CN101035889B - 低pH值的结构化表面活性剂组合物 - Google Patents
低pH值的结构化表面活性剂组合物 Download PDFInfo
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- CN101035889B CN101035889B CN200580033923.6A CN200580033923A CN101035889B CN 101035889 B CN101035889 B CN 101035889B CN 200580033923 A CN200580033923 A CN 200580033923A CN 101035889 B CN101035889 B CN 101035889B
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Abstract
一种低pH值的水性结构化表面活性剂组合物，其含有：在100重量份的该组合物中，占约3重量份到约40重量份的选自阴离子磷酸酯表面活性剂、阴离子磺酸盐表面活性剂和阴离子羧酸盐表面活性剂中的一种或多种阴离子表面活性剂，其中所述组合物具有小于约5的pH值、表现出剪切变稀的粘度、并且能够使非水溶性或部分水溶性成分悬浮。
Description
技术领域
本发明涉及表面活性剂组合物，更具体地说，本发明涉及低pH值的液体结构化表面活性剂组合物。
背景技术
结构化表面活性剂组合物是可泵送的流体组合物，其中该组合物表现出剪切变稀的粘度、并且能够使非水溶性或部分水溶性成分物理悬浮。通常，表面活性剂相以堆积的球粒(即，层状小滴)的形式而存在，该球粒由水溶液形成。
结构化表面活性剂组合物可用于：个人护理应用，例如香波、沐浴液、洗手皂、护肤液、乳霜、调理剂、剃须产品、洗面奶、中性香波、皮肤护理用品；家庭护理应用，例如液体洗涤剂、洗衣剂、硬质表面清洁剂、餐具洗涤液、抽水马桶清洗剂；和其它应用，例如油田应用和农用化学品应用。
针对个人护理市场的结构化表面活性剂组合物通常具有约5到7的pH值。在很多情况下，用于已知的结构化表面活性剂组合物中的表面活性剂在低pH值体系中并不适用，这是因为这类组合物的典型组分在pH值低于约5时会变得不稳定并失效。
在一些应用方面，需要将非水溶性或部分水溶性成分悬浮在低pH值的水性组合物中。例如，美国专利No.6,416,768公开了使用油包水型乳剂将活性成分引入到低pH值的组合物中。但是，油包水型乳剂只能使亲脂性试剂悬浮，并且通常随着时间的延长其稳定性是有限的。
人们需要的是这样一种结构化表面活性剂组合物，该组合物在低pH值下可提供典型的结构化表面活性剂的特性，即，剪切变稀的粘度以及使非水溶性或部分水溶性成分悬浮的能力。
发明概述
在第一方面，本发明涉及一种低pH值的水性结构化表面活性剂组合物，其含有：在100重量份(“pbw”)的该组合物中，占约3pbw到约40pbw的选自阴离子磷酸酯表面活性剂、阴离子磺酸盐表面活性剂和阴离子羧酸盐表面活性剂中的一种或多种阴离子表面活性剂，其中，该组合物具有小于约5的pH值、表现出剪切变稀的粘度、并且能够使非水溶性或部分水溶性成分悬浮。
在第二方面，本发明涉及一种低pH值的水性组合物，其含有：
连续的结构化表面活性剂相，所述的结构化表面活性剂相含有水和选自阴离子磷酸酯表面活性剂、阴离子磺酸盐表面活性剂和阴离子羧酸盐表面活性剂中的一种或多种阴离子表面活性剂，并且表现出剪切变稀的粘度，以及
一种或多种非水溶性或部分水溶性成分，该成分悬浮在该结构化表面活性剂相中，
其中所述组合物的pH值小于约5。
在第三方面，本发明涉及一种低pH值的水性组合物，其含有至少基本上不同的至少两个相，其中至少一个相是结构化表面活性剂相，该相含有水和选自阴离子磷酸酯表面活性剂、阴离子磺酸盐表面活性剂和阴离子羧酸盐表面活性剂中的一种或多种阴离子表面活性剂，并且表现出剪切变稀的粘度，其中，所述组合物的pH值小于约5。
发明详述和优选实施方式
本文所用的涉及粘度的术语“剪切变稀”是指这样的粘度，其随着剪切速率的增大而减小。剪切变稀可以被描述为“非牛顿流体”行为，这是因为其不同于典型的牛顿流体(例如，水)，在典型的牛顿流体中，粘度不依赖于剪切速率。
本文所用的涉及水性组合物的成分的术语“非水溶性成分或部分水溶性成分”是指该成分在水性组合物中的浓度高于该成分的溶解度极限，因此，在非水溶性成分的情况中，该成分在水性组合物中基本保持不溶；在部分水溶性成分的情况中，至少一部分该成分在水性组合物中保持不溶。
本文用于描述水性组合物的特征的术语“能够使非水溶性成分或部分水溶性成分悬浮”或者“使非水溶性成分或部分水溶性成分悬浮”是指：该组合物基本上可防止所述成分漂浮在该组合物中，或可防止所述成分在该组合物中下沉，使得所述成分在该组合物中表现出平衡的浮力，并且在所预计的该低pH值水性组合物的加工、储存和使用条件下，所述成分保持至少基本悬浮在该组合物中的状态。
本文所用的涉及低pH值水性组合物的成分的术语“化学稳定”是指该成分在所预计的该低pH值水性组合物的加工、储存和使用条件下均保持至少基本不分解。
本文所用的术语“层状相”是指这样一种物相，其含有多个平行排列并被液体介质隔开的表面活性剂双层。层状相可通过(例如)小角X射线测试或在正交偏光显微镜下观察到的双折射现象来进行检测。层状相包括球粒相和典型形式的液晶G相及其混合物。“G相”在文献中有时也被称为“Lα相”，它通常是可泵送的、非牛顿型的、各向异性的制品，其外观不透明并且在流动时呈现出特征性的“易弄脏的”外观。层状相可以以几种不同的形式而存在，这些形式包括平行的片状区(其构成上述典型的G相的主体)以及球粒(所述的球粒是由大量同中心的球形外壳形成的，其中每一个外壳都是表面活性剂双层)。在本说明书中，术语“G相”专用于至少部分为上述前一种形式的组合物。球粒的直径通常为0.1-50微米，因此其与胶束根本不同。与胶束溶液不同的是，球粒组合物通常是各向异性以及非牛顿型的。在球粒紧密堆积的情况下，该球粒具有优异的固体悬浮性，并且可以掺入非水溶性或部分水溶性的固体、液体和/或气体来作为悬浮在由表面活性剂组合物构成的连续基质中的独立的非连续相。
