CN115297836A - 用于装饰性化妆应用的生物基聚氨酯分散体 - Google Patents
用于装饰性化妆应用的生物基聚氨酯分散体 Download PDFInfo
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- CN115297836A CN115297836A CN202180026433.2A CN202180026433A CN115297836A CN 115297836 A CN115297836 A CN 115297836A CN 202180026433 A CN202180026433 A CN 202180026433A CN 115297836 A CN115297836 A CN 115297836A
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- polyurethane
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Abstract
本发明涉及含有特定聚氨酯或其水性分散体并含有提供装饰效果的成分的装饰性化妆品组合物。
Description
本发明涉及含有特定聚氨酯或其水性分散体和提供装饰效果的成分的装饰性化妆品组合物。
装饰性化妆品组合物,如本发明的装饰性化妆品组合物,用于人类皮肤、粘膜、半粘膜、指甲,尤其是手指甲或脚趾甲,和毛发,尤其是眼睑和眉毛的装饰性造型,尤其是有色造型。通过至少一种提供效果的组分实现装饰效果。根据本发明的装饰性组合物可以例如是面部彩妆(粉底)、润色霜(日霜)、腮红、胭脂、睫毛膏、眼线笔、眼影粉、眼影、口红、唇彩。这些特殊的化妆品制剂用于改变颜色或为身体化妆,以例如遮盖黑眼圈、肤色不均或其它皮肤瑕疵,如发红、斑点、皱纹或粉刺,由此让使用者的外形更美观。上述装饰产品清单当然不是限制性的。
装饰性化妆品组合物通常包含一种或多种着色剂,其例如选自可溶性着色剂、无机颜料如氧化铁、氧化铬、群青、锰紫、有机颜料和珍珠质。根据制剂形式,这样的装饰性化妆品组合物可由基于组合物的总重量计最多80重量%的着色剂和填料组成。
消费者在使用装饰性化妆品制剂时自然想要持久的装饰效果。特别是,消费者期望良好的防水性,例如在沐浴或淋浴期间,以及对泪液或汗液的耐受性,尤其是在体育活动期间。
使用成膜聚合物改进装饰产品对水、泪液或汗液的耐受性(通常称为防水性)。所选的优选成膜聚合物是基于丙烯酸酯或乙烯基吡咯烷酮的聚合物。这样的成膜聚合物的缺点是本领域技术人员已知的。这是因为丙烯酸酯聚合物形成硬而脆的膜。由此导致在产品带妆时不舒适的感觉。由于皮肤感觉发粘,乙烯基吡咯烷酮只能以有限浓度使用。
在装饰性化妆品中聚氨酯分散体的使用也是已知的。例如,US 2007/0154440描述了在化妆品制剂中使用分子量为至少50000的成膜聚氨酯以在皮肤上形成长效膜。FR2832058描述了水性聚氨酯分散体在眼线组合物中的用途。US 20070025943描述了在化妆品组合物中的成膜(甲基)丙烯酸酯共聚物和成膜聚氨酯的组合。EP 0775483(DE69621104)描述了合成的成膜聚合物颗粒的水性分散体在唇部化妆组合物中的用途。EP1010418描述了水性聚氨酯分散体在无蜡睫毛膏组合物中的用途。WO 2003039445描述了水性聚氨酯分散体在化妆品组合物中的用途。WO02070577A1(US 2004/0197293)描述了可用于化妆品组合物的阴离子型聚氨酯。但是没有描述化妆品组合物的具体实例。所述阴离子型聚氨酯具有相对低的耐水性并形成相对高粘度的水性聚氨酯分散体,以使其加工更加困难。
因此,现有技术中的尤其用于提供装饰效果的含聚氨酯的化妆品组合物在带妆舒适性,特别是降低的粘性、耐受性,特别是防水性和光泽度方面仍有改进的空间。此外,现有技术中所用的水性聚氨酯分散体通常具有不利的高粘度,这使它们难以加工或难以并入化妆品制剂中。
本发明的目的因此是提供装饰性化妆品组合物,其含有在很大比例上来源于可再生资源的组分,特别是聚氨酯。此外,该装饰性化妆品组合物应该具有高带妆舒适性,特别是降低的粘性,高耐受性,特别是耐磨损强度,和改进的光泽性质。此外,根据本发明使用的水性聚氨酯分散体应该具有相对低的粘度,以使它们可容易地并入装饰用化妆品组合物中。
令人惊讶地,通过使用特定聚氨酯或其水性分散体实现该目的,所述聚氨酯可通过使一种或多种水不溶性、水不分散性、异氰酸酯官能的聚氨酯预聚物A与一种或多种氨基官能化合物B)反应获得,其特征在于所述聚氨酯预聚物A)可通过使一种或多种具有至少-50℃的玻璃化转变温度Tg的聚酯多元醇和一种或多种多异氰酸酯反应获得。
本发明因此提供装饰性化妆品组合物,其含有至少一种可通过使一种或多种水不溶性、水不分散性、异氰酸酯官能的聚氨酯预聚物A与一种或多种氨基官能化合物B)反应获得的聚氨酯,其特征在于所述聚氨酯预聚物A)可通过使一种或多种具有至少-50℃的玻璃化转变温度Tg的聚酯多元醇和一种或多种多异氰酸酯反应获得。
优选地,本发明提供根据本发明的装饰性化妆品组合物,其含有至少一种可通过使一种或多种基本没有离子基团和离子源基团的异氰酸酯官能的聚氨酯预聚物A)与一种或多种氨基官能化合物B)反应获得的聚氨酯。
在本发明中,术语“水不溶性、水不分散性聚氨酯预聚物”特别是指根据本发明使用的预聚物在23℃下的水溶度小于10克/升,更优选小于5克/升,且该预聚物在23℃下在水,尤其是去离子水中不产生抗沉降分散体。换言之,当尝试将其分散在水中时,该预聚物沉降出来。
优选地,根据本发明使用的聚氨酯预聚物A)具有末端异氰酸酯基团,意味着异氰酸酯基团在该预聚物的链端。聚合物的所有链端特别优选都具有异氰酸酯基团。
此外,根据本发明使用的聚氨酯预聚物A)优选基本没有离子基团和离子源基团(即能够形成离子基团),即离子基团和离子源基团的含量适宜地低于15毫当量/100克聚氨酯预聚物A),优选低于5毫当量,特别优选低于1毫当量,非常特别优选低于0.1毫当量/100克聚氨酯预聚物A)。
氨基官能化合物B)优选选自伯胺和/或仲胺和/或二胺。特别地,氨基官能化合物B)包含至少一种二胺。氨基官能化合物B)优选选自具有离子基团或离子源基团的氨基官能化合物B2)和没有离子基团或离子源基团的氨基官能化合物B1)。
在本发明的一个特别优选的实施方案中,氨基官能化合物B)包含至少一种具有离子基团和/或离子源基团的氨基官能化合物B2)。作为离子基团和/或离子源基团,特别优选使用磺酸根和/或磺酸基团,更优选磺酸钠基团。
在本发明的另一个优选的实施方案中,氨基官能化合物B)包含具有离子基团和/或离子源基团的氨基官能化合物B2)和没有离子基团和/或离子源基团的氨基官能化合物B1)。
在本发明中,聚氨酯相应地是具有至少两个,优选至少三个含氨基甲酸酯基团的重复单元的聚合化合物:
根据本发明,也包括由于制备过程而也包含含脲基团的重复单元的此类聚氨酯:
如特别在异氰酸酯封端预聚物A)与氨基官能化合物B)的反应过程中形成。
根据本发明的装饰性化妆品组合物也可以是聚氨酯分散在其中,即以基本未溶解形式存在于其中的含水的,即水性的组合物。除任选存在的其它液体介质,例如溶剂外,基于根据本发明的化妆品组合物中的液体分散介质的总量计,水可能是分散介质的主要成分(> 50重量%),任选也可能是唯一的液体分散介质。
根据本发明的装饰性化妆品组合物优选具有基于装饰性化妆品组合物计小于80重量%,更优选小于55重量%,再更优选小于40重量%的挥发性有机化合物(VOC)含量。
用于生产根据本发明的装饰性化妆品组合物的水性聚氨酯分散体优选具有基于水性聚氨酯分散体计小于10重量%,更优选小于3重量%,再更优选小于1重量%的挥发性有机化合物(VOC)含量。
在本发明中,尤其通过气相色谱分析测定挥发性有机化合物(VOC)的含量。
根据本发明使用的水不溶性和水不分散性、异氰酸酯官能的聚氨酯预聚物基本没有离子基团和离子源基团。水不溶性或缺乏水分散性涉及未添加表面活性剂的去离子水。在本发明中,这意味着离子基团和/或离子源基团,特别例如阴离子基团,如羧酸根或磺酸根或阳离子基团的比例小于15毫当量/100克聚氨酯预聚物A),优选小于5毫当量,特别优选小于1毫当量,非常特别优选小于0.1毫当量/100克聚氨酯预聚物A)。
在酸性离子基团和/或离子源基团的情况下,该预聚物的酸值适宜地低于30 mgKOH/g预聚物,优选低于10 mg KOH/g预聚物。酸值是指中和1克受检查的样品所需的以毫克计的氢氧化钾质量,根据DIN EN ISO 211测量。经中和的酸,即相应的盐自然具有零或降低的酸值。根据本发明在此至关重要的是相应游离酸的酸值。
用于生产聚氨酯的预聚物A)可通过使一种或多种具有至少-50℃的玻璃化转变温度TG的聚酯多元醇和一种或多种多异氰酸酯反应获得。用于生产预聚物A)的所述一种或多种聚酯多元醇更优选具有-50至0℃,特别优选-40至-10℃的玻璃化转变温度Tg,在每种情况下通过根据DIN 65467的DSC测量在20 K/min的加热速率下测定。
根据本发明使用的聚氨酯优选具有至少-50℃,特别优选-50至0℃,尤其优选-30至0℃,非常特别优选-20至-10℃的玻璃化转变温度Tg,在每种情况下通过根据DIN 65467的DSC测量在20 K/min的加热速率下测定。
优选地,根据本发明使用一种或多种聚氨酯,其中用于形成聚氨酯的组分,特别是所述一种或多种聚酯多元醇,更优选用于形成聚酯多元醇的二羧酸和/或二羟基化合物的至少50重量%来源于可再生资源。在至少50重量%的程度上基于生物基原料的所得聚合物可根据标准ISO 16128-1被认定为“天然衍生”(“天然来源的成分”)。
根据本发明更优选地,术语“来自可再生资源”意味着选择相应材料的来源以使被称为“来自可再生资源”的材料在至少90重量%,优选至少95重量%,尤其优选至少99重量%的程度上来自植物或发酵过程(其中只有活生物体和植物参与该发酵过程)。
根据本发明使用的聚氨酯优选在至少30摩尔%,特别优选至少40摩尔%,尤其优选至少50摩尔%的程度上由可再生资源制成,即生物基。
