CN115884750A - 防腐剂体系和包含其的组合物 - Google Patents
防腐剂体系和包含其的组合物 Download PDFInfo
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- CN115884750A CN115884750A CN202180050980.4A CN202180050980A CN115884750A CN 115884750 A CN115884750 A CN 115884750A CN 202180050980 A CN202180050980 A CN 202180050980A CN 115884750 A CN115884750 A CN 115884750A
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Abstract
本发明涉及一种包含取代的氨基酸及苯甲酸和/或其衍生物的天然防腐剂体系。该防腐剂体系为最终用途组合物提供了优异的抗微生物益处,即使将组合物配制成具有3.5至8.2范围内的pH时也是如此。
Description
技术领域
本发明涉及防腐剂体系和包含该防腐剂体系的组合物。更具体地,本发明涉及一种包含取代的氨基酸与苯甲酸和/或其衍生物的组合的防腐剂体系。令人惊讶的是,本发明的防腐剂体系为最终用途组合物提供了优异的抗微生物益处,即使将此类组合物配制成具有3.5至8.2范围内的pH时也是如此。此外,在基本上不含脱氢乙酸钠的组合物中配制时,这种体系出乎意料地提供优异的抗微生物益处以及卓越的颜色稳定性。
背景技术
DMDM乙内酰脲、对羟基苯甲酸酯、甲基异噻唑啉酮以及甲基氯异噻唑啉酮是消费品中存在的常用防腐剂。这些防腐剂已经安全地使用多年,并且已知在保持某些最终用途组合物的完整性和稳定性方面很好地起作用。另一种适用于消费品的防腐剂是苯甲酸钠。然而,苯甲酸钠虽然通常被认为是安全的,但众所周知其用于完全在酸性pH范围内的组合物中。尽管如此,仍然希望开发新的防腐剂体系,特别是可以包括天然来源的适于在宽的pH值范围下配制的全范围的消费品中良好地起作用的组分的体系。防腐剂体系,包括天然来源的那些,应当有效地对产品进行防腐,不是皮肤致敏的,并且不会对消费品(特别是局部施用的那些)的感官特征产生负面影响。它们也不应对加入它们的产品引起任何负面的组合物特性,如颜色变化。
除了提供优异的抗微生物益处外,防腐剂体系应该对环境无害,并且足够温和以用于最脆弱的消费者-婴儿。
因此,本发明涉及一种防腐剂体系,其可以包含天然来源的组分并且适用于在宽的pH值范围下配制的组合物中。防腐剂体系包含取代的氨基酸及苯甲酸和/或其衍生物。令人惊讶的是,本发明的防腐剂体系为最终用途组合物提供了优异的抗微生物益处,即使此类组合物配制成具有3.5至8.2范围内的pH时也是如此。此外,这种体系出乎意料地不会对最终用途组合物的颜色和气味产生负面影响,并且在基本上不含脱氢乙酸钠的组合物中配制时提供优异的抗微生物益处。
附加信息
已经公开了用于制备防腐剂体系的努力。在美国公开的专利申请2012/0190744A1中,描述了用于化妆品制剂的防腐剂体系。
还公开了制备防腐剂体系的其它努力。在美国专利申请No.A1中,描述了无毒的防腐剂组合物。
甚至已经公开了用于制备协同混合物的其它努力。在美国专利No.7,582,681B2中,描述了具有1,2-烷烃二醇的抗微生物活性化合物。
上述附加信息都没有描述本发明要求保护的防腐剂体系和具有这种体系的最终用途组合物。
发明内容
在第一方面中,本发明涉及一种防腐体系,其包含:
(a)包含取代的氨基酸的第一组分;和
(b)包含苯甲酸和/或其衍生物的第二组分,
第一组分和第二组分以1:4至4:1的重量比存在,其中组合物任选地包含脱氢乙酸钠,并且当存在时,脱氢乙酸钠和第二组分以其中脱氢乙酸钠占防腐剂体系中脱氢乙酸钠和第二组分总重量的小于5重量%(优选小于3重量%,且最优选小于2重量%)的量存在。
在第二方面中,本发明涉及一种防腐体系,其包含:
(a)包含C6至C20脂族或脂环族取代的氨基酸的第一组分;和
(b)包含苯甲酸和/或其衍生物的第二组分,
其中组合物基本上不含脱氢乙酸盐。
在第三方面中,本发明涉及一种防腐剂体系,其包含:
(a)包含取代的氨基酸的第一组分,所述取代的氨基酸包含癸酰基甘氨酸、N-辛酰基甘氨酸、N-十一烯酰基甘氨酸、N-十一烯酰基苯丙氨酸或其混合物;
(b)包含苯甲酸钠、苯甲酸钾、氨基苯甲酸盐或其混合物的第二组分,
第一组分和第二组分的重量比为1:4至4:1,其中组合物基本上不含脱氢乙酸钠。
在第四方面中,本发明涉及包含本发明的第一、第二和/或第三方面的防腐剂组合物的最终用途组合物,所述最终用途组合物是局部施用或口服摄取的并且具有3.5至8.2范围内的pH的产品。
在第五方面中,本发明涉及一种对最终用途组合物防腐的方法,该方法包括在最终用途组合物中包含本发明的第一、第二和/或第三方面的防腐剂组合物的步骤,其中最终用途组合物包含30至82重量%的水。