在一个实施方案中，本发明组合物的pH值为约1.5到低于约5，更通常为约2到约4.5，甚至更通常为约3到约4。
在一个实施方案中，本发明的结构化表面活性剂组合物含有：在100pbw的该组合物中，占约3到约40pbw、更通常为占约5到约30pbw、并且更通常为占约8到约20pbw的一种或多种阴离子表面活性剂。
适合用作本发明阴离子表面活性剂成分的化合物是：阴离子磷酸酯表面活性剂，如单烷基磷酸酯表面活性剂和二烷基磷酸酯表面活性剂；阴离子磺酸盐表面活性剂，如线性烷基苯磺酸盐表面活性剂、α-烯烃磺酸盐表面活性剂和链烷烃磺酸盐表面活性剂；以及阴离子羧酸盐表面活性剂，如烷基醚羧酸盐表面活性剂；及其混合物。在一个实施方案中，所述单烷基磷酸酯表面活性剂、二烷基磷酸酯表面活性剂、线性烷基苯磺酸盐表面活性剂和烷基醚羧酸盐表面活性剂的烷基取代基是(C8-C24)烷基，其可以是支链或直链；所述α-烯烃磺酸盐表面活性剂的α-烯烃取代基是烯键式不饱和(C8-C24)烯基，其可以是支链或直链。适合用作本发明组合物中阴离子表面活性剂成分的阴离子表面活性剂包括(例如)月桂基磷酸酯、十六烷基磷酸酯、十三烷基磷酸酯、山嵛基磷酸酯、月桂基聚氧乙烯(2)醚磷酸酯、十六烷基聚氧乙烯(3)醚磷酸酯、十三烷基聚氧乙烯(4)醚磷酸酯、十三烷基聚氧乙烯(6)醚磷酸酯、山嵛基聚氧乙烯(4)醚磷酸酯、二月桂基磷酸酯、双十六烷基磷酸酯、双十三烷基磷酸酯、二山嵛基磷酸酯、二月桂基聚氧乙烯(2)醚磷酸酯、二烷基聚氧乙烯(3)醚磷酸酯、双十六烷基聚氧乙烯(4)醚磷酸酯、双十三烷基聚氧乙烯(4)醚磷酸酯、双十三烷基聚氧乙烯(6)醚磷酸酯、二山嵛基聚氧乙烯(6)醚磷酸酯、十三烷基苯磺酸盐、十二烷基苯磺酸盐、月桂基聚氧乙烯(3)醚羧酸盐、十三烷基聚氧乙烯(7)醚羧酸盐、十六烷基聚氧乙烯(4)醚羧酸盐、山嵛基聚氧乙烯(5)醚羧酸盐、或其混合物，其中，可以将阴离子表面活性剂以酸的形式(非中和形式)或作为中和后的盐加入到制剂中。
中和后，任意一种阴离子表面活性剂中的阳离子通常为钠，但是可供选用的其它阳离子为钾、锂、钙、镁、铵、(C1-C6)烷基铵、或(C1-C6)烷醇铵，例如，异丙基铵、单乙醇铵、二乙醇铵和三乙醇铵。铵盐和乙醇铵盐一般比钠盐更易溶解。也可以应用以上阳离子的混合物。
在一个实施方案中，阴离子表面活性剂包含一种或多种磷酸酯的非中和的酸，例如Dermalcare MAP L-210(月桂基聚氧乙烯(2)醚磷酸酯)和Rhodifac RS-410(十三烷基聚氧乙烯(4)醚磷酸酯)。所述表面活性剂分散在水中时，容易在低pH值下形成层状相，而不需要结构化剂。形成层状相的倾向使所述表面活性剂尤其适合用于配制低pH值的结构化液体制剂。
在一个实施方案中，本发明中的结构化表面活性剂组合物可任选地含有至少有效量的一种或多种结构化试剂。可在低pH值下具有化学稳定性的合适的结构化试剂包括：阳离子表面活性剂，如胺盐、季铵化合物和氧化胺；非离子表面活性剂，如脂肪醇、乙氧化醇和脂肪酸；以及电解质。上述结构化试剂的有效量是可以有助于形成剪切变稀相的用量，其中所述的剪切变稀相能够使非水溶性或部分水溶性成分悬浮。
合适的阳离子表面活性剂是公知的化合物。可用于预定的最终用途并且在所需的配方pH值条件下具有化学稳定性的任何阳离子表面活性剂，都适合用作本发明组合物中的结构化剂成分，该阳离子表面活性剂包括(例如)下式(1)所表示的阳离子表面活性剂：
其中：
R1、R2、R3和R4独立地为氢或有机基团，条件是R1、R2、R3和R4中的至少一个不是氢；并且
X-为阴离子。
如果上述R基团中的一个到三个是氢，则可以将该化合物称为胺盐。阳离子胺盐的一些例子包括聚乙氧基化(2)油胺/硬脂胺、乙氧基化牛油胺、椰油烷基胺(cocoalkylamine)、油胺和牛油烷基胺。
对于季铵化合物(通常称为“季铵”)，R1、R2、R3和R4可以是相同或不同的有机基团，但不可为氢。在一个实施方案中，R1、R2、R3和R4各自为(C8-C24)的支链或直链，这些基团可具有附加的官能性，例如：脂肪酸或其衍生物(包括脂肪酸酯以及带有乙氧基化基团的脂肪酸)、烷基酰氨基、芳环、杂环、磷酸基、环氧基和羟基。氮原子也可作为杂环或芳环体系的一部分，例如：十六烷基乙基磺乙基吗啉或司吡氯铵(steapyrium chloride)。
合适的阴离子包括(例如)：氯离子、溴离子、甲基硫酸根、乙基硫酸根、乳酸根、糖精离子(saccharinate)、乙酸根或磷酸根。
单烷基胺衍生物类的季铵化合物的例子包括：十六烷基三甲基溴化铵(也称为CETAB或西曲溴铵)、十六烷基三甲基氯化铵(也称为鲸蜡基三甲基氯化铵)、十四烷基三甲基溴化铵(也称为肉豆蔻基三甲基溴化铵或季铵盐-13)、十八烷基二甲基苄基氯化铵(也称为硬脂基二甲基苄基氯化铵)、顺十八碳-9-烯基二甲基苄基氯化铵(也称为油烯基二甲基苄基氯化铵)、甲基硫酸月桂基/肉豆蔻基三甲基铵(也称为甲基硫酸椰油基三甲基铵)、二氢磷酸十六烷基-二甲基-(2)羟乙基铵(也称为二氢磷酸羟乙基十六烷基二甲基铵)、巴苏棕榈油酰氨基丙基二甲基苄基氯化铵(bassuamidopropylkonium chloride)、椰油基三甲基氯化铵、双十八烷基二甲基氯化铵、麦芽酰氨丙基二甲基苄基氯化铵(wheat germ-amidopropalkonium chloride)、甲基硫酸十八烷基辛基二甲基铵、异十八烷基氨基丙基二甲基苄基氯化铵、二羟丙基PEG-5亚麻油基甲基氯化铵、PEG-2十八烷基二甲基氯化铵(PEG-2stearmonium chloride)、季铵盐18(Quaternium 18)、季铵盐80、季铵盐82、季铵盐84、山嵛基三甲基氯化铵、双十六烷基二甲基氯化铵、甲基硫酸山嵛基三甲基铵、牛油基三甲基氯化铵和乙基硫酸山嵛酰氨丙基乙基二甲基铵。
