CN115362006A - 个人护理组合物、使用此组合物的方法及其对沉积效果的改进 - Google Patents
个人护理组合物、使用此组合物的方法及其对沉积效果的改进 Download PDFInfo
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- CN115362006A CN115362006A CN202180021723.8A CN202180021723A CN115362006A CN 115362006 A CN115362006 A CN 115362006A CN 202180021723 A CN202180021723 A CN 202180021723A CN 115362006 A CN115362006 A CN 115362006A
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Abstract
本发明涉及一种至少包含生物表面活性剂和亲水阳离子性或假阳离子性活性化合物的个人护理组合物。本发明还涉及一种增强或促进亲水阳离子性或假阳离子性活性化合物在角蛋白材料,如毛发或皮肤上沉积的方法。
Description
技术领域
本发明涉及一种个人护理组合物、一种使用该组合物的方法以及一种在将该组合物施用于角蛋白材料上时促进或增强沉积效果的方法。
背景技术
许多个人护理或化妆品组合物包含以洗去型配制剂施用于皮肤和/或毛发的活性物质。尽管该洗去型配制剂在使用之后再次从皮肤和/或毛发漂洗掉,但活性物质应沉积于皮肤和/或毛发上。通常直接将活性物质混入组合物,例如洗发剂、沐浴露、洗面奶或者固体或液体皂中。该程序具有的缺点是在大多数情况下在使用时仅少量活性物质保留在皮肤上,从而可以在那里发挥其作用。大多数活性物质通常在使用洗去型配制剂时再次洗掉。这导致必须向配制剂中掺入大量昂贵的活性物质以实现所需效果。然而,当适当地将大量活性物质用于洗去型配制剂中时,通常在使用配制剂时观察到不希望的皮肤刺激。这里的活性成分尤其是通常用于个人护理配制剂中的阳离子活性成分,例如己脒定二羟乙基磺酸盐,后者为用于发用化妆品配制剂中的一种新型去头屑剂;另一实例是生物碱奎宁或其盐,也声称其使头皮清爽并预防脱发。然而,将为亲水性或者甚至具有相对更高水溶性的该类活性成分保留在该配制剂中并在皮肤和/或毛发上有效产生其功能性益处将更具挑战性。
已经进行很多尝试以通过开发凝聚技术来改善沉积效果,尤其是在洗去型产品中。然而,该技术对于疏水性活性成分发展得更好。近年来对个人护理组合物,尤其是洗去型个人护理组合物的需求不断增加,一方面允许将活性成分的用量保持在低水平以避免皮肤刺激并因此降低成本,另一方面在使用过程中允许改善为亲水性或者甚至具有相对良好水溶性的活性成分的沉积效果并产生所需效果。
因此,本发明的目的是要满足市场对化妆品清洁和调理组合物的不断增长的需求,这些组合物提供了改善的活性成分沉积,尤其是改善的亲水阳离子性或假阳离子性活性成分沉积,并且还在皮肤和/或毛发上提供良好的清洁和调理效果。
槐糖脂类是由几种酵母物种,例如Starmerella产生的全天然和消费者友好型发酵表面活性剂。该生物表面活性剂分子的亲水性结构部分是二糖(即槐糖)并且疏水性部分是经由糖苷键连接于槐糖的ω-或(ω-1)-羟基脂肪酸。最常见的是含有16-18个碳原子的该脂肪酸链可以是不饱和的并且内酯化为该二糖。作为生物表面活性剂的槐糖脂类可以用作广泛用于洗涤剂和化妆品配制剂中的环境友好型表面活性剂。EP 0550276 A1描述了一种个人护理组合物,包含与辅助表面活性剂(例如SLS)一起使用的温和的发泡糖脂。WO1998016192 A1公开了一种适合清洁水果、蔬菜、皮肤和毛发的杀菌组合物。该组合物可以包含阴离子表面活性剂和槐糖脂类生物表面活性剂的混合物。美国专利申请2014/0349902A1公开了一种用于获得改善的护肤益处和发泡性能的毛发和皮肤清洁组合物,包含水、至少一种生物表面活性剂和至少一种脂肪酸。
本申请现已出人意料地发现一种含有糖脂生物表面活性剂和亲水阳离子性或假阳离子性活性成分的个人护理组合物使得可以增强和/或促进该亲水阳离子性或假阳离子性活性成分在角蛋白材料上的沉积效果,更具体而言,该个人护理组合物是一种洗去型组合物。
发明概述
因此,本发明的主题是一种个人护理组合物,至少包含:
a)糖脂生物表面活性剂,
b)亲水阳离子性或假阳离子性活性化合物;
其中该糖脂优选为槐糖脂。
优选10-90重量%的该槐糖脂生物表面活性剂呈酸性形式。
优选亲水阳离子性或假阳离子性活性化合物是含有至少一个碱性或季铵化氮原子的化合物,更优选亲水阳离子性或假阳离子性活性化合物包括脒化合物、碱性氨基酸、双胍化合物、生物碱化合物、咪唑类杀菌化合物和阳离子蛋白和/或蛋白水解物。
本发明在另一方面提供了个人护理组合物和增强或促进亲水阳离子性或假阳离子性活性化合物在角蛋白材料上的沉积的方法,包括至少一个将有效量的个人护理组合物施用于角蛋白材料的步骤,尤其是在漂洗施用过程中或之后。
本发明在另一方面还涉及本发明个人护理组合物在增强或促进亲水阳离子性或假阳离子性活性化合物在角蛋白材料上沉积中的用途。本发明在再一方面涉及该个人护理组合物在同时护理和洗涤角蛋白材料,如毛发和/或皮肤中的用途。