在第六方面中,本发明涉及一种通过使皮肤在美容上与本发明第五方面的最终用途组合物接触来处理皮肤的方法。
在第七方面中,本发明涉及本发明的第一或第二方面的防腐剂体系用于保持最终用途组合物的颜色、香味和微生物稳定性的用途。
从下面的描述和实施例中,本发明的所有其它方面将更容易变得显而易见。
如本文所用,皮肤意指包括手臂(包括腋下)、面部、足部、颈部、胸部、手部、腿部、臀部和头皮(包括毛发)上的皮肤。如本文所用,体系是指组合物或配方,其包括取代的氨基酸和苯甲酸和/或其衍生物的混合物。取代的氨基酸包括烃/脂质取代的氨基酸。最终用途组合物意在包括准备用于局部施用的组合物,如霜剂、洗剂、香膏、精华素、凝胶、摩丝、气雾剂、除臭剂、止汗剂、洗发剂、护发素、化妆品或个人洗涤剂,包括条和液体。这样的最终用途组合物还可以是食品或饮料组合物、药物组合物(即,用于医疗目的的药物组合物)、口服补充剂或家庭护理组合物,如硬表面清洁剂或洗衣洗涤剂组合物。在一个实施方式中,最终用途组合物是用于非治疗性和美容性目的(例如,去除引起污垢和/或气味的细菌)的液体个人洗涤组合物,并且最优选地,非治疗性和美容性液体沐浴露。在另一个实施方式中,最终用途组合物是洗发剂组合物。如下文所述,本发明的最终用途组合物可任选地包含加入其中的皮肤有益成分,如润肤剂、维生素和/或其衍生物、间苯二酚类、视黄酸前体、着色剂、保湿剂、防晒剂及其混合物等。皮肤有益成分可以是水溶性或油溶性的。因此,最终用途组合物是pH为3.5至8.2的水基组合物,并且该组合物可以是水或油连续的,但优选是水连续的。如本文所用,粘度用Brookfield Helipath TD在25℃的温度下以4rpm持续1分钟来获取。在再另一个实施方式中,本发明的最终用途组合物是非治疗性和美容性组合物,其为免洗型皮肤洗剂或霜剂。在没有另外明确说明的情况下,本文所述的所有范围意在包括其中包含的所有范围。如本文所用,基本上不含是指小于0.0125重量%。颜色稳定性是指没有负面的和可辨别的颜色变化,如白色到棕色的颜色变化。抗微生物益处意指在14天时至少2的对数杀灭(log kill),如美国药典(USP)的General Chapter 51中所述,其中在14天时低于2的对数杀灭将是不可接受的、失败的。术语“包含”意在涵盖术语“基本上由……组成”和“由……组成”。为了避免疑义,并且为了说明,包含油、水、苯甲酸钠和取代的胺的本发明的最终用途组合物意指包括基本上由其组成的组合物和由其组成的组合物。除了在操作比较例中,或另外明确指出的情况下,否则本说明书中表示材料或条件的量或比率和/或材料和/或用途的物理性质的所有数字应理解为由词语“约”修饰。
具体实施方式
关于本发明的防腐剂体系,第一组分和第二组分的重量比通常为1:4至4:1,包括其中包含的所有重量比。在本发明的一个实施方式中,第一组分与第二组分的重量比为1:3至3:1,并且在又一个实施方式中,第一组分与第二组分的重量比为1:2至2:1,包括其中包含的所有重量比。
关于本发明的最终用途组合物,第一组分和第二组分的总重量为最终用途组合物总重量的0.2至4重量%,包括其中包含的所有范围。在本发明的一个实施方式中,第一组分和第二组分的总重量为最终用途组合物总重量的0.4至3重量%,并且在再另一个实施方式中为0.5至2重量%。在又一个实施方式中,最终用途组合物中第一组分和第二组分的总重量为最终用途组合物总重量的0.6至1.2重量%。
第一组分包含取代的氨基酸。通常并且优选地,取代的氨基酸包含C6至C20,并且优选C7至C8,并且最优选C8至C12脂族或脂环族取代的氨基酸。在本发明的一个实施方式中,第一组分包含鉴定的取代的氨基酸(即癸酰基甘氨酸、N-辛酰基甘氨酸、N-十一烯酰基甘氨酸和/或N-十一烯酰基苯丙氨酸)中的1至3种。在本发明的另一个实施方式中,第一组分包含鉴定的取代的氨基酸中的1至2种。在本发明的再另一个实施方式中,N-辛酰基甘氨酸或十一碳烯酰基甘氨酸或两者存在于本发明的第一组分中。在本发明的又一个实施方式中,第一组分是N-辛酰基甘氨酸或十一碳烯酰基甘氨酸,或其混合物,其重量比为1:5至5:1,优选3:1至1:3,最优选2:1至1:2(甚至更优选1:1.5至1.5:1),包括其中包含的所有重量比。在甚至另一个实施方式中,第一组分是十一烯酰基苯丙氨酸。
关于第二组分,其包含苯甲酸和/或其衍生物。在本发明的一个实施方式中,第二组分包含苯甲酸衍生物,如苯甲酸钠、苯甲酸钾、氨基苯甲酸盐或其混合物。在本发明的另一个实施方式中,第二组分包含苯甲酸钠或苯甲酸钾,或两者,其重量比为1:5至5:1,优选3:1至1:3,最优选2:1至1:2,包括其中包含的所有重量比。在再另一个实施方式中,第二组分是苯甲酸钠或苯甲酸钾或其混合物。关于氨基苯甲酸盐,优选的适合使用的氨基苯甲酸盐包括对氨基苯甲酸钠或对氨基苯甲酸钾或其混合物。
脱氢乙酸钠在本发明中是任选使用的,并且当使用时,其通常占具有本发明的防腐剂体系的最终用途组合物的小于0.0125重量%。因此,使用本发明的防腐剂组合物的最终用途组合物基本上不含脱氢乙酸钠。在本发明的一个实施方式中,脱氢乙酸钠以最终用途组合物的0.0001%至小于0.075重量%存在。在再另一个实施方式中,防腐剂体系和最终用途组合物不含(即,0.0重量%)脱氢乙酸钠。