二烷基胺衍生物类的季铵化合物包括：双十八烷基二甲基氯化铵、双十六烷基二甲基氯化铵、甲基硫酸十八烷基辛基二甲基铵、甲基硫酸二氢化棕榈基乙基羟乙基甲基铵(dihydrogenated palmoylethylhydroxyethylmonium methosulfate)、甲基硫酸二棕榈酰乙基羟乙基甲基铵(dipalmitoylethyl hydroxyethylmonium methosulfate)、甲基硫酸二油酰乙基羟乙基甲基铵、羟丙基双十八烷基二甲基氯化铵(hydroxypropyl bisstearyldimonium chloride)、及其混合物。
咪唑啉衍生物类的季铵化合物包括(例如)：异十八烷基苄基咪唑啉盐酸盐(isostearyl benzylimidonium chloride)、椰油酰基苄基羟乙基咪唑啉盐酸盐(cocoyl benzyl hydroxyethyl imidazoliniumchloride)、椰油酰基羟乙基咪唑啉PG-盐酸磷酸盐(cocoylhydroxyethylimidazolinium PG-chloride phosphate)、季铵盐32和十八烷基羟乙基咪唑啉盐酸盐(stearyl hydroxyethylimidoniumchloride)、及其混合物。
合适的阳离子表面活性剂包括(例如)：胺盐，如聚乙氧基化(2)油胺/硬脂胺、乙氧基化牛油胺、椰油烷基胺、油胺和牛油烷基胺)；或季铵化合物，如十六烷基三甲基溴化铵(也称为CETAB或西曲溴铵)、十六烷基三甲基氯化铵(也称为鲸蜡基三甲基氯化铵)、十四烷基三甲基溴化铵(也称为肉豆蔻基三甲基溴化铵或季铵盐-13)、十八烷基二甲基苄基氯化铵(也称为硬脂基二甲基苄基氯化铵)、顺十八碳-9-烯基二甲基苄基氯化铵(也称为油烯基二甲基苄基氯化铵)、甲基硫酸月桂基/肉豆蔻基三甲基铵(也称为甲基硫酸椰油基三甲基铵)、二氢磷酸十六烷基-二甲基-(2)羟乙基铵(也称为二氢磷酸羟乙基十六烷基二甲基铵)、巴苏棕榈油酰氨基丙基二甲基苄基氯化铵、椰油基三甲基氯化铵、双十八烷基二甲基氯化铵、麦芽酰氨丙基二甲基苄基氯化铵、甲基硫酸十八烷基辛基二甲基铵、异十八烷基氨基丙基二甲基苄基氯化铵、二羟丙基PEG-5亚麻油基甲基氯化铵、PEG-2十八烷基二甲基氯化铵、季铵盐18、季铵盐80、季铵盐82、季铵盐84、山嵛基三甲基氯化铵、双十六烷基二甲基氯化铵、甲基硫酸山嵛基三甲基铵、牛油基三甲基氯化铵和乙基硫酸山嵛酰氨丙基乙基二甲基铵，双十八烷基二甲基氯化铵、双十六烷基二甲基氯化铵、甲基硫酸十八烷基辛基二甲基铵、甲基硫酸二氢化棕榈基乙基羟乙基甲基铵、甲基硫酸二棕榈酰乙基羟乙基甲基铵、甲基硫酸二油酰乙基羟乙基甲基铵、羟丙基双十八烷基二甲基氯化铵，异十八烷基苄基咪唑啉盐酸盐、椰油酰基苄基羟乙基咪唑啉盐酸盐、椰油酰基羟乙基咪唑啉PG-盐酸磷酸盐、季铵盐32和十八烷基羟乙基咪唑啉盐酸盐、及其混合物。
此外，由于氧化胺在低pH值下具有阳离子的性质，所以氧化胺也可用作结构化试剂。合适的氧化烷基胺的具体例子可以包括(例如)氧化月桂基胺、氧化椰油基胺、氧化椰油酰氨丙基胺和氧化月桂酰氨丙基胺。
非离子表面活性剂是公知的。可用于预定的最终用途并且在所需的配方pH值条件下具有化学稳定性的任何非离子表面活性剂，都适合用作本发明组合物中的结构化剂成分。
合适的脂肪醇包括(例如)：(C10-C22)饱和或不饱和的支链或直链醇，例如癸醇、月桂醇、十三烷醇、肉豆蔻醇、鲸蜡醇、硬脂醇、油醇、亚油醇和亚麻醇。
合适的乙氧化醇包括(C10-C22)饱和或不饱和的支链或直链醇的烷氧基化(通常是乙氧基化)衍生物，可包括：每一分子上平均含有1到22个烷氧基单元的乙氧化醇，例如，月桂基聚氧乙烯(1)醚、月桂基聚氧乙烯(2)醚、月桂基聚氧乙烯(4)醚、月桂基聚氧乙烯(5)醚、月桂基聚氧乙烯(7)醚、月桂基聚氧乙烯(9)醚、十三烷基聚氧乙烯(1)醚、十三烷基聚氧乙烯(2)醚、十三烷基聚氧乙烯(3)醚、(C11-15)烷基聚氧乙烯(3)醚、(C12-13)烷基聚氧乙烯(5)醚、(C14-15)烷基聚氧乙烯(9)醚。
合适的脂肪酸包括(C10-C22)饱和或不饱和羧酸，例如月桂酸、油酸、硬脂酸、异硬脂酸、肉豆蔻酸、十六/十八烷酸(cetearic acid)、异硬脂酸、亚油酸、亚麻酸、蓖麻酸、反油酸、花生四烯酸、肉豆蔻烯酸、棕榈油酸、及其被中和的形式。
适合用作本发明组合物中的结构化剂成分的电解质包括：多价阴离子盐，例如焦磷酸钾、三聚磷酸钾、以及柠檬酸钠或柠檬酸钾；多价阳离子盐，包括碱土金属盐(例如氯化钙和溴化钙)、以及卤化锌、氯化钡和硝酸钙；一价阳离子与一价阴离子形成的盐，包括碱金属卤化物或卤化铵(例如氯化钾、氯化钠、碘化钾、溴化钠和溴化铵)、碱金属硝酸盐或硝酸铵；以及聚电解质，例如未封端的聚丙烯酸盐、聚马来酸盐或聚羧酸盐、木质素磺酸盐或萘磺酸盐甲醛共聚物。
