CN1087343C - 液体餐具洗涤剂 - Google Patents

液体餐具洗涤剂 Download PDF

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CN1087343C
CN1087343C CN96199580A CN96199580A CN1087343C CN 1087343 C CN1087343 C CN 1087343C CN 96199580 A CN96199580 A CN 96199580A CN 96199580 A CN96199580 A CN 96199580A CN 1087343 C CN1087343 C CN 1087343C
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anion surfactant
dishwashing detergent
hydrotropic
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E·H·布鲁姆鲍
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Tongda Commercial Group International Co.
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Abstract

本发明制备了显示增加的粘度、较好的溶解速率和在硬水中的惊人的改善的洗涤性能的液体餐具洗涤剂组合物，其包括约1%-约90%的阴离子表面活性剂和约1%至约30%的选自烷氧基化甘油酯、烷氧基化甘油、烷氧基化甘油的酯、烷氧基化脂肪酸、甘油酯和聚甘油酯和它们的混合物的溶剂水溶助长剂。

Description

液体餐具洗涤剂
发明背景
本发明涉及轻垢餐具洗涤剂，尤其涉及含有脂肪酸或甘油衍生物作为水溶助长剂的轻垢餐具洗涤剂组合物。
以下说明书中使用的术语“餐具”表示需要洗涤以除去食物颗粒和其它食物残渣、油腻、蛋白质、淀粉、胶状物、染料、油和烧焦有机残渣的器皿。
轻垢液体餐具洗涤剂，例如适用于洗涤餐具的洗涤剂是已知的，并由于它们良好的洗涤和发泡性质和便利的使用方式而满足消费者的高度要求。许多现有的餐具洗涤剂配方含有阴离子表面活性剂，它会成胶除非被各种溶剂或水溶助长剂保护。水溶助长剂是粘度控制剂、凝胶抑制剂、稳定剂和分散助剂。常规使用的水溶助长剂包括醇和醇衍生物，包括二醇和烷氧基化醇。
醇和二醇所遇到的问题是达到配方稳定性所需的量会足以降低组合物的总体粘度至消费者将会认为它们不是获得最佳餐具洗涤制剂的程度。高含量的醇还可影响在组合物中使用的香料的感觉，影响消费者对产品的感觉。此外，醇和二醇会产生低于最佳的溶解速率。而且，醇是可燃的，因而会存在危险情况。醇还会导致使用者手的干燥。
本发明通过用选自烷氧基化甘油酯、烷氧基化甘油、烷氧基化甘油的酯、烷氧基化脂肪酸、甘油酯和聚甘油酯和它们的混合物的水溶助长剂全部或部分替代常规使用的水溶助长剂解决了这些问题。
与工业中现有的配方相比，本发明的水溶助长剂提供了最佳的粘度和组合物稳定性。我们还惊奇地发现本发明的水溶助长剂改善了洗涤剂组合物在硬水中的洗涤性能，增加了溶解速率和增加了洗涤剂组合物的柔和性。
发明概述
本发明涉及餐具洗涤剂组合物，其含有约1-约90％的阴离子表面活性剂并还使用约1％-约30％的选自烷氧基化甘油酯、烷氧基化甘油、烷氧基化甘油的酯、烷氧基化脂肪酸、甘油酯和聚甘油酯和它们的混合物的溶剂水溶助长剂。
