CN113518613B - 生物基珠光蜡 - Google Patents
生物基珠光蜡 Download PDFInfo
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- CN113518613B CN113518613B CN202080016295.5A CN202080016295A CN113518613B CN 113518613 B CN113518613 B CN 113518613B CN 202080016295 A CN202080016295 A CN 202080016295A CN 113518613 B CN113518613 B CN 113518613B
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- ethylene glycol
- acid
- wax
- glycol ester
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Abstract
本发明涉及生物基蜡状酯,其特别地呈蜡分散体的形式,在化妆品清洁产品中产生不透明和/或珠光效果。本发明进一步涉及所述蜡在化妆品产品中的用途、其制备和化妆品产品。
Description
发明领域
本发明涉及特定的蜡状酯领域,其特别地以蜡分散体的形式在化妆品清洁剂中产生混浊和/或珠光。本发明还提供了所述蜡在化妆品组合物中的用途、其制备和化妆品组合物本身。
现有技术
用于皮肤和/或头发的化妆品清洁剂,例如洗发香波、头发调理剂、淋浴凝胶或液体洗手皂,通常被配制成视觉上吸引人的。化妆品清洁剂可以配制成具有通常也称为珠光的有光泽的云母效果,或具有称为混浊或白色的无光泽的乳状颜色。
作为化妆品清洁剂用不透明剂,通常使用通常基于(甲基)丙烯酸和苯乙烯的共聚物的细碎聚合物分散体。由于生态原因,希望替换这些。
德国专利DE19511572公开了基于蜡体与亲水性和疏水性乳化剂的不透明剂浓缩物。根据该文献,乙二醇二硬脂酸酯(蜡体)与糖表面活性剂(亲水性乳化剂)和单甘油酯(疏水性乳化剂)组合提供低粘度、混浊的蜡分散体。所用的乙二醇二硬脂酸酯是通过石化手段制备的基于乙二醇的脂肪酸酯。
具有这种石化基的蜡,例如乙二醇单硬脂酸酯(EGMS)和/或乙二醇二硬脂酸酯(EGDS),作为珠光剂和珠光浓缩物中的蜡体也是现有技术中已知的。例如,根据国际专利申请WO98/38973通过特别高的C18脂肪酸含量或根据国际专利申请WO2012/177886通过晶体形成的特定性质实现了非常好的珠光效果。此外,存在能够将蜡EDMS和/或EDGS转化成蜡分散体的大量现有技术,例如根据国际专利申请WO03/066796通过非离子表面活性剂。
迄今为止,这些蜡仅仅是乙二醇与石化基(即化石来源)的酯。
本发明的目的尤其是提供用于蜡分散体的蜡,其相对于环境能够实现持续的人类行为。因此,至少蜡应完全基于植物,并且如果可能的话,整个蜡分散体不应基于石化或化石原料。
然而,同时,如果可能甚至更好的品质,则呈其蜡分散体形式的蜡应当继续具有至少与珠光剂或不透明剂相同的品质。
该目的通过蜡状乙二醇酯实现,特别适合作为化妆品清洁剂中的不透明剂和/或珠光剂,其中根据14C分析,酯中的乙二醇具有至少99%的生物源碳比例,根据DIN EN 15440定义,在13.6dpm/gC下,独立于基质,标准偏差为+/-0至+/-4。
优选地,根据14C分析,酯中的乙二醇具有100%的生物源碳比例,根据DIN EN15440定义,在13.6dpm/gC下,独立于基质,标准偏差为+/-0至+/-4。
完全令人惊奇的是,与基于石化或化石乙二醇的先前酯相比,蜡分散体形式的具有生物源含量的14C同位素的乙二醇的这些蜡状酯显示出改进的白度。这是出乎意料的,因为14C同位素在乙二醇酯中的比例极低。
此外,本发明的乙二醇酯与可比的石化乙二醇酯相比具有更低的熔化焓,这意味着与相同质量的石化乙二醇酯相比,需要更少的能量来熔化限定量的本发明的蜡。这使得能够更经济和能量有效地生产蜡分散体和它们在化妆品组合物中的可加工性。
同位素是具有相同原子序数(=质子数)但核中存在不同数目的中子且因此具有不同质量数[=核子数目,原子核中存在的核子(质子和中子)的数目]的核素。除了质量之外,同位素在角动量(核自旋)、磁矩和电四极矩方面也不同。
为了明确地鉴定同位素,使用(通常对于核素是常规的)符号AzX(X=化学符号,A=质量数,Z=原子序数),因此对于碳126C的稳定同位素;或者,使用符号12C或C-12。
元素碳总共具有2个稳定同位素,12C和13C。12C实际上具有约98.9%的丰度,13C具有1.1%的丰度。除了这两种稳定的同位素之外,还存在许多不稳定的同位素。最著名的不稳定同位素是14C,半衰期为5730年。14C由14N通过大气中的自然核反应形成:地球经常暴露于宇宙射线,当这些射线撞击地球大气的最上层时,它们产生自由中子。这些中子又与存在于较低大气中的空气中的氮以大约80%的水平反应。发生以下反应:
质量数为14的氮原子核(7个中子,7个质子)吸收中子。放射性碳同位素14C(8个中子,6个质子)是在质子离开时由氮原子形成的,因此质量数保持相同。相反,12C碳具有6个中子和6个质子-因此它比14C轻。
在大气中产生的14C与可利用的氧结合形成二氧化碳。14C然后由于植物的光合作用而进入生物圈。由于生物体在代谢过程中不断与大气交换碳,因此在生物体中建立了与大气中存在的相同的3种碳同位素12C、13C和14C的分配比例:生物体每1012个稳定的12C和13C同位素包含约1.2放射性14C同位素。
如果从该循环中回收碳(即,碳变成化石碳),则14C与12C之间的该比例改变,因为衰变的14C同位素未被新的同位素替代。
1亿年前形成的化石燃料如原油、天然气或煤,也就是说,这些燃料不再包含任何14C同位素,因为最初存在的14C同位素已经衰变并且没有新的14C同位素被测定。因此,源自化石来源的烃不包含任何14C同位素。
在本发明的一个优选实施方案中,14C同位素相对于稳定的12C和13C同位素的比例为6×10-13至1.2×10-12。参比参数为乙二醇中存在的所有烃。
样品的14C含量可以通过在液体闪烁光谱仪中在盖革计数器(Libby的盖革计数器方法)中对衰变的14C同位素计数来测定,或者通过使用加速器质谱对剩余的14C同位素计数来测定。加速器质谱(缩写:AMS)可用于在核测量方法的帮助下以极小的样品量(毫克范围)检测ppt至ppq范围(10-12至10-16)内的14C同位素。目前的100%生物源活性根据DIN 15440在13.6dpm/gC下关于2018而定义,与基质无关。
本发明的乙二醇酯可以通过酯化包含14C同位素的特定乙二醇来制备。这种乙二醇,也称为“生物-乙二醇”或“生物-单乙二醇”,或简称为“生物-MEG”,可通过各种方法获得。“生物-”是指来自可再生或植物基原料来源。根据India Glycols Ind.,印度的较古老方法之一,首先被称为“生物-乙醇”的物质由甘蔗或甘蔗糖浆生产。从化学角度来看,生物-乙醇本身是乙醇。所需的乙二醇(“生物-MEG”)通过India Glycols Ind.方法由生物-乙醇生产。为此,首先通过催化脱水(催化消除水)制备乙烯,然后通过氧化制备氧化乙烯,最后通过加入水将其转化为生物-MEG。
根据另一方法,在酵母,特别是囊菌(子囊菌(ascomycetes))类真菌存在下,由甘蔗汁或糖蜜或甘蔗渣厌氧生产生物-乙醇,该生物-乙醇被转化成乙烯,并通过氧化成醋和随后氢化为生物-MEG而产生。以这种方式生产的生物-MEG也经常用于生产所谓的PlantBottleTM,即包含30%生物-MEG的PET瓶。
由于消费的增加,不久的将来预计生产生物-MEG的另外两家工厂开始生产。根据Braskem S.A.和Haldo TopSoe A/S的公布的方法,MOSAIKTM方法(MOnoSAccharideIndustrial Cracker)与Haldor TopsoeTM方法结合,使得糖首先氧化为较小的分子,并且在非均相非贵金属催化剂的存在下转化为乙二醇和丙二醇。
Avantium Chemicals B.V.计划通过MekongTM方法生产生物-MEG,目的是在催化剂存在下和在消除水的情况下,在单阶段方法中用氢气由单糖和二糖生产生物-MEG。