在本发明的又一个实施方式中,最终用途组合物包含30至82重量%的水,优选40至80重量%的水,最优选45至78重量%的水。在本发明的甚至另一个实施方式中,最终用途组合物包含50至77重量%,优选52至76重量%,最优选53至75重量%的水。在本发明的再另一个实施方式中,防腐剂体系中第一组分的总重量和第二组分的总重量不相等,并且防腐剂体系中第一组分的总重量通常为防腐剂体系中第二组分的55至80重量%,优选58至75重量%,最优选60至70重量%。
关于最终用途组合物,其可以是饮料,如茶饮料、运动饮料等。茶饮料包括由茶植物如中国茶(Camellia sinensis var.sinensis)或阿萨姆茶(Camellia sinensisvar.assamica)植物制备的那些饮料。它们还包括从南非红茶(Aspalathus linearis)植物获得的路易波氏茶饮料。茶饮料旨在包括从新鲜采摘的茶叶和干茶(包括分类为红茶、乌龙茶、绿茶或其混合物的那些)获得的饮料。
运动饮料可以是碳酸化饮料(只要饮料的pH为3.5或更高),并且它们可以包括维生素、植物提取物、人造和天然的甜味剂以及咖啡因。
家庭护理组合物可以是硬表面清洁剂,包括桌面、厕所和窗户清洁剂以及洗衣洗涤剂。这样的组合物是常规的和水基的。清洁和消毒表面的组合物通常包含具有表面活性剂的溶液,其被倾倒、喷出或喷洒到目标清洁表面上。溶液可以用常规增稠剂增稠,以防止它们过快地从表面排干。特别地,对于厕所清洁目的,它们通常包装在设置有喷口的容器中,使得它们可以通过挤压容器而被递送到表面。这种喷口以允许按照消费者友好的方式排出产品的方式安装在容器上。
适合作为具有本发明防腐剂体系的最终用途组合物的洗衣洗涤剂可含有由阴离子表面活性剂、非离子表面活性剂或两者组成的表面活性剂体系,和任选地洗涤助洗剂、去污聚合物(例如水分散性磺化聚酯)、香料和水。
在本发明的一个实施方式中,最终用途组合物是乳液和局部施用于身体并留在皮肤、头皮、指甲和/或毛发上的组合物。
局部施用的最终用途组合物(例如,免洗型组合物)中使用的油仅限于其在室温下为液体并且适用于局部组合物的程度。
适合使用的油的说明性实例包括硅油。硅油可分为挥发性和非挥发性种类。本文所用的术语“挥发性”是指在环境温度下具有可测量的蒸气压的那些材料。挥发性硅油优选选自含有3至9个,优选4至5个硅原子的环状或直链聚二甲基硅氧烷。可用于本发明的非挥发性硅油包括聚烷基硅氧烷、聚烷基芳基5硅氧烷和聚醚硅氧烷共聚物。可用于本文的此类基本上非挥发性的聚烷基硅氧烷包括例如在25℃下粘度为5至100,000厘沲的聚二甲基硅氧烷(如二甲硅油)。通常优选的硅氧烷源是环戊硅氧烷和二甲硅油溶液。
用于具有本发明防腐剂体系的最终用途组合物的合适酯包括:(1)具有10至20个碳原子的脂肪酸的烯基或烷基酯,如棕榈酸异丙酯、异硬脂酸异丙酯、异壬基isonanonoate、肉豆蔻酸油烯基酯、肉豆蔻酸异丙酯、硬脂酸油烯基酯和油酸油烯基酯;(2)醚酯,例如乙氧基化脂肪醇的脂肪酸酯;(3)多元醇酯,例如乙二醇单-和二-脂肪酸酯、二乙二醇单-和二-脂肪酸酯、聚乙二醇(200-6000)单-和二-脂肪酸酯、丙二醇单-和二-脂肪酸酯、聚丙二醇2000单油酸酯、聚丙二醇2000单硬脂酸酯、乙氧基化丙二醇单硬脂酸酯、甘油单-和二-脂肪酸酯、聚甘油聚脂肪酸酯、乙氧基化甘油单硬脂酸酯、1,3-丁二醇单硬脂酸酯、1,3-丁二醇二硬脂酸酯、聚氧乙烯多元醇脂肪酸酯、脱水山梨糖醇脂肪酸酯和聚氧乙烯脱水山梨糖醇脂肪酸酯;(4)甾醇酯,其中大豆甾醇和胆固醇脂肪酸酯是其实例。这些的混合物也是适合使用的。
可以使用的其他油包括甘油三酯(动物和/或植物),如大豆油(包括氢化大豆油)、葵花油、椰子油、棕榈仁油、蓖麻油、菜籽油、棕榈油、葡萄籽油、乳木果油、辛酸/癸酸甘油三酯、红花油、鱼油或其混合物。
甚至其它适合使用的油包括矿物油、霍霍巴油、异链烷烃、C12-C15烷基苯甲酸酯、聚α-烯烃、异十六烷、凡士林、其混合物(包括与上述那些油的混合物)等。大豆油和葵花油通常是优选的甘油三酯油。辛酸/癸酸甘油三酯是包含在最终用途组合物中的另一种通常优选的油。
对于油连续的最终用途组合物,乳化剂是适合使用的,并且它们通常具有2.5至7.5,且优选3至6.5,且最优选3至6的HLB,包括其中包含的所有范围。对于水连续的最终用途组合物,适合使用的乳化剂通常具有超过7.5至18,且优选8至15,且最优选8至12的HLB,包括其中包含的所有范围。当最终用途组合物例如是免洗型洗剂或霜剂时,此类乳化剂是优选的。