在优选实施方案中，阴离子表面活性剂含有至少一个硫基。餐具洗涤剂还可含有约1％-约40％的选自非离子表面活性剂、两性表面活性剂和它们的混合物的表面活性剂组分。已知辅助剂和添加剂，例如香精、香料等还可以按组合物重量计少于约10％的附聚物的正常含量存在。水可用作平衡。
出人意料地是，我们发现，与仅含有醇或醇衍生物作为水溶助长剂的常规使用的洗涤剂组合物相比较，加入本发明的水溶助长剂的餐具洗涤剂显示最佳粘度和配方稳定性、改善的分散性和改善的在硬水中的洗涤性能。
应说明，除非另有说明，所有在说明书和所附的权利要求书中的百分数是指重量百分数。
还应说明的是，在说明书和所附的权利要求书中使用的硬度值是指以碳酸钙表示的硬度。
研究如下优选实施方案的详细说明将会更好理解本发明的这些和其它目的、优点和特征。
优选实施方案的详细描述
本发明的液体餐具洗涤剂组合物含有阴离子表面活性剂和选自烷氧基化甘油、烷氧基化甘油酯、烷氧基化甘油的酯、烷氧基化脂肪酸、甘油酯和聚甘油酯和它们的混合物的溶剂水溶助长剂。
用于本发明的洗涤剂配方的阴离子表面活性剂包括，但不限制于，在McCutcheon的《乳化剂和洗涤剂》(McCutcheon’sEmulsifiers & Detergents)，1992年年鉴和转让给本发明的同一受让人的US5298195中列出的那些，两篇文献列为本文参考文献。
用于本发明的阴离子表面活性剂包括含有至少一个硫基的物质，因此，例如用于本发明的阴离子表面活性剂包括硫酸化和磺化阴离子表面活性剂。适用的硫酸化阴离子表面活性剂包括，但不限制于，伯和仲烷基硫酸盐、伯和仲乙氧基化醇的硫酸盐和脂肪酯硫酸盐。适用的磺化阴离子表面活性剂包括，但不限制于，烷基苯磺酸盐、十二烷基苯磺酸盐、十三烷基苯磺酸盐、伯和仲烷基磺酸盐、α-烯烃磺酸盐、萘和烷基萘磺酸盐和石油磺酸盐。其它适用的含有一个硫基的阴离子表面活性剂包括，但不限制于，肌氨酸盐、磺基琥珀酰胺酸盐、磺基琥珀酸盐和牛磺酸盐。此外，含有羧基的阴离子表面活性剂也适用于本发明中。含有羧基的阴离子表面活性剂包括脂肪酸盐，通常称为皂，和羧基化醇乙氧基化物，通常称为羧酸盐。这些阴离子表面活性剂的具体实例包括，但不限制于，在McCutcheon’s中可找到的那些。
本发明的尤其优选的阴离子表面活性剂包括醚硫酸盐。醚硫酸盐包括，例如烷基醚硫酸盐，例如聚氧乙烯烷基醚硫酸盐和十三烷基醚硫酸盐、由天然醇得到的烷基醚硫酸盐，例如十二烷基醇聚乙二醇醚硫酸钠和脂肪醇醚硫酸钠、由合成醇得到的烷基醚硫酸盐，和由脂族羧酸得到的醚硫酸盐，例如十二烷基醚硫酸钠、十四烷基醚硫酸钠、聚氧乙烯十二烷基醚硫酸盐、三乙醇胺十二烷基醚硫酸盐和十二烷基醚硫酸铵。
在本发明的洗涤剂组合物中存在的阴离子表面活性剂的量为约1％-约90％，优选约5％-约70％，尤其优选约15％-约50％。
本发明的水溶助长剂包括烷氧基化甘油，例如乙氧基化甘油和烷氧基化甘油酯，例如乙氧基化甘油酯。乙氧基化甘油和乙氧基化甘油酯是优选的，因为它们是可生物降解的。
用于本发明的乙氧基化甘油具有如下通式：
Figure C9619958000051
其中：“l”、“m”和“n”分别是0-约20的数值，l+m+n＝约2-约60，优选约10-约45，R表示H、CH3或C2H5。
式(I)的乙氧基化甘油可通过常规的方法制备，例如通过在碱催化剂例如氢氧化钾或氢氧化钠存在下甘油和环氧乙烷反应制备。乙氧基化甘油的制备实例在Pujol等的US5425891中找到，其列为本文参考文献。
用于本发明的乙氧基化甘油酯是乙氧基化单和二甘油酯，可根据常规方法制备，例如通过单或二甘油酯脂肪与环氧乙烷反应制备。用于本发明的乙氧基化甘油酯有如下通式：
