CN100360108C - 包含清洁相和独立有益相的具有改善稳定性的条纹状液体个人清洁组合物 - Google Patents
包含清洁相和独立有益相的具有改善稳定性的条纹状液体个人清洁组合物 Download PDFInfo
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- CN100360108C CN100360108C CNB2003801022525A CN200380102252A CN100360108C CN 100360108 C CN100360108 C CN 100360108C CN B2003801022525 A CNB2003801022525 A CN B2003801022525A CN 200380102252 A CN200380102252 A CN 200380102252A CN 100360108 C CN100360108 C CN 100360108C
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- A—HUMAN NECESSITIES
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Landscapes
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- Veterinary Medicine (AREA)
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- General Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Dermatology (AREA)
- Chemical & Material Sciences (AREA)
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- Cosmetics (AREA)
- Detergent Compositions (AREA)
Abstract
个人清洁组合物包含(A)包含表面活性剂和水的清洁相;和(B)包含疏水性物质的独立有益相;其中清洁相和有益相被包装在一起,并且直接接触。这两相以直接接触形式被包装在一起,并且在环境条件下可保持独立和稳定至少约180天。这些组合物和相应的方法提供了改善的美容、皮肤感觉和/或皮肤有益效果功效。
Description
发明领域
本发明涉及包含清洁相和独立有益相的条纹状液体个人清洁组合物,其中这两相以直接接触形式包装,并具有改善的稳定性。
发明背景
试图提供皮肤护理有益效果的个人清洁组合物是已知的。这些组合物中有许多是含水体系,其包含乳化调理油或其他与发泡表面活性剂相组合的类似物质。虽然这些产品可提供调理和清洁有益效果,但是通常难以配制出一种可在使用期间在皮肤上沉积足量的皮肤调理剂的产品。为防止皮肤调理剂被清洁表面活性剂所乳化,要将大量的皮肤调理剂加入到组合物中。然而,这引起了另一个问题,该问题与具有清洁和调理双重功能的这些产品相关。为达到增加沉积目的而提高皮肤调理剂的含量,将负面影响产品的起泡效果和稳定性。
由个人清洁产品提供调理和清洁有益效果,同时保持稳定性的一种尝试是使用双室包装。这些包装包含独立的清洁组合物和调理组合物,并且使这两者在一种流体或两种流体中共分配。从而,独立调理组合物和清洁组合物在长期的储存期间以及恰好使用之前,保持了物理上的独立和稳定,但是分配期间或分配之后则混合在一起,由物理上稳定的系统提供调理和清洁有益效果。虽然与使用常规系统相比,上述双室递送系统可提供改善的调理有益效果,但通常难于达到相容和均匀的性能,这是因为来自这些双室包装的清洁相和调理相之间的分配比不均匀。此外,这些包装系统增加了成品相当大的成本。
因此,仍需要一种个人清洁组合物,其可以同时提供清洁和改善的皮肤调理有益效果。还需要一种包含两相的个人清洁组合物,其中这两相直接接触并可保持长期稳定。
因此,本发明的目的是提供包含清洁相和有益相的条纹状液体个人清洁组合物,其中这两相以直接接触形式包装并同时保持稳定,其中该组合物提供了调理剂在皮肤上改善的沉积效果。
现已发现,可配制包含清洁相和有益相的条纹状液体个人清洁组合物,以在使用中和使用后提供改善的美容效果和皮肤感觉,同时还提供极好的皮肤调理和清洁有益效果,其中清洁相和有益相以直接接触形式包装并同时保持稳定。已发现,上述组合物可使用足够高含量的有益剂配制,而不会影响产品的起泡效果和稳定性。优异的起泡效果可借助于本文所述的泡沫体积方法证明。
也据发现,可以通过清洁相与有益相的密度匹配,以及通过向清洁相和/或有益相中掺入密度调节剂,将条纹状的个人清洁组合物配制成具有改善的稳定性。
发明概述
本发明涉及条纹状的个人清洁组合物,该组合物包含第一条纹和至少一种附加条纹,第一条纹包含清洁相,该清洁相包含表面活性剂、水和任选的常规个人清洁成分;附加条纹包含独立有益相,按重量计,该有益相包含至少约20%具有的Vaughan溶解度参数为约5至约15的疏水物质,其中该有益相所具有的稠度值为约0.1(1)至约1,000Pa·s(10,000泊)。
本发明进一步涉及条纹状液体个人清洁组合物,该组合物包含:
a)包含清洁相的第一条纹,所述清洁相包含按所述清洁相的重量计至少约1%至约50%的表面活性剂,所述表面活性剂选自阴离子表面活性剂、非离子表面活性剂、两性离子表面活性剂、阳离子表面活性剂、皂以及它们的混合物;
其中清洁相是非牛顿剪切致稀的,并且具有的粘度等于或大于约3Pa·s(3,000cps),具有的屈服应力值为至少约0.1Pa;和
b)有益相,该有益相包含按所述有益相的重量计约20%至约100%的疏水物质,该疏水物质选自类脂、烃、脂肪、油类、疏水性植物浸出液、脂肪酸、精油、硅油、以及它们的混合物;
其中该疏水物质所具有Vaughan溶解度参数为约5至约15,此外,其中清洁相和有益相之间的重量比为约1∶9至约99∶1,并且清洁相和有益相以直接接触形式装于同一包装中,并在环境条件下可保持稳定至少约180天;并且其中清洁相和有益相以条纹状存在,其中条纹尺寸为至少约0.1mm宽,至少约1mm长。
其中清洁相和/或有益相包含密度调节剂,以使清洁相的密度同有益相的密度相匹配。
本发明进一步涉及包含清洁相和有益相的条纹状个人清洁组合物,其中至少一相包含着色剂,其中两相装于单一包装中,这样使两相形成图案。
本发明还涉及通过将上述组合物涂敷到皮肤上来清洁和保湿皮肤的方法。在施用期间,这些组合物提供了皮肤有益剂在皮肤上改善的沉积效果。
发明详述
本发明的条纹状个人清洁组合物和方法包括由包含清洁相的第一条纹和至少一种包含独立有益相的附加条纹组成的个人清洁组合物。这些和其他该组合物的基本限定条件和本发明的方法,以及适用于本文的许多任选成分将在下文详细描述。
除非另外指明,本文所用术语“无水的”是指那些按重量计包含低于约10%、更优选低于约5%、甚至更优选低于约3%、甚至更优选0%的水的组合物或物质。
除非另外指明,本文所用术语“环境条件”是指一个(1)大气压、50%相对湿度和25℃的环境条件。
除非另外指明,本文所用术语“稳定的”指的是在环境条件下以直接接触形式可使至少两个“独立的”相保持至少约180天的组合物。“独立的”是指组合物分配之前肉眼观测到基本上不混合的状态。
除非另外指明,本文所用术语“个人清洁组合物”是指本发明的组合物,其中该组合物意指仅包括那些局部施用于皮肤或毛发的组合物,并且具体地讲,排除那些主要涉及其他应用(如硬质表面清洁、织物或衣物清洁、以及类似其他应用)而非主要旨在局部施用于毛发或皮肤的组合物。
本文所用的Vaughan溶解度参数(VSP)是用于定义亲脂物质溶解度的一个参数。Vaughan溶解度参数在各种化学和制剂领域是熟知的,并且典型具有5至25的值。
本文所用术语“稠度”或“k”是类脂粘度的量度,并与剪切指数联合使用以定义物质的粘度,该物质的粘度为剪切力的函数。测量是在35℃进行的,并且单位是泊(等于0.1Pa·s(100cps))。
本文所用术语“剪切指数”或“n”是类脂粘度的量度,并与稠度联合使用以定义物质的粘度,该物质的粘度为剪切力的函数。测量在35℃进行的,单位是无量纲的。
除非另外指明,本文所用短语“基本上不含”指的是组合物包含少于约5%、优选少于约3%、更优选少于约1%、最优选少于约0.1%的规定成分。
本文所用术语“条纹状的”个人清洁组合物是包含形成图案的几种独立相的组合物,所述图案选自条纹、几何纹、大理石纹、以及它们的混合。优选地,条纹尺寸为至少约0.1mm宽,并且至少约1mm长。更优选地,条纹尺寸为至少约0.5mm宽,并且至少约10mm长。甚至更优选地,条纹尺寸为至少约1mm宽,并且至少约20mm长。
除非另外指明,本文使用的所有百分比、份数和比率均按总组合物的重量计。有关所列成分的所有重量均基于活性物质的含量,因此除非另外指明,它们不包括可能包括在市售材料中的溶剂或副产物。
本发明的个人清洁组合物和方法可包括、由或基本上由本文所述的基本成分和限制、以及本文所述的或换句话讲可用于旨在局部应用于毛发或皮肤的个人清洁组合物中的任何附加的或任选的成分、组分或限制组成。
产品形式
本发明的个人清洁组合物为旨在局部应用于皮肤的液体、半液体、霜膏、露剂或凝胶形式的组合物。这些组合物包含清洁相和有益相,其将在下文中被更详细地描述。