本发明还涉及聚氨酯,其可通过使一种或多种水不溶性、水不分散性、异氰酸酯官能的聚氨酯预聚物A与一种或多种氨基官能化合物B)反应获得,其特征在于所述聚氨酯预聚物A)可通过使一种或多种具有至少-50℃的玻璃化转变温度Tg的聚酯多元醇和一种或多种多异氰酸酯反应获得。关于根据本发明的组合物所述的内容相应地适用于根据本发明的聚氨酯。
根据本发明的装饰性化妆品组合物中所含的聚氨酯由于预聚物A)而含有一种或多种具有所述特定玻璃化转变温度的生物基来源的上述聚酯多元醇。此外,根据本发明存在的预聚物可含有至少一种选自聚醚、聚碳酸酯、聚醚-聚碳酸酯和其它聚酯序列的序列。根据本发明,这可意味着该聚氨酯含有含醚基团和/或含碳酸酯基团的重复单元和酯基团重复单元。根据本发明存在的聚氨酯例如可以仅含基于上述具有至少-50℃的玻璃化转变温度Tg的聚酯多元醇的聚酯序列。但是,它们可另外包含聚醚和聚碳酸酯序列,如例如在使用聚醚二醇生产聚碳酸酯多元醇时形成。此外,它们可包含如下文更详细描述使用聚醚-聚碳酸酯多元醇产生的聚醚-聚碳酸酯序列。
根据本发明优选的聚氨酯使用具有至少-50℃的玻璃化转变温度Tg的聚合聚酯多元醇获得,该聚合聚酯多元醇具有优选大约400至大约6000 g/mol的数均分子量,这些和随后所示的分子量数据通过在四氢呋喃中在23℃下对照聚苯乙烯标样的凝胶渗透色谱法测定。它们在聚氨酯或聚氨酯预聚物的生产中的使用由于与多异氰酸酯的反应而导致在聚氨酯中形成具有这些序列的相应摩尔质量的相应聚酯序列。特别优选的是由具有线性结构的具有至少-50℃的玻璃化转变温度Tg的聚合聚酯多元醇和任选另外聚醚二醇和/或聚合聚碳酸酯二醇和/或聚醚-聚碳酸酯多元醇或其它聚酯多元醇获得的根据本发明的聚氨酯。
根据本发明的聚氨酯优选是基本线性分子,但也可能支化,尽管这较不优选。
根据本发明优选使用的聚氨酯的数均分子量为例如大约1000至200000 g/mol,优选5000至150000 g/mol。
根据本发明的装饰性化妆品组合物中所含的聚氨酯特别作为水性分散体添加到所述组合物中。
要根据本发明使用的优选聚氨酯或聚氨酯分散体可如下获得
A) 由以下组分生产异氰酸酯官能预聚物
A1) 有机多异氰酸酯,
A2) 聚合聚酯多元醇,其具有至少-50℃的玻璃化转变温度Tg,优选具有400至8000 g/mol的数均分子量,这些和随后所示的分子量数据通过在四氢呋喃中在23℃下对照聚苯乙烯标样的凝胶渗透色谱法测定,更优选400至6000 g/mol,特别优选600至3000 g/mol,和优选1.5至6,更优选1.8至3,特别优选1.9至2.1的OH官能度,
A3) 任选地,具有优选62至399 g/mol的分子量的羟基官能化合物,和
A4) 任选地,非离子型亲水化剂,
和
B) 然后使其游离NCO基团全部或部分地与一种或多种氨基官能化合物B),如伯胺和/或仲胺和/或二胺反应。
根据本发明使用的聚氨酯优选在步骤B)之前、之中或之后分散在水中。
特别优选的是在步骤B)中在扩链下进行与一种二胺或多种二胺的反应。在此,可另外作为链终止剂加入单官能胺以控制分子量。
作为组分B),特别可以使用没有离子基团和/或离子源基团,如阴离子型亲水化基团的胺,下文称为组分B1),并且可以使用具有离子基团和/或离子源基团,特别例如阴离子型亲水化基团的胺,下文称为组分B2)。
优选地,在该预聚物的反应的步骤B)中,使组分B1)和组分B2)的混合物反应。通过组分B1)的使用,可形成高摩尔质量,而预先制成的异氰酸酯官能预聚物的粘度没有升高到阻碍加工的程度。通过组分B1)和B2)的组合的使用,可建立亲水性和链长之间的最佳平衡并因此建立宜人的皮肤感觉。
根据本发明使用的聚氨酯优选具有阴离子基团,优选磺酸根基团。经由在步骤B)中反应的胺组分B2)将这些阴离子基团引入根据本发明使用的聚氨酯。根据本发明使用的聚氨酯任选另外包括用于亲水化的非离子组分。特别优选地,根据本发明使用的聚氨酯中仅含有磺酸根基团用于亲水化,这些经由作为组分B2)的相应二胺引入聚氨酯。
为了实现良好的沉降稳定性,在用去离子水稀释后借助激光相关光谱学(所用仪器:Malvern Zetasizer 1000, Malvern Inst. Limited)测定的该特定聚氨酯分散体的数均粒度优选小于750 nm,特别优选小于500 nm。
优选用于生产本发明的装饰性化妆品组合物的聚氨酯分散体的固含量通常为10重量%至70重量%,优选30重量%至65重量%,特别优选30重量%至50重量%。根据本发明通过将称重的样品在125℃下加热至恒重而确定固含量。在恒重下,通过将样品再称重来计算固含量。
优选地,这些聚氨酯分散体包含基于分散体的质量计小于5重量%,特别优选小于0.2重量%的未结合有机胺。在装饰性化妆品组合物中的含量相应地更低。
组分A1)的合适多异氰酸酯特别是本身为本领域技术人员已知的具有大于或等于2的NCO官能度的脂族、芳族或脂环族多异氰酸酯。
这样的合适多异氰酸酯的实例包括1,4-丁二异氰酸酯、1,6-己二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、2,2,4-和/或2,4,4-三甲基己二异氰酸酯、异构双-(4,4'-异氰酸根合环己基)甲烷或具有任意异构体含量的其混合物、1,4-环己二异氰酸酯、4-异氰酸根合甲基辛烷1,8-二异氰酸酯(壬烷三异氰酸酯)、1,4-苯二异氰酸酯、2,4-和/或2,6-甲苯二异氰酸酯、1,5-萘二异氰酸酯、二苯甲烷2,2'-和/或2,4'-和/或4,4'-二异氰酸酯、1,3-和/或1,4-双(2-异氰酸根合丙-2-基)苯(TMXDI)、1,3-双(异氰酸根合甲基)苯(XDI)和具有C1-C8-烷基的2,6-二异氰酸根合己酸烷基酯(赖氨酸二异氰酸酯)。
除上述多异氰酸酯外,还可以一定比例地使用具有脲二酮、异氰脲酸酯、氨基甲酸酯、脲基甲酸酯、缩二脲、亚氨基噁二嗪二酮或噁二嗪三酮结构的具有≥ 2的官能度的改性二异氰酸酯,以及这些的混合物。
优选的是具有仅脂族或脂环族键合的异氰酸酯基团或其混合物和2至4,优选2至2.6,特别优选2至2.4,非常特别优选2的该混合物的平均NCO官能度的上述类型的多异氰酸酯或多异氰酸酯混合物。
在A1)中特别优选使用己二异氰酸酯、异佛尔酮二异氰酸酯或异构双(4,4'-异氰酸根合环己基)甲烷以及上述二异氰酸酯的混合物。
在A2)中使用具有至少-50℃的玻璃化转变温度Tg并具有优选400至8000 g/mol,更优选400至6000 g/mol,特别优选600至3000 g/mol的数均分子量Mn的聚合聚酯多元醇。这些优选具有1.5至6,更优选1.8至3,最优选1.9至2.1的OH官能度。
术语“聚合”聚酯多元醇在此特别是指所提到的多元醇具有至少两个,优选至少三个互相键合的重复单元。
具有至少-50℃的玻璃化转变温度Tg的根据本发明的聚酯多元醇可单独地或以与彼此的任意混合物用于A2)。可任选另外存在的其它多元醇是本身为本领域技术人员已知的聚酯多元醇、聚丙烯酸酯多元醇、聚氨酯多元醇、聚碳酸酯多元醇、聚醚多元醇、聚酯聚丙烯酸酯多元醇、聚氨酯聚丙烯酸酯多元醇、聚氨酯聚酯多元醇、聚氨酯聚醚多元醇、聚氨酯聚碳酸酯多元醇和聚酯聚碳酸酯多元醇。
根据本发明使用的聚酯多元醇是二醇和任选三醇和四醇与二羧酸和任选三羧酸和四羧酸或羟基羧酸或内酯的本身已知的缩聚物。对于聚酯的生产,也可以使用相应的多羧酸酐或相应的多羧酸低碳醇酯代替游离多羧酸。
合适的二醇的实例是乙二醇、丁二醇、二乙二醇、三乙二醇、聚烷撑二醇,如聚乙二醇,以及丙-1‚2-二醇、丙-1‚3-二醇、丁-1,3-二醇、丁-1,4-二醇、己-1,6-二醇和异构体、新戊二醇或羟基特戊酸新戊二醇酯,其中优选的是己-1,6-二醇和异构体、丁-1,4-二醇、新戊二醇和羟基特戊酸新戊二醇酯。此外,也可以使用多元醇,如三羟甲基丙烷、甘油、赤藓糖醇、季戊四醇、三羟甲基苯或异氰脲酸三羟乙酯。
所用二羧酸可以包括邻苯二甲酸、间苯二甲酸、对苯二甲酸、四氢邻苯二甲酸、六氢邻苯二甲酸、环己烷二甲酸、己二酸、壬二酸、癸二酸、戊二酸、四氯邻苯二甲酸、马来酸、富马酸、衣康酸、丙二酸、琥珀酸、辛二酸、2-甲基琥珀酸、3,3-二乙基戊二酸和/或2,2-二甲基琥珀酸。也可以使用相应的酐作为酸源。
上文描述了具有多于两个OH基团的多元醇。代替其或除了其以外,也可以使用多元醇,如三羟甲基丙烷、甘油、赤藓糖醇、季戊四醇、三羟甲基苯或异氰脲酸三羟乙酯。如果要酯化的多元醇的平均官能度> 2,另外也可以连同使用单羧酸,如苯甲酸和己烷甲酸。
优选的酸是上述类型的脂族或芳族酸,特别优选脂族酸。特别优选的是琥珀酸、己二酸、间苯二甲酸和邻苯二甲酸。
优选用于生产根据本发明使用的聚酯多元醇的琥珀酸优选获自可再生资源。在此,如例如DE 10 2008 051727 A1和DE 10 2007 019184中所述,例如通过淀粉或生物质的发酵生产琥珀酸。优选地,根据本发明,所用琥珀酸的至少50重量%源于可再生资源。此外或另外,根据本发明的聚酯多元醇中所用的二羟基化合物的至少一部分也可源于可再生资源,并因此提高源于可再生资源的聚氨酯组分的比例。根据本发明使用的聚酯多元醇中优选存在选自更优选源于可再生资源的丁-1,4-二醇、丙-1,3-二醇、异丙二醇、己-1,6-二醇、乙二醇及其混合物的至少一种二羟基化合物。
可连同用作具有端羟基的聚酯多元醇的生产中的共反应物的羟基羧酸的实例包括羟基己酸、羟基丁酸、羟基癸酸、羟基硬脂酸等。合适的内酯是己内酯、丁内酯和同系物。优选的是己内酯。
作为用于生产聚氨酯的组分A2),根据本发明特别优选的是具有至少-50℃的玻璃化转变温度Tg并具有600至3000 g/mol的数均分子量的聚酯多元醇,尤其是基于脂族羧酸和脂族多元醇,特别是基于琥珀酸或己二酸和脂族醇,如丁-1,4-二醇、己-1,6-二醇和/或新戊二醇的脂族聚酯多元醇。
除上文作为组分A2)描述的聚酯多元醇外,在根据本发明使用的聚氨酯中可任选存在其它多元醇,例如具有优选400至8000 g/mol,优选600至3000 g/mol的数均分子量Mn的含羟基的聚碳酸酯,优选聚碳酸酯二醇。这些可通过使碳酸衍生物,如碳酸二苯酯、碳酸二甲酯或光气与多元醇,优选二醇反应获得。
