CN1142769C - 个人清洁组合物 - Google Patents
个人清洁组合物 Download PDFInfo
- Publication number
- CN1142769C CN1142769C CNB988018896A CN98801889A CN1142769C CN 1142769 C CN1142769 C CN 1142769C CN B988018896 A CNB988018896 A CN B988018896A CN 98801889 A CN98801889 A CN 98801889A CN 1142769 C CN1142769 C CN 1142769C
- Authority
- CN
- China
- Prior art keywords
- personal cleansing
- cleansing composition
- surfactants
- present
- hair
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229940045998 sodium isethionate Drugs 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
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- UMEWSJNRBXKWKZ-UHFFFAOYSA-M sodium;1,4-dioxo-1,4-dipentoxybutane-2-sulfonate Chemical compound [Na+].CCCCCOC(=O)CC(S([O-])(=O)=O)C(=O)OCCCCC UMEWSJNRBXKWKZ-UHFFFAOYSA-M 0.000 description 1
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- DUXXGJTXFHUORE-UHFFFAOYSA-M sodium;4-tridecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 DUXXGJTXFHUORE-UHFFFAOYSA-M 0.000 description 1
- BCKVHQYOHIGCIC-UHFFFAOYSA-M sodium;benzenesulfonate;dodecane Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1.CCCCCCCCCCCC BCKVHQYOHIGCIC-UHFFFAOYSA-M 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明的组合物涉及改进的包括表面活性剂体系、约0.1%以上至1%以下的非离子或阴离子水溶性聚合物、相分离引发剂和水的个人清洁组合物。这些组合物提供了改善的起泡和调理效果。
Description
技术领域
本发明涉及包括一种清洁组分以及一种调理组分的个人清洁组合物。
背景技术
由于和周围环境的接触及大量头皮分泌的皮屑,头发会变得脏污。脏污的头发会导致不洁的感觉和失去美感的外观。脏污的头发需要经常定期清洗。
通过除去过量的脏物和皮屑,香波可以清洁头发。然而,这种香波清洗有缺点,使头发处于湿的、缠结和通常不易梳理的状态。而且香波清洗会使头发变得干燥或“卷结”、缺乏光泽,这是由于头发的天然油脂和其它天然调理和保湿成分被除去的缘故。在香波清洗后,头发也会由于逐渐干燥,而失去“柔软性”,这是使用者可以想象到的。另外,头发在香波清洗后也会由于干燥,而引起静电量增加。这影响梳理,因此而得到飞扬的头发。目前,已经开发出许多方法以缓解香波洗发后所带来的问题,包括向香波中引入头发调理助剂至在使用香波后应用头发调理剂,即头发漂洗剂(hair rinses)。头发漂洗通常是一种液体物质,必须在香波清洗后,单独使用,保持在头发上一段时间,然后用清水洗去。当然,这种方法是非常耗时的,并且肯定不如同时包括清洗和调理头发成分的香波使用方便。
虽然已经公开了许多包括调理助剂的香波,但由于各种原因这些产品不能完全满足各种需要。由于阳离子调理剂具有抗静电、改善湿缠结性、给使用者带来丝般的湿发感,因此在头发调理中更倾向于使用阴离子调理剂。在香波中遇到的一个问题是许多通常用作调理剂的常规阳离子试剂与具有良好清洗性的阴离子表面活性剂间的相容性问题。目前,已经进行了各种努力试图通过使用替代的表面活性剂和改进的阳离子调理剂来减小不利的相互作用。在头发漂洗产品中,提供良好的整体调理效果的阳离子表面活性剂通常倾向于与阴离子清洁表面活性剂复合使用,在香波中的调理效果不好。具体地,使用的可溶性阳离子表面活性剂会形成可溶性的离子复合物,不能很好地沉积在头发上。形成不溶性离子复合物的可溶性阳离子表面活性剂虽然可以沉积在头发上,但是它不能提供良好的头发调理作用,并且易于使头发变脏,有黏着感。例如三鲸蜡基甲基氯化铵的不溶性阳离子表面活性剂的使用能带来突出的抗静电作用,但是不能提供良好的整体调理作用。许多阳离子聚合物易于积累在头发上,产生令人不舒服的“不清洁的”黏着感。因此,通常是使用有限量的阳离子聚合物以尽量减小这类问题。但是,这也限制了所得到的整体的调理效果。另外,阳离子调理剂通常不会提供最佳的整体调理效果,特别是在“柔软性”方面,尤其是在香波组合物中用作一种成分时更是如此。
可改善柔软性的材料是非离子硅氧烷类。香波组合物中使用的硅氧烷己经由大量的不同出版物公开过。这种出版物包括US 2,826,551(1958年3月11日授予Geen);US 3,964,500(1976年6月22日授予Drakoff);USP4,364,837(1982年12月21日授予Pader);BP 849,433(1960年9月28日授予Woolston)。虽然这些专利公开了含硅氧烷的组合物,但是它们并没有提供完全令人满意的产品,因为它们很难使硅氧烷很好地分散和悬浮在产品中。近来,稳定的、不溶性的含硅氧烷的头发调理香波组合物已经由US4,741,855(1988年5月3日授予Grote和Russell)、US 4,788,066(1988年11月29日授予Bolich和Williams)公开。这些香波组合物给各种不同类型的头发均带来了优异的整体调理作用,同时其还保持了优异的清洁性能,即使是在与阴离子去污表面活性剂一同使用时也是如此。
最近,改进的调理香波已由系列申请号07/622,699(1990年12月5日申请,Robert L.Wells,已放弃)的美国申请和其连续申请07/778,765(1991年10月21日申请)得到,其中公开的香波包含阴离子表面活性剂、分散的不溶性硅氧烷以及某种较低离子强度的阳离子聚合物(大于约0.4meq./g)。这些组合物对各种类型的头发,尤其是对染发、漂白、定形等处理而受到损害的头发,均能提供优异的清洁和调理作用。
Hirota等人的日本专利申请(特许公开号为56-72095,1981年6月16日,Kao Soap Corp.)也披露了包含阳离子聚合物和硅氧烷调理剂的香波。涉及包含阳离子剂和硅氧烷的香波的专利公开还有很多,包括EPO申请公开0 413417,公开于1991年2月20日,Hartnett等人。
另一种提供香波组合物头发调理效果的方法是使用摸起来为油性的物质。这些材料改善了头发的光泽和亮泽。在香波配方中,油性物质是与阳离子物质结合使用。日本专利申请Showa 53-35902(特许公开1979年10月6日(Showa 53-129135),N.Uchino(Linon Yusho Co.)公开了头发处理组合物,包括阳离子聚合物、脂肪酸盐、以及至少10%的油性组分,该组合物在香波清洗前或后使用。合适的油性组分是烃、高级醇、脂肪酸酯、甘油酯和脂肪酸。日本专利申请62[1987]-327266(1987年12月25日申请,公开于1989年7月4日,特许公开号为HEI 1[1987]-168612,Horie等人)公开了包含阳离子表面活性剂和/或阳离子聚合物,阴离子表面活性剂以及具体的酯RCOOR’(其中R和R’是直链或支链烷基)。