惊人且出人意料地发现上述目的由含有糖脂生物表面活性剂和亲水阳离子性或假阳离子性活性成分的个人护理组合物实现。该组合物产生该亲水阳离子性或假阳离子性活性成分在角蛋白材料上的增强沉积效果,该个人护理组合物尤其是一种洗去型产品。
发明详述
在包括权利要求书在内的通篇说明书中,除非另有说明,术语“包含一种”或“包含”应理解为与术语“包含至少一种”是同义词,并且“在……之间”应理解为包括极限值。
术语“一个”、“一种”和“该”用来指该冠词的一个或不止一个(即至少一个)语法宾语。
术语“和/或”包括含义“和”、“或”以及还有与该术语关联的要素的所有其他可能组合。
本文所用术语“亲水性(亲水)”是指该化合物对水具有强亲和力。
本文所用术语“电荷密度”是指单体单元(聚合物由其构成)上的正电荷数与所述单体单元的分子量之比。电荷密度乘以聚合物分子量决定了给定聚合物链上带正电荷位点的数目。
本文所用术语“活性化合物”涉及一种或多种改善或维持皮肤屏障的健康的成分。
本文所用术语“假阳离子性化合物”涉及不具有固有正电荷,但具有类似于带正电荷化合物的行为的化合物。由于这些化合物中的给电或受电原子和/或基团而在这些化合物中出现伪带电行为。
本文所用术语“化妆品上可接受的”是指所述组合物、配制剂或组分适合与人角蛋白材料接触而使用,没有过度毒性、不相容性、不稳定性、过敏反应等。
本文所用术语“角蛋白材料”意欲包含毛发、嘴唇、皮肤、头皮和体表生长物如睫毛、眉毛和指甲。
本文所用术语“洗去型”涉及在上下文中使用该组合物,其中该组合物在施用该产品之后或之中最终从被处理表面(例如皮肤或毛发)漂洗或洗净。
应注意的是在规定浓度、重量比或量的任何范围时,浓度、重量比或量的任何特定上限可以分别与浓度、重量比或量的任何特定下限关联。除非另有说明,所有百分数按重量计。
本发明涉及一种个人护理组合物,至少包含:
a)糖脂生物表面活性剂,
b)亲水阳离子性或假阳离子性活性化合物;
其中该糖脂优选为槐糖脂。
本发明的个人护理组合物可以增强和/或促进亲水阳离子性或假阳离子性活性化合物在角蛋白材料,尤其是毛发上的显著沉积,包括至少一个将有效量的本发明组合物施用于角蛋白材料的步骤。
本发明组合物是一种个人护理组合物或者一种化妆品组合物,优选一种个人护理清洁组合物,即一种用于清洁、调理、整洁、美化或在其他方面增强人体外观目的的组合物。个人护理产品尤其包括护肤产品、化妆产品,止汗剂,祛臭剂,香水,盥洗用品,肥皂,浴油,女性护理产品,护发产品,口腔卫生产品,脱毛剂,包括洗发剂、调理剂、直发产品和其他护发产品,彩妆品如口红,霜,美容品,护肤膏,洗液(优选由油包水或水包油乳液构成),剃须膏和剃须胶,剃须后乳液和剃须调理组合物以及防晒产品。在优选方面中,本发明的个人护理组合物包括护发和护肤产品,尤其是洗发剂、调理剂、漂洗液、顺发露产品、染发产品、沐浴露、美容品、口红、护肤膏和其他护肤产品。
在一些实施方案中,本发明的个人护理组合物可以用于包含中草药并且基于中医理论制备的中药组合物中。中草药的一些实例例如包括滋养毛发生长和强的人参,苦参如有助于毛发生长并预防脱发的苦参(sophora flavescens)提取物,用于血液循环的麦蓝菜属(vaccaria)和用于所需湿润效果的桑葚。
糖脂生物表面活性剂
本发明的组合物包含至少一种糖脂生物表面活性剂。
生物表面活性剂应理解为是由微生物形成并且通常由细胞排出的物质。像经典表面活性剂一样,生物表面活性剂是降低液体的表面张力并因此促进含水(亲水)相和拒水(疏水)相的混合的表面活性物质。生物表面活性剂需要很少能量的温和生产条件下生产。它们通常易于生物降解并且非常环境友好。此外,它们无毒,而且在其生产过程中也不产生任何有毒副产物。将糖水化合物,尤其是糖类,例如葡萄糖和/或疏脂性碳源如脂肪、油、偏甘油酯、脂肪酸、脂肪醇、长链饱和或不饱和烃类用作微生物生产所述生物表面活性剂的原料。根据本发明,该生物表面活性剂优选是通过发酵生产的生物表面活性剂。
生物表面活性剂包括糖脂类、脂肽类、脂蛋白类、磷脂类、中性脂质类和聚合物表面活性剂,它们全部也可以用于用于本发明中。可以用于本发明中的糖脂类是其中一个或多个单糖单元糖苷键合于脂质结构部分的化合物。作为可以根据本发明使用的生物表面活性剂的糖脂类的实例是槐糖脂类、鼠李糖脂类、纤维二糖脂类、甘露糖赤藓糖醇脂类、海藻糖脂类及其生物化学改性物。
槐糖脂类通过使用酵母如球拟假丝酵母(Starmerella Bombicola(雄蜂生假丝酵母(Candida Bombicola)))(也已知为球拟酵母(Torulopsis bombicola))、解脂耶氏酵母(Yarrowia lipolytica)、蜜生假丝酵母(Candida apicola)(蜜蜂生球拟酵母(Torulopsisapicola))和Candida bogoriensis发酵,使所述酵母在糖类、烃类、植物油或其混合物上生长而生产。槐糖脂类具有下式(a)(内酯形式)和(b)(游离酸),这两种形式通常以混合物提供:
