%的一种或多种含氧漂白剂,d)0重量%至10重量%的一种或多种漂白活化剂,e)1重量%至85重量%的一种或多种pH调节剂,f)0重量%至10重量%的一种或多种表面活性物质,以及g)0重量%至5重量%的一种或多种酶;其中组分a)到g)的所述量与组合物的总量有关。该组合物在洗碗机中使用时具有优异的适用性。
尽管在过去已经进行了许多尝试,但仍然存在对在自动盘碟洗涤中去除茶渍并同时提供良好的清洁和光泽的尚未满足的需求。已经发现,茶渍去除高度依赖于在自动盘碟洗涤过程中使用的水的性质。这似乎与水中高水平的硬度和碳酸氢盐的存在特别相关。
最近,单位剂量产品诸如小袋已经广泛用于自动盘碟洗涤中。由于单位剂量产品从洗碗机分配器递送,因此它必须具有一定体积使得可以装配到分配器中。这限制了每次洗涤可使用的化学物质的量。
本发明的目的之一是提供一种自动盘碟洗涤组合物,其在各种水硬度的整个范围内提供良好的茶渍去除,并且同时提供其他污垢的良好清洁和光泽。优选地,所述组合物应适合以单位剂型存在。
发明内容
根据本发明的第一方面,提供了一种自动盘碟洗涤组合物。所述组合物提供有效的清洁,特别是茶渍去除,同时使洗涤的物品有光泽并提供对物品的护理。组合物适合以单位剂型提供。
自动盘碟洗涤剂组合物包含混合助洗剂体系。该混合助洗剂体系包含可溶性助洗剂和结晶硅酸盐。可溶性助洗剂和结晶硅酸盐的重量比为8:1至15:1。已经发现,可溶性助洗剂与结晶硅酸盐的重量比对于获得良好的清洁并且具有良好的光泽至关重要。具有在该范围之外的可溶性助洗剂与结晶硅酸盐比率的组合物似乎对经洗涤物品的成膜具有负面影响。
还已发现,该助洗剂体系需要多种助洗剂。不同的助洗剂似乎具有不同的助洗机制。即使使用较高水平的体系,利用具有较少种类的助洗剂的助洗剂体系也似乎不能获得相同的清洁和光泽性能。该混合助洗剂体系包含可溶性助洗剂和结晶硅酸盐。该可溶性助洗剂包含络合剂、膦酸盐和聚合物分散剂。
组合物还包含漂白体系。所述漂白体系包含漂白剂、漂白催化剂和漂白活化剂。
组合物还包含低水平的碳酸盐,优选地按组合物的重量计少于20%,更优选地少于15%。
具有一定重量比的可溶性助洗剂和结晶硅酸盐的混合助洗剂体系、漂白剂体系和低水平碳酸盐的特定组合产生了尤其是对于茶渍去除具有优异清洁特性的组合物。组合物还提供良好的光泽。即使当组合物呈单位剂型时也是如此。即使利用具有高水平碳酸氢盐的水,所述组合物也在广泛的水硬度范围内表现良好。
本发明的自动盘碟洗涤剂组合物包含:
a)混合助洗剂体系。该混合助洗剂体系包含可溶性助洗剂和结晶硅酸盐助洗剂。该可溶性助洗剂包含络合剂、膦酸盐和聚合物分散剂。该组合物中每种可溶性助洗剂的水平为:
a1)按所述组合物的重量计15%至40%的络合剂;
a2)按所述组合物的重量计2%至7%的膦酸盐;和
a3)按所述组合物的重量计1%至7%的聚合物分散剂
其中所述可溶性助洗剂和所述结晶硅酸盐助洗剂的重量比为8:1至15:1
b)漂白体系,所述漂白体系包含漂白剂、漂白催化剂和漂白活化剂;
以及
c)按所述组合物的重量计0%至20%的碳酸盐。
根据本发明的第二方面,提供了一种水溶性自动盘碟洗涤清洁小袋,其包含水溶性包封材料和本发明的组合物。
根据本发明的第三方面,提供了使用本发明的组合物进行自动盘碟洗涤的方法。该方法提供非常好的清洁,包括在广泛的水硬度条件下的茶清洁、光泽和护理。
根据本发明的第四方面,提供了本发明的组合物在自动盘碟洗涤中使用包含高水平碳酸氢盐的水(硬水)提供茶清洁的用途。
结合本发明的第一方面描述的本发明的组合物的元素作必要修改之后适用于本发明的其他方面。
具体实施方式
本发明设想了一种自动盘碟洗涤剂组合物,其包含混合助洗剂体系、漂白体系和低水平的碳酸盐。该混合助洗剂体系对于提供良好的清洁,特别是良好的茶清洁至关重要。
混合助洗剂体系包含多种助洗剂:高水平的非磷酸盐助洗剂,优选MGDA,更优选甲基甘氨酸-N,N-二乙酸的三钠盐,高水平的1-羟基乙烷1,1-二膦酸(HEDP)、聚合物分散剂和结晶硅酸盐。
漂白体系包含漂白剂、漂白催化剂和漂白活化剂。
本文的所述组合物优选地不含磷酸盐。所谓“不含磷酸盐”在本文中被理解为所述组合物包含按所述组合物的重量计少于1%、优选地少于0.1%的磷酸盐。
洗涤剂组合物
本发明的洗涤剂组合物可以以任何形式存在。优选地,该组合物或其部分呈松散粉末的形式,并且更优选地该组合物以单位剂型提供。本发明的组合物非常适于以多隔室包装的形式存在,更具体地以包括具有不同物理形式的组合物的隔室的多隔室包装的形式存在,例如一个隔室包含松散粉末形式的组合物并且另一个隔室包含液体形式的组合物。所述组合物优选地被水溶性薄膜如聚乙烯醇包封。组合物包含混合助洗剂体系和漂白体系,低水平的碳酸盐和任选的非离子表面活性剂、酶和玻璃和/或金属护理剂。优选地,组合物包含MGDA的三钠盐、HEDP、聚合物分散剂,优选包含2-丙烯酰胺基-2-甲基丙磺酸单体的磺化聚合物、结晶硅酸钠、碳酸钠、漂白剂,优选过碳酸钠、漂白活化剂,优选TAED、漂白催化剂,优选锰漂白催化剂和任选地但优选地蛋白酶和淀粉酶以及非离子表面活性剂。组合物优选地不含柠檬酸盐。组合物还可包含提供抗斑染有益效果的阳离子聚合物。
本发明的组合物优选地具有如在20℃下以1%重量/体积水性溶液在蒸馏水中测得的约9至约12、更优选约10至小于约11.5并且尤其是约10.5至约11.5的pH。