为限定本发明的组合物和方法,所设想的所有产品形式均为洗去型制剂,这是指产品可被局部涂敷在皮肤或毛发上,接着随后(即在几分钟内)用水漂洗掉,或换句话讲,用基质或其他合适的去除方法擦拭掉。
本发明的个人清洁组合物优选具有清洁相密度和同其匹配的有益相密度。优选地,匹配的密度为约低于0.15g/cm3,更优选低于约0.1g/cm3,甚至更优选低于0.05g/cm3,甚至更优选低于0.01g/cm3。
清洁相
本发明的个人清洁组合物包含含水的清洁相,该相包含适于涂敷到皮肤或毛发上的表面活性剂。适用于本文的表面活性剂包括适于涂敷到皮肤上的任何已知或其他有效的清洁表面活性剂,并且该表面活性剂还要与组合物含水清洁相中的其他基本成分相容。这些清洁表面活性剂包括阴离子表面活性剂、非离子表面活性剂、阳离子表面活性剂、两性离子或两性表面活性剂,或它们的组合。
个人护理组合物的含水清洁相所包含的清洁表面活性剂的浓度,按所述含水清洁相的重量计,优选为约1%至约50%,更优选为约4%至约30%,甚至更优选为约5%至约25%。该清洁相优选的pH值范围为约5至约8。
适用于清洁相中的阴离子表面活性剂包括烷基硫酸盐和烷基醚硫酸盐。这些物质分别具有化学式ROSO3M和RO(C2H4O)xSO3M,其中R是含有约8个至约24个碳原子的烷基或链烯基,x为1至10,M是水溶性阳离子,例如铵离子、钠离子、钾离子或三乙醇胺离子。该烷基醚硫酸盐典型地可以作为环氧乙烷和含有约8个至约24个碳原子的一元醇的缩合产物制备。优选地,在烷基硫酸盐和烷基醚硫酸盐中R含有约10个至约18个碳原子/约10个至约18个碳原子。该醇可衍生自脂肪,例如椰子油或牛油,或是合成的。本文优选月桂醇和衍生自椰子油的直链醇。上述醇可与约1至约10、优选约3至约5、且更优选约3摩尔比的环氧乙烷进行反应,并且将所得分子种类的混合物(例如,每摩尔醇具有平均3摩尔环氧乙烷)经硫酸处理并中和。
可用于清洁相中的烷基醚硫酸盐的具体实施例是椰油烷基三甘醇醚的硫酸钠盐和硫酸铵盐、牛油烷基三甘醇醚的硫酸钠盐和硫酸铵盐、以及牛油烷基六氧化乙烯的硫酸钠盐和硫酸铵盐。高度优选的烷基醚硫酸盐是包含单个化合物的混合物的那些,所述的混合物具有的平均烷基链长度为约10个至约16个碳原子,平均乙氧基化度为约1至约4摩尔的环氧乙烷。
其他合适的阴离子表面活性剂包括有机硫酸反应产物的水溶性盐,其通式为[R1-SO3-M],其中R1选自含有约8个至约24个、优选约10个至18个碳原子的直链或支链的饱和脂族烃基;并且M是阳离子。合适的实施例是甲烷系列烃的有机硫酸反应产物的盐,包括含有约8个至约24个碳原子、优选约10个至约18个碳原子的异、新、外和正链烷烃以及磺化剂,例如,根据已知磺化方法(包括漂白和水解)所得的SO3、H2SO4和发烟硫酸。优选的是磺化的C10-18正链烷烃的碱金属盐和铵盐。
其他合适的表面活性剂描述于M.C.Publishing Co.出版的McCutcheon的“Emulsifiers and Detergents”(1989年年刊)和美国专利3,929,678。
可用于清洁相中的优选的阴离子表面活性剂包括:十二烷基硫酸铵、聚氧乙烯月桂基醚硫酸铵、月桂基硫酸三乙基胺、聚氧乙烯月桂基醚硫酸三乙基胺、月桂基硫酸三乙醇胺、聚氧乙烯月桂基醚硫酸三乙醇胺、月桂基硫酸单乙醇胺、聚氧乙烯月桂基醚硫酸单乙醇胺、月桂基硫酸二乙醇胺、聚氧乙烯月桂基醚硫酸二乙醇胺、月桂酸甘油单酯硫酸钠、月桂基硫酸钠、聚氧乙烯月桂基醚硫酸钠、聚氧乙烯月桂基醚硫酸钾、月桂基肌氨酸钠、月桂酰肌氨酸钠、肌氨酸月桂酯、椰油基肌氨酸、椰油基硫酸铵、十二烷酰基硫酸铵、椰油基硫酸钠、月桂酰硫酸钠、椰油基硫酸钾、月桂基硫酸钾、椰油基硫酸一乙醇胺、十三烷基苯磺酸钠、十二烷基苯磺酸钠、以及它们的组合。
例如,在一些实施方案中,优选具有支链烷基链的阴离子表面活性剂,如聚氧乙烯十三烷基醚硫酸钠。可在一些实施方案中,使用阴离子表面活性剂的混合物。
可将选自两性表面活性剂、两性离子表面活性剂、阳离子表面活性剂和/或非离子表面活性剂类别中的附加表面活性剂掺入到清洁相组合物中。
适用于清洁相中的两性表面活性剂包括被统称为脂族仲胺和叔胺衍生物的那些,其中脂族基团可以是直链或支链的,并且其中,一个脂肪族取代基包含约8个至约18个碳原子,且一个脂肪族取代基包含阴离子水溶性基团,如羧基、磺酸根、硫酸根、磷酸根或膦酸根。属于该定义的化合物的实施例是:3-十二烷基氨基丙酸钠,3-十二烷基氨基丙烷磺酸钠、月桂基肌氨酸钠、N-烷基牛磺酸(如依照美国专利2,658,072中所提出的,由十二烷基胺与羟乙基磺酸钠进行反应而制得的那些)、N-高级烷基天冬氨酸(如依照美国专利2,438,091中所提出的方法制得的那些)、以及在美国专利2,528,378中所描述的那些产物。
适用于清洁相中的两性离子表面活性剂包括被统称为脂族季铵、鏻鎓和锍化合物衍生物的那些,其中脂族基团可是直链或支链的,并且其中一个脂族取代基包含约8个至约18个碳原子,且一个脂族取代基包含阴离子基团,如羧基、磺酸根、硫酸根、磷酸根或膦酸根。上述合适的两性离子表面活性剂如下式所示:
其中R2包含烷基、链烯基或者羟烷基,该羟烷基含有约8个至约18个碳原子、0至约10个环氧乙烷基团和0至约1个甘油基;Y选自氮、磷和硫原子;R3是包含约1个至约3个碳原子的烷基或单羟基烷基;当Y是硫原子时,X为1,而当Y是氮原子或磷原子时,X为2;R4是含有约1个至约4个碳原子的亚烷基或羟亚烷基,并且Z是选自羧酸根、磺酸根、硫酸根、膦酸根和磷酸根的基团。
适用于清洁相的其他两性离子表面活性剂包括含高级烷基甜菜碱在内的甜菜碱,如椰油二甲基羧甲基甜菜碱、椰油酰氨基丙基甜菜碱、椰油基甜菜碱、月桂酰氨基丙基甜菜碱、油烯基甜菜碱、月桂二甲基羧甲基甜菜碱、月桂二甲基-α-羧乙基甜菜碱、鲸蜡基二甲基羧甲基甜菜碱、月桂双-(2-羟乙基)羧甲基甜菜碱、硬脂双-(2-羟丙基)羧甲基甜菜碱、油烯基二甲基-γ-羧丙基甜菜碱和月桂双-(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、硬脂二甲基磺基丙基甜菜碱、月桂基二甲基磺乙基甜菜碱、月桂双-(2-羟基乙基)磺基丙基甜菜碱及其类似物;氨基甜菜碱和氨基磺基甜菜碱(其中RCONH(CH2)3基团与甜菜碱中的氮原子相连)也适用于本发明。
还可使用两性基乙酸盐和两性基二乙酸盐。
两性基乙酸盐
两性基二乙酸盐
两性基乙酸盐和两性基二乙酸盐与上式相符,其中R是含有8个至18个碳原子的脂族基团。M是阳离子,如钠离子、钾离子、铵离子或取代的铵离子。在一些实施方案中,优选N-月桂酰胺基乙基-N-羟乙基乙酸钠、N-椰油酰胺基乙基-N-羟乙基乙酸钠、N-月桂酰胺基乙基-N-羟乙基二乙酸钠和N-椰油酰胺基乙基-N-羟乙基二乙酸钠。
在清洁相中,还可使用阳离子表面活性剂,但通常较不优选,并且按所述组合物的重量计,优选含量小于约5%。
适用于含水清洁相的非离子表面活性剂包括烯化氧基团(本身亲水)与有机疏水化合物缩合的产物,该有机疏水化合物本身可为脂族化合物或烷基芳族化合物。
稳定性增强剂
密度调节剂
为进一步在压力条件下(例如高温和高振动)改善稳定性,优选的是调整各独立相的密度,使得它们基本上相等。为达到这个目的,将低密度的微球体加入条纹状组合物的清洁相。用于减小清洁相总体密度的低密度微球体是颗粒,它们具有的密度低于0.7g/cm3,优选低于0.2g/cm3,更优选低于0.1g/cm3,最优选低于0.05g/cm3。低密度微球体通常具有的直径小于200μm,优选小于100μm,最优选小于40μm。优选地,清洁相与有益相之间的密度差小于0.15g/cm3,更优选地,密度差小于0.10g/cm3,甚至更优选地,密度差小于0.05g/cm3,最优选地,密度差小于0.01g/cm3。
微球体由任何适当的无机物质或有机物质制成,能在皮肤上使用,即无刺激性并且无毒。优选地,微球体不会负面影响产物的起泡效果。
由热塑性材料制成的膨胀微球体是已知的,并且可以依照,例如专利和专利申请EP-56219、EP-348372、EP-486080、EP-320473、EP-112807和美国专利3,615,972中所描述的方法获得。
这些微球体可以由任何无毒和无刺激的热塑性材料制成。例如,可以使用丙烯腈的或1,1-二氯乙烯的聚合物或共聚物。可能使用,例如一种共聚物,其按重量计包含0至60%衍生自1,1-二氯乙烯的单元,20至90%衍生自丙烯腈的单元和0至50%衍生自丙烯酸或苯乙烯单体的单元,百分比(按重量计)的总和等于100。丙烯酸的单体是,例如丙烯酸甲酯或丙烯酸乙酯或甲基丙烯酸甲酯或甲基丙烯酸乙酯。苯乙烯单体是,例如α-甲基苯乙烯或苯乙烯。这些微球体可以处于干燥或水合状态。
膨胀中空微球体的内部空腔包含气体,该气体可以是烃例如异丁烷或异戊烷,或可供选择地是空气。在能够使用的中空微球体中,可以特别提到的是由Akzo Nobel Company以商标名EXPANCEL(热塑性的可膨胀微球体)市售的那些,特别是DE(干态)或WE (水合态)等级的那些:其实施例包括:Expancel091 DE 40 d30;Expancel091 DE 80 d30;Expancel051 DE 40 d60;Expancel091 WE 40 d24;Expancel053 DE 40 d20。
衍生自无机物质的代表性微球体包括,例如“Qcel中空微球体”和“EXTENDOSPHERESTM陶瓷中空球体”,两者均购自PQCorporation。实施例为:Qcel300;Qcel6019;Qcel6042S。
