CN105518118A - 通过新的螯合剂组合来协同去污 - Google Patents
通过新的螯合剂组合来协同去污 Download PDFInfo
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- CN105518118A CN105518118A CN201380079435.3A CN201380079435A CN105518118A CN 105518118 A CN105518118 A CN 105518118A CN 201380079435 A CN201380079435 A CN 201380079435A CN 105518118 A CN105518118 A CN 105518118A
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- cleanser compositions
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- concentrated cleanser
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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
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
-
- 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
- C11D3/33—Amino carboxylic acids
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
- C11D7/12—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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
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Abstract
本发明涉及一种浓缩的清洁剂组合物,其包含碱金属碳酸盐、甲基甘氨酸二乙酸、谷氨酸N,N-二乙酸和碱金属三聚磷酸盐。该组合物特别适于在器皿清洗应用中除去茶和咖啡污垢。
Description
本发明涉及浓缩的清洁剂组合物,其包含螯合剂(络合剂)混合物,用于器皿清洗,特别是用于除去茶和咖啡污垢。
在清洁剂化学领域中已知的是通常存在于硬水中的钙和镁离子可以与清洁剂组合物的组分反应,来形成不溶性沉淀物。这是一种非常不利的效应,因为它导致在洁净商品上形成了结垢和不利地影响清洁剂的除垢能力。
因此清洁剂通常包含络合剂,其结合到金属离子上和由此降低了含水体系中的自由金属离子的浓度。大部分络合剂充当了多齿配体来与金属离子形成螯合络合物。通常使用的络合剂例如是磷酸盐,柠檬酸,葡糖酸,甲基甘氨酸二乙酸(MGDA),氨三乙酸(NTA),乙二胺四乙酸(EDTA),二亚乙基三胺五乙酸(DTPA),羟基乙二胺三乙酸(HEDTA)或者亚氨基二琥珀酸酯/盐(IDS)。
通过结合游离的镁或钙离子,络合剂降低了水硬度和防止结垢形成。络合剂甚至还可通过螯合镁或钙离子(其被结合和稳定了沉淀的结垢),来帮助再溶解结垢。络合剂因此通过降低水硬度和再溶解结垢而发挥了双重作用。络合剂进一步可以防止金属离子参与典型的化学反应,例如通过锰、铁和铜离子催化的过氧化物化合物的化学分解。络合剂因此特别用于增强包含过氧化物漂白剂的清洁组合物的性能。
已知的是螯合给定浓度的金属离子所需的络合剂的量取决于络合剂和金属离子的结合化学计量比和取决于该结合平衡的解离常数。用作水软化剂的络合剂通常的特征在于它们的钙结合能力,其是给定量的络合剂在给定的pH和温度下结合钙的量的度量。对于络合剂混合物,假定该混合物的总结合能力是单个结合能力之和。用于清洁剂应用所需的络合剂的总量因此可以作为已知的钙结合能力和水硬度的函数来计算。