这样的二醇的实例是乙二醇、丙-1,2-和-1,3-二醇、丁-1,3-和-1,4-二醇、己-1,6-二醇、辛-1,8-二醇、新戊二醇、1,4-双羟甲基环己烷、2-甲基丙-1,3-二醇、2,2,4-三甲基戊-1,3-二醇、二丙二醇、聚丙二醇、二丁二醇、聚丁二醇、双酚A和内酯改性的上述类型的二醇。
该二醇组分优选包含40重量%至100重量%的己二醇,优选的是己-1,6-二醇和/或己二醇衍生物。这样的己二醇衍生物基于己二醇并且不仅具有OH端基,还具有酯基团或醚基团。这样的衍生物可通过己二醇与过量己内酯的反应或通过己二醇自醚化以提供二-或三己二醇而获得。
代替或除了纯聚碳酸酯二醇外,也可使用聚醚-聚碳酸酯二醇。
含羟基的聚碳酸酯优选具有线性结构。
除了根据本发明的聚酯多元醇外同样还可以使用聚醚多元醇。
特别合适的实例是如通过四氢呋喃的阳离子开环聚合可获得的本身在聚氨酯化学中已知的聚四亚甲基二醇聚醚。
同样合适的聚醚多元醇是氧化苯乙烯、环氧乙烷、环氧丙烷、环氧丁烷和/或表氯醇加成到二官能或多官能起始剂分子上的本身已知的加成产物。例如特别可使用聚烷撑二醇,如聚乙二醇、聚丙二醇和/或聚丁二醇,其尤其具有上述优选分子量。
可用的合适起始剂分子是现有技术中已知的所有化合物,例如水、丁基二甘醇、甘油、二乙二醇、三羟甲基丙烷、丙二醇、山梨糖醇、乙二胺、三乙醇胺、丁-1,4-二醇。
除组分A2)外还可存在的特别优选的多元醇是聚四亚甲基二醇聚醚和聚碳酸酯多元醇或其混合物,特别优选是聚四亚甲基二醇聚醚。
在本发明的一个优选实施方案中,除了根据本发明的聚酯多元醇(组分A2)外,还可以使用以下多元醇混合物:含有至少一种聚醚多元醇和至少一种聚碳酸酯多元醇的混合物、含有多于一种聚醚多元醇的混合物或多种具有不同分子量的聚醚多元醇的混合物,其中这些特别是聚(四亚甲基二醇)聚醚多元醇(如HO-(CH2-CH2-CH2-CH2-O)x-H),包含多于一种聚醚多元醇和至少一种聚碳酸酯多元醇以及上文提到的聚酯多元醇的混合物,其中该多元醇组分根据定义基本没有离子基团和离子源基团。
作为组分A3),任选可以使用具有最多20个碳原子的62至399 mol/g的所述优选分子量范围的多元醇,尤其是非聚合多元醇,如乙二醇、二乙二醇、三乙二醇、丙-1,2-二醇、丙-1,3-二醇、丁-1,4-二醇、1,3-丁二醇、环己二醇、环己烷-1,4-二甲醇、己-1,6-二醇、新戊二醇、氢醌二羟乙基醚、双酚A(2,2-双(4-羟苯基)丙烷)、氢化双酚A(2,2-双(4-羟基环己基)丙烷)、三羟甲基丙烷、三羟甲基乙烷、甘油、季戊四醇和它们与彼此的任意混合物,尤其是新戊二醇。
所述分子量范围的酯二醇也合适,如ε-羟基己酸α-羟丁酯、γ-羟基丁酸ω-羟己酯、己二酸β-羟乙酯或对苯二甲酸双(β-羟乙基)酯。
也可使用含羟基的单官能异氰酸酯反应性化合物作为组分A3)。这样的单官能化合物的实例是乙醇、正丁醇、乙二醇单丁基醚、二乙二醇单甲基醚、二乙二醇单丁基醚、丙二醇单甲基醚、二丙二醇单甲基醚、三丙二醇单甲基醚、二丙二醇单丙基醚、丙二醇单丁基醚、二丙二醇单丁基醚、三丙二醇单丁基醚、2-乙基己醇、1-辛醇、1-十二烷醇、1-十六烷醇。
在本发明的一个优选实施方案中,根据本发明使用的聚氨酯包含小于大约10重量%的组分A3),优选小于5重量%的组分A3),在每种情况下基于聚氨酯的总质量计,更优选不使用组分A3)生产聚氨酯。
作为组分A4),一种或多种特别异氰酸酯反应性的非离子型亲水化剂任选用于生产根据本发明使用的聚氨酯。用作组分A4)的亲水化剂特别不同于组分A2)和A3)。
作为组分A4)的合适的非离子型亲水化化合物是例如具有异氰酸酯反应性基团,如羟基、氨基或硫醇基团的聚氧化烯醚。优选的是如可通过合适的起始剂分子的烷氧基化以本身已知的方式获得的具有每分子统计平均5至70,优选7至55个环氧乙烷单元的单羟基官能聚环氧烷聚醚醇(例如在Ullmanns Encyclopädie der technischen Chemie, 第4版,第19卷, Verlag Chemie, Weinheim第31-38页中)。这些是纯聚环氧乙烷醚或混合聚环氧烷醚,其中它们含有基于所含的所有环氧烷单元计至少30摩尔%,优选至少40摩尔%的环氧乙烷单元。
特别优选的非离子化合物是具有40至100摩尔%的环氧乙烷单元和0至60摩尔%的环氧丙烷单元的单官能混合聚环氧烷聚醚。
用于这样的非离子型亲水化剂的合适起始剂分子尤其是饱和单醇,如甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、仲丁醇、异构戊醇、己醇、辛醇和壬醇、正癸醇、正十二烷醇、正十四烷醇、正十六烷醇、正十八烷醇、环己醇、异构甲基环己醇或羟甲基环己烷、3-乙基-3-羟甲基氧杂环丁烷或四氢糠醇、二乙二醇单烷基醚,例如二乙二醇单丁基醚,不饱和醇,如烯丙醇、1,1-二甲基烯丙醇或油醇,芳醇,如苯酚、异构甲酚或甲氧基酚,芳脂族醇,如苄醇、茴香醇或肉桂醇,仲单胺,如二甲胺、二乙胺、二丙胺、二异丙基胺、二丁胺、双(2-乙基己基)胺、N-甲基-和N-乙基环己基胺或二环己基胺,以及杂环仲胺,如吗啉、吡咯烷、哌啶或1H-吡唑。优选的起始剂分子是上述类型的饱和单醇。特别优选使用二乙二醇单丁基醚或正丁醇作为起始剂分子。
适用于烷氧基化反应的环氧烷特别是环氧乙烷和环氧丙烷,它们可以以任意顺序或以混合物形式用于烷氧基化反应。
组分B)优选选自伯胺或仲胺和/或二胺。其尤其包含二胺。
作为组分B),特别可以使用没有离子基团和/或离子源基团,如阴离子型亲水化基团的胺(下文称为组分B1)),并可以使用具有离子基团和/或离子源基团,特别例如阴离子型亲水化基团的胺(下文称为组分B2))。优选地,在该预聚物的反应的步骤B)中,使组分B1)和组分B2)的混合物反应。
例如,所用组分B1)可以是有机二胺或多胺,例如乙-1,2-二胺、1,2-和1,3-二氨基丙烷、1,4-二氨基丁烷、1,6-二氨基己烷、异佛尔酮二胺、2,2,4-和2,4,4-三甲基己二胺的异构体混合物、2-甲基戊二胺、二亚乙基三胺、4,4-二氨基二环己基甲烷、水合肼和/或二甲基乙二胺。
此外,所用组分B1)也可以是不仅具有伯氨基还具有仲氨基,或不仅具有氨基(伯或仲)还具有OH基团的化合物。其实例是伯/仲胺,如二乙醇胺、3-氨基-1-甲基氨基丙烷、3-氨基-1-乙基氨基丙烷、3-氨基-1-环己基氨基丙烷、3-氨基-1-甲基氨基丁烷、烷醇胺,如N-氨基乙基乙醇胺、乙醇胺、3-氨基丙醇、新戊醇胺。
所用组分B1)可进一步是单官能异氰酸酯反应性胺化合物,例如甲基胺、乙基胺、丙基胺、丁基胺、辛基胺、月桂胺、硬脂胺、异壬氧基丙基胺、二甲基胺、二乙基胺、二丙基胺、二丁基胺、N-甲基氨基丙基胺、二乙基(甲基)氨基丙基胺、吗啉、哌啶或它们的合适的取代衍生物、由二伯胺和单羧酸形成的酰胺胺、二伯胺的单酮亚胺(Monoketim)、伯/叔胺,如N,N-二甲基氨基丙基胺。
所用组分B1)优选是乙-1,2-二胺、双(4-氨基环己基)甲烷、1,4-二氨基丁烷、异佛尔酮二胺、乙醇胺、二乙醇胺和二亚乙基三胺。
组分B)特别优选包含至少一种组分B2)。作为组分B2)的合适的阴离子型亲水化化合物优选含有磺酸基团或磺酸根基团,特别优选磺酸钠基团。作为组分B2)的合适的阴离子型亲水化化合物尤其是单-和二氨基磺酸的碱金属盐。这样的阴离子型亲水化剂的实例是2-(2-氨基乙基氨基)乙磺酸的盐、乙二胺丙基磺酸或乙二胺丁基磺酸的盐、丙-1,2-或1,3-二胺-β-乙磺酸或牛磺酸的盐。来自WO-A 01/88006的环己基氨基丙磺酸(CAPA)的盐也可用作阴离子型亲水化剂。
特别优选的阴离子型亲水化剂B2)是包含磺酸根基团作为离子基团和两个氨基的那些,如2-(2-氨基乙基氨基)乙磺酸和丙-1,3-二胺-β-乙磺酸的盐。
根据本发明使用的聚氨酯特别优选包含至少一个磺酸根基团。
组分B2)中的阴离子基团也可任选是羧酸根或羧酸基团。此时,组分B2)优选选自二氨基羧酸。但是,这一实施方案较不优选,因为基于羧酸的组分B2)必须以较高浓度使用。
阴离子型亲水化剂B2)和非离子型亲水化剂A4)的混合物也可用于亲水化。
在用于生产该特定聚氨酯分散体的一个优选实施方案中,组分A1)至A4)和B1)至B2)以下列量使用,其中各个量始终合计达100重量%:
5重量%至40重量%的组分A1),
55重量%至90重量%的A2),
0.5重量%至20重量%的组分A3)和/或B1)之和,
0.1重量%至25重量%的组分A4)和/或B2)之和,其中基于组分A1)至A4)和B1)至B2)的总量计,特别优选使用0.1重量%至5重量%的阴离子型或潜在阴离子型亲水化剂B2)。
在用于生产该特定聚氨酯分散体的一个特别优选的实施方案中,组分A1)至A4)和B1)至B2)以下列量使用,其中各个量始终合计达100重量%:
5重量%至35重量%的组分A1),
60重量%至90重量%的A2),
0.5重量%至15重量%的组分A3)和/或B1)之和,
0.1重量%至15重量%的组分A4)和/或B2)之和,其中基于组分A1)至A4)和B1)至B2)的总量计,特别优选使用0.2重量%至4重量%的阴离子型或潜在阴离子型亲水化剂B2)。
在用于生产该特定聚氨酯分散体的一个非常特别优选的实施方案中,组分A1)至A4)和B1)至B2)以下列量使用,其中各个量始终合计达100重量%:
10重量%至30重量%的组分A1),
65重量%至85重量%的A2),
0.5重量%至14重量%的组分A3)和/或B1)之和,
0.1重量%至13.5重量%的组分A4)和/或B2)之和,其中基于组分A1)至A4)和B1)至B2)的总量计,特别优选使用0.5重量%至3.0重量%的B2)的阴离子型或潜在阴离子型亲水化剂。
根据本发明,非常特别优选使用INCI名称为聚氨酯-93和/或聚氨酯-99的聚氨酯。INCI名称是对化妆品成分的国际命名法。INCI代表“化妆品成分的国际命名(International Nomenclature of Cosmetic Ingredients)”。
聚氨酯分散体的生产可在一个或多个阶段中在均相中进行,或在多级反应的情况下,部分地在分散相中进行。在A1)至A4)的完全或部分进行的加聚后,优选进行分散、乳化或溶解步骤。此后任选在分散相中发生进一步加聚或改性。
在此可以使用现有技术中已知的所有方法,例如预聚物混合法、丙酮法或熔体分散法。优选使用丙酮法。