虽然已经进行了同时提供清洁能力和头发调理性方面的尝试,但是仍需要提供改进的起泡和调理效果的个人清洁组合物。本发明人发现将某些混有表面活性剂的非离子或阴离子聚合物与很少量的相分离引发剂结合使用的组合物形成了稳定的水乳液-其中该乳液包括悬浮于含水表面活性剂相中的含水聚合物相液滴。该分散的浓聚合物相改进了头发和皮肤的调理性,并且清洁感没有因此而损失。这些组合物可以被制成各种常用形式,包括,但不限于,调理香波,泡沫剂,摩丝,凝胶,洗液,喷雾剂等。
除上述护发益处外,还发现本发明的阴离子或非离子聚合物和表面活性剂体系组成的乳液还可以被加入各种个人清洁组合物中,或者与起泡物一起使用。这些组合物提供了一种皮肤调理组分,其更易于并且均匀地沉积在皮肤上,使人感觉舒适。这种组合物包括液体肥皂,沐浴胶,洗液等。适宜的起泡物包括无纺基质,纺织基质,水喷射交缠的基质(hydroentangled substrates),气流喷射交缠基质(air entangled substrates),天然海绵,合成海绵,聚合的网化网眼物(polymeric netted meshes)等。
因此,本发明的目的是提供一种起泡和调理性能改进的个人清洁组合物。
本发明的另一个目的是提供包括非离子或阴离子聚合物,表面活性剂体系和最少量相分离引发剂的改进型个人清洁组合物。
本发明还有一个目的是提供以乳液形式存在的个人清洁组合物,包括在含水表面活性剂相中的聚合物浓缩的含水相。
本发明的又一个目的是提供能包括更少量或减少量表面活性剂的个人清洁组合物。
本发明的再一个目的是提供在一种香波中加调理剂组合物产品,这种产品能提供优异的清洁性能和改善的调理效果,同时它还可以将过量使用调理剂积累而引起不利的副反应减至最小。
本发明的目的还有提供清洁和调理皮肤和头发的方法,它能提供优异的清洁作用和改善的调理作用。
下文对本发明进行了详细的叙述,更清楚地讲述了本发明的上述和其它目的。
发明内容
本发明涉及稳定的含水乳液形式的个人清洁组合物,包括
a)4-50%重量的表面活性剂体系,所述体系包含至少一种选自下列的表面活性剂:阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂、两性表面活性剂以及它们的混合物;
b)0.1%以上至小于1.0%重量的非离子或阴离子水溶性聚合物;
c)0.1-5%重量的包含电解质的相分离引发剂,其中该电解质是包括阴离子和阳离子的盐,所述阴离子选自磷酸根、硫酸根、硝酸根、柠檬酸根、卤素离子以及它们的混合物,所述阳离子选自钠、钾、铵、镁以及它们的混合物的离子;和
d)50-95%重量的水,
其中所述聚合物在含水表面活性剂体系中形成视觉可分辨的含水液滴。
本发明还涉及该个人清洁组合物的使用方法。
具体实施方式
本发明的个人清洁组合物可包括、组成或基本组成为:本发明的基本组分和本发明所限定的内容,以及任意的附加和任选成分、组分或所作的限定。
除非特别说明,所有百分数、份数和比例均是基于本发明的个人清洁组合物的总重量。除非特别说明,涉及所列成分的所有的这类重量比都是基于活性物质的量,因此不包括可能包括在市售物质中的载体或副产品。
本发明所用的术语“相分离”是指形成两个热动力学上稳定的液相,其不是以明显的松散层的形式存在,而是一种稳定的包括分散在一相中的另一相液滴的乳液。
本发明中所用的术语“视觉可分辨的”是指悬浮在一连续相中的液滴或液滴相,因此,任选地,当用裸眼观察时,液滴或液滴相是可被看出是与连续相分离的,明显不同于连续相。
本发明中所用的“水溶性”是指可充分溶解在水中的任意物质,只要其在25℃时在水中形成浓度为1.0%或以上重量的物质、肉眼看起来基本澄清的溶液。相反,术语“水不溶性”是指所有不能充分溶解在水中,不能在25℃的水中形成浓度为1.0%以上重量的物质、肉眼看来澄清的物质。
本发明的个人清洁组合物包括基本组分和任选组分,具体见下文详述。
基本组分
表面活性剂体系
本发明组合物包括作为基本组分的适宜的表面活性剂体系。
本发明的表面活性剂体系在个人清洁组合物中的存在量优选为约4%-50%,更优选约4%-40%,进一步优选约4%-30%,还优选约5%-20%,最优选约6%-16%。但是应该认识到表面活性剂体系的浓度随所需的清洁或起泡性能、表面活性剂体系体系中用到的表面活性剂、所需的产品浓度、组合物中存在的其它成分以及本领域中公知的其它因素而改变。
本发明的表面活性剂体系包括主去污表面活性剂,选自阴离子表面活性剂、两性表面活性剂及其混合物,以及附加的去污表面活性剂,所述的附加的表面活性剂选自非离子表面活性剂、阳离子表面活性剂或其混合物。使用去污表面活性剂的目的是使组合物具有清洁性能。本发明组合物使用的两性表面活性剂组分包括已知的可用在个人清洁组合物中的那些,并且优选其含有在本发明组合物的pH值时为阴离子的基因。这种表面活性剂成分在本发明表面活性剂体系中的浓度优选约为表面活性剂体系重量的0.5%-20%,更优选约1%-10%,最优选2%-7%。适用在本发明个人清洁组合物中的两性表面活性剂的实例在US 5104646(Bolich Jr等人)和US 5106609(Bolich Jr等人)中有述,本发明引入上述专利作为参考文献。本发明组合物中所用的两性去污表面活性剂的实例是普遍被称为脂肪族仲胺和叔胺衍生物的那些,其中脂族基团可以是支链或直链的,并且一个脂族取代基含有约8-18个碳原子,还有一个脂族取代基含有阴离子水溶性基团,例如羧基、磺酸基、硫酸根、磷酸根或膦酸根。符合这个定义的化合物的实例是3-十二烷基氨基丙酸钠、3-十二烷基氨基丙烷磺酸钠、月桂酰基两性乙酸钠、N-酰基牛磺酸(如根据US 2658072将十二烷胺与羟乙磺酸钠反应得到的物质)、N-高级烷基天冬氨酸(如根据US 2438091制备的那些)、商品名为MIRANOLTM的产品以及US2528378中描述的那些。
本发明中也可以使用其它的两性物质(有时候也被归类为两性离子类),如甜菜碱类。这类两性离子类物质在本发明中被视为两性物,其中两性离子物质具有一个在该组合物的pH值时是阴离子的结合基团。本发明使用的甜菜碱类的实例是高级烷基甜菜碱,如椰油二甲基羧甲基甜菜碱,椰油酰氨基丙基甜菜碱,椰油甜菜碱,月桂酰氨基丙基甜菜碱,油基甜菜碱,月桂基二甲基羧甲基甜菜碱,月桂基二甲基-α-羧乙基甜菜碱,十六烷基二甲基羧甲基甜菜碱,月桂基双-(2-羟乙基)羧甲基甜菜碱、硬脂基双-(2-羟丙基)羧甲基甜菜碱、油基二甲基r-羧丙基碱和月桂基双-(2-羟丙基)-α-羧乙基甜菜碱。磺基甜菜碱的代表是椰油二甲基磺基丙基甜菜碱,硬脂基二甲基磺基丙基甜菜碱,月桂基二甲基磺基乙基甜菜碱,月桂基双-(2-羟乙基)磺基丙基甜菜碱等;本发明还可使用酰氨基甜菜碱和酰氨基磺基甜菜碱,其中基团RCONH(CH2)3是接在甜菜碱的氮原子上。本发明最优选使用的是椰油酰氨基丙基甜菜碱。
适宜的阴离子表面活性剂包括烷基硫酸酯、烷基乙氧基化的硫酸酯或它们的混合物。这些物质的通式为(I)ROSO3M和(II)RO(C2H4O)xSO3M,其中R是具有约8-30个碳原子的烷基或链烯基,x是1-10,M是H或成盐阳离子如铵、烷醇胺,所述烷醇胺包括1-3个碳原子的烷基,例如为三乙醇胺、一价和多价金属,如碱金属和碱土金属。优选的金属包括钠、钾、镁和钙。优选应对阴离子表面活性剂的阳离子M进行选择,使得阴离子表面活性剂组分是水溶性的。阴离子表面活性剂的溶解性通常取决于特定的阴离子表面活性剂和所选择的阳离子。作为帮助确定合适的阴离子表面活性剂混合物的方式,阴离子表面活性剂经选择后使得Krafft温度约为15℃或更低,优选约10℃或更低,更优选约0℃或更低。还优选该阴离子表面活性剂溶解在组合物中。