本发明的组合物在9.5的pH下优选地具有如在20℃下以100mL产品在NaOH中测得的约10至约20、更优选约12至约18的储备碱度。
混合助洗剂体系
络合剂
络合剂是能够螯合硬度离子,特别是钙和/或镁的材料。本发明的组合物包含高水平的络合剂,然而水平不应太高,否则酶特别是蛋白酶可能受到负面影响。过高水平的络合剂也可能对玻璃护理产生负面影响。
本发明的组合物包含按所述组合物的重量计15%至40%,优选20%至40%,更优选20%至35%的选自由以下项组成的组的络合剂:甲基甘氨酸-N,N-二乙酸(MGDA)、柠檬酸、谷氨酸-N,N-二乙酸(GLDA)及其盐以及它们的混合物。用于本文的特别优选的络合剂是MGDA的盐,特别是MGDA的三钠盐。优选地,本发明的组合物包含按所述组合物的重量计15%至40%的MGDA的三钠盐。
结晶硅酸钠
本发明的组合物包含按所述组合物的重量计2%至8%、优选地3%至6%的结晶硅酸钠。所述结晶硅酸钠优选地为层状硅酸盐,并且优选地具有组成NaMSix O2x+1.y H2O,其中M表示钠或氢,x为1.9至4并且y为0至20。
根据本发明使用的结晶硅酸钠在扫描电子显微镜照片中被证明是层状的。
根据式Na2SixO2x+1.y H2O的已知化合物,相应的化合物NaHSix O2x+1.y H2O可以通过用酸处理并且在一些情况下也用水处理来制备。由数字y给出的水含量在结晶水和附着水之间没有区分。M优选地表示钠。x的优选值为1.9至4。具有组成NaMSi2O5.y H2O的化合物是特别优选的。由于根据本发明所采用的硅酸钠是结晶化合物,因此它们可以容易地通过其X射线衍射图来表征。
优选的层状结晶硅酸盐是其中前述通式中的x假设值为1.9至3.5的那些。
特别地,δ-和β-二硅酸二钠(Na2Si2O5■yH2O)两者是优选的,其中β-二硅酸二钠可以例如通过WO 91/08171 A1中所述的方法获得。可以根据日本专利申请JP04/238809A或JP04/260610A制备具有介于1.9和3.2之间的SiO 2/Na 2O摩尔比的β-硅酸二钠。其还可以由无定形硅酸盐、实际上为上述通式(1)的无水结晶碱金属硅酸盐制备,其中x是1.9至2.1的数。
在此类试剂的另一优选实施方案中,使用具有1.8至3的SiO2/Na2O摩尔比的结晶钠层硅酸盐。在优选的形式中,结晶层状二硅酸二钠助洗剂由不同百分比的多态相α、β和δ一起形成。在商业生产的产品中,也可以存在无定形部分。
α、β和δ二硅酸二钠的定义是已知的,并且可以例如见于EP0164514A1中,如下所示。二钠状态优选地是层状结晶二硅酸二钠,其由二硅酸二钠的多态相和非层状硅酸钠性质的硅酸钠的多态相中的至少一种组成。特别优选的是使用含量为80重量%至100重量%的δ-二硅酸二钠的结晶钠层硅酸盐。在另外优选的变型中,也可以使用含量为70重量%至100重量%的β二钠二硅酸二钠的结晶钠层硅酸盐。
特别优选使用的结晶钠层硅酸盐含有1重量%至40重量%的α二硅酸二钠、0重量%至50重量%,具体地0重量%至45重量%的β二硅酸二钠、50重量%至98重量%的δ二硅酸二钠和0重量%至40重量%的非硅酸盐硅酸钠(无定形部分)。
非常特别优选地使用的结晶层状硅酸钠含有7重量%至21重量%的α二硅酸二钠、0重量%至12重量%的β二硅酸二钠、65重量%至95重量%的δ二硅酸二钠和0重量%至20重量%的无定形部分。
上述α-二硅酸二钠对应于EP0164514 A1中描述的Na-SK-S5,其通过由分配给α-Na2Si2O5的X射线衍射数据再现的那些来表征。X射线衍射图可从粉末衍射标准联合委员会获得并以号18-1241,22-1397、22-1397A、19-1233、19-1234和19-1237注册。
上述β-二硅酸二钠对应于EP064514 A1中描述的Na-SKS-7,其通过分配给β-Na2Si2O5的X射线衍射数据那里再现的那些来表征。X射线衍射图可从粉末衍射标准联合委员会获得并以号24-1 123和29-1261注册。
上述δ-二硅酸二钠对应于EP0164514A中描述的Na-SKS-6,其通过分配给δ-Na2Si2O5的X射线衍射数据那里再现的那些来表征。X射线衍射图案以号22-1396向粉末衍射标准联合委员会注册。
根据本发明的组合物包含颗粒形式的式(1)的结晶钠层硅酸盐,以及含有结晶钠层硅酸盐和微溶金属碳酸盐的共颗粒,如例如WO2007/101622 A1中所述。
在本发明的另一优选实施方案中,根据本发明的组合物含有结晶二硅酸钠Na2Si205■yH20,其中y=0至2。
在优选的形式中,结晶层状硅酸钠另外含有阳离子和/或阴离子成分。阳离子成分优选为碱金属和/或碱土金属阳离子和/或Fe、W、Mo、Ta、Pb、Al、Zn、Ti、V、Cr、Mn、Co和/或Ni的组合。
阴离子成分优选为铝酸盐、硫酸盐、氟化物、氯化物、溴化物、碘化物、碳酸盐、碳酸氢盐、硝酸盐、氧化物水合物、磷酸盐和/或硼酸盐。
在结晶层状硅酸钠的替代优选形式中,含有基于SiO2的总含量计至多10mol%的硼。在结晶层状硅酸钠的另一替代优选形式中,包含基于SiO2的总含量计至多20mol%的磷。
另外,特别优选的是由式β-Na水热制备的二硅酸钠为2Si205,如专利文献WO92/09526 A1、US-A-5,417,951、DE 41 02 743 A1和WO92/13935 A1中所描述,