通常，阴离子表面活性剂的含量(该含量依赖于其溶解度)越高，则为了形成能够支持固体物质的结构和/或为了引起结构化表面活性剂絮凝而需要的结构化剂的量就越少。结构化剂的掺入量要足以与一种或多种阴离子表面活性剂一起来促进这样一种结构化表面活性剂组合物的形成，该组合物表现出剪切变稀的粘度、并且能够使非水溶性或部分水溶性成分悬浮，结构化剂可以以单独的方式或掺合到其它原材料之一中的方式被加入到制剂中。
在一个实施方案中，本发明的结构化表面活性剂组合物含有：在100pbw的结构化表面活性剂中，最高占约40pbw、更通常为约0.5到约25pbw、并且更通常为约1到约10pbw的一种或多种结构化剂。
在另一个实施方案中，本发明的结构化表面活性剂组合物不需要结构化剂来形成层状相。
在一个实施方案中，本发明的结构化表面活性剂组合物含有低于有效量的结构化试剂。在另一个实施方案中，本发明的结构化表面活性剂组合物不含结构化剂。
除了阴离子表面活性剂和任意的阳离子表面活性剂以外，本发明的组合物还可任选地含有用作结构化试剂的非离子表面活性剂和/或电解质、一种或多种阳离子表面活性剂、一种或多种非离子表面活性剂、一种或多种电解质、一种或多种两性表面活性剂、一种或多种两性离子表面活性剂、或其混合物。所述可任选的阳离子表面活性剂、非离子表面活性剂和/或电解质可各自独立地以超过最低有效量的含量存在以作为结构化剂。
上文所述的阳离子表面活性剂、非离子表面活性剂和电解质也分别适合用作可任选的附加的阳离子表面活性剂、非离子表面活性剂和电解质。
合适的两性离子表面活性剂是公知的化合物。可用于预定的最终用途并且在所需的配方pH值条件下具有化学稳定性的任何两性离子表面活性剂，都适合用作本发明组合物中的可任选的两性离子表面活性剂成分，其包括(例如)：可以广泛地称为脂肪族季铵、季
和季锍化合物的衍生物的那些，其中脂肪烃基可为直链或支链，并且其中一个脂肪族取代基包含约8到约24个碳原子，一个脂肪族取代基包含阴离子型水溶性基团，如羧基、磺酸根、硫酸根、磷酸根或膦酸根。合适的两性离子表面活性剂的具体例子包括：烷基甜菜碱，如椰油基二甲基羧甲基甜菜碱、月桂基二甲基羧甲基甜菜碱、月桂基二甲基α-羧基乙基甜菜碱、十六烷基二甲基羧甲基甜菜碱、月桂基双(2-羟乙基)羧基甲基甜菜碱、十八烷基双(2-羟丙基)羧基甲基甜菜碱、油烯基二甲基γ-羧基丙基甜菜碱、月桂基双(2-羟丙基)α-羧基乙基甜菜碱、酰氨基丙基甜菜碱；烷基磺基甜菜碱，如椰油基二甲基磺丙基甜菜碱、十八烷基二甲基磺丙基甜菜碱、月桂基二甲基磺乙基甜菜碱、月桂基双(2-羟乙基)磺丙基甜菜碱；以及烷基酰氨基丙基羟基磺基甜菜碱。
合适的两性表面活性剂是公知的化合物。可用于预定的最终用途并且在所需的配方pH值条件下具有化学稳定性的任何两性表面活性剂，都适合用作本发明的组合物中的可任选的两性表面活性剂成分，其包括(例如)：可以广泛地描述为其中脂肪烃基可为支链或直链的那些化合物，其中所述化合物的一个脂肪族取代基包含约8到约24个碳原子，一个脂肪族取代基包含阴离子型水溶性基团，如羧基、磺酸根、磷酸根或膦酸根。合适的两性表面活性剂的具体例子包括：烷基丙酸盐，如椰油基两性丙酸盐(cocoamphopropionate)、月桂酰两性丙酸盐、十三烷基两性丙酸盐、油基两性丙酸盐、癸酰基两性丙酸盐、山嵛基两性丙酸盐；二丙酸盐，如椰油基两性二丙酸盐、月桂酰两性二丙酸盐、十三烷基两性二丙酸盐、油基两性二丙酸盐、癸酰基两性二丙酸盐、山嵛基两性二丙酸盐；和两性磺酸盐，如椰油基两性羟丙基磺酸盐、月桂酰两性羟丙基磺酸盐、十三烷基两性羟丙基磺酸盐、油基两性羟丙基磺酸盐、癸酰基两性羟丙基磺酸盐、山嵛基两性羟丙基磺酸盐。
在一个实施方案中，本发明的组合物含有：在100pbw的该组合物(其包含用作结构化剂的任何表面活性剂)中，总量占约0.1pbw到约20pbw、更通常为约0.5pbw到约15pbw、并且更通常为约1pbw到约10pbw的一种或多种阳离子表面活性剂、非离子表面活性剂、两性表面活性剂、和/或两性离子表面活性剂。
在一个实施方案中，通过以下方法来制备结构化表面活性剂组合物：将表面活性剂和水加到一起并且混合，并且可任选地调节其pH值，然后加入任何可任选的结构化剂。可以按需进行混合，从而形成均匀的溶液。
在一个实施方案中，可以在已知的混合设备(例如高剪切混合器或均化器)中对结构化表面活性剂进行高剪切混合。
剪切变稀的粘度采用已知的粘度测量法进行测定，例如用旋转粘度计(如布氏粘度计)进行测定。在一个实施方案中，当使用装有合适转子的布氏旋转粘度计以约0.1转/分(“rpm”)到约60rpm的转速对本发明的组合物进行粘度测量时，该组合物表现出剪切变稀行为。
本发明的组合物能够使非水溶性的颗粒或部分水溶性的成分(如植物油、矿物油、硅油、固体颗粒、研磨剂和类似物)悬浮。所述的组合物提供了一种手段，其可在表面活性剂混合物中引入用其它方法难以混合的成分，这样，通过这种手段可以获得具有多重功效的化妆品制剂，这些功效(在某些情况下)包括清洁、增湿、改善的皮肤感觉、磨皮/磨砂、焕然一新的外观、或这些功效的综合。
组合物使非水溶性或部分水溶性成分悬浮的能力通常通过以下方法评价：充分搅拌组合物以将气泡捕获在组合物中，然后目视观察在一定时期内(例如12到24小时内)在一定的环境条件(例如室温)下，气泡是否还留在组合物中。在一个实施方案中，本发明的组合物能够使气泡悬浮至少1周，更通常为至少3个月。能够在室温下使气泡悬浮至少12小时的组合物被认为是在通常所预计的该组合物的加工、储存和使用条件下，一般能够使该组合物中的非水溶性成分或部分水溶性的成分悬浮。对于空气以外的成分，应该通过使用所关心的成分进行类似的悬浮试验，来对空气悬浮试验的结果进行证实。对于非常苛刻的加工、储存和/或使用条件，更严格的试验可能是合适的。