其中R1和R1'独立地表示可以是线性或支化的并且可以包括一个或多个羟基的具有8-20个,尤其是12-18个,更优选14-18个碳原子的饱和烃链或者单或多不饱和,尤其是单不饱和烃链,R2和R2'独立地表示氢原子或甲基。优选其中R1和R1'是具有15个碳原子的单不饱和线性烃链的槐糖脂。还优选R2和R2'表示甲基或氢原子或者可以是线性或支化的并且可以包括一个或多个羟基的具有1-9个碳原子的饱和烷基官能基团或者单或多不饱和,尤其是单不饱和烷基官能基团,以及R3、R3'、R4和R4'独立地表示氢原子或乙酰基。
根据本发明,优选其中酸性形式和内酯形式以混合物存在的槐糖脂类,其中优选约10-90重量%,更优选约20-60重量%,仍更优选约25-40重量%的槐糖脂呈酸性形式并且剩余的槐糖脂呈内酯形式。
适合用于本发明的槐糖脂类可以市购得到,例如以名称Sopholiance S购自Soliance以及以名称购自Allied carbon solution。Allied CarbonSolution供应的槐糖脂约30重量%游离酸形式以与内酯形式的混合物存在。
根据本发明实施方案中的任一种,本发明组合物相对于该组合物的总重量包含0.1-30重量%,优选0.2-20重量%,更优选0.2-15重量%,仍更优选0.5-10重量%槐糖脂表面活性剂。
亲水阳离子性或假阳离子性活性化合物
本发明的组合物包含至少一种亲水阳离子性或假阳离子性活性化合物,其中该化合物含有至少一个碱性或季铵化氮原子。该碱性氮原子通常为可以通过强酸滴定的氮原子,例如伯、仲或叔胺氮,优选碱性氮原子中的至少一个是伯或仲胺氮,更优选至少一个是伯胺氮。
在一些实施方案中,该亲水阳离子性或假阳离子性活性化合物包括一种或多种脒化合物,如己脒定、戊烷脒、苯甲脒、其盐、其衍生物和/或其混合物。脒化合物对细菌、酵母和真菌呈现宽的杀菌活性谱。这些化合物可以用于本发明的组合物中作为毛发生长调节剂,即哺乳动物毛发生长,包括减少、调节、抑制、减弱、延缓、促进、增强和/或缩减毛发生长。本文所提到的“哺乳动物毛发”包括哺乳动物身体任何部位的毛发并且可以包括面毛、颅毛或体毛。可以用于本发明中的脒类毛发生长调节剂的非限制性实例包括:
-己脒定
-戊烷脒
-苯甲脒
本发明的组合物优选基于该组合物的重量包含约0.0001-10%,更优选约0.001-5%,仍更优选约0.01-1%,最优选约0.02-0.5%的脒化合物。
在一些优选实施方案中,本发明的组合物包含安全且有效量的一种或多种己脒定化合物、其盐和衍生物。本文所用己脒定衍生物包括己脒定化合物的任何异构体和互变异构体,包括但不限于有机酸和无机酸,例如磺酸、羧酸等。仍更优选该己脒定是己脒定二羟乙基磺酸盐,以HP100由BASF市购。
在一些实施方案中,本发明的组合物包含一种或多种碱性氨基酸作为亲水阳离子性或假阳离子性活性化合物,已知它们对角蛋白材料的营养,如发根的营养和人发的生长而言是重要的。“碱性氨基酸”是指天然存在的碱性氨基酸,如精氨酸、赖氨酸和组氨酸,以及任何在该分子中具有羧基和氨基的碱性氨基酸,其是水溶性的并且提供pH为7或更高的水溶液。因此,碱性氨基酸包括但不限于精氨酸、赖氨酸、瓜氨酸、鸟氨酸、肌酸、组氨酸、二氨基丁酸、二氨基丙酸、其盐或其组合。在优选实施方案中,该碱性氨基酸是肌酸、二氨基丙酸或二氨基丁酸、其盐或其组合。本发明的组合物包含呈游离形式或化妆品上可接受的盐形式的碱性氨基酸化合物。“化妆品上可接受的盐形式”是指以所提供的浓度加入角蛋白材料如毛发或皮肤中的盐形式。本发明的组合物优选基于该组合物的重量包含约0.001-20%,更优选约0.01-10%,仍更优选约0.1-5%的碱性氨基酸。
在一些实施方案中,本发明的组合物包含亲水阳离子性或假阳离子性活性化合物,后者可以是一种或多种咪唑杀菌剂,如苯并咪唑、苯并噻唑、联苯苄唑、硝酸布康唑、氯咪巴唑、克霉唑、氯康唑、艾伯康唑、益康唑、新康唑、芬替康唑、氟康唑、氟曲马唑、异康唑、酮康唑、拉诺康唑、甲硝哒唑、咪康唑、奈替康唑、奥莫康唑、硝酸奥昔康唑、舍他康唑、硝酸硫康唑、噻康唑、噻唑,以及三唑类如特康唑、伊曲康唑或其组合。作为杀菌活性物,可以将安全且有效量的杀菌活性物加入本发明组合物中。在一些实施方案中,该组合物基于该组合物的重量可以包含约0.0001%,0.001%,0.01%,0.05%,0.1%,0.5%或1%至约30%,25%,20%,10%,7%,5%或3%的一种或多种咪唑类杀菌剂。
在一些实施方案中,本发明的组合物包含一种或多种生物碱化合物作为亲水阳离子性或假阳离子性活性化合物,其包括但不限于甲基黄嘌呤类,例如咖啡因、茶碱、氨茶碱、阿托品、奎宁及其盐或混合物。尤其优选用于本发明个人护理组合物中的生物碱是奎宁和咖啡因。尤其可以将奎宁及其盐(硫酸氢盐、硫酸盐、氯化物、油酸盐和鞣酸盐)用于本发明中以使脱发最小化并刺激毛发生长。适合本发明的另一优选生物碱尤其是咖啡因,更具体为无水咖啡因。咖啡因是皮肤渗透力高的甲基黄嘌呤并且通过促进脂肪分解而在脂肪细胞深处起作用,促使测量值下降。它也在真皮中起作用,刺激成纤维细胞而合成胶原蛋白、弹性蛋白和其他细胞外基质成分,导致皮肤紧致度增加。本发明的组合物优选基于该组合物的重量包含约0.001-20%,更优选约0.01-10%,仍更优选约0.1-5%的生物碱化合物。
在一些实施方案中,本发明的组合物包含可以为双胍化合物的亲水阳离子性或假阳离子性活性化合物。“双胍化合物”是指具有下列官能基团的化学品:
其中n=1或2。当n=2时,=NHn基团的氮原子可以画成四价的并且因此带正电。