原则上,生物-MEG也可以天然地由除甘蔗或甜菜之外的其他可再生原料产生,例如由淀粉植物如谷类、马铃薯和玉米或由纤维素原料如稻草和木材产生。
优选基于甘蔗或甜菜的乙二醇酯,尤其是糖浆形式的乙二醇酯。
这种植物基乙二醇可从例如India Glycols Ltd获得,也参见http://www.indiaglycols.com/product_groups/monoethylene_glycol.htm。
术语“乙二醇”或单乙二醇理想地理解为意指通式(I)的1,2-单乙二醇:
HOCH2CH2OH (I)
然而,实际上,化学产生的化合物包含不同浓度的副产物。就本发明而言,优选基于乙二醇酯,其具有99.7%至99.9%的纯度,也就是说99.7%至99.9%的单乙二醇。特别优选的是那些乙二醇,其包括至多0.06重量%的水和ppm范围内的残余催化剂量。
本发明的酯优选直接由脂肪酸和植物基乙二醇制备。这里优选存在催化剂,优选草酸锡,其量为基于混合物的0.01-0.5重量%。高温(优选高于脂肪酸的熔融温度)是有利的。
就本发明而言,酯优选是乙二醇的单酯和二酯的混合物,优选是如下的混合物:
0.5-10重量%,优选3-10重量%的乙二醇单酯,和
90-99.5重量%,优选90-97重量%的乙二醇二酯。
这种酯混合物可通过摩尔比为0.9:2-1.5:2,特别是1:2-1.1:2的乙二醇:羧酸或脂肪酸获得。
合适的羧酸或脂肪酸的实例包括具有6-22个碳原子,优选具有12-22个碳原子的脂肪酸,例如己酸、辛酸、癸酸、月桂酸、肉豆蔻酸、棕榈酸、棕榈油酸、硬脂酸、异硬脂酸、羟基硬脂酸、油酸、反油酸、岩芹酸、亚油酸、亚麻酸、桐酸、花生酸、鳕油酸、山酸和芥酸,及其工业级混合物。
特别合适的酯是乙二醇与具有6-22个碳原子,优选具有12-22个碳原子的脂肪酸的单酯和二酯,特别是乙二醇与由如下物质组成的脂肪酸混合物的酯:
40-100重量%的硬脂酸,和
0-60重量%的棕榈酸,和
0-20重量%的月桂酸和/或肉豆蔻酸。
根据一个实施方案,本发明涉及乙二醇与由如下物质组成的脂肪酸混合物的酯:
85-100重量%的硬脂酸,和
0-15重量%的棕榈酸,和
0-15重量%的月桂酸和/或肉豆蔻酸,所述重量%加起来为100。
这些酯适合作为不透明剂和用于产生白度,优选以它们在化妆品组合物中的分散体形式。
根据第二实施方案,本发明涉及乙二醇与由如下物质组成的脂肪酸混合物的酯:
40-60重量%的硬脂酸,和
40-60重量%的棕榈酸,和
0-20重量%的月桂酸和/或肉豆蔻酸,所述重量%加起来为100。
在该第二实施方案中,优选的是由如下物质组成的脂肪酸混合物的那些:
40-60重量%的硬脂酸,和
40-60重量%的棕榈酸,所述重量%加起来为100。
这种脂肪酸混合物可市购,例如以商品名Edenor 从马来西亚KLK Oleo市购。
由其衍生的酯适于产生珠光,优选以其在化妆品组合物中的分散体形式。
就本发明而言,优选由3-10重量%的乙二醇与脂肪酸或由40-60重量%的硬脂酸和40-60重量%的棕榈酸组成的脂肪酸混合物的单酯和90-97重量%的二酯组成的酯。
优选的乙二醇酯具有以下特征:
根据DIN 53402的酸值AN为5.5-7,尤其是6-6.5;
根据DIN 53240的羟值OHN为5-7,尤其是5.5-6.5;
根据DIN 53401的皂化值SN为185-210,尤其是195-200。
在本发明的范围内,所述的酯是蜡状的。在本申请中,术语“蜡”或“蜡状”应理解为是指在室温下为固体的化合物,通常可捏合并且熔融而不分解。就本发明而言,熔点根据ISO 6321在Kofler热台上测量,优选高于40℃,优选低于75℃,尤其是在45℃和65℃之间。
本发明进一步提供蜡分散体,其包含根据权利要求1-6中至少一项的酯,优选以15-30重量%的量,优选以20-30重量%的量,基于蜡分散体计。
本发明的蜡分散体优选另外包含表面活性剂和任选地防腐剂。
根据一个实施方案,蜡分散体包含:
a)15-30重量%的作为蜡的乙二醇酯,和
b)10-30重量%的表面活性剂,优选不含氧化烯的表面活性剂
c)任选地0.01-1.0重量%的防腐剂。
表面活性剂
表面活性物质(表面活性剂)可包括阴离子、非离子、两性或两性离子表面活性剂,其在蜡分散体中的比例通常为约10-30重量%。
阴离子表面活性剂的典型实例为皂、烷基苯磺酸盐、烷烃磺酸盐、烯烃磺酸盐、烷基醚磺酸盐、甘油醚磺酸盐、α-甲基酯磺酸盐、磺基脂肪酸、烷基硫酸盐、烷基醚硫酸盐、甘油醚硫酸盐、脂肪酸醚硫酸盐、羟基混合醚硫酸盐、甘油单酯(醚)硫酸盐、脂肪酸酰胺(醚)硫酸盐、单和二烷基磺基琥珀酸盐、单和二烷基磺基琥珀酰胺酸盐、磺基甘油三酯、酰胺皂、醚羧酸及其盐、烷(烯)基聚乙二醇醚柠檬酸化物及其盐、脂肪酸羟乙基磺酸盐、脂肪酸肌氨酸盐、脂肪酸牛磺酸盐、N-酰基氨基酸如酰基乳酸盐、酰基酒石酸盐、酰基谷氨酸盐和酰基天冬氨酸盐,烷基低聚葡糖苷硫酸盐、蛋白质脂肪酸缩合物(尤其是基于小麦的植物产品)和烷基(醚)磷酸盐。如果阴离子表面活性剂包含聚乙二醇醚链,则这些可具有常规的同系物分布,但优选具有窄同系物分布。特别合适的温和的,即特别对皮肤友好的表面活性剂的典型实例是脂肪醇聚乙二醇醚硫酸盐,例如平均乙氧基化度为1或2的月桂基醚硫酸盐,其例如可以商品名N70获得,甘油单酯硫酸盐,单和/或二烷基磺基琥珀酸盐,脂肪酸羟乙基磺酸盐,脂肪酸肌氨酸盐,脂肪酸牛磺酸盐,脂肪酸谷氨酸盐,α-烯烃磺酸盐,醚羧酸,脂肪酸葡糖酰胺和/或蛋白质-脂肪酸缩合物。
阳离子表面活性剂的典型实例为季铵化合物,例如二甲基二硬脂基氯化铵。优选铵卤化物,尤其是氯化物和溴化物,例如烷基三甲基氯化铵、二烷基二甲基氯化铵和三烷基甲基氯化铵,例如鲸蜡基三甲基氯化铵、硬脂基三甲基氯化铵、二硬脂基二甲基氯化铵、月桂基二甲基氯化铵、月桂基二甲基苄基氯化铵和三鲸蜡基甲基氯化铵。此外,可使用可非常容易生物降解的季酯化合物作为阳离子表面活性剂,例如以商品名和相应的系列产品销售的二烷基铵硫酸二甲酯和甲基羟基烷基二烷氧基氧基烷基铵硫酸二甲酯。术语“酯季化物”通常应理解为意指季化的脂肪酸三乙醇胺酯盐。特别优选的阳离子表面活性剂包括已知为/>L80、/>F 75、/>A-CA的产品。
合适的两性或两性离子表面活性剂是烷基甜菜碱、烷基酰胺基甜菜碱、氨基丙酸盐、氨基甘氨酸盐、咪唑啉甜菜碱和磺基甜菜碱。合适烷基甜菜碱的实例是仲胺,尤其是叔胺的羧烷基化产物。典型实例为如下物质的羧甲基化产物:己基甲胺、己基二甲胺、辛基二甲胺、癸基二甲胺、十二烷基甲胺、十二烷基二甲胺、十二烷基乙基甲胺、C12/14椰油烷基二甲胺、肉豆蔻基二甲胺、鲸蜡基二甲胺、硬脂基二甲胺、硬脂基乙基甲胺、油基二甲胺、C16/18牛油烷基二甲胺及其工业级混合物。此外,还有用的是酰胺基胺的羧烷基化产物。典型实例为具有6-22个碳原子的脂肪酸,即己酸、辛酸、癸酸、月桂酸、肉豆寇酸、棕榈酸、棕榈油酸、硬脂酸、异硬脂酸、油酸、反式十八烯酸、岩芹酸、亚油酸、亚麻酸、桐酸、花生酸、顺-9-二十碳烯酸、山酸和芥酸及其工业级混合物与N,N-二甲氨基乙胺、N,N-二甲氨基丙胺、N,N-二乙氨基乙胺和N,N-二乙氨基丙胺的反应产物,其与氯乙酸钠缩合。非常特别优选已知为椰油酰胺基丙基甜菜碱的物质,其可以商品名/>PK 45市购。
此外,还合适的是咪唑啉甜菜碱。这些物质也是已知物质,其例如可通过使1或2摩尔脂肪酸与多官能胺,例如氨基乙基乙醇胺(AEEA)或二亚乙基三胺环化缩合而获得。相应的羧烷基化产物为不同开链甜菜碱类的混合物。典型实例为上述脂肪酸与AEEA的缩合产物,优选基于月桂酸的咪唑啉类,或再次C12/14椰油脂肪酸,其随后用氯乙酸钠甜菜碱化。
非离子表面活性剂的典型实例为脂肪醇聚乙二醇醚、烷基酚聚乙二醇醚、脂肪酸聚乙二醇酯、脂肪酸酰胺聚乙二醇醚、脂肪胺聚乙二醇醚、烷氧基化甘油三酯、混合醚和混合缩甲醛、烷基(链烯基)低聚葡糖苷、部分氧化的烷基(链烯基)低聚葡糖苷和葡糖醛酸衍生物、脂肪酸N-烷基葡糖酰胺、多元醇脂肪酸酯、糖酯、脱水山梨糖醇酯、聚山梨醇酯和氧化胺。如果非离子表面活性剂包含聚乙二醇醚链,则它们可具有常规的同系物分布,但优选具有窄同系物分布。合适的非离子表面活性剂的实例是乙氧基化脂肪醇,例如用4mol氧化乙烯乙氧基化的脂肪醇或具有C12/C14比例的乙氧基化脂肪醇混合物,例如可市购的LS4。
在非离子表面活性剂中,尤其是就温和制备而言,优选式(II)的烷基和/或链烯基低聚葡糖苷:
RO-[G]p (II)