对于通过丙酮法生产,通常最初装载全部或一部分的成分A2)至A4)和多异氰酸酯组分A1)以生产异氰酸酯官能预聚物,并任选用与水混溶但对异氰酸酯基团呈惰性的溶剂稀释,并加热到50至120℃的温度。可以使用聚氨酯化学中已知的催化剂加速异氰酸酯加成反应。
合适的溶剂是常规脂族酮官能溶剂,如丙酮、2-丁酮,它们不仅可在生产开始时加入,也可任选在稍后阶段分份加入。丙酮和2-丁酮是优选的,丙酮特别优选。也可以加入无异氰酸酯反应性基团的其它溶剂,但不优选。
随后加入任选在该反应开始时未加入的A1)至A4)的成分。
在由A1)至A4)生产聚氨酯预聚物时,异氰酸酯基团与异氰酸酯反应性基团的摩尔比通常为1.05至3.5,优选1.1至3.0,特别优选1.1至2.5。
将组分A1)至A4)部分或完全转化成预聚物,但优选完全。由此获得纯形式或溶液形式的含游离异氰酸酯基团的聚氨酯预聚物。
在中和步骤中,使用碱,如叔胺,例如在各烷基中具有1至12,优选1至6个碳原子,特别优选2至3个碳原子的三烷基胺,或非常特别优选碱金属碱,如相应的氢氧化物,以使潜在阴离子基团部分或完全转化成阴离子基团。不优选使用有机胺。
可用的中和剂优选包括无机碱,如氨水溶液或氢氧化钠或氢氧化钾。
优选的是氢氧化钠和氢氧化钾。
该碱的摩尔量为要中和的酸基的摩尔量的50至125摩尔%,优选70至100摩尔%。当分散水已含有中和剂时,也可在分散的同时实现中和。
随后,如果这尚未实现或仅部分实现,在进一步工艺步骤中使用脂族酮,如丙酮或2-丁酮溶解所得预聚物。
将组分A1)至A4)部分或完全转化成预聚物,但优选完全。由此获得纯形式或溶液形式的含游离异氰酸酯基团的聚氨酯预聚物。
在阶段B)的扩链中,使NH2-和/或NH-官能组分与该预聚物的剩余异氰酸酯基团反应。优选在水中分散之前进行扩链/链终止。
适用于扩链的组分B)特别是有机二胺或多胺B1),如乙二胺、1,2-和1,3-二氨基丙烷、1,4-二氨基丁烷、1,6-二氨基己烷、异佛尔酮二胺、2,2,4-和2,4,4-三甲基己二胺的异构体混合物、2-甲基戊二胺、二亚乙基三胺、二氨基二环己基甲烷和/或二甲基乙二胺。
也可使用不仅具有伯氨基还具有仲氨基,或不仅具有氨基(伯或仲)还具有OH基团的化合物B1)。这些的实例是伯/仲胺,如二乙醇胺、3-氨基-1-甲基氨基丙烷、3-氨基-1-乙基氨基丙烷、3-氨基-1-环己基氨基丙烷、3-氨基-1-甲基氨基丁烷、烷醇胺,如N-氨基乙基乙醇胺、乙醇胺、3-氨基丙醇、新戊醇胺,用于扩链或链终止。
通常使用具有异氰酸酯反应性基团的胺B1),例如甲基胺、乙基胺、丙基胺、丁基胺、辛基胺、月桂胺、硬脂胺、异壬氧基丙基胺、二甲基胺、二乙基胺、二丙基胺、二丁基胺、N-甲基氨基丙基胺、二乙基(甲基)氨基丙基胺、吗啉、哌啶或它们的合适的取代衍生物、由二伯胺和单羧酸形成的酰胺胺、二伯胺的单酮亚胺、伯/叔胺,如N,N-二甲基氨基丙基胺实现链终止。
当具有NH2基团或NH基团的根据定义B2)的阴离子型亲水化剂用于扩链时,优选在分散前进行该预聚物的扩链。
扩链程度,即用于扩链和链终止的化合物的NCO反应性基团与该预聚物的游离NCO基团的当量比通常在40%至150%之间,优选在50%至110%之间,特别优选在60%至100%之间。
胺类组分B1)和B2)可任选以水或溶剂稀释形式单独或混合用于本发明的方法,其中各种添加顺序原则上都可行。
当连同使用水或有机溶剂作为稀释剂时,则在B)中用于扩链的组分中的稀释剂含量优选为40重量%至95重量%。
优选在扩链后进行分散。为此,任选在高剪切,例如剧烈搅拌下将溶解并扩链的聚氨酯聚合物引入分散水中,或相反,将分散水搅拌到扩链的聚氨酯聚合物溶液中。优选将水添加到溶解的扩链聚氨酯聚合物中。
然后通常通过蒸馏除去在分散步骤后仍包含在分散体中的溶剂。同样可以已在分散过程中除去。
由此制成的聚氨酯分散体中的有机溶剂的残留含量通常为基于总分散体计的小于10重量%,优选小于3重量%。
根据本发明使用的水性聚氨酯分散体的pH值通常小于8.0,优选小于7.5,特别优选在5.5至7.5之间。
根据本发明的装饰性化妆品组合物优选含有0.1重量%至20重量%的上述聚氨酯,尤其是0.5重量%至10重量%,在每种情况下基于该组合物的总重量计。
本发明的装饰性化妆品组合物用于人类皮肤、粘膜、半粘膜、毛发,特别是眼睑和眉毛,更优选不是头发,和指甲,特别是手指甲或脚趾甲的装饰性造型,特别是有色或提供效果的造型。通过至少一种提供效果,特别是提供颜色和/或效果的成分实现装饰效果,即有色效果或其它效果,例如闪光效果、金属效果等。根据本发明的装饰性组合物可以例如是面部彩妆,例如粉底,润色霜,特别是日霜,腮红、胭脂、睫毛膏、眼线笔、眼影粉、眼影、口红、唇彩;指甲油。装饰性化妆品组合物的特征通常在于它们是所谓的“免洗”产品,其在施加后至少部分保留在皮肤或毛发上。
根据本发明的装饰性化妆品组合物特别可以是固体、液体或半固体。例如,该组合物可以水性颜料分散体、水包油、油包水、硅油包水、水包硅油、油包水包油、水包油包水或固体乳状液,即通过固体稳定的乳状液,如皮克林乳液的形式存在。根据本发明的制剂也可用推进剂气体发泡。根据本发明的制剂也可以“散粉”,即松散粉末、粉饼、泡沫(所谓的摩丝)、棒的形式或上述液体或粘性乳状液的形式存在。
根据本发明的组合物含有至少一种提供效果的成分。所提到的成分尤其可提供颜色或提供其它不同效果,如闪光和/或金属效果。根据本发明的组合物优选包含至少一种着色剂,其优选选自亲脂着色剂、亲水着色剂、颜料和珍珠质。根据本发明特别有利地,着色剂的浓度为0.01重量%至40重量%,特别有利地1.0重量%至30重量%,非常特别有利地2.0重量%至25重量%,在每种情况下基于该组合物的总重量计。
例如,可以使用亲脂着色剂,如苏丹I(黄色)、苏丹II(橙色)、苏丹III(红色)、苏丹IV(猩红色)、DC Red 17、DC Green 6、β-胡萝卜素、大豆油、DC Yellow 11、DC Violet 2、DCOrange 5和DC Yellow 10。
颜料原则上可以是用于化妆品或皮肤病学组合物的所有无机或有机颜料。根据本发明使用的颜料可以是例如白色或有色的,它们可以被包封或用疏水处理剂涂覆或未涂覆。
有利地,颜料选自金属氧化物,如铁的氧化物(尤其是黄色、红色、棕色或黑色的氧化物)、二氧化钛、氧化锌、氧化铈、氧化锆、氧化铬;锰紫、群青蓝、普鲁士蓝、群青和铁蓝、氯氧化铋、珍珠质、用钛或氯氧化铋涂覆的云母颜料、彩色珠光颜料,例如包含氧化铁的钛-云母颜料、尤其包含铁蓝或氧化铬的钛-云母颜料、包含上述类型的有机颜料的钛-云母颜料,和基于氯氧化铋的珠光颜料、炭黑、D&C类型的颜料,和基于胭脂虫红、钡、锶、钙和铝及其混合物的漆料。
特别有利地使用氧化铁或二氧化钛颜料。
为了颜料可更好地被脂肪相的油润湿,优选用疏水处理剂处理颜料表面。疏水处理剂优选选自硅酮,如聚甲基硅氧烷、聚二甲基硅氧烷、全氟烷基硅烷;脂肪酸,如硬脂酸;金属皂,如二肉豆蔻酸铝、氢化牛脂谷氨酸的铝盐、全氟烷基磷酸盐、全氟烷基硅烷、全氟烷基硅氮烷、聚六氟环氧丙烷、包含全氟烷基全氟聚醚基团的聚有机基硅氧烷、氨基酸;N-酰化氨基酸或其盐;卵磷脂、三异硬脂基钛酸异丙酯及其混合物。N-酰化氨基酸可包含具有8至22个碳原子的酰基,例如2-乙基己酰基、己酰基、月桂酰基、肉豆蔻酰基、棕榈酰基、硬脂酰基或椰油酰基。这些化合物的盐可以是铝盐、镁盐、钙盐、锆盐、锡盐、钠盐或钾盐。氨基酸可以是例如赖氨酸、谷氨酸或丙氨酸。
本发明的装饰性化妆品组合物可含有一种或多种乳化剂或表面活性剂。
因此,本发明的水包油乳状液(O/W)优选含有至少一种HLB值> 7的乳化剂和任选助乳化剂。
有利地使用下列非离子型乳化剂:
·a) 多元醇的脂肪酸偏酯和脂肪酸酯及其乙氧基化衍生物(例如单硬脂酸甘油酯、山梨糖醇酐硬脂酸酯、柠檬酸甘油酯硬脂酯、蔗糖硬脂酸酯)
·b) 乙氧基化脂肪醇和脂肪酸。
特别有利的非离子型O/W乳化剂是乙氧基化脂肪醇或脂肪酸,优选PEG-100硬脂酸酯、PEG-40硬脂酸酯、鲸蜡硬脂醇聚醚-20、鲸蜡醇聚醚-20、硬脂醇聚醚-20、鲸蜡硬脂醇聚醚-12、鲸蜡醇聚醚-12、硬脂醇聚醚-12,以及单糖、寡糖或多糖与脂肪酸的酯,优选鲸蜡硬脂基葡糖苷、甲基葡萄糖二硬脂酸酯。
有利的阴离子型乳化剂是皂,例如硬脂酸或棕榈酸的钠盐或三乙醇胺盐,和柠檬酸酯,如甘油硬脂酸酯柠檬酸酯。
用于根据本发明的O/W乳状液的合适的助乳化剂可以是具有8至30个碳原子的脂肪醇、具有8至24个碳原子,尤其是12至18个碳原子的链长的饱和或不饱和、支化或非支化烷羧酸的单甘油酯、具有8至24个碳原子,尤其是12至18个碳原子的链长的饱和或不饱和、支化或非支化烷羧酸的丙二醇酯,以及具有8至24个碳原子,尤其是12至18个碳原子的链长的饱和或不饱和、支化或非支化烷羧酸的山梨糖醇酐酯。
特别有利的助乳化剂是单硬脂酸甘油酯、单油酸甘油酯、单硬脂酸二甘油酯、山梨糖醇酐单异硬脂酸酯、蔗糖二硬脂酸酯、鲸蜡醇、硬脂醇、山嵛醇、异山嵛醇和聚乙二醇(2)硬脂醚(硬脂醇聚醚-2)。
在本发明中可以有利地使用附加乳化剂。这可例如用于进一步提高根据本发明的制剂的防水性。合适的乳化剂的实例是烷基聚甲基硅氧烷共聚醇和烷基聚二甲基硅氧烷共聚醇,特别是鲸蜡基聚二甲基硅氧烷共聚醇、月桂基聚甲基硅氧烷共聚醇、W/O乳化剂,如山梨糖醇酐硬脂酸酯、硬脂酸甘油酯、甘油硬脂酸酯、山梨糖醇酐油酸酯、卵磷脂、异硬脂酸甘油酯、聚甘油-3油酸酯、聚甘油-3二异硬脂酸酯、PEG-7氢化蓖麻油、聚甘油-4异硬脂酸酯、丙烯酸酯/丙烯酸C10-30烷基酯交联聚合物、山梨糖醇酐异硬脂酸酯、泊洛沙姆101、聚甘油-2二聚羟基硬脂酸酯、聚甘油-3二异硬脂酸酯、聚甘油-4二聚羟基硬脂酸酯、PEG-30二聚羟基硬脂酸酯、二异硬脂酰基聚甘油-3二异硬脂酸酯、二醇二硬脂酸酯和聚甘油-3二聚羟基硬脂酸酯。
根据本发明的O/W组合物可有利地含有水相的增稠剂。有利的增稠剂是:
- 交联或非交联的丙烯酸或甲基丙烯酸均聚物或共聚物。这些包括甲基丙烯酸或丙烯酸的交联均聚物、丙烯酸和/或甲基丙烯酸和衍生自其它丙烯酸系或乙烯基单体的单体,如丙烯酸C10-30烷基酯、甲基丙烯酸C10-30烷基酯和乙酸乙烯酯的共聚物。