作为钠层硅酸盐,特别优选根据WO00/09444 A1的那些。
另外优选的钠层硅酸盐是根据EP 0 550 048 A1和EP 0 630 855 A1的那些。
用于本文的特别优选的硅酸盐具有式:Na2Si2O5。
碳酸盐
本发明的组合物包含低水平的碳酸盐。其包含按所述组合物的重量计0%至20%,优选地0%至15%的碳酸钠。
膦酸盐
本发明的组合物包含高水平的膦酸盐,优选HEDP。其包含按所述组合物的重量计2%至7%,优选地2%至6%的HEDP。
聚合物分散剂
聚合物分散剂以按所述组合物的重量计约1%至约7%、优选地2%至约6%的任意合适的量使用。
聚合物分散剂能够在自动盘碟洗涤过程中混悬钙或碳酸钙。优选地,所述聚合物分散剂为多元羧酸的磺化衍生物,并且可包含两种、三种、四种或更多种不同的单体单元。优选的共聚物包含:
至少一个衍生自具有通式(III)的羧酸单体的结构单元:
其中R1至R3独立地选自氢、甲基、具有2至12个碳原子的直链或支链的饱和烷基基团、具有2至12个碳原子的直链或支链的单不饱和或多不饱和的烯基基团、如前述被–NH2或-OH、或–COOH、或COOR4取代的烷基或烯基基团,其中R4选自氢、碱金属或具有2至12个碳的直链或支链的、饱和或不饱和的烷基或烯基基团;
优选的羧酸单体包括下列中的一种或多种:丙烯酸、马来酸、马来酸酐、衣康酸、柠康酸、2-苯基丙烯酸、肉桂酸、巴豆酸、富马酸、甲基丙烯酸、2-乙基丙烯酸、亚甲基丙二酸或山梨酸。丙烯酸和甲基丙烯酸是更优选的。
任选地,一个或多个衍生自至少一种具有通式(IV)的非离子单体的结构单元:
其中R5至R7独立地选自氢、甲基、苯基或含有1至6个碳原子的羟烷基基团,并且可以是环状结构的一部分,X为选自-CH2-、-COO-、-CONH-或-CONR8-的任选地存在的间隔基团,并且R8选自具有1至22个碳原子的直链或支链的饱和烷基基团或具有6至22个碳原子的不饱和、优选芳族的基团。
优选的非离子单体包括下列中的一种或多种:丁烯、异丁烯、戊烯、2-甲基戊-1-烯、3-甲基戊-1-烯、2,4,4-三甲基戊-1-烯、2,4,4-三甲基戊-2-烯、环戊烯、甲基环戊烯、2-甲基-3-甲基-环戊烯、己烯、2,3-二甲基己-1-烯、2,4-二甲基己-1-烯、2,5-二甲基己-1-烯、3,5-二甲基己-1-烯、4,4-二甲基己-1-烯、环己烯、甲基环己烯、环庚烯、具有10个或更多个碳原子的α-烯烃诸如癸-1-烯、十二碳-1-烯、十六碳-1-烯、十八碳-1-烯和二十二碳-1-烯,优选的芳族单体为苯乙烯、α-甲基苯乙烯、3-甲基苯乙烯、4-十二烷基苯乙烯、2-乙基-4-苄基苯乙烯、4-环己基苯乙烯、4-丙基苯乙烯、1-乙烯基萘、2-乙烯基萘;优选的羧酸酯单体为(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯和(甲基)丙烯酸二十二烷基酯;优选的酰胺为N-甲基丙烯酰胺、N-乙基丙烯酰胺、N-叔丁基丙烯酰胺、N-2-乙基己基丙烯酰胺、N-辛基丙烯酰胺、N-月桂基丙烯酰胺、N-硬脂基丙烯酰胺、N-二十二烷基丙烯酰胺;以及至少一个衍生自至少一种具有通式(V)和(VI)的磺酸单体的结构单元:
其中R7为包含至少一个sp2键的基团,A为O、N、P、S、酰胺基或酯键,B为单环或多环芳族基团或脂族基团,每个t独立地为0或1,并且M+为阳离子。在一个方面,R7为C2至C6烯烃。在另一方面,R7为乙烯、丁烯或丙烯。
优选的磺化单体包括下列中的一种或多种:1-丙烯酰胺-1-丙磺酸、2-丙烯酰胺-2-丙磺酸、2-丙烯酰胺-2-甲基-1-丙磺酸、2-甲基丙烯酰胺-2-甲基-1-丙磺酸、3-甲基丙烯酰胺-2-羟基-丙磺酸、烯丙基磺酸、甲基烯丙基磺酸、烯丙氧基苯磺酸、甲基烯丙氧基苯磺酸、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、3-磺基丙基、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、以及所述酸的混合物或它们的水溶性盐。
优选地,所述聚合物包含以下含量的单体:按所述聚合物的重量计约40%至约90%、优选地约60%至约90%的一种或多种羧酸单体;按所述聚合物的重量计约5%至约50%、优选地约10%至约40%的一种或多种磺酸单体;以及任选地按所述聚合物的重量计约1%至约30%、优选地约2%至约20%的一种或多种非离子单体。特别优选的聚合物包含按所述聚合物的重量计约70%至约80%的至少一种羧酸单体,以及按所述聚合物的重量计约20%至约30%的至少一种磺酸单体。
在所述聚合物中,羧酸基团或磺酸基团中的全部或一些可以中和形式存在,即,一些或全部酸基团中的羧酸基团和/或磺酸基团的酸性氢原子可用金属离子、优选地碱金属离子并且具体地用钠离子替代。
羧酸优选地为(甲基)丙烯酸。磺酸单体优选地为2-丙烯酰胺-2-丙磺酸(AMPS)。
优选的可商购获得的聚合物包括:由Alco Chemical提供的Alcosperse 240、Aquatreat AR 540和Aquatreat MPS;由Dow提供的Acumer 3100、Acumer 2000、Acusol587G和Acusol 588G;由BF Goodrich提供的Goodrich K-798、K-775和K-797;以及由ISPtechnologies Inc提供的ACP 1042。特别优选的聚合物是由Rohm&Haas提供的Acusol 587G和Acusol 588G。