其中R为具有4-22个碳原子的烷基和/或链烯基,G为具有5或6个碳原子的糖基,p为1-10的数。它们可以通过制备有机化学的相关方法得到。烷基和/或链烯基低聚葡糖苷可由具有5或6个碳原子的醛糖或酮糖衍生,优选由葡萄糖衍生。因此,优选的烷基和/或链烯基低聚葡糖苷是烷基和/或链烯基低聚葡糖苷。指数p规定低聚度(DP),即单-和低聚葡糖苷的分布,是1-10的数。而给定化合物中的p必须总是整数,在这里可以特别假定p值=1-6,就特定烷基低聚葡糖苷而言的p值是分析确定的计算参数,在大多数情况下是分数。优选使用平均低聚度p为1.1-3.0的烷基和/或链烯基低聚葡糖苷。从技术应用的角度来看,优选低聚度小于1.7,尤其是1.2-1.4的那些烷基和/或链烯基低聚葡糖苷。
烷基或链烯基R可衍生自具有4-11个,优选8-10个碳原子的伯醇。典型实例为丁醇、己醇、辛醇、癸醇和十一烷醇及其工业级混合物,如例如在工业级脂肪酸甲酯的氢化中或者在获自Roelen羰基合成法的醛氢化过程中获得。优选具有C8-C10链长的烷基低聚葡糖苷(DP=1-3),其在工业级C8-C18椰油脂肪酸的蒸馏分离中作为初馏物获得且可被如下馏分污染:小于6重量%C12醇,以及基于工业级C9/11羰基合成醇的烷基低聚葡糖苷(DP=1-3)。烷基或链烯基R也可进一步衍生自具有12-22个,优选12-14个碳原子的伯醇。典型实例为月桂醇、肉豆寇醇、鲸蜡醇、棕榈油醇、硬脂醇、异硬脂醇、油醇、反式十八烯醇、岩芹醇、花生醇、顺-9-二十碳烯醇(gadoleyl alcohol)、山醇、瓢儿菜醇、巴西基醇(brassidyl alcohol)及其工业级混合物,其可如上所述获得。优选基于氢化C12/14椰油醇且具有1-3的DP的烷基低聚葡糖苷。
特别优选的非离子表面活性剂包括包含基于活性物质计1.5:1-2.5:1的重量比的C12烷基葡糖苷和C8-10烷基葡糖苷的烷基聚葡糖苷的混合物。
特别优选地,存在于蜡分散体中的表面活性剂是非离子表面活性剂,并且蜡分散体优选包含:
a)15-30重量%的作为蜡的乙二醇酯,和
b)10-30重量%的非离子表面活性剂,优选选自烷基和/或亚烷基聚葡糖苷,和
c)任选地0.01-0.5重量%的防腐剂。
当蜡分散体包含如下物质时,可获得优异的白色混浊/珠光:
a)15-30重量%的作为蜡的乙二醇酯,由a1)3-10重量%的乙二醇单酯,和2)90-97重量%的乙二醇二酯组成,和
b)10-30重量%的非离子表面活性剂,选自烷基和/或亚烷基聚葡糖苷,和
c)任选地0.01-0.5重量%的防腐剂。
在该组中,有利的是包含如下物质的蜡分散体:
a)15-30重量%的作为蜡的乙二醇酯,由3-10重量%的乙二醇与由40-60重量%的硬脂酸和40-60重量%的棕榈酸组成的脂肪酸混合物的单酯和90-97重量%的二酯组成,和
b)10-30重量%的非离子表面活性剂,选自烷基和/或亚烷基聚葡糖苷,和
c)任选地0.01-0.5重量%的防腐剂,
特别是包含如下物质的蜡分散体:
a)15-30重量%的作为蜡的乙二醇酯,由3-10重量%的乙二醇与由40-60重量%的硬脂酸和40-60重量%的棕榈酸组成的脂肪酸混合物的单酯和90-97重量%的二酯组成,和
b)10-30重量%的烷基聚葡糖苷混合物,由基于活性物质计1.5:1-2.5:1重量比的C12烷基葡糖苷和C8-10烷基葡糖苷组成,和
c)任选地0.01-0.5重量%的防腐剂。
可以存在的合适防腐剂的实例是柠檬酸和苯甲酸和/或其盐、苯氧基乙醇、甲醛溶液、对羟基苯甲酸酯、戊二醇、山梨酸、乙酰丙酸和花生四烯酸,以及以名称已知的银络合物,和在化妆品规范的附录6,A和B部分中列出的另外的物质种类。柠檬酸和苯甲酸和/或其盐,例如Na盐是特别合适的。
本发明的蜡分散体总是包含水,加至100重量%。
在本发明的上下文中,蜡分散体包含最小量的,优选0-10重量%的石化化合物,尤其是不含石化化合物,基于蜡分散体计。因此,蜡分散体的优选活性成分应尽可能完全基于可再生原料,优选基于蜡分散体计90-100重量%,尤其是完全基于可再生原料。
本发明进一步提供了根据权利要求1-6中至少一项的本发明的酯作为蜡,优选以根据权利要求7-13中任一项的本发明的分散体的形式,用于在含水介质中产生混浊或珠光,优选用于在用于清洁皮肤和/或头发的化妆品组合物中产生混浊或珠光的用途。
根据本发明的蜡优选以根据权利要求7-13中任一项的本发明的蜡分散体的形式使用。
化妆品组合物
本发明进一步提供了用于皮肤和头发的化妆品清洁剂,其包含根据权利要求1的乙二醇酯作为珠光剂或不透明剂。
用于清洁头发的化妆品组合物应理解为意指洗去型组合物。用于清洁头发的化妆品组合物应理解为所有旨在单独清洁头发的化妆品头发处理组合物,以及旨在护理、干燥、改变头发颜色或改变头发结构并包括清洁步骤的那些。例如,这旨在包括洗发剂、头发调理剂、调理洗发剂、头发漂洗剂、头发处理剂、头发发膜、生发油、烫发定型溶液、头发着色洗发剂、头发着色剂或它们的组合。
用于清洁皮肤的化妆品组合物应理解为去除皮肤表面的污垢和油脂并且任选地为皮肤提供护理的组合物,例如淋浴凝胶、淋浴浴液、淋浴油、泡沫浴、液体洗手皂、私密洗液、面部清洁洗液。
取决于预期用途,这些制剂包含一系列其他助剂和添加剂,例如其他表面活性剂、油体、乳化剂、助表面活性剂、(阳离子)聚合物、基础剂、增稠剂、富脂剂、稳定剂、硅氧烷化合物、脂肪、蜡、卵磷脂、磷脂、UV光保护因子、生物源活性成分、抗氧化剂、去头屑剂、成膜剂、溶胀剂、酪氨酸抑制剂(脱色剂)、水溶助长剂、加溶剂、防腐剂、香料油、染料等。
在本发明的化妆品组合物中,蜡有利地以分散体的形式存在,优选以0.1-5.0,优选0.2-2.5重量%,尤其是0.3-2.0重量%的量存在,基于乙二醇酯的含量计。
下文给出了适用于本发明用途和本发明化妆品组合物的其他成分。
表面活性剂
在本发明的上下文中,化妆品组合物可包含阴离子、非离子、阳离子和两性或两性离子表面活性剂。表面活性剂的选择取决于预期的用途。在本申请的上下文中,已经通过与根据本发明的蜡分散体的表面活性剂有关的实例列出了合适的表面活性剂。这些实例也适合作为化妆品组合物的其他表面活性剂。除了本发明的蜡分散体之外,用于调理头发处理的化妆品组合物通常包含阴离子表面活性剂。
阴离子表面活性剂的典型实例为皂、烷基苯磺酸盐、烷烃磺酸盐、烯烃磺酸盐、烷基醚磺酸盐、甘油醚磺酸盐、α-甲基酯磺酸盐、磺基脂肪酸、烷基硫酸盐、烷基醚硫酸盐、甘油醚硫酸盐、脂肪酸醚硫酸盐、羟基混合醚硫酸盐、甘油单酯(醚)硫酸盐、脂肪酸酰胺(醚)硫酸盐、单和二烷基磺基琥珀酸盐、单和二烷基磺基琥珀酰胺酸盐、磺基甘油三酯、酰胺皂、醚羧酸及其盐、烷(烯)基聚乙二醇醚柠檬酸化物及其盐、脂肪酸羟乙基磺酸盐、脂肪酸肌氨酸盐、脂肪酸牛磺酸盐、N-酰基氨基酸如酰基乳酸盐、酰基酒石酸盐、酰基谷氨酸盐和酰基天冬氨酸盐,烷基低聚葡糖苷硫酸盐、蛋白质脂肪酸缩合物(尤其是基于小麦的植物产品)和烷基(醚)磷酸盐。如果阴离子表面活性剂包含聚乙二醇醚链,则这些可具有常规的同系物分布,但优选具有窄同系物分布。所用的阴离子表面活性剂特别优选是已经在本发明的蜡分散体中描述的脂肪醇(醚硫酸盐),尤其是具有1或2mol氧化乙烯的月桂基醚硫酸盐。
除了本发明的蜡分散体和阴离子表面活性剂之外,用于调理头发处理的化妆品组合物优选还包含两性或两性离子表面活性剂。合适的两性或两性离子表面活性剂是烷基甜菜碱、烷基酰胺基甜菜碱、氨基丙酸盐、氨基甘氨酸盐、咪唑啉甜菜碱和磺基甜菜碱。合适烷基甜菜碱的实例是仲胺,尤其是叔胺的羧烷基化产物。典型实例为如下物质的羧甲基化产物:己基甲胺、己基二甲胺、辛基二甲胺、癸基二甲胺、十二烷基甲胺、十二烷基二甲胺、十二烷基乙基甲胺、C12/14椰油烷基二甲胺、肉豆蔻基二甲胺、鲸蜡基二甲胺、硬脂基二甲胺、硬脂基乙基甲胺、油基二甲胺、C16/18牛油烷基二甲胺及其工业级混合物。此外,还有用的是酰胺基胺的羧烷基化产物。典型实例为具有6-22个碳原子的脂肪酸,即己酸、辛酸、癸酸、月桂酸、肉豆寇酸、棕榈酸、棕榈油酸、硬脂酸、异硬脂酸、油酸、反式十八烯酸、岩芹酸、亚油酸、亚麻酸、桐酸、花生酸、顺-9-二十碳烯酸、山酸和芥酸及其工业级混合物与N,N-二甲氨基乙胺、N,N-二甲氨基丙胺、N,N-二乙氨基乙胺和N,N-二乙氨基丙胺的反应产物,其与氯乙酸钠缩合。非常特别优选已知为椰油酰胺基丙基甜菜碱的物质,其可以商品名/>PK 45市购。
油体