- 天然来源的增稠聚合物,其例如基于纤维素、瓜尔胶、黄原胶、硬葡聚糖、结冷胶、鼠李胶和刺梧桐树胶、藻酸盐、麦芽糖糊精、淀粉及其衍生物、刺槐豆胶、透明质酸、角叉菜胶、多糖。
- 非离子、阴离子、阳离子或两性缔合聚合物,其例如基于聚乙二醇及其衍生物或聚氨酯。
- 基于丙烯酰胺或甲基丙烯酰胺的交联或非交联均聚物或共聚物,如2-丙烯酰氨基-2-甲基丙磺酸的均聚物、丙烯酰胺或甲基丙烯酰胺和甲基丙烯酰氧基乙基三甲基氯化铵的共聚物、或丙烯酰胺和2-丙烯酰氨基-2-甲基丙磺酸的共聚物。
特别有利的增稠剂是天然来源的增稠聚合物、交联丙烯酸或甲基丙烯酸均聚物或共聚物和2-丙烯酰氨基-2-甲基丙磺酸的交联共聚物。
非常特别有利的增稠剂是黄原胶,如CP Kelco公司以Keltrol®和Kelza®为名供应的产品或以Rhodopol®为名来自RHODIA公司的产品,和瓜尔胶,如可以Jaguar® HP105为名获自RHODIA公司的产品。
非常特别有利的增稠剂还有甲基丙烯酸或丙烯酸的交联均聚物,其可以Carbopol® 940、Carbopol® 941、Carbopol® 980、Carbopol® 981、Carbopol® ETD 2001、Carbopol®EDT 2050、Carbopol® 2984、Carbopol® 5984和Carbopol® Ultrez 10为名购自Lubrizol公司、以Synthalen® K、Synthalen® L和Synthalen® MS为名购自3V公司和以Modarez® V1250 PX、Modarez® V2000 PX、Viscaron® A1600 PE和Viscaron® A700 PE为名购自PROTEX公司。
非常特别有利的增稠剂是丙烯酸或甲基丙烯酸和丙烯酸C10-30-烷基酯或甲基丙烯酸C10-30-烷基酯的交联共聚物和丙烯酸或甲基丙烯酸和乙烯基吡咯烷酮的共聚物。此类聚合物可以例如以Carbopol® 1342、Carbopol® 1382、Pemulen® TR1或Pemulen® TR2为名购自Lubrizol公司和以Ultrathix® P-100(INCI: 丙烯酸/VP交联聚合物)为名购自Ashland公司。
非常特别有利的增稠剂是2-丙烯酰氨基-2-甲基丙磺酸的交联共聚物。此类共聚物可以例如以Aristoflex® AVC(INCI: 丙烯酰二甲基牛磺酸铵/VP共聚物)为名获自Clariant公司。
这些增稠剂通常以基于根据本发明的组合物的总重量计大约0重量%至2重量%,优选0重量%至1重量%的浓度存在。
根据本发明的进一步组合物可以是油包水或硅酮包水乳状液。优选的是包含一种或多种具有≤ 8的HLB值的硅酮乳化剂(W/S)或一种或多种具有< 7的HLB值的W/O乳化剂和任选一种或多种具有> 10的HLB值的O/W乳化剂的油包水(W/O)或硅酮包水乳状液(W/Si)。
硅酮乳化剂可有利地选自烷基聚二甲基硅氧烷共聚醇,如鲸蜡基PEG/PPG 10/1聚二甲基硅氧烷共聚醇(来自Degussa公司的ABIL® EM 90)或月桂基PEG/PPG-18/18聚二甲基硅氧烷(来自Dow Corning Ltd.公司的Dow Corning® 5200)和聚二甲基硅氧烷共聚醇,如PEG-10聚二甲基硅氧烷(来自Shin Etsu公司的KF-6017)、PEG/PPG-18/18聚二甲基硅氧烷(来自Dow Corning Ltd.公司的Dow Corning 5225C)或PEG/PPG-19/19聚二甲基硅氧烷(来自Dow Corning Ltd.公司的Dow Corning BY-11 030)。
具有< 7的HLB值的W/O乳化剂可有利地选自山梨糖醇酐硬脂酸酯、山梨糖醇酐油酸酯、异硬脂酸甘油酯、聚甘油-3油酸酯、季戊四醇异硬脂酸酯、甲基葡萄糖二油酸酯、PEG-7氢化蓖麻油、聚甘油-4异硬脂酸酯、月桂酸己酯、山梨糖醇酐异硬脂酸酯、聚甘油-2二聚羟基硬脂酸酯、聚甘油-3二异硬脂酸酯、PEG-30二聚羟基硬脂酸酯、二异硬脂酰基聚甘油-3二异硬脂酸酯、聚甘油-3二聚羟基硬脂酸酯。聚甘油-4二聚羟基硬脂酸酯、聚甘油-3油酸酯和羊毛蜡醇(Eucerit)。
具有> 10的HLB值的O/W乳化剂可有利地选自卵磷脂、三月桂醇聚醚-4磷酸酯、聚山梨酯20、聚山梨酯60、PEG-22十二烷基二醇共聚物、蔗糖硬脂酸酯和蔗糖月桂酸酯。
为了稳定根据本发明的W/O乳状液以防水滴沉降或絮凝,可有利地使用油增稠剂。
特别有利的油增稠剂是有机改性粘土,如有机改性膨润土(来自Rheox公司的Bentone® 34)、有机改性水辉石(来自Rheox公司的Bentone® 27和Bentone® 38)或有机改性蒙脱石、疏水气相二氧化硅,其中硅烷醇基团被三甲基甲硅烷氧基取代(来自Degussa公司的Aerosil® R812)或被二甲基甲硅烷氧基或聚二甲基硅氧烷取代(来自Degussa的Aerosil® R972、Aerosil® R974、来自Cabot的Cab-O-Sil® TS-610、Cab-O-Sil® TS-720)、硬脂酸镁或硬脂酸铝或苯乙烯共聚物,如苯乙烯-丁二烯-苯乙烯、苯乙烯-异丙烯-苯乙烯、苯乙烯-乙烯/丁烯-苯乙烯或苯乙烯-乙烯/丙烯-苯乙烯。
脂肪相的增稠剂可以基于乳状液的总重量计0.1重量%至5重量%,更好地0.4重量%至3重量%的量存在。
水相可另外包含稳定剂。稳定剂可以是例如氯化钠、氯化镁或硫酸镁及其混合物。
在W/O、W/Si和O/W乳状液中可以使用油。
如果存在,根据本发明的组合物的脂肪相包含至少一种不挥发油。该组合物的脂肪相还可进一步包含挥发油和蜡。该O/W组合物有利地包含基于组合物的总重量计0重量%至45重量%的油,特别有利地0重量%至20重量%的油。该W/O或W/Si组合物有利地包含基于组合物的总重量计至少20重量%的油。
不挥发油有利地选自矿物、动物、植物或合成来源、极性或非极性油及其混合物。
极性油可选自卵磷脂和脂肪酸甘油三酯,即具有8至24,尤其是12至18个碳原子的链长的饱和和/或不饱和、支化和/或非支化烷羧酸的甘油三酯。例如,脂肪酸甘油三酯可选自椰油酸甘油酯、橄榄油、葵花油、大豆油、花生油、菜籽油、扁桃仁油、棕榈油、椰子油、蓖麻油、小麦胚芽油、葡萄籽油、红花油、月见草油、澳洲坚果油、杏仁油、鳄梨油等。
进一步有利的极性油可选自具有3至30个碳原子的链长的饱和和/或不饱和、支化和/或非支化烷羧酸和具有3至30个碳原子的链长的饱和和/或不饱和、支化和/或非支化醇的酯,以及芳族羧酸和具有3至30个碳原子的链长的饱和和/或不饱和、支化和/或非支化醇的酯。例如,酯油可优选选自苯甲酸苯乙酯、棕榈酸辛酯、椰油酸辛酯、异硬脂酸辛酯、肉豆蔻酸辛基十二烷基酯、辛基十二烷醇、异壬酸鲸蜡硬脂醇酯、肉豆蔻酸异丙酯、棕榈酸异丙酯、硬脂酸异丙酯、油酸异丙酯、硬脂酸正丁酯、月桂酸正己酯、油酸正癸酯、己二酸二异丙酯、硬脂酸异辛酯、硬脂酸异壬酯、异壬酸异壬酯、棕榈酸2-乙基己酯、月桂酸2-乙基己酯、月桂酸2-己基癸酯、硬脂酸2-己基癸酯、棕榈酸2-辛基十二烷基酯、肉豆蔻酸2-辛基十二烷基酯、乳酸2-辛基十二烷基酯、琥珀酸2-乙基己酯、二异硬脂醇苹果酸酯、三异硬脂酸甘油酯、三异硬脂酸二甘油酯、硬脂醇庚酸酯、油酸油醇酯、芥酸油醇酯、瓢儿菜醇油酸酯、瓢儿菜醇芥酸酯、硬脂酸十三烷基酯、偏苯三酸十三烷基酯,以及此类酯的合成、半合成和天然混合物,例如荷荷巴油。
极性油可有利地选自二烷基醚和碳酸二烷基酯;有利的实例是二辛基醚(来自BASF Personal Care & Nutrition GmbH公司的Cetiol® OE)和/或碳酸二辛酯(例如来自BASF Personal Care & Nutrition GmbH公司的Cetiol® CC)。
极性油进一步优选选自异二十烷、新戊二醇二庚酸酯、丙二醇二辛酸酯/二癸酸酯、辛酸/癸酸/二甘油琥珀酸酯、丁二醇二辛酸酯/二癸酸酯、乳酸C12-13-烷基酯、酒石酸二-C12-13-烷基酯、苯甲酸C12-15-烷基酯、肉豆蔻酸肉豆蔻醇酯、新戊酸异癸酯、三异硬脂精、二季戊四醇六辛酸酯/六癸酸酯、丙二醇单异硬脂酸酯、三辛酸甘油酯、二甲基异山梨醇、水杨酸丁基辛酯(如例如以商品名Hallbrite® BHB获自CP Hall公司)、苯甲酸十六烷基酯和苯甲酸丁基辛酯及其混合物(Hallstar® AB)和/或萘二甲酸二乙基己酯(来自Symrise的Hallbrite® TQ或Corapan® TQ)。
不挥发油同样可有利地也是选自支化和非支化烃,特别是矿物油、凡士林油、石蜡油、角鲨烷和角鲨烯、聚烯烃,例如聚癸烯、氢化聚异丁烯、C13-16异链烷烃和异十六烷的非极性油。
非极性的不挥发油可选自不挥发硅酮油。
不挥发硅酮油可包括任选苯基化的聚二甲基硅氧烷(PDMS),如苯基聚三甲基硅氧烷,或任选被脂族和/或芳族基团或被官能团,例如羟基、硫醇基团和/或氨基取代的聚二甲基硅氧烷(PDMS);被脂肪酸、脂肪醇或聚氧化烯改性的聚硅氧烷,及其混合物。
根据本发明的组合物可进一步包含蜡。
在本文中,蜡被定义为在室温(25℃)下是固体并在30℃至200℃的熔融温度下表现出可逆固/液状态变化的亲脂脂肪物质。在高于熔点时,蜡的粘度低并变得与油混溶。
该蜡有利地选自天然蜡,例如棉蜡、巴西棕榈蜡、小烛树蜡、茅草蜡、日本蜡、蒙旦蜡、甘蔗蜡、蜂蜡、羊毛蜡、虫胶、微晶蜡、地蜡、石蜡、小冠椰子蜡、软木纤维蜡、褐煤蜡、果蜡、牛油树脂或合成蜡,如石蜡、聚乙烯蜡、通过费托合成制成的蜡、氢化油、脂肪酸酯和在25℃下为固体的甘油酯、硅酮蜡和衍生物(烷基衍生物、烷氧基衍生物和/或聚甲基硅氧烷的酯)及其混合物。该蜡可以胶体蜡颗粒的稳定分散体形式存在,其可通过已知方法,例如根据"Microemulsions Theory and Practice", L.M. Prince Ed., Academic Press(1977), 第21-32页制成。
可以基于组合物的总重量计0重量%至30重量%,优选0重量%至20重量%的量包含蜡。
根据本发明的组合物可进一步包含选自挥发性烃、硅化油和氟化油的挥发油。
可以基于乳状液的总重量计0重量%至25重量%,优选0重量%至20重量%,更优选0重量%至15重量%的量包含该挥发油。
