CN1311813A - 含有机二胺的餐具洗涤剂组合物 - Google Patents
含有机二胺的餐具洗涤剂组合物 Download PDFInfo
- Publication number
- CN1311813A CN1311813A CN99809286A CN99809286A CN1311813A CN 1311813 A CN1311813 A CN 1311813A CN 99809286 A CN99809286 A CN 99809286A CN 99809286 A CN99809286 A CN 99809286A CN 1311813 A CN1311813 A CN 1311813A
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- Prior art keywords
- composition
- alkyl
- detergent
- diamines
- washing
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 202
- 239000003599 detergent Substances 0.000 title claims abstract description 83
- 150000004985 diamines Chemical class 0.000 title claims abstract description 80
- 238000004851 dishwashing Methods 0.000 title claims abstract description 17
- 238000005406 washing Methods 0.000 claims description 45
- 150000001412 amines Chemical class 0.000 claims description 42
- -1 alkylbenzene sulfonate Chemical class 0.000 claims description 36
- 125000000217 alkyl group Chemical group 0.000 claims description 31
- 102000004190 Enzymes Human genes 0.000 claims description 30
- 108090000790 Enzymes Proteins 0.000 claims description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 22
- 239000003945 anionic surfactant Substances 0.000 claims description 22
- 239000004094 surface-active agent Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000011777 magnesium Substances 0.000 claims description 16
- 235000013599 spices Nutrition 0.000 claims description 15
- 239000000872 buffer Substances 0.000 claims description 14
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 14
- 229930195729 fatty acid Natural products 0.000 claims description 14
- 239000000194 fatty acid Substances 0.000 claims description 14
- 150000004665 fatty acids Chemical class 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000003381 stabilizer Substances 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
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- 150000003839 salts Chemical class 0.000 claims description 11
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
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- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 2
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- 239000003112 inhibitor Substances 0.000 claims description 2
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 8
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- 150000004702 methyl esters Chemical class 0.000 claims 1
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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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0094—High foaming 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/65—Mixtures of anionic with cationic compounds
- C11D1/652—Mixtures of anionic compounds with carboxylic amides or alkylol amides
-
- 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
- C11D1/38—Cationic compounds
- C11D1/65—Mixtures of anionic with cationic compounds
- C11D1/655—Mixtures of sulfonated products with alkylolamides of 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/94—Mixtures with anionic, cationic or non-ionic 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
- C11D3/0026—Low foaming or foam regulating 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
- C11D3/26—Organic compounds containing nitrogen
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Abstract
本发明涉及含低分子量有机二胺的洗涤剂组合物。更特别地,本发明涉及去脂性能和起泡性得到改善的手洗餐具洗涤用洗涤剂组合物。本发明洗涤剂还有改善的低温稳定性和溶解性。
Description
发明领域
本发明涉及含低分子量有机二胺的洗涤剂组合物。更特别地,本发明涉及去脂性能和起泡性得到改善的手洗餐具洗涤用洗涤剂组合物。本发明洗涤剂还有改善的低温稳定性和优异的溶解作用,以及改善的难洗食物污渍去污力和抗菌性。