Figure C9619958000061
其中：R1和R2各自是
Figure C9619958000062
或 R3＝H，CH3或C2H5，和“l”是约1至约60的数值，和“n”是约6至约24的数值。
用于本发明的乙氧基化甘油酯的实例包括，但不限制于乙氧基化单甘油酯和乙氧基化二甘油酯。尤其优选的乙氧基化甘油酯是乙氧基化单甘油酯。
本发明的水溶助长剂还包括烷氧基化甘油的酯。用于本发明的烷氧基化甘油的酯可根据常规方法，例如用酰氯醇解(alkolysis)烷氧基化甘油制备。用于本发明的烷氧基化甘油的酯的具体实例包括，但不限制于，在McCutcheon’s中找到的那些物质。
本发明的水溶助长剂还包括烷氧基化脂肪酸。用于本发明的烷氧基化脂肪酸可根据常规方法，例如在碱催化剂如氢氧化钾或氢氧化钠存在下使脂肪酸与环氧乙烷反应制备。
适用于本发明的烷氧基化脂肪酸包括，但不限制于，脂肪酸聚乙二醇酯、脂肪酸聚氧乙烯酯、羧酸聚乙二醇酯、脂肪酸聚乙二醇酯和脂肪酸聚丙二醇酯。烷氧基化脂肪酸的具体实例包括，但不限制于，在McCutcheon’s中找到的那些物质。
本发明的水溶助长剂还包括甘油的酯。用于本发明的甘油的酯可根据常规方法，例如用酰氯醇解甘油制备。用于本发明的甘油的酯的具体实例包括，但不限制于，在McCutcheon’s中找到的那些物质。
本发明的水溶助长剂还包括聚甘油酯。用于本发明的聚甘油的酯可根据常规方法制备。聚甘油可通过使用碱催化剂，例如氢氧化钠使甘油脱水制备。聚甘油还可进一步被脂肪酸酯化以形成聚甘油酯。用于本发明的聚甘油酯的具体实例包括，但不限制于，在McCutcheon’s中找到的那些物质。
在本发明的洗涤剂组合物中存在的溶剂水溶助长剂的量为约1％-约30％，优选约2％-约20％。溶剂水溶助长剂更优选以约3％-约10％的量存在，约4％-约8％是尤其优选的。
本发明的溶剂水溶助长剂可含有上述组分及单个化合物的组合。
本发明的洗涤剂组合物还可含有其它表面活性剂，例如非离子和两性表面活性剂。用于本发明的非离子表面活性剂包括，但不限制于，链烷醇酰胺、氧化胺、烷氧基化醇和苯酚、嵌段聚合物、烷氧基化胺、烷基多糖、葡糖酰胺、糖酯和它们的混合物。非离子表面活性剂的具体实例包括，但不限制于McCutcheon’s和US5298195中可找到的那些物质。两性表面活性剂包括单和二乙酸盐、甜菜碱、甘氨酸盐、咪唑啉和它们的衍生物、羟乙磺酸盐、单和二丙酸盐、羟基磺基甜菜碱和牛磺酸盐。两性表面活性剂的具体实例包括，但不限制于在McCutcheon’s中可找到的那些物质。这些表面活性剂组分在洗涤剂组合物中存在的量为约1-约40％，优选约15％-约40％。
此外，本发明可含有选择性的组分，例如碱源、酸化剂、pH缓冲剂、pH控制剂。酸化剂的实例包括，但不限制于，柠檬酸、乙酸、苯甲酸、苯酚和棕榈酸。pH控制剂的实例包括，但不限制于，碱金属碳酸盐和碳酸氢盐、单乙醇胺、三乙醇胺、三羟基甲胺、氢氧化铵、碱土金属和碱金属氢氧化物。优选单、二和三乙醇胺，可加入多至约5％的含量。
也可加入助洗剂，虽然它们在餐具洗涤剂组合物中只具有有限的价值。无机或有机助洗剂可单独或混合地使用。这种助洗剂的实例包括，但不限制于碱金属碳酸盐、磷酸盐、多磷酸盐和硅酸盐。
螯合剂也可以加入组合物中，螯合剂的实例包括，但不限制于，碱金属多羧酸盐，例如柠檬酸钠和钾、酒石酸钠和钾、柠檬酸、乙二胺四乙酸钠和钾(EDTA)、三乙酸盐、次氮基三乙酸钠和钾(NTA)和它们的混合物。可使用多达约5％的螯合剂。