正如可以将低密度微球体加入本发明的清洁相以改善振动稳定性那样,也可以将高密度物质加入有益相以提高它的密度,这对于稳定性也有相同的影响。
用于清洁相的任选成分
清洁相中其他合适的任选成分是一种或多种湿润剂和溶剂。可使用各种湿润剂和溶剂,并且它们的含量为约0.1%至约50%,优选约0.5%至约35%,并且更优选约2%至约20%,它们是非挥发性有机物,具有的溶解度达到每10份水中可至少溶解5份。优选的水溶性有机物选自:具有
R1-O(CH2-CR2HO)nH
结构的多元醇(其中,R1=H、C1-C4烷基;R2=H、CH3,并且n=1至200;C2-C10的链烷二醇、胍、乙醇酸以及甘醇酸盐(如铵盐和四烷基铵盐)、乳酸及乳酸盐(如铵盐和四烷基铵盐)、多羟基醇(如山梨醇、甘油、己三醇、丙二醇、己二醇等)、聚乙二醇、糖和淀粉、糖和淀粉的衍生物(如烷氧基化的葡萄糖)、泛醇(包括D-、L-和D,L-构型)、吡咯烷酮羧酸、透明质酸、乳酰胺单乙醇胺、乙酰胺单乙醇胺、尿素、以及通式为(HOCH2CH2)xNHy的乙醇胺(其中x=1至3;y=0至2,并且x+y=3)、以及它们的混合物。最优选的多元醇选自甘油、聚氧丙烯(1)甘油和聚氧丙烯(3)甘油、山梨醇、丁二醇、丙二醇、蔗糖、尿素和三乙醇胺。
非离子性聚乙烯/聚丙二醇聚合物可优选用作皮肤调理剂。可用于本文的尤其优选的聚合物是:PEG-2M,其中x等于2,并且n的平均值为约2,000(PEG2-M还被称为Polyox WSRN-10(得自Union Carbide)和PEG-2,000);PEG-5M,其中x等于2,并且n的平均值为约5,000(PEG5-M还被称为Polyox WSR35和PolyoxWSRN-80(两者均得自Union Carbide)以及PEG-5,000和Polyethylene Glycol 200,000);PEG-7M,其中x等于2,并且n的平均值为约7,000(PEG 7-M还被称为Polyox WSRN-750,得自Union Carbide);PEG-9M,其中x等于2,并且n的平均值为约9,000(PEG 9-M还被称为Polyox WSRN-3333,得自UnionCarbide);PEG-14M,其中x等于2,并且n的平均值为约14,000(PEG 14-M还被称为Polyox WSR-205和Polyox WSRN-3000,两者均得自Union Carbide);以及PEG-90M,其中x等于2,并且n的平均值为约90,000(PEG-90M还被称为Polyox WSR-301,得自Union Carbide)。
这些任选成分的其他非限制性实施例包括:维生素及其衍生物(如抗坏血酸、维生素E、生育酚乙酸酯等)、防晒剂、增稠剂(如多元醇烷氧基酯,以商品名Crothix得自Croda)、用于保持清洁组合物抗微生物完整性的防腐剂、抗痤疮药剂(间苯二酚、水杨酸等)、抗氧化剂、皮肤抚慰和康复剂(如芦荟提取物、尿囊素等)、螯合剂和多价螯合剂、以及适于美学目的试剂(如芳香剂、精油、皮肤增感剂、颜料、珠光剂(如云母和二氧化钛)、色淀、着色剂,等等(如丁香油、薄荷醇、樟脑、桉树油和丁子香酚))。
合适的羧基共聚物、乳化剂、润肤剂以及其他附加成分的非限制性实施例,公开于1991年4月30日公布的授予Ciotti等人的美国专利5,011,681。
不受理论的束缚,据信在一些实施例中,本发明的组合物可具有层状结构。本发明的组合物具有易流动的非牛顿剪切稀化性能,和悬浮组分的能力(这已知为层状相表面活性剂组合物的性质)。
在本发明另一个优选的实施方案中,用于清洁相的表面活性剂组合物显示具有非牛顿剪切致稀行为(本文称为易流动组合物)。这些表面活性剂组合物包含水、至少一种阴离子表面活性剂、电解质和至少一种链烷醇酰胺。据发现,通过使用显示具有非牛顿剪切致稀释行为的清洁相,可提高所得个人清洁组合物的稳定性。
链烷醇酰胺(若存在的话)具有的通式结构为:
其中R是C8至C24、或优选(在某些实施方案中)C8至C22、或优选(在其他实施方案中)C8至C18的饱和或不饱和的、直链或支链的脂族基团,R1和R2为相同或不同的C2-C4的直链或支链的脂族基团,x=0至10;y=1至10,并且其中x和y之和小于或等于10。
组合物中链烷醇酰胺的量按重量计典型地为约0.1%至约10%,并且在某些实施方案中按所述清洁相的重量计优选约2%至约5%。一些优选的链烷醇酰胺包括Cocamide MEA(椰油基单乙醇酰胺)和Cocamide MIPA(椰油基单异丙醇酰胺)。
可将电解质(如果使用的话)本身加入到组合物中,或可通过包括于一种原料中的反离子就地形成电解质。优选地,电解质包括阴离子(包括磷酸根、氯离子、硫酸根或柠檬酸根)和阳离子(包括钠离子、铵离子、钾离子、镁离子或它们的混合物)。一些优选的电解质是氯化钠或氯化铵,或硫酸钠或硫酸铵。
电解质(如果存在的话)应以易于形成易流动组合物的含量存在。通常,按所述清洁相的重量计,该量为约0.1%至约15%,优选约1%至约6%,但可以变化(如果需要的话)。
通常,表面活性剂作为水或其他溶剂的的溶液出售,这些溶剂将它们稀释为小于100%的活性表面活性剂,因此“活性表面活性剂”指的是,从商业表面活性剂制剂中将表面活性剂递送到易流动组合物中的实际量。
典型地,所有表面活性剂(如将阴离子表面活性剂、非离子表面活性剂、两性和/或两性离子表面活性剂、以及阳离子表面活性剂合在一起)的总量为约8%至约30%的活性表面活性剂,并且优选约10%至约20%的活性表面活性剂。在一些实施方案中,优选至少一种表面活性剂具有脂族链,该脂族链可具有支链或不饱和度,或它们的组合。
清洁相组合物的粘度
可使用Wells-Brookfield Cone/Plate Model DV-II+来测定本文所述个人清洁组合物的粘度。在25℃下用2.4cm3°锥体测量系统进行测定,其中在分别位于锥体和平板的两根小针之间,有0.013mm的间隙。通过在锥体和平板之间注射0.5mL要分析的样品,并且以设定的转速0.105rad/s(1rpm)旋转锥体进行测量。锥体的转动阻力产生了扭矩,其与液体样品的剪切应力成比例。根据锥体几何常数、转速和与应力相关的扭矩,用粘度计读出扭矩的数值,并计算成绝对厘泊单位(cps)。
优选地,清洁相具有的粘度大于3Pa·s(3,000cps)。更优选地,粘度大于5Pa·s(5,000cps)。甚至更优选地,粘度大于10Pa·s(10,000cps)。最优选地,粘度大于20Pa·s(20,000cps)。
清洁相组合物的屈服点
可使用Carrimed CSL 100可控应力流变仪来测定本文所述个人清洁组合物的屈服点。对于本文的目的,屈服点为在个人清洁组合物上产生1%应变所需的应力值。在25℃下用设有51微米间隙的4cm2°锥体测量系统进行测定。并且随着时间的增加由程序控制施加剪切应力(典型地约0.006Pa(0.06达因/平方厘米)至约50Pa(500达因/平方厘米))进行测定。该应力值造成了样品的变形。可作出剪切应力对应变的曲线。从该曲线上,可计算出个人清洁组合物的屈服点。
优选地,清洁相具有的屈服点大于0.1Pa·s。更优选地,屈服点大于1Pa·s。甚至更优选地,屈服点大于10Pa·s。最优选地,屈服点大于30Pa·s。
有益相
本发明的独立有益相优选是无水的。有益相包含为约20%至约100%、优选至少约35%、最优选至少约50%的疏水性皮肤有益剂。适用于本发明的有益剂所具有的Vaughan溶解度参数为约5至约15。该有益剂优选选自如下文所述的指定流变性质的那些,包括指定的稠度(k)和剪切指数(n)。这些优选的流变性质尤其有助于向个人清洁组合物提供有益剂在皮肤上改善的沉积效果。
Vaughan溶解度参数值(VSP)
用于组合物有益相的疏水性皮肤有益剂所具有的Vaughan溶解度参数(VSP)为约5至约15,优选约6至小于10,更优选约6至约9。这些溶解度参数在制剂领域是熟知的,并且由Vaughan定义于“Cosmetics and Toiletries”第103卷,第47至69页中(1988年10月)。
具有VSP值为约5至约15的疏水性皮肤有益剂的非限制性实施例包括下列:
VAUGHAN溶解度参数*
环状聚甲基硅氧烷 5.92
角鲨烯 6.03
凡士林 7.33
棕榈酸异丙基酯 7.78
肉豆蔻酸异丙酯 8.02
蓖麻油 8.90
胆固醇 9.55
*报道于“Solubility,Effects in Product,Package,Penetration and Preservation”,C.D.Vaughan,Cosmeticsand Toiletries,第103卷,1988年10月。
B)
流变学
用于组合物有益相中的疏水性皮肤有益剂具有由稠度(k)和剪切指数(n)所规定出的优选的流变学特征。优选的稠度范围是0.1-1,000Pa·s(1-10,000泊)(1/seC)n-1,优选1-200Pa·s(10-2000泊)(1/sec)n-1,并且更优选5-100Pa·s(50-1000泊)(1/sec)n-1。剪切指数的范围是0.1-0.8,优选0.1-0.5,并且更优选0.20-0.4。
疏水性皮肤有益剂可用上述范围所规定的稠度(k)和剪切指数(n)值来表征,其中选择这些规定的范围,是为了在将个人清洁组合物施用于毛发或皮肤过程中或之后,提供增强的沉积效果和降低的粘稠度。