优选双胍化合物在本发明中用作杀菌剂,如聚合双胍化合物。特别优选的聚合双胍化合物是聚六亚甲基双胍(PHMB)或其衍生物。在一个实施方案中,本发明的组合物可以包含邻甲苯基双胍,后者作为抗氧化剂用于个人护理组合物中,尤其是用于护肤组合物中。本发明的组合物优选基于该组合物的重量包含约0.0001-10%,更优选约0.001-5%,仍更优选约0.01-1%,最优选0.02-0.5%的双胍化合物。
在一些实施方案中,本发明的组合物包含一种或多种阳离子蛋白和/或蛋白水解物作为亲水阳离子性或假阳离子性活性化合物。合适的蛋白水解物是可以通过蛋白质的酸、碱或酶催化降解而得到的产物混合物。适合本发明的蛋白质来自动物、植物和/或海洋。合适的动物蛋白水解物例如是弹性蛋白、胶原蛋白、角蛋白、丝蛋白和/或乳蛋白水解物,它们也可以以盐形式存在。该类产品例如以商标(BASF SE),(BASF SE),(BASF SE)和kerasol(Croda)销售。合适的植物来源蛋白水解物例如是大豆、杏仁、大米、豌豆、土豆、菜籽和/或小麦蛋白水解物。该类产品例如以商标(BASF SE)和(Croda)购得。合适的海洋来源蛋白水解物例如包括鱼或藻类胶原蛋白水解物以及贻贝蛋白水解物或珍珠水解物。还可以使用阳离子化蛋白水解物,其中基础蛋白水解物可以衍生于上述动物、植物和/或海洋来源。阳离子衍生物所基于的蛋白水解物可以由相应蛋白质通过化学水解,尤其是碱性或酸性水解,通过酶催水解和/或这两种类型水解的组合得到。蛋白质的水解通常得到分子量分布为约100-50,000道尔顿的蛋白水解物。优选那些分子量为200-25,000道尔顿,例如200-10000道尔顿,例如250-5000道尔顿的阳离子蛋白水解物。此外,阳离子蛋白水解物应理解为指季铵化氨基酸及其混合物。蛋白水解物或氨基酸的季铵化通常使用季铵盐如N,N-二甲基-N-正烷基-N-(2-羟基-3-氯正丙基)卤化铵进行。此外,阳离子蛋白水解物也可以进一步衍生化。阳离子蛋白水解物和衍生物的典型实例包括以INCI名称已知的产品:椰油基二甲基铵羟丙基水解胶原蛋白,椰油基二甲基铵羟丙基水解酪蛋白,椰油基二甲基铵羟丙基水解胶原蛋白,椰油基二甲基铵羟丙基水解角蛋白,椰油基二甲基铵羟丙基水解大米蛋白,椰油基二甲基铵羟丙基水解丝蛋白,椰油基二甲基铵羟丙基水解大豆蛋白,椰油基二甲基铵羟丙基水解小麦蛋白,椰油基二甲基铵羟丙基水解蚕丝氨基酸类,羟丙基精氨酸月桂基/肉豆蔻基醚HCl,羟丙基三甲基氯化铵明胶,羟丙基三甲基氯化铵水解酪蛋白,羟丙基三甲基氯化铵水解胶原蛋白,羟丙基三甲基氯化铵水解壳蛋白,羟丙基三甲基氯化铵水解角蛋白,羟丙基三甲基氯化铵水解米糠蛋白,羟丙基三甲基氯化铵水解丝蛋白,羟丙基三甲基氯化铵水解大豆蛋白,羟丙基水解植物蛋白,羟丙基三甲基氯化铵水解小麦蛋白,羟丙基三甲基氯化铵水解小麦蛋白/甲硅烷氧基硅酸盐,月桂基二甲基铵羟丙基水解大豆蛋白,月桂基二甲基铵羟丙基水解小麦蛋白,月桂基二甲基铵羟丙基水解小麦蛋白/甲硅烷氧基硅酸盐,月桂基二甲基铵羟丙基水解酪蛋白,月桂基二甲基铵羟丙基水解胶原蛋白,月桂基二甲基铵羟丙基水解角蛋白,月桂基二甲基铵羟丙基水解丝蛋白,月桂基二甲基铵羟丙基水解大豆蛋白,硬脂基二甲基铵羟丙基水解酪蛋白,硬脂基二甲基铵羟丙基水解胶原蛋白,硬脂基二甲基铵羟丙基水解角蛋白,硬脂基二甲基铵羟丙基水解大米蛋白,硬脂基二甲基铵羟丙基水解丝蛋白,硬脂基二甲基铵羟丙基水解大豆蛋白,硬脂基二甲基铵羟丙基水解植物蛋白,硬脂基二甲基铵羟丙基水解小麦蛋白,硬脂基三甲基铵羟乙基水解胶原蛋白,季铵盐-76水解胶原蛋白,季铵盐-79水解胶原蛋白,季铵盐-79水解角蛋白,季铵盐-79水解乳蛋白,季铵盐-79水解丝蛋白,季铵盐-79水解大豆蛋白,季铵盐-79水解小麦蛋白。根据本发明实施方案中的任一种,该组合物基于该组合物的总重量含有0.01-30重量%,优选0.1-20重量%,更优选0.5-10重量%,最优选1-5重量%的至少一种阳离子蛋白和/或蛋白水解物。
调理剂
根据本发明实施方案中的任一种,本发明组合物可以进一步包含调理剂,尤其是阳离子性或两性调理剂。可以使用的合适阳离子性调理聚合物包括阳离子性多糖聚合物,如阳离子性纤维素衍生物、阳离子性淀粉衍生物和阳离子性瓜尔胶衍生物。合适的是该类阳离子性多糖聚合物具有在0.1-4meq/g范围内的电荷密度。在一些实施方案中,该调理剂可以是阳离子性纤维素。阳离子性纤维素可以以其Polymer JR(商标)和LR(商标)系列聚合物购自Amerchol Corp.(Edison,N.J.,USA),呈与三甲基铵取代的环氧化物反应的羟乙基纤维素的盐,在本行业(CTFA)称为聚季铵盐10。另一类阳离子性纤维素包括与月桂基二甲基铵取代的环氧化物反应的羟乙基纤维素的聚合季铵盐,在本行业(CTFA)称为聚季铵盐24。这些材料可以以牌号Polymer LM-200购自Amerchol Corp.(Edison,N.J.,USA)。