有用油体是例如基于具有6-18,优选8-10个碳原子的脂肪醇的格尔伯特醇,直链C6-C22脂肪酸与直链或支化C6-C22脂肪醇的酯或支化C6-C13羧酸与直链或支化C6-C22脂肪醇的酯,例如肉豆蔻酸肉豆蔻酯、棕榈酸肉豆蔻酯、硬脂酸肉豆蔻酯、异硬脂酸肉豆蔻酯、油酸肉豆蔻酯、山酸肉豆蔻酯、芥酸肉豆蔻酯、肉豆蔻酸鲸蜡酯、棕榈酸鲸蜡酯、硬脂酸鲸蜡酯、异硬脂酸鲸蜡酯、油酸鲸蜡酯、山/>酸鲸蜡酯、芥酸鲸蜡酯、肉豆蔻酸硬脂醇酯、棕榈酸硬脂醇酯、硬脂酸硬脂醇酯、异硬脂酸硬脂醇酯、油酸硬脂醇酯、山/>酸硬脂醇酯、芥酸硬脂醇酯、肉豆蔻酸异硬脂醇酯、棕榈酸异硬脂醇酯、硬脂酸异硬脂醇酯、异硬脂酸异硬脂醇酯、油酸异硬脂醇酯、山/>酸异硬脂醇酯、油酸异硬脂醇酯、肉豆蔻酸油醇酯、棕榈酸油醇酯、硬脂酸油醇酯、异硬脂酸油醇酯、油酸油醇酯、山/>酸油醇酯、芥酸油醇酯、肉豆蔻酸山醇酯、棕榈酸山/>醇酯、硬脂酸山/>醇酯、异硬脂酸山/>醇酯、油酸山/>醇酯、山/>酸山/>醇酯、芥酸山/>醇酯、肉豆蔻酸瓢儿菜醇酯、棕榈酸瓢儿菜醇酯、硬脂酸瓢儿菜醇酯、异硬脂酸瓢儿菜醇酯、油酸瓢儿菜醇酯、山/>酸瓢儿菜醇酯、芥酸瓢儿菜醇酯。还合适的为直链C6-C22脂肪酸与支化醇,尤其是2-乙基己醇的酯,C18-C38烷基羟基羧酸与直链或支化C6-C22脂肪醇的酯,尤其是苹果酸二辛酯,直链和/或支化脂肪酸与多元醇(例如丙二醇、二聚体二醇或三聚体三醇)和/或格尔伯特醇的酯,基于C6-C10脂肪酸的甘油三酯,基于C6-C18脂肪酸的液体甘油单/二/三酯混合物,C6-C22脂肪醇和/或格尔伯特醇与芳族羧酸,尤其是苯甲酸的酯,C2-C12二羧酸与具有1-22个碳原子的直链或支化醇或具有2-10个碳原子和2-6个羟基的多元醇的酯,植物油,支化伯醇,取代的环己烷,直链和支化C6-C22脂肪醇碳酸酯,例如碳酸二辛酯(/>CC),基于具有6-18个,优选8-10个碳原子的脂肪醇的格尔伯特碳酸酯,苯甲酸与直链和/或支化C6-C22醇的酯(例如/>TN),每个烷基具有6-22个碳原子的直链或支化的对称或不对称的二烷基醚,例如二辛基醚(/>OE),环氧化脂肪酸酯与多元醇的开环产物,硅油(环状聚二甲基硅氧烷,称为(INCI)环聚甲基硅氧烷,聚甲基硅氧烷类,称为(INCI)聚二甲基硅氧烷,氨基官能聚硅氧烷,称为(INCI)氨基封端聚二甲基硅氧烷(尤其是例如三甲基甲硅烷基氨基封端聚二甲基硅氧烷)和/或脂族或环烷烃,如角鲨烷、角鲨烯或二烷基环己烷。合适的硅油描述于欧洲专利EP1830798第8-14页,在此明确将其作为参考。
乳化剂
合适的乳化剂是例如选自如下组中的至少一种的非离子表面活性剂:
·2-30摩尔氧化乙烯和/或0-5摩尔氧化丙烯在具有8-22个碳原子的线性脂肪醇上、在具有12-22个碳原子的脂肪酸上、在烷基中具有8-15个碳原子的烷基酚以及烷基中具有8-22个碳原子的烷基胺上的加合物;
·1-15摩尔氧化乙烯在蓖麻油和/或氢化蓖麻油上的加合物;
·15-60摩尔氧化乙烯在蓖麻油和/或氢化蓖麻油上的加合物;
·1-30摩尔氧化乙烯在甘油和/或脱水山梨糖醇与具有12-22个碳原子的不饱和的直链或饱和的支化的脂肪酸和/或具有3-18个碳原子的羟基羧酸的偏酯上的加合物;
·聚甘油(平均自缩合度为2-8)、聚乙二醇(分子量400-5000)、脱水山梨糖醇、三羟甲基丙烷、季戊四醇、糖醇如山梨糖醇、烷基葡糖苷(例如甲基葡糖苷、丁基葡糖苷、月桂基葡糖苷)和聚葡糖苷(例如纤维素)与具有12-22个碳原子的饱和和/或不饱和的直链或支化脂肪酸和/或具有3-18个碳原子的羟基羧酸的偏酯,及其与1-30摩尔氧化乙烯的加合物;
·季戊四醇、脂肪酸、柠檬酸和脂肪醇的混合酯和/或具有6-22个碳原子的脂肪酸,甲基葡萄糖和多元醇,优选甘油或聚甘油的混合酯;
·磷酸单-、二-和三烷基酯以及磷酸单-、二-和/或三-PEG-烷基酯及其盐;
·羊毛蜡醇;
·聚硅氧烷-聚烷基-聚醚共聚物和相应衍生物;
·嵌段共聚物,例如二聚羟基硬脂酸聚乙二醇30酯;
·聚合物乳化剂,例如来自Goodrich的Pemulen型(TR-1、TR-2);
·聚亚烷基二醇;和
·甘油碳酸酯。
特别优选的乳化剂是氧化乙烯在C12/18脂肪酸单-和二酯上的加合物,1-30摩尔,优选5-10摩尔氧化乙烯在羟基硬脂酸单甘油酯、羟基硬脂酸二甘油酯、异硬脂酸单甘油酯、异硬脂酸二甘油酯、油酸单甘油酯、油酸二甘油酯、蓖麻油酸单甘油酯、蓖麻油酸二甘油酯、亚油酸单甘油酯、亚油酸二甘油酯、亚麻酸单甘油酯、亚麻酸二甘油酯、芥酸单甘油酯、芥酸二甘油酯、酒石酸单甘油酯、酒石酸二甘油酯、柠檬酸单甘油酯、柠檬酸二甘油酯、苹果酸单甘油酯、苹果酸二甘油酯及其工业级混合物上的加合物。1-30摩尔,优选5-10摩尔氧化乙烯在脱水山梨糖醇酯上的加合物同样是合适的。有用的脱水山梨糖醇酯包括脱水山梨糖醇单异硬脂酸酯、脱水山梨糖醇倍半异硬脂酸酯、脱水山梨糖醇二异硬脂酸酯、脱水山梨糖醇三异硬脂酸酯、脱水山梨糖醇单油酸酯、脱水山梨糖醇倍半油酸酯、脱水山梨糖醇二油酸酯、脱水山梨糖醇三油酸酯、脱水山梨糖醇单芥酸酯、脱水山梨糖醇倍半芥酸酯、脱水山梨糖醇二芥酸酯、脱水山梨糖醇三芥酸酯、脱水山梨糖醇单蓖麻油酸酯、脱水山梨糖醇倍半蓖麻油酸酯、脱水山梨糖醇二蓖麻油酸酯、脱水山梨糖醇三蓖麻油酸酯、脱水山梨糖醇单羟基硬脂酸酯、脱水山梨糖醇倍半羟基硬脂酸酯、脱水山梨糖醇二羟基硬脂酸酯、脱水山梨糖醇三羟基硬脂酸酯、脱水山梨糖醇单酒石酸酯、脱水山梨糖醇倍半酒石酸酯、脱水山梨糖醇二酒石酸酯、脱水山梨糖醇三酒石酸酯、脱水山梨糖醇单柠檬酸酯、脱水山梨糖醇倍半柠檬酸酯、脱水山梨糖醇二柠檬酸酯、脱水山梨糖醇三柠檬酸酯、脱水山梨糖醇单马来酸酯、脱水山梨糖醇倍半马来酸酯、脱水山梨糖醇二马来酸酯、脱水山梨糖醇三马来酸酯及其工业级混合物。合适的聚甘油酯的典型实例是聚甘油-2二聚羟基硬脂酸酯(PGPH)、聚甘油-3二异硬脂酸酯(/>TGI)、聚甘油-4异硬脂酸酯(/>GI 34)、聚甘油-3油酸酯、二异硬脂酰基聚甘油-3二异硬脂酸酯(/>PDI)、聚甘油-3甲基葡萄糖二硬脂酸酯(Tego/>450)、聚甘油-3蜂蜡(Cera/>)、聚甘油-4癸酸酯(Polyglycerol CaprateT2010/90)、聚甘油-3鲸蜡基醚(/>NL)、聚甘油-3二硬脂酸酯/>GS 32)和聚甘油聚蓖麻醇酸酯(/>WOL 1403)、聚甘油二聚酸酯二异硬脂酸酯及其混合物。其他合适的多元醇酯的实例是(任选地与1-30摩尔氧化乙烯反应的)三羟甲基丙烷或季戊四醇与月桂酸、椰油脂肪酸、牛油脂肪酸、棕榈酸、硬脂酸、油酸、山/>酸等的单-、二-和三酯。还优选三甲基丙烷EO/PO三油酸酯,可通过三羟甲基丙烷三油酸酯与氧化乙烯和氧化丙烯在碱性条件下反应而获得的混合物。这里,氧化乙烯单元(EO)和氧化丙烯单元(PO)至少部分引入三羟甲基丙烷三油酸酯的酯基中。三甲基丙烷EO/PO三油酸酯的特征在于其每分子的EO和PO单元含量的统计平均值。在本发明的一个实施方案中,使用具有120个氧化乙烯单元(EO)和10个氧化丙烯单元(PO)的三甲基丙烷EO/PO三油酸酯。
偏甘油酯是甘油与直链、饱和和/或部分不饱和脂肪酸的单酯和/或二甘油酯,所述脂肪酸例如为己酸、辛酸、癸酸、月桂酸、肉豆蔻酸、棕榈酸、棕榈油酸、牛油脂肪酸、硬脂酸、山酸及其工业级混合物。它们具有式(III):/>
其中R5CO为具有6-22个碳原子的酰基,优选具有6-22个碳原子的直链饱和酰基,R6和R7各自独立地为氢或R5CO,x、y和z总计为0或1-30的数,X为碱金属或碱土金属,条件是两个基团R6和R7中的至少一个为氢。典型实例为月桂酸甘油单酯、月桂酸甘油二酯、椰子脂肪酸甘油单酯、椰子脂肪酸甘油三酯、棕榈酸甘油单酯、棕榈酸甘油三酯、硬脂酸甘油单酯、硬脂酸甘油二酯、牛油脂肪酸甘油单酯、牛油脂肪酸甘油二酯、山酸甘油单酯、山/>酸甘油二酯及其工业级混合物,其仍可包含来自制备工艺的少量甘油三酯。
还适合作为优选组的蜡体为任选被羟基取代的多元羧酸与具有6-22个碳原子的脂肪醇的酯。这些酯的合适酸组分例如为丙二酸、马来酸、富马酸、己二酸、癸二酸、壬二酸、十二烷二酸、邻苯二甲酸、间苯二甲酸,特别是琥珀酸,还有苹果酸、柠檬酸,特别是酒石酸及其混合物。脂肪醇在烷基链中包含6-22个,优选12-18个,尤其是16-18个碳原子。典型实例为己醇、辛醇、2-乙基己醇、癸醇、月桂醇、异十三烷醇、肉豆蔻醇、十六醇、棕榈醇、硬脂醇、异硬脂醇、油醇、反十八烯醇、岩芹醇、亚油醇、亚麻醇、桐醇(elaeostearyl alcohol)、花生醇、顺-9-二十碳烯醇、山醇,瓢儿菜醇和巴西基醇及其工业级混合物。所述酯可以以全酯或偏酯的形式存在,优选使用羧酸或羟基羧酸的单酯,尤其是二甘油酯。典型实例为琥珀酸单和二月桂基酯,琥珀酸单和二(鲸蜡硬脂烷基)酯,琥珀酸单和二硬脂基酯,酒石酸单和二月桂基酯,酒石酸单和二椰油烷基酯,酒石酸单和二(鲸蜡硬脂烷基)酯,柠檬酸单-、二-和三月桂基酯,柠檬酸单-、二-和三-三椰油烷基酯和柠檬酸单-、二-和三(鲸蜡硬脂烷基)酯。