优选,烷基和烷基乙氧化的硫酸酯中的R基具有约10-18个碳原子。烷基乙氧化的硫酸酯通常是由环氧乙烷和一元醇缩合制备的,所述一元醇具有约8-24个碳原子。上述醇可以得自脂肪,例如椰子油,棕榈仁油或牛脂,或者是合成醇。优选这类醇与约1-10,更优选约1-4,最优选约2-3.5摩尔比例的环氧乙烷反应,所得的各种分子形式的混合物每摩尔醇具有,例如,平均3摩尔的环氧乙烷,将该混合物硫酸化以后,中和。
可用在本发明中的烷基醚硫酸酯盐的具体实例是椰油烷基三甘醇醚硫酸酯的钠和铵盐;牛脂烷基三甘醇醚硫酸酯的钠和铵盐;以及牛脂烷基六氧亚乙基硫酸酯的钠和铵盐。特别优选的烷基醚硫酸酯盐是包括单个化合物的混合物,所述混合物的平均烷基链长为约12-16个碳原子,平均乙氧化度是约1-4摩尔的环氧乙烷。
硫酸酯表面活性剂优选包含乙氧化硫酸酯和非乙氧化硫酸酯的混合物。烷基硫酸酯可提供优良的清洁和起泡性能。烷基乙氧化的硫酸酯可提供突出的清洁性能,并对皮肤而言是温和的。
其它合适的阴离子去污表面活性剂包括,但不限于,通式为[R1-SO3-M]的有机硫酸化反应产物的水溶性盐,其中R1选自具有约8-24、优选约10-18个碳原子的直链或支链、饱和脂族烃基;M是阳离子,如铵离子、烷醇胺(如三乙醇胺)、一价金属离子(如钠和钾离子)、多价金属阳离子(如镁和钙离子)。应对阴离子去污表面活性剂中的阳离子M进行选择,使得去污表面活性剂成分是水溶性的。溶解度取决于特定的阴离子去污表面活性剂和所选的阳离子。这类去污表面活性剂的实例是甲烷系列烃的有机磺酸反应产物的盐,包括根据已知的磺化方法,包括漂白和水解,将具有约8-24个、优选约10-18个碳原子的异、新和正烷烃和一种磺化剂,例如SO3,H2SO4,反应得到。优选磺化的C10-18正烷烃的碱金属和铵的盐。
本发明适用的另一类阴离子去污表面活性剂是脂肪族酸用羟乙磺酸酯化、用氢氧化钠中和的反应产物,其中,例如,脂肪酸得自椰子油或棕榈仁油;牛磺酸甲酯(methyl tauride)的脂肪酸酰胺的铵盐、四乙铵或钾盐,其中的脂肪酸例如得自椰子油或棕榈仁油。其它类似的阴离子去污表面活性剂见US2486921、US 2486922和US 2396278,本文引入该专利作为参考文献。
适用在本发明中的其它的去污表面活性剂是琥珀酸盐,实例包括N-十八烷基磺基琥珀酸二钠;月桂基磺基琥珀酸二钠;月桂基磺基琥珀酸二铵;N-(1,2-二羧乙基)-N-十八烷基磺基琥珀酸四钠;磺基琥珀酸钠的二戊酯;磺基琥珀酸钠的二己酯;磺基琥珀酸钠的二辛酯。
其它适宜的阴离子去污表面活性剂包括烷基甘油基醚磺酸酯表面活性剂(也称为AGS表面活性剂)、其衍生物和盐。这些AGS表面活性剂是得自含磺酸酯和磺酸盐基团的烷基甘油基醚。这些化合物通常被描述成包含磺酸酯(盐)基团的甘油的烷基单醚。
这些AGS表面活性剂符合下述结构:
其中R是饱和或不饱和的直链、支链或环烷基,具有约10-18个碳原子,优选约11-16个碳原子,最优选具有约12-14个碳原子,X是阳离子,选自铵、单烷基取代的铵、二烷基取代的铵、三烷基取代的铵、四烷基取代的铵、碱金属、碱土金属及其混合物。更优选,上式中的烷基R是饱和的直链。
不限于理论,认为AGS表面活性剂中烷基链长的分布对整个清洁组合物的性能具有某种效果。通过使用得自椰子油和牛脂的脂肪醇利用可工业操作的方式达到令人满意的分布。也可使用其它的起始原料达到烷基链长的等效分布。在制备用于提供AGS烷基的椰油脂肪醇中,优选使用中间馏分的椰子油。根据需要可将高沸点的馏分与中间馏分椰子油一起使用。在制备牛脂脂肪醇的过程中,包括氢化步骤以确保它们基本饱和。
优选的AGS化合物是那些烷基得自至少50%来自约10-18个碳原子醇、主要存在的是单甘油基,同时存在着少于约30%二甘油基的化合物。下述实施例中使用的AGS包括约15%的二甘油基醚磺酸酯,这种AGS是优选使用的,因为这种材料是易于生产的。术语“AGS”用来包括单甘油基、二甘油基和痕量的高级甘油基化合物。可存在少量(少于约3%总量)的三甘油基醚磺酸酯和四甘油基醚磺酸酯。还包括衍生自具有支链或支链和直链混合的甘油基醚,其链长超过直链链长。
本发明中可用的AGS表面活性剂在US 2,979,465(1961年4月20日授予Parran等人);US 3,179,599(1965年4月20日授予Eaton等人);BP848,224(1960年9月14日公开);BP 791,415(1958年3月5日公开);US5,322,643(1994年6月21日授予Scbwartz等人)和US 5,084,212(1992年1月28日授予Farris等人)中有更全面的描述,本文引入这些专利作为参考文献。这些参考文献也公开了可使用本发明AGS表面活性剂的各种清洁产品。
其它的适宜的阴离子去污表面活性剂包括具有约10-24个碳原子的烯烃磺酸酯盐。术语“烯烃磺酸酯盐”是指将α-烯烃用未复合的SO3磺化后,中和酸性反应混合物而得到的产品,其中反应中形成的任意的磺内酯(sulfone)经水解得到相应的羟烷基磺酸酯盐。SO3可以为液态或气态,通常(不是必须的)要用惰性稀释剂稀释,例如当以液态形式使用时,可用液态SO2、氯化烃等稀释;当用作气态时,可用空气、氮气、气态SO2等稀释。
制备烯烃磺酸盐的α-烯烃是具有约10-24、优选约12-16个碳原子的单烯烃。优选是直链烯烃。
除了真正的烯烃磺酸酯盐和部分羟烷基磺酸酯盐外,烯烃磺酸盐中还可包含少量的其它物质,如烯烃二磺酸盐,这取决于磺化反应中的反应条件/反应物比例、起始烯烃的性质、原料烯烃中的杂质、副反应。
上述类型的具体的α-烯烃磺酸盐在US 3332880中有更详细的描述,其被本文引入作为参考文献。
本发明中可用的另一类阴离子去污表面活性剂是β-烷氧基烷烃磺酸盐,具有下列通式:
其中R1是具有约6-20个碳原子的直链烷基,R2是优选具有约1-3个碳原子的低级烷基,M是如上述的水溶性阳离子。
优选用在本发明中的附加的阳离子去污表面活性剂包括烷基甘油基醚磺酸盐、月桂基硫酸铵、月桂基聚氧乙烯醚硫酸铵、月桂基硫酸三乙胺、月桂基聚氧乙烯醚硫酸三乙胺、月桂基硫酸三乙醇胺、月桂基聚氧乙烯醚三乙醇胺、月桂基硫酸单乙醇胺、月桂基聚氧乙烯醚单乙醇胺、月桂基硫酸二乙醇胺、月桂基聚氧乙烯醚二乙醇胺、月桂酸单甘油酯硫酸钠、月桂基硫酸钠、月桂基聚氧乙烯醚硫酸钠、月桂基硫酸钾、月桂基聚氧乙烯醚硫酸钾、月桂基肌氨酸钠、月桂酰基肌氨酸钠、月桂基肌氨酸、椰油(酰)基肌氨酸、椰油(酰)基硫酸铵、月桂酰基硫酸铵、椰油(酰)基硫酸钠、月桂酰基硫酸钠、椰油(酰)基硫酸钾、月桂基硫酸钾、月桂基硫酸三乙醇胺、月桂基硫酸三乙醇胺、椰油(酰)基硫酸单乙醇胺、月桂基硫酸单乙醇胺、十三烷基苯磺酸钠、十二烷基苯磺酸钠以及其混合物。
存在于本发明表面活性剂体系中的阴离子去污表面活性剂的优选浓度是约3%-20%、更优选约4%-17%、最优选约6%-14%。
另一类阴离子表面活性剂是脂肪酸皂。虽然它们可以用在本发明中,但是在硬水中较高浓度的这类表面活性剂会使得在头发和皮肤上积累,对清洗作用有不利的影响,使皮肤和头发产生不好的感觉。因此,如果本发明组合物中要加入脂肪酸皂,其引入量优选小于约3%、更优选小于约1%。
本发明的表面活性剂体系还可以包括非离子表面活性剂、阳离子表面活性剂。适宜的各种非离子表面活性剂包括:
1.烷基酚的聚环氧乙烷缩合物,例如具有直链或支链构型的约6-12个碳原子的烷基的烷基酚与环氧乙烷的缩合产物,所述环氧乙烷的存在量是每摩尔烷基酚约10-60摩尔环氧乙烷。该化合物中的烷基取代基,例如,可得自聚合的丙烯、二异丁烯、辛烷或乇烷。
2.那些得自环氧乙烷和环氧丙烷与乙二胺反应产物的缩合产品,取决于所需的亲水和亲油部分间的平衡,其成分可以变化。例如,环氧乙烷与疏水基反应得到的含有约40%-80%重量的聚氧乙烯、分子量约为5,000-11,000的化合物是令人满意的化合物,其中疏水基是乙二胺和过量环氧丙烷的反应产物,分子量为约2,500-3,000。
3.具有约8-18个碳原子、直链或支链构型的脂肪醇与环氧乙烷的缩合产物。例如椰子醇环氧乙烷缩合物,其每摩尔椰子醇具有约10-30摩尔环氧乙烷,椰子醇部分具有约10-14个碳原子。
4.对应于下式的长链叔胺氧化物;