二胺配入手洗餐具洗涤剂中,有效替代餐具洗涤领域中已知作为表面活性增强剂而少量使用的Ca/Mg离子。所述二胺同时具有去脂、起泡、溶解、硬水洗涤和低温稳定性等益处,而没有与Ca/Mg相伴的缺点。
发明背景
典型的商业手洗餐具洗涤剂组合物掺入二价离子(Mg,Ca)以确保在软水中具有适当的去脂性能。然而,在含有阴离子、非离子、或其它表面活性剂(例如氧化胺、烷基乙氧基化物、链烷酰葡糖酰胺、烷基甜菜碱)的配方中存在二价离子导致产品与水的混合速度较慢(因而快速起泡性较差)、漂洗较差、和低温稳定性较差。此外,由于随着pH升高与Ca和Mg相伴的沉淀问题,很难制备稳定的含Ca/Mg的餐具洗涤剂。适用于手洗餐具洗涤的洗涤剂组合物中包含氧化胺和阴离子表面活性是很理想的,因为此表面活性剂组合不仅提供优异的洗净力,而且使配方的起泡性得到改善,特别是在含有粒状污垢的溶液中。大于2%的氧化胺与阴离子表面活性剂和Ca/Mg洗涤剂组合物组合造成低温稳定性问题如低于5℃下产品固化也是公知的。因此,需要一种适用于手洗餐具洗涤的洗涤剂组合物,它在低温下稳定,还能在硬水中和传统的Ca/Mg体系不稳定而不能提供去脂性和难洗食物洗净力的pH(典型地pH9或更低)下提供去脂和难冼食物洗净力。
背景技术
US 4 556 509和JP 63-131124-A(88/06/03)。
发明概述
现已确定使用某些有机二胺(如后面详述的)以特定摩尔比与氧化胺和阴离子表面活性剂组合导致难洗食物污渍的洗净力和去脂/去油率比传统洗涤剂组合物中使用Mg或Ca离子得到改善。意外地,这些有机二胺还改善在污垢特别是含脂肪酸和蛋白质的污垢存在下的泡沫稳定性。
此外,本文所述二胺的强去脂性能允许在保持去脂性能的同时消除配方中的Mg/Ca离子。消除Mg/Ca还使溶解、漂洗和产品的低温稳定性得到改善。
根据本发明的第一方面,所述洗涤剂组合物包含:
a)一种具有pK1和pK2的低分子量有机二胺,其中所述二胺的pK1和pK2均在约8.0至约11.5的范围内;
b)一种阴离子表面活性剂;
c)一种氧化胺表面活性剂;
所述组合物基本上无镁和钙盐;其中pH(以10%水溶液测量)为约5.0至约12.5,所述阴离子表面活性剂与所述氧化胺与所述二胺之摩尔比为约100∶40∶1至约9∶0.5∶1。
根据本发明的第二方面,提供一种适用于手洗餐具洗涤的洗涤剂组合物,所述组合物包含:
a)约0.1%至约5%重量分子量小于或等于400g/mol的二胺;
b)约5%至约50%重量阴离子表面活性剂;
c)约0.5%至约10%重量氧化胺表面活性剂;
d)约0.001%至约2%重量香料;
e)约0.01%至约5%重量聚合型泡沫稳定剂,选自:
其中R1为氢、C1-C6烷基、及其混合物;条件是(ⅱ)与(ⅰ)之比为
约2∶1至约1∶2;其中所述聚合型泡沫稳定剂的分子量为约1000
至约2 000 000道尔顿;
所述组合物基本上无镁和钙盐;其中pH(以10%水溶液测量)为约5.0至约12.5,所述阴离子表面活性剂与所述氧化胺与所述二胺之摩尔比为约27∶8∶1至约11∶3∶1。
根据本发明的第三方面,提供一种适用于手洗餐具洗涤的洗涤剂组合物,所述组合物包含:
a)一种有pK1和pK2的低分子量有机二胺,其中所述二胺的pK1和pK2均在约8.0至约11.5的范围内;
b)一种阴离子表面活性剂;
所述组合物基本上无镁和钙盐;其中pH(以10%水溶液测量)为约5.0至约12.5,所述阴离子表面活性剂与所述二胺之摩尔比大于9∶1。
除非另有说明,本文所用的所有份数、百分率和比例均以重量百分率表示。引用的所有文献(相关部分)均引入本文供参考。
发明详述
定义-本发明洗涤剂组合物包含“有效量”或“改善去脂量”的本文所定义各组分。“有效量”的本文所述二胺和本文所述附加成分意指足够以90%的可信度定向地或显著地改善所述组合物对目标污垢和污渍中至少一些的清洗效果的量。因此,在其目标包括某些油渍的组合物中,应使用足量的二胺以至少定向地改善对此污渍的清洗效果。重要地,在全配方洗涤剂中,可使用这样量的二胺以至少定向改善对各种污垢和污渍的清洗效果,如后面实施例中所示。
如前面所述,本文中二胺与洗涤剂用表面活性剂组合用于洗涤剂组合物,其含量能有效地实现至少定向改善清洗效果。在手洗餐具洗涤组合物内容中,此“用量”不仅可随污垢和污渍的类型和强度改变,而且随洗水温度、洗涤水体积和餐具与洗涤水的接触时间而改变。
由于洗涤剂组合物的使用者的习惯不同,该组合物优选含有至少约0.1%、更优选至少约0.2%、甚至更优选至少约0.25%、甚至还更优选至少约0.5%重量所述二胺组合物。该组合物还优选含有不大于约15%、更优选不大于约10%、甚至更优选不大于约6%、甚至更优选不大于约5%、甚至还更优选不大于约1.5%重量所述二胺组合物。
在本发明几个方面之一,本发明提供一种通过本发明特定二胺与表面活性剂组合提高油脂污垢去污力的方法。“日常”的脂状/油状污垢是甘油三酸酯、类脂类、复合多糖类、脂肪酸、无机盐和蛋白质类物质的混合物。
不受理论限制,据信所述有机二胺在宽硬度范围(以CaCO3表示高达约1000ppm)内实现的强去脂性能导致在手洗餐具洗涤剂中不需使用二价离子就可提高在软水中的去脂性能。值得注意的是,消除传统手洗餐具洗涤配方中的二价离子导致在产品与水的混合速度(称为“溶解作用”)、快速起泡、漂洗、和低温稳定性方面获益。
取决于用户的喜好,本发明组合物可以高于约50厘泊、优选高于约100厘泊、更优选约100至约400厘泊的粘度配制。对于欧洲配方,所述组合物可以最高约1000厘泊的粘度配制。
此外,消除二价离子所获得的优异溶解速度甚至允许在保持溶解和清洗效果极佳的同时以甚至比传统配方明显更高的粘度(例如1000厘泊或更高)配制手洗餐具洗涤剂(特别是浓缩配方。这对于在保持溶解作用可接受的同时制备有更高粘度的浓缩产品具有重要的潜在优势。“浓缩”或“超浓缩”意指水含量比常规液体洗涤剂减少的洗涤剂配方。水含量低于洗涤剂组合物的50%重量,优选低于30%重量。所述浓缩产品为用户和生产者提供便利,用户有可以更少的量使用的产品,生产者的运输成本更低。
二胺-优选本发明所用二胺基本上无杂质。即“基本上无”意指所述二胺的纯度高于95%、优选高于97%、更优选高于99%、还更优选高于99.5%、无杂质。商供二胺中可能存在的杂质的例子包括2-甲基-1,3-二氨基丁烷和烷基氢化嘧啶。此外,相信所述二胺应无氧化反应物以避免二胺降解和生成氨。而且,如果存在氧化胺和/或其它表面活性剂,所述氧化胺或表面活性剂应无过氧化氢,特别是所述组合物含有酶时。所述氧化胺或氧化胺的表面活性剂膏中过氧化氢的优选含量为0-40ppm、更优选0-15ppm。应使氧化胺和甜菜碱(如果存在的话)中胺杂质最少至上面对过氧化氢的含量水平。然而,常规的氧化胺即无过氧化氢的那些可用于本发明组合物。
所述组合物含酶时,使组合物不含过氧化氢是重要的。过氧化物可与酶反应而破坏酶加入组合物的任何有益性能。甚至少量的过氧化氢也可能给含酶配方造成问题。然而,二胺可与存在的任何过氧化物反应,起酶稳定剂的作用,防止过氧化氢与酶反应。由二胺产生此酶稳定作用的唯一缺陷是据信所产生的氮化合物导致含二胺的组合物中可能存在臭气。有二胺作为酶稳定剂还防止二胺给所述组合物提供其最初实现的益处即去脂、起泡、溶解和低温稳定性。因此,由于可能产生臭味化合物和可用于发挥其主要作用的二胺量减少,优选使用基本上无过氧化氢的组分和/或使用非二胺类抗氧化剂(即使所述二胺可起酶稳定剂的作用)使本发明组合物中作为杂质存在的过氧化氢量最少。
还优选本发明组合物无“臭味”。即顶空的气味不使消费者产生不良的嗅觉反应。这可以许多方式实现,包括使用香料掩盖任何不希望的气味,使用稳定剂如抗氧化剂、螯合剂等,和/或使用基本上无杂质的二胺。不想受理论限制,相信二胺中存在的杂质是本发明组合物中多数臭味起因。这些杂质可能在二胺的制备和储存期间形成。用稳定剂如抗氧化剂和螯合剂抑制和/或防止组合物从制备至最终被消费者使用的时间内形成这些杂质。因此,最优选通过加香料、稳定剂和/或使用基本上无杂质的二胺防止形成这些臭味。