剪切指数(n)和稠度(k)值是记录材料的粘度特征的熟知并公认的工业标准,所述材料的粘度为所施加剪切速率的函数。
任何物质的粘度(μ)可用关系式或方程来表示
[μ=σ/γ′]
其中,σ为剪切应力,并且γ′为剪切速率,因此任何物质的粘度可通过使用剪切速率和测量所得的剪切应力来测量,反之亦然。
可使用Carrimed CSL 100可控应力流变仪来测定本文疏水性皮肤有益剂的剪切指数(n)和稠度(k)。在35℃使用典型设有51微米间隙的4cm2°锥体测量系统进行测定,并且随着时间的增加由程序控制施加剪切应力(典型地为约0.006Pa(0.06达因/sq.cm)至约500Pa(5,000达因/sq.cm))进行测定。如果这种应力导致样品的变形,即测量的几何应变为至少10至4rad/sec,那么此应变速率被记作剪切速率。使用这些数据,作出疏水性皮肤有益剂物质的粘度(μ)对剪切速率(γ′)的流变曲线。这条流变曲线可作为模型,以给出描述在具体剪切应力和剪切速率范围内的物质特性的数学表达式。这些结果与下列普遍公认的幂律模型相符:(参见例如:Coulson和Richardson的“Chemical Engineering”(Pergamon,1982年)或Bird、Stewart和Lightfoot的“TransportPhenomena”(Wiley,1960年)):
[μ=k(γ′)n-1]
利用Carrimed CSL 100可控应力流变仪在35℃时使用典型设有51微米间隙的4cm2°锥体测量系统进行振动测试。35℃下,振动测试分2步进行。第一步是在频率扫描的预期起始和终止频率进行应力振幅扫描。这些测试可以确定测试条件在预期的频率范围内是否处于待测材料的线性粘弹性区内。线性粘弹性区是应力和应变呈线性关系的区域。第二步是在线性粘弹性区内某个应力值下进行频率扫描。频率扫描可以测量待测材料的粘弹性特性。在可控应力流变仪上的振动测试是这样做的:以振动方式施加应力,然后测量待测材料的所得振动应变响应和施加应力波形与所得应变波形的相位偏移。所得的复数模量以材料的弹性(G′)和粘性(G″)分量的组合来表示。弹性模量G′是材料贮存可恢复能量能力的量度。这种能量贮存可以是复杂的聚合物、结构网状物或这些材料的组合在变形后恢复贮存能量能力的结果。粘性或损耗模量G″是不可恢复能量的量度,能量是由于粘性流动而损耗的。
适于用于本文的疏水性皮肤有益剂可包括多种烃、油和蜡、硅氧烷、脂肪酸衍生物、胆固醇、胆固醇衍生物、甘油二酯、甘油三酯、植物油、植物油衍生物、乙酸甘油酯、烷基酯、链烯基酯、羊毛脂及其衍生物、蜡酯、蜂蜡衍生物、甾醇和磷脂、以及它们的组合。
适用于本文的烃油和蜡的非限制性实施例包括凡士林、矿物油、微晶蜡、聚烯烃、石蜡、野樱素、地蜡、聚乙烯、全氢化角鲨烯、以及它们的组合。
适于用作本文疏水性皮肤有益剂的硅油的非限制性实施例包括:聚二甲基硅氧烷共聚多元醇、二甲基聚硅氧烷、二乙基聚硅氧烷、混合的C1-C30烷基聚硅氧烷、苯基聚二甲基硅氧烷、聚二甲基硅氧烷醇、以及它们的组合。优选的是非挥发性硅氧烷,其选自聚二甲基硅氧烷、聚二甲基硅氧烷醇、混合的C1-C30烷基聚硅氧烷以及它们的组合。可用于本文的硅氧烷油的非限制性实施例描述于美国专利5,011,681(Ciotti等人)中。
适于用作本文疏水性皮肤有益剂的甘油二酯和甘油三酯的非限制性实施例包括:蓖麻油、大豆油、衍生大豆油(如马来酸大豆油)、红花油、棉籽油、玉米油、胡桃油、花生油、橄榄油、鳕鱼肝油、杏仁油、鳄梨油、棕榈油和芝麻油、植物油、向日葵籽油、以及植物油衍生物、椰子油及衍生椰子油、棉籽油及衍生棉籽油、霍霍巴油、椰子油、以及它们的组合。
适于用作本文疏水性皮肤有益剂的乙酸甘油酯的非限制性实施例包括乙酰化的单酸甘油酯。
适于用作本文疏水性皮肤有益剂的烷基酯的非限制性实施例包括:脂肪酸异丙酯和长链(即C10-C24)脂肪酸的长链酯(如蓖麻油酸鲸蜡酯),其非限制性实施例包括:棕榈酸异丙酯、肉豆蔻酸异丙酯、蓖麻油酸鲸蜡酯和蓖麻油酸十八烷基酯。其他实施例为:月桂酸己酯、月桂酸异己酯、肉豆蔻酸十四烷基酯、棕榈酸异己酯、油酸癸酯、油酸异癸酯、硬脂酸十六烷酯、硬脂酸癸酯、异硬脂酸异丙酯、己二酸二异丙酯、己二酸二异己酯、己二酸二己基癸基酯、癸二酸二异丙酯、酰基异壬酸酯、乳酸月桂酯、乳酸十四烷酯、乳酸鲸蜡酯、以及它们的组合。
适于用作本文疏水性皮肤有益剂的链烯基酯的非限制性实施例包括:肉豆蔻酸油烯酯、硬脂酸油烯酯、油酸油烯酯、以及它们的组合。
适于用作本文疏水性皮肤有益剂的羊毛脂和毛脂衍生物的非限制性实施例包括:羊毛脂、羊毛脂油、羊毛脂蜡、羊毛脂醇、羊毛脂脂肪酸、羊毛脂酸异丙酯、乙酰化羊毛脂、乙酰化羊毛脂醇、亚油酸羊毛脂醇酯、蓖麻油酸羊毛脂醇酯、以及它们的组合。
其它合适的疏水性皮肤有益剂还包括牛奶甘油三酯(如羟基化牛奶甘油酯)和多元醇脂肪酸聚酯。
其它合适的疏水性皮肤有益剂还包括蜡酯,其非限制性实施例包括蜂蜡和蜂蜡衍生物、鲸蜡、肉豆蔻酸十四烷基酯、硬脂酸十八烷基酯、以及它们的组合。有用的还有植物蜡如巴西棕榈蜡和小烛树蜡;甾醇如胆固醇、脂肪酸胆固醇酯;磷脂如卵磷脂和衍生物、鞘脂类、神经酰胺、糖鞘脂;以及它们的组合。
组合物的有益相优选包含一种或多种疏水性皮肤有益剂,其中按重量计,至少20%的疏水性皮肤有益剂选自凡士林、矿物油、向日葵籽油、微晶蜡、石蜡、地蜡、聚乙烯、聚丁烯、聚癸烯和全氢化角鲨烯聚二甲基硅氧烷、环状聚甲基硅氧烷、烷基硅氧烷、聚甲基硅氧烷和甲基苯基聚硅氧烷、羊毛脂、羊毛脂油、羊毛脂蜡、羊毛脂醇、羊毛脂脂肪酸、羊毛脂酸异丙酯、乙酰化羊毛脂、乙酰化羊毛脂醇、亚油酸羊毛脂醇酯、蓖麻油酸羊毛脂醇酯、蓖麻油、大豆油、马来酸大豆油、红花油、棉籽油、玉米油、胡桃油、花生油、橄榄油、鳕鱼肝油、杏仁油、鳄梨油、棕榈油和芝麻油、以及它们的组合。更优选地,按重量计,至少约50%的亲脂性皮肤调理剂选自凡士林、矿物油、石蜡、聚乙烯、聚丁烯、聚癸烯、聚二甲基硅氧烷、烷基硅氧烷、环状聚甲基硅氧烷、羊毛脂、羊毛脂油、羊毛脂蜡。剩余部分的亲脂性皮肤调理剂优选选自:棕榈酸异丙酯、蓖麻油酸鲸蜡酯、异壬酸辛酯、棕榈酸辛酯、硬脂酸异十六烷基酯、羟基化牛奶甘油酯、以及它们的组合。
稳定性增强剂
结构剂
条纹状个人清洁组合物的有益相可包含结构剂,其改善了组合物的高温稳定性。可适用于本发明的优选结构剂包括那些不与含水清洁相混溶的而且可以采取蜡、疏水硅胶土、疏水粘土、聚合物或它们的混合物形式的结构剂。在本发明的一个实施方案中,结构剂包含结晶的、含多羟基的稳定剂。三(羟基硬脂酸)甘油酯是最优选的。三(羟基硬脂酸)甘油酯可以商品名Thixcin R购自Rheox,并且可以商品名Flowtone购自Southern Clay Products。
另外,结构剂可以包含疏水改性的分散的无定形二氧化硅。本发明所用趸术语“分散的无定形二询硅”指微小的、细分的非晶型二氧化硅,其附聚物粒径小于约100微米。
热解法二氧化硅,是通过在氢氧火焰中气相水解四氯化硅产生的。据信燃烧过程中产生了二氧化硅,其冷凝后形成了颗粒。
该颗粒碰撞、附着并烧结在一起。通过该方法得到的是三维支链聚集体。一旦该聚集体冷至低于二氧化硅的熔点(约1710℃),进一步的碰撞会导致链的进一步机械缠结而形成附聚物。沉淀的二氧化硅和硅凝胶通常在水相制成。参见Cabot Technical DataPamphlet TD-100,标题为“CAB-O-SIL Untreated Fumed SilicaProperties and Functions”,1993年10月,和CabotTechnical Data Pamphlet TD-104标题为“CAB-O-SIL FumedSilica in Cosmetic and Personal Care Products”,1992年3月。
热解法二氧化硅优选具有平均附聚物粒径范围为约0.1微米至约100微米,更优选约1微米至约50微米,并且还更优选约10微米至约30微米。该附聚物由平均粒径从约0.01微米至约15微米的聚集体组成,优选约0.05微米至约10微米,更优选约0.1微米至约5微米,并且还更优选约0.2微米至约0.3微米。该二氧化硅具有的表面积优选大于50sq.m/g,更优选大于约130sq.m/g,并且还更优选大于约180sq.m./g。
通过加入非极性部分到二氧化硅表面对热解法二氧化硅进行疏水改性。用于本发明的疏水改性的热解法二氧化硅的实施例包括,但不限于,二甲基甲硅烷化二氧化硅,其中热解法二氧化硅的表面被二甲基甲硅烷基改性,可以以商品名Aerosil R972和Aerosil R974购得,两者都购自Degussa;和以商品名CAB-O-SIL TS-610和CAB-O-SIL TS-720购得,两者都购自Cabot;硅烷化二氧化硅,其中热解法二氧化硅的表面被三甲基甲硅氧基修饰,可以以商品名Aerosil R812和Sipernat D17购得,两者都购自Degussa-,以及以商品名CAB SIL TS-530购自Cabot。
此外,结构剂可以包含疏水改性的分散的绿土粘土,该粘土选自膨润土、锂蒙脱石、以及它们的混合物。膨润土是一种胶状的硫酸铝粘土。参见Merck Index,Eleventh Edition,1989,第1062条,第164页。锂蒙脱石是一种含有钠、镁、锂、硅、氧、氢和氟的粘土。参见Merck Index,Eleventh Edition,1989,第4538条,第729页。