络合物是基于它们的钙结合能力,一般的金属结合能力和它们的成本来选择的。另外还必须考虑性能例如毒性,清洁剂相容性和环境限制。为了尽可能成本有效的使用络合剂,令人期望的是使得用于给定应用所需的络合剂的量最小化。所以需要增加络合剂的效率。
本发明涉及温和碱性清洁剂组合物,其用于在器皿清洗应用中除去茶和咖啡污垢。温和碱性清洁剂是基于作为碱源的碱性碳酸盐,特别是碳酸钠来配制的。茶和咖啡污垢被认为包含由硅酸钙桥连的氧化多酚(例如单宁)。这种类型的污垢被证实特别难以溶解。所以本发明的目标是提供一种非常有效的清洁剂组合物,用于在器皿清洗应用中除去茶和咖啡污垢。
令人惊讶的已经发现络合剂甲基甘氨酸二乙酸(MGDA)、谷氨酸N,N-二乙酸(GLDA)和三聚磷酸钠(STPP)的组合在碳酸盐基清洁剂组合物中,在除去茶和咖啡污垢方面表现出协同效应。协同效应表示实现清洁效应所需的三种络合剂的总浓度低于基于每种试剂的单个钙结合能力所预期的总浓度。这能够将清洁剂组合物中络合剂的用量最小化。
本发明所以提供一种浓缩的清洁剂组合物,其包含:
碱金属碳酸盐,
甲基甘氨酸二乙酸,
谷氨酸N,N-二乙酸,和
碱金属三聚磷酸盐。
通常,该浓缩的清洁剂组合物包含有效量的碱金属碳酸盐。在本发明上下文中,有效量的碱金属碳酸盐是这样的量,其提供了在室温(20℃)下所测量的pH至少6,优选pH至少8,更优选pH是9.5-11,最优选10-10.3的使用溶液。为了测定使用溶液的pH,这种使用溶液被定义为溶解在1升蒸馏水中的1g浓缩的清洁剂组合物的溶液。
为了提供所需碱度,该浓缩的清洁剂组合物典型地包含至少5重量%的碱金属碳酸盐,优选该组合物包含10-80重量%,更优选15-70重量%,最优选20-60重量%的碱金属碳酸盐。
合适的碱金属碳酸盐例如是碳酸钠或钾,碳酸氢钠或钾,倍半碳酸钠或钾及其混合物。
归因于将碱金属碳酸盐用作碱源,不需要其他碱源例如碱金属氢氧化物。优选该浓缩的清洁剂组合物因此不包含碱金属氢氧化物。
浓缩的清洁剂组合物包含络合剂甲基甘氨酸二乙酸(MGDA),谷氨酸N,N-二乙酸(GLDA)和碱金属三聚磷酸盐。在本发明的上下文中,甲基甘氨酸二乙酸和谷氨酸N,N-二乙酸可以用作游离酸或者盐。通常,所述化合物的钠盐将包括在该清洁剂组合物中。碱金属三聚磷酸盐优选是三聚磷酸钠(STPP)。
络合剂是本领域技术人员容易获得的。例如甲基甘氨酸二乙酸的三钠盐是在商标名TrilonM下由BASF销售的,和谷氨酸N,N-二乙酸的四钠盐是在商标名DissolvineGL下由AkzoNobel销售的。
三种络合剂的浓度通常是基于碱金属碳酸盐的存在量来调整的,使得一旦稀释浓缩的组合物即碱金属碳酸盐和络合剂二者的合适的工作浓度。优选谷氨酸N,N-二乙酸,甲基甘氨酸二乙酸和碱金属三聚磷酸盐的总和与碱金属碳酸盐的摩尔比是0.01-0.5,更优选0.05-0.12,最优选0.07-0.12。
三种络合剂的相对量可以调整来使得清洁效率最大化。优选甲基甘氨酸二乙酸与碱金属三聚磷酸盐的摩尔比因此是0.14-14.3,更优选0.5-5,最优选1.35-1.7。另外,谷氨酸N,N-二乙酸与甲基甘氨酸二乙酸和碱金属三聚磷酸盐的总和的摩尔比优选是0.03-29,更优选0.05-2,最优选0.08-0.45。
在另一优选的实施方案中,谷氨酸N,N-二乙酸,甲基甘氨酸二乙酸和碱金属三聚磷酸盐的总浓度是1-50重量%,基于浓缩的清洁剂组合物的总重量,更优选14-28重量%,最优选18-26重量%。谷氨酸N,N-二乙酸的量优选是1-30重量%,基于浓缩的清洁剂组合物的总重量,更优选1-23重量%,最优选2-8重量%。甲基甘氨酸二乙酸的量优选是1-30重量%,基于浓缩的清洁剂组合物的总重量,更优选2-22重量%,最优选8-10重量%。碱金属三聚磷酸盐的量优选是1-30重量%,基于浓缩的清洁剂组合物的总重量,更优选2-23重量%,最优选8-10重量%。
本发明的浓缩的清洁剂组合物可以进一步包含选自以下的至少一种化合物:表面活性剂,漂白剂,活化剂,螯合剂/多价螯合剂(chelating/sequesteringagent),硅酸盐,清洁剂填料或者粘合剂,消泡剂,抗再沉积剂,酶,染料,气味剂,催化剂,阈值聚合物,污垢悬浮剂,抗菌剂及其混合物。