优选的有机二胺是其中pK1和pK2在约8.0至约11.5的范围内、优选在约8.4至约11的范围内、甚至更优选约8.6至约10.75范围内的那些。从性能和供应考虑,优选的物质是1,3-二(甲胺)-环己烷、1,3-丙二胺(pK1=10.5;pK2=8.8)、1,6-己二胺(pK1=11;pK2=10)、1,3-戊二胺(Dytek EP)(pK1=10.5;pK2=8.9)、2-甲基-1,5-戊二胺(Dytek A)(pK1=11.2;pK2=10.0)。其它优选物质是有C4至C8范围内的亚烷基间隔基的伯/伯胺。一般地,相信伯二胺比仲和叔二胺更优选。
pK1和pK2的定义-本文所用“pKa1”和“pKa2”是本领域技术人员统称为“pKa”类型的量。本文中以与化学领域技术人员公知的相同方式使用pKa。本文中参考的值可来自文献中,如来自Smith andMartel,“临界稳定常数(Critical Stability Constants):第2卷,胺类”,Plenum出版社,纽约和伦敦,1975。关于pKa’s的其它信息可来自相关公司的文献,如二胺供应商杜邦公司提供的信息。
作为本文的工作定义,二胺的pKa是在25℃、离子强度在0.1和0.5M之间的全水溶液中确定。所述pKa是平衡常数,可随温度和离子强度而改变;因此,文献中所报道的根据测量方法和条件不同有时不一致。为消除不确定性,本发明pKa’s所用的相关条件和/或基准如本文中或“临界稳定常数:第2卷,胺类”中所定义。一类测量方法是用氢氧化钠电位滴定所述酸,通过以下文献中所描述和参考的适合方法确定pKa:Shugar和Dean,“化学家速查参考手册(TheChemist’s Ready Reference Handbook)”,McGraw Hill,纽约,1990。
已确定pK1和pK2降至低于约8.0的取代基和结构变化是不理想的,导致性能损失。这可包括取代形成乙氧基化二胺、羟乙基取代的二胺、在间隔基中相对于氮的β-位(和更低如γ-位)有氧的二胺(如Jeffamine EDR 148)。此外,基于乙二胺的物质是不适用的。
适用于本发明的二胺可由以下结构定义:其中R2-5独立地选自H、甲基、-CH3CH2、和氧化乙烯;Cx和Cy独立地选自亚甲基或支链烷基,其中x+y为约3至约6;A可选地存在,选自为将所述二胺的pKa调节至要求的范围所选的给电子或吸电子部分。如果存在A,则x和y必须均为1或更大。
-(R7O)mR8其中R7为C2-C4直链或支链的亚烷基、及其混合物;R8为氢、C1-C4烷基、及其混合物;m为1至约10;X为选自以下的单元:
ⅰ)C3-C10直链亚烷基、C3-C10支链亚烷基、C3-C10环状亚烷基、C3-C10支链的环状亚烷基、下式的亚烷氧基亚烷基:
-(R7O)mR7-
其中R7和m与前面定义的相同;
ⅱ)C3-C10直链亚烷基、C3-C10支链亚烷基、C3-C10环状亚烷基、C3-C10支链的环状亚烷基、C6-C10亚芳基,其中所述单元包括一个或多个使所述二胺的pKa大于约8的给电子或吸电子部分;和
ⅲ)(ⅰ)和(ⅱ)的混合物,
条件是使所述二胺具有至少约8的pKa。
优选二胺的例子包括以下:
1,6-已二胺:
异佛尔酮二胺:
及其混合物。
聚合型泡沫稳定剂-本发明组合物可任选地含有聚合型泡沫稳定剂。这些聚合型泡沫稳定剂在不牺牲所述液体洗涤剂组合物的去脂能力的情况下提供扩大的泡沫体积和泡沫持续时间。这些聚合型泡沫稳定剂选自:
ⅰ)下式的丙烯酸(N,N-二烷氨基)烷基酯的均聚物:
其中每个R独立地为氢、C1-C8烷基、及其混合物,R1为氢、C1-C6烷基、及其混合物,n为2至约6;和
ⅱ)(ⅰ)与下式化合物的共聚物:
其中R1为氢、C1-C6烷基、及其混合物;条件是(ⅱ)与(ⅰ)之比为约2∶1至约1∶2;其中所述聚合型泡沫促进剂的分子量(通过常规的凝胶渗透色谱法确定)为约1000至约2 000 000道尔顿、优选约5000至约1 000 000、更优选约10 000至约750 000、更优选约20 000至500 000、甚至更优选约35 000至约200 000。所述聚合型泡沫稳定剂可任选地以盐(无机或有机盐)如丙烯酸(N,N-二甲氨基)烷基酯的柠檬酸盐、硫酸盐或硝酸盐的形式存在。
一种优选的聚合型泡沫稳定剂是丙烯酸(N,N-二甲氨基)烷基酯,即
所述组合物中存在聚合型泡沫促进剂时,其在组合物中的存在量可为约0.01至约15%、优选约0.05至约10%、更优选约0.1至约5%重量。
阴离子表面活性剂-适用于本发明的阴离子表面活性剂优选选自直链烷基苯磺酸盐、α-烯烃磺酸盐、石蜡烃磺酸盐、烷基酯磺酸盐、烷基硫酸盐、烷基烷氧基硫酸盐、烷基磺酸盐、烷基烷氧基羧酸盐、烷基烷氧基化硫酸盐、肌氨酸盐、牛磺酸盐、及其混合物。本发明中可使用有效量、典型地约0.5至约90%、优选约5至约50%、更优选约10至约30%重量洗涤剂用阴离子去污表面活性剂。
烷基硫酸盐表面活性剂是另一类适用于本发明的重要的阴离子表面活性剂。与多羟基脂肪酸酰胺(见后面)组合使用时,除提供极好的总清洁能力包括在宽温度、洗液浓度和洗涤时间范围内良好脂/油洗净力之外,还可获得烷基硫酸盐的溶解作用,并使液体洗涤剂配方的配方能力得到改善。烷基硫酸盐表面活性剂是式ROSO3M的水溶性盐或酸,其中R优选为C10-C24烃基、优选烷基或有C10-C20烷基组分的羟烷基、更优选C12-C18烷基或羟烷基,M为H或阳离子,例如碱(第ⅠA族)金属阳离子(例如钠、钾、锂)、取代或未取代的铵阳离子如甲基-、二甲基-、和三甲基铵和季铵阳离子(例如四甲铵和二甲基哌啶翁)、和由链烷醇胺如乙醇胺、二乙醇胺、三乙醇胺及其混合物衍生的阳离子等。典型地,对于较低洗涤温度(例如低于约50℃)优选C12-16的烷基链;对于较高洗涤温度(例如高于约50℃)优选C16-18烷基链。
烷基烷氧基化硫酸盐表面活性剂是另一类适用的阴离子表面活性剂。这些表面活性剂是式RO(A)mSO3M的水溶性盐或酸,其中R为未取代的C10-C24烷基或有C10-C24烷基组分的羟烷基、优选C12-C20烷基或羟烷基、更优选C12-C18烷基或羟烷基,A为乙氧基或丙氧基单元,m大于0、典型地在约0.5和约6之间、更优选在约0.5和约3之间,M为H或阳离子例如金属阳离子(如钠、钾、锂等)、铵或取代的铵阳离子。本文中包括烷基乙氧基化硫酸盐及烷基丙氧基化硫酸盐。取代的铵阳离子的具体例子包括甲基-、二甲基-、三甲基-铵和季铵阳离子,如四甲铵、二甲基哌啶鎓和由链烷醇胺如单乙醇胺、二乙醇胺、和三乙醇胺衍生的阳离子、及其混合物。表面活性剂的例子是C12-C18烷基聚乙氧基化(1.0)硫酸盐、C12-C18烷基聚乙氧基化(2.25)硫酸盐、C12-C18烷基聚乙氧基化(3.0)硫酸盐、和C12-C18烷基聚乙氧基化(4.0)硫酸盐,其中M便于选自钠和钾。适用于本发明的表面活性剂可由天然或合成的醇原料制备。链长代表平均烃分布,包括支链的。
适用的阴离子表面活性剂的例子见“表面活性剂和洗涤剂(Surface Active Agents and Detergents)”(第Ⅰ和第Ⅱ卷,Schwartz,Perry和Berch)。这种表面活性剂一般地公开在1975年12月30日授予Laughlin等的US 3 929 678第23栏58行至第29栏23行。
氧化胺-氧化胺是半极性非离子表面活性剂,包括:含有一个约10至约18个碳原子的烷基部分和两个选自含约1至约3个碳原子的烷基和羟烷基的部分的水溶性氧化胺;含有一个约10至约18个碳原子的烷基部分和两个选自含约1至约3个碳原子的烷基和羟烷基的部分的水溶性氧化膦;和含有一个约10至约18个碳原子的烷基部分和一个选自约1至约3个碳原子的烷基和羟烷基的部分的水溶性亚砜。
半极性非离子的洗涤剂用表面活性剂包括下式的氧化胺表面活性剂:其中R3为含约8至约22个碳原子的烷基、羟烷基、或烷基苯基或其混合物;R4为含约2至约3个碳原子的亚烷基或羟基亚烷基或其混合物;x为0至约3;每个R5为含约1至约3个碳原子的烷基或羟烷基或含约1至约3个氧乙烯基的聚氧乙烯基。所述R5基可通过氧或氮原子相互连接形成环结构。
这些氧化胺表面活性剂特别地包括C10-C18烷基二甲基氧化胺和C8-C12烷氧基乙基二羟乙基氧化胺。
所述组合物中优选存在有效量、更优选约0.1至约20%、甚至更优选约0.1至约15%、甚至更优选约0.5至约10%重量氧化胺。适用的氧化胺表面活性剂的例子见“表面活性剂和洗涤剂”(第Ⅰ和Ⅱ卷,Schwartz,Perry和Berch)。
非离子型洗涤剂用表面活性剂-适用的非离子型洗涤剂用表面活性剂一般地公开在1975年12月30日授予Laughlin等的US 3 929678第13栏14行至第16栏6行,引入本文供参考。适用的非离子表面活性剂类型的非限制性例子包括:烷基乙氧基化物、链烷酰葡糖酰胺、烷基甜菜碱、磺基甜菜碱及其混合物。