疏水改性的分散的绿土粘土叫做有机粘土,是由季铵化合物与绿土粘土反应形成有机粘土络合物而制备的。本发明所用有机粘土的非限定实施例包括二氢化牛油苄基季铵锂蒙脱石(以商品名BentoneSD-3购自Rheox),季铵-18锂蒙脱石(以商品名Bentone购得),和M-P-A14、Bentone Gel DOA、Bentone Gel ECO 5、Bentone Gel EUG、Bentone Gel IPP、Bentone Gel ISD、BentoneGel MIO、Bentone Gel MIO-A40、Bentone Gel SS-71、BentoneGel 10ST、Bentone Gel VS-5、Bentone Gel VS-8、Bentone GelVS-38、Bentone Gel VS-5PC与Bentone Gel YVS的混合物(均购自Rheox);季铵-18膨润土(以商品名Bentone 34购自Rheox)和Claytone 40与Claytone SO(购自Southern Clay);季铵-18/烷基苄基二甲基铵膨润土(以Claytone HT购自SouthernClay);硬脂基二甲基苄基铵膨润土(以商品名Claytone AF购自Southern Clay),Toxogel LG和Tixogel VZ(购自UnitedCatalysts)和Viscogel B7(购自Bentec);硬脂基二甲基苄基铵锂蒙脱石(以Bentone 27购自Rheox)和Bentone Gel CAO、Bentone Gel IPM、Bentone Gel LOI、Bentone Gel M-20、Bentone Gel RSS、Bentone Gel SIL以及Bentone Gel TN的混合物(均购自Rheox)。
结构剂也可包含使用金属皂、均聚物、离子同聚物和共聚物、以及嵌段共聚物。可用于本发明的某些普通胶凝剂包括锂、钙、钠、铝、锌和钡的脂肪酸皂。也可使用许多同聚物和共聚物,它们包括无规乙烯-丙烯。具有下垂盐基团的均聚物或共聚物也在非极性基质中形成富离子聚集体。然而,这些组合物的离子交互作用和所得聚合物性能取决于聚合物主链的类型、离子部分的类型以及阳离子的类型。磺化的聚苯乙烯例示了这种体系。用于本发明的嵌段体系包括苯乙烯-异戊二烯、苯乙烯-丁二烯和苯乙烯环氧乙烷共聚物。
市售的热塑性橡胶类聚合物在有益相中作为结构剂是尤其有用的。它们以商标Kraton由Shell Chemical Company出售。Kraton橡胶聚合物被描述为弹性体,它们具有与众不同的高强度和低粘度组合,并且具有独特的直链二嵌段、三嵌段和放射聚合物的分子结构。据称Kraton橡胶的每个分子都由苯乙烯单体单元和橡胶单体单元的嵌段片段组成。每个嵌段片段可由100个或更多个单体单元组成。最普通的结构是直链的ABA嵌段类、苯乙烯-丁二烯-苯乙烯(SBS)和苯乙烯-异戊二烯-苯乙烯(SIS)、KratonD橡胶系列。该系列的第二代聚合物是KratonG系列,它们是苯乙烯-乙烯-丁烯-苯乙烯类(S-EB-S)聚合物。二嵌段聚合物包括ABA类和SB、苯乙烯-乙烯丙烯(S-EP)和(S-EB)。Kraton橡胶分子的ABA结构包含聚苯乙烯末端嵌段和弹性体中间嵌段。Kroton的实施例是购自ShellCompany的G1701、G1702、D1107、D1111、D1320。二嵌段和三嵌段共聚物的混合物用作本发明的有益相结构剂是优选的。使用二嵌段和三嵌段共聚物混合物的胶凝烃油由Penreco以商品名Versagel市售。例如,Versagel M是胶凝的矿物油基、Versagel ME是胶凝的氢化聚异丁烯基、Versagel MP是胶凝的棕榈酸异丙酯基、Versagel MC是胶凝的异十六烷基、以及Versagel MD是胶凝的异十二烷基。
当存在时,有益相典型包含结构剂的量基于有益相的重量计,为约0.01%至约30%,更优选为约0.1%至约20%,并且更优选还为约1%至约10%。
条纹状液体个人清洁组合物的独立有益相可任选地包含用于增强这些有益物质在皮肤上递送的下列皮肤有益成分。任选成分的浓度按所述个人清洁组合物的重量计,优选为约0.1%至约10%,更优选约0.2%至约5%,甚至更优选约0.5%至约4%。
合适的任选成分包括但不限于脱屑活性物质、抗痤疮活性物质、抗皱/抗萎缩活性物质、抗氧化剂或自由基清除剂、螯合剂、类黄酮、抗炎剂、抗蜂窝炎剂、局部麻醉剂、晒黑剂、亮肤剂、皮肤抚慰或皮肤愈合活性物质、抗微生物活性物质、防晒活性物质和固体颗粒。
本发明的个人清洁组合物可进一步包含其他任选成分,它们可改进该组合物的物理、化学、美容或美学特性,或者当沉积在皮肤上时充当附加的“活性”组分。组合物还可包含任选的惰性成分。许多上述任选成分已知用于个人护理组合物中,也可用于本文的个人清洁组合物中,前提条件是上述任选物质与本文所述的基本物质相容,或不另外过度地损害产品的性能。
这些任选成分最典型地为那些被认可用于化妆品中的物质和描述于参考书如“CTFA Cosmetic Ingredient Handbook”第二版(TheCosmetic,Toiletries,and Fragrance Association,Inc.1988年,1992年)中的那些物质。这些任选物质可被用于本发明组合物的任何方面,包括如本文所述的活性相或清洁相。
用于本发明组合物清洁相的任选成分可包括任何本文所述的有益相物质,所述有益相物质也要与清洁相中所选成分相容。同样地,用于本发明组合物有益相中的任选成分可包括任何本文所述的清洁相物质,所述清洁相物质也要与有益相中指定的成分相容。
用于组合物任一相(优选有益相)的其它任选成分包括硅氧烷弹性体粉末和流体,以向各种产品提供各种有益效果,包括改善的产品稳定性有益效果、施用美容有益效果、润肤有益效果、调理有益效果,等等。组合物中硅氧烷弹性体的浓度按所述组合物的重量计,优选地为约0.1%至约20%,更优选为约0.5%至约10%。在此上下文中,重量百分比是基于硅氧烷弹性体材料自身的重量,排除了任何在配制过程中典型地伴随此类硅氧烷弹性体的包含硅氧烷的流体。适宜选用于本文的硅氧烷弹性体包括乳化和非乳化硅氧烷弹性体,其非限制性实施例描述于U.S.S.N.09/613,266(转让给The Procter&Gamble Company)中。
密度调节剂
正如可以将低密度微球体加入本发明的清洁相以改善稳定性,也可以将高密度物质加入有益相以提高它的密度,这对于稳定性也有相同的影响。用于增大有益相总体密度的高密度微球体是颗粒,它们具有的密度大于1.1g/cm3,优选大于1.5g/cm3,更优选大于2.0g/cm3,最优选大于2.5g/cm3。高密度颗粒通常具有的直径小于200μm,优选小于100μm,最优选小于40μm。优选地,高密度颗粒选自水不溶性的无机物质、金属、金属氧化物、金属合金、以及它们的混合物。非限制性实施例包括碳酸钙、二氧化硅、粘土、云母、滑石、铁、锌、铜、铅、二氧化钛、氧化锌等等。
使用方法
本发明的条纹状个人清洁组合物优选局部施用于皮肤或毛发的所需区域,其量足以向所施用的区域有效地递送皮肤调理剂,或足以提供有效的皮肤调理有益效果。通过使用清洁粉扑、毛巾、海绵或其它器具,将该组合物直接或间接地施用到皮肤上。在局部施用之前、期间或之后,优选用水稀释该组合物,然后接着漂洗或擦拭所施用的表面,优选用水或水不溶性基质与水的组合,漂洗所施用的表面。
如果个人清洁组合物包含多种颜色的条纹,则需要将这些组合物装于透明的包装盒中,以便消费者能透过包装盒看到组合物的图案。由于本发明组合物的粘度,还需要包括使用说明,指导消费者将包装盒倒置于其盖子上储存,以促进分配。
因此,本发明还涉及通过上述本发明组合物的施用,来清洁皮肤的方法。本发明的方法还涉及通过上述本发明组合物的施用,向所施用的表面提供所需皮肤活性剂有效递送以及提供由本文所述有效递送所得的有益效果的方法。
制备方法
本发明的个人清洁组合物可通过任何已知的或其他有效的技术制备,该技术适于制造和配制所需的条纹状产品形式。将牙膏管填充技术与旋转台设计结合,是尤其优选的。当它们被应用于本发明的具体实施方案时,此类方法的具体非限制性实施例在下文所述的实施例中描述。
泡沫体积
使用量筒和旋转设备,测定条纹状液体个人清洁组合物的泡沫体积。选择一个1,000mL的量筒,该量筒以10mL递增进行标记,并且从其内底至1,000mL的标记处,高度为36.83cm(14.5英寸)(例如,Pyrex No.2982)。向量筒中加入蒸馏水(23℃下100克)。将量筒固定于旋转装置中,该装置将量筒固定在其旋转轴线横切过量筒中心的位置。将1克完整的个人清洁组合物(0.5g清洁相和0.5g有益相)加入到量筒中,并将量筒盖上盖。以3.14rad/s(约20秒10转)的速度旋转量筒,并且在竖直位置停下,完成第一次旋转。将定时器设置为30秒,以使由此产生的泡沫排出。在30秒的上述排出过程之后,通过记录泡沫从底部算起的的高度(mL)(包括泡沫漂浮在其上的排到底部的所有水),测得第一次的泡沫体积最接近10mL的标记。