多种表面活性剂可以用于本发明的组合物,例如阴离子,非离子,阳离子和两性离子表面活性剂。浓缩的清洁剂组合物可以包含0.5-20重量%的表面活性剂,基于浓缩的清洁剂组合物的总重量,优选1.5-15重量%。
合适的阴离子表面活性剂例如是羧酸酯/盐例如烷基羧酸酯(羧酸盐)和聚烷氧基羧酸酯/盐,醇乙氧化物羧酸酯/盐,壬基酚乙氧化物羧酸酯/盐;磺酸酯/盐例如烷基磺酸酯/盐,烷基苯磺酸酯/盐,烷基芳基磺酸酯/盐,磺酸化的脂肪酸酯/盐;硫酸酯例如硫酸化的醇,硫酸化的醇乙氧化物,硫酸化的烷基酚,烷基硫酸酯/盐,磺基琥珀酸酯/盐,烷基醚硫酸酯/盐;和磷酸酯例如烷基磷酸酯。示例性阴离子表面活性剂包括烷基芳基磺酸钠,α-烯烃磺酸酯/盐和脂肪醇硫酸酯/盐。
合适的非离子表面活性剂例如是具有聚环氧烷聚合物作为表面活性剂分子的一部分的那些。这样的非离子表面活性剂包括例如氯-,苄基-,甲基-,乙基-,丙基-,丁基-和其他类似烷基-封端的脂肪醇的聚乙二醇醚;聚环氧烷游离非离子物例如烷基糖苷;山梨聚糖和蔗糖酯和它们的乙氧基化物;烷氧化的乙二胺;醇烷氧化物例如醇乙氧化物丙氧化物,醇丙氧化物,醇丙氧化物乙氧化物丙氧化物,醇乙氧化物丁氧基化物等;壬基酚乙氧化物,聚氧乙二醇醚等;羧酸酯例如甘油酯,聚氧乙烯酯,乙氧化的和脂肪酸的二醇酯等;羧基酰胺例如二乙醇胺缩合物,单烷醇胺缩合物,聚氧乙烯脂肪酸酰胺等;和包括环氧乙烷/环氧丙烷嵌段共聚物的聚环氧烷嵌段共聚物例如在商标名Pluronic(BASF)下市售的那些,和其他类似非离子化合物。还可以使用有机硅表面活性剂。
合适的阳离子表面活性剂包括例如胺例如具有C18烷基或者烯基链的伯,仲和叔单胺,乙氧化的烷基胺,乙二胺的烷氧化物,咪唑例如1-(2-羟乙基)-2-咪唑啉,2-烷基-1-(2-羟基乙基)-2-咪唑啉;和季铵盐例如烷基季化氯化铵表面活性剂例如正烷基(C12-C18)二甲基苄基氯化铵,正十四烷基二甲基苄基氯化铵单水合物,亚萘基取代的季氯化铵例如二甲基-1-萘基甲基氯化铵。阳离子表面活性剂可以用于提供消毒性能。
合适的两性离子表面活性剂包括例如甜菜碱,咪唑啉,胺氧化物和丙酸酯/盐。
如果浓缩的清洁剂组合物意在用于自动洗碗机或者器皿清洗机,则所选择的表面活性剂(如果使用任何的表面活性剂的话)可以是当用于洗碗机或者器皿清洗机内时提供了可接受水平的发泡的那些。应当理解的是用于自动洗碗机或者器皿清洗机的器皿清洗组合物通常被认为是低起泡组合物。
合适的漂白剂包括例如过氧化合物,例如碱金属过碳酸盐,特别是过碳酸钠,碱金属过硼酸盐,碱金属过硫酸盐,过氧化脲,过氧化氢;和次氯酸盐,例如次氯酸钠或者次氯酸钙。这些化合物可以例如作为钠,锂,钾,钡,钙或者镁盐来使用。在另一实施方案中,过氧源是有机过氧化物或者过氧化氢化合物。根据另一实施方案,过氧源是使用电化学发生器原位产生的过氧化氢或者其他原位制备过氧化氢的装置。
碱金属过碳酸盐是特别优选的漂白剂。漂白剂的存在量可以是5-60重量%,基于浓缩的清洁剂组合物的总重量,优选5-50重量%,最优选10-40重量%。
如果清洁剂组合物包括过氧化合物,则可以包括活化剂来进一步增加该过氧化合物的活性。合适的活化剂包括4-苯甲酰氧苯磺酸钠(SBOBS);N,N,N',N'-四乙酰基乙二胺(TAED);1-甲基-2-苯甲酰氧苯-4-磺酸钠;4-甲基-3-苯甲酰氧苯甲酸钠;SPCC三甲基甲苯甲酰氧苯磺酸铵;壬酰氧苯磺酸钠,3,5,5-三甲基己酰氧苯磺酸钠;五乙酰基葡萄糖(PAG);辛酰基四乙酰基葡萄糖和苯甲酰四乙酰基葡萄糖。浓缩的清洁剂组合物可以包含浓度为1-8重量%的活化剂或者活化剂混合物,基于浓缩的清洁剂组合物的总重量,优选2-5重量%。
除了上述的络合剂之外,清洁剂组合物可以包含另外的螯合剂/多价螯合剂。合适的另外的螯合剂/多价螯合剂例如是柠檬酸酯/盐,氨基羧酸,缩合的磷酸酯/盐,膦酸酯/盐和聚丙烯酸酯/盐。在本发明上下文中,螯合剂是这样的分子,其能够配位(即,结合)通常存在于天然水中的金属离子来防止该金属离子干扰清洁组合物的其他清洁成分的作用。螯合剂/多价螯合剂可以通常称作一类增洁剂。当以有效量包括时,螯合剂也可以充当阈剂。浓缩的清洁剂组合物可以包含0.1-70重量%的螯合剂/多价螯合剂,基于浓缩的清洁剂组合物的总重量,优选5-60重量%,更优选5-50重量%,最优选10-40重量%。