烷基酚的聚氧乙烯、聚氧丙烯、和聚氧丁烯缩合物。一般地,优选聚氧乙烯缩合物。这些化合物包括有直链或支链构型的含约6至约12个碳原子的烷基的烷基酚与烯化氧的缩合产物。在优选实施方案中,所述环氧乙烷的存在量等于约5至约25mol环氧乙烷/mol烷基酚。商购的此类非离子表面活性剂包括GAF公司出售的IgepalCO-630;和Rohm & Haas公司出售的Triton X-45、X-114、X-100、和X-102。这些化合物通常称为烷基酚烷氧基化物(例如烷基酚乙氧基化物)。
脂族醇与约1至约25mol环氧乙烷的缩合产物。所述脂族醇的烷基链可为直链或支链的(伯或仲),一般含有约8至约22个碳原子。特别优选有含约10至约20个碳原子的烷基的醇与约2至约18mol环氧乙烷/mol醇的缩合产物。可商购的此类非离子表面活性剂的例子包括联合碳化物公司(Union Carbide Corporation)出售的Tergitol15-S-9(C11-C15直链仲醇与9mol环氧乙烷的缩合产物)、Tergitol24-L-6NMW(窄分子量分布的C12-C14伯醇与6mol环氧乙烷的缩合产物);壳牌化学公司(Shell Chemical Company)出售的Neodol45-9(C14-C15直链醇与9mol环氧乙烷的缩合产物)、Neodol23-6.5(C12-C13直链醇与6.5mol环氧乙烷的缩合产物)、Neodol45-7(C14-C15直链醇与7mol环氧乙烷的缩合产物)、Neodol45-4(C14-C15直链醇与4mol环氧乙烷的缩合产物);和(The Procter & GambleCompany)出售的KyroEOB(C13-C15醇与9mol环氧乙烷的缩合产物)。其它可商购的非离子表面活性剂包括壳牌公司出售的Dobanol 91-8和Hoechst出售的Genapol UD-080。此类非离子表面活性剂一般称为“烷基乙氧基化物”。
优选的烷基多苷有下式:
R2O(CnH2nO)t(葡糖基)x其中R2选自烷基、烷基苯基、羟烷基、羟烷基苯基、及其混合物,其中所述烷基含有约10至约18、优选约12至约14个碳原子;n为2或3、优选2;t为0至约10、优选0;和x为约1.3至约10、优选约1.3至约3、最优选约1.3至约2.7。所述葡糖基优选由葡萄糖衍生。为制备这些化合物,先形成醇或烷基多乙氧基醇,然后与葡萄糖或葡萄糖源反应形成葡糖苷(在1-位相连)。然后可使其它葡糖基单元连接在它们的1-位和前面葡糖基单元的2-、3-、4-和/或6-位(优选主要是2-位)之间。
优选的酰胺是C8-C20氨酰胺、单乙醇酰胺、二乙醇酰胺、和异丙醇酰胺。
本发明组合物中存在非离子表面活性剂时,其存在量优选为有效量、更优选约0.1至约20%、甚至更优选约0.1至约15%、甚至还更优选约0.5至约10%重量。
多羟基脂肪酸酰胺表面活性剂-本发明洗涤剂组合物可还包含有效量的多羟基脂肪酸酰胺表面活性剂。“有效量”意指组合物的配方师可选择掺入组合物中的多羟基脂肪酸酰胺的量使其可以改善洗涤剂组合物的清洗效果。一般地,对于常用量,掺入约1%重量多羟基脂肪酸酰胺将提高清洗效果。
本发明洗涤剂组合物典型地包含约1%重量多羟基脂肪酸酰胺表面活性剂,优选约3至约30%多羟基脂肪酸酰胺。所述多羟基脂肪酸酰胺表面活性剂组分包括以下结构式的化合物:其中:R1为H、C1-C4烃基、2-羟乙基、2-羟丙基、或其混合物,优选C1-C4烷基、更优选C1或C2烷基、最优选C1烷基(即甲基);R2为C5-C31烃基、优选直链的C7-C19烷基或烯基、更优选直链的C9-C17烷基或烯基、最优选直链的C11-C15烷基或烯基、或其混合物;和Z为有至少3个羟基直接与直链烃基链相连的多羟基烃基、或其烷氧基化衍生物(优选乙氧基化或丙氧基化衍生物)。Z优选由还原糖在还原胺化反应中衍生得到;更优选Z为glycityl。适用的还原糖包括葡萄糖、果糖、麦芽糖、乳糖、半乳糖、甘露糖、和木糖。可用高葡萄糖玉米糖浆、高果糖玉米糖浆、和高麦芽糖玉米糖浆及以上所列各糖作为原料。这些玉米糖浆可产生糖组分的混合物用于Z。应理解决不是要排除其它适用的原料。Z优选自-CH2-(CHOH)n-CH2OH、-CH(CH2OH)-(CHOH)n-1-CH2OH、-CH2-(CHOH)2(CHOR’)(CHOH)-CH2OH、及其烷氧基化衍生物,其中n为3至5的整数(包括端值在内),R’为H或环状或脂族单糖。最优选糖基(glycityls),其中n为4,特别是-CH2-(CHOH)4-CH2OH。
R’可以是例如N-甲基、N-乙基、N-丙基、N-异丙基、N-丁基、N-2-羟乙基、或N-2-羟丙基。
R2-CO-N<可以是例如椰油酰胺、硬脂酰胺、油酰胺、月桂酰胺、肉豆蔻酰胺、癸酰胺、棕榈酰胺、牛油酰胺等。
Z可以是1-脱氧葡糖基、2-脱氧果糖基、1-脱氧麦芽糖基、1-脱氧乳糖基、1-脱氧半乳糖基、1-脱氧甘露糖基、1-脱氧麦芽三糖基等。
多羟基脂肪酸酰胺的制备方法为本领域已知。一般地,可在还原胺化反应中使烷基胺与还原糖反应形成相应的N-烷基多羟基胺,然后在缩合/酰胺化步骤中使N-烷基多羟基胺与脂肪族酯反应形成N-烷基、N-多羟基脂肪酸酰胺产品。含多羟基脂肪酸酰胺的组合物的制备方法公开在例如1959年2月18日公开的GB 809 060(Thomas Hedley& Co.,Ltd.)、1960年12月20日授予E.R.Wilson的US 2 965 576、1955年3月8日授予Anthony M.Schwartz的US 2 703 798、和1934年12月25日授予Piggott的US1 985 424中,这些文献均引入本文供参考。
阴离子/氧化胺/二胺之比
在本发明组合物的某些方面,所述阴离子表面活性剂∶氧化胺∶二胺之摩尔比为约100∶40∶1至约9∶0.5∶1,优选约27∶8∶1至约11∶3∶1。已发现含有此特定摩尔比的阴离子表面活性剂、氧化胺和二胺的洗涤剂组合物提供改善的低温稳定性、在低于12.5的pH下给予更好的去脂和难洗食物清洗效果、和改善的硬水洗净力。
在本发明的另一方面,已发现阴离子表面活性剂与二胺之摩尔比大于9∶1、优选大于20∶1获得改善的低温稳定性、给予更好的去脂和难洗食物清洗效果、和改善的硬水洗净力。
助洗剂-本发明组合物可进一步包括助洗剂体系。任何常用的助洗剂体系均适用于本发明,包括硅铝酸盐材料、硅酸盐、多羧酸盐和脂肪酸、诸如四乙酸乙二胺等材料、金属离子(多价)螯合剂如氨基聚膦酸盐特别是乙二胺四亚甲基膦酸和二亚乙基三胺五亚甲基膦酸。尽管因显而易见的环境原因不优选,但磷酸盐助洗剂也可用于本发明。
适用于本发明的多羧酸盐助洗剂包括柠檬酸(水溶性盐形式的)、式R-CH(COOH)CH2(COOH)的琥珀酸衍生物,其中R为C10-20烷基或烯基,优选C12-16,或者其中R可被羟基、磺基次硫酸基(sulfoxyl)或砜取代基取代。具体实例包括月桂基琥珀酸盐、肉豆蔻基琥珀酸盐、棕榈基琥珀酸盐、2-十二碳烯基琥珀酸盐、2-十四碳烯基琥珀酸盐。琥珀酸盐助洗剂优选以其水溶性盐形式使用,包括钠、钾、铵和链烷醇铵盐。
其它适用的多羧酸盐是氧代琥珀酸氢盐和一琥珀酸酒石酸酯和二琥珀酸酒石酸酯,如US4 663 071中所述。
尤其对于本发明的液体实施方案,适用于本发明的脂肪酸助洗剂是饱和或不饱和的C10-C18脂肪酸以及相应的皂。优选的饱和物质在烷基链中有12至16个碳原子。优选的不饱和脂肪酸是油酸。其它优选用于液体组合物的助洗剂体系是基于十二碳烯基琥珀酸和柠檬酸。
助洗剂盐的量通常为所述组合物的3至50%重量,优选5至30%重量,最优选5至25%重量。
任选的洗涤剂成分:
酶-本发明洗涤剂组合物可还包括一或多种提供清洗性能的酶。所述酶包括选自纤维素酶、半纤维素酶、过氧化物酶、蛋白酶、葡糖淀粉酶、淀粉酶、脂肪酶、角质素酶、果胶酶、木聚糖酶、还原酶、氧化酶、酚氧化酶、脂肪氧合酶、木质素酶、支链淀粉酶、丹宁酸酶、戊聚糖酶、苹果酸酶(malanase)、β-葡聚糖酶、阿拉伯糖酶或其混合物的酶。优选的组合是具有常用酶如蛋白酶、淀粉酶、脂肪酶、角质素酶和/或纤维素酶的鸡尾酒的洗涤剂组合物。组合物中存在酶时,其量为洗涤剂组合物的约0.0001至约5%重量。