在本文中,挥发油是在室温和大气压下在与皮肤接触时在不到1小时内蒸发的油。挥发油在室温下是液体,并在室温和大气压下具有0.13至40000 Pa(10-3至300 mmHg),优选1.3至13000 Pa(0.01至100 mmHg),更优选1.3至1300 Pa(0.01至10 mmHg)的蒸气压和150至260℃,优选170至250℃的沸点。
烃油被理解为是指基本由碳原子和氢原子和任选氧原子或氮原子形成的油,并且不含硅原子或氟原子;其中其也可由碳原子和氢原子组成,但其还可含有酯基团、醚基团、氨基或酰胺基团。
硅酮油被理解为是指含有至少一个硅原子,尤其是Si-O基团的油,特别例如聚二有机基硅氧烷。
氟化油被理解为是指含有至少一个氟原子的油。根据本发明的挥发性烃油可选自具有40至102℃,优选40至55℃,更优选40至50℃的闪点的烃油。
挥发性烃油的实例是具有8至16个碳原子的那些及其混合物,特别是支化C8-16烷烃,如具有8至16个碳原子的异烷烃(也称为异链烷烃)、异十二烷、异癸烷、异十六烷和例如以商品名Isopars®或Permetyls®销售的油;和支化C8-16酯,如新戊酸异己酯及其混合物。
特别有利的是挥发性烃油,如异十二烷、异癸烷和异十六烷。
根据本发明的挥发性硅化油可选自具有40至102℃的闪点,优选超过55℃和最多95℃,特别优选65至95℃的闪点的硅化油。
例如,挥发性硅化油是具有2至7个硅原子的直链或环状硅酮油,其中这些硅酮任选含有具有1至10个碳原子的烷基或烷氧基。
特别有利的是如下挥发性硅化油,如八甲基环四硅氧烷、十甲基环五硅氧烷、十二甲基环六硅氧烷、七甲基己基三硅氧烷、七甲基辛基三硅氧烷、六甲基二硅氧烷、八甲基三硅氧烷、十甲基四硅氧烷、十二甲基五硅氧烷及其混合物。挥发性氟化油通常不具有闪点。
例如,挥发性氟化油是九氟乙氧基丁烷、九氟甲氧基丁烷、十氟戊烷、十四氟己烷、十二氟戊烷及其混合物。
根据本发明的组合物的优选化妆品可接受的介质包含水和任选化妆品兼容的水混溶的合适有机溶剂。
根据本发明的组合物中所用的水可以是花水、纯软化水、矿泉水、温泉水和/或海水。
在O/W组合物作为根据本发明的组合物的情况下,水含量可在基于组合物的总重量计40重量%至95重量%的范围内,优选在50重量%至90重量%的范围内,最优选在60重量%至80重量%的范围内。在W/O组合物的情况下,水含量在基于组合物的总重量计0重量%至60重量%的范围内,优选在10重量%至50重量%的范围内,最优选在30重量%至50重量%的范围内。
优选的溶剂是例如具有C1-4个碳原子的脂族醇,如乙醇和异丙醇;多元醇及其衍生物,如丙二醇、二丙二醇、丁-1,3-二醇、聚丙二醇、二醇醚如单-、二-或三丙二醇或单-、二-或三乙二醇的烷基(C1-4)醚及其混合物。
根据本发明的组合物中的一种溶剂或多种溶剂的用量比例可以例如在基于组合物的总重量计0重量%至25重量%,优选0重量%至15重量%的范围内。
本发明的进一步组合物可以是“散粉”或粉饼。
根据本发明的装饰性化妆品组合物可优选也提供所谓的粉底效果,借此可以抚平皮肤不均匀,如皱纹等。
根据本发明的装饰性化妆品组合物可含有化妆品中常规的附加添加剂,例如:抗氧化剂、光稳定剂和/或其它辅助剂和添加剂,如乳化剂、界面活性物质、消泡剂、增稠剂、表面活性剂、活性成分、保湿剂、感官添加剂、紫外线过滤剂、成膜剂、溶剂、聚结剂、香料、吸味剂、香精、凝胶形成剂和/或其它聚合物分散体,如基于聚丙烯酸酯的分散体、填料、增塑剂、颜料、流平剂和/或触变剂、软化剂、防腐剂。各种添加剂的量的使用范围是本领域技术人员已知的,并且例如在基于组合物的总重量计0重量%至25重量%的范围内。
根据本发明的装饰性化妆品组合物还可包含感官添加剂。感官添加剂被理解为是指例如进一步改进制剂的感官性质并且例如让皮肤感觉像天鹅绒般柔软或丝滑的无色或白色、矿物或合成、层状、球形或细长惰性颗粒或非粒状感官添加剂。
感官添加剂可以例如以基于组合物的总重量计0重量%至10重量%,优选0%至7%的量包含在根据本发明的组合物中。
在本发明中有利的粒状感官添加剂是滑石、云母(云母)、二氧化硅、高岭土、淀粉及其衍生物(例如木薯淀粉、磷酸双淀粉、淀粉辛烯基琥珀酸铝和淀粉辛烯基琥珀酸钠等)、气相二氧化硅、完全没有紫外线过滤剂作用也没有着色作用的颜料(例如氮化硼等)、氮化硼、碳酸钙、磷酸氢钙、碳酸镁、碳酸氢镁、羟磷灰石、微晶纤维素、合成聚合物的粉末如聚酰胺(例如可以商品名"Nylon®"获得的聚合物)、聚乙烯、聚-β-丙氨酸、聚四氟乙烯("Teflon®")、聚丙烯酸酯、聚氨酯、月桂酰赖氨酸、硅酮树脂(例如可以商品名"Tospearl®"获自KoboProducts Inc.公司的聚合物)、聚偏二氟乙烯/丙烯腈的中空颗粒(来自Akzo Nobel公司的Expancel®)或二氧化硅的中空颗粒(来自MAPRECOS公司的Silica Beads®)。
有利的非粒状感官添加剂可选自聚二甲基硅氧烷醇(例如来自Dow Corning Ltd.公司的Dow Corning 1503 Fluid)、硅酮共聚物(例如二乙烯基聚二甲基硅氧烷/聚二甲基硅氧烷共聚物,来自Dow Corning Ltd.公司的Dow Corning HMW 2220)或硅酮弹性体(例如聚二甲基硅氧烷交联聚合物,来自Dow Corning Ltd.公司的Dow Corning 9040硅酮弹性体共混物)。
根据本发明的组合物可任选也包含防晒过滤剂,其中防晒过滤剂的总量为基于根据本发明的组合物的总重量计0重量%至30重量%,有利地0重量%至20重量%,特别有利地0重量%至10重量%。防晒过滤剂(或紫外线过滤剂)特别可选自有机过滤剂、物理过滤剂及其混合物。
根据本发明的组合物可包含UV-A过滤剂、UV-B过滤剂或广谱过滤剂。所用紫外线过滤剂可以是油溶性或水溶性的。下面提到的紫外线过滤剂的所附名单当然不是限制性的。
UV-B过滤剂的实例包括:
• (1) 水杨酸衍生物,特别是水杨酸三甲环己酯、水杨酸辛酯和水杨酸4-异丙基苄酯;
• (2) 肉桂酸衍生物,尤其是可以Parsol MCX®为名获自DSM的对甲氧基肉桂酸2-乙基己酯,和4-甲氧基肉桂酸异戊酯;
• (3) 液态β,β'-二苯基丙烯酸酯衍生物,尤其是可以UVINUL N539®为名获自BASF公司的α,β'-二苯基丙烯酸2-乙基己酯或奥克立林;
• (4) 对氨基苯甲酸衍生物,尤其是4-(二甲基氨基)苯甲酸2-乙基己酯、4-(二甲基氨基)苯甲酸戊酯;
• (5) 3-亚苄基樟脑衍生物,尤其是可以EUSOLEX 6300®为名购自Merck公司的3-(4-甲基亚苄基)樟脑、3-亚苄基樟脑、亚苄基樟脑磺酸和聚丙烯酰氨基甲基亚苄基樟脑;
• (6) 可以EUSOLEX 232®为名获自Merck公司的2-苯基苯并咪唑-5-磺酸;
• (7) 1,3,5-三嗪衍生物,特别是:– BASF公司以UVINUL T150®为名供应的2,4,6-三[p-(2'-乙基己基-1'-氧基羰基)苯胺基]-1,3,5-三嗪,和– Sigma 3V公司以UVASORBHEB®为名供应的二辛基丁酰氨基三嗪酮;
• (8) 亚苄丙二酸的酯,尤其是4-甲氧基亚苄丙二酸二(2-乙基己基)酯和可以Parsol® SLX为名获自DSM公司的3-(4-(2,2-双乙氧基羰基乙烯基)苯氧基)丙烯基)甲氧基硅氧烷/二甲基硅氧烷共聚物;和
• (9) 这些过滤剂的混合物。
UV-A过滤剂的实例包括:
• (1) 二苯甲酰甲烷衍生物,特别是DSM公司以PARSOL 1789®为名供应的4-(叔丁基)-4'-甲氧基二苯甲酰基甲烷,和1-苯基-3-(4'-异丙基苯基)丙-1,3-二酮;
• (2) 苯-1,4-[二(3-亚甲基樟脑-10-磺酸)],其任选完全或部分中和,可以MEXORYL SX®为名购自Chimex;
• (3) 2-(4'-二乙基氨基-2'-羟基苯甲酰基)苯甲酸己酯(也称为氨基二苯甲酮);
• (4) 具有二苯甲酮基团的硅烷衍生物或聚有机基硅氧烷;
• (5) 邻氨基苯甲酸酯,特别是Symrise公司以NEO HELIOPAN MA®为名供应的邻氨基苯甲酸薄荷酯;
• (6) 每分子含有至少两个苯并唑基(Benzoazolyl)或至少一个苯并二唑基的化合物,尤其是可购自Symrise公司的1,4-双(苯并咪唑基)亚苯基-3,3',5,5'-四磺酸及其盐;
• (7) N-取代的苯并咪唑基苯并唑的硅衍生物,或苯并呋喃基苯并唑的硅衍生物,尤其是:– 2-[1-[3-[1,3,3,3-四甲基-1-[(三甲基甲硅烷基)氧基]二硅氧烷基]丙基]-1H-苯并咪唑-2-基]苯并噁唑;– 2-[1-[3-[1,3,3,3-四甲基-1-[(三甲基甲硅烷基)氧基]二硅氧烷基]丙基]-1H-苯并咪唑-2-基]-苯并噻唑;– 2-[1-(3-三甲基硅烷基丙基)-1H-苯并咪唑-2-基]苯并噁唑;– 6-甲氧基-1,1'-双(3-三甲基硅烷基丙基)-1H,1'H-[2,2']二苯并咪唑基苯并噁唑;– 2-[1-(3-三甲基硅烷基丙基)-1H-苯并咪唑-2-基]苯并噻唑;它们描述在专利申请EP-A-1 028 120中;
• (8) 三嗪衍生物,尤其是3V公司以Uvasorb®K2A为名供应的2,4-双[5-1(二甲基丙基)苯并噁唑-2-基-(4-苯基)亚氨基]-6-(2-乙基己基)亚氨基-1,3,5-三嗪;和
• (9) 它们的混合物。
广谱过滤剂的实例是:
(1) 二苯甲酮衍生物,例如
– 2,4-二羟基二苯甲酮(二苯甲酮-1);
– 2,2',4,4'-四羟基二苯甲酮(二苯甲酮-2);
– 可以UNIVNUL M40®为名获自BASF公司的2-羟基-4-甲氧基二苯甲酮(二苯甲酮-3);
– 可以UVINUL MS40®为名购自BASF公司的2-羟基-4-甲氧基二苯甲酮-5-磺酸(二苯甲酮-4)及其磺酸盐形式(二苯甲酮-5);
– 2,2'-二羟基-4,4'-二甲氧基二苯甲酮(二苯甲酮-6-);
– 5-氯-2-羟基二苯甲酮(二苯甲酮-7-);
– 2,2'-二羟基-4-甲氧基二苯甲酮(二苯甲酮-8);
– 2,2'-二羟基-4,4'-二甲氧基二苯甲酮-5,5'-二磺酸的二钠盐(二苯甲酮-9-);