在一个实施方案中，在更严格的条件下对非水溶性成分或部分水溶性成分的悬浮能力进行评价，即，对混合后的样品进行一次或多次冷冻/解冻循环，其中每次冷冻/解冻循环是由-10℃下12小时和25℃下12小时构成的，然后目视评价该样品。在一个实施方案中，本发明的组合物在经历一次冷冻/解冻循环(更通常为3次冷冻/解冻循环)后，仍然能够悬浮气泡。
在一个实施方案中，本发明的组合物还含有一种或多种非水溶性或部分水溶性的成分。所述成分可以是固体、液体、或气体的形式，并且可以含有选自非水溶性或部分水溶性并且化学稳定的有益试剂、以及非水溶性或部分水溶性并且化学稳定的外观调节用添加剂中的一种或多种物质，所述有益试剂例如(就个人护理应用而言)为润肤剂、调理剂、增湿剂、维生素、维生素衍生物、抗UV剂、抗菌剂、抗真菌剂、皮肤变黑加速剂、抗老化剂、抗皱剂、防汗剂、除臭剂、香精油、香水、空气、或研磨剂，所述外观调节用添加剂例如为有色的或具有反射性的颗粒或小珠)。
在另一个实施方案中，本发明的组合物含有本发明的结构化表面活性剂成分(即，一种含有水和选自阴离子磷酸酯表面活性剂、阴离子磺酸盐表面活性剂和阴离子羧酸盐表面活性剂中的一种或多种阴离子表面活性剂的成分)，该成分形成第一相(如上所述，其本身可具有多个相，包括水性相、层状表面活性剂相和球粒状表面活性剂相)；该组合物还可含有一个或多个附加相，该附加相与所述的第一相至少基本不同。本文所用的涉及本发明的多相实施方案中的多个相的术语“基本不同”是指：这些相各自在指定的相中表现出基本均匀的性质，并且这些相至少在一种特性或性质上是不同的，所述特性或性质例如为视觉特征(例如颜色、透明性和珠光)、或物理/化学性质(例如粘度、滑润性和/或有益试剂的含量)。
在一个实施方案中，结构化表面活性剂成分形成第一相，该第一相表现出剪切变稀的粘度并且能够使非水溶性成分或部分水溶性成分悬浮。
在一个实施方案中，结构化表面活性剂成分形成第一相，该第一相表现出剪切变稀的粘度以及能够使非水溶性成分或部分水溶性成分悬浮，并且组合物具有至少一个附加相，该附加相至少基本不同于所述第一相、并且不表现出剪切变稀的粘度以及/或者不能使非水溶性成分或部分水溶性成分悬浮。
在一个实施方案中，结构化表面活性剂成分形成第一相，该第一相表现出剪切变稀的粘度以及能够使非水溶性成分或部分水溶性成分悬浮，并且组合物具有至少一个附加相(如根据本发明的附加的结构化表面活性剂成分)，该附加相与所述第一相至少基本不同、并且表现出剪切变稀的粘度以及能够使非水溶性成分或部分水溶性成分悬浮。
在一个实施方案中，结构化表面活性剂成分形成第一相，并且所述组合物还具有至少一个附加相，该附加相与所述第一相至少基本不同，其中各个所述的相都是连续相，并且这些相被彼此相邻地设置。
在一个实施方案中，结构化表面活性剂成分形成第一相，并且组合物具有至少基本上不同于所述第一相的至少一个附加相，其中所述相中的一个是连续相，而其它的相是非连续相，并且该非连续相与该连续相被相邻设置、或该非连续相分散在该连续相中。
在一个实施方案中，结构化表面活性剂成分形成第一相，并且组合物具有至少看起来基本不同于该第一相的至少一个附加相，例如，其中所述的至少一个附加相是悬浮在该第一相中的不透明的非水溶性成分。
在一个实施方案中，本发明的组合物具有两个不同的相，其中每一个相都是连续相，并且各个相被彼此相邻地设置。
在一个实施方案中，本发明的组合物具有两个不同的相，其中一个相是连续相，另一个相是非连续相，并且该非连续相与该连续相被相邻设置、或该非连续相分散在该连续相中。
在一个实施方案中，本发明的组合物具有两个不同的相，其中每一个相都是连续相，并且这两个相被设置成互穿网络的形式。
在一个实施方案中，本发明的组合物具有两个或多个看起来不同的相，例如，这样的两个或多个看起来不同的相，其表现出交替的看起来不同的条纹状外观。
本发明的组合物可用于(例如)个人护理应用，例如香波、沐浴液、洗手皂、护肤液、乳霜、调理剂、剃须产品、洗面奶、中性香波和皮肤护理用品；家庭护理应用，例如液体洗涤剂、洗衣剂、硬质表面清洁剂、餐具洗涤液、抽水马桶清洗剂；和其它应用，例如油田应用和农用化学品应用。
在一个实施方案中，本发明的组合物是个人护理组合物。
在一个实施方案中，本发明的结构化表面活性剂组合物可用作个人护理组合物。
在一个实施方案中，本发明的个人护理组合物含有本发明的结构化表面活性剂组合物和水性载体。
在一个实施方案中，本发明的个人护理组合物还含有一种或多种化学稳定的有益试剂，所述有益试剂为例如润肤剂、增湿剂、调理剂、皮肤调理剂、头发调理剂、维生素或其衍生物、抗氧化剂、自由基清除剂、研磨剂、染料、头发着色剂、漂白剂、头发漂白剂、抗UV剂、UV吸收剂、抗微生物剂、抗菌剂、抗真菌剂、黑色素调节剂、皮肤变黑促进剂、脱色剂、皮肤染色剂、调脂剂、减肥剂、抗痤疮剂、抗皮脂溢出剂、抗衰老剂、抗皱剂、角质层分离剂、抗炎剂、清新剂、愈合剂、脉管保护剂、防汗剂、除臭剂、免疫调节剂、营养剂、防脱发剂、烫发用还原剂、香精油和香水。