蛋白水解酶-所述蛋白水解酶可以是动物、植物或微生物(优选)源的。用于本发明洗涤剂组合物的蛋白酶包括但不限于胰蛋白酶、枯草杆菌蛋白酶、糜蛋白酶、和弹性蛋白酶型蛋白酶。优选用于本发明的是枯草杆菌蛋白酶型蛋白水解酶。特别优选的是来自枯草芽孢杆菌和/或地衣芽孢杆菌的细菌丝氨酸蛋白水解酶。
适用的蛋白水解酶包括Novo Industri A/S Alcalase(优选)、Esperase、Savinase(哥本哈根,丹麦)、Gist-brocades’Maxatase、Maxacal和Maxapem 15(protein engineeredMaxacal)(Delft,荷兰),和枯草杆菌蛋白酶BPN和BPN’(优选),这些均可商购。优选的蛋白水解酶也是改性细菌丝氨酸蛋白酶,如Genencor International,Inc.(旧金山,加洲)制造的那些,描述在1994年12月28日授权的EP 251 446B(特别是第17、24和98页)中,本文中也称为“蛋白酶B”。1991年7月9日授予Venegas的US5 030 378提及一种改性细菌丝氨酸蛋白水解酶(GenencorInternational),本文中称为“蛋白酶A”(与BPN’相同)。特别参见US 5 030 378第2和3栏关于蛋白酶A及其变种的描述包括氨基序列。其它蛋白酶以下列商品名出售:Primase、Durazym、Opticlean和Optimase。优选的蛋白水解酶选自Alcalase(Novo IndustriA/S)、BPN’、Protease A和Protease B(Genencor),及其混合物。最优选蛋白酶B。
本发明特别关心的是US 5 470 733中描述的蛋白酶。
我们的共同待审申请USSN 08/136 797中所述蛋白酶也可包括在本发明洗涤剂组合物中。
另一种优选的蛋白酶(称为“蛋白酶 D”)是有自然界中未发现的氨基酸序列的羰基水解酶变体由羰基水解酶前体通过用不同的氨基酸代替所述羰基水解酶中相当于+76位的多数氨基酸残基衍生得到,优选还与一或多种相当于按解淀粉芽孢杆菌枯草溶菌素(Bacillus amyloliquefaciens subtilisin)的计数选自+99、+101、+103、+104、+107、+123、+27、+105、+109、+126、+128、+135、+156、+166、+195、+197、+204、+206、+210、+216、+217、+218、+222、+260、+265、和/或+274的那些氨基酸残基位组合,如1995年4月20日公开的Genencor International的WO95/10615(A.Baeck等题为“含蛋白酶的清洗组合物”,1994年10月13日申请的US序号08/322 676)中所述。
适用的蛋白酶还描述在以下文献中:1995年11月9日公开的TheProcter & Gamble Company的WO 95/30010;1995年11月9日公开的The Procter & Gamble Company的WO 95/30011;1995年11月9日公开的普罗克特-甘布尔公司(The Procter & Gamble Company)的WO 95/29979。
本发明组合物中蛋白酶的掺入量可为组合物重量的0.0001至2%重量的活性酶。
淀粉酶-可包括淀粉酶(α和/或β)以去除碳水化合物基污渍。适用的淀粉酶是Termamyl(Novo Nordisk)、Fungamyl和BAN(NovoNordisk)。这些酶可以是任何适合源的,如植物、动物、细菌、真菌和酵母源。淀粉酶在洗涤剂组合物中的掺入量通常为洗涤剂组合物的0.0001%至2%、优选约0.0001%至约0.5%、更优选约0.0005%至约0.1%、甚至更优选约0.001%至约0.05%重量的活性酶。
淀粉酶还包括WO95/26397和Novo Nordisk的共同待审申请PCT/DK96/00056中所述的那些。用于本发明洗涤剂组合物的其它淀粉酶包括:
(a)特征在于在25至55℃的温度范围和8至10范围内的pH值下通过Phadebasα-淀粉酶活性鉴定法测量的比活度比Termamyl的比活度高至少25%的α-淀粉酶。Phadebasα-淀粉酶活性鉴定法描述在WO95/26397的第9-10页。
(b)包含上面所引参考文献中SEQ ID表中所示氨基序列的根据(a)的α-淀粉酶,或者与SEQ ID表中的氨基酸序列至少80%同系的α-淀粉酶。
(c)由嗜碱杆菌种得到的根据(a)的α-淀粉酶,在N-端包括以下氨基序列:His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp。
如果与各种氨基酸序列对比(通过算法进行),多肽被认为是亲代淀粉酶的X%同系物,如Lipman和Pearson,科学(Science)227,1985,1435页描述了一种算法,揭示了X%的本体。
(d)根据(a-c)的α-淀粉酶,其中所述α-淀粉酶可来自嗜碱杆菌种;特别是来自菌株NCIB 12289、NCIB 12512、NCIB 12513和DSM 935的任一种。
本文中术语“可来自”不仅意指由杆菌菌株产生的淀粉酶,而且指由从这种杆菌菌株分离的DNA序列编码和用所述DNA序列变换的宿主有机体中产生的淀粉酶。
(e)对具有分别相应于(a-d)中那些α-淀粉酶的氨基酸序列的α-淀粉酶产生的抗体呈阳性免疫交叉反应的α-淀粉酶。
(f)以下亲代α-淀粉酶的变种:(ⅰ)有分别对应于(a-e)中那些α-淀粉酶所示的氨基酸序列之一,或(ⅱ)与所述氨基酸序列的一种或多种显示至少80%同系,和/或对具有所述氨基酸序列的一种α-淀粉酶产生的抗体显示出免疫交叉反应,和/或由具有所述氨基酸序列之一的DNA序列编码的α-淀粉酶相同的探子杂交的DNA序列进行编码;这些变种中:
1.已去掉所述亲代α-淀粉酶的至少一个氨基酸残基;和/或
2.所述亲代α-淀粉酶的至少一个氨基酸残基已被不同的氨基酸残基替换;和/或
3.已对所述亲代α-淀粉酶插入至少一个氨基酸残基;
所述变种有α-淀粉酶活性,并相对于所述亲代α-淀粉酶表现出至少一种以下性质:热稳定性提高、对氧化的稳定性提高、Ca离子依赖性降低、在中性至较高pH值下的稳定性和/或α-淀粉分解活性提高、在较高温度下的α-淀粉分解活性提高、和等电点(pI)升高或下降以使α-淀粉酶变种的pI值更好地与介质的pH匹配。
所述变种描述在专利申请PCT/DK 96/00056中。
适用于本发明的其它淀粉酶包括例如GB1 296 839(Novo)中所述α-淀粉酶;RAPIDASE,国际生物合成有限公司;和TERMAMYL,Novo。来自Novo的FUNGAMYL特别适用。用于改善稳定性例如氧化稳定性的酶工程是已知的。例如,参见生物化学杂志(J.BiologicalChem),第260卷第11期1985年6月,6518-6521页。本发明某些优选实施方案可在洗涤剂如自动餐具洗涤型洗涤剂中使用有改善稳定性的淀粉酶,特别是相对于1993工业使用的TERMAMYL的基准点测量的氧化稳定性得到改善。这些优选的淀粉酶具有“稳定性提高的”淀粉酶的特性,特征在于至少以下性质的一种或多种有可测量出的改善:氧化稳定性,例如在pH9-10的缓冲溶液中对过氧化氢/四乙酰基乙二胺;热稳定性,例如在常用洗涤温度如约60℃下;或碱稳定性,例如在约8至约11的pH下,相对于上述基准点淀粉酶测量。稳定性可用本领域公开的任何测试技术测量。例如,参见WO94/02597中所公开的。稳定性提高的淀粉酶可来自Novo或来自GenencorInternational。一类非常优选的淀粉酶具有利用定位诱变由一或多种杆菌淀粉酶特别是杆菌α-淀粉酶衍生的共性,无论是一、二、还是多个淀粉酶菌株是所述直接前体。相对于上述基准淀粉酶氧化稳定性提高的淀粉酶优选用于本发明漂白、更优选氧漂白(区别于氯漂白)洗涤剂组合物。这种优选的淀粉酶包括:(a)根据前面引入的WO94/02597(Novo,94年2月3日)的淀粉酶,用其中所述地衣芽孢杆菌α-淀粉酶(称为TERMAMYL)197位的甲硫氨酸残基用丙氨酸或苏氨酸(优选苏氨酸)取代的突变体、或类似亲代淀粉酶如淀粉解凝杆菌、枯草芽孢杆菌或嗜热脂肪芽孢杆菌的同系位变体;(b)稳定性提高的淀粉酶,如Genencor International在第207期美国化学协会全国会议(American Chemical Society National Meeting)(1994年3月13-17日)上由C.Mitchinson提出的题为“耐氧化α-淀粉酶(Oxidatively Resistant alpha-Amylases)”的论文中所述。其中注意到自动餐具洗涤剂中的漂白剂使α-淀粉酶钝化但Genencor已由地衣芽孢杆菌NCIB8061制备出氧化稳定性改善的淀粉酶。甲硫氨酸(Met)被确定为最可能被改性的残基。Met在8、15、197、256、304、366和438位被取代(每次一个)产生特殊的突变体,特别重要的是M197L和M197T,M197T变体是最稳定的表达变体。稳定性在CASCADE和SUNLIGHT中测量;(c)本文中特别优选的淀粉酶包括如WO95/10603中所述直接亲体中有其它改性的淀粉酶变种,可商购自Novo,DURAMYL。其它特别优选的氧化稳定性提高的淀粉酶包括WO94/18314(Genencor International)和WO 94/02597(Novo)中所述的那些。任何其它的氧化稳定性提高的淀粉酶均可使用,例如由已知的嵌合、杂交或单突变母体形式的可用淀粉酶通过定位诱变衍生的那些。其它优选的酶改性也可以。参见WO95/09909(Novo)。