合适的氨基羧酸包括例如N-羟乙基亚氨基二乙酸,氨三乙酸(NTA),乙二胺四乙酸(EDTA),N-羟乙基-乙二胺三乙酸(HEDTA)和二亚乙基三胺五乙酸(DTPA)。
缩合的磷酸酯/盐的例子包括正磷酸钠和钾,焦磷酸钠和钾,六偏磷酸钠等。缩合的磷酸酯/盐还可通过固定组合物中作为水合的水存在的游离水来在有限程度上帮助凝固该组合物。
组合物可以包括膦酸酯/盐例如1-羟基乙烷-1,1-二膦酸CH3C(OH)[PO(OH)2]2(HEDP);氨基三(亚甲基膦酸)N[CH2PO(OH)2]3;氨基三(亚甲基膦酸酯/盐),钠盐(NaO)(HO)P(OCH2N[CH2PO(ONa)2]2);2-羟乙基亚氨基双(亚甲基膦酸)HOCH2CH2N[CH2PO(OH)2]2;二亚乙基三胺五(亚甲基膦酸)(HO)2POCH2N[CH2CH2N[CH2PO(OH)2]2]2;二亚乙基三胺五(亚甲基膦酸酯/盐),钠盐C9H(28-X)N3NaxO15P5(x=7);六亚甲基二胺(四亚甲基膦酸酯/盐),钾盐C10H(28-x)N2KxO12P4(x=6);双(六亚甲基)三胺(五亚甲基膦酸)(HO2)POCH2N[(CH2)6N[CH2PO(OH)2]2]2;和亚磷酸H3PO3。
优选的膦酸酯/盐是1-羟基亚乙基-1,1-二膦酸(HEDP),氨基三(亚甲基膦酸)(ATMP)和二亚乙基三胺五(亚甲基膦酸)(DTPMP)。
当加入膦酸酯/盐时,在加入到混合物之前,优选的是中和的或者碱性膦酸酯/盐,或者膦酸酯/盐与碱源的组合,以使得中和反应所产生的热或气体很少或者没有。膦酸酯/盐可以包括有机膦酸的钾盐(膦酸钾)。膦酸材料的钾盐可以通过在固体清洁剂制造过程中,用氢氧化钾水溶液中和膦酸来形成。膦酸多价螯合剂可以以合适的比例与氢氧化钾溶液组合,来提供化学计量比量的氢氧化钾来中和该膦酸。可以使用浓度为大约1-大约50wt%的氢氧化钾。膦酸可以溶解或者悬浮在含水介质中,并且氢氧化钾然后可以加入膦酸中来进行中和。
螯合剂/多价螯合剂也可以是水调节聚合物,其可以作为增洁剂形式来使用。示例性的水调节聚合物包括聚羧酸酯/盐。可以用作水调节聚合物的示例性聚羧酸酯/盐包括聚丙烯酸,马来酸/烯烃共聚物,丙烯酸/马来酸共聚物,聚甲基丙烯酸,丙烯酸-甲基丙烯酸共聚物,水解的聚丙烯酰胺,水解的聚甲基丙烯酰胺,水解的聚酰胺-甲基丙烯酰胺共聚物,水解的聚丙烯腈,水解的聚甲基丙烯腈和水解的丙烯腈-甲基丙烯腈共聚物。
浓缩的清洁剂组合物可以包含0.1-20重量%量的水调节聚合物,基于浓缩的清洁剂组合物的总重量,优选0.2-5重量%。
硅酸盐也可以包括在浓缩的清洁剂组合物中。硅酸盐通过形成沉淀物来软化水,该沉淀可容易地冲洗掉。它们通常具有润湿和乳化性能,并且充当了针对酸性化合物例如酸性污垢的缓冲剂。此外,硅酸盐可以通过合成清洁剂和络合磷酸酯/盐来抑制不锈钢和铝的腐蚀。特别适用的硅酸盐是偏硅酸钠,其可以是无水的或者水合的。浓缩的清洁剂组合物可以包含1-10重量%的硅酸盐,基于浓缩的清洁剂组合物的总重量。
组合物可以包含有效量的清洁剂填料或者粘合剂。适用于本发明组合物的清洁剂填料或者粘合剂的例子包括硫酸钠,氯化钠,淀粉,糖和C1-C10亚烷基二醇例如丙二醇。清洁剂填料可以占1-20重量%的量,基于浓缩的清洁剂组合物的总重量,优选3-15重量%。
用于降低泡沫稳定性的消泡剂也可以包括在该组合物中来降低起泡。消泡剂可以以0.01-20重量%的量提供,基于浓缩的清洁剂组合物的总重量。
合适的消泡剂包括例如环氧乙烷/丙烯嵌段共聚物例如在名称PluronicN-3下市售的那些,有机硅化合物例如分散在聚二甲基硅氧烷中的二氧化硅,聚二甲基硅氧烷,和官能化的聚二甲基硅氧烷,脂肪酰胺,烃蜡,脂肪酸,脂肪酯,脂肪醇,脂肪酸皂,乙氧化物,矿物油,聚乙二醇酯,消泡乳液和烷基磷酸酯例如磷酸单硬脂基酯。
所述组合物可以包含抗再沉积剂,用于促进污垢在清洁溶液中的持久悬浮和防止所除去的污垢再沉积到所清洁的基底上。合适的抗再沉积剂的例子包括脂肪酸酰胺,碳氟表面活性剂,络合的磷酸酯,苯乙烯马来酸酐共聚物,和纤维素衍生物例如羟乙基纤维素,羟丙基纤维素等。抗再沉积剂可以占0.01-25重量%的量,基于浓缩的清洁剂组合物的总重量,优选1-5重量%。