根据本发明实施方案中的任一种,合适的阳离子性调理聚合物之一可以是阳离子性瓜尔胶聚合物,其为阳离子取代的半乳甘露聚糖(瓜尔)胶衍生物。用于制备这些瓜尔胶衍生物的瓜尔胶通常作为来自瓜尔胶植物的种子的天然存在材料得到。该瓜尔胶分子本身是直链甘露聚糖,其以规则间隔在交替甘露糖单元上以单一成员半乳糖单元支化。甘露糖单元借助γ(1-4)糖苷键相互连接。半乳糖支化通过ω(1-6)键产生。瓜尔胶的阳离子衍生物通过该聚半乳甘露聚糖的羟基和反应性季铵化合物之间的反应得到。该阳离子性瓜尔胶聚合物具有10,000-5,000,000g/mol的重均分子量和约0.05-2.5meq/g的电荷密度;优选该阳离子性瓜尔胶聚合物具有15,000-2,500,000g/mol,更优选200,000-1,500,000g/mol的重均分子量;并且具有0.2-2.2meq/g,或0.3-2.0meq/g,或0.4-1.8meq/g的电荷密度。合适的阳离子性瓜尔胶聚合物包括阳离子性瓜尔胶衍生物,如瓜尔胶羟丙基三甲基氯化铵。在一些实施方案中,该阳离子性瓜尔胶聚合物是瓜尔胶羟丙基三甲基氯化铵。瓜尔胶羟丙基三甲基氯化铵的具体实例包括由Rhone-Poulenc Incorporated市购的系列。其他合适的瓜尔胶羟丙基三甲基氯化铵是具有约0.7meq/g的电荷密度和600,000g/mol的分子量并且购自Rhodia的Hi-Care 1000,具有约0.7meq/g的电荷密度和约425,000g/mol的分子量并且购自ASI的N-Hance 3269和N-Hance 3270;具有0.9meq/g的电荷密度和50,000g/mol的分子量并且购自ASI的AquaCat CG518。
根据本发明实施方案中的任一种,合适的阳离子性调理聚合物之一可以是水溶性阳离子改性淀粉聚合物。本文所用术语“阳离子改性淀粉”涉及在该淀粉降解至更小分子量之前在其上加入阳离子基团的淀粉,或者其中在改性该淀粉以实现所需分子量之后加入阳离子基团的淀粉。术语“阳离子改性淀粉”的定义还包括两性改性淀粉。术语“两性改性淀粉”涉及在其上加入阳离子基团和阴离子基团的淀粉水解物。用于本发明个人洗涤组合物中的阳离子改性淀粉聚合物具有约850,000-15,000,000和/或约900,000-5,000,000的分子量。本发明中所用阳离子改性淀粉聚合物具有约0.2-5meq/g,优选约0.2-2meq/g的电荷密度。
可以使用本领域已知的其他阳离子性或两性调理剂,条件是它们与本发明组合物相容。尤其可以提到合成阳离子聚合物(例如包含具有季铵基团或叔铵基团的单元以及任选地,中性单元的聚合物)和合成两性共聚物(例如包含具有季铵基团或叔铵基团的单元、具有阴离子(通常为酸性)基团的单元以及任选地,中性单元的聚合物)。调理剂被本领域熟练技术人员已知。典型调理剂的实例包括(INCI名称):聚季铵盐-1;聚季铵盐-2;聚季铵盐-4;聚季铵盐-5;聚季铵盐-6;聚季铵盐-7;聚季铵盐-8;聚季铵盐-9;聚季铵盐-10;聚季铵盐-11;聚季铵盐-12;聚季铵盐-13;聚季铵盐-14;聚季铵盐-15;聚季铵盐-16;聚季铵盐-17;聚季铵盐-18;聚季铵盐-19;聚季铵盐-20;聚季铵盐-22;聚季铵盐-24;聚季铵盐-27;聚季铵盐-28;聚季铵盐-29;聚季铵盐-30;聚季铵盐-31;聚季铵盐-32;聚季铵盐-33;聚季铵盐-34;聚季铵盐-35;聚季铵盐-36;聚季铵盐-37;聚季铵盐-39;聚季铵盐-43;聚季铵盐-44;聚季铵盐-45;聚季铵盐-46;聚季铵盐-47;聚季铵盐-48;聚季铵盐-49;聚季铵盐-50;聚季铵盐-52;聚季铵盐-53;聚季铵盐-54;聚季铵盐-55;聚季铵盐-56;聚季铵盐-57;聚季铵盐-58;聚季铵盐-59;聚季铵盐-60;聚季铵盐-63;聚季铵盐-64;聚季铵盐-65;聚季铵盐-66;聚季铵盐-67;聚季铵盐-70;聚季铵盐-85;聚季铵盐-86;聚β-丙氨酸;聚ε-赖氨酸;聚赖氨酸;PEG-8/SMDI共聚物;PPG-12/SMDI共聚物;PPG-51/SMDI共聚物;PPG-7/琥珀酸共聚物;IPDI/PEG-15椰油胺共聚物;IPDI/PEG-15椰油胺共聚物二聚亚油酸酯;IPDI/PEG-15大豆油胺共聚物;IPDI/PEG-15大豆油胺氧化物共聚物;IPDI/PEG-15大豆油胺乙醇硫酸甲酯共聚物;聚季铵盐-4/羟丙基淀粉共聚物;决明胶羟丙基三甲基氯化铵;脱乙酰壳多糖羟丙基三甲基氯化铵;葡聚糖羟丙基三甲基氯化铵;半乳糖阿拉伯聚糖羟丙基三甲基氯化铵;人参羟丙基三甲基氯化铵;瓜尔胶羟丙基三甲基氯化铵;羟丙基瓜尔胶羟丙基三甲基氯化铵;刺槐角豆胶羟丙基三甲基氯化铵;淀粉羟丙基三甲基氯化铵;羟丙基三甲基氯化铵水解小麦淀粉;羟丙基三甲基氯化铵水解玉米淀粉;羟丙基氧化淀粉PG-三甲基氯化铵;酸豆(Tamarindus Indica)羟丙基三甲基氯化铵;聚丙烯酰胺丙基三甲基氯化铵;聚甲基丙烯酰胺丙基三甲基氯化铵;聚甲基丙烯酰胺丙基三甲基铵甲基硫酸盐;丙基三甲基氯化铵甲基丙烯酰胺/二甲基丙烯酰胺共聚物;丙烯酰胺/苄基羟乙基二甲基氯化铵丙烯酸盐共聚物;丙烯酰胺/乙基三甲基氯化铵丙烯酸盐/苄基羟乙基二甲基氯化铵丙烯酸盐共聚物;丙烯酸酯/氨基甲酸酯共聚物;己二酸/甲基DEA交联聚合物;二甘醇/DMAP丙烯酰胺/PEG-180/HDI共聚物;二羟乙基牛脂胺/IPDI共聚物;二甲胺/乙二胺/表氯醇共聚物;HEMA葡糖苷/甲基丙烯酸乙酯三甲基氯化铵共聚物;水解小麦蛋白/PEG-20乙酸酯共聚物;水解小麦蛋白/PVP交联聚合物;乙基三甲基氯化铵甲基丙烯酸酯/羟乙基丙烯酰胺共聚物。