本发明中还可包括各种赋予抗菌活性的糖酶。这种酶包括内糖苷酶、Ⅱ型内糖苷酶和葡糖苷酶,如US5 041 236、5 395 541、5 238843和5 356 803中所公开的,这些文献引入本文供参考。当然,其它有抗菌活性的酶以及过氧化物酶、氧化酶和各种其它酶也可使用。
本发明组合物中存在任何酶时,组合物中还可包括酶稳定体系。
香料-适用于本发明组合物和方法中的香料和香精组分包括各种天然和合成的化学成分,包括但不限于醛、酮、和酯类等。还包括各种天然提取物和香料,可能包含多种成分的复杂混合物,如橙油、柠檬油、玫瑰提取物、薰衣草、麝香、广藿香、香脂香料、檀香木油、松油、雪松等。成品香料可能包括这些成分的极复杂的混合物。成品香料典型地占本发明洗涤剂组合物的约0.01%至约2%重量,各单独香精组分可占成品香料组合物的约0.0001%至约90%。
适用于本发明的香料成分的非限制实例包括:7-乙酰基-1,2,3,4,5,6,7,8-八氢-1,1,6,7-四甲基萘;甲基紫罗兰酮;γ-甲基紫罗兰酮;甲基柏木酮;二氢茉莉酮酸甲酯;甲基1,6,10-三甲基-2,5,9-环十二碳三烯-1-基酮;7-乙酰基-1,1,3,4,4,6-六甲基萘满;4-乙酰基-6-叔丁基-1,1-二甲基茚满;对羟苯基丁酮;二苯酮;甲基β-萘基酮;6-乙酰基-1,1,2,3,3,5-六甲基茚满;5-乙酰基-3-异丙基-1,1,2,6-四甲基茚满;1-十二醛;4-(4-羟基-4-甲基戊基)-3-环己烯-1-甲醛;7-羟基-3,7-二甲基辛醛;10-十一碳烯-1-醛;异己烯基环己基甲醛;甲酰基三环癸烷;羟基香茅醛与邻氨基苯甲酸甲酯的缩合产物;羟基香茅醛与吲哚(indol)的缩合产物;苯乙醛与吲哚的缩合产物;2-甲基-3-(对叔丁基苯基)-丙醛;乙基香兰素;天芥菜精;己基肉桂醛;戊基肉桂醛;2-甲基-2-(对异丙基苯基)-丙醛;香豆素;γ-癸内酯;环十五烷内酯;16-羟基-9-十六碳烯酸内酯;1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基环戊-γ-2-苯并吡喃;β-萘酚甲醚;降龙涎香烷(ambroxane);十二氢-3a,6,6,9a-四甲基萘并[2,1b]呋喃;雪松醇,5-(2,2,3-三甲基环戊-3-烯基)-3-甲基戊-2-醇;2-乙基-4-(2,2,3-三甲基-3-环戊烯-1-基)-2-丁烯-1-醇;石竹烯醇;丙酸三环癸烯酯;乙酸三环癸烯酯;水杨酸苄酯;乙酸柏木酯;和乙酸对叔丁基环己酯。
特别优选的香料是在含有纤维素酶的产品组合物中提供最大气味改善的那些。这些香料包括但不限于:己基肉桂醛;2-甲基-3-(对叔丁基苯基)-丙醛;7-乙酰基-1,2,3,4,5,6,7,8-八氢-1,1,6,7-四甲基萘;水杨酸苄酯;7-乙酰基-1,1,3,4,4,6-六甲基萘满;乙酸对叔丁基环已酯;二氢茉莉酮酸甲酯;β-萘酚甲醚;甲基β-萘基酮;2-甲基-2-(对异丙基苯基)-丙醛;1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基环戊-γ-2-苯并吡喃;十二氢-3a,6,6,9a-四甲基萘并[2,1b]呋喃;茴香醛;香豆素;雪松醇;香兰素;环十五烷内酯;乙酸三环癸烯酯;和丙酸三环癸烯酯。
其它香料包括来自各种源的香精油、香膏和树脂,包括但不限于:秘鲁香脂、乳香膏、苏合香脂、岩蔷薇树脂、肉豆蔻、桂皮油、安息香树脂、芫荽、和薰衣草素(lavandin)。其它的香料化学物质包括苯乙醇、松油醇、芳樟醇、乙酸芳樟酯、香叶醇、橙花醇、2-(1,1-二甲基乙基)环己醇乙酸酯、乙酸苄酯、和丁子香酚。成品香料组合物中可使用载体如邻苯二甲酸二乙酯。
螯合剂-本发明洗涤剂组合物还可任选地包含一或多种铁和/或镁螯合剂。这种螯合剂可选自氨基羧酸盐、氨基膦酸盐、多官能取代的芳族螯合剂及其混合物,如下文中所述。不想受理论限制,相信这些物质的益处部分是因为它们通过形成可溶性螯合物而从洗涤溶液中除去铁和镁离子的特殊能力。
适合用作可选螯合剂的氨基羧酸盐包括乙二胺四乙酸盐、N-羟乙基乙二胺三乙酸盐、腈基-三乙酸盐、乙二胺四丙酸盐、三亚乙基四胺六乙酸盐、二亚乙基三胺五乙酸盐、和乙醇二甘氨酸,其碱金属、铵和取代的铵盐及其混合物。
当洗涤剂组合物中至少允许少量总磷时,氨基膦酸盐也适合在本发明组合物中作为螯合剂,包括乙二胺四(亚甲基膦酸盐)如DEQUEST。优选地,这些氨基膦酸盐不含有多于约6个碳原子的烷基或链烯基。
多官能取代的芳族螯合剂也适用于本发明组合物。参见1974年5月21日授予Connor等的US 3 812 044。优选的酸型此类化合物是二羟基二磺基苯如1,2-二羟基-3,5-二磺基苯。
优选用于本发明的可生物降解的螯合剂是乙二胺二琥珀酸盐(“EDDS”),特别是[S,S]异构体,如1987年11月3日授予Hartman和Perkins的US4 704 233中所述。
本发明组合物可还含有水溶性甲基甘氨酸二乙酸(MGDA)盐(或酸形式)作为螯合剂或助洗剂。类似地,所谓“弱”助洗剂如柠檬酸也可用作螯合剂。
如使用,这些螯合剂-般占本发明洗涤剂组合物的约0.1%至约15%重量。更优选地,如使用,所述螯合剂占组合物的约0.1%至约3.0%重量。
组合物的pH
本发明餐具洗涤剂组合物投入使用即被稀释而用于带污垢餐具时,经受食物污垢产生的酸性应力。如果要使pH大于7的组合物更有效,优选含有能在组合物和稀释溶液即所述组合物的约0.1%至0.4%重量水溶液中提供较高的碱性pH的缓冲剂。此缓冲剂的pKa值应比所述组合物的要求pH值(如前面所述确定)低约0.5至1.0pH单位。优选地,所述缓冲剂的pKa应为约7至约10。在这些条件下,所述缓冲剂在用量最少的情况下最有效地控制pH。
所述缓冲剂本身可以是高效洗涤剂,或者可以是在此组合物中仅用于保持碱性pH的低分子量有机或无机物。优选用于本发明组合物的缓冲剂是含氮物质。一些例子是氨基酸如赖氨酸或低级醇胺如一-、二-、和三-乙醇胺。其它优选的含氮缓冲剂是三(羟甲基)氨基甲烷(HOCH2)3CNH3(TRIS)、2-氨基-2-乙基-1,3-丙二醇、2-氨基-2-甲基-丙醇、2-氨基-2-甲基-1,3-丙醇、谷氨酸二钠、N-甲基二乙醇酰胺、1,3-二氨基丙醇、N,N’-四甲基-1,3-二氨基-2-丙醇、N,N-二(2-羟乙基)甘氨酸(二甘氨酸)和N-三(羟甲基)甲基甘氨酸(三甘氨酸)。以上之任意的混合物也可接受。适用的无机缓冲剂/碱度源包括碱金属碳酸盐和碱金属磷酸盐,例如碳酸钠、聚磷酸钠。关于其它缓冲剂,参见McCutcheon的“乳化剂和洗涤剂”(EMULSIFIERSAND DETERGENTS),北美编辑1997,McCutcheon分部,MC出版公司Kirk和WO95/07971,均引入本文供参考。
如使用,所述缓冲剂在本发明组合物中的存在量占组合物的约0.1%至15%、优选约1%至10%、最优选约2至8%重量。