组合物可以包含酶,其提供了令人期望的活性来除去蛋白质基,碳水化合物基或者甘油三酸酯基污垢。虽然不限制本发明,但是适于清洁组合物的酶可以通过降解或者改变在陶器上所遇到的一种或多种类型的污垢残留物来发挥作用,由此除去污垢或者使得污垢可以通过表面活性剂或者清洁组合物的其他组分来更易除去。合适的酶包括任何合适的来源的蛋白酶,淀粉酶,脂肪酶,葡糖酶,纤维酶,过氧化物酶,过氧化氢酶或者其混合物,例如植物,动物,细菌,真菌或者酵母来源的。浓缩的清洁剂组合物可以包含0.01-30重量%的酶,基于浓缩的清洁剂组合物的总重量,优选0.01-15重量%,更优选0.01-10重量%,最优选0.01-8重量%。
蛋白水解酶的例子(其可以用于本发明的清洁组合物中)包括(商标名)一种来源于Bacilluslentus类型的蛋白酶,例如和来源于地衣形芽孢杆菌(Bacilluslicheniformis)的蛋白酶,例如 或者DeterzymePAG510/220;来源于液化芽孢杆菌(Bacillusamyloliquefaciens)的蛋白酶例如和来源于嗜热芽孢杆菌(Bacillusalcalophilus)的蛋白酶例如DeterzymeAPY。示例性市售蛋白酶包括在商标名 或者下由NovoIndustriesA/S(丹麦)销售的那些;在商标名或者下由Gist-Brocades(荷兰)销售的那些;在商标名PurafectOX和Properase下由GenencorInternational销售的那些;在商标名或者下由SolvayEnzymes销售的那些;在商标名DeterzymeAPY和DeterzymePAG510/220下由DeerlandCorporation销售的那些等等。
优选的蛋白酶将提供良好的蛋白质除去和清洁性能,将不留下残留物,和将容易配制和形成稳定的产品。市售自Novozymes的是一种丝氨酸类型的内蛋白酶,并且在pH范围8-12和温度范围20℃-60℃内具有活性。当形成液体浓缩物时Savinase是优选的。还可以使用蛋白酶的混合物。例如市售自Novozymes的是来源于地衣形芽孢杆菌(Bacilluslicheniformis),并且在pH范围6.5-8.5和温度范围45℃-65℃内具有活性。和市售自Novozymes的来源于芽孢杆菌属(Bacillussp.),并且具有碱性pH活性范围和温度范围50℃-85℃。当形成固体浓缩物时Esperase和Alcalase的组合是优选的,因为它们形成了稳定的固体。在一些实施方案中,浓缩产物中的总蛋白酶浓度是大约1-大约15重量%,大约5-大约12重量%,或者大约5-大约10重量%。在一些实施方案中,对于每份Esperase存在着至少1-6份的Alcalase(例如Alcalase:Esperase是1:1,2:1,3:1,4:1,5:1或者6:1)。
清洁性蛋白酶描述在以下专利公开中,包括:属于Novo的GB1243784,WO9203529A(酶/抑制剂体系),WO9318140A和WO9425583(重组体胰岛素类蛋白酶);属于Procter&Gamble的WO9510591A,WO9507791(具有降低的吸附性和增加的水解的蛋白酶),WO95/30010,WO95/30011,WO95/29979;属于GenencorInternational的WO95/10615(液化芽孢杆菌枯草杆菌蛋白酶(Bacillusamyloliquefacienssubtilisin));EP130756A(蛋白酶A);EP303761A(蛋白酶B);和EP130756A。变体蛋白酶优选是与这些参考文献中的蛋白酶的氨基酸序列至少80%同源的,优选具有至少80%的序列相同度。
不同的蛋白水解酶的混合物可以掺入本公开的组合物中。虽然上面已经描述了不同的特定酶,但是要理解的是可以使用任何这样的蛋白酶,其能够为组合物赋予期望的蛋白水解酶活性。
除了蛋白酶之外,本公开的组合物可以任选地包括不同的酶。示例性酶包括淀粉酶,脂肪酶,纤维酶及其他。