此外，如果需要，本发明的洗涤剂组合物可含有其它选择性的组分，包括任何通常使用的辅助剂、稀释剂和添加剂，例如香料、酶、染料、防晦暗剂、抗菌剂、磨料、手柔软剂，例如芦荟vera凝胶、碱土金属的水溶性盐，例如硫酸镁等，只要它们不损害本发明的组合物的有利性质。
该组合物可含有多达约10％的这些选择性组分。
应理解，占本发明的洗涤剂组合物的余量的水量可根据最终产品的所需浓度变化。
如下实施例用于说明本发明的组合物。
实施例
在实施例中，使用的缩写有如下含义：
缩写    说明
CDEA    椰子油二乙醇酰胺
CAPAO   椰油酰氨丙基氧化胺
SLES    十二烷基乙氧基硫酸钠在如下的实施例中的餐具洗涤剂含有常规的组合物(组合物A)：组合物A
组分    重量％
SLES    22.5
CDEA    18.0
CAPAO    4.5
柠檬酸   0.9
通过将下面的常规水溶助长剂(组合物B)加入组合物A制备比较洗涤剂配方(配方X)：
组合物B
组分              重量％
丙二醇            5
非离子表面活性剂
C11，含7摩尔EO    2.5
配方X的粘度，用ASTM方法编号D1200，#4 Ford Cup测定，是60秒厘泊。
                   实施例1
含有本发明的水溶助长剂和组合物A的洗涤剂配方与配方X比较用于评价配方透明性、粘度和溶解速率。
表1概括了结果。
                     表1
配方 溶剂/水溶助长剂 用量wt％1   配方透明性2 粘度3(厘泊) 溶解速率4
  1 聚乙二醇-4月桂酸酯     5   分层
  2 聚乙二醇-4月桂酸酯和丙二醇   2.5+2.5   透明   70
  3 聚乙二醇-8月桂酸酯     5   透明   67   ＞配方X
  4 聚乙二醇-9月桂酸酯     5   透明   69   ＞配方X
  5 Glycereth-7三辛酸酯     5   分层
  6 Glycereth-7三辛酸酯+丙二醇   2.5+2.5   透明   49
  7 Glycereth-26三辛酸酯     5   透明   63 ＞＞配方X
  8 Glycereth-26三辛酸酯     3   透明   65 ＞＞配方X
  9 Glycereth-26三辛酸酯     1   透明   93
  10 Glycereth-26三辛酸酯+己二醇     1+1   透明   62 ≥配方X
  11 甘油三(2-乙基己酸酯)     5   分层
  12 甘油三(2-乙基己酸酯)+丙二醇   2.5+2.5   透明   62
  13 聚乙二醇-18甘油油酸酯/月桂酸酯     5   透明   79  ＞配方X
  14 聚甘油基-4异硬脂酸酯     5   分层
  15 聚甘油基-4异硬脂酸酯+丙二醇   2.5+2.5   透明   59  ＞配方X
  16 聚甘油基-3油酸酯     5   分层
  17 聚甘油基-3油酸酯+丙二醇   2.5+2.5   透明   59  ＞配方X
  18 聚乙二醇-3甘油基月桂酸酯     5   透明   80 ＜＜配方X
  19 聚乙二醇-20甘油基月桂酸酯     5   透明   82  ＜配方X
  20 聚乙二醇-7甘油基椰子酸酯     5   透明   65 ＞＞配方X
  21 聚乙二醇-7甘油基椰子酸酯     3   透明   80 ≥配方X
  22 聚乙二醇-7甘油基椰子酸酯     1   透明   103
  23 Glycereth-26     3   透明   64 ＞＞配方X
  24 Glycereth-26     1   透明   92  ＞配方X