其它成分-所述洗涤剂组合物进一步优选包括一种或多种洗涤剂用添加剂,选自:去污聚合物、聚合型分散剂、电解质(如氯化钠)、多糖、磨料、杀菌剂、晦暗抑制剂、助洗剂、酶、染料、缓冲剂、抗真菌或霉控制剂、驱虫剂、香料、增溶剂、增稠剂、加工助剂、增泡剂、增白剂、防腐助剂、稳定剂、抗氧化剂和螯合剂。本发明组合剂中可包括各种各样适用于洗涤剂组合物的其它成分,包括其它活性成分、载体、增溶剂、抗氧化剂、加工助剂、染料或颜料、用于液体配方的溶剂、用于条状组合物的固体填料等。如果要求高度起泡,可向组合物中掺入增泡剂如C10-C16链烷醇酰胺,典型地在1-10%的水平。C10-C14一乙醇和二乙醇酰胺是典型的一类此增泡剂。这种增泡剂与高度起泡的附加表面活性剂如上述氧化胺、甜菜碱和磺基甜菜碱一起使用也是有利的。
抗氧化剂可任选地加入本发明洗涤剂组合物中。它们可以是任何常用于洗涤剂组合物中的抗氧化剂,如2,6-二叔丁基-4-甲基苯酚(BHT)、甲氨酸盐、抗坏血酸、硫代硫酸盐、单乙醇胺(MEA)、二乙醇胺、三乙醇胺等。存在抗氧化剂时,其在所述组合物中的存在量优选为约0.001%至约5%重量。
用于本发明组合物的各种洗涤成分可任选地通过以下方法进一步稳定:将所述成分吸收在多孔疏水基质上、然后用疏水涂料涂布所述基质。优选地,使所述洗涤成分与表面活性剂混合,然后吸收至多孔基质中。使用中,所述洗涤成分从所述基质中释放至含水洗液中,发挥其去污作用。
为更详细地说明此技术,使多孔疏水氧化硅(商标SIPERNAT D10DeGussa)与含3-5%C13-15乙氧基化醇(E07)非离子表面活性剂的蛋白水解酶溶液混合。典型地,所述酶/表面活性剂溶液为二氧化硅重量的2.5倍。在搅拌下使所得粉末分散在硅油中(可使用粘度在500-12 500范围内的各种硅油)。使所得硅油分散体乳化或加入最终洗涤剂基体中。这样,诸如上述酶、漂白剂、助漂剂、漂白催化剂、光活化剂、染料、荧光增白剂、织物调理剂和可水解表面活性剂等成分可被“保护”用于洗涤剂,包括洗衣用液体洗涤剂组合物。
此外,这些手洗餐具洗涤剂实施方案优选还包括水溶助长剂。适用的水溶助长剂包括甲苯磺酸、萘磺酸、枯烯磺酸,二甲苯磺酸的钠、钾、铵或水溶性取代铵盐。
本发明洗涤剂组合物可以是任何形式的,包括粒状、膏状、凝胶或液体。非常优选的实施方案是液体或凝胶形式。液体洗涤剂组合物可含水和其它溶剂作为载体。低分子量的伯或仲醇如甲醇、乙醇、丙醇和异丙醇是适用的。为溶解表面活性剂,优选一元醇,但多元醇如含2至约6个碳原子和2至约6个羟基的那些(例如1,3-丙二醇、乙二醇、丙三醇和1,2-丙二醇)也可使用。所述组合物可含有5%至90%、典型地10%至50%这种载体。
本发明洗涤剂组合物颗粒的制备方法之一例如下:加入直链烷基苯磺酸盐、柠檬酸、硅酸钠、硫酸钠、香料、二胺和水,加热,通过搅和机混合。将所得浆液喷雾干燥成为颗粒形式。
本发明液体洗涤剂组合物的制备方法的一个例子如下:向自由水中加入柠檬酸盐并使之溶解。向此溶液中加入氧化胺、甜菜碱、乙醇、水溶助长剂和非离子表面活性剂。如果游离水不能利用,则将所述柠檬酸盐加入上述混合物中,然后搅拌直至溶解。这里加入酸以中和所述配方。所述酸优选选自有机酸如马来酸和柠檬酸,但无机酸也可使用。在优选实施方案中,将这些酸加入所述配方中,然后加入二胺。最后加入AExS。
非水基液体洗涤剂
包含非水载体介质的液体洗涤剂组合物可根据以下文献中所公开的方法制备:US 4 753 570;4 757 558;4 772 413;4 889 652;4 892 673;GB-A-2 158 838;GB-A-2 195 125;GB-A-2 195 649;US 4 988 462;US 5 266 233;EP-A-225 654(6/16/87);EP-A-510 762(10/28/92);EP-A-540 089(5/5/93);EP-A-540 090(5/5/93);US 4 615 820;EP-A-565 017(10/13/93);EP-A-030096(6/10/81),这些文献引入本文供参考。这种组合物可包含各种稳定地悬浮于其中的各种颗粒洗涤成分。这种非水基组合物包括液相和(任选地但优选地)固相,如后面详述和引用的参考文献中所述。
本发明组合物可用于形成手洗餐具洗涤用的含水洗涤溶液。一般地,将有效量的所述组合物加入水中形成这种含水洗涤或浸泡溶液。然后使如此形成的水溶液与餐具和烹饪用具接触。
加入水中形成含水洗涤溶液的有效量的本发明洗涤剂组合物可包括足以在水溶液中形成约500至20 000ppm组合物的量。更优选地,在含水洗液中提供约800至5 000ppm本发明洗涤剂组合物。
以下实施例说明本发明,但决不限制或限定其范围。除非另有说明,本文中所有份数、百分率和比例均基于重量。
以下实施例中所有含量均以组合物的%重量形式给出。
实施例
表Ⅰ
实施例1 | 实施例2 | |
AE0.6S1 | 28.80 | 28.80 |
氧化胺2 | 7.20 | 7.20 |
柠檬酸 | 3.00 | --- |
马来酸 | --- | 2.50 |
增泡聚合物3 | 0.22 | 0.22 |
枯烯磺酸钠 | 3.30 | 3.30 |
乙醇40B | 6.50 | 6.50 |
C10E8 | --- | --- |
C11E94 | 3.33 | 3.33 |
二胺5 | 0.55 | 0.55 |
香料 | 0.31 | 0.30 |
水 | 余量 | 余量 |
粘度(eps@70F) | 330 | 330 |
pH@10% | 9.0 | 9.0 |
表Ⅱ
实施例3 | 实施例4 | 实施例5 | 实施例6 | 实施例7 | |
AEO.6S1 | 26 | 26 | 26 | 26 | 26 |
氧化胺2 | 6.5 | 6.5 | 7.5 | 7.5 | 7.5 |
柠檬酸 | 3.0 | - | 2.5 | - | 3.0 |
马来酸 | - | 2.5 | - | 3.0 | - |
C10E86 | 3 | 3 | 4.5 | 4.5 | 4.5 |
二胺5 | 0.5 | 0.5 | 1.25 | 0 | 1.25 |
二胺7 | 0 | 0 | 0 | 1 | |
增泡聚合物3 | 0 | 0.2 | 0.5 | 0.5 | 0.5 |
枯烯磺酸钠 | 3.5 | 3.5 | 2 | 2 | 2 |
乙醇 | 8 | 8 | 8 | 8 | 8 |
pH | 9 | 9 | 9 | 8 | 10 |
阴离子∶氧化胺∶二胺的摩尔比 | 27∶8∶1 | 27∶8∶1 | 11∶3.5∶1 | 11∶3.5∶1 | 11∶3.5∶1 |
表Ⅲ
实施例8 | 实施例9 | 实施例10 | 实施例11 | |
AEO.6S1 | 26.09 | 26.09 | 26.09 | 28.80 |
氧化胺2 | 6.50 | 6.50 | 6.50 | 7.20 |
增泡聚合物3 | 0.20 | 0.20 | 0.20 | 0.22 |
枯烯磺酸钠 | 3.50 | 3.50 | 3.50 | 3.90 |
C10E8 | 3.00 | 3.00 | 3.00 | 3.30 |
二胺5 | 0.50 | 0.50 | 0.50 | 0.55 |
水和其他 | 余量 | 余量 | 余量 | 余量 |
粘度(cps@70F) | 150 | 330 | 650 | 330 |
pH@10% | 8.3 | 9.0 | 9.0 | 9.0 |
1:平均含0.6个乙氧基的C12-13烷基乙氧基磺酸盐。
2:C12-C14氧化胺。
3:聚合物为甲基丙烯酸(N,N-二甲氨基)乙酯均聚物。
4:含9个乙氧基的C11烷基乙氧基化表面活性剂。
5:1,3-二(甲胺)-环己烷。
6:含8个乙氧基的C10烷基乙氧基化表面活性剂。
7:1,3-戊二胺。
Claims (15)
1.一种手洗餐具洗涤剂组合物,包含:
a)一种具有pK1和pK2的低分子量有机二胺,其中所述二胺的pK1和pK2均在8.0至11.5的范围内;
b)一种阴离子表面活性剂;
c)一种氧化胺表面活性剂;
所述组合物基本上无镁和钙盐;其中以10%水溶液测量的pH为5.0至12.5,所述阴离子表面活性剂与所述氧化胺与所述二胺之摩尔比为100∶40∶1至9∶0.5∶1。
2.权利要求1的手洗餐具洗涤剂组合物,其中所述二胺选自:
其中R2-5独立地选自H、甲基、乙基、和氧化乙烯;Cx和Cy独立地选自亚甲基或支链烷基,其中x+v为约3至约6;A可选地存在,选自为将所述二胺的pKa调节至要求范围所选的给电子或吸电子部分;如果存在A,则x和y必须均为2或更大。