5.对应于下式的氧化叔膦
其中R含有具有约8-18个碳原子的烷基、链烯基、或单羟基烷基,约0-10个环氧乙烷部分和约0-1个甘油基,R′和R″各自分别是含有约1-3个碳原子的烷基或单羟基烷基。式中的箭头是半极化键的一种惯用表达方式。适宜的氧化膦的实例是:氧化十二烷基二甲基膦、氧化十四烷基二甲基膦、氧化十四烷基甲基乙基膦、3,6,9-三氧杂十八烷基二甲基膦氧化物、氧化十六烷基二甲基膦,3-十二烷氧基-2-羟基丙基二(2-羟乙基)膦氧化物、氧化硬脂基二甲基膦、氧化十六烷基乙基丙基膦、氧化油基二乙基膦、氧化十二烷基二乙基膦、氧化十四烷基二乙基膦、氧化十二烷基二丙基膦、氧化十二烷基二乙基膦、氧化十四烷基二乙基膦、氧化十二烷基二丙基膦、氧化十二烷基二(羟甲基)膦、氧化十二烷基二(2-羟乙基)膦、氧化十四烷基甲基-2-羟丙基膦、氧化油基二甲基膦、2-羟基十二烷基二甲基膦氯化物。
6.长链二烷基亚砜,其含有具有约1-3个碳原子的短链烷基或羟基烷基(通常是甲基)和一个长疏水链,所述疏水链包括含有约8-20碳原子的烷基、链烯基、羟烷基或酮烷基、约0-10个环氧乙烷部分和约0-1个甘油基部分。实例包括:十八烷基甲基亚砜、2-酮十三烷基甲基亚砜、3,6,9-三氧杂十八烷基2-羟乙基亚砜、十二烷基甲基亚砜、油基3-羟丙基亚砜,十四烷基甲基亚砜、3-甲氧基十三烷基亚砜、3-羟基十三烷基甲基亚砜、3-羟基-4-十二烷氧基丁基甲基亚砜。
7.聚环氧烷改性的二甲基聚硅氧烷,也称作:聚二甲基硅氧烷共聚醇(dimethicone copolys)。这类物质包括下式的聚环氧烷的改性的二甲基聚硅氧烷:
和 R′-Si-[[O-Si-(CH3)2]x(OC2H4)a-(OC3H6)b-OR″]3
其中R是H、具有约1-12个碳原子的烷基、具有约1-6个碳原子的烷氧基或羟基;R′和R″是具有约1-12个碳原子的烷基;x是1-100的整数,优选20-30;y是1-20的整数,优选2-10;a和b是0-50的整数,优选20-30。本发明可用的聚二甲基硅氧烷共聚醇中的一些披露于下述专利文件中,本文引入作为参考:1978年10月24日授予Gee等人的US 4122029;1981年5月5日授予Keil的US 4,265,878;1983年12月20日授予Dixon等人的US4,421,769。用于本发明的市售聚二甲基硅氧烷共聚醇包括Silwet SurfaceActive Copolymers(Union Carbide Corporation生产);Dow Corning SiliconeSurfactants(Dow Corning Corporation生产);Silicone Copolymer F-754(SWSSilicones Corp.生产);Rhodorsil 70646 Fluid(Rhone Poulenc,Inc.生产)。
阳离子表面活性剂也可用在本发明中,通常包含氨基或季铵亲水部分,其在溶解在本发明的含水组合物中时,带正电。本发明可用的阳离子表面活性剂中的一些叙述于下述文件(本发明引入作为参考)中:M.C.Publishing Co.,McCutcheon′s Detergents & Emulsifiers(North American edition 1989);Schuarz等,
Surface Active Agents,Their Chemistry and Technology、NewYork:Interscience Publisheris,1949;USP 3,155,591(1964年11月3日授予Hilfer);USP 3,929,678(1975年12月30日授予Laughlin等人);USP3,959,461(1976年5月25日授予Bailey等);USP 4,387,090(1983年6月7日授予Bolich,Jr等人)。如果阳离子表面活性剂用在本发明的组合物中,那么所用的阳离子表面活性剂不应干扰个人清洁组合物的使用性能和最终效果。
可用在本发明中的含季铵的阳离子表面活性剂物质是下式代表的物质:
其中R1-R4独立地是具有约1-22个碳原子的脂肪族基团,或芳基、烷氧基、聚氧乙烯基、烷酰胺基、羟烷基、具有约12-22个碳原子的芳基或烷芳基;X是阴离子,选自:卤素、乙酸根、磷酸根、硝酸根和烷基硫酸根。脂族基除C、H原子外还可以包括醚键,其它基团如氨基。
其它可用在本发明中的季铵盐具有下述通式:
其中R1是具有约16-22个碳原子的脂族基团,R2、R3、R4、R5和R6选自H和具有约1-4个碳原子的烷基,X是选自卤素、乙酸根、磷酸根、硝酸根和烷基硫酸根的离子。这类季铵盐包括二氯化牛脂丙烷二铵。
优选的季铵盐包括单烷基三甲基氯化铵和二烷基二甲基氯化铵和三烷基甲基氯化铵,其中至少一个烷基具有约12-22个碳原子的烷基,得自长链脂肪酸,如氢化牛脂脂肪酸(牛脂脂肪酸得到季化物,其中长链烷基主要具有16-18个碳原子)。本发明可用的季铵盐的实例包括硬脂基三甲基氯化铵、二牛脂二甲基氯化铵、二牛脂二甲基甲基硫酸铵、二(十六烷基)二甲基氯化铵、二(氢化牛脂)二甲基氯化铵、二(十八烷基)二甲基氯化铵、二(二十烷基)二甲基氯化铵、二(二十二烷基)二甲基氯化铵、二(氢化牛脂)二甲基乙酸铵、二(十六烷基)二甲基氯化铵、二(十六烷基)二甲基乙酸铵、二牛脂二丙基磷酸铵、二牛脂二甲基硝酸铵、二(椰子烷基)二甲基氯化铵,和硬脂基二甲基苄基氯化铵、二牛脂二甲基氯化铵、二(十六烷基)二甲基氯化铵、硬脂基二甲基苄基氯化铵和鲸蜡基三甲基氯化铵是本发明优选的季铵盐。二(氢化牛脂)二甲基氯化铵和二(十六烷基)甲基氯化铵是特别优选的季铵盐。这些物质给本发明的香波实施方案带来抗静电效果。
本领域已知的用于头发或个人清洁用品中的其它表面活性剂也可用在本发明的表面活性剂体系中,条件是这种表面活性剂与本发明的基本成分在化学和物理性能上都相容,或者是其不会过分地损害产品的性能、美观或稳定性。优选用在本发明表面活性剂体系中的是阴离子和/或两性表面活性剂。
虽然对本发明组合物,非离子或阳离子表面活性剂也是有用的,但它们会减少皂和香波组合物的起泡性能。为了维持充分的起泡性,优选低浓度的非离子或阳离子表面活性剂。通常,本发明的表面活性剂体系将包含小于3%,更优选小于1%的非离子和阳离子表面活性剂。
非离子或阴离子水溶性聚合物
本发明的另一基本成分是非离子或阴离子水溶性聚合物。合适的非离子聚合物包括下列的水溶性聚合物,如纤维素醚(例如羟丁基甲基纤维素、羟丙基纤维素、羟丙基甲基纤维素、乙基羟基乙基纤维素和羟乙基纤维素),丙二醇藻酸酯、聚丙烯酰胺、聚(环氧乙烷)、聚乙烯醇,聚乙烯吡咯烷酮、羟丙基瓜耳胶、刺槐豆胶、直链淀粉、羟乙基直链淀粉、淀粉和淀粉衍生物及其混合物。优选非离子聚合物包括羟乙基纤维素、聚氧化乙烯、聚乙烯吡咯烷酮、聚乙烯醇、聚丙烯酰胺、羟丙基纤维素、乙基羟基乙基纤维素、葡聚糖、聚氧化丙烯和羟丙基瓜耳胶。
合适的阴离子水溶性聚合物包括羧甲基纤维素、角叉胶(carrageenan)、黄原胶、聚苯乙烯磺酸酯、瓜耳胶、印度胶、刺梧桐树胶、果胶、藻酸盐、以及聚(丙烯酸)和丙烯酸或甲基丙烯酸衍生物,如丙烯酸、甲基丙烯酸的碱金属和铵盐。也可使用上述阴离子水溶性聚合物的混合物。
这些聚合物可以是均聚物或者它们可以是与本领域已知的其它共聚用单体的共聚物或三元聚合物。本领域公知的共聚用单体的实例包括(但不限于)乙烯、丙烯、异丁烯、苯乙烯、聚苯乙烯、α-甲基苯乙烯、乙酸乙烯酯、甲酸乙烯酯、烷基醚、丙烯腈、甲基丙烯腈、氯乙烯、偏氯乙烯、丙烯酸烷基酯、甲基丙烯酸烷基酯、富马酸烷基酯、马来酸烷基酯、以及其它的烯属单体可共聚用单体,只要所得的聚合物在本发明组合物中是水溶性且是相分离的即可。阴离子和非离子单体如丙烯酸和甲基丙烯酸与丙烯酰胺、甲基丙烯酰胺、N-烷基取代的酰胺、N-氨基烷基酰胺、相应的N-烷基氨基烷基取代的酰胺、氨烷基丙烯酸酯、氨烷基甲基丙烯酰胺以及丙烯酸或甲基丙烯酸的N-烷基取代的氨烷基酯的共聚物。
优选的阴离子聚合物包括聚丙烯酸、羧甲基纤维素钠、聚丙烯酸酯、聚甲基丙烯酸酯、聚硫酸酯如聚乙烯硫酸酯、聚苯乙烯磺酸酯、聚磷酸酯、葡聚糖硫酸钠、藻酸盐和果胶酸盐。