适用于这种油连续乳液的乳化剂类型的说明性实例是丙二醇异硬脂酸酯、二醇硬脂酸酯脱水山梨糖醇倍半油酸酯、卵磷脂、油醇聚醚-2、硬脂醇聚醚-2、鲸蜡醇聚醚-2甘油基硬脂酸酯、PEG-30二聚羟基硬脂酸酯。再其它适用的乳化剂包括二醇二硬脂酸酯、油酸甘油酯、脱水山梨糖醇单油酸酯、脱水山梨糖醇三硬脂酸酯、脱水山梨糖醇三油酸酯、脱水山梨糖醇单棕榈酸酯、月桂基PEG-10、(三甲基甲硅烷氧基)甲硅烷基乙基聚二甲基硅氧烷(DowES-5300)或其混合物。对于水连续的组合物,适合使用的示例性乳化剂包括脱水山梨糖醇月桂酸酯、聚山梨醇酯20、聚山梨醇酯85、油醇聚醚-10、鲸蜡醇聚醚-10、卵磷脂、peg-7橄榄油酸酯、PEG-8二油酸酯、吐温40、60、80或其混合物。
乳化剂通常占最终用途组合物的0.3至10,且优选2.5至8,且最优选3.5至7.5重量%。
在本发明的一个实施方式中,最终用途组合物是洗液,包括液体沐浴露(bodywash),其足够安全且温和以用于婴儿。此类沐浴露包含常规表面活性剂体系,其可包含或不包含硫酸盐。沐浴露可包括作为表面活性剂的皂和/或合成洗涤剂。
关于可用于洗涤组合物中的阴离子表面活性剂,其可包括脂族磺酸盐,如伯烷烃(例如C8-C22)磺酸盐、伯烷烃(例如C8-C22)二磺酸盐、C8-C22烯烃磺酸盐、C8-C22羟基烷烃磺酸盐或烷基甘油醚磺酸盐(AGS);或芳族磺酸盐,如烷基苯磺酸盐。阴离子表面活性剂还可以是烷基硫酸盐(例如C12-C18烷基硫酸盐)或烷基醚硫酸盐(包括烷基甘油醚硫酸盐)。其中烷基醚硫酸盐是具有下式的那些:
RO(CH2CH2O)nSO3M,
其中R是具有8至18个碳,优选12至18个碳的烷基或烯基,n的平均值至少为1.0,且优选小于5,且最优选1至4,且M是增溶阳离子,如钠、钾、铵或取代的铵。
阴离子表面活性剂还可以是烷基磺基琥珀酸盐(包括单烷基和二烷基,例如C6-C22磺基琥珀酸盐);烷基和酰基牛磺酸盐(通常为甲基牛磺酸盐)、烷基和酰基肌氨酸盐、磺基乙酸盐、C8-C22烷基磷酸盐和膦酸盐、烷基磷酸酯和烷氧基烷基磷酸酯、酰基乳酸盐、C8-C22单烷基琥珀酸盐和马来酸盐、磺基乙酸盐、烷基葡糖苷和酰基羟乙磺酸盐等。
磺基琥珀酸盐可以是具有下式的单烷基磺基琥珀酸盐:
R1O2CCH2CH(SO3M)CO2M;
和下式的酰胺-MEA磺基琥珀酸盐:
R1CONHCH2CH2O2CCH2CH(SO3M)CO2M,其中R1范围为C8-C22烷基。
肌氨酸盐通常由下式表示:
R2CON(CH3)CH2CO2M,其中R2范围为C8-C20烷基。
牛磺酸盐通常由下式表示:
R3CONR4CH2CH2SO3M,
其中R3是C8-C20烷基,R4是C1-C4烷基。
M是如前所述的增溶阳离子。
最终用途洗涤组合物可含有C8-C12酰基羟乙基磺酸盐。这些酯通过碱金属羟乙基磺酸盐与具有6至18个碳原子且碘值小于20的混合脂族脂肪酸之间的反应制备。至少75%的混合脂肪酸具有12至18个碳原子,并且至多25%具有6至10个碳原子。
酰基羟乙基磺酸盐可以是烷氧基化的羟乙基磺酸盐,如1995年2月28日授权的Ilardi等的发明名称为“Fatty Acid Esters of Polyalkoxylated Isethonic Acid”的美国专利No.5,393,466中所述的;其通过引用并入本文。这种化合物具有以下通式:
R5C-(O)-O-C(X)H-C(Y)H-(OCH2-CH2)m-SO3M,
其中R5是具有8至18个碳的烷基,m是1至4的整数,X和Y各自独立地是氢或具有1至4个碳的烷基,并且M是如前所述的增溶阳离子。
在本发明的一个实施方式中,使用的阴离子表面活性剂是月桂酰甘氨酸钠、椰油酰甘氨酸钠、月桂酰谷氨酸钠、椰油酰谷氨酸钠、月桂酰羟乙基磺酸钠、椰油酰羟乙基磺酸钠、甲基月桂酰牛磺酸钠、甲基椰油酰牛磺酸钠或其混合物。此类阴离子表面活性剂可从供应商如Galaxy Surfactants、Clariant、Sino Lion和Innospec商购获得。
适用于洗涤组合物的两性表面活性剂(取决于pH,其可以是两性离子的)包括酰基两性乙酸钠、酰基两性丙酸钠、酰基两性二乙酸二钠和酰基两性二丙酸二钠,其中酰基(即烷酰基)可以包含C7-C18烷基部分。适用的两性表面活性剂的示例性实例包括月桂酰两性基乙酸钠、椰油酰两性基乙酸钠、月桂酰两性基乙酸钠、椰油酰两性基乙酸钠及其混合物。
关于可用于洗涤组合物中的两性离子表面活性剂,此类表面活性剂包括至少一个酸基团。这样的酸基团可以是羧酸或磺酸基团。它们通常包括季氮,且因此可以是季氨基酸。它们通常应包括7至18个碳原子的烷基或烯基,通常符合总体结构式:
R6--[--C(O)--NH(CH2)q--]r--N+--(R7--)(R8)A--B,
其中R6是7至18个碳原子的烷基或烯基;R7和R8各自独立地为具有1至3个碳原子的烷基、羟烷基或羧基烷基;q为2至4;r为0至1;A是任选被羟基取代的具有1至3个碳原子的亚烷基,并且B是--CO2--或-SO3--。
用于本发明并在上述通式内的合适的两性离子表面活性剂包括下式的简单甜菜碱:
R6--N+--(R7)(R8)CH2CO2 -
和下式的酰胺基甜菜碱:
R6--CONH(CH2)t--N+--(R7)(R8)CH2CO2 -,其中t是2或3。
在两个式中,R6、R7和R8如先前所定义。R6特别地可以是源自椰子油的C12和C14烷基的混合物,使得至少一半,优选至少四分之三的基团R6具有10至14个碳原子。R7和R8优选是甲基。