根据本发明实施方案中的任一种,调理剂在该组合物中的量基于该组合物的总重量可以在0.01-15重量%,例如0.05-10重量%,0.1-10重量%,0.1-5重量%范围内。
额外的表面活性剂
本发明的组合物可以进一步包含一种或多种额外的阴离子表面活性剂。在一些实施方案中,所述额外的阴离子表面活性剂可以选自烷基硫酸盐、烷基酰胺硫酸盐、烷基醚硫酸盐、烷基酰胺基醚硫酸盐、烷基芳基醚硫酸盐、甘油单酯硫酸盐和氨基酸型表面活性剂。该类表面活性剂的典型实例包括月桂基硫酸钠(SLS)、月桂醇聚醚硫酸酯钠(SLES)、月桂基硫酸铵(ALS)或月桂醇聚醚硫酸铵(ALES)。在一些实施方案中,单独或者作为非离子/阴离子表面活性剂混合物的一部分使用的该阴离子表面活性剂可以包含选自如下的化合物,由其构成或者基本由其构成:磺酸、磺基琥珀酸酯、羧酸、肌氨酸、羟乙基磺酸、磺基乙酸酯的铵盐、碱金属盐或碱土金属盐及其组合。在一些优选实施方案中,本发明所用阴离子表面活性剂包括氨基酸型表面活性剂,如N-酰基酸性氨基酸及其盐,例如N-酰基谷氨酸、N-酰基天冬氨酸、其盐(钠、钾、铵或三乙醇胺(TEA)盐)或其混合物。
本发明的组合物可以进一步包含一种或多种两性表面活性剂,后者可以包含选自椰油酰胺基丙基甜菜碱、椰油酰胺基羟基磺基甜菜碱、椰油酰两性基乙酸盐、椰油酰基甲基牛磺酸钠及其组合的化合物,由其构成或者基本由其构成。
适合用于本发明中的非离子表面活性剂可以包含选自烷基聚葡糖苷、椰油酰胺单乙醇胺、椰油酰胺二乙醇胺、甘油烷基酯、聚乙二醇及其组合的化合物,由其构成或者基本由其构成。优选该非离子表面活性剂是用于本发明的烷基聚葡糖苷。
适合用于该个人护理组合物中的额外表面活性剂组分在这里包括已知用于护发或其他个人护理组合物中的那些。
根据本发明实施方案中的任一种,额外的表面活性剂相对于该组合物的总重量可以以在0.1-70重量%,尤其例如1-50重量%,1-30重量%,仍具体为5-20重量%,更具体为10-15重量%范围内的量存在。
为了避免任何疑问,表面活性剂的量涉及在该组合物中存在的活性表面活性剂化合物的实际量。换言之,它不包括可能作为杂质存在于市售表面活性剂混合物中的残余物。
额外的有益剂
本发明的组合物可以进一步包含一种或多种可以对待清洁底物,例如毛发和皮肤提供正面和/或有益效果的有益剂。熟练技术人员能够根据配制个人护理组合物如洗发剂、沐浴露和洗手液领域中的常识以及与其相关的大量文献选择适合应用目的的该类任选成分。在一个实施方案中,本发明的组合物进一步包含一种或多种有益剂,如润肤剂,保湿剂,调理剂,皮肤调理剂,或者头发调理剂如聚硅氧烷如挥发性聚硅氧烷、树胶或油,或者非氨基聚硅氧烷及其混合物,矿物油,酯类,如肉豆蔻酸丁酯、棕榈酸鲸蜡酯、油酸癸酯、月桂酸甘油酯、蓖麻醇酸甘油酯、硬脂酸甘油酯、异硬脂酸甘油酯、月桂酸己酯、棕榈酸异丁酯、硬脂酸异鲸蜡酯、异硬脂酸异丙酯、月桂酸异丙酯、亚油酸异丙酯、肉豆蔻酸异丙酯、棕榈酸异丙酯、硬脂酸异丙酯、丙二醇单月桂酸酯、丙二醇蓖麻醇酸酯、丙二醇硬脂酸酯和丙二醇异硬脂酸酯,动物脂肪,包括乙酰化羊毛脂醇、羊毛脂、猪油、貂油和牛脂,以及脂肪酸和醇,包括山酸、棕榈酸、硬脂酸、山醇、鲸蜡醇、二十烷醇和异鲸蜡醇;维生素或其衍生物,如复合维生素B,包括硫胺素、烟酸、生物素、泛酸、胆碱、核黄素、维生素B6、维生素B12、吡哆醇、肌醇、肉毒碱,维生素A、C、D、E、K及其衍生物,如维生素A棕榈酸酯,以及维生素原,例如泛醇(维生素原B5)、泛醇三乙酸酯及其混合物;抗氧化剂;自由基清除剂;天然或合成磨料;染料;染发剂;漂白剂;漂发剂;UV吸收剂,如二苯甲酮、波尼酮、PABA(对氨基苯甲酸)、丁基PABA、肉桂酰胺丙基三甲基氯化铵、二苯乙烯基联苯二磺酸二钠、甲氧基肉桂酸钾;抗UV剂,如丁基甲氧基二苯甲酰甲烷、甲氧基肉桂酸辛酯、氧苯酮、奥克立林、水杨酸辛酯、苯基苯并咪唑磺酸、羟丙基氨基苯甲酸乙酯、薄荷醇邻氨基苯甲酸酯、氨基苯甲酸、西诺沙酯、二乙醇胺甲氧基肉桂酸盐、氨基苯甲酸甘油酯、二氧化钛、氧化锌、氧苯酮、辛基二甲基PABA(帕地马酯)、红矿脂;杀菌剂;抗菌剂,如杆菌肽、红霉素、三氯生、新霉素、四环素、金霉素、苄索氯铵、苯酚、对氯间二甲酚(PCMX)、三氯卡班(TCC)、葡萄糖酸氯己定(CHG)、吡啶硫酮锌、硫化硒;抗真菌剂;黑素调节剂;晒黑促进剂;脱色剂,如类视黄醇类如视黄醇,曲酸及其衍生物,例如曲酸二棕榈酸酯,氢醌及其衍生物如熊果苷,氨甲环酸,维生素如烟酸,维生素C及其衍生物,壬二酸,胎盘,甘草,提取物如春黄菊和绿茶,其中优选视黄醇、曲酸和氢醌;亮肤剂如氢醌、儿茶酚及其衍生物、抗坏血酸及其衍生物;皮肤着色剂,如二羟基丙酮;血脂调节剂;减肥剂;抗痤疮剂;抗皮脂溢剂;抗老化剂;抗皱剂;角质溶解剂;抗炎剂;抗痤疮剂,如维甲酸、异维甲酸、莫维A胺、阿达帕林、他扎罗汀、壬二酸、视黄醇、水杨酸、过氧化苯甲酰、间苯二酚,抗生素如四环素及其异构体,红霉素,抗炎剂如布洛芬、萘普生、hetprofen,植物提取物如桤木属、山金车属、菌陈蒿、细辛根、金盏花属、春黄菊、长蓖藻属、聚合草、茴香、五倍子、山楂、鱼腥草、金丝桃、枣树、奇异果、甘草、木兰、橄榄、薄荷、喜林芋属、鼠尾草属、竹(sasa