当与含水表面活性剂体系和相分离引发剂结合时(将在下文叙述),水溶性阴离子或非离子聚合物分离形成悬浮在连续的含水相中的含水液滴。聚合物液滴的平均颗粒大小为约0.1-10,000μm,优选约1.0-5000μm,最优选约5-1000μm。
本发明中最优选的是乙基羟乙基纤维素、羟乙基纤维素、羟丙基瓜耳胶和聚苯乙烯磺酸酯。
本文所述的聚合物优选以约0.1-1.0%、更优选约0.15-0.75%,最优选约0.2-0.5%的量存在。
相分离引发剂
本发明的另一基本组分是相分离引发剂。本发明中的术语“相分离引发剂”是指当与包括表面活性剂体系和非离子或阴离子水溶性聚合物合并时能引起相分离的电解质、两亲物或其混合物。
本发明中用的术语“两亲物”通常是指同时包含亲水基和疏水基(亲脂基)的物质。优选用在本发明中的两亲物是通常不形成胶束或液晶相的那些,包括(但不限于):脂肪酸酰胺、脂肪醇、脂肪酯、脂肪酸的甘醇单和双酯、甘油酯。
包括烷醇酰胺的酰胺是脂肪酸和伯、仲胺或烷醇胺的缩合产品,得到下式产品:
其中RCO是脂肪酸残基,R是C8-20;X是烷基、芳基或烷醇(CHR′CH2OH,其中R′是H或C1-6烷基);Y是H、烷基、烷醇或X。合适的酰胺包括(但不限于)椰油酰胺、月桂酰胺、油酰胺、硬脂酰胺。合适的烷醇酰胺包括(但不限于)椰油酸二乙醇酰胺、椰油酸单乙醇酰胺、椰油酸单异丙醇酰胺(cocamide MIPA),异硬脂酸二乙醇酰胺、异硬脂酸单乙醇酰胺、异硬脂酸单异丙醇酰胺,羊毛脂二乙醇酰胺(lanolinamide DEA)、月桂酸二乙醇酰胺、月桂酸单乙醇酰胺、月桂酸单异丙醇酰胺、亚油酸二乙醇酰胺、亚油酸单乙醇酰胺、亚油酸单异丙醇酰胺、肉豆蔻酸二乙醇酰胺、肉豆蔻酸单乙醇酰胺、肉豆蔻酸单异丙醇酰胺、油酸二元醇酰胺、油酸单乙醇酰胺、油酸单异丙醇酰胺、棕榈酸二乙醇酰胺、棕榈酸单乙醇酰胺、棕榈仁二乙醇酰胺、棕榈仁单乙醇酰胺、棕榈仁单异丙醇酰胺、花生单乙醇酰胺、花生单异丙醇酰胺、大豆二乙醇酰胺、硬脂酸二乙醇酰胺、硬脂酸单乙醇酰胺、硬脂酸单异丙醇酰胺、牛油二乙醇酰胺、妥尔二乙醇酰胺(tallamide DEA)、牛油二乙元醇酰胺(tallowamide DEA)、牛油单乙醇酰胺、十一烷酸二乙醇酰胺、十一烷酸单乙醇酰胺。缩合反应可以与游离脂肪酸或与各种类型的脂肪酸酯如脂和油、特别是甲酯一起进行。反应条件和原料来源决定了终产品中的各物质的共混物和杂质的性质。
脂肪醇是高分子量的非挥发性伯醇,如下式:
RCH2OH
其中R是C8-20烷基。它们可由天然油和脂通过还原脂肪酸的-COOH得到-OH而制得。或者,可根据本领域公知的常规方法生产同样或类似结构的脂肪醇。合适的脂肪醇包括(但不限于)二十二醇、C9-11醇、C12-13醇、C12-15醇、C12-16醇、C14-15醇、辛醇、十六/十八醇(cetearyl alcohol)、椰子醇、十六醇、异十六醇、异硬脂醇、十二醇、油醇、棕榈仁醇、硬脂醇、十六醇、牛油醇、十三醇或十四醇。甘油酯包括一小组(Subgroup)酯,主要是与其它醇等反应改性的脂肪酸单甘油酯和甘油酯或双油三酯优选的甘油酯是甘油单和双酯合适的甘油酯及其衍生物包括(但不限于)乙酰化的氢化牛油甘油酯、二十二酸甘油酯、辛酸甘油酯、癸酸甘油酯、辛酸/癸酸甘油酯、甘油二月桂酸酯、甘油二油酸酯、芥酸甘油酯、羟基硬脂酸甘油酸、异硬脂酸甘油酯、羊毛酸甘油酯(glyceryllanolate)、月桂酸甘油酯、亚油酸甘油酯、油酸甘油酯、硬脂酸甘油酯、肉豆蔻酸甘油酯、甘油二硬脂酸酯及其混合物。
也可用作本发明两亲物的是长链乙二醇酯或其混合物。包括具有约8-22个碳原子的脂肪酸的乙二醇酯。式如RCO-OR′的脂肪酯也可用作本发明中合适的两亲物,其中R和R′中的一个是C8-22烷基,另一个是C1-3烷基。
本发明的两亲物也可包含各种表面活性剂,如非离子和阴离子表面活性剂。如果这些表面活性剂被引入到本发明中,它们将成为用作两亲物的附加表面活性剂以引发相分离,与本发明表面活性剂体系的表面活性剂和烷基甘油基磺酸盐表面活性剂分离并分开。
本发明优选的两亲物包括椰油酸单乙醇酰胺、十六醇、硬脂醇。
本发明两亲物在个人清洁组合物中的存在量优选0-约4%,更优选约0.5%-2%。
合适的电解质包括一价、两价或三价无机盐以及有机盐。表面活性剂盐本身不是本发明上述定义的电解质,但其它盐是。合适的盐包括(但不限于)磷酸盐、硫酸盐、硝酸盐,柠檬酸盐和卤化物。这些盐的抗衡离子是(但不限于)钠、钾、铵、镁或其它一、二或三价阳离子。本发明组合物中最优选使用的电解质包括NaCl、NH4Cl、柠檬酸钠、MgSO4。应认识到这些盐除用作相分离引发剂外,还可用作增稠助剂或缓冲添加剂。电解质的用量通常依赖于引入的两亲物的量,但可以以约0.1%-4%、优选约0.2%-2%的量存在。
包括电解质和/或两亲物的相分离引发剂的量随表面活性剂和聚合物的种类而变化,通常的存在量是约0.1%-5%,优选约0.2%-3%。
鉴于上述的相分离引发剂的基本性质和活性,本发明的组合物优选是基本上不含有阻止产生或形成分离相的物质。此处所用的“基本不含有”是指本发明的组合物包含少于约0.5%的这种物质、优选少于0.25%,优选为0。通常这种物质包括乙二醇、丙二醇、乙醇等。
本发明的组合物也优选基本不含有其它会不恰当地减少分离和明显区分的液相的形成的成分,特别是不给本发明组合物带来明显益处的成分。
水
本发明的个人清洁组合物包括约50%-95%,优选约60%-90%,更优选约75%-85%重量的水。
任选成分
硅氧烷组分
本发明的组合物可任选地包括非挥发性硅氧烷调理组分。通常将硅氧烷组分混合入含水的个人清洁组合物中形成分离的、不连续的硅氧烷相。硅氧烷调理组分包括一种硅氧烷流体调理剂如硅氧烷流体,还可包括其它的成分,如硅氧烷树脂以提高硅氧烷流体的沉积效率或提高头发的光泽度(特别是当使用高折光指数(例如高于约1.46)的硅氧烷调理剂(例如高度苯基化的硅氧烷)时。
本发明所用的“非挥发性”是指在环境条件下蒸汽压很小或不明显的硅氧烷材料,这是本领域技术人员易于理解的。一个大气压(atm)下的沸点优选至少约为250℃、更优选至少约为275℃、最优选至少约为300℃。蒸汽压优选在25℃或以下时约为0.2mmHg,优选在25℃或以下时约为0.lmmHg。
硅氧烷调理剂相可包括挥发性硅氧烷,非挥发性硅氧烷或其混合物。通常,如果存在挥发性硅氧烷时,它将同时用作市售形式的非挥发性硅氧烷材料成分的(如硅氧烷胶和硅氧烷树脂)的溶剂或载体。
优选用在本发明组合物中的硅氧烷调理剂在25℃时的粘度为约20-200,000厘沲,更优选约1,000-1,800,000厘沲,进一步优选约10,000-1,500,000厘沲;最优选约30,000-1,000,000厘沲。该粘度可用Dow Corning Corporate TestMethod CTM0004(1970年7月20日)之中示的玻璃毛细管粘度计测定。
可用在本组合物中的任选的硅氧烷流体包括可流动的硅氧烷油,其在25℃时的粘度小于1,000,000厘沲,优选约5-1,000,000厘沲,更优选约10-600,000厘沲,更优选约10-500,000厘沲,最优选10-300,000厘沲。合适的硅氧烷油包括聚烷基硅氧烷、聚芳基硅氧烷、聚烷基芳基硅氧烷、聚醚硅氧烷共聚物和其混合物。也可使用其它具有调理性的不溶性的非挥发性硅氧烷流体。
组合物中所用的任选的硅氧烷油包括满足下式的聚烷基或聚芳基硅氧烷:
其中R是脂族,优选烷基或链烯基,或芳基,R可被取代或不被取代,x是1-约8,000的整数。合适的未取代的R基包括烷氧基、芳氧基、烷芳基、芳烷基、芳基链烯基、烷氨基,醚取代的、羟基取代的和卤素取代的脂族或芳族基团。适宜的R基还包括阳离子胺和季铵基团。
在硅氧烷链上取代的脂族或芳族基团可具有任意结构,只要所得的硅氧烷仍旧在室温下为流体、疏水,当用到头发或皮肤上时不刺激、无毒、无害,与上述其它个人清洁组合物中的组分相容,在正常使用和储存条件下具有化学稳定性,不溶在本发明组合物中,能沉积在头发和皮肤上,并对其进行调理。