示例性淀粉酶可以来源于植物,动物或者微生物。淀粉酶可以来源于微生物例如酵母,霉菌或者细菌。示例性淀粉酶包括来源于杆菌的那些,例如地衣形芽孢杆菌(B.licheniformis),液化芽孢杆菌(B.amyloliquefaciens),枯草芽孢杆菌(B.subtilis)或者嗜热脂肪芽杆菌(B.stearothermophilus)。淀粉酶可以是净化的或者是微生物提取物的组分,且是野生类型或者变体(化学的或者重组体)。
示例性淀粉酶包括在商标名Rapidase下由(荷兰)销售的那些;在商标名或者下由Novo销售的那些;在商标名PurastarSTL或者PurastarOXAM下由Genencor销售的那些;在商标名L340或者PAG510/220下由DeerlandCorporation销售的那些等等。还可以使用淀粉酶的混合物。
示例性纤维酶可以来源于植物,动物或者微生物,例如真菌或者细菌。来源于真菌的纤维酶包括真菌腐质酶(Humicolainsolens),腐质菌株DSM1800,或者属于气单胞菌属(genusAeromonas)的产生纤维酶212的真菌和提取自海洋软体动物DolabellaAuriculaSolander的肝胰腺的那些。纤维酶可以是净化的或者是提取物的组分,且是野生类型或者变体(化学的或者重组体)。
纤维酶的例子包括在商标名或者下由Novo销售的那些;在商标名Cellulase下由Genencor销售的那些;在商标名DeerlandCellulase4000或者DeerlandCellulaseTR下由DeerlandCorporation销售的那些;等等。还可以使用纤维酶的混合物。
示例性脂肪酶可以来源于植物,动物或者微生物,例如真菌或者细菌。示例性脂肪酶包括来源于假单胞菌(Pseudomonas)的那些,例如施氏假单胞菌(Pseudomonasstutzeri)ATCC19.154,或者来自于腐质霉属(Humicola),例如Humicolalanuginosa的那些(典型的在米曲霉(Aspergillusoryzae)中重组所生产的)。脂肪酶可以是净化的或者是提取物的组分,且是野生类型或者变体(化学的或者重组体)。
示例性脂肪酶包括在商标名LipaseP“Amano”或者“Amano-P”下由日本名古屋的AmanoPharmaceuticalCo.Ltd.所销售的,或者在商标名下由Novo所销售的等等。其他市售的脂肪酶包括Amano-CES,来源于Chromobacterviscosum的脂肪酶,例如来自于日本Tagata的ToyoJozoCo.的Chromobacterviscosumvar.lipolyticumNRRLB3673;来自于美国U.S.BiochemicalCorp.和DisoynthCo.的Chromobacterviscosum脂肪酶,和来源于唐菖蒲假单胞菌(Pseudomonasgladioli)或者来源于Humicolalanuginosa的脂肪酶。优选的脂肪酶是在商标名下由Novo销售的。还可以使用脂肪酶的混合物。
另外的合适的酶包括角质酶,过氧化物酶,葡糖酶等。示例性的角质酶描述在Genencor的WO8809367A中。示例性过氧化物酶包括山葵过氧化物酶,木质素酶和卤代过氧化物酶例如氯-或者溴-过氧化物酶。示例性过氧化物酶还公开在Novo的WO89099813A和WO8909813A中。这些另外的酶可以来源于植物,动物或者微生物。该酶可以是净化的或者是提取物的组分,且是野生类型或者变体(化学的或者重组体)。还可以使用不同的另外的酶的混合物。
不同的染料,气味剂(包括香料)和其他审美增强剂可以包括在组合物中。可以包括染料来改变组合物的外观,例如直接蓝86(Miles),FastusolBlue(MobayChemicalCorp.),酸性橙7(AmericanCyanamid),碱性紫10(Sandoz),酸性黄23(GAF),酸性黄17(SigmaChemical),暗绿(KeystoneAnalineandChemical),间胺黄(KeystoneAnalineandChemical),酸性蓝9(HiltonDavis),SandolanBlue/酸性蓝182(Sandoz),HisolFastRed(CapitolColorandChemical),荧光素(CapitolColorandChemical),酸性绿25(Ciba-Geigy)。