合适的聚合物分散剂包括低分子量的阴离子羧酸聚合物。它们可以是重均分子量小于或等于约200000g/mol、或小于或等于约75000g/mol、或小于或等于约50000g/mol、或约3000g/mol至约50000g/mol、优选地约5000g/mol至约45000g/mol的均聚物或共聚物。聚合物分散剂可以是聚丙烯酸酯的低分子量均聚物,其平均分子量为1000至20000,具体地2000至10000,并且具体地优选3000至5000。
聚合物分散剂可以是分子量小于70000的丙烯酸与甲基丙烯酸的共聚物、丙烯酸和/或甲基丙烯酸与马来酸的共聚物、以及丙烯酸和/或甲基丙烯酸与富马酸的共聚物。其分子量在2000g/mol至80000g/mol并且更优选地20000g/mol至50000g/mol并且具体地30000g/mol至40000g/mol的范围内,并且(甲基)丙烯酸酯与马来酸酯或延胡索酸酯链段的比率为30:1至1:2。
聚合物分散剂可以是分子量为3000至100000或者4000至20000的丙烯酰胺和丙烯酸酯的共聚物,并且也可使用按聚合物分散剂的重量计小于50%或者小于20%的丙烯酰胺含量。另选地,此类聚合物分散剂可具有按所述聚合物的重量计4000至20000的分子量和0%至15%的丙烯酰胺含量。
适用于本文的聚合物分散剂还包括衣康酸均聚物和共聚物。另选地,聚合物分散剂可选自由烷氧基化聚亚烷基亚胺、烷氧基化聚羧酸酯、聚乙二醇、苯乙烯共聚物、硫酸纤维素酯、羧化多糖、两亲性接枝共聚物以及它们的混合物组成的组。
漂白体系
漂白剂
本发明的组合物优选地包含按所述组合物的重量计约8%至约30%、更优选地约9%至约25%、甚至更优选地约9%至约20%的漂白剂。
无机漂白剂和有机漂白剂适用于本文。无机漂白剂包括过氧化氢合物盐,诸如过硼酸盐、过碳酸盐、过硫酸盐和过硅酸盐。无机过氧化氢合物盐通常为碱金属盐。无机过氧化氢合物盐可作为结晶固体包含在内,而无需另外的保护。另选地,盐可为经涂覆的。合适的涂料包含硫酸钠、碳酸钠、硅酸钠以及它们的混合物。所述涂料可作为混合物施加到表面或依次施加成层。
碱金属过碳酸盐、具体地过碳酸钠是优选用于本文的漂白剂。过碳酸盐最优选地以涂覆形式掺入到产品中,这提供了产品内的稳定性。
过氧单过硫酸钾是可用于本文的另一种无机过氧化氢合物盐。
典型的有机漂白剂是有机过氧酸,尤其是十二烷二过氧酸、十四烷二过氧酸和十六烷二过氧酸。单过壬二酸和二过壬二酸、单过十三烷二酸和二过十三烷二酸也适用于本文。二酰基和四酰基过氧化物例如过氧化二苯甲酰和过氧化二月桂酰是可用于本发明上下文的其他有机过氧化物。
其他典型的有机漂白剂包括过氧酸,具体示例是烷基过氧酸和芳基过氧酸。优选的代表是(a)过氧苯甲酸及其环取代的衍生物,诸如烷基过氧苯甲酸,以及过氧-α-萘甲酸和单过邻苯二甲酸镁,(b)脂族或取代的脂族过氧酸,诸如过氧月桂酸、过氧硬脂酸、ε-邻苯二甲酰亚胺过氧己酸[邻苯二甲酰亚氨基过氧己酸(PAP)]、邻羧基苯甲酰胺基过氧己酸、N-壬烯酰胺基过己二酸和N-壬烯酰胺基过琥珀酸盐,以及(c)脂族和芳脂族过氧二羧酸,诸如1,12-二过氧羧酸、1,9-二过氧壬二酸、二过氧癸二酸、二过氧十三烷二酸、二过氧邻苯二甲酸、2-癸基二过氧丁烷-1,4-二酸、N,N-对苯二甲酰二(6-氨基过己酸)。
漂白活化剂
漂白活化剂通常是能在60℃和更低的温度下在清洁过程中增强漂白作用的有机过酸前体。适用于本文的漂白活化剂包括在过水解条件下提供优选具有1至12个碳原子、具体地2至10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。合适的物质具有指定碳原子数的O-酰基和/或N-酰基基团和/或任选取代的苯甲酰基基团。优选的是聚酰化亚烷基二胺、具体地四乙酰基乙二胺(TAED),酰化三嗪衍生物、具体地1,5-二乙酰基-2,4-二氧代六氢-1,3,5-三嗪(DADHT),酰化甘脲、具体地四乙酰基甘脲(TAGU),N-酰基酰亚胺、具体地N-壬酰基琥珀酰亚胺(NOSI),酰化酚磺酸盐、具体地正壬酰基或异壬酰基氧基苯磺酸盐(正-或异-NOBS)、癸酰氧基苯甲酸(DOBA),羧酸酐具体地邻苯二甲酸酐,酰化多元醇、具体地甘油三乙酸酯、乙二醇二乙酸酯和2,5-二乙酰氧基-2,5-二氢呋喃,以及乙酰柠檬酸三乙酯(TEAC)。如果存在的话,本发明的组合物包含按所述组合物的重量计0.01%至5%、优选地0.2%至2%的漂白活化剂,优选TAED。
漂白催化剂
本文的组合物优选地包含漂白催化剂,优选含金属的漂白催化剂。更优选地,所述含金属的漂白催化剂是含过渡金属的漂白催化剂,尤其是含锰或钴的漂白催化剂。
优选用于本文的漂白催化剂包括锰三氮杂环壬烷及相关络合物;Co、Cu、Mn和Fe联吡啶胺及相关络合物;以及五胺乙酸钴(III)及相关络合物。
优选地,本发明的组合物包含按所述组合物的重量计0.001%至0.5%、更优选地0.002%至0.05%的漂白催化剂。优选地,所述漂白催化剂为锰漂白催化剂。
表面活性剂
适用于本文的表面活性剂包括非离子表面活性剂,优选地,所述组合物不含任何其他表面活性剂。传统上,非离子表面活性剂已在自动盘碟洗涤中被用于表面改性目的,具体地用于片材,以避免成膜和斑染并改善光泽度。据发现,非离子表面活性剂还可有助于防止污垢再沉积。