每个单体硅氧烷单元的Si上的两个R基可相同或不同。优选两个R基相同。
优选的烷基和链烯基取代基是C1-C5烷基和链烯基,更优选C1-C4,最优选C1-C2。其它含烷基、链烯基或链炔基(如烷氧基、烷芳基和烷氨基)的脂族部分可是直链或支链,优选具有约1-5个碳原子,更优选具有1-4个,进一步优选1-3个,最优选1-2个碳原子。如上所述,此处所用的R取代基还可包括氨基官能团,例如烷胺基,可以是伯、仲、叔或季铵。这些包括单、双、三烷氨基和烷氧氨基,其中脂族部分的链长优选如上所述。R取代基也可被其它基团取代,如卤素(例如氟、氯、溴),卤化脂或芳基、羟基(如羟基取代的脂肪基)。合适的卤化R基可包括,例如,三卤化(优选F)烷基如-R′-CF3,其中R1是C1-C3烷基。这种聚硅氧烷的实例包括聚甲基-3,3,3-三氟丙基硅氧烷。
合适的R基包括甲基、乙基、丙基、苯基、甲基苯基和苯基甲基。优选的硅氧烷是聚二甲基硅氧烷、聚二乙基硅氧烷和聚甲基苯基硅氧烷。特别优选聚二甲基硅氧烷。其它合适的R基包括甲基、甲氧基、乙氧基、丙氧基和芳氧基。硅氧烷端部的三个R基可相同或不同。
可用的非挥发性聚烷基硅氧烷流体包括,例如聚二甲基硅氧烷。这些硅氧烷,例如,得自General Elcetric Company,为其Viscasil R和SF 96系列,来自Dow Corning的Dow Corning 200系列。
可使用的聚烷基芳基硅氧烷流体还包括,例如,聚甲基苯基硅氧烷。这些硅氧烷例如可来自General Electric Company的SF 1075甲基苯基流体或来自Dow Corning的556化妆品级流体。可使用的聚醚硅氧烷共聚物包括,例如,聚环氧丙烷改性的聚二甲基硅氧烷(例如Dow Corning DC-1248),虽然也可使用环氧乙烷或环氧乙烷和环氧丙烷的混合物。环氧乙烷和环氧丙烷的量应足够低以防止溶解在水及组合物中。
其它用在硅氧烷调理剂中的适宜的硅氧烷流体是不溶性硅氧烷胶(silicone gums)。这些胶是聚有机硅氧烷,其在25℃时的粘大于或等于1,000,000厘拖。在US 4,152,416;Noll和Walter,
Chemistry and Technology of Silicones,New York:Academic Press 1968;以及General Electric SiliconeRubber Product Data Sheets SE 30,SE33,SE54和SE76中有关于硅氧烷胶的叙述,本发明引入上述文献作为参考。通常硅氧烷胶的重均分子量超过约200,000,通常在200,000-1,000,000之间,其具体的实例包括聚二甲基硅氧烷,(聚二甲基硅氧烷)(甲基乙烯基硅氧烷)共聚物,聚(二甲基硅氧烷)(二苯基硅氧烷)(甲基乙烯基硅氧烷)共聚物及它们的混合物。
硅氧烷调理剂还包括聚二甲基硅氧烷胶(粘度大于约1,000,000厘拖)和聚二甲基硅氧烷油(粘度约为10-100,000厘沲)的混合物,其中胶和流体的比是约30∶70-70∶30,优选约40∶60-60∶40。
公开一些适用在个人清洁组合物中的硅氧烷流体实例的参考文献包括US 2,826,551,US 3,964,500,US 4,364,837,BP 849,433和
Silicon Compounds,Petrarch Systems,Inc.(1984),其被引入本文作为参考。
硅氧烷调理剂中还可包含硅氧烷树脂。这些树脂是高度交联的聚合硅氧烷体系。在硅氧烷树脂的生产过程中,使三官能度和四官能度与单官能度或双官能度或二种硅烷结合而引入交联。众所周知,为生成硅氧烷树脂所需要的交联度可依据硅氧烷树脂中加入的特定硅烷单元而变化。通常,认为含有足够量的三官能度和四官能度硅氧烷单体单元(因而充分交联)从而它们干燥后成为刚性或硬的膜状物质的硅氧烷材料是硅氧烷树脂。氧原子与硅原子的比值反映了特定硅氧烷材料的交联度。每摩尔硅原子至少有约1.1摩尔氧原子的硅氧烷材料通常是本发明的硅氧烷树脂。优选氧原子与硅原子的比值至少为1.2∶1.0。生产硅氧烷树脂所用的硅烷包括一甲基-、二甲基-、三甲基-、一苯基-、二苯基-、甲基苯基-、一乙烯基-和甲基乙烯基-氯代硅烷、四氯硅烷,最常使用甲基取代的硅烷。优选的树脂为General Electric提供的GE SS4230和SS 4267。商购的硅氧烷树脂通常为溶解形式的低粘度挥发性或不挥发硅氧烷流体提供。本发明所用的硅氧烷树脂应以这种溶解的形式提供并掺入本发明的组合物中,这是本领域的普通技术人员所公知的。
有关硅氧烷,包括硅氧烷流体、胶、树脂,和硅氧烷生产方法的背景材料见“高分子科学与工程百科全书”,第十五卷,第二版,204-308页,JohnWiley & Sons,Inc.,1989,将其引入本文作为参考。
硅氧烷材料,特别是硅氧烷树脂可方便的按照本领域内技术人员所熟知的快速命名法“MDTQ”命名法来识别。在该命名法中,硅氧烷是按照组成硅氧烷的不同硅氧烷单体单元的存在进行描述的。简而言之,符号M表示单官能度单元(CH3)3SiO.5;D表示双官能度单元(CH3)2SiO;T表示三官能度单元(CH3)SiO1.5;Q表示四官能度单元SiO2。单元符号的上撇号如M′、D′、T′和Q′表示除甲基外的取代基,由每次的具体情况决定。典型的可替换的取代基包括基团如乙烯基、苯基、氨基、羟基等。不同单元的摩尔比,或者以符号的下标表示硅氧烷中每种类型单元的总数(或其平均值)或者以具体标明的比值与分子量结合来描述MDTQ系统中的硅氧烷材料。在硅氧烷树脂中,T、Q、T′和/或Q′与D、D′、M和/或M′相对较高的摩尔比,表明交联程度较高。但是,如前所述,交联的总量也可由氧原子与硅原子的比值来表示。
本发明所用的硅氧烷树脂优选是MQ、MT、MTQ、MDT和MDTQ树脂。因此,优选的硅氧烷取代基是甲基。特别优选MQ树脂,其中M∶Q约为0.5∶1.0-1.5∶1.0,树脂的平均分子量约为1000-10,000。
非挥发性硅氧烷流体(折光指数低于1.46)与硅氧烷树脂组分(当使用时)的重量比优选约4∶1-400∶1,优选该比例是9∶1-200∶1,更优选约19∶1-100∶1,特别当硅氧烷流体组分是如上所述的聚二甲基硅氧烷流体或聚二甲基硅氧烷流体和聚二甲基硅氧烷胶的混合物时更是如此。因为硅氧烷树脂形成了一部分与硅氧烷流体相同的相,即调理活性,在确定组合物中的硅氧烷调理剂的量时应同时包括硅氧烷流体和树脂的总量。
任选的硅氧烷组分的数均粒径取决于配方和/或所需的特征可有各种不同的变化。优选用在本发明中的数均粒径约为10纳米至约100微米,更优选约30纳米至约20微米。
其它任选组分
本发明的个人清洁组合物还可以包括一种或多种香波、调理和其它个人清洁组合物中常用的任选组分,条件是任选组分在物理和化学性质均与上述的基本组分相容,或者不过分的损害产品的稳定性、美观或性能。任选组分的浓度通常是的个人清洁组合物约0.001%-30%重量。
任选组分包括抗静电剂、阳离子调理聚合物如Polyquaterinum-10、染料、有机溶剂或稀释剂、润滑剂(如聚异丁烯、矿物油、凡士林、异鲸蜡基硬脂基硬脂酯)、珠光助剂、泡沫引发剂、灭虱药、pH调节剂、香料、防腐剂、蛋白质、抗氧化剂;螯合剂和多价螯合剂;美观组分如香味剂、着色剂、基本的油、皮肤感觉剂、收敛剂、皮肤平滑剂、皮肤治疗剂等,这些美观组分的非限制性实例包括羟泛酸及其衍生物(例如乙基羟泛酸)、泛酸及其衍生物、丁子香油、薄荷醇、樟脑、桉树油、丁子香酚、乳酸孟酯、金缕梅馏出液、尿囊素、红没药醇(bisabalol)、甘草酸二钾等,悬浮剂、定形聚合物、防晒剂、增稠剂、维生素及其衍生物(例如维生素C、维生素E、乙酸生育酯、视黄酸、视黄醇、视黄质等)、粘度调节剂。所列的任选组分不是排他性的,也可使用其它的任选组分。
生产方法