另一种可能性是两性离子表面活性剂是下式的磺基甜菜碱:
R6--N+--(R7)(R8)(CH2)3SO3 -
或
R6--CONH(CH2)u--N+--(R7)(R8)(CH2)3SO3 -
其中u是2或3,或其中--(CH2)3SO3 -被--CH2C(OH)(H)CH2SO3 -替代的这些的变体。
在这些式中,R6、R7和R8如前所定义。
适合使用的两性离子表面活性剂的说明性实例包括甜菜碱,如椰油二甲基羧甲基甜菜碱、椰油酰胺丙基甜菜碱和月桂酰胺丙基甜菜碱。适合使用的其他两性离子表面活性剂包括椰油酰胺丙基磺基甜菜碱。此类表面活性剂可从供应商如Stepan Company商购获得,并且使用上述表面活性剂的混合物在本发明的范围内。
非离子表面活性剂可用于本发明的最终用途组合物中。使用时,非离子表面活性剂通常以低至0.5、1、1.5或2重量%的水平和高至6、8、10或12的水平使用。可以使用的非离子表面活性剂特别包括具有疏水基团和反应性氢原子的化合物(例如脂族醇、酸、酰胺或烷基酚)与环氧烷(尤其是单独的环氧乙烷或环氧乙烷与环氧丙烷)的反应产物。具体的非离子表面活性剂化合物是烷基(C6-C22)酚环氧乙烷缩合物、脂族(C8-C18)伯或仲直链或支链醇与环氧乙烷的缩合产物,以及通过环氧乙烷与环氧丙烷和乙二胺的反应产物的缩合制备的产物。其它非离子表面活性剂包括长链叔胺氧化物、长链叔膦氧化物、二烷基亚砜等。
在本发明的一个实施方式中,非离子表面活性剂包括具有以下结构的脂肪酸/醇乙氧基化物:a)HOCH2(CH2)s(CH2CH2O)vH或b)HOOC(CH2)c(CH2CH2O)dH;其中s和v各自独立地是至多18的整数;并且c和d各自独立地是1或更大的整数。在本发明的一个实施方式中,s和v各自独立地是6至18;c和d各自独立地是1至30。非离子表面活性剂的其他选择包括具有式HOOC(CH2)i-CH=CH--(CH2)k(CH2CH2O)zH的那些,其中i、k各自独立地是5至15;且z是5至50。在本发明的另一个实施方式中,i和k各自独立地是6至12;且z是15至35。
非离子表面活性剂还可以包括糖酰胺,如多糖酰胺。具体地,表面活性剂可以是1995年2月14日授权的Au等的发明名称为“Compositions Comprising NonionicGlycolipid Surfactants”的美国专利No.5,389,279中描述的乳糖酰胺(lactobionamides)之一;将其通过引入并入,或可以是1991年4月23日授权的Kelkenberg的发明名称为“Use of N-Poly Hydroxyalkyl Fatty Acid Amides as ThickeningAgents for Liquid Aqueous Surfactant Systems”的美国专利No.5,009,814中描述的糖酰胺之一;其通过引入并入本申请中。
在本发明的一个实施方式中,阳离子表面活性剂可用于最终用途洗涤组合物中。
一类阳离子表面活性剂包括杂环铵盐,如氯化十六烷基或硬脂基吡啶鎓、甲基硫酸烷基酰氨乙基吡咯(pyrrylinodium)和拉匹氯铵。
四烷基铵盐是适用的另一类阳离子表面活性剂。实例包括鲸蜡基或硬脂基三甲基氯化铵或溴化铵;氢化棕榈或牛脂三甲基卤化铵;二十二烷基三甲基卤化铵或甲基硫酸铵;癸基异壬基二甲基卤化铵;二牛脂(或二硬脂基)二甲基卤化铵和二十二烷基二甲基氯化铵。
可以使用的其它类型的阳离子表面活性剂是各种乙氧基化季胺和酯季铵盐。实例包括PEG-5硬脂基乳酸铵(例如,由Clariant制造的Genamin KSL)、PEG-2椰油基氯化铵、PEG-15氢化牛油基氯化铵、PEG 15硬脂基氯化铵、二棕榈酰乙基甲基氯化铵、二棕榈酰羟乙基甲基硫酸酯和硬脂酰胺丙基二甲基乳酸胺。
其它适用的阳离子表面活性剂包括丝、小麦和角蛋白的季铵化水解产物,并且使用上述阳离子表面活性剂的混合物也在本发明的范围内。
如果使用,阳离子表面活性剂通常占最终用途组合物的不超过1.0重量%。存在时,它们通常占最终用途洗涤组合物的0.01至0.7重量%,且更通常0.1至0.5重量%,包括其中包含的所有范围。
在本发明的一个实施方式中,最终用途洗涤组合物可基本上不含聚合季铵化合物(包括其盐)。在另一个实施方式中,洗液将包含小于0.1重量%的聚合季铵化合物。在又一个实施方式中,洗液将包含小于0.01重量%的聚合季铵化合物。在甚至另一个实施方式中,洗涤液不含聚合季铵化合物(即0.0%)。
在本发明的再另一个实施方式中,水占最终用途组合物的70至80重量%,包括其中包含的所有范围。
在本发明的一个实施方式中,最终用途组合物(或存在水时的防腐剂体系)的pH为4.5至8.0。在本发明的再另一个实施方式中,最终用途组合物的pH为5.2至7.8。在本发明的又一个实施方式中,组合物的pH为超过6至7.7,且优选6.2至7.5,且最优选6.4至7.1,包括其中包含的所有范围。在另一个实施方式中,最终用途组合物的pH为6.5至7.1,并且在再另一个实施方式中为6.6至7.1。