  25 Glycereth-26+丙二醇     1+1   透明   77  ＝配方X
1水溶助长剂的用量，重量百分数。
2水溶助长剂配方形成透明溶液，或分层的溶液。
3用ASTM D1200测量的。
4与配方X比较。
在试验的配方中，含有水溶助长剂乙氧基化甘油、乙氧基化甘油酯、乙氧基化脂肪酸和乙氧基化单甘油酯的配方显示可接受的配方稳定性和分散性。含有甘油酯和聚甘油酯的洗涤剂配方，当水溶助长剂与乙二醇混合使用时，显示可接受的配方稳定性和分散性。
实施例2
进行餐具洗涤性能测试以评价含有组合物A和本发明的水溶助长剂的餐具洗涤剂配方和含有组合物A和B的比较洗涤剂配方。所有洗涤剂配方用0.075％Crisco  Soil在120°F下试验。
在第一试验，小碟(Mini-Dish)试验I中，使用硬度为15ppm和450ppm的水。在第二试验，小碟试验II中，使用硬度为450ppm的水。小碟试验I的结果显示于表2中，小碟试验II的结果显示于表3中。
                     表2.小碟试验I
试验 水溶助长剂/溶剂 水溶助长剂的量(重量％) 餐具洗涤性能(餐具编号)
      水硬度
  15ppm   450ppm
  1 丙二醇+非离子表面活性剂C11-7EO(组合物B)     5+2.5     11     9.5
  2     Glycereth-26     3     11+     10.5
  3 Glycereth-26三辛酸酯     3     10.5     10.5
  4 聚乙二醇-7甘油基椰子酸酯     3     10.5     9.5
                   表3.小碟试验II
试验 水溶助长剂/溶剂 水溶助长剂的量(重量％)   餐具洗涤性能(餐具编号)水硬度450ppm
    1 丙二醇+非离子表面活性剂C11-7EO(组合物B)     5+2.5     10
    2 Glycereth-26三辛酸酯     3     11
    3 Glycereth-26     3     10.75
    4 聚乙二醇-4月桂酸酯+丙二醇     2.5+2.5     10.5
    5 聚乙二醇-18甘油基油酸酯/月桂酸酯     5     10+
    6 聚乙二醇-20甘油基月桂酸酯     5     10
    7 聚乙二醇-9月桂酸酯     5     9.5
    8 聚甘油基-3油酸酯+丙二醇     2.5+2.5     9.5
    9 甘油三(2-乙基己酸酯)+丙二醇     2.5+2.5     8.5
在试验的配方中，含有水溶助长剂乙氧基化甘油、乙氧基化甘油酯、乙氧基化脂肪酸和乙氧基化单甘油酯的配方显示好的餐具洗涤性能。
根据本发明的优选实施方案，餐具洗涤剂基本上由约1％-约90％的选自伯和仲烷基硫酸盐、伯和仲乙氧基化醇的硫酸盐、脂肪酯硫酸盐、烷基苯磺酸盐、十二烷基苯磺酸盐、十三烷基苯磺酸盐、伯和仲烷基磺酸盐、α-烯烃磺酸盐、萘和烷基萘磺酸盐、石油磺酸盐、肌氨酸盐、磺基琥珀酰胺酸盐、磺基琥珀酸盐、牛磺酸盐、脂肪酸盐、羧基化醇乙氧基化物、醚硫酸盐和它们的混合物的阴离子表面活性剂，约1％-约30％的选自烷氧基化甘油、烷氧基化甘油酯、烷氧基化甘油的酯、烷氧基化脂肪酸、甘油酯和聚甘油酯和它们的混合物的溶剂水溶助长剂、约1％-约40％的选自非离子表面活性剂，例如链烷醇酰胺、氧化胺、烷氧基化醇、烷氧基化苯酚、嵌段聚合物、烷氧基化胺、烷基多糖、葡糖酰胺、糖酯和它们的混合物和两性表面活性剂，例如单乙酸酯、二乙酸酯、甜菜碱、甘氨酸盐、咪唑啉和它们的衍生物、羟乙磺酸盐、单丙酸盐、二丙酸盐、羟基磺基甜菜碱和牛磺酸盐和它们的混合物的表面活性剂和多达约10％的添加剂。