通常本发明的组合是在升温下(例如约72℃)将水和表面活性剂以及其它需要熔融的固体(例如两亲物)混合在一起,加速搅拌成为个人清洁组合物。附加成分,包括电解质可加到该热预混物中,也可在预混物冷却后加入。在预混物冷却后,可将非离子或阴离子聚合物以水溶液的形式加入。在升温下将各组分充分混合后,泵压通过高剪切研磨机,然后通过一个热交换器冷却到室温。硅氧烷可以在室温下在浓的表面活性剂中被乳化,然后加入到冷却后的产品中。或者,例如可将硅氧烷调理剂与阴离子表面活性剂和脂肪醇(如十六烷醇和硬脂醇)在升温下混合,形成包含分散硅氧烷的预混物。然后将该预混物加到其余的个人清洁组合物材料中,并与其混合,泵压通过高剪切研磨机后冷却。
使用方法
本发明的个人清洁组合物的使用方法与常规的清洁和调理皮肤或头发的方法一样。将有效量的用于清洁和调理皮肤或头发的组合物施用到已被事先润湿的头发或皮肤上,然后漂洗掉。有效量的范围通常是约1-50克,优选约1-20克。在头发上的使用通常包括揉抚头发,使大部分或全部头发都与组合物接触。
清洁和调理头发和皮肤的方法包括下列步骤:
a)用水润湿头发和/或者皮肤,
b)将有效量的个人清洁组合物施用在头发和/或者皮肤上,和
c)从头发和/或者皮肤上漂洗掉组合物。
根据需要,可以重复上述步骤直到达到所需的清洁和调理功效。
实施例
在实施例I-X例示的个人清洁组合物只是举例说明了本发明个人清洁组合物的具体实施方案,并不是用来限制本发明的。本领域普通技术人员在不脱离本发明精神和范围内可作出各种改变。这些示例性的本发明个人清洁组合物的实施方案提供了个人清洁组合物,改进了调理性能。
所有的例示的组合物均可以通过常规的配制和混合技术制得。所列的是重量百分比,不包括微量材料,如稀释剂、填料等。因此,所列的配方包括所列的各种组分以及与其有关的微量材料。
成分 | I | II | III | IV | V |
月桂基聚氧乙烯醚硫酸铵 | 5.00 | -- | -- | -- | -- |
月桂基硫酸铵 | 5.00 | 7.50 | 7.50 | 7.50 | 7.50 |
烷基甘油磺酸钠 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 |
椰油酰胺丙基甜菜碱 | -- | -- | -- | -- | -- |
甘醇二硬脂酸酯 | 2.00 | 1.50 | 2.00 | 2.00 | 2.00 |
椰油单乙醇酰胺 | 0.60 | 0.85 | 0.85 | 0.85 | 0.85 |
十六醇 | 0.42 | 0.42 | 0.42 | 0.42 | 0.42 |
硬脂醇 | 0.18 | 0.18 | 0.18 | 0.18 | 0.18 |
EDTA(乙二胺四乙酸) | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 |
磷酸一钠 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 |
磷酸二钠 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 |
苯甲酸钠 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 |
羟乙基纤维素1 | 0.10 | 0.25 | -- | -- | -- |
羟丙基瓜耳胶2 | -- | -- | 0.25 | -- | -- |
羟乙基乙基纤维素3 | -- | -- | 0.25 | -- | |
聚苯乙烯磺酸酯 | -- | -- | -- | 0.25 | |
三鲸蜡基甲基氯化铵 | 0.58 | -- | -- | -- | -- |
香料 | 0.60 | 0.60 | 0.60 | 0.60 | 0.60 |
聚二甲基硅氧烷 | 1.00 | 1.50 | 1.50 | 1.50 | 1.50 |
Glydant | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 |
NaCl | 0.30 | 0.30 | 1.00 | 1.00 | 1.00 |
水和微量物质 | 适量至100% |
成分 | VI | VII | VIII | IX | X |
月桂基聚氧乙烯醚硫酸铵 | -- | 9.00 | 14.00 | 6.60 | 8.00 |
月桂基硫酸铵 | 6.00 | -- | -- | 6.60 | -- |
烷基甘油磺酸钠 | 1.00 | 2.50 | -- | -- | -- |
椰油酰胺丙基甜菜碱 | -- | 2.50 | 2.70 | -- | -- |
甘醇二硬脂酸酯 | 1.50 | 1.50 | 1.50 | 1.50 | 2.00 |
椰油单乙醇酰胺 | 0.85 | 0.85 | 0.85 | 0.85 | -- |
十六醇 | 0.42 | 0.42 | 0.42 | 0.42 | 0.40 |
硬脂醇 | 0.18 | 0.18 | 0.18 | 0.18 | 0.18 |
EDTA(乙二胺四乙酸) | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 |
磷酸一钠 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 |
磷酸二钠 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 |
苯甲酸钠 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 |
羟乙基纤维素1 | 0.25 | 0.25 | 0.10 | 0.75 | 0.25 |
羟丙基瓜耳胶2 | -- | -- | -- | -- | -- |
羟乙基乙基纤维素3 | -- | -- | -- | -- | -- |
聚苯乙烯磺酸酯 | -- | -- | -- | -- | |
三鲸蜡基甲基氯化铵 | -- | -- | -- | -- | -- |
香料 | 0.60 | 0.60 | 0.60 | 0.60 | 0.60 |
聚二甲基硅氧烷 | 1.50 | 1.50 | 1.50 | -- | -- |
Glydant | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 |
月桂两性乙酸钠 | -- | -- | -- | -- | 3.60 |
Polyquaternium-10 | -- | -- | -- | -- | 0.20 |
NaCl | 0.30 | 0.30 | 0.30 | 0.30 | -- |
水和微量物质 | 适量至100% |
1来自Aqualon的Natrosol 250 HHR
2来自Rhone-Poulenc的Jaguar HP60
3来自Akzo Nobel的Bermocoll E411
Claims (15)
1.稳定的含水乳液形式的个人清洁组合物,包括
a)4-50%重量的表面活性剂体系,所述体系包含至少一种选自下列的表面活性剂:阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂、两性表面活性剂以及它们的混合物;
b)0.1%以上至小于1.0%重量的非离子或阴离子水溶性聚合物;
c)0.1-5%重量的包含电解质的相分离引发剂,其中该电解质是包括阴离子和阳离子的盐,所述阴离子选自磷酸根、硫酸根、硝酸根、柠檬酸根、卤素离子以及它们的混合物,所述阳离子选自钠、钾、铵、镁以及它们的混合物的离子;和
d)50-95%重量的水,
其中所述聚合物在含水表面活性剂体系中形成视觉可分辨的含水液滴。
2.权利要求1的个人清洁组合物,其中聚合物液滴的数均粒径大于0.1微米。
3.权利要求1的个人清洁组合物,其中表面活性剂体系的存在浓度为4-30%。
4.权利要求3的个人清洁组合物,其中表面活性剂体系的存在浓度为5-20%。