作为第三组优选的蜡体,可使用具有式(IV)的脂肪醇:
R8OH (IV)
其中R8为具有16-48个,优选18-36个碳原子的任选被羟基取代的直链烷基和/或酰基。合适醇的典型实例为鲸蜡硬脂醇、羟基硬脂醇、山醇和长链石蜡的氧化产物。
适合作为组分的脂肪酮优选具有式(V):
R9-CO-R10 (V)
其中R9和R10各自独立地为具有1-22个碳原子的烷基和/或链烯基,条件是它们总共具有至少24个,优选32-48个碳原子。所述酮可通过现有技术的方法制备,例如通过热解相应的脂肪酸镁盐。所述酮在结构上可为对称的或非对称的;然而,优选两个基团R13和R14仅相差一个碳原子,并且衍生自具有16-22个碳原子的脂肪酸。
适合作为蜡体的脂肪醛优选对应于式(VI):
R11COH (VI)
其中R11CO为具有24-48个,优选28-32个碳原子的直链或支化酰基。
同样合适的为脂肪醚,优选具有式(VII):
R12-O-R13 (VII)
其中R12和R13各自独立地为具有1-22个碳原子的烷基和/或链烯基,条件是它们总共具有至少24个,优选32-48个碳原子。所述类型的脂肪醚通常通过相应脂肪醇的酸缩合而制备。具有特别有利的珠光性质的脂肪醚通过具有16-22个碳原子的脂肪醇如十六醇、鲸蜡硬脂醇、硬脂醇、异硬脂醇、油醇、山醇和/或瓢儿菜醇的缩合获得。
作为组分还合适的为脂肪族碳酸酯,优选具有式(VIII):
R14O-CO-OR15 (VIII)
其中R14和R15各自独立地为具有1-22个碳原子的烷基和/或链烯基,条件是它们总共具有至少24个,优选32-48个碳原子。所述物质以本身已知的方式通过酯交换,例如碳酸二甲酯或碳酸二乙酯与相应脂肪醇酯交换而获得。因此,脂肪族碳酸酯在结构上可为对称的或非对称的。然而,优选使用其中R14和R15相同且为具有16-22个碳原子的烷基的碳酸酯。特别优选碳酸二甲酯或碳酸二乙酯与十六醇、鲸蜡硬脂醇、硬脂醇、异硬脂醇、油醇、山醇和/或瓢儿菜醇的呈其单酯和二甘油酯形式的酯交换产物,或其工业级混合物。
环氧化物开环产物是已知的物质,其通常通过端或内烯烃环氧化物与脂族醇的酸催化反应而制备。所述反应产物优选具有式(IX):
其中R16和R17为氢或具有10-20个碳原子的烷基,条件是R16和R17的碳原子总和为10-20,R18为具有12-22个碳原子的烷基和/或链烯基,和/或为具有2-15个碳原子和2-10个羟基的多元醇的基团。典型实例为环氧α-十二碳烯、环氧α-十六碳烯、环氧α-十八碳烯、环氧α-二十碳烯、环氧α-二十二碳烯、环氧异十二碳烯、环氧异十六碳烯、环氧异十八碳烯、环氧异二十碳烯和/或环氧异二十二碳烯与月桂醇、椰油脂肪醇、肉豆蔻醇、十六醇、鲸蜡硬脂醇、硬脂醇、异硬脂醇、油醇、反十八烯醇、岩芹醇、亚油醇、亚麻醇、山醇和/或瓢儿菜醇的开环产物。优选使用环氧十六碳烯和/或环氧十八碳烯与具有16-18个碳原子的脂肪醇的开环产物。如果使用多元醇代替脂肪醇进行开环,则它们例如为以下物质:甘油;亚烷基二醇,例如乙二醇、二甘醇、丙二醇、丁二醇、己二醇和平均分子量为100-1000道尔顿的聚乙二醇;自缩合度为1.5-10的工业级低聚甘油混合物,例如双甘油含量为40-50重量%的工业级双甘油混合物;羟甲基化合物,例如特别是三羟甲基乙烷、三羟甲基丙烷、三羟甲基丁烷、季戊四醇和二季戊四醇;低级烷基葡糖苷,特别是烷基中具有1-8个碳原子的那些,例如甲基葡糖苷和丁基葡糖苷;具有5-12个碳原子的糖醇,例如山梨糖醇或甘露糖醇;具有5-12个碳原子的糖,例如葡萄糖或蔗糖;氨基糖,例如葡糖胺。
基础剂和增稠剂
合适的基础剂主要是具有12-22个碳原子,优选16-18个碳原子的脂肪醇或羟基脂肪醇,还有偏甘油酯、脂肪酸或羟基脂肪酸。这些物质与烷基低聚葡糖苷和/或相同链长的脂肪酸N-甲基葡糖酰胺和/或聚甘油聚-12-羟基硬脂酸酯的组合是优选的。合适的增稠剂是例如Aerosil型(亲水性二氧化硅),多糖,尤其是黄原胶、瓜尔胶、琼脂、海藻酸盐和纤维乙酸钠、羧甲基纤维素、羟乙基纤维素和羟丙基纤维素,此外还有脂肪酸的较高分子量聚乙二醇单酯和二酯,聚丙烯酸酯(例如来自Goodrich的和Pemulen型;来自Sigma的/>来自Kelco的Keltrol型;来自Seppic的Sepigel型;来自AlliedColloids的Salcare型),聚丙烯酰胺,聚合物,聚乙烯醇和聚乙烯基吡咯烷酮。也已证实特别有效的物质是膨润土,例如/>Gel VS-5PC(Rheox),它是环戊硅氧烷、二硬脂基二甲铵水辉石(Disteardimonium Hectorite)和碳酸亚丙酯的混合物。表面活性剂,例如乙氧基化脂肪酸甘油酯、脂肪酸与多元醇如季戊四醇或三羟甲基丙烷的酯、具有窄同系物分布的脂肪醇乙氧基化物或烷基低聚葡糖苷和电解质如氯化钠和氯化铵也是有用的。
富脂剂
可以使用的富脂剂的实例包括如下物质:例如羊毛脂和卵磷脂以及聚乙氧基化或酰化羊毛脂和卵磷脂衍生物,多元醇脂肪酸酯,甘油单酯和脂肪酸链烷醇酰胺,后者同时用作泡沫稳定剂。
稳定剂
使用的稳定剂可以是脂肪酸的金属盐,例如硬脂酸或蓖麻酸镁、硬脂酸或蓖麻酸铝和/或硬脂酸或蓖麻酸锌。
(阳离子)聚合物
除了本发明的蜡分散体、阴离子表面活性剂和任选地两性或两性离子表面活性剂之外,用于调理头发处理的化妆品组合物优选还包含阳离子聚合物。合适的阳离子聚合物优选为如下那些:来自阳离子改性纤维素衍生物,PQ 10,PQ 67,阳离子改性瓜尔胶衍生物,例如Guar N,瓜尔胶羟丙基三甲基氯化铵,基于丙烯酰胺的阳离子均聚物或共聚物,基于乙烯基吡咯烷酮的阳离子均聚物或共聚物,基于季铵化乙烯基咪唑的阳离子均聚物或共聚物以及基于甲基丙烯酸酯的阳离子均聚物或共聚物。
合适的阳离子聚合物是例如季铵化的羟乙基纤维素(也可由Amerchol以名称Polymer获得),阳离子淀粉,二烯丙基铵盐和丙烯酰胺的共聚物,季铵化的乙烯基吡咯烷酮/乙烯基咪唑聚合物如/>(BASF),聚二醇和胺的缩合产物,季铵化的蛋白质水解物,多肽和氨基酸,如月桂基二甲基铵羟丙基水解胶原(/>L/Grünau),季铵化的小麦多肽,聚乙烯亚胺,阳离子聚硅氧烷聚合物如氨基封端的聚二甲基硅氧烷,己二酸和二甲基氨基羟丙基二亚乙基三胺的共聚物/>丙烯酸与二甲基二烯丙基氯化铵的共聚物(/>550/Chemviron),聚氨基聚酰胺(例如如FR-A2252840中所述)及其交联的水溶性聚合物,阳离子甲壳质衍生物如季铵化的壳聚糖,任选以微晶分布,二卤代烷烃(如二溴丁烷)与双二烷基胺(如双二甲基氨基-1,3-丙烷)的缩合产物,阳离子瓜尔胶如来自Celanese的/>CBS、/>C-17、/>C-16,季铵化的铵盐聚合物如来自Miranol的/>A-15、/>AD-1、/>AZ-1。尤其合适的阳离子聚合物为聚季铵盐(polyquaternium)-68,可作为/>Supreme AT 1获得,或聚季铵盐-11,可作为/>PQ 11 AT 1获得。
有用的阴离子、两性离子、两性和非离子聚合物是例如乙酸乙烯酯/巴豆酸共聚物,乙烯基吡咯烷酮/丙烯酸乙烯酯共聚物,乙酸乙烯酯/马来酸丁酯/丙烯酸异冰片酯共聚物,甲基乙烯基醚/马来酸酐共聚物及其酯,未交联和多元醇交联的聚丙烯酸,丙烯酰胺基丙基三甲基氯化铵/丙烯酸酯共聚物,辛基丙烯酰胺/甲基丙烯酸甲酯/甲基丙烯酸叔丁基氨基乙酯/甲基丙烯酸2-羟丙酯共聚物,聚乙烯基吡咯烷酮,乙烯基吡咯烷酮/乙酸乙烯酯共聚物,乙烯基吡咯烷酮/甲基丙烯酸二甲氨基乙酯/乙烯基己内酰胺三元共聚物和任选地衍生化纤维素醚和聚硅氧烷。
聚硅氧烷化合物
合适的聚硅氧烷化合物是例如二甲基聚硅氧烷,甲基苯基聚硅氧烷,环状聚硅氧烷和氨基、脂肪酸、醇、聚醚、环氧、氟、糖苷和/或烷基改性的聚硅氧烷化合物,其可以在室温下为液体或呈树脂形式。还合适的是水合硅石聚二甲基硅氧烷,其为具有平均链长200-300个二甲基硅氧烷单元的聚二甲基硅氧烷和氢化硅酸盐的混合物。
UV光保护过滤剂