如果泡沫的上表面不平坦,则将可能看得见的量筒横断面中间最低高度处作为第一次泡沫体积(以mL标值)。如果泡沫非常粗大,以致仅有一个或少数泡沫单体(“气泡”)伸展在整个量筒中,则将至少需要10个泡沫单体才能充满的空间的高度作为第一次泡沫体积,还是从底部算起,以mL标值。任何尺寸上都大于1英寸的泡沫单体,无论它们产生于何处,都将被视为空气,而不是泡沫。如果顶部的泡沫是在其自身的连续层中,则将聚集在量筒的顶部而不排出的泡沫也包括在测量中,使用直尺测定层的厚度,将聚集在那儿的泡沫的ml数,加到所测定的从底部算起的泡沫ml数中。最大泡沫高度为1,000mL(即使总泡沫高度超过量筒上标记的1,000mL)。在第一次旋转结束1分钟后,开始第二次旋转,这次旋转的速度和持续时间与第一次旋转相同。在30秒的排出时间之后,用与第一次相同的方式记录第二次的泡沫体积。完成第三次旋转,以相同的方式测量第三次的泡沫体积,在每次排出和测量之间停留相同的时间。
每次测量之后,将泡沫体积值加在一起,并将三次测量之和确定为总泡沫体积,以mL标值。瞬时泡沫体积(Flash LatherVolume)是仅在第一次旋转后所得的泡沫体积值,以mL标值,即第一次泡沫体积。在该测试中,依照本发明的组合物比常规乳液形式的类似组合物,表现显著更好。
密度(比重)方法
使用金属比重计测定表面活性剂相和有益相组合物的密度(比重)。建议的一种金属比重计可得自Fisher,3-347。也可使用其他相当的比重计。以下过程是测量清洁相和有益相组合物密度(比重)的步骤。
步骤1)清洁:
使用前,金属比重计必须清洁并干燥。完全拆开金属比重计,并且用水好好清洗所有部件。水漂洗后再用醇漂洗。用干燥清洁的气流吹干醇。
步骤2)标准化
在25℃,用蒸馏水充满清洁干燥的比重计。将封盖放在比重计的主体上,并且适当拧紧帽。用薄纸好好擦干比重计的外面,并且称重量,精确至0.001g。依照上文所示说明清洁并且弄干比重计。安装,并且称量干比重计的重量,精确至0.001g。
水的重量=比重计和水的重量-空比重计的重量
步骤3)样品测定
依照上文所示说明清洁并且弄干比重计。让样品平衡至室温。将样品倒入比重计,当心避免向比重计的样品中引入空气。加入过量样品,使得样品稍微高出螺纹的顶端。将封盖放入帽中,并且将帽拧紧在比重计的主体上。任何过量的样品将被推着沿比重计封盖中的孔流出。用薄纸仔细擦掉过量的样品。称填充样品的比重计的重量,精确至0.001g。
样品的重量=比重计和样品的重量-比重计的重量。
步骤4)比重=样品的重量/水的重量
清洁相与有益相之间的密度差小于0.15g/cm3,优选地,密度差小于0.10g/cm3,更优选地,密度差小于0.05g/cm3,最优选地,密度差小于0.01g/cm3。
实施例
下列实施例进一步描述和证明了本发明范围内的实施方案。所给的这些实施例仅仅是说明性的,而不可理解为是对本发明的限制,因为在不背离本发明精神和范围的条件下可以进行多种改变。除非另外指明,所有的示例量均为按总组合物重量计的浓度,即重量百分比。
每个举例说明的组合物提供了由各制备组合物递送的皮肤调理剂或任选成分改善的沉积效果或有效性。
实施例1至3
下列描述于表1中的实施例是清洁相和有益相组合物的非限制性实施例。
表1:清洁相和有益相组合物
实施例1 | 实施例2 | 实施例3 | |
成分 | 重量百分比(%) | 重量百分比(%) | 重量百分比(%) |
I. 清洁相组合物 | |||
聚氧乙烯月桂基醚-3硫酸铵 | 3.0 | 3.0 | 3.0 |
N-月桂酰胺基乙基-N-羟乙基乙酸钠Miranol L-32 Ultra,得自Rhodia) | 16.7 | 16.7 | 16.7 |
十二烷基硫酸铵 | 1.0 | 1.0 | 1.0 |
月桂酸 | 0.9 | 0.9 | 0.9 |
三(羟基硬脂酸)甘油酯(Thi xcin R) | 2.0 | 2.0 | 2.0 |
瓜耳羟丙基三甲基氯化铵(N-Hance 3196,得自Aqualon) | 0.17 | 0.75 | 0.75 |
瓜耳羟丙基三甲基氯化铵(Jaguar C-17,得自Rhodia) | 0.58 | - | - |
聚季铵10(UCARE聚合物JR-30M,得自Amerchol) | 0.45 | - | - |
聚甲基丙烯酰胺丙基三甲基氯化铵(Polycare133,得自Rhodia) | - | 0.24 | - |
聚季铵-39(Merqurt Plus 3300,得自Calgon) | - | 0.81 | - |
PEG 90M(Polyox WSR 301,得自UnionCarbide) | 0.25 | - | - |
PEG-14M(Polyox WSR N-3000H,得自Union | 0.45 | 2.45 | 2.45 |
Carbide) | |||
亚油酰胺丙基仿生磷脂氯化铵聚二甲基硅氧烷(Monasil PLN,得自Uniqema) | - | 1.0 | 4.0 |
甘油 | 1.4 | 4.9 | 4.9 |
氯化钠 | 0.3 | 0.3 | 0.3 |
苯甲酸钠 | 0.25 | 0.25 | 0.25 |
乙二胺四乙酸二钠 | 0.13 | 0.13 | 0.13 |
1,3-二羟甲基-5,5-二甲基乙内酰脲 | 0.37 | 0.37 | 0.37 |
柠檬酸 | 1.6 | 0.95 | 0.95 |
二氧化钛 | 0.5 | 0.5 | 0.5 |
香料 | 0.5 | 0.5 | 0.5 |
Expancel 091 DE 40 d30(得自Expancel,Inc.) | 0.4 | 0.4 | 0.4 |
水 | 适量 | 适量 | 适量 |
II.有益相组合物 | |||
凡士林(SuperWhite Protopet,得自WITC0) | 75 | 99.92 | 90 |
矿物油(Hyd robrite 1000 P0 White M0,得自WITC0) | 24.92 | - | 9.92 |
颜料 | 0.08 | 0.08 | 0.08 |
上述组合物可通过常规制剂和混合技术来制备。通过首先产生下列预混物来制备清洁组合物1:柠檬酸以1∶3比率预混于水中、瓜耳聚合物和Jaguar C-17以及N-Hance 3196以1∶10比率预混于水中、UCARE和J R-30M以约1∶30比率预混于水中、以及Polyox和PEG-90M以及PEG-14M以约1∶2比率预混于甘油中。然后,将下列成分加入到主要混合容器中:十二烷基硫酸铵、聚氧乙烯月桂基醚-3硫酸铵、柠檬酸预混物、Miranol L-32ultra、氯化钠、苯甲酸钠、乙二胺四乙酸二钠、月桂酸、Thixcin R、瓜耳预混物、UCARE预混物、Polyox预混物,和其余的水。搅拌下加热该容器,直至其达到88℃(190)。混合约10分钟。在缓慢搅拌下,用冷水浴冷却批料,直至其达到43℃(110)。加入下列成分:1,3-二羟甲基-5,5-二甲基乙内酰脲、香料、二氧化钛、Expancel。持续搅拌,直至形成均匀溶液。
通过首先产生下列预混物来制备清洁组合物2:柠檬酸以1∶3比率预混于水中、瓜耳聚合物和N-Hance 3196以1∶10比率预混于水中、以及Polyox和PEG-14M以约1∶2比率预混于甘油中。然后,将下列成分加入到主要混合容器中:十二烷基硫酸铵、聚氧乙烯月桂基醚-3硫酸铵、柠檬酸预混物、Miranol L-32ultra、氯化钠、苯甲酸钠、乙二胺四乙酸二钠、月桂酸、Thixcin R、瓜耳预混物、Polyox预混物、Polycare 133、Merquat Plus 3300、MonosilPLN,和其余的水。搅拌下加热该容器,直至其达到88℃(190)。混合约10分钟。在缓慢搅拌下,用冷水浴冷却批料,直至其达到43℃(110)。加入下列成分:1,3-二羟甲基-5,5-二甲基乙内酰脲、香料、二氧化钛、Expancel。持续搅拌,直至形成均匀溶液。
通过首先产生下列预混物来制备清洁组合物3:柠檬酸以1∶3比率预混于水中、瓜耳聚合物和N-Hance 3196以1∶10比率预混于水中、以及Polyox和PEG-14M以约1∶2比率预混于甘油中。然后,将下列成分加入到主要混合容器中:十二烷基硫酸铵、聚氧乙烯月桂基醚-3硫酸铵、柠檬酸预混物、Miranol L-32ultra、氯化钠、苯甲酸钠、乙二胺四乙酸二钠、月桂酸、Thixcin R、瓜耳预混物、Polyox预混物、Monasil PLN,和其余的水。搅拌下加热该容器,直至其达到88℃(190)。混合约10分钟。在缓慢搅拌下,用冷水浴冷却批料,直至其达到43℃(110)。加入下列成分:1,3-二羟甲基-5,5-二甲基乙内酰脲、香料、二氧化钛、Expancel。搅拌,直至形成均匀溶液。
制备有益相,将凡士林加入混合容器。将容器加热至60℃(140)。然后,在搅拌下加入矿物油和美容颜料。缓慢搅拌下,使容器冷却。
清洁相和有益相的密度匹配至0.05g/cm3以内。用常规的牙膏管装填设备将两相包装入单一容器。在填充过程中,样品台旋转底部,以产生条纹状外观。条纹的尺寸为约6mm宽和100mm长。
实施例4至6
描述于表2中的下列实施例是本发明清洁相和有益相组合物的非限制性实施例。
表2:清洁相和有益相组合物
实施例4 | 实施例5 | 实施例6 | |
成分 | 重量百分比(%) | 重量百分比(%) | 重量百分比(%) |
I.清洁相组合物 | |||
Miracare SLB-365(得自Rhodia)(聚氧乙烯十三烷基醚硫酸钠、N-月桂酰胺基乙基-N-羟乙基乙酸钠、椰油基单乙醇酰胺) | 47.4 | 47.4 | 47.4 |
聚季铵10(UCare KG-30M) | 0.7 | - | - |
Jaguar C-17(得自Rhodia) | 0.7 | ||