在一个实施方案中，本发明的个人护理组合物还含有一种或多种化学稳定的有益试剂，所述有益试剂选自：酸，如抗坏血酸、水杨酸、α-羟基酸，β-羟基酸、可任选地为内酯形式的α-酮酸、曲酸、咖啡酸、植酸、金鸡纳酸、苯-1，4-双(3-亚甲基樟脑磺酸)、乙醇酸、乳酸、扁桃酸、苹果酸、酒石酸、柠檬酸、羟基丁酸、葡萄糖酸、抗坏血酸、水杨酸、龙胆酸、尿黑酸和丙酮酸；吡啶硫酮锌；维生素B；维生素E醋酸酯；硅氧烷液；有机硅材料，如硅橡胶胶料，聚有机硅氧烷液和交联聚有机硅氧烷树脂；碳氢化合物调理剂，如矿脂、矿物油和胶状矿物油；增稠聚合物和/或有益聚合物，如琥珀酰聚糖(succinoglycan)(Rheozan，得自Rhodia公司)，诸如羧甲基纤维素胶(AqualonCMC-7HOF，得自Aqualon公司)之类的甲基纤维素产品，诸如羟丙基淀粉磷酸钠(Pure-Gel 980和Pure-Gel 998，得自Grain Processing公司)和改性的马铃薯淀粉(Structure-Solanace，得自National Starch公司)之类的改性淀粉，诸如丙烯酸酯/氨基丙烯酸酯/C10-30烷基PEG-20衣康酸酯共聚物(Structure-Plus，得自National Starch公司)之类的丙烯酸酯共聚物，阳离子聚合物(Rheovis CSP、Rheovis CDE和Rheovis CDP，得自Ciba公司)，聚丙烯酰亚氨基甲基丙磺酸盐/聚季铵盐-4(Plexagel ASC，得自ISP公司)，疏水改性的非离子多元醇(Acusol 880和Acusol 882，得自Rohm & Haas公司)。
在一个实施方案中，本发明的个人护理组合物还含有：最多约40pbw、更通常为约0.1pbw到约40pbw、甚至更通常为约0.3pbw到约20pbw、并且更通常为约0.5pbw到10pbw的一种或多种化学稳定的有益试剂。
本发明的个人护理组合物还可任选地含有其它成分，例如防腐剂，如苯甲醇、羟苯甲酸甲酯、对羟基苯甲酸丙酯和咪唑烷基脲；粘度调节剂；电解质，如氯化钠和硫酸钠；pH调节剂，如柠檬酸、琥珀酸、磷酸、氢氧化钠、氢氧化钾和碳酸钠；香料；染料；和螯合剂，如乙二胺四乙酸二钠。
通常，根据本发明个人护理组合物的所需性能，该个人护理组合物可任选地含有：分别占100pbw该个人护理组合物的最多约10pbw、优选为0.5pbw到约5.0pbw的各种上述其它组分。
实施例1-3
实施例1-3的组合物是通过以下方法制备的：将表I所列的各种成分以各自的相对用量混合在一起，并使它们在实验室环境温度下静置过夜。通常，首先将单烷基磷酸酯(“MAP”)成分溶解到水中，然后根据应用情况调节pH值。所有用量都以pbw/(100pbw组合物)来表示。目视观察混合后的组合物是否含有捕获的气泡。
表I
| 成分 | 实施例1 | 实施例2 | 实施例3 |
| 月桂基聚氧乙烯(1)醚磷酸酯(Dermalcare MAP L-210，得自Rhodia公司) | 24.9 | 24.7 | 24.5 |
| 50％ NaOH | 0.5 | 1.0 | 2 |
| 水 | 74.6 | 74.3 | 73.5 |
根据目视观察到静置过夜后的样品含有捕获气泡的结果，对实施例1-3制备的组合物分别作出其能够悬浮空气的评价。对实施例1-3制备的组合物分别进行一次冷冻/解冻循环(在-10℃下12小时和在25℃下12小时)，根据目视观察到各样品在进行冷冻/解冻循环后均含有捕获气泡的结果，对这些样品作出其在经过冷冻/解冻循环后仍然具有悬浮空气的能力的评价。
实施例4-7
实施例4-7的组合物是通过以下方法制备的：将表II所列的各种成分以各自的相对用量混合在一起，并且使它们在实验室环境温度下静置过夜。通常，将MAP酯溶解到水中，然后根据应用情况调节pH值。所有用量都以pbw/(100pbw组合物)来表示。
表II
| 成分 | 实施例4 | 实施例5 | 实施例6 | 实施例7 |
| 月桂基聚氧乙烯(1)醚磷酸酯(Dermalcare MAP L-210，得自Rhodia公司) | 16.7 | 16.4 | 24.9 | 8.3 |
| 异硬脂酸 | 1.3 | 1.3 | ||
| 西曲溴铵(RhodaquatM242B/99，得自Rhodia公司) | 0.9 | 0.9 | 0.5 | 0.17 |
| 月桂基聚氧乙烯(2)醚(Genapol 26-L-2) | 7.1 | 8.7 | ||
| 琥珀酰聚糖(Rheozan，得自Rhodia公司) | 1.33 | |||
| 50％ NaOH | 1.8 | 1.8 | ||
| 水 | 72.2 | 70.9 | 74.6 | 90.2 |
采用以上参照实施例1-3制备的组合物所描述的方法对实施例4-7制备的组合物的悬浮空气的能力进行评价，结果发现各组合物均能悬浮空气并且经过冷冻/解冻循环后仍然具有悬浮空气的能力。
实施例8-10
实施例8-10的组合物是通过以下方法制备的：将表III所列的各种成分以各自的相对用量混合在一起，并且使它们在实验室环境温度下静置过夜。通常，将MAP酯溶解到水中，然后根据应用情况调节pH值以及加入其它表面活性剂和盐。所有用量都以pbw/(100pbw组合物)来表示。
表III
| 成分 | 实施例8 | 实施例9 | 实施例10 |
| 十三烷基聚氧乙烯(4)醚磷酸酯(Rhodifac RS-410，得自Rhodia公司) | 12.2 | 12.6 | 12.4 |
| 十三烷基聚氧乙烯(7)醚羧酸(Nikkol ECT-7，得自Nikko公司) | 3.8 | ||
| 月桂基甜菜碱(Mirataine BB/FLA，得自Rhodia公司) | 4.9 | 5.0 | 5.0 |
| 月桂基聚氧乙烯(2)醚(Genapol26-L-2) | 4.6 | ||
| 异硬脂酸 | 1.9 | ||
| 氯化钠 | 3.6 | 3.7 | 2.8 |
| 50％ NaOH | 1.3 | 1.3 | 1.3 |
| 水 | 73.4 | 75.5 | 74.8 |
采用以上参照实施例1-3制备的组合物所描述的方法对实施例8-10制备的组合物的悬浮空气的能力进行评价，结果发现各组合物均能悬浮空气并且经过冷冻/解冻循环后仍然具有悬浮空气的能力。
实施例11-12