– 2-羟基-4-甲氧基-4'-甲基二苯甲酮(二苯甲酮-10);
– 二苯甲酮-11;
– 2-羟基-4-(辛氧基)二苯甲酮(二苯甲酮-12)
• (2) 三嗪衍生物,尤其是BASF公司以TINOSORB S®为名供应的2,4-双{[4-2-乙基己氧基]-2-羟基}苯基}-6-(4-甲氧基苯基)-1,3,5-三嗪,和可以TINOSORB M®为名获自BASF公司的2,2'-亚甲基双[6-(2H-苯并三唑-2-基)-4-(1,1,3,3-四甲基丁基)酚];和
• (3) INCI名为Drometrizole Trisiloxane的2-(1H-苯并三唑-2-基)-4-甲基-6-[2-甲基-3-[1,3,3,3-四甲基-1-[(三甲基甲硅烷基)氧基]二硅氧烷基]丙基]酚。
也可以使用多种过滤剂的混合物,和UV-B过滤剂、UV-A过滤剂和广谱过滤剂的混合物,以及与物理过滤剂的混合物。
物理过滤剂可包括钡的硫酸盐,钛的氧化物(二氧化钛,非晶或以金红石和/或锐钛矿形式结晶)、锌的氧化物、铁的氧化物、锆的氧化物、铈的氧化物、硅的氧化物、锰的氧化物或其混合物。金属氧化物可以尺寸在微米范围或纳米范围(纳米颜料)内的颗粒形式存在。纳米颜料的平均粒度为例如5至100 nm。
本发明的装饰性化妆品组合物可包含一种或多种保湿剂(湿润剂)。
本发明中特别有利的湿润剂是例如甘油、聚甘油、山梨糖醇、二甲基异山梨酯、乳酸和/或乳酸盐,尤其是乳酸钠,丁二醇、丙二醇、生物糖胶1、大豆甘氨酸、羟乙基脲、乙基己氧基甘油、吡咯烷酮甲酸和脲。此外,尤其有利的是使用选自水溶性和/或水溶胀性多糖和/或可借助水胶凝的多糖的聚合“湿润剂”。尤其有利的是例如透明质酸、壳聚糖和/或可以Fucogel™ 1000为名获自SOLABIA S.A公司的富含岩藻糖的多糖。
在本发明中,可以特别有利地使用水溶性抗氧化剂,如维生素,例如抗坏血酸及其衍生物。维生素E及其衍生物,以及维生素A及其衍生物尤其有利。
根据本发明的组合物中的其它有利的活性成分是α-羟基酸,如乙醇酸、乳酸、苹果酸、酒石酸、柠檬酸和扁桃酸,β-羟基酸,如水杨酸及其酰化衍生物,2-羟基烷酸及其衍生物;天然活性成分和/或其衍生物,如α-硫辛酸、叶酸、八氢番茄红素、D-生物素、辅酶Q10、α-葡糖基芸香苷、肉毒碱、肌肽、天然和/或合成异黄酮、肌酸、肌酸酐、牛磺酸和/或[β]-丙氨酸和8-十六烯-1,16-二甲酸(Dioic acid,CAS号20701-68-2;临时INCI名Octadecenedioicacid)和甘草查尔酮A和植物提取物。
有利的成膜剂是三甲基甲硅烷氧基硅酸酯、硅酮丙烯酸酯共聚物(例如来自DowCorning公司的TIB4-200或来自Shin Etsu公司的KP-561)、三甲基五苯基三硅氧烷(来自Dow Corning Ltd.公司的Dow Corning 555 Cosmetic Fluid)或乙烯基吡咯烷酮共聚物(例如PVP/二十烯共聚物或PVP/十六烷共聚物)。
使用实施例阐释本发明,其中这些实施例不应被理解为限制。除非另行指明,所有的用量数据、比例和百分比基于重量和总量或该组合物的总重量计。
实施例:
所用材料:
PUD 1(对比): 聚氨酯分散体(固含量40重量%),基于合成生产的聚酯多元醇1、二环己基甲烷二异氰酸酯、乙二胺和氨基乙磺酸钠盐,聚氨酯是100摩尔%合成的。
PUD 2(根据本发明): 聚氨酯分散体(固含量30重量%),基于生物基聚酯多元醇2、异佛尔酮二异氰酸酯、异佛尔酮二胺和氨基乙磺酸钠盐,聚氨酯是55摩尔%生物基的。PUD 2中所含的聚氨酯对应于根据INCI命名法的聚氨酯-93。
PUD 3(根据本发明): 聚氨酯分散体(固含量40重量%),基于生物基聚酯多元醇2、二环己基甲烷二异氰酸酯、乙二胺和氨基乙磺酸钠盐,聚氨酯是60摩尔%生物基的。PUD 3中所含的聚氨酯对应于根据INCI命名法的聚氨酯-99。
聚酯多元醇1(对比): 由己二酸、新戊二醇和己-1,6-二醇合成生产
聚酯多元醇2:(根据本发明): 由琥珀酸、丁-1,4-二醇和新戊二醇形成的生物基聚酯多元醇
DSC测量:
通过以下方法测量在每种情况下作为干燥膜的对比聚酯多元醇1和根据本发明的聚酯多元醇2,以及对比聚氨酯分散体PUD 1和根据本发明的聚氨酯分散体PUD 2和PUD 3的玻璃化转变温度Tg:
通过使用来自Mettler-Toledo公司的DSC3+e量热计随温度测量热容量而测定物理转换,如熔点或玻璃化转变温度Tg。使用正庚烷、铟、铅和锌校准温度和熔化焓。所用吹扫气体是氮气,流量为20 ml/min。借助液氮实施冷却。温度梯度为20 K/min。在-70至+150℃之间的温度范围内进行测量(2次加热运行)。
在没有预调理的情况下,对供应时的形式,即直接对水性聚氨酯分散体进行测量。在可气密密封的穿孔铝标准坩埚中,样品重量为10至12毫克的样品质量。
评估: 作为在第二次加热运行中在玻璃化转变的半高处的温度测定玻璃化转变温度Tg。
测量结果显示在表1中。
表1: DSC结果
编号 | 名称 | Tg [℃] |
V1 | 聚酯多元醇1 | -60.1 |
2 | 聚酯多元醇2 | -38.6 |
V3 | PUD 1 | -44.1 |
4 | PUD 2 | -16.5 |
5 | PUD 3 | -21.0 |
V 对比。
用于睫毛膏:
在表2中给出受试睫毛膏的组成:
表2: 受试睫毛膏制剂
相 | 组分(INCI名称) | 量[重量%] |
A | 水 | 加至100 |
羟乙基纤维素 | 0.70 | |
三乙醇胺(99%) | 2.30 | |
尼龙66 | 1.50 | |
B | 黑色氧化铁 | 8.00 |
C | 硬脂酸甘油酯 | 2.30 |
硬脂酸 | 5.60 | |
蜂蜡 | 7.00 | |
巴西棕榈蜡 | 7.00 | |
聚二甲基硅氧烷 | 0.50 | |
D | 苯氧基乙醇 | 0.80 |
聚氨酯(作为固体) | 4.00 | |
总和 | 100.00 |
根据以下方法制备受试睫毛膏:
1. 将相A的成分溶解在水中并加热至80℃。
2. 一旦相A均匀,在搅拌下加入颜料,将整个混合物均质化。
3. 在单独容器中,混合相C的成分并加热至80℃。
4. 一旦相C均匀,将相C缓慢添加到相A/B中。将该乳状液均质化。
5. 在冷却过程中加入相D。
6. 在检查pH值后,必要时将其调节到pH 6.5至7.0。
通过以下方法测试睫毛膏的防水性:
用调温至37℃的水润湿两个棉片。将睫毛膏制剂以Z形图案施加到由人发制成的假睫毛上10次。在干燥后,将睫毛放在两个棉片之间,在轻施压力下从根部拉动到末梢。使用表3中的量表评估棉片上的残留物。
化妆棉上的残留物进行了评估。
表3: 防水性的评估
防水性的程度 | 值 |
棉片上无残留物 | 5 |
棉片上的残留物面积0至1 cm<sup>2</sup> | 4 |
棉片上的残留物面积1至2 cm<sup>2</sup> | 3 |
棉片上的残留物面积2至4 cm<sup>2</sup> | 2 |
棉片上的残留物面积大于4 cm<sup>2</sup> | 1 |
防水性试验的结果显示在表4中。该值越高,防水性越好。
表4: 防水性试验的结果
试验 | PUD 1 | PUD 2 | PUD 3 |
值 | 4 | 5 | 5 |
用于眼线产品:
根据下示方法制备表5中所示的眼线制剂。
在室温下将相A的所有成分在搅拌下添加到容器中。一旦相A均匀,加入相B。将这种混合物均质化。然后在搅拌下加入相C。
表5: 眼线制剂:
相 | 组分(INCI名称) | 量[重量%] |
A | 水 | 加至100 |
黄原胶 | 0.50 | |
微晶(和)藻胶 | 0.30 | |
B | 氧化铁(黑) | 10.00 |
山梨糖醇酐月桂酸酯(和)聚甘油-4月桂酸酯(和)二月桂醇柠檬酸酯 | 1.50 | |
C | 丙二醇 | 2.00 |
聚氨酯(固体) | 5.00 | |
甲基丙二醇(和)辛二醇(和)苯基丙醇 | 1.50 | |
总和 | 100.00 |
评估耐磨损强度的方法:
将相应的眼线制剂作为线施加到皮肤上。一旦制剂干燥,眼线用燕尾夹摩擦10次。如表6中所示评估眼线膜的品质。该值越高,耐磨损强度越好。
表6: 耐磨损强度的评估
膜品质的评估 | 值 |
膜无变化 | 5 |
膜上有轻微划痕 | 4 |
膜上有划痕 | 3 |
膜被部分擦掉 | 2 |
膜(几乎完全)擦掉 | 1 |
耐磨损强度试验的结果显示在表7中:
表7: 耐磨损强度试验的结果
聚氨酯 | PUD 1 | PUD 2 |
值 | 3 | 5 |
用于粉底:
用表8中所示的组分根据以下方法制备受试粉底。
1. 相A在室温下预分散,增稠剂在此单独分散;
2.将来自相B的TiO2添加到相A中,然后搅拌;
3. 将C相加热至75℃,将B相的剩余成分,即颜料和云母添加到相C中,并将混合物均质化10分钟之久;
4. 将相A和B的混合物加热至75℃,然后将相C和B的混合物在75℃下添加到相A和B的混合物中,搅拌并均质化10分钟;
5.在45℃下加入相E。
表8: 粉底制剂
相 | 组分(INCI名称) | 量[重量%] |
A | 水 | 加至100.00 |
羧甲基纤维素钠 | 0.30 | |
硅酸镁铝 | 0.35 | |
聚山梨醇酯20 | 0.40 | |
三乙醇胺(10%) | 1.25 | |
丁二醇 | 6.00 | |
B | 二氧化钛 | 4.00 |
红色氧化铁 | 0.27 | |
黄色氧化铁 | 0.54 | |
黑色氧化铁 | 0.09 | |
云母 | 1.00 | |
C | 异二十烷 | 9.00 |
异硬脂酸 | 1.00 | |
硬脂酸 | 0.50 | |
硬脂酸甘油酯 | 0.50 | |
鲸蜡硬脂醇 | 3.50 | |
硬脂酸甘油酯SE | 2.00 | |
D | 环硅氧烷 | 2.00 |
聚甲基倍半硅氧烷 | 1.00 | |
E | 聚氨酯(固体) | 2.00 |
苯氧基乙醇(和)乙基己基甘油 | 0.80 | |
总和 | 100.00 |