可以包括在组合物中的香料或香味剂包括例如萜类例如香茅醇,醛类例如戊基肉桂醛,茉莉例如C1S-茉莉或者茉莉吡喃,和香草醛等。
浓缩的清洁剂组合物可以例如以固体,粉末,液体,凝胶或者糊的形式来提供。优选浓缩的清洁剂组合物是以固体或者粉末形式来提供。
用于形成浓缩的清洁剂组合物的组分可以包括含水介质例如水作为加工助剂。可以预期的是含水介质将帮助提供具有期望的粘度的组分用于加工。另外,可以预期的是当期望形成作为固体的浓缩的清洁剂组合物时,含水介质可以帮助凝固方法。当浓缩的清洁剂组合物是作为固体来提供时,它可以例如以块或者小球的形式来提供。可以预期的是所述块的大小是至少大约5g,和可以包括大于大约50g的大小。可以预期的是浓缩的清洁剂组合物将包含0.001-50重量%的量的水,基于浓缩的清洁剂组合物的总重量,优选2-20重量%。
当加工来形成浓缩的清洁剂组合物的组分被加工成块时,可以预期的是所述组分可以通过已知的凝固技术来加工,例如诸如挤出技术或者浇铸技术。通常,当所述组分加工成块时,浓缩的清洁剂组合物中水的存在量应当是0.001-40重量%,基于浓缩的清洁剂组合物的总重量,优选0.001-20重量%。如果所述组分通过挤出技术加工,则据信浓缩的清洁剂组合物可以包括与浇铸技术相比相对更少量的水作为加工助剂。通常,当通过挤出来制备固体时,可以预期的是浓缩的清洁剂组合物可以包含0.001-20重量%的水,基于浓缩的清洁剂组合物的总重量。当通过浇铸来制备固体时,可以预期的是水量是0.001-40重量%,基于浓缩的清洁剂组合物的总重量。
在第二方面,本发明涉及浓缩的清洁剂组合物的使用溶液。该使用溶液是0.1-10g浓缩的清洁剂组合物/每升水溶液的水溶液,优选0.5-5g/L,最优选1-1.5g/L。
归因于本发明的络合剂组合所实现的协同效应,可以基于硬水来配制使用溶液。此处所用的术语“硬水”是基于CaCO3的浓度来定义的。根据美国地质勘测,具有至少61mg/L浓度的CaCO3的水被称作温和硬水,具有至少121mg/L浓度的CaCO3的水被称作硬水,和具有至少181mg/L浓度的CaCO3的水被称作非常硬的水。
通常本发明不限于硬水的情况。但是在一种优选的实施方案中,用于制备使用溶液的水的硬度是至少50mg/L的CaCO3,更优选至少61mg/L的CaCO3,甚至更优选至少85mg/L,最优选至少121mg/L。
在第三方面,本发明还涉及将上述浓缩的清洁剂组合物作为器皿清洗清洁剂用于除去茶和咖啡污垢。这种污垢的特征在于存在着氧化多酚和硅酸钙。浓缩的清洁剂组合物因此通常可以作为器皿清洗清洁剂用于除去包含氧化多酚和硅酸钙的污垢。
优选浓缩的清洁剂组合物是以0.1-10g的浓缩的清洁剂组合物/每升最终溶液的浓度来稀释的,优选0.5-5g/L,最优选1-1.5g/L,来提供使用溶液。重要地是,本发明允许使用硬水来稀释清洁剂组合物。在一种优选的实施方案中,浓缩的清洁剂组合物因此是用硬度为至少50mg/L的CaCO3,更优选至少61mg/L的CaCO3,甚至更优选至少85mg/L,最优选至少121mg/L的水来稀释的,来提供使用溶液。
实施例
以下实施例通过测试从瓷砖上除去茶和咖啡污垢来说明本发明。
将瓷砖(5.1x15.2cm白色釉面砖)用茶污垢(立顿牌茶)根据下面的程序来玷污。将硬度>249.9mg/LCaCO3的硬水加热到>71℃。该茶然后混入热硬水中。瓷砖然后浸入茶中1min,然后取出1min来干燥。重复这个程序直到形成污点(其通常是在25个周期之后)。瓷砖然后在室温固化48小时。在此时,将该瓷砖备用测试。
清洁测试是在常规的自动化洗碗机中进行的。清洁效率是通过目视来评价的,将一个完全的清洁周期后留在瓷砖上的污垢量与清洁程序之前瓷砖上的污垢量进行比较。结果是根据表1来分级的。
表1
等级 | 去污率% |
1 | 100 |
2 | 80-99.9 |
3 | 20-79.9 |
4 | <20 |
5 | 未除去 |