瓜耳羟丙基三甲基氯化铵(N-Hance 3196,得自Aqualon) | - | - | 0.7 |
PEG 90M(Polyox WSR 301,得自DowChemical) | - | - | 0.2 |
氯化钠 | 3.5 | 3.5 | 3.5 |
乙二胺四乙酸二钠 | 0.05 | 0.05 | 0.05 |
1,3-二羟甲基-5,5-二甲基乙内酰脲 | 0.67 | 0.6 7 | 0.67 |
柠檬酸 | 0.4 | 0.4 | 0.4 |
香料 | 2.0 | 2.0 | 2.0 |
Expancel 091 DE 40 d30(得自Expancel,Inc.) | 0.4 | 0.4 | 0.4 |
水 | 适量 | 适量 | 适量 |
(pH) | (6.0) | (6.0) | (6.0) |
II.有益相组合物 | |||
凡士林(SuperWhite Protopet,得自WITCO) | 75 | 75 | 75 |
Bentone Gel MIO(得自Rheox) | 24.92 | - | - |
矿物油(Hydrobrite 1000 PO White MO,得自WITCO) | - | 23.92 | 23.92 |
Kraton G1702(得自Shell) | - | 1 | - |
Claytone HY(得自Southern Clay) | - | - | 1 |
Colorona洋红色美容颜料(得自Rona) | 0.08 | 0.08 | 0.08 |
上述组合物通过常规制剂和混合技术来制备。通过首先将柠檬酸以1∶3比率加入到水中形成柠檬酸预混物,来制备清洁相组合物。然后,按下列顺序,将下列成分加入到主要混合容器中:水、Miracare SLB-365、氯化钠、苯甲酸钠、乙二胺四乙酸二钠、1,3-二羟甲基-5,5-二甲基乙内酰脲。开动主要混合容器的搅拌。在另一个混合容器中,将聚合物(聚季胺10、JaguarC-17或N-Hance3196)以1∶10比率分散入水中,并形成聚合物预混物。连续搅拌下,将完全分散的聚合物预混物加入到主要混合容器中。将PolyoxWSR 301分散到水中,并加入到主要混合容器中。然后,将其余的水、香料和Expancel加入到批料中。持续搅拌,直至形成均匀溶液。
通过将凡士林加入到混合容器中来制备有益相。将容器加热至190。然后,在搅拌下加入矿物油、Bentone Gel、Kraton聚合物或Claytone HY。高剪切包含Bentone Gel或Claytone的样品。加入美容颜料,并且在缓慢搅拌下使容器冷却。
清洁相和有益相的密度匹配至0.05g/cm3以内。用常规的牙膏管装填设备将两相包装入单一容器。在填充过程中,样品台旋转底部,以产生条纹状外观。条纹的尺寸为约6mm宽和100mm长。
实施例7至9
描述于表3中的下列实施例是本发明清洁相和有益相组合物的非限制性实施例。
表3:清洁相和有益相组合物
实施例7 | 实施例8 | 实施例9 | |
成分 | 重量百分比(%) | 重量百分比(%) | 重量百分比(%) |
I.清洁相组合物 | |||
Miracare SLB-365(得自Rhodia)(聚氧乙烯十三烷基醚硫酸钠、N-月桂酰胺基乙基-N-羟乙基乙酸钠、椰油基单乙醇酰胺) | 47.4 | 47.4 | 47.4 |
氯化钠 | 3.5 | 3.5 | 3.5 |
乙二胺四乙酸二钠 | 0.05 | 0.05 | 0.05 |
1,3-二羟甲基-5,5-二甲基乙内酰脲 | 0.67 | 0.67 | 0.67 |
柠檬酸 | 0.4 | 0.4 | 0.4 |
香料 | 2.0 | 2.0 | 2.0 |
Expancel 091 DE 40d30(得自Expancel,Inc.) | 0.4 | 0.4 | 0.4 |
水(pH) | 适量(6.0) | 适量(6.0) | 适量(6.0) |
II.有益相组合物 | |||
Versagel M500(胶凝矿物油,得自Penreco) | 99.92 | - | - |
Versagel MC1600(胶凝异链烷烃,得自Penreco) | - | 99.92 | - |
Versagel ME500(胶凝氢化聚异丁烯,得自Penreco) | - | - | 99.92 |
Colorona洋红色美容颜料(得自Rona) | 0.08 | 0.08 | 0.08 |
上述组合物可通过常规制剂和混合技术来制备。通过首先将柠檬酸以1∶3比率加入到水中形成柠檬酸预混物,来制备清洁相组合物。然后,按下列顺序,将下列成分加入到主要混合容器中:水、Miracare SLB-365、氯化钠、苯甲酸钠、乙二胺四乙酸二钠、1,3-二羟甲基-5,5-二甲基乙内酰脲。开动主要混合容器的搅拌。然后,将香料加入到批料中。持续搅拌,直至形成均匀溶液。
通过将Versagel加入到混合容器中,来制备有益相。将容器加热至88℃(190)。然后,搅拌下加入美容颜料。缓慢搅拌下,使容器冷却。
清洁相和有益相的密度匹配在0.05g/cm3以内。用常规的牙膏管装填设备将两相包装入单一容器。在填充过程中,样品台旋转底部,以产生条纹状外观。条纹的尺寸为约6mm宽和100mm长。
在发明详述中引用的所有文献的相关部分均引入本文以供参考;任何文献的引用并不可理解为是对其作为本发明的现有技术的认可。
尽管说明和描述了本发明的具体实施方案,但对于本领域的技术人员显而易见的是,在不背离本发明的精神和保护范围的情况下可作出许多其它的变化和修改。因此有意识地在附加的权利要求书中包括本发明范围内的所有这些变化和修改。
Claims (18)
1.条纹状个人清洁组合物,所述组合物包含:
(a)包含清洁相的第一条纹,所述清洁相包含
(i)按所述清洁相的重量计1%至50%的表面活性剂,
所述表面活性剂选自阴离子表面活性剂、非离子表面活性剂、两性离子表面活性剂、阳离子表面活性剂、皂、以及它们的混合物;
其中所述清洁相为非牛顿剪切致稀,并且具有的粘度等于或大于3,000cps,具有的屈服值为至少0.1Pa;
(ii)按所述清洁相的重量计0.1%至15%的电解质,所述电解质包括选自磷酸根、氯离子、硫酸根、柠檬酸根以及它们的混合物的阴离子和选自钠离子、铵离子、钾离子、镁离子以及它们的混合物的阳离子;和
(iii)水;和
(b)附加条纹,所述条纹包含有益相,所述有益相包含按所述清洁相的重量计20%至100%的有益剂,所述有益剂选自烃、油和蜡、硅氧烷、胆固醇、甘油二酯、甘油三酯、植物油、乙酸甘油酯、烷基酯、链烯基酯、羊毛脂、蜡酯、甾醇、磷脂、以及它们的混合物;
其中所述有益剂所具有的Vaughan溶解度参数为5至15;
其中所述清洁相和所述有益相具有基本上相同的密度;
其中所述清洁相与所述有益相之间的比率为1∶9至99∶1;
其中所述清洁相和所述有益相以直接接触包装。
2.条纹状个人清洁组合物,所述组合物包含:
a)包含清洁相的第一条纹,所述清洁相包含按所述清洁相的重量计1%至50%的表面活性剂,所述表面活性剂选自阴离子表面活性剂、非离子表面活性剂、两性离子表面活性剂、阳离子表面活性剂、皂、以及它们的混合物;
其中所述清洁相为非牛顿剪切致稀,并且具有的粘度等于或大于3,000cps,具有的屈服值为至少0.1Pa;
和
b)至少一种包含独立有益相的附加条纹,所述有益相包含按所述有益相的重量计20%至100%的疏水性有益剂,所述疏水性有益剂选自烃、油和蜡、硅氧烷、胆固醇、甘油二酯、甘油三酯、植物油、乙酸甘油酯、烷基酯、链烯基酯、羊毛脂、蜡酯、甾醇、磷脂、以及它们的混合物;
其中所述有益剂所具有的Vaughan溶解度参数为5至15;
其中所述清洁相和所述有益相具有基本上相同的密度;其中所述清洁相与所述有益相之间的比率为1∶9至99∶1;
其中所述清洁相和所述有益相以直接接触包装,并在环境温度下保持稳定180天;和
其中所述清洁相和所述有益相以条纹状存在,其中所述条纹的尺寸为至少0.1mm宽和至少1mm长。
3.如权利要求1所述的条纹状个人清洁组合物,其中所述清洁相还包含密度调节剂,所述密度调节剂包含低密度微球体。
4.如权利要求3所述的条纹状个人清洁组合物,其中所述低密度微球体包含颗粒,所述颗粒具有的密度低于0.7g/cm3。
5.如权利要求3所述的条纹状个人清洁组合物,其中所述低密度微球体选自无机物质、有机物质、以及它们的混合物。
6.如权利要求1所述的条纹状个人清洁组合物,其中所述独立有益相基本上是无水的。
7.如权利要求1所述的条纹状个人清洁组合物,其中所述独立有益相基本上不含表面活性剂。
8.如权利要求1所述的条纹状个人清洁组合物,其中所述有益相所具有的稠度值为1泊至10,000泊。
9.如权利要求1所述的条纹状个人清洁组合物,其中所述有益相所具有的剪切指数为0.1至0.8。
10.如权利要求1所述的条纹状个人清洁组合物,其中按重量计,所述有益相包含至少50%的有益剂。
11.如权利要求1所述的条纹状个人清洁组合物,其中按重量计,至少20%的所述有益相选自凡士林、矿物油、微晶蜡、石蜡、地蜡、聚乙烯、聚丁烯、聚癸烯和全氢化角鲨烯、聚二甲基硅氧烷、环状聚甲基硅氧烷、烷基硅氧烷、聚甲基硅氧烷和甲基苯基聚硅氧烷、羊毛脂、羊毛脂油、羊毛脂蜡、羊毛脂醇、羊毛脂脂肪酸、羊毛脂酸异丙酯、乙酰化羊毛脂、乙酰化羊毛脂醇、亚油酸羊毛脂醇酯、蓖麻油酸羊毛脂醇酯、蓖麻油、大豆油、向日葵籽油、马来酸大豆油、红花油、棉籽油、玉米油、胡桃油、花生油、橄榄油、鳕鱼肝油、杏仁油、鳄梨油、棕榈油和芝麻油、以及它们的组合。