albomarginata),咪唑类如酮康唑和新康唑;清新剂;愈合剂;血管保护剂;减少头屑(去头屑剂)、脂溢性皮炎或银屑病的试剂,如吡啶硫酮盐,其由重金属如锌、锡、镉、镁、铝、钠和锆形成,如吡啶硫酮锌,页岩油及其衍生物如磺化页岩油,硫化硒,硫,水杨酸,煤焦油,聚维酮碘,咪唑类如酮康唑,二氯苯基咪唑并二氧戊环,克霉唑,伊曲康唑,咪康唑,氯咪巴唑,噻康唑,硫康唑,布康唑,氟康唑,亚硝酸咪康唑及其任何可能的立体异构体和衍生物如蒽林、吡罗克酮乙醇胺盐(Octopirox),硫化硒,环吡酮胺,抗银屑病剂如维生素D类似物,例如钙泊三醇、钙三醇和三苯乙醇(tacaleitrol),维生素A类似物如维生素A的酯,包括维生素A棕榈酸酯,类视黄醇类,视黄醇类和视黄酸,皮质类固醇类如皮质醇、氯倍他松、丁酸酯、丙酸氯倍他索;止汗剂或祛臭剂,如水合氯化铝、水合氯化铝锆;免疫调节剂;滋养剂;脱毛剂,如巯基乙酸钙、巯基乙酸镁、巯基乙酸钾、巯基乙酸锶;抗脱发剂;长效卷发还原剂;反射剂,如云母、氧化铝、硅酸钙、乙二醇二油酸酯、乙二醇二硬脂酸酯、二氧化硅、氟硅酸钠镁;精油和香料。
根据一些本发明实施方案,本发明的组合物可以进一步包含聚合物增稠剂或非聚合物增稠剂以使该组合物具有对使用目的而言令人满意的粘度。该组合物可以包含小于10重量%的额外增稠剂。用于本发明组合物的增稠剂的合适类别包括但不限于氯化钠、氯化钾、氯化铵、硫酸钠、脂肪酸羟烷基酰胺、纤维素衍生物、羧酸聚合物、交联聚丙烯酸酯聚合物、聚丙烯酰胺聚合物、多糖、树胶及其混合物。合适增稠剂的非限制性实例描述于theCTFA International Cosmetic Ingredient Dictionary,第10版(2004),第2294-96页中。
根据本发明实施方案中的任一种,该组合物进一步包含化妆品上可接受的载体。在一些实施方案中,该载体是含水载体。该载体的量和化学根据与其他组分的相容性和产品的其他所需特性选择。在一些实施方案中,该载体选自水和低级烷基醇的水溶液。在一些实施方案中,该载体是化妆品上可接受的含水载体并且以约20-95%或约60-85%的水平存在。
根据本发明实施方案中的任一种,该个人护理组合物以本领域已知的方式使用,例如在清洁剂或洗发剂的情况下通过将该清洁剂或洗发剂施用于皮肤和/或毛发并任选用水将该清洁剂或洗发剂从皮肤和/或毛发漂洗掉。根据本发明实施方案中的任一种,本发明组合物可以具有4-11,例如4-6的pH。
本发明的个人护理组合物可以通过使用现有技术中已知的任何传统共混技术如传统搅拌、振摇或转动将单个组分混合而制备。这些组分可以作为由熟练技术人员以合适比例稀释和/或合并的浓溶液供应。本发明涵盖待用作组成成分以制备本发明组合物的任何浓缩物,以及尤其是由于成本和环境角度的一些原因含有有效水平的水的浓缩物。
实施例:
材料
配制程序
1.在200rpm搅拌下将阳离子聚合物(聚季铵盐-10,瓜尔胶羟丙基三甲基氯化铵和丙烯酰胺丙基三甲基氯化铵/丙烯酰胺共聚物)加入水(60mL)中,直到该阳离子聚合物均匀分散并在水中完全溶胀。
2.在200rpm搅拌的同时将表面活性剂加入含有聚合物的溶液(在步骤1中得到)中。需要将椰油酰羟乙磺酸酯钠加热至70℃以完全溶于溶液中。
3.在200rpm搅拌下将亲水阳离子性或假阳离子性活性成分溶于水(5mL)中,然后在200rpm搅拌下加入在步骤2中得到的溶液中,直到体系均匀。
4.在200rpm搅拌下将包括增稠剂(PEG/PPG-120/10三羟甲基丙烷三油酸酯(和)月桂醇聚醚-2)、防腐剂(苯甲酸钠)和氯化钠在内的其他成分加入在步骤3中得到的溶液中。
5.将水加入在步骤4中得到的溶液中至100g并用柠檬酸溶液或三乙醇胺将该配制剂溶液的pH调节为4.5-5.5。
评价方法
将一块羊毛织物(5cm×5cm,0.6g)放入150mL烧杯的底部,然后将3g具有活性成分的配制剂加于该织物上并加入12g去离子水以稀释。将该稀释配制剂在该织物上在100rpm下用磁力搅拌棒搅拌1小时以提供足够的时间来凝聚沉积。然后将该羊毛织物从该烧杯取出并在500g纯水中搅拌15秒以除去松散附着的凝聚沉积。然后将该羊毛织物移入离心机中并用30g MeOH浸没过夜,直到附着的凝聚层和活性成分完全溶解。在将该羊毛织物从管中取出之后通过在3000rpm下离心10分钟而收集上清液。
沉积测量方法
收集的上清液通过使用紫外分光光度法(Perkin Elmer 365)在特定波长(对于己脒定的265nm和对于奎宁的280nm)下在MeOH中测试。然后使用扣除使用没有活性成分的配制剂测量的空白对照值的UV吸收值来基于标准曲线计算MeOH中的活性成分量。沉积率通过除以加入该配制剂中的初始活性成分量确定。
亲水阳离子性或假阳离子性活性成分的沉积率
Ex.=实施例;Comp Ex.=对比例
沉积试验结果表明包含槐糖脂表面活性剂的发明例导致各种个人护理配制剂中的亲水阳离子性或假阳离子性活性成分的沉积显著且惊人地提高。由于存在槐糖脂表面活性剂,发明例1(Ex.1)比对比例1(Comp Ex.1)具有更高的活性成分(己脒定二羟乙基磺酸盐)沉积率;发明例2(Ex.2)具有比对比例2(Comp Ex.2)高得多的活性成分(己脒定二羟乙基磺酸盐)沉积率;发明例3(Ex.3)比对比例3A和3B(Comp Ex.3A和3B)具有改进的活性成分(己脒定二羟乙基磺酸盐)沉积效果;并且对于活性成分硫酸奎宁,含有槐糖脂表面活性剂的实施例4显示出比对比例4A和4B(Comp Ex.4A和4B)提高的沉积率。