UV光保护因子应理解为意指例如如下有机物质(光保护过滤剂):在室温下为液体或晶体,且能够吸收紫外线并以较长波长的辐射形式再释放所吸收的能量,例如热。UVB过滤剂可以是油溶性的或水溶性的。油溶性物质的实例是:
·所述的3-亚苄基樟脑或3-亚苄基降樟脑及其衍生物,例如3-(4-甲基亚苄基)樟脑;
·4-氨基苯甲酸衍生物,优选4-(二甲基氨基)苯甲酸2-乙基己基酯,4-(二甲基氨基)苯甲酸2-辛基酯和4-(二甲基氨基)苯甲酸戊酯;
·肉桂酸酯,优选4-甲氧基肉桂酸2-乙基己酯,4-甲氧基肉桂酸丙酯,4-甲氧基肉桂酸异戊酯,2-氰基-3,3-苯基肉桂酸2-乙基己酯(氰双苯丙烯酸辛酯);
·水杨酸酯,优选水杨酸2-乙基己酯,水杨酸4-异丙基苄酯,水杨酸高薄荷酯;
·二苯甲酮的衍生物,优选2-羟基-4-甲氧基二苯甲酮,2-羟基-4-甲氧基-4′-甲基二苯甲酮,2,2′-二羟基-4-甲氧基二苯甲酮;
·亚苄基丙二酸的酯,优选4-甲氧基亚苄基丙二酸二-2-乙基己酯;
·三嗪衍生物,例如2,4,6-三苯胺基-(对-羰基-2′-乙基-1′-己氧基)-1,3,5-三嗪和辛基三嗪酮(octyltriazone)或二辛基丁酰胺基三嗪酮(HEB);
·丙烷-1,3-二酮,例如1-(4-叔丁基苯基)-3-(4′-甲氧基苯基)丙烷-1,3-二酮;
·酮三环(5.2.1.0)癸烷衍生物。
合适的水溶性物质为:
·2-苯基苯并咪唑-5-磺酸及其碱金属、碱土金属、铵、烷基铵、链烷醇铵和葡糖铵盐;
·二苯甲酮的磺酸衍生物,优选2-羟基-4-甲氧基二苯甲酮-5-磺酸及其盐;
·3-亚苄基樟脑的磺酸衍生物,例如4-(2-氧代-3-亚冰片基-甲基)苯磺酸和2-甲基-5-(2-氧代-3-亚冰片基)磺酸及其盐。
合适的典型UVA过滤剂尤其是苯甲酰基甲烷的衍生物如1-(4′-叔丁基苯基)-3-(4′-甲氧基苯基)丙烷-1,3-二酮、4-叔丁基-4′-甲氧基二苯甲酰基甲烷(1789)、1-苯基-3-(4′-异丙基苯基)丙烷-1,3-二酮和烯胺化合物。UVA和UVB过滤剂当然也可以混合物形式使用。特别有利的组合由苯甲酰基甲烷的衍生物如4-叔丁基-4′-甲氧基二苯甲酰基甲烷(/>1789)和2-氰基-3,3-苯基肉桂酸2-乙基己酯(氰双苯丙烯酸辛酯)与肉桂酸酯(优选4-甲氧基肉桂酸2-乙基己酯和/或4-甲氧基肉桂酸丙酯和/或4-甲氧基肉桂酸异戊酯)的组合组成。该类组合有利地与水溶性过滤剂,例如2-苯基苯并咪唑-5-磺酸及其碱金属、碱土金属、铵、烷基铵、链烷醇铵和葡糖铵盐组合。
除了所提及的可溶性物质外,为此还可以使用不溶性光保护颜料,具体地细分散的金属氧化物和盐。合适的金属氧化物的实例尤其是氧化锌和二氧化钛,以及铁、锆、硅、锰、铝和铈的氧化物及其混合物。所用盐可以是硅酸盐(滑石)、硫酸钡或硬脂酸锌。氧化物和盐以颜料的形式用于皮肤护理和皮肤保护乳液以及用于装饰性化妆品。颗粒的平均直径在这里应小于100nm,优选5-50nm,特别是15-30nm。它们可以具有球形形状,但是也可以使用具有椭圆形状或以某些其他方式偏离球形结构的那些颗粒。颜料也可以呈表面处理形式,即亲水化或疏水化。典型实例是经涂覆的二氧化钛,例如二氧化钛T 805(Degussa)或T2000(Merck)。合适的疏水涂料特别为聚硅氧烷,具体为三烷氧基辛基硅烷或水合硅石聚二甲基硅氧烷。所谓的微米或纳米颜料优选用于防晒组合物中。优选使用微粉化的氧化锌。
生物源活性成分和抗氧化剂
生物源活性成分应理解为是指例如生育酚、生育酚乙酸酯、生育酚棕榈酸酯、抗坏血酸、(脱氧)核糖核酸及其片段产物、β-葡聚糖、视黄醇、红没药醇、尿囊素、植烷三醇、泛醇、AHA酸、氨基酸、神经酰胺、拟神经酰胺、精油、植物提取物(例如李属植物提取物,Bambara坚果提取物)或维生素复合物。
抗氧化剂中断当UV辐射穿透到皮肤时引发的光化学反应链。其典型实例是氨基酸(例如甘氨酸、组氨酸、酪氨酸、色氨酸)及其衍生物、咪唑(例如尿刊酸)及其衍生物、肽(例如D,L-肌肽、D-肌肽、L-肌肽)及其衍生物(例如鹅肌肽)、类胡萝卜素、胡萝卜素(例如α-胡萝卜素、β-胡萝卜素、番茄红素)及其衍生物、绿原酸及其衍生物、脂酮酸及其衍生物(例如二氢脂酮酸)、硫金代葡萄糖、丙基硫氧嘧啶及其他硫醇(例如硫氧还蛋白、谷胱甘肽、半胱氨酸、胱氨酸、胱胺及其糖基、N-乙酰基、甲基、乙基、丙基、戊基、丁基和月桂基、棕榈酰基、油基、亚油基、胆甾醇基和甘油基的酯)及其盐、硫代二丙酸二月桂基酯、硫代二丙酸二硬脂基酯、硫代二丙酸及其衍生物(酯、醚、肽、类脂、核苷酸、核苷和盐)以及非常低耐受剂量(例如pmol至μmol/kg)的亚砜亚胺化合物(例如丁硫氨酸-亚砜亚胺(Buthioninsulfoximine),高半胱氨酸亚砜亚胺(Homocysteinsulfoximine),丁硫氨酸砜,以及戊-、己-、庚硫氨酸亚砜亚胺),此外还有(金属)螯合剂(例如α-羟基脂肪酸、棕榈酸、植酸、乳铁蛋白)、α-羟基酸(例如柠檬酸、乳酸、苹果酸)、腐殖酸、胆汁酸、胆汁提取物、胆红素、胆绿素、EDTA、EGTA及其衍生物、不饱和脂肪酸及其衍生物(例如γ-亚麻酸、亚油酸、油酸)、叶酸及其衍生物、泛醌和泛醇及其衍生物、维生素C和衍生物(例如抗坏血酸棕榈酸酯、抗坏血酸磷酸镁、抗坏血酸乙酸酯)、生育酚和衍生物(例如维生素E乙酸酯)、维生素A和衍生物(维生素A棕榈酸酯)以及安息香树脂的苯甲酸松柏醇酯、芸香酸及其衍生物、α-糖基芸香苷、阿魏酸、亚糠基葡糖醇、肌肽、丁基羟基甲苯、丁基羟基苯甲醚、去甲二氢愈创木树脂酸(nordihydroguaiacresin acid)、去甲二氢愈创木酸、三羟基苯丁酮、尿酸及其衍生物、甘露糖及其衍生物、超氧化物歧化酶、锌及其衍生物(例如ZnO、ZnSO4)、硒及其衍生物(蛋氨酸硒)、茋及其衍生物(例如均二苯代乙烯氧化物、反式-均二苯代乙烯氧化物)以及这些描述的活性化合物的根据本发明合适的衍生物(盐、酯、醚、糖、核苷酸、核苷、肽和类脂)。
成膜剂
常用成膜剂是例如壳聚糖、微晶壳聚糖、季铵化壳聚糖、聚乙烯基吡咯烷酮、乙烯基吡咯烷酮/乙酸乙烯酯共聚物、丙烯酸系聚合物、季铵纤维素衍生物、骨胶原、透明质酸及其盐和类似化合物。
去头皮屑活性成分
有用的去头皮屑活性成分包括吡罗克酮乙醇胺盐(1-羟基-4-甲基-6-(2,4,4-三甲基戊基)-2-(1H)-吡啶酮单乙醇胺盐)、(氯咪巴唑(climbazole))、/>4-乙酰基-1-{-4-[2-(2,4-二氯苯基)r-2-(1H-咪唑-1-基甲基)-1,3-二氧戊环-c-4-基甲氧基苯基}哌嗪、酮康唑、新康唑、二硫化硒、胶态硫、硫聚乙二醇脱水山梨醇单油酸酯、硫蓖麻醇聚乙氧基化物、硫-焦油馏份、水杨酸(和/或与六氯酚的组合)、十一碳烯酸单乙醇酰胺磺基琥珀酸钠盐、/>UD(蛋白质-十一碳烯酸缩合物)、吡啶硫酮锌、吡啶硫酮铝和吡啶硫酮镁/双吡啶硫酮-硫酸镁。
其他添加剂
可用于水相的溶胀剂为蒙脱石、粘土矿物、Pemulen和烷基改性Carbopol型(Goodrich)。其他合适的聚合物和溶胀剂可以在R.Lochhead的Cosm.Toil.108,95(1993)的概述中找到。合适的驱虫剂是N,N-二乙基-间甲苯甲酰胺、1,2-戊二醇或丁基乙酰胺基丙酸乙酯。合适的自晒黑剂是二羟基丙酮。防止形成黑色素并用于脱色剂的合适的酪氨酸抑制剂是例如熊果苷、阿魏酸、曲酸、香豆酸和抗坏血酸(维生素C)。
蛋白质水解物
如果需要的话,可使用由现有技术已知的其他蛋白质水解物,例如基于角蛋白,例如市购Keratin W PP,或基于小麦,例如/>WLM Benz、/>WK或/>WP。还可以加入少量游离氨基酸如赖氨酸或精氨酸。
水溶助长剂
流动行为还可以通过使用水溶助长剂而改进,例如乙醇、异丙醇或多元醇。在此合适的多元醇优选具有2-15个碳原子和至少两个羟基。多元醇还可以包含其他官能团,特别是氨基,或者可以用氮改性。典型的实例是:
·甘油;
·亚烷基二醇,例如乙二醇、二乙二醇、丙二醇、丁二醇、己二醇和平均分子量为100-1,000道尔顿的聚乙二醇;
·具有1.5-10的自缩合度的工业级低聚甘油混合物,例如具有40-50重量%的双甘油含量的工业级双甘油混合物;
·羟甲基化合物,例如尤其是三羟甲基乙烷、三羟甲基丙烷、三羟甲基丁烷、季戊四醇和二季戊四醇;
·低级烷基葡糖苷,尤其是烷基中具有1-8个碳原子的那些,例如甲基和丁基葡糖苷;
·具有5-12个碳原子的糖醇,例如山梨糖醇或甘露糖醇;
·具有5-12个碳原子的糖,例如葡萄糖或蔗糖;
·氨基糖,例如葡糖胺;