优选地,本发明的组合物包含非离子表面活性剂或非离子表面活性剂体系,更优选地,所述非离子表面活性剂或非离子表面活性剂体系具有介于40℃和70℃之间、优选地介于45℃和65℃之间的相转化温度,如在蒸馏水中以1%的浓度测得。所谓“非离子表面活性剂体系”在本文中是指两种或更多种非离子表面活性剂的混合物。优选用于本文的是非离子表面活性剂体系。与单一非离子表面活性剂相比,非离子表面活性剂体系似乎具有改善的清洁和修整特性以及在产品中更好的稳定性。
相转化温度是这样的温度,在低于该温度时,表面活性剂或其混合物作为油溶胀的胶束优先分配到水相中,并且在高于该温度时,则作为水溶胀的反相胶束优先分配到油相中。相转化温度可通过识别在哪个温度下发生浑浊而目视确定。
非离子表面活性剂或体系的相转化温度可如下测定:制备在蒸馏水中包含按所述溶液的重量计1%的对应表面活性剂或混合物的溶液。在相转化温度分析之前轻轻搅拌溶液,以确保该过程在化学平衡下发生。通过在75mm密封玻璃试管中浸入溶液,在热稳定浴中获取相转化温度。为了确保不存在渗漏,在相转化温度测量之前和之后称量试管的重量。温度以小于1℃/分钟的速率逐渐升高,直到温度达到低于预估的相转化温度几度。相转化温度在第一浊度标志下目视确定。
合适的非离子表面活性剂包括:i)乙氧基化非离子表面活性剂,其通过具有6至20个碳原子的一羟基链烷醇或烷基酚与优选每摩尔醇或烷基酚至少12摩尔、尤其优选至少16摩尔并且还更优选至少20摩尔的环氧乙烷的反应制备;ii)具有6至20个碳原子和至少一个乙氧基和丙氧基基团的醇烷氧基化表面活性剂。优选可用于本文的是表面活性剂i)和ii)的混合物。
其他合适的非离子表面活性剂是由下式表示的环氧封端的聚(烷氧基化)醇:
R1O[CH2CH(CH3)O]x[CH2CH2O]y[CH2CH(OH)R2] (I)
其中R1为具有4至18个碳原子的直链或支链的脂族烃基;R2为具有2至26个碳原子的直链或支链的脂族烃基;x为平均值为0.5至1.5、更优选地约1的整数;并且y为值为至少15、更优选地至少20的整数。
优选地,式I的表面活性剂在末端环氧化物单元[CH2CH(OH)R2]中具有至少约10个碳原子。根据本发明,式I的合适表面活性剂是Olin Corporation的SLF-18B非离子表面活性剂,如1994年10月13日由Olin Corporation公布的WO 94/22800中所述。
酶
在描述本文的酶变体时,使用以下命名法以便于参考:原始氨基酸:位置:取代的氨基酸。使用用于氨基酸的标准酶IUPAC 1-字母代码。
蛋白酶
本发明的组合物在去除蛋白质污垢的方面是有益的,特别是糖类燃烧污垢诸如焦糖布丁。
合适的蛋白酶包括金属蛋白酶和丝氨酸蛋白酶(包括中性或碱性微生物丝氨酸蛋白酶),诸如枯草杆菌蛋白酶(EC 3.4.21.62)以及其经化学改性或经基因修饰的突变体。合适的蛋白酶包括枯草杆菌蛋白酶(EC 3.4.21.62),包括来源于芽孢杆菌属(Bacillus),诸如迟缓芽孢杆菌(Bacillus lentus)、嗜碱芽孢杆菌(B.alkalophilus)、枯草芽孢杆菌(B.subtilis)、解淀粉芽孢杆菌(B.amyloliquefaciens)、短小芽孢杆菌(Bacilluspumilus)和吉氏芽孢杆菌(Bacillus gibsonii)的那些。
用于本发明的洗涤剂的特别优选的蛋白酶是表现出与来自迟缓芽孢杆菌的野生型酶的至少90%、优选至少95%、更优选至少98%、甚至更优选至少99%、特别是100%的同一性的多肽,使用如WO00/37627(其以引用方式并入本文)中所示的BPN'编号系统和氨基酸缩写,所述多肽在下列位置中的一个或多个、优选两个或更多个、并且更优选三个或更多个位置中包含突变:V68A、N87S、S99D、S99SD、S99A、S101G、S101M、S103A、V104N/I、G118V、G118R、S128L、P129Q、S130A、Y167A、R170S、A194P、V205I和/或M222S。
最优选地,蛋白酶选自相对于PB92野生型(WO 08/010925中的SEQ ID NO:2)或枯草杆菌蛋白酶309野生型(按照PB92主链的序列,除了包含自然变异N87S外)包含下列突变(BPN'编号系统)的组。
(i)G118V+S128L+P129Q+S130A
(ii)S101M+G118V+S128L+P129Q+S130A
(iii)N76D+N87R+G118R+S128L+P129Q+S130A+S188D+N248R
(iv)N76D+N87R+G118R+S128L+P129Q+S130A+S188D+V244R
(v)N76D+N87R+G118R+S128L+P129Q+S130A
(vi)V68A+N87S+S101G+V104N
合适的可商购获得的蛋白酶包括由Novozymes A/S(Denmark)以商品名和销售的那些,由Genencor International以商品名Purafect和Purafect销售的那些,由Solvay Enzymes以商品名和销售的那些,购自Henkel/Kemira的那些,即BLAP。
本发明的组合物中蛋白酶的优选含量包括每克组合物约0.2mg至约2mg活性蛋白酶。