可以使用适于改变本发明的防腐剂体系和最终用途组合物的pH的调节剂。这样的pH调节剂包括三乙胺、NaOH、KOH、H2SO4、HCl、C6H8O7(即柠檬酸)或其混合物。pH调节剂的添加量使得防腐剂体系(当包括水时)和最终用途组合物的最终pH各自独立地为3.5至8.2,包括其中包含的所有范围。
关于适用于本发明的任选皮肤有益剂,其仅限于它们能够局部应用并且在所需pH下在最终用途组合物中相容的程度。
适合包括在此类组合物的水部分中的有益剂的说明性实例是酸,如氨基酸,如精氨酸、缬氨酸或组氨酸。适用的其他水溶性有益剂包括维生素B2、烟酰胺(维生素B3)、维生素B6、维生素C,其混合物等。也可以使用这些维生素的水溶性衍生物。例如,维生素C衍生物,如抗坏血酸四异棕榈酸酯、抗坏血酸磷酸镁和抗坏血酸糖苷可以单独使用或彼此组合使用。适用的其它水溶性有益剂包括4-乙基间苯二酚、提取物如鼠尾草、芦荟、绿茶、葡萄籽、百里香、洋甘菊、蓍草、黄瓜、甘草、迷迭香提取物,或其混合物。也可以使用水溶性防晒剂,如恩索利唑。存在于本发明的最终用途组合物中时,任选的水溶性有益剂(包括混合物)的总量可以为基于最终用途组合物的总重量的0.0至10重量%,优选0.001至8重量%,并且最优选0.01至6重量%,并且包括其中包含的所有范围。
任选地包括油溶性(即非水溶性)有益剂也在本发明的范围内。关于此类油溶性有益剂的唯一限制是局部施用时,其适于向皮肤提供益处。
可任选地用于本发明的最终用途组合物中的油溶性有益剂类型的说明性实例包括以下组分,如硬脂酸、维生素如维生素A、D、E和K(及其油溶性衍生物)、防晒剂如乙基己基甲氧基肉桂酸酯、双乙基己氧基苯酚甲氧基苯酚三嗪、2-乙基己基-2-氰基-3,3-二苯基-2-丙酸、甲酚曲唑三硅氧烷、3,3,5-三甲基环己基-2-羟基苯甲酸酯、2-乙基己基-2-羟基苯甲酸酯或其混合物。
适用的其它任选的油溶性有益剂包括间苯二酚,如4-己基间苯二酚、4-苯乙基间苯二酚、4-环戊基间苯二酚、4-环己基间苯二酚、4-异丙基间苯二酚或其混合物。此外,可以使用5-取代的间苯二酚,如4-环己基-5-甲基苯-1,3-二醇、4-异丙基-5-甲基苯-1,3-二醇、其混合物等。5-取代间苯二酚及其合成描述于共同持有的美国公开专利申请No.2016/0000669A1中。
甚至其它适用的油溶性活性物质包括ω-3脂肪酸、ω-6脂肪酸、氯咪巴唑、法呢醇、熊果酸、肉豆蔻酸、香叶基香叶醇、油基甜菜碱、椰油酰基羟乙基咪唑啉、己酰基鞘氨醇、12-羟基硬脂酸、岩芹酸、共轭亚油酸、硬脂酸、棕榈酸、月桂酸、萜品醇、百里酚、其混合物等。
在本发明的一个实施方式中,所用的任选油溶性有益剂是视黄酸前体。优选地,视黄酸前体是视黄醇、视黄醛、丙酸视黄酯、棕榈酸视黄酯、乙酸视黄酯或其混合物。丙酸视黄酯、棕榈酸视黄酯及其混合物通常是最优选的。
在本发明的最终组合物的油相中使用任选的(即0.0至1.5重量%)油溶性活性物质时,其通常占最终用途组合物总重量的0.001至1.3重量%,并且在另一个实施方式中,0.05至1.2重量%,并且在又一个实施方式中,0.1至0.5重量%。
如果需要,在最终用途组合物中可以任选地包括传统防腐剂(除了本发明的防腐剂体系之外)以防止潜在有害微生物的生长。化妆品化学家熟悉合适的防腐剂,并且通常选择它们以满足防腐剂挑战测试并提供产品稳定性。供使用的合适的传统但任选的防腐剂包括乙内酰脲衍生物和丙酸盐。特别优选的防腐剂是碘代丙炔基丁基氨基甲酸酯、苯氧基乙醇、羟基苯乙酮、乙基己基甘油、对羟基苯甲酸甲酯、对羟基苯甲酸丙酯、咪唑烷基脲、二甲基-二甲基(DMDM)乙内酰脲和苄醇,及其混合物。另一种适合使用的防腐剂包括氯苯甘醚。防腐剂的选择应考虑到组合物的用途以及防腐剂与乳液中其他成分之间可能的不相容性。当使用时,这些任选的防腐剂可以以最终组合物总重量的0.001%至2重量%范围的量使用,包括其中包含的所有范围。在本发明的优选实施方式中,仅使用本发明的防腐剂体系而不使用任何另外的和任选的防腐剂。
使用常规防腐增强剂如己二醇和1,2-辛二醇等也在本发明的范围内,其通常为最终用途组合物的0.2至1重量%。
在本发明的一个任选但优选的实施方式中,本发明中使用的苯甲酸是天然的,且因此,从如水果、蔬菜、浆果和海鲜的来源获得,并且其衍生物如苯甲酸钠衍生自天然存在的苯甲酸。因此,苯甲酸衍生物通过苯甲酸的标准中和反应制备。