5.根据权利要求1的个人清洁组合物,其中非离子或阴离子聚合物选自羟乙基纤维素、聚环氧乙烷、聚乙烯基吡咯烷酮、聚乙烯醇、聚丙烯酰胺、羟丙基纤维素、乙基羟乙基纤维素、葡聚糖、聚环氧丙烷、羟丙基瓜耳胶、瓜耳胶、聚丙烯酸、聚苯乙烯、羧甲基纤维素钠、聚羧酸酯、聚磺酸盐、聚磷酸盐、葡聚糖硫酸钠、藻酸盐、果胶酸盐、其衍生物和其混合物。
6.根据权利要求5的个人清洁组合物,其中非离子或阴离子聚合物选自羟乙基纤维素、乙基羟乙基纤维素、羟丙基瓜耳胶、聚苯乙烯和其混合物。
7.根据权利要求1的个人清洁组合物,其中表面活性剂体系包括选自月桂基硫酸铵、月桂基聚氧乙烯醚硫酸铵、椰油酰胺基丙基甜菜碱、月桂两性乙酸钠、烷基甘油基醚磺酸盐,其衍生物及其混合物的表面活性剂。
8.根据权利要求1的个人清洁组合物,其中所述相分离引发剂包含占组合物重量的0.1%-4%的电解质和占组合物重量的0%-4%的两亲物。
9.根据权利要求8的个人清洁组合物,其中两亲物选自椰油单乙醇酰胺、鲸蜡醇、硬脂醇、其衍生物及其混合物。
10.根据权利要求1的个人清洁组合物,还包括聚硅氧烷调理组分。
11.根据权利要求10的个人清洁组合物,其中聚硅氧烷的数均粒径为10纳米至100微米。
12.根据权利要求1的个人清洁组合物,其形式为香波、泡沫、摩丝、凝胶、乳剂、喷剂、液体皂、沐浴凝胶或洗液。
13.护理头发的方法,通过施用安全、有效量的权利要求1组合物而进行。
14.护理皮肤的方法,通过施用安全、有效量的权利要求1组合物而进行。
15.清洁头发和皮肤的方法,通过施用安全、有效量的权利要求1组合物而进行。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US08/786,578 | 1997-01-21 | ||
US08/786,578 US5785979A (en) | 1997-01-21 | 1997-01-21 | Personal cleansing compositions |
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CN1243433A CN1243433A (zh) | 2000-02-02 |
CN1142769C true CN1142769C (zh) | 2004-03-24 |
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CNB988018896A Expired - Fee Related CN1142769C (zh) | 1997-01-21 | 1998-01-21 | 个人清洁组合物 |
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US (2) | US5785979A (zh) |
EP (1) | EP0967957B1 (zh) |
JP (1) | JP2001504133A (zh) |
CN (1) | CN1142769C (zh) |
AR (1) | AR011428A1 (zh) |
AT (1) | ATE249189T1 (zh) |
AU (1) | AU6033798A (zh) |
BR (1) | BR9806739A (zh) |
CA (1) | CA2277152A1 (zh) |
CO (1) | CO4940380A1 (zh) |
DE (1) | DE69818021T2 (zh) |
PE (1) | PE40799A1 (zh) |
WO (1) | WO1998031327A1 (zh) |
ZA (1) | ZA98454B (zh) |
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-
1997
- 1997-01-21 US US08/786,578 patent/US5785979A/en not_active Expired - Fee Related
-
1998
- 1998-01-19 CO CO98001930A patent/CO4940380A1/es unknown
- 1998-01-20 AR ARP980100242A patent/AR011428A1/es active IP Right Grant
- 1998-01-20 ZA ZA98454A patent/ZA98454B/xx unknown
- 1998-01-21 DE DE69818021T patent/DE69818021T2/de not_active Expired - Fee Related
- 1998-01-21 BR BR9806739-7A patent/BR9806739A/pt not_active IP Right Cessation
- 1998-01-21 AU AU60337/98A patent/AU6033798A/en not_active Abandoned
- 1998-01-21 PE PE1998000046A patent/PE40799A1/es not_active Application Discontinuation
- 1998-01-21 JP JP53465998A patent/JP2001504133A/ja not_active Ceased
- 1998-01-21 WO PCT/US1998/001097 patent/WO1998031327A1/en active IP Right Grant
- 1998-01-21 AT AT98903609T patent/ATE249189T1/de not_active IP Right Cessation
- 1998-01-21 CA CA002277152A patent/CA2277152A1/en not_active Abandoned
- 1998-01-21 CN CNB988018896A patent/CN1142769C/zh not_active Expired - Fee Related
- 1998-01-21 EP EP98903609A patent/EP0967957B1/en not_active Expired - Lifetime
- 1998-05-21 US US09/082,877 patent/US6096697A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
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EP0967957A1 (en) | 2000-01-05 |
CN1243433A (zh) | 2000-02-02 |
WO1998031327A1 (en) | 1998-07-23 |
CO4940380A1 (es) | 2000-07-24 |
JP2001504133A (ja) | 2001-03-27 |
DE69818021T2 (de) | 2004-07-08 |
US5785979A (en) | 1998-07-28 |
ATE249189T1 (de) | 2003-09-15 |
AU6033798A (en) | 1998-08-07 |
DE69818021D1 (de) | 2003-10-16 |
US6096697A (en) | 2000-08-01 |
BR9806739A (pt) | 2000-02-29 |
CA2277152A1 (en) | 1998-07-23 |
AR011428A1 (es) | 2000-08-16 |
PE40799A1 (es) | 1999-06-04 |
ZA98454B (en) | 1998-07-30 |
EP0967957B1 (en) | 2003-09-10 |
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