实施例11-12的组合物是通过以下方法制备的：将表IV所列的各种成分以各自的相对用量混合在一起，并且使它们在实验室环境温度下静置过夜。通常，将MAP酯溶解到水中，然后根据应用情况调节pH值。所有用量都以pbw/(100pbw组合物)来表示。
表IV
| 成分 | 实施例11 | 实施例12 |
| 十三烷基聚氧乙烯(4)醚磷酸酯(Rhodifac RS-410，得自Rhodia公司) | 22.9 | 16.0 |
| 十二烷基苯磺酸(Rhodacal SSA/A，得自Rhodia公司) | 1.6 | 1.1 |
| 50％ NaOH | 0.5 | 0.3 |
| 水 | 75.0 | 82.5 |
采用以上参照实施例1-3制备的组合物所描述的方法对实施例11-12制备的组合物的悬浮空气的能力进行评价，结果发现各组合物均能悬浮空气并且经过冷冻/解冻循环后仍然具有悬浮空气的能力。
实施例13-15
实施例13-15的组合物是通过以下方法制备的：将表V所列的各种成分以各自的相对用量混合在一起，并且使它们在实验室环境温度下静置过夜。通常，将MAP酯溶解到水中，然后根据应用情况调节pH值，并加入非离子表面活性剂和氯化钠。所有用量都以pbw/(100pbw组合物)来表示。
表V
| 成分 | 实施例13 | 实施例14 | 实施例15 |
| 月桂基聚氧乙烯(2)醚磷酸酯(Dermalcare MAP L-210，得自Rhodia公司) | 9.1 | 11.3 | 9.1 |
| 十三烷基聚氧乙烯(4)醚磷酸酯(Rhodifac RS-410，得自Rhodia公司) | 4.7 | 4.7 | |
| 月桂基聚氧乙烯(2)醚(Genapol 26-L-2) | 6.0 | 13.0 | 6.0 |
| 氯化钠 | 0.6 | 0.4 | |
| 10％ NaOH | 7.3 | 9.1 | 7.3 |
| 水 | 72.4 | 66.6 | 72.6 |
采用以上参照实施例1-3制备的组合物所描述的方法对实施例13-15制备的组合物的悬浮空气的能力进行评价，结果发现各组合物均能悬浮空气并且经过冷冻/解冻循环后仍然具有悬浮空气的能力。
Claims (24)
1.一种低pH值的水性结构化表面活性剂组合物，其含有：在100重量份的该组合物中，占3重量份到40重量份的选自一种或多种磷酸酯的非中和酸的阴离子表面活性剂，其中所述组合物具有小于5的pH值、表现出剪切变稀的粘度、并且能够使非水溶性或部分水溶性成分悬浮。
2.权利要求1所述的组合物，其中所述阴离子表面活性剂选自单烷基磷酸酯表面活性剂、二烷基磷酸酯表面活性剂及其混合物。
3.权利要求1所述的组合物，其中至少一部分该组合物为层状形式。
4.权利要求1所述的组合物，该组合物还含有选自阳离子表面活性剂、非离子表面活性剂、电解质及其混合物中的结构化试剂。
5.权利要求1所述的组合物，该组合物还含有选自胺盐、季铵化合物、氧化胺、脂肪醇、乙氧化醇、脂肪酸及其混合物中的结构化试剂。
6.权利要求1所述的组合物，其中该组合物含有：在100重量份的该组合物中，占0.5到25重量份的结构化试剂。
7.权利要求1所述的组合物，该组合物还含有选自非离子表面活性剂、两性表面活性剂、两性离子表面活性剂、阳离子表面活性剂及其混合物中的表面活性剂。
8.权利要求1所述的组合物，其中所述的一种或多种阴离子表面活性剂选自单烷基磷酸酯表面活性剂和二烷基磷酸酯表面活性剂，并且所述单烷基磷酸酯表面活性剂和二烷基磷酸酯表面活性剂的烷基取代基选自C8-C24烷基。
9.一种个人护理组合物，其含有权利要求1所述的结构化表面活性剂组合物。
10.权利要求9所述的个人护理组合物，其中该个人护理组合物选自香波、沐浴液、洗手皂、护肤液、剃须产品和洗面奶。
11.权利要求9所述的个人护理组合物，其中该个人护理组合物选自皮肤护理用品。
12.权利要求9所述的个人护理组合物，其中该个人护理组合物选自乳霜。
13.权利要求9所述的个人护理组合物，其中该个人护理组合物选自调理剂。
14.权利要求9所述的个人护理组合物，该个人护理组合物还含有一种或多种悬浮在该组合物中的非水溶性或部分水溶性成分。
15.权利要求9所述的个人护理组合物，该个人护理组合物还含有一种或多种有益试剂。
16.权利要求15所述的个人护理组合物，其中所述一种或多种有益试剂选自调理剂、抗氧化剂、研磨剂、染料、漂白剂、抗UV剂、抗微生物剂、黑色素调节剂、调脂剂、抗衰老剂、抗炎剂、清新剂、愈合剂、脉管保护剂、防汗剂、营养剂、防脱发剂、烫发用还原剂、香精油及其混合物。
17.权利要求15所述的个人护理组合物，其中所述一种或多种有益试剂选自增湿剂、自由基清除剂、头发着色剂、UV吸收剂、抗菌剂、皮肤变黑促进剂、头发漂白剂、皮肤染色剂、减肥剂、抗痤疮剂、抗皱剂、除臭剂、角质层分离剂、免疫调节剂、香水及其混合物。
18.权利要求15所述的个人护理组合物，其中所述一种或多种有益试剂选自皮肤调理剂、头发调理剂、抗真菌剂、脱色剂、抗皮脂溢出剂、维生素或其衍生物及其混合物。
19.权利要求15所述的个人护理组合物，其中所述一种或多种有益试剂选自润肤剂。
20.权利要求9所述的个人护理组合物，其中该组合物含有：在100重量份的该个人护理组合物中，占0.1到40重量份的有益试剂。
21.权利要求9所述的组合物，其中该组合物具有两个或多个不同的相。
22.权利要求9所述的组合物，其中所述的两个或多个相为条纹状。
23.一种低pH值的水性组合物，其含有：
连续的结构化表面活性剂相，所述的结构化表面活性剂相含有水和选自一种或多种磷酸酯的非中和酸的阴离子表面活性剂，并且表现出剪切变稀的粘度，以及
一种或多种非水溶性或部分水溶性成分，该成分悬浮在该结构化表面活性剂相中，
其中所述组合物的pH值小于5。