增稠剂任选地适用于本发明的最终用途组合物中。特别有用的是多糖。实例包括纤维、淀粉、天然/合成树胶和纤维素制品。代表性的淀粉是化学改性淀粉,如羟丙基淀粉磷酸钠和淀粉辛烯基琥珀酸铝。通常优选木薯淀粉,麦芽糖糊精也是如此。合适的树胶包括黄原胶、菌核、果胶、刺梧桐树胶、***胶、琼脂、瓜尔胶(包括塞内加尔***胶)、角叉菜胶、藻酸盐及其组合。合适的纤维素包括羟丙基纤维素、羟丙基甲基纤维素、乙基纤维素、羧甲基纤维素钠(纤维素胶/羧甲基纤维素)和纤维素(例如纤维素微纤丝、纤维素纳米晶体或微晶纤维素)。纤维素微纤丝的来源包括次生细胞壁材料(例如木浆、棉花)、细菌纤维素和初生细胞壁材料。优选地,初生细胞壁材料的来源选自来自果实、根、鳞茎、块茎、种子、叶及其组合的薄壁组织;更优选地选自柑橘果实、番茄果实、桃果实、南瓜果实、猕猴桃果实、苹果果实、芒果果实、甜菜、甜菜根、芜菁、欧洲防风、玉米、燕麦、小麦、豌豆及其组合;并且甚至更优选地选自柑橘果实、番茄果实及其组合。初生细胞壁材料的最优选来源是来自柑橘果实的薄壁组织。柑橘类纤维,如可从公司以AQ Plus获得的那些,也可用作纤维素微纤丝的来源。纤维素源可以通过任何已知方法进行表面改性,包括在ColloidalPolymer Science,Kalia等,“Nanofibrillated cellulose:surface modification andpotential applications”(2014),第292卷,第5-31页中描述的那些。
合成聚合物是又一类有效的增稠剂。该类别包括交联的聚丙烯酸酯,如卡波姆、丙烯酸酯共聚物、丙烯酸酯/丙烯酸(C10-C30)烷基丙烯酸酯交联聚合物、聚丙烯酰胺如305和牛磺酸盐共聚物如/>EG和/>AVC,所述共聚物通过相应的INCI命名法被标识为丙烯酸钠/丙烯酰二甲基牛磺酸钠和丙烯酰二甲基牛磺酸/乙烯基吡咯烷酮共聚物。适用于增稠的另一种优选的合成聚合物是由Seppic市售并以名称Simulgel INS100销售的基于丙烯酸酯的聚合物。还可以使用碳酸钙、热解法二氧化硅和硅酸镁铝。
当使用时,增稠剂的量可以为最终用途组合物的0.001至5重量%的范围。麦芽糖糊精、黄原胶和羧甲基纤维素是通常优选的增稠剂。
最终用途组合物的粘度通常为750至55,000cps,优选1,000至40,000cps,最优选2,500至30,000cps。
香料、固定剂、螯合剂(如EDTA)、盐(如NaCl)、遮光剂(如TiO2)和去角质剂可任选地包含在本发明的最终用途组合物中。这些物质中的每一种的范围可以在最终用途组合物总重量的约0.03至约5重量%,优选0.1至3重量%的范围内,包括其中包含的所有范围。在使用去角质剂的情况下,选择的那些应具有足够小的粒度,使得它们不妨碍用于分配本发明的最终用途组合物的任何泵和致动器的性能。
常规湿润剂可任选地用作本发明中的添加剂,以在局部施用此类乳液时帮助润湿皮肤。这些通常是多元醇型材料。典型的多元醇包括甘油(即丙三醇或甘油)、丙二醇、二丙二醇、聚丙二醇(例如PPG-9)、聚乙二醇、山梨糖醇、羟丙基山梨糖醇、己二醇、1,3-丁二醇、异戊二醇、1,2,6-己三醇、乙氧基化甘油、丙氧基化甘油及其混合物。最优选的是甘油、丙二醇或其混合物。所用湿润剂的量可在液体和组合物总重量的0.0至35重量%的任何范围内。通常,湿润剂占最终用途组合物总重量的0.0至20重量%,优选0.001至15重量%(最优选2至12重量%)。
适合使用的另一种任选的添加剂包括具有2.5至25重量%的***萜酚和/或0.5至10重量%的***二酚的***油。当使用时,这种油占最终用途组合物的0.0001至12重量%,优选占最终用途组合物的0.01至5重量%,包括其中包含的所有范围。
当制备本发明的防腐剂体系和最终用途组合物时,可以使用常规设备在中等剪切和大气条件下混合所需成分,温度为环境温度至90℃。
最终用途组合物的包装仅限于消费者期望使用并且适于携带本发明的最终用途组合物的程度。
通常,包装可以是瓶、罐、喷雾泵、管或桶。优选地,包装是耐用但轻质的,并且包含至少10重量%或更多的消费后树脂(PCR),以确保其对环境的影响是有限的。在优选的实施方式中,本发明的防腐体系是天然的或天然衍生的,并且包装是全部PCR或可生物降解的。
所提供的实施例有助于理解本发明。它们不旨在限制权利要求的范围。
实施例
实施例中的制剂通过在大气条件下和约35℃至70℃的温度下以中等剪切混合成分来制备。将制备的每种制剂分成5个不同/单独的等份并称重。然后将5个不同的等份用如下所示的相应生物体或生物体混合物接种,从而得到攻击的制剂。接种物等于制剂重量的1%,并且在开始时不改变所测试制剂的特性。在接种后手动充分混合所有制剂以均匀地分布相应的微生物。然后将受攻击的制剂在约25℃下储存测试的持续时间。
然后在第7天、第14天和第28天对攻击的制剂以对于存活微生物取样。将这些样品涂布于培养皿中,并在适合于此类测试生物体且如美国典型培养物保藏中心(ATCC)所确定的常规条件下孵育,其中标准由范围定义时,以所选择范围的中间点。孵育后,计数微生物菌落的数量,并将所得数字乘以适当的稀释因子以获得每个样品单位的微生物数量。
AI--如之后确定的
AI-如之后在以下基质中鉴定的
抗微生物符号说明
池1:铜绿假单胞菌(Pseudomonas aeruginosa)+洋葱伯克霍尔德菌(Burkholderia cepacia)(革兰氏阴性)
池2:肺炎克雷伯氏菌(Klebsiella pneumoniae)+格氏肠杆菌(Enterobactergergoviae)(革兰氏阴性)
3:金黄色葡萄球菌(Staphylococcus aureus)(Staph.aur.)