12.如权利要求1所述的条纹状个人清洁组合物,其中所述清洁相还包含按清洁相的重量计0.1%至10%的链烷醇酰胺。
13.如权利要求1所述的条纹状个人清洁组合物,所述组合物还包含结构剂。
14.如权利要求13所述的条纹状个人清洁组合物,其中所述结构剂选自三(羟基硬脂酸)甘油酯、二氧化硅、粘土和聚合物。
15.如权利要求1所述的条纹状个人清洁组合物,所述组合物还包含阳离子沉积聚合物。
16.如权利要求1所述的条纹状个人清洁组合物,其中所述清洁相和所述有益相在所述包装内形成图案。
17.如权利要求1所述的条纹状个人清洁组合物,其中所述组合物被装于透明容器中。
18.向皮肤或毛发递送皮肤调理有益效果的方法,所述方法包括下列步骤:
a)将有效量的如权利要求1所述的组合物分散在器具上,所述器具选自清洁粉扑、毛巾、海绵和人的手;
b)使用所述器具向所述皮肤或毛发局部施用所述组合物;和
c)通过用水漂洗将所述组合物从所述皮肤或毛发上除去。
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US20070141001A1 (en) * | 2005-12-15 | 2007-06-21 | The Procter & Gamble Company | Non-migrating colorants in multi-phase personal cleansing compositions |
US8104616B2 (en) * | 2006-02-11 | 2012-01-31 | The Procter & Gamble Company | Clamshell package for holding and displaying consumer products |
US8153144B2 (en) | 2006-02-28 | 2012-04-10 | The Proctor & Gamble Company | Stable multiphase composition comprising alkylamphoacetate |
US7839979B2 (en) | 2006-10-13 | 2010-11-23 | Koninklijke Philips Electronics N.V. | Electron optical apparatus, X-ray emitting device and method of producing an electron beam |
-
2003
- 2003-10-31 US US10/699,469 patent/US7511003B2/en not_active Expired - Lifetime
- 2003-10-31 CN CNB2003801022525A patent/CN100360108C/zh not_active Expired - Lifetime
- 2003-10-31 KR KR1020057007761A patent/KR100828468B1/ko active IP Right Grant
- 2003-10-31 AU AU2003302598A patent/AU2003302598B9/en not_active Ceased
- 2003-10-31 EP EP03812431A patent/EP1558208A1/en not_active Withdrawn
- 2003-10-31 JP JP2004557156A patent/JP4276179B2/ja not_active Expired - Fee Related
- 2003-10-31 CA CA2502760A patent/CA2502760C/en not_active Expired - Fee Related
- 2003-10-31 BR BR0315831-4A patent/BR0315831A/pt not_active Application Discontinuation
- 2003-10-31 WO PCT/US2003/034675 patent/WO2004050055A1/en active Application Filing
- 2003-10-31 MX MXPA05004808A patent/MXPA05004808A/es active IP Right Grant
-
2007
- 2007-08-20 US US11/894,080 patent/US20080045429A1/en not_active Abandoned
- 2007-08-20 US US11/894,078 patent/US20080039353A1/en not_active Abandoned
- 2007-08-20 US US11/894,143 patent/US8124573B2/en not_active Expired - Fee Related
- 2007-08-20 US US11/894,079 patent/US20080045428A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US5612307A (en) * | 1994-07-19 | 1997-03-18 | Lever Brothers Company, Division Of Conopco, Inc. | Detergent compositions containing separate stripes of surface active agents and benefit agent |
US6268322B1 (en) * | 1999-10-22 | 2001-07-31 | Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. | Dual chamber cleansing system, comprising multiple emulsion |
US6383999B1 (en) * | 2000-02-10 | 2002-05-07 | Unilever Home & Personal Care Usa. Division Of Conopco, Inc. | Personal washing bar having adjacent emollient rich and emollient poor phases |
WO2001070926A1 (en) * | 2000-03-20 | 2001-09-27 | Unilever Plc | Extrudable multiphase composition comprising lamellar phase inducing structurant in each phase |
US6306806B1 (en) * | 2000-03-22 | 2001-10-23 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc | Dual chamber cleansing system comprising water-in-oil emulsion as benefit stripe |
Also Published As
Publication number | Publication date |
---|---|
US8124573B2 (en) | 2012-02-28 |
US20080045429A1 (en) | 2008-02-21 |
JP4276179B2 (ja) | 2009-06-10 |
US20070293411A1 (en) | 2007-12-20 |
WO2004050055A1 (en) | 2004-06-17 |
CN1708286A (zh) | 2005-12-14 |
US7511003B2 (en) | 2009-03-31 |
US20040092415A1 (en) | 2004-05-13 |
AU2003302598B9 (en) | 2006-11-23 |
CA2502760A1 (en) | 2004-06-17 |
KR20050067218A (ko) | 2005-06-30 |
AU2003302598A1 (en) | 2004-06-23 |
EP1558208A1 (en) | 2005-08-03 |
CA2502760C (en) | 2010-05-04 |
MXPA05004808A (es) | 2005-07-22 |
US20080039353A1 (en) | 2008-02-14 |
KR100828468B1 (ko) | 2008-05-13 |
US20080045428A1 (en) | 2008-02-21 |
BR0315831A (pt) | 2005-09-13 |
JP2006516026A (ja) | 2006-06-15 |
AU2003302598B2 (en) | 2006-10-05 |
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