等级1被认为是优异的结果。等级2(至少80%去污率)被认为是可接受的清洁性能。测试了表2所示的络合剂的清洁效率的结果。对于每个络合剂,覆盖85.5mg/L的CaCO3的水硬度所需的100%活性化合物的理论浓度是基于钙结合能力和原料活性来计算的。所给的浓度涉及各自的钠盐。应当注意地是表2的钙结合能力给出了给定量的原料(其活性可以低于100%)所结合的CaCO3的量,如表2所示。
表2
测试了含有1000mg/L碳酸钠和不同量的络合剂的不同的清洁剂配料的清洁效率。全部配料是在硬度为85.5mg/L的CaCO3的水中制备的。所给浓度涉及使用溶液中100%活性化合物的浓度。
第一系列的测试包括不同量的MGDA,STPP和GLDA的组合。基于钙结合能力和表2中给出的原料的活性,计算了每种配料的所覆盖的水硬度的理论量(以mg/L的CaCO3表达),并且与通过配料所实现的清洁效果进行了比较。测试数据显示在表3中。
表3
该结果表明在碳酸盐基清洁溶液中使用本发明的络合剂组合可以实现可接受的到优异的清洁结果,甚至在络合剂总浓度小于覆盖85.5mg/L的CaCO3的水硬度所需理论总浓度的情况下(实施例1,6,9和10)。因此在碳酸盐基清洁剂组合物中GLDA,MGDA和STPP的组合表现出在清洁效果方面的协同效应。这允许将清洁剂组合物中所用的络合剂的总量最小化。
第二系列包括MGDA,STPP和IDS的组合(表4)。
第二系列的结果表明IDS,MGDA和STPP组合的整体清洁性能低于GLDA,MGDA和STPP的组合,即使络合剂总浓度相同也是如此。这是出人意料的,因为覆盖85.5mg/L的CaCO3的水硬度理论上所需的IDS的量低于GLDA,且因此IDS应当比GLDA更有效(表2)。此外,当络合剂总浓度下降至低于完全覆盖85.5mg/L的CaCO3的水硬度所需的量时(实施例1和10),清洁效率变得不可接受的,这与GLDA,MGDA和STPP的组合是相反的。IDS,MGDA和STPP的组合因此未表现出协同效应。
Claims (15)
1.浓缩的清洁剂组合物,其包含:
碱金属碳酸盐,
甲基甘氨酸二乙酸,
谷氨酸N,N-二乙酸,和
碱金属三聚磷酸盐。
2.根据前述任一项权利要求的浓缩的清洁剂组合物,其中甲基甘氨酸二乙酸与碱金属三聚磷酸盐的摩尔比是0.14-14.3。
3.根据前述任一项权利要求的浓缩的清洁剂组合物,其中谷氨酸N,N-二乙酸与甲基甘氨酸二乙酸和碱金属三聚磷酸盐总和的摩尔比是0.03-29。
4.根据前述任一项权利要求的浓缩的清洁剂组合物,其中谷氨酸N,N-二乙酸、甲基甘氨酸二乙酸和碱金属三聚磷酸盐的总和与碱金属碳酸盐的摩尔比是0.01-0.5。
5.根据前述任一项权利要求的浓缩的清洁剂组合物,其中所述组合物包含至少5重量%的碱金属碳酸盐。
6.根据前述任一项权利要求的浓缩的清洁剂组合物,其中所述碱金属碳酸盐是碳酸钠或钾、碳酸氢钠或钾、倍半碳酸钠或钾或者其混合物。
7.根据前述任一项权利要求的浓缩的清洁剂组合物,其中所述碱金属三聚磷酸盐是三聚磷酸钠。
8.根据前述任一项权利要求的浓缩的清洁剂组合物,其中当在蒸馏水中稀释到1g/L的浓度和在20℃温度测量时,该组合物提供了至少6的pH。
9.根据前述任一项权利要求的浓缩的清洁剂组合物,其中所述组合物进一步包含选自如下的至少一种化合物:表面活性剂、漂白剂、活化剂、螯合剂/多价螯合剂、硅酸盐、清洁剂填料或者粘合剂、消泡剂、抗再沉积剂、酶、染料、气味剂、催化剂、阈值聚合物、污垢悬浮剂、抗菌剂及其混合物。
10.根据前述任一项权利要求的浓缩的清洁剂组合物,其中所述组合物是以固体、粉末、液体、凝胶或者糊的形式提供的。
11.水溶液,其包含0.1-10g/L的根据权利要求1-10的浓缩的清洁剂组合物。
12.根据权利要求1-10任一项的浓缩的清洁剂组合物的用途,其作为器皿清洗清洁剂用于除去包含氧化多酚和硅酸钙的污垢。
13.根据权利要求12的用途,其中将所述浓缩的清洁剂组合物稀释来提供浓度为0.1-10g/L的使用溶液。
14.根据权利要求13的用途,其中所述浓缩的清洁剂组合物用硬度为至少50mg/L的CaCO3的水稀释。
15.根据权利要求12-14任一项的用途,其中所述器皿清洗清洁剂用于除去茶和咖啡污垢。
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