淀粉酶
本发明的组合物可包含淀粉酶。优选的碱性淀粉酶来源于芽孢杆菌(Bacillus)的菌株,诸如地衣芽孢杆菌(Bacillus licheniformis)、解淀粉芽孢杆菌(Bacillusamyloliquefaciens)、嗜热脂肪芽胞杆菌(Bacillus stearothermophilus)、枯草芽孢杆菌(Bacillus subtilis)或其他芽孢杆菌属(Bacillus sp.),诸如芽孢杆菌属NCIB 12289、NCIB 12512、NCIB 12513、DSM 9375(USP 7,153,818)DSM 12368、DSMZ号12649、KSM AP1378(WO 97/00324)、KSM K36或KSM K38(EP 1,022,334)。优选的淀粉酶包括:
(a)US 5,856,164和WO99/23211、WO 96/23873、WO00/60060和WO 06/002643中所述的变体,特别是相对于AA560 SEQ ID No.3在以下位置中具有一个或多个置换的变体:
9、26、30、33、82、37、106、118、128、133、149、150、160、178、182、186、193、195、202、214、231、256、257、258、269、270、272、283、295、296、298、299、303、304、305、311、314、315、318、319、320、323、339、345、361、378、383、419、421、437、441、444、445、446、447、450、458、461、471、482、484,这些变体优选地还包含D183*和G184*的缺失。
(b)表现出与来自芽孢杆菌属707(Bacillus sp.707)的野生型酶(US 6,093,562中的SEQ ID NO:7)具有至少95%同一性的变体,尤其是包含一个或多个以下突变的那些:M202、M208、S255、R172和/或M261。优选地,所述淀粉酶包括M202L或M202T突变中的一者。
合适的可商购获得的α-淀粉酶包括 TERMAMYL STAINZYME 和(Novozymes A/S,Bagsvaerd,Denmark),AT 9000 Biozym Biotech TradingGmbH Wehlistrasse 27b A-1200 Wien Austria、 OPTISIZE HTEXCELLENZTM S系列(包括EXCELLENZTM S 1000和EXCELLENZTM S 2000)和PURASTAR(DuPont Industrial Biosciences.,Palo Alto,California)和(Kao,14-10Nihonbashi Kayabacho,1-chome,Chuo-ku Tokyo 103-8210,Japan)。特别优选用于本文的淀粉酶包括 STAINZYMEEXCELLENZTMS 1000、EXCELLENZTM S2000以及它们的混合物。
优选地,本发明的组合物包含至少0.005mg、优选地约0.0025mg至约0.025mg、更优选地约0.05mg至约0.3mg、特别是约0.01mg至约0.25mg活性淀粉酶。
优选地,本发明组合物的蛋白酶和/或淀粉酶为颗粒形式,所述颗粒包含按所述颗粒的重量计大于29%的硫酸钠,并且/或者硫酸钠和活性酶(蛋白酶和/或淀粉酶)的重量比介于3:1和100:1之间,或优选地介于4:1和30:1之间,或更优选地介于5:1和20:1之间。
金属护理剂
金属护理剂可防止或减少金属(包括铝、不锈钢和有色金属,诸如银和铜)的失泽、腐蚀或氧化。优选地,本发明的组合物包含按产品的重量计0.1%至5%、更优选0.2%至4%并且尤其是0.3%至3%的金属护理剂,优选地,该金属护理剂为苯并三唑(BTA)。
玻璃护理剂
玻璃护理剂可在盘碟洗涤过程中保护玻璃物品的外观。优选地,本发明的组合物包含按组合物的重量计0.1%至5%、更优选0.2%至4%并且尤其是0.3%至3%的金属护理剂,优选地,该玻璃护理剂为含锌材料,尤其是水锌矿。
阳离子聚合物
所述组合物优选地包含按组合物的重量计0.5%至5%,优选地0.5%至2%的阳离子聚合物。该阳离子聚合物提供成膜有益效果。该阳离子聚合物以共聚形式包含:
i.60重量%至99重量%的至少一种式I的单烯键式不饱和聚环氧烷单体(单体(A))的阳离子聚合物
其中变量具有以下含义:
如果Y为-O-,则X为-CH2-或-CO-;
如果Y为-NH-,则X为-CO-;
Y为-O-或-NH-;
R1为氢或甲基;
R2为相同或不同的C2-C6亚烷基基团;
R3为H或C1-C4烷基;
n为3至100、优选地15至60的整数,
ii.1重量%至40重量%的至少一种季铵化含氮单体(单体(B))的阳离子聚合物,所述至少一种季铵化含氮单体选自由式IIa至式IId的单体中的至少一者组成的组
其中变量具有以下含义:
R为C1-C4烷基或苄基;
R'为氢或甲基;
Y为-O-或-NH-;
A为C1-C6亚烷基;
X-为卤离子、C1-C4烷基硫酸根、C1-C4烷基磺酸根和C1-C4烷基碳酸根,
iii.0重量%至15重量%的至少一种阴离子单烯键式不饱和单体(单体(C))的阳离子聚合物,以及