Claims (17)
1.一种个人护理组合物,至少包含a)糖脂生物表面活性剂和b)亲水阳离子性或假阳离子性活性化合物;其中所述糖脂优选是槐糖脂。
2.根据权利要求1的组合物,其中所述槐糖脂生物表面活性剂是酸性形式和内酯形式的混合物;其中优选约10-90重量%,更优选约20-60重量%,仍更优选约25-40重量%的所述槐糖脂呈酸性形式并且剩余的槐糖脂呈内酯形式。
3.根据权利要求1或2的组合物,其中所述亲水阳离子性或假阳离子性活性化合物是任一种含有至少一个碱性或季铵化氮原子的活性化合物;优选所述亲水阳离子性或假阳离子性活性化合物包含至少一种选自脒化合物、碱性氨基酸、双胍化合物、生物碱化合物、咪唑类杀菌化合物和阳离子蛋白和/或蛋白水解物的化合物。
4.根据前述权利要求中任一项的组合物,其中所述槐糖脂相对于所述组合物的总重量以在0.1-30重量%,优选0.2-20重量%,更优选0.2-15重量%,仍更优选0.5-10重量%槐糖脂表面活性剂范围内的量存在。
5.根据前述权利要求中任一项的组合物,其中所述亲水阳离子性或假阳离子性活性化合物包含脒化合物、其盐或其衍生物,尤其是己脒定化合物、其盐或其衍生物;优选所述脒化合物以在0.0001%至约10%,更优选约0.001-5%,仍更优选约0.01-1%,最优选约0.02-0.5%范围内的量存在。
6.根据权利要求1-4中任一项的组合物,其中所述亲水阳离子性或假阳离子性活性化合物包含碱性氨基酸,尤其是精氨酸、赖氨酸、瓜氨酸、鸟氨酸、肌酸、组氨酸、二氨基丁酸、二氨基丙酸、其盐或其组合;优选所述碱性氨基酸基于所述组合物的重量以在0.001-20%,更优选0.01-10%,仍更优选0.1-5%范围内的量存在。
7.根据权利要求1-4中任一项的组合物,其中所述亲水阳离子性或假阳离子性活性化合物包含双胍化合物;尤其是邻甲苯基双胍;优选所述双胍化合物基于所述组合物的重量以在0.0001-10%,更优选约0.001-5%,仍更优选0.01-1%,最优选0.02-0.5%范围内的量存在。
8.根据权利要求1-4中任一项的组合物,其中所述亲水阳离子性或假阳离子性活性化合物包含生物碱化合物,尤其是咖啡因,茶碱,氨茶碱,阿托品,奎宁,其盐或其混合物;优选所述生物碱化合物基于所述组合物的重量以在0.001-20%,更优选约0.01-10%,仍更优选0.1-5%范围内的量存在。
9.根据权利要求1-4中任一项的组合物,其中所述亲水阳离子性或假阳离子性活性化合物包含咪唑化合物,尤其是苯并咪唑,苯并噻唑,联苯苄唑,硝酸布康唑,氯咪巴唑,克霉唑,氯康唑,艾伯康唑,益康唑,新康唑,芬替康唑,氟康唑,氟曲马唑,异康唑,酮康唑,拉诺康唑,甲硝哒唑,咪康唑,奈替康唑,奥莫康唑,硝酸奥昔康唑,舍他康唑,硝酸硫康唑,噻康唑,噻唑,以及三唑类如特康唑和伊曲康唑或其组合;优选所述咪唑化合物基于所述组合物的重量以在0.0001%,0.001%,0.01%,0.05%,0.1%,0.5%或1%至约30%,25%,20%,10%,7%,5%或3%范围内的量存在于所述组合物中。
10.根据权利要求1-4中任一项的组合物,其中所述亲水阳离子性或假阳离子性活性化合物包含阳离子蛋白和/或蛋白水解物;优选所述阳离子蛋白和/或蛋白水解物基于所述组合物的重量以在0.01-30重量%,优选0.1-20重量%,更优选0.5-10重量%范围内的量存在于所述组合物中。
11.根据前述权利要求中任一项的组合物,进一步包含至少一种调理剂,例如阳离子性或两性调理剂;优选所述组合物包含选自阳离子性多糖及其衍生物的调理剂。
12.根据前述权利要求中任一项的组合物,进一步包含一种或多种阴离子表面活性剂、非离子表面活性剂和/或两性表面活性剂;所述表面活性剂尤其包含氨基酸型表面活性剂,如N-酰基酸性氨基酸及其盐,和/或烷基聚葡糖苷。
13.根据前述权利要求中任一项的组合物,进一步包含一种或多种额外的有益剂。
14.根据前述权利要求中任一项的组合物,其中所述个人护理组合物是洗去型产品。
15.一种增强或促进亲水阳离子性或假阳离子性活性化合物在角蛋白材料上沉积的方法,包括至少一个将有效量的如前述权利要求中任一项所定义的组合物施用于角蛋白材料的步骤。
16.如权利要求1-14中任一项所定义的组合物在增强或促进亲水阳离子性或假阳离子性活性化合物在角蛋白材料上沉积的用途。
17.如权利要求1-14中任一项所定义的组合物同时护理和洗涤角蛋白材料,如毛发和皮肤的用途。
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US20230107595A1 (en) | 2023-04-06 |
EP4121174A1 (en) | 2023-01-25 |
WO2021185675A1 (en) | 2021-09-23 |
KR20220155304A (ko) | 2022-11-22 |
BR112022018500A2 (pt) | 2022-10-25 |
JP2023519193A (ja) | 2023-05-10 |
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