24.一种低pH值的水性组合物，其含有至少两个不同的相，其中至少一个所述的相是结构化表面活性剂相，该相含有水和选自一种或多种磷酸酯的非中和酸的阴离子表面活性剂，并且表现出剪切变稀的粘度，其中所述组合物的pH值小于5。
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-
2005
- 2005-08-17 CN CN200580033923.6A patent/CN101035889B/zh active Active
- 2005-08-17 AU AU2005277512A patent/AU2005277512B2/en not_active Ceased
- 2005-08-17 JP JP2007527971A patent/JP5154931B2/ja not_active Expired - Fee Related
- 2005-08-17 EP EP05786818.4A patent/EP1786893B2/en active Active
- 2005-08-17 CA CA2577460A patent/CA2577460C/en not_active Expired - Fee Related
- 2005-08-17 MX MX2007002002A patent/MX2007002002A/es active IP Right Grant
- 2005-08-17 RU RU2007109814/13A patent/RU2378333C2/ru not_active IP Right Cessation
- 2005-08-17 US US11/205,877 patent/US20060040837A1/en not_active Abandoned
- 2005-08-17 WO PCT/US2005/029240 patent/WO2006023548A2/en active Application Filing
- 2005-08-17 BR BRPI0514461-2A patent/BRPI0514461A/pt not_active Application Discontinuation
- 2005-08-17 ES ES05786818T patent/ES2401115T3/es active Active
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2007
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- 2007-03-16 KR KR1020077006172A patent/KR101344387B1/ko not_active IP Right Cessation
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2012
- 2012-03-16 US US13/422,667 patent/US20120177709A1/en not_active Abandoned
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1429264A (zh) * | 2000-03-20 | 2003-07-09 | 荷兰联合利华有限公司 | 在各相均包含层状相诱导结构剂的可挤压多相组合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2005277512B2 (en) | 2011-11-17 |
| EP1786893B1 (en) | 2012-12-19 |
| US20060040837A1 (en) | 2006-02-23 |
| RU2378333C2 (ru) | 2010-01-10 |
| EP1786893B2 (en) | 2016-11-02 |
| JP5154931B2 (ja) | 2013-02-27 |
| WO2006023548A2 (en) | 2006-03-02 |
| EP1786893A4 (en) | 2009-05-06 |
| KR20070044061A (ko) | 2007-04-26 |
| RU2007109814A (ru) | 2008-09-27 |
| CA2577460C (en) | 2013-05-14 |
| MX2007002002A (es) | 2007-04-23 |
| US20120177709A1 (en) | 2012-07-12 |
| IL181359A0 (en) | 2007-07-04 |
| CA2577460A1 (en) | 2006-03-02 |
| WO2006023548A3 (en) | 2006-10-12 |
| CN101035889A (zh) | 2007-09-12 |
| EP1786893A2 (en) | 2007-05-23 |
| AU2005277512A1 (en) | 2006-03-02 |
| BRPI0514461A (pt) | 2008-06-10 |
| ES2401115T3 (es) | 2013-04-17 |
| JP2008510847A (ja) | 2008-04-10 |
| KR101344387B1 (ko) | 2013-12-23 |
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