使用移液管将0.02克粉底制剂施加到皮肤的特定区域上。以圆圈形式(30个圆圈)将制剂均匀分布在皮肤上。2名受试者评价制剂性质。评价等级对于性质:分布、粘性、粉状皮肤感觉、颜色分布、小轮形成(Röllchenbildung)在0至5之间;其中5意味着该性质完全存在。
感官评价的结果显示在图1中。图中的附图标记具有以下含义:
1 干燥前
2 干燥后
3 分布
4 粘性
5 粉状皮肤感觉
6 颜色分布
7 小轮形成
8 无聚氨酯
9 含PUD 1
10 含PUD 2。
Claims (14)
1.装饰性化妆品组合物,其含有至少一种可通过使一种或多种水不溶性、水不分散性、异氰酸酯官能的聚氨酯预聚物A与一种或多种氨基官能化合物B)反应获得的聚氨酯,其特征在于所述聚氨酯预聚物A)可通过使一种或多种具有至少-50℃的玻璃化转变温度TG的聚酯多元醇和一种或多种多异氰酸酯反应获得。
2.如权利要求1中所述的装饰性化妆品组合物,其特征在于一种或多种异氰酸酯官能的聚氨酯预聚物A)基本没有离子基团和离子源基团。
3.如权利要求1或2中所述的装饰性化妆品组合物,其特征在于所述氨基官能化合物B)选自伯胺和/或仲胺和/或二胺。
4.如权利要求1至3任一项中所述的装饰性化妆品组合物,其特征在于所述氨基官能化合物B)包含至少一种二胺。
5.如权利要求1至4任一项中所述的装饰性化妆品组合物,其特征在于所述氨基官能化合物B)选自具有离子基团和/或离子源基团的氨基官能化合物B2)和没有离子基团和/或离子源基团的氨基官能化合物B1)。
6.如权利要求1至5任一项中所述的装饰性化妆品组合物,其特征在于所述氨基官能化合物B)包含至少一种具有离子基团和/或离子源基团的氨基官能化合物B2),优选2-(2-氨基乙基氨基)乙磺酸和/或其盐。
7.如权利要求1至6任一项中所述的装饰性化妆品组合物,其特征在于所述氨基官能化合物B)包含至少一种没有离子基团和/或离子源基团的氨基官能化合物B1),优选没有离子基团和/或离子源基团的二胺。
8.如权利要求1至7任一项中所述的装饰性化妆品组合物,其特征在于所述氨基官能化合物B)包含具有离子基团和/或离子源基团的氨基官能化合物B2)和没有离子基团和/或离子源基团的氨基官能化合物B1)。
9.如权利要求1至8任一项中所述的装饰性化妆品组合物,其特征在于所述聚氨酯含有至少一个磺酸和/或磺酸根基团,优选磺酸钠基团。
10.如权利要求1至9任一项中所述的装饰性化妆品组合物,其特征在于其含有一种或多种产生装饰效果,如提供颜色或提供效果的效果的成分。
11.含有至少一种可通过使一种或多种水不溶性、水不分散性、异氰酸酯官能的聚氨酯预聚物A)与一种或多种氨基官能化合物B)反应获得的聚氨酯的组合物作为装饰性化妆品组合物的用途,其中所述聚氨酯预聚物A)可通过使一种或多种具有至少-50℃的玻璃化转变温度TG的聚酯多元醇和一种或多种多异氰酸酯反应获得。
12.聚氨酯,其可通过使一种或多种水不溶性、水不分散性、异氰酸酯官能的聚氨酯预聚物A与一种或多种氨基官能化合物B)反应获得,其特征在于所述聚氨酯预聚物A)可通过使一种或多种具有至少-50℃的玻璃化转变温度TG的聚酯多元醇和一种或多种多异氰酸酯反应获得。
13.在皮肤和/或毛发上产生装饰效果的化妆方法,其包括将含有至少一种可通过使一种或多种水不溶性、水不分散性、异氰酸酯官能的聚氨酯预聚物A)与一种或多种氨基官能化合物B)反应获得的聚氨酯的组合物施加到皮肤和/或毛发上,其中所述聚氨酯预聚物A)可通过使一种或多种具有至少-50℃的玻璃化转变温度TG的聚酯多元醇和一种或多种多异氰酸酯反应获得。
14.如权利要求13中所述的化妆方法,其特征在于所述组合物在施加到皮肤上后至少部分地保留在皮肤上。
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EP20167029.6 | 2020-03-31 | ||
EP20167029.6A EP3888627A1 (de) | 2020-03-31 | 2020-03-31 | Biobasierte polyurethan-dispersionen für dekorative kosmetische anwendungen |
PCT/EP2021/057872 WO2021198051A1 (de) | 2020-03-31 | 2021-03-26 | Biobasierte polyurethan-dispersionen für dekorative kosmetische anwendungen |
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US (1) | US20230135505A1 (zh) |
EP (2) | EP3888627A1 (zh) |
CN (1) | CN115297836A (zh) |
BR (1) | BR112022019614A2 (zh) |
WO (1) | WO2021198051A1 (zh) |
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DE202021106358U1 (de) * | 2021-11-22 | 2023-02-23 | Schwan Cosmetics International GmbH | Farbgebende kosmetische Zubereitung und Verwendungen derselben |
DE102021130521A1 (de) | 2021-11-22 | 2023-05-25 | Schwan Cosmetics International GmbH | Farbgebende kosmetische Zubereitung und Verwendungen derselben |
FR3131208A1 (fr) | 2021-12-23 | 2023-06-30 | L'oreal | Composition cosmétique comprenant un copolymère polyhydroxyalcanoate à chaine hydrocarbonée (in)saturé, et au moins un latex de polyuréthane |
FR3136969A1 (fr) | 2022-06-24 | 2023-12-29 | L'oreal | Composition aqueuse de soin et/ou du maquillage des matières kératiniques comprenant un monoester d’acide gras, un sel d’acide gras, une dispersion aqueuse de polyuréthane avec un alcanediol |
FR3137832A1 (fr) | 2022-07-13 | 2024-01-19 | L'oreal | Emulsion huile-dans-eau comprenant un polyuréthanne et une charge spécifiques |
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FR2789682B1 (fr) | 1999-02-12 | 2001-05-04 | Oreal | Nouveaux derives silicies de benzimidazole-benzazoles n-substitues ou de benzofuranyl-benzazoles filtres, compositions cosmetiques photoprotectrices les contenant et utilisations |
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FR2821621B1 (fr) | 2001-03-05 | 2004-11-05 | Oreal | Polyurethannes anioniques a caractere elastique et leur utilisation dans des compositions cosmetiques |
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2020
- 2020-03-31 EP EP20167029.6A patent/EP3888627A1/de active Pending
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2021
- 2021-03-26 CN CN202180026433.2A patent/CN115297836A/zh active Pending
- 2021-03-26 WO PCT/EP2021/057872 patent/WO2021198051A1/de unknown
- 2021-03-26 US US17/912,548 patent/US20230135505A1/en active Pending
- 2021-03-26 BR BR112022019614A patent/BR112022019614A2/pt not_active Application Discontinuation
- 2021-03-26 EP EP21713981.5A patent/EP4125800A1/de active Pending
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WO2021198051A1 (de) | 2021-10-07 |
EP4125800A1 (de) | 2023-02-08 |
EP3888627A1 (de) | 2021-10-06 |
BR112022019614A2 (pt) | 2022-11-16 |
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