当然，应理解对上述实施方案可进行各种改变和改进，因此上述描述说明而不是限制本发明，限定本发明的是如下的权利要求书，包括所有的等同物。

Claims (9)

1.一种液体餐具洗涤剂组合物，其含有：
a)1％-90％的阴离子表面活性剂；
b)1％-30％选自烷氧基化甘油、烷氧基化脂肪酸和它们的混合物的溶剂水溶助长剂；和
c)1％-40％选自非离子表面活性剂、两性表面活性剂和它们的混合物的表面活性剂组分。
2.根据权利要求1的液体餐具洗涤剂，其中阴离子表面活性剂的存在量为5％-70％。
3.根据权利要求1的液体餐具洗涤剂，其中溶剂水溶助长剂的存在量为2％-20％。
4.根据权利要求1的组合物，其中阴离子表面活性剂含有至少一个硫基。
5.根据权利要求1的组合物，其中阴离子表面活性剂选自硫酸化阴离子表面活性剂、磺化阴离子表面活性剂、磺基琥珀酰胺酸盐、磺基琥珀酸盐、牛磺酸盐、脂肪酸的盐、羧基化醇乙氧基化物、醚硫酸盐和它们的混合物。
6.权利要求1的组合物，其中水溶助长剂的存在量为3％-10％。
7.权利要求1的组合物，其含有15％-50％的醚硫酸盐阴离子表面活性剂，2％-20％的乙氧基化甘油溶剂水溶助长剂，15％-40％的选自非离子表面活性剂、两性表面活性剂和它们的混合物的表面活性剂组分，0％-10％的添加剂和余量的水。
8.权利要求1的液体餐具洗涤剂，其中非离子表面活性剂选自链烷醇酰胺、氧化胺、烷氧基化醇、烷氧基化苯酚、嵌段聚合物、烷氧基化胺、烷基多糖、葡糖酰胺、糖酯和它们的混合物。
9.权利要求1的液体餐具洗涤剂，其中两性表面活性剂选自单乙酸盐、二乙酸盐、甜菜碱、甘氨酸盐、咪唑啉、咪唑啉衍生物、羟乙磺酸盐、单丙酸盐、二丙酸盐、羟基磺基甜菜碱和它们的混合物。
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KR100441677B1 (ko) 2004-10-26
JP2000502118A (ja) 2000-02-22
TW426731B (en) 2001-03-21
BR9612494A (pt) 1999-11-23
MX9803899A (es) 1998-09-30
WO1997018284A3 (en) 1997-06-19
CA2237694C (en) 2002-01-22
CN1207760A (zh) 1999-02-10
EP0906388A4 (zh) 1999-04-07
HK1019232A1 (en) 2000-01-28
CA2237694A1 (en) 1997-05-22
WO1997018284A2 (en) 1997-05-22
US5998355A (en) 1999-12-07
DE69634211D1 (de) 2005-02-24
KR19990067606A (ko) 1999-08-25
EP0906388A2 (en) 1999-04-07
AU7733196A (en) 1997-06-05
AR004325A1 (es) 1998-11-04
AU705326B2 (en) 1999-05-20
DE69634211T2 (de) 2005-06-23
EP0906388B1 (en) 2005-01-19
ATE287438T1 (de) 2005-02-15

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