·二元醇胺,例如二乙醇胺或2-氨基-1,3-丙二醇。
防腐剂
合适的防腐剂的实例是苯甲酸盐、苯氧乙醇、甲醛溶液、对羟基苯甲酸酯、戊二醇、山梨酸、乙酰丙酸和花生四烯酸,以及以名称已知的银络合物,和在化妆品规范的附录6,A和B部分中列出的另外的物质种类。
香料油和芳香化合物
作为香料油,可以提及天然和合成的香料的混合物。天然香料是来自花(百合、熏衣草、玫瑰、茉莉、苦橙、依兰),茎和叶(天竺葵、广藿香、苦橙叶),果实(茴香子、芫荽、芡蒿子(caraway)、刺柏),果皮(香柠檬、柠檬、柑橘),根(肉豆蔻、当归、芹菜、小豆蔻、木香、鸢尾、菖蒲),木(松木、檀香木、愈创木、柏木、蔷薇木),草本植物和禾本植物(龙嵩、香茅、鼠尾草、百里香),针叶和枝桠(云杉、枞树、松树、山松(dwarf pine)),树脂和香脂(古篷香脂、榄香脂、安息香、没药、乳香、防风根)的提取物。还合适的是动物原料,例如麝猫香和海狸香。典型的合成香料化合物是酯类、醚类、醛类、酮类、醇类和烃类的产物。酯类的香料化合物是例如乙酸苄酯、异丁酸苯氧基乙酯、乙酸对叔丁基环己酯、乙酸芳樟酯、乙酸二甲基苄基甲酯、乙酸苯乙酯、苯甲酸芳樟酯、甲酸苄酯、甲基苯基甘氨酸乙酯、环己基丙酸烯丙基酯、丙酸苏合香酯和水杨酸苄酯。醚包括例如苄基乙基醚,醛包括例如具有8-18个碳原子的直链链烷醛、柠檬醛、香茅醛、香茅酰氧基乙醛、仙客来醛、羟基香茅醛、铃兰醛和波洁红醛(Bourgeonal),酮包括例如紫罗兰酮、α-异甲基紫罗酮和甲基柏木酮,醇包括茴香脑、香茅醇、丁子香酚、异丁子香酚、香叶醇、芳樟醇、苯乙醇和萜品醇,烃主要包括萜和香脂。然而,优选使用不同香料的混合物,这些混合物一起产生令人愉悦的香调。通常用作芳香组分的相对低挥发性的精油也适合作为香料油,例如鼠尾草油、春黄菊油、丁子香油、蜂花油、薄荷油、肉桂叶油、椴树花油、刺柏油、岩兰油、乳香油、古蓬油、岩蔷薇油和杂薰衣草油。优选以其本身或混合物形式使用香柠檬油、二氢月桂烯醇、铃兰醛、新铃兰醛(lyral)、香茅醇、苯乙醇、α-己基肉桂醛、香叶醇、苄基丙酮、仙客来醛、芳樟醇、乙氧基甲氧基环十一烷(boisambrene forte)、龙涎呋喃(ambroxan)、吲哚、二氢茉莉酮酸甲酯(hedione)、Sandelice、柠檬油、红橘油、橙油、戊基甘醇酸烯丙酯、女贞醛(cyclovertal)、杂薰衣草油、香紫苏油(muskateller salbeiol)、β-突厥酮、波旁香叶油、水杨酸环己酯、vertofixcoeur、龙涎酮(iso-E-super)、Fixolide NP、合成橡苔(evernyl)、γ-甲基紫罗兰酮(iraldein gamma)、苯乙酸、乙酸香叶酯、乙酸苄基酯、玫瑰醚、romilat、irotyl和floramat。合适的芳香化合物的实例包括薄荷油(peppermint oil)、薄荷油(spearmintoil)、茴香油、八角茴香油、页蒿子油、桉叶油、小茴香油、柠檬油、冬青油、丁子香油、薄荷醇等。
染料
可以使用的染料是批准和适合用于化妆品目的的物质,例如列于出版物“Kosmetische ”[化妆品着色剂],Farbstoffkommission der DeutschenForschungsgemeinschaft[德国研究会染料委员会],Verlag Chemie,Weinheim,1984,第81-106页中。实例是胭脂红A(C.I.16255),专利蓝V(C.I.42051),靛蓝(C.I.73015),叶绿酸(C.I.75810),喹啉黄(C.I.47005),二氧化钛(C.I.77891),阴丹士林蓝RS(C.I.69800)和茜素红色淀(C.I.58000)。还可以存在鲁米诺作为荧光染料。这些染料通常基于总混合物以0.001-0.1重量%的浓度使用。
颜料
特别是呈其蜡分散体形式,本发明的酯可以在化妆品组合物中产生突出的白色混浊。如果希望进一步增强珠光,则可以加入颜料。
术语颜料包括任何种类的颗粒,其是白色或有色的,有机或无机的,不可溶于制剂并起到赋予制剂增加的光泽的用途。
有利的是光泽颜料,其根据DIN 55944:2003-11包括金属效应颜料和珠光颜料。
一些具体效应颜料不能归于这两类,例如石墨薄片、氧化铁薄片和微粉化二氧化钛,其中微粉化二氧化钛不产生光泽效果,而是角度依赖性光散射效果。根据DIN 55943:2001-10的光泽颜料主要是效应颜料薄片。平行取向的光泽颜料表现出特有的光泽。光泽颜料的视觉效果基于在金属粒子(金属效应颜料)上、在高折射率透明颗粒(珠光颜料)上或在干涉现象(干涉颜料)上的定向反射(DIN 55944:2003-11)。
根据本发明优选的市售效应颜料的实例为:获自Merck的和#174;获自Merck的/>和#174(用于装饰工业应用的珠光和有色光泽颜料);获自Merck的和#174(深色晶体效应颜料)。
颜料还可有利地以市售油性或水性预分散体的形式使用。
化妆品头发处理组合物
在本发明的特定实施方案中,要求保护用于调理头发处理的化妆品组合物,其包含本发明的蜡分散体、阴离子表面活性剂和任选地阳离子聚合物和任选地两性和/或两性离子表面活性剂和乳化剂或其他常规成分以及补充至100重量%的水。
基于活性物质含量,以下物质优选存在于调理头发处理组合物中:
0.1-5.0重量%,优选0.2-2.5重量%的本发明的蜡分散体,
1.0-15重量%,优选7.5-12重量%的阴离子表面活性剂,
0.0-1重量%,优选0.05-0.4重量%的至少一种阳离子改性的聚合物,和/或
0.0-15重量%,优选0.1-5重量%的两性和/或两性离子表面活性剂,
可以存在0.0重量%至10重量%的乳化剂和任选地其他常规成分,并且水用于补充至100重量%。
蜡分散体、阴离子表面活性剂和任选存在的阳离子聚合物和两性和/或两性离子表面活性剂以及任选地其他常规成分已经在本申请的上文中描述。
方法
本发明还提供了一种生产本发明的化妆品清洁剂的方法。根据本发明的方法之一,本发明的蜡状乙二醇酯以蜡分散体的形式优选在室温下,优选在15-30℃下加入到化妆品组合物的一种或多种最初加入的组分中,并特别使用商业搅拌器搅拌-所谓的冷法。
根据另一方法变化方案,化妆品组合物可通过将本发明的乙二醇酯加热至高于其熔点的温度并将其与化妆品组合物的至少一种剩余组分一起搅拌来制备。优选将蜡状乙二醇酯与化妆品组合物的其他在室温下为固体的组分一起加热到高于本发明酯的熔点的温度并搅拌,然后加入化妆品组合物的其他剩余组分并搅拌。
实施例
A)本发明乙二醇二硬脂酸酯的制备实施例
本发明实施例A1
将2172.5g(=35mol)植物基乙二醇(指数:至少99.8重量%单乙二醇和至多0.06重量%二甘醇;至多0.06重量%水;可从India Glycols Bio MEG市购)和19913.6g(=70mol)工业级硬脂酸(组成C16脂肪酸:C18脂肪酸=1:1;可作为Palmera从KLKOleo市购)和11g草酸锡(酯化催化剂,可作为/>2001从PMC Organometallix,Inc.市购)的混合物加热至160℃。在16小时内蒸馏出约80%理论量的水。
然后将混合物加热至240℃,在26小时内除去剩余量的水。
对于后处理,将产物与NaOH溶液(184.6g溶解于500g去离子水中)在80℃下搅拌30分钟,过滤并干燥。
这得到14998g白色固体产物,具有以下特征:
根据DIN 53402的酸值AN=1.6
根据DIN 53240的羟值OHN=4.7
根据DIN 53401的皂化值SN=196.2
Kofler热台熔点=63.2℃
对比例乙二醇二硬脂酸酯A2(不根据本发明)
作为对比的是由石化乙二醇(指数:至少99.9重量%的单乙二醇和至多0.05重量%的二甘醇;至多0.05重量%的水)制备的乙二醇二硬脂酸酯,其具有以下特征:
根据DIN 53402的酸值AN<1
根据DIN 53240的羟值OHN<15
Kofler热台熔点=63.2℃
例如可作为AGS,BASF Personal Care&Nutrition GmbH市购。
目前100%的生物源活性,即14C碳的生物源比例,以%计,根据DIN在13.6dpm/gC下关于2018而定义,与基质无关。
根据实施例1制备的本发明乙二醇二硬脂酸酯和根据对比例的石化乙二醇二硬脂酸酯具有以下14C含量(8次测量):
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B)蜡分散体/珠光浓缩物的制备