3.权利要求1或2的手洗餐具洗涤剂组合物,其中所述二胺选自二甲氨基丙胺、1,6-己二胺、1,3-丙二胺、2-甲基-1,5-戊二胺、1,3-戊二胺、1,3-二氨基丁烷、1,2-二(2-氨基乙氧基)乙烷、异佛尔酮二胺、1,3-二(甲胺)-环己烷及其混合物。
4.权利要求1-3任一的手洗餐具洗涤剂组合物,还包含一种聚合型泡沫稳定剂,选自:
ⅰ)下式的丙烯酸(N,N-二烷氨基)烷基酯的均聚物:
其中每个R独立地为氢、C1-C8烷基、及其混合物,R1为氢、C1-C6烷基、及其混合物,n为2至约6;和
ⅱ)(ⅰ)与下式化合物的共聚物:
其中R1为氢、C1-C6烷基、及其混合物;条件是(ⅱ)与(ⅰ)之比为约2∶1至约1∶2;其中所述聚合型泡沫稳定剂的分子量为1000至2000000道尔顿。
5.一种适用于手洗餐具洗涤的洗涤剂组合物,所述组合物包含:
a)0.1%至5%重量分子量小于或等于400g/mol的有机二胺;
b)5%至50%重量的阴离子表面活性剂;
c)0.5%至10%重量的氧化胺表面活性剂;
d)0.001%至2%重量的香料;
e)0.01%至5%重量的聚合型泡沫稳定剂,选自:
ⅰ)下式的丙烯酸(N,N-二烷氨基)烷基酯的均聚物:
其中每个R独立地为氢、C1-C8烷基、及其混合物,R1为氢、C1-C6烷基、及其混合物,n为2至6;和
ⅱ)(ⅰ)与下式化合物的共聚物:
其中R1为氢、C1-C6烷基、及其混合物;条件是(ⅱ)与(ⅰ)之比为2∶1至1∶2;其中所述聚合型泡沫稳定剂的分子量为1000至2 000 000道尔顿;
所述组合物基本上无镁和钙盐;其中以10%水溶液测量的pH为5.0至12.5,所述阴离子表面活性剂与所述氧化胺与所述二胺之摩尔比为27∶8∶1至11∶3∶1。
其中每个R6独立地选自氢、C1-C4直链或支链烷基、有下式的亚烷氧基:
-(R7O)mR8
其中R7为C2-C4直链或支链亚烷基、及其混合物;R8为氢、C1-C4烷基、及其混合物;m为1至10;X为选自以下的单元:
ⅰ)C3-C10直链亚烷基、C3-C10支链亚烷基、C3-C10环状亚烷基、C3-C10支链的环状亚烷基、下式的亚烷氧基亚烷基:
-(R7O)mR7-
其中R7和m与前面定义的相同;
ⅱ)C3-C10直链亚烷基、C3-C10支链亚烷基、C3-C10环状亚烷基、C3-C10支链的环状亚烷基、C6-C10亚芳基,其中所述单元包括一个或多个使所述二胺的pKa大于8的给电子或吸电子部分;和
ⅲ)(ⅰ)和(ⅱ)的混合物,
使所述二胺具有大于8的pKa。
7.一种适用于手洗餐具洗涤的洗涤剂组合物,所述组合物包含:
a)一种具有pK1和pK2的低分子量有机二胺,其中所述二胺的pK1和pK2均在8.0至11.5的范围内;
b)一种阴离子表面活性剂;
所述组合物基本上无镁和钙盐;其中以10%水溶液测量的pH为5.0至12.5,所述阴离子表面活性剂与所述二胺的摩尔比大于9∶1。
8.权利要求1-7任一的手洗餐具洗涤剂组合物,还包含一种非离子表面活性剂,选自多羟基脂肪酸酰胺、甜菜碱、磺基甜菜碱、烷基多苷、烷基乙氧基化物、及其混合物。
9.权利要求1-8任一的手洗餐具洗涤剂组合物,其中所述阴离子表面活性剂选自直链烷基苯磺酸盐、α-烯烃磺酸盐、石蜡烃磺酸盐、甲酯磺酸盐、烷基硫酸盐、烷基烷氧基硫酸盐、烷基磺酸盐、烷基烷氧基化硫酸盐、肌氨酸盐、牛磺酸盐、烷基烷氧基羧酸盐、及其混合物。
10.权利要求1-9任一的手洗餐具洗涤剂组合物,还包含一种多羧酸盐助洗剂,其中所述多羧酸盐助洗剂选自柠檬酸、马来酸、琥珀酸衍生物及其混合物。
11.权利要求1-10任一的手洗餐具洗涤剂组合物,还包含一种或多种洗涤剂用添加剂,选自:污垢解脱聚合物、聚合型分散剂、多糖、磨料、杀菌剂、晦暗抑制剂、助洗剂、酶、染料、香料、增稠剂、抗氧化剂、加工助剂、增泡剂、缓冲剂、抗真菌或霉控制剂、驱虫剂、防腐助剂、和螯合剂。
12.液体形式的权利要求1-11任一的手洗餐具洗涤剂组合物。
13.权利要求1-12任一的组合物,其中所述有机二胺为1,3-二(甲胺)-环己烷。
14.权利要求1-13任一的手洗餐具洗涤剂组合物,还包含0.1%至15%重量pKa为7至10的缓冲剂,其中所述缓冲剂选自碱金属碳酸盐、碱金属磷酸盐、赖氨酸、三(羟甲基)氨基甲烷及其混合物。
15.一种餐具洗涤方法,所述方法包括使需要清洗的带污垢餐具与权利要求1-14任一组合物的水溶液接触。
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US8769398P | 1998-06-02 | 1998-06-02 | |
US60/087,693 | 1998-06-02 |
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CN99809286A Pending CN1311813A (zh) | 1998-06-02 | 1999-02-05 | 含有机二胺的餐具洗涤剂组合物 |
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US (1) | US6589926B1 (zh) |
EP (1) | EP1073703B1 (zh) |
JP (1) | JP4007478B2 (zh) |
KR (1) | KR20010071376A (zh) |
CN (1) | CN1311813A (zh) |
AU (1) | AU2496599A (zh) |
BR (1) | BR9911614A (zh) |
CA (1) | CA2333610A1 (zh) |
CZ (1) | CZ20004477A3 (zh) |
DE (1) | DE69901703T2 (zh) |
ES (1) | ES2175937T3 (zh) |
HU (1) | HUP0102742A2 (zh) |
ID (1) | ID27533A (zh) |
PL (1) | PL344646A1 (zh) |
TR (1) | TR200100188T2 (zh) |
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- 1999-02-05 PL PL99344646A patent/PL344646A1/xx unknown
- 1999-02-05 ID IDW20002520A patent/ID27533A/id unknown
- 1999-02-05 CZ CZ20004477A patent/CZ20004477A3/cs unknown
- 1999-02-05 HU HU0102742A patent/HUP0102742A2/hu unknown
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CZ20004477A3 (cs) | 2002-01-16 |
HUP0102742A2 (hu) | 2002-01-28 |
ES2175937T3 (es) | 2002-11-16 |
DE69901703T2 (de) | 2003-01-30 |
AU2496599A (en) | 1999-12-20 |
TR200100188T2 (tr) | 2002-01-21 |
BR9911614A (pt) | 2001-02-06 |
US6589926B1 (en) | 2003-07-08 |
EP1073703A1 (en) | 2001-02-07 |
KR20010071376A (ko) | 2001-07-28 |
PL344646A1 (en) | 2001-11-19 |
DE69901703D1 (de) | 2002-07-11 |
JP2002517549A (ja) | 2002-06-18 |
JP4007478B2 (ja) | 2007-11-14 |
CA2333610A1 (en) | 1999-12-09 |
WO1999063034A1 (en) | 1999-12-09 |
EP1073703B1 (en) | 2002-06-05 |
ID27533A (id) | 2001-04-12 |
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