iv.0重量%至30重量%的至少一种其他非离子单烯键式不饱和单体(单体(D))的阳离子聚合物,
并且所述阳离子聚合物具有2,000g/mol至500,000g/mol,优选地25,000g/mol至200,000g/mol的重均分子量(Mw)。
在优选的阳离子聚合物中,单体(A)的变量具有以下含义:
X为-CO-;
Y为-O-;
R1为氢或甲基;
R2为亚乙基、直链或支链亚丙基或它们的混合物;
R3为甲基
n为15至60的整数,
优选地,阳离子聚合物包含60重量%至98重量%的单体(A)和1重量%至39重量%的单体(B)以及0.5重量%至6重量%的单体(C)。
在优选的阳离子聚合物中,单体(A)是甲基聚乙二醇(甲基)丙烯酸酯,并且其中单体(B)是3-甲基1-乙烯基咪唑的盐。
优选地,阳离子聚合物包含69至89%的单体(A)和9至29%的单体(B)。
在优选的阳离子聚合物中,单体(A)与单体(B)的重量比≥2:1,并且对于其中共聚物包含单体(C)的情况,单体(B)与单体(C)的重量比也≥2:1,更优选地≥2.5:1,并且优选地单体(A)包括甲基聚乙二醇(甲基)丙烯酸酯且单体(B)包括3-甲基1-乙烯基咪唑的盐。
本发明的自动盘碟洗涤组合物优选地具有如在25℃下以1%重量/体积水性溶液在蒸馏水中测得的大于10,更优选地大于10.5的pH。
本发明的自动盘碟洗涤组合物在pH为9.5下优选具有约10至约20、更优选约12至约18的储备碱度,如在20℃下以100克产品在NaOH中测得的。
根据本发明的优选组合物包含:
a1)按所述组合物的重量计20%至40%的MGDA,优选甲基甘氨酸-N,N-二乙酸的三钠盐;
a2)按所述组合物的重量计2%至6%的结晶硅酸钠,其具有结晶层状结构和组成NaMSix O2x+1.y H2O,其中M表示钠或氢,x为1.9至4的数字并且y为0至20的数字,所述结晶硅酸钠优选地具有式Na2Si2O5。
a3)按所述组合物的重量计0%至20%的碳酸盐;
a4)按所述组合物的重量计2%至6%的HEDP;
a5)按所述组合物的重量计2%至6%的聚合物分散剂,优选磺酸盐聚合物;
b1)按所述组合物的重量计8%至30%的过碳酸钠;
b2)按所述组合物的重量计0.001%至0.5%的锰漂白催化剂;
b3)按所述组合物的重量计0.5%至5%的TAED;
c)非离子表面活性剂;
d)淀粉酶;
e)蛋白酶;以及任选的
f)玻璃和/或金属护理剂。
自动盘碟洗涤方法
本发明的方法包括使餐具接触本发明的组合物的步骤。该方法在所有类型的水,即具有不同硬度的水,即使是含有高水平的碳酸氢盐的水中提供非常好的清洁。所谓“硬水”在本文中是指具有2.5mmol/l至6.5mmol/l的钙和镁离子的水。
实施例
制备两种自动盘碟洗涤清洁组合物。根据本发明的比较组合物A和比较组合物B。评估茶渍去除。
MGDA:甲基甘氨酸-N,N-二乙酸的三钠盐
(1)Sokalan PA25CL
(2)无定形二硅酸钠Britesil H20
茶杯制备
制备下列溶液:
储备溶液#1:将6.56g CaCl2.2H2O溶解在100ml脱矿质水中
储备溶液#2:将3.80g MgSO4.7H2O溶解在100ml脱矿质水中
储备溶液#3:将6.72g NaHCO3溶解在100ml脱矿质水中
合成硬度水:将50ml的储备溶液1、2和3中的每一者置于具有7升脱矿质水的容器中,并且用额外的脱矿质水填充至10升。用HCl或NaOH将pH调节至7.5。
铁储备溶液:将5g Fe2(SO4)3和1ml HCl(37%)溶解于脱矿质水中至1升总体积。
称重2×30g“Twinnings Assam”散装茶叶,并转移到2个茶袋中。
将4升合成硬度水置于水壶中。在水壶中加入0.2ml的铁(III)溶液。将水壶通电,并使茶溶液煮沸。一旦茶溶液煮沸,就切断水壶的电源,并加入2个茶袋。让茶泡5分钟,然后去除茶袋。
将茶杯填充有100ml茶溶液。5分钟后,去除20ml茶溶液。这重复5次,使得所有茶从茶杯中去除。在5次去除20ml茶溶液后,也去除茶杯底部处的茶溶液的剩余薄层。用新鲜冲煮的茶溶液再次重复此整个过程。
自动洗碗机中的洗涤测试
具有21gpg水的Miele GSL 50C R-zeit 2(8min)KI 65用于测试。
将组合物在小瓶中称重,所述小瓶在分配器的打开时刻在洗碗机的底部处倒置。在洗涤循环开始时放入50g IKW压载污垢(“Recommendations for the QualityAssessment of the Cleaning Performance of Dishwasher Detergents(部分B,更新2015),SOFW-Journal第142卷,2016年6月)。
茶清洁的评估
洗涤后,将茶杯从洗碗机中取出并使其干燥。然后通过目视检查对茶杯进行分级。向每个杯给出在1(=最差污渍去除)至10(=最佳污渍去除)范围内的茶渍去除得分。通过与等级介于1-10之间的参考茶杯进行比较给出得分。计算整个洗涤循环中每个茶杯类型的平均茶杯得分。
结果
茶杯清洁等级:
A | B | |
茶杯 | 3.3 | 8.8 |
即使本发明的组合物具有比比较组合物更低水平的碳酸盐,本发明的组合物的茶渍去除也更好。
本文所公开的量纲和值不应理解为严格限于所引用的精确数值。相反,除非另外指明,否则每个此类量纲旨在表示所述值以及围绕该值功能上等同的范围。例如,公开为“40mm”的量纲旨在表示“约40mm”。