制备了以下珠光浓缩物/蜡分散体(表1)。量以活性物质AS的重量%给出,基于蜡分散体/珠光浓缩物。
为了制备蜡分散体,最初加入2/3总量的水并加热到85℃。将(本发明或对比的)乙二醇二硬脂酸酯和烷基聚葡糖苷依次搅拌到热相中。在64℃,加入总水量的最后1/3,搅拌混合物。从40℃开始,加入苯甲酸钠、硫酸钠和柠檬酸并搅拌。
表1:蜡分散体
表1(续)
pH | 4.7 | 4.7 |
粘度 | 8800 | 12 360 |
在40℃增稠后的粘度 | 12 120 | 18 200 |
外观白度 | + | 0 |
外观珠光 | + | 0 |
*基于活性物质的量
粘度通过Brookfield法(23℃,锭子5,10rpm,mPas)测定。
通过肉眼相互对比,目测确定白度/珠光。
由表1可知,本发明的含有植物基乙二醇二硬脂酸酯A1的蜡分散体与含有石化基乙二醇二硬脂酸酯A2的蜡分散体相比,具有更好的白度/珠光和更低的粘度。
C)制备其他蜡分散体/珠光浓缩物
根据表2制备其他珠光浓缩物/蜡分散体。量以活性物质AS的重量%给出,基于蜡分散体/珠光浓缩物。
为了制备蜡分散体,将水、乙二醇二硬脂酸酯(根据本发明)和表面活性剂月桂基聚氧乙烯(4)醚(用平均4mol氧化乙烯乙氧基化的C12脂肪醇)、椰油酰胺基丙基甜菜碱和月桂基聚氧乙烯醚硫酸钠(用平均1mol氧化乙烯乙氧基化的C12醚硫酸钠的Na盐)和苯甲酸钠在大约50rpm搅拌下加热到85℃。在大约50rpm搅拌下将分散体冷却至25℃。然后加入柠檬酸并搅拌混合物。
表2:蜡分散体C1-C4
表2(续)
D)用蜡分散体B1)制备洗发剂
为了制备洗发剂,首先根据表3在室温下加入水,并将瓜尔胶羟丙基三甲基氯化铵(增稠剂)分散并分散。将表面活性剂月桂基聚氧乙烯(4)醚(用平均4mol氧化乙烯乙氧基化的C12脂肪醇)和椰油酰胺基丙基甜菜碱溶解于其中。然后加入实施例B1)的蜡分散体和其他组分,并搅拌混合物。表3中的量以重量%计,蜡分散体的重量%与B1)的蜡分散体有关,表面活性剂的重量%与活性物质含量AS有关。
表3:洗发剂D1)
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Claims (34)
1.蜡状乙二醇酯,其中根据14C分析,酯中的乙二醇具有至少99%的生物源碳比例,根据DIN EN 15440定义,在13.6dpm/gC下,独立于基质,标准偏差为+/-0至+/-4。
2.根据权利要求1的蜡状乙二醇酯,其中根据14C分析,酯中的乙二醇具有100%的生物源碳比例,根据DIN EN 15440定义,在13.6dpm/gC下,独立于基质,标准偏差为+/-0至+/-4。
3.根据权利要求1的蜡状乙二醇酯,其包含乙二醇单酯和乙二醇二酯的混合物。
4.根据权利要求1的蜡状乙二醇酯,其包含如下物质的混合物:
0.5-10重量%的乙二醇单酯,和
90-99.5重量%的乙二醇二酯。
5.根据权利要求2的蜡状乙二醇酯,其包含乙二醇单酯和乙二醇二酯的混合物。
6.根据权利要求2的蜡状乙二醇酯,其包含如下物质的混合物:
0.5-10重量%的乙二醇单酯,和
90-99.5重量%的乙二醇二酯。
7.根据权利要求1-6中任一项的蜡状乙二醇酯,其为乙二醇与具有6-22个碳原子的脂肪酸的单酯或二酯。
8.根据权利要求1-6中任一项的蜡状乙二醇酯,其为乙二醇与具有12-22个碳原子的脂肪酸的单酯或二酯。
9.根据权利要求1-6中任一项的蜡状乙二醇酯,其包含乙二醇与由如下物质组成的脂肪酸混合物的单酯和二酯:
40-100重量%的硬脂酸,和
0-60重量%的棕榈酸,和
0-20重量%的月桂酸和/或肉豆蔻酸。
10.根据权利要求1-6中任一项的蜡状乙二醇酯,其包含3-10重量%的由40-60重量%的硬脂酸和40-60重量%的棕榈酸组成的脂肪酸混合物的乙二醇单酯和90-97重量%的由40-60重量%的硬脂酸和40-60重量%的棕榈酸组成的脂肪酸混合物的乙二醇二酯。
11.蜡分散体,其基于蜡分散体包含15-30重量%的根据权利要求1-10中任一项的蜡状乙二醇酯。
12.根据权利要求11的蜡分散体,其包含:
a)15-30重量%的作为蜡的乙二醇酯,和
b)10-30重量%的表面活性剂,和
c)任选地0.01-1.0重量%的防腐剂。
13.根据权利要求12的蜡分散体,其中表面活性剂不含氧化烯。
14.根据权利要求11的蜡分散体,其包含:
a)15-30重量%的作为蜡的乙二醇酯,
b)10-30重量%的非离子表面活性剂,和
c)任选地0.01-0.5重量%的防腐剂。
15.根据权利要求14的蜡分散体,其中非离子表面活性剂选自烷基和/或亚烷基聚葡糖苷。
16.根据权利要求13的蜡分散体,其包含:
a)15-30重量%的作为蜡的乙二醇酯,
b)10-30重量%的非离子表面活性剂,和
c)任选地0.01-0.5重量%的防腐剂。
17.根据权利要求16的蜡分散体,其中非离子表面活性剂选自烷基和/或亚烷基聚葡糖苷。
18.根据权利要求11的蜡分散体,其包含:
a)15-30重量%的作为蜡的乙二醇酯,由a1)3-10重量%的乙二醇单酯,和a2)90-97重量%的乙二醇二酯组成,和
b)10-30重量%的非离子表面活性剂,选自烷基和/或亚烷基聚葡糖苷,和
c)任选地0.01-0.5重量%的防腐剂。
19.根据权利要求11的蜡分散体,其包含:
a)15-30重量%的作为蜡的乙二醇酯,包含3-10重量%的由40-60重量%的硬脂酸和40-60重量%的棕榈酸组成的脂肪酸混合物的乙二醇单酯和90-97重量%的由40-60重量%的硬脂酸和40-60重量%的棕榈酸组成的脂肪酸混合物的乙二醇二酯,和
b)10-30重量%的非离子表面活性剂,选自烷基和/或亚烷基聚葡糖苷,和
c)任选地0.01-0.5重量%的防腐剂。
20.根据权利要求11-19中任一项的蜡分散体,其不含任何石化化合物。
21.根据权利要求11-19中任一项的蜡分散体,其中乙二醇酯具有高于40℃的熔点。
22.根据权利要求21的蜡分散体,其中乙二醇酯具有低于75℃的熔点。
23.根据权利要求21的蜡分散体,其中乙二醇酯具有在45℃和65℃之间的熔点。
24.根据权利要求20的蜡分散体,其中乙二醇酯具有高于40℃的熔点。
25.根据权利要求24的蜡分散体,其中乙二醇酯具有低于75℃的熔点。
26.根据权利要求24的蜡分散体,其中乙二醇酯具有在45℃和65℃之间的熔点。
27.根据权利要求1-10中任一项的乙二醇酯作为蜡的用途,用于产生混浊或珠光。
28.根据权利要求1-10中任一项的乙二醇酯作为蜡的用途,其中所述蜡呈根据权利要求11-26中任一项的其分散体的形式,用于产生混浊或珠光。
29.根据权利要求1-10中任一项的乙二醇酯作为蜡的用途,用于在用于清洁皮肤和/或头发的化妆品组合物中产生混浊或珠光。
30.根据权利要求1-10中任一项的乙二醇酯作为蜡的用途,其中所述蜡呈根据权利要求11-26中任一项的其分散体的形式,用于在用于清洁皮肤和/或头发的化妆品组合物中产生混浊或珠光。
31.一种用于皮肤和头发的化妆品清洁剂,其包含根据权利要求1-10中任一项的乙二醇酯作为珠光剂或不透明剂。
32.一种制备根据权利要求31的化妆品清洁剂的方法,其中在室温下将呈根据权利要求11-26中任一项的分散体形式的根据权利要求1-10中任一项的乙二醇酯在搅拌下加入到化妆品组合物的一种或多种初始加入的组分中。
33.一种制备根据权利要求31的化妆品清洁剂的方法,其中在室温下将呈根据权利要求11-26中任一项的分散体形式的根据权利要求1-10中任一项的乙二醇酯在搅拌下在15℃和30℃之间加入到化妆品组合物的一种或多种初始加入的组分中。
34.一种制备根据权利要求31的化妆品清洁剂的方法,其中将根据权利要求1-10中任一项的乙二醇酯加热至高于熔点的温度,并与化妆品组合物的至少一种剩余组分一起搅拌。
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EP (1) | EP3930670B1 (zh) |
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BR112021014943A2 (pt) | 2021-09-28 |
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