4:白色念珠菌(Candida albicans)(酵母)
5:巴西曲霉(Aspergillus brasiliensis)(霉菌)
完全根除(“CE”)-破坏/杀死存在的所有抗微生物
在以下确定的时间目视评估颜色外观。
收集的数据表明根据本发明制备和使用防腐剂体系时,实现了优异的抗微生物益处(至少2的对数杀灭,完全根除)以及颜色稳定性,并且令人惊讶地,在配制不含脱氢乙酸盐的组合物时。此外,受过训练的小组成员还得出结论根据本发明使用的防腐剂体系不会不利地影响它们配制在其中的组合物的香味,并且在稳定性测试完成后,组合物不会原位产生任何异味。
与本发明不一致的组合物,即具有制剂O作为基质的组合物,没有表现出优异的抗微生物益处。
Claims (14)
1.一种用于具有5.2至7.8的pH并且包含羟乙基磺酸盐的洗涤组合物的防腐剂体系,该防腐剂体系包含:
(a)包含取代的氨基酸的第一组分;和
(b)包含苯甲酸、苯甲酸钠、苯甲酸钾、氨基苯甲酸盐或其混合物的第二组分,
所述第一组分和第二组分以1:4至4:1的重量比存在,其中所述组合物任选地包含脱氢乙酸钠,并且当存在时,脱氢乙酸钠和所述第二组分以其中所述脱氢乙酸钠占基于所述防腐剂体系中脱氢乙酸钠和第二组分的总重量小于5重量%,优选小于3重量%,且最优选小于2重量%的量存在,并且其中除了所述第一组分和第二组分外,所述洗涤组合物中不存在防腐剂。
2.一种用于具有5.2至7.8的pH并且包含羟乙基磺酸盐的洗涤组合物的防腐剂体系,该防腐剂体系包含:
(a)包含取代的氨基酸的第一组分,所述取代的氨基酸包含癸酰基甘氨酸、N-辛酰基甘氨酸、N-十一烯酰基甘氨酸、N-十一烯酰基苯丙氨酸或其混合物;
(b)包含苯甲酸钠、苯甲酸钾、氨基苯甲酸盐或其混合物的第二组分,
所述第一组分和第二组分的重量比为1:4至4:1,并且其中所述组合物基本上不含脱氢乙酸钠,并且其中除了所述第一组分和第二组分之外,所述洗涤组合物中不存在防腐剂。
3.一种包含防腐剂体系的洗涤组合物,该组合物是包含羟乙基磺酸盐且是局部施用的,并且具有5.2至7.8的pH的组合物,其中所述防腐剂体系包含:
(a)包含取代的氨基酸的第一组分;和
(b)包含苯甲酸和/或其衍生物的第二组分,
其中所述第一组分和第二组分以1:4至4:1的重量比存在,其中所述组合物任选地包含脱氢乙酸钠,并且当存在时,脱氢乙酸钠和所述第二组分以其中所述脱氢乙酸钠占基于所述防腐剂体系中脱氢乙酸钠和第二组分的总重量小于5重量%,优选小于3重量%,且最优选小于2重量%的量存在,所述组合物包含30至82重量%的水,和
其中除了所述第一组分和第二组分外,所述组合物中不存在防腐剂。
4.根据权利要求3所述的组合物,其中所述组合物包含小于0.125重量%的脱氢乙酸钠,并且所述组合物包含40至80重量%的水。
5.根据权利要求3或4所述的组合物,其中所述第一组分是癸酰基甘氨酸、N-辛酰基甘氨酸、N-十一烯酰基甘氨酸、N-十一烯酰基苯丙氨酸或其混合物,和所述第二组分是苯甲酸钠、苯甲酸钾、氨基苯甲酸盐或其混合物,并且所述组合物具有4.5至8的pH。
6.根据权利要求3至5任一项所述的组合物,其中所述组合物的pH为6至7.7,优选6.4至7.1。
7.根据权利要求3至6任一项所述的组合物,其中所述第一组分是N-辛酰基甘氨酸或十一碳烯酰基甘氨酸或其混合物,并且所述第二组分是苯甲酸钠。
8.根据权利要求3至7任一项所述的组合物,其中所述组合物是婴儿沐浴露。
9.根据权利要求3至8任一项所述的组合物,其中所述第一组分和第二组分以组合物的0.2至4重量%的总重量存在于所述组合物中,并且所述组合物的pH为5.2至7.8。
10.根据权利要求3至9任一项所述的组合物,其中所述组合物还包含***萜酚和/或***二酚。
11.根据权利要求3至10任一项所述的组合物,其中所述组合物具有40至85重量%的水和6.2至7.5的pH。
12.根据权利要求3至11任一项所述的组合物,其中所述第一组分包含重量比为2:1至1:2,优选1.5:1至1:1.5的十一烯酰基苯丙氨酸和辛酰基甘氨酸。
13.根据权利要求3至12任一项所述的组合物,其中所述第一组分包含十一烯酰基苯丙氨酸,并且所述组合物具有6.4至7.1,且优选6.5至7.1,且最优选6.6至7.1的pH,并且水占30至85重量%的水。
14.一种通过使皮肤与根据权利要求3至13任一项所述的组合物接触来处理皮肤的方法。
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