Claims (16)
1.一种自动盘碟洗涤清洁组合物,其包含:
a)混合助洗剂体系,所述混合助洗剂体系包含可溶性助洗剂和结晶硅酸盐,
其中所述可溶性助洗剂包含络合剂、膦酸盐和聚合物分散剂,并且
其中所述组合物中每种可溶性助洗剂的水平为:
a1)按所述组合物的重量计15%至40%的所述络合剂;
a2)按所述组合物的重量计2%至7%的所述膦酸盐;和
a3)按所述组合物的重量计1%至7%的所述聚合物分散剂,
其中所述可溶性助洗剂和所述结晶硅酸盐的重量比为8:1至15:1;
b)漂白体系,所述漂白体系包含漂白剂、漂白催化剂和漂白活化剂;以及
c)按所述组合物的重量计0%至20%的碳酸盐。
2.根据权利要求1所述的组合物,其中所述络合剂选自由以下项组成的组:甲基甘氨酸-N,N-二乙酸(MGDA)、柠檬酸、谷氨酸-N,N-二乙酸(GLDA)、它们的盐以及它们的混合物。
3.根据权利要求1或2中任一项所述的组合物,其包含:
a1)按所述组合物的重量计20%至40%的所述络合剂;
a2)按所述组合物的重量计2%至6%的膦酸盐;
a3)按所述组合物的重量计2%至6%的聚合物分散剂。
4.根据前述权利要求中任一项所述的组合物,其中所述络合剂包括MGDA,并且所述漂白体系包含过碳酸盐、锰催化剂和TAED。
5.根据前述权利要求中任一项所述的组合物,其中所述硅酸盐包括具有式NaMSixO2x+1.y H2O的结晶层状结构的硅酸盐,其中M表示钠或氢,x为1.9至4的数字并且y为0至20的数字。
6.根据前述权利要求中任一项所述的组合物,其中所述硅酸盐具有式Na2Si2O5。
7.根据前述权利要求中任一项所述的组合物,其中所述聚合物分散剂包含磺酸盐单体。
8.根据前述权利要求中任一项所述的组合物,其包含:
a1)按所述组合物的重量计20%至40%的MGDA;
a2)按所述组合物的重量计2%至6%的HEDP;
a3)按所述组合物的重量计2%至6%的包含磺酸盐单体的聚合物分散剂;
a4)按所述组合物的重量计2%至6%的具有式Na2Si2O5的结晶硅酸盐;和
b1)按所述组合物的重量计8%至30%的过碳酸钠;
b2)按所述组合物的重量计0.001%至1%的漂白催化剂;
b3)按所述组合物的重量计0.5%至5%的TAED。
9.根据前述权利要求中任一项所述的组合物,其还包含非离子表面活性剂。
10.根据前述权利要求中任一项所述的组合物,其还包含选自由以下项组成的组的酶:淀粉酶、蛋白酶以及它们的混合物。
11.根据前述权利要求中任一项所述的组合物,其还包含阳离子聚合物,其中所述阳离子聚合物以共聚形式包含:
i.60重量%至99重量%的至少一种式I的单烯键式不饱和聚环氧烷单体(单体(A))的阳离子聚合物,
其中变量具有以下含义:
如果Y为-O-,则X为-CH2-或-CO-;
如果Y为-NH-,则X为-CO-;
Y为-O-或-NH-;
R1为氢或甲基;
R2为相同或不同的C2-C6亚烷基基团;
R3为H或C1-C4烷基;
n为3至100、优选地15至60的整数,
ii.1重量%至40重量%的至少一种季铵化含氮单体(单体(B))的阳离子聚合物,所述至少一种季铵化含氮单体选自由式IIa至式IId的单体中的至少一者组成的组,
其中变量具有以下含义:
R为C1-C4烷基或苄基;
R'为氢或甲基;
Y为-O-或-NH-;
A为C1-C6亚烷基;
X-为卤离子、C1-C4烷基硫酸根、C1-C4烷基磺酸根和C1-C4烷基碳酸根,
iii.0重量%至15重量%的至少一种阴离子单烯键式不饱和单体(单体(C))的阳离子聚合物,以及
iv.0重量%至30重量%的至少一种其他非离子单烯键式不饱和单体(单体(D))的阳离子聚合物,
并且所述阳离子聚合物具有2,000g/mol至500,000g/mol,优选地25,000g/mol至200,000g/mol的重均分子量(Mw)。
12.一种水溶性自动盘碟洗涤清洁小袋,其包含水溶性包封材料和根据前述权利要求中任一项所述的组合物。
13.根据前述权利要求所述的小袋,其中所述组合物的至少一部分呈松散粉末的形式。
14.根据权利要求12或13中任一项所述的小袋,其中所述小袋的重量为15克至20克。
15.一种在洗碗机中从餐具去除茶渍的方法,其包括以下步骤:
i)提供染污的餐具;
ii)用洗涤液体或用根据权利要求12至14中任一项所述的小袋处理所述餐具,所述洗涤液体包含具有约250ppm至450ppm的碳酸氢盐的水和根据权利要求1至11中任一项所述的清洁组合物;以及
iii)任选地冲洗所述盘碟。
16.根据权利要求1至11中任一项所述的清洁组合物或根据权利要求12至14中任一项所述的小袋在使用包含250ppm至450ppm碳酸氢盐的洗涤液体的自动盘碟洗涤中提供茶清洁去除的用途。
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US20210002587A1 (en) | 2021-01-07 |
JP2022537793A (ja) | 2022-08-29 |
CA3144814A1 (en) | 2021-01-28 |
US11459528B2 (en) | 2022-10-04 |
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