CN117956968A - 热敏组合物及其制备方法 - Google Patents
热敏组合物及其制备方法 Download PDFInfo
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- CN117956968A CN117956968A CN202280060676.2A CN202280060676A CN117956968A CN 117956968 A CN117956968 A CN 117956968A CN 202280060676 A CN202280060676 A CN 202280060676A CN 117956968 A CN117956968 A CN 117956968A
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Abstract
本发明涉及一种热敏组合物,其包含i)包含至少两个聚环氧乙烷嵌段和至少一个聚环氧丙烷嵌段的水溶性嵌段共聚物;以及(ii)至少一种基于酯的润肤剂和/或基于烷烃的润肤剂,尤其是用于递送化妆品活性成分的热敏组合物,及其制备方法。
Description
技术领域
本发明涉及一种热敏组合物,尤其是用于递送化妆品活性成分的热敏组合物,及其制备方法。
背景技术
化妆品应用中的热敏体系可以提供许多独特的益处,例如质地转变、智能粘度控制、活性释放控制、热力SPF增强、成膜以及均匀的粉末分布。
聚环氧乙烷和聚环氧丙烷的水溶性嵌段共聚物是具有热敏行为的经典系列材料。
目前,这些具有热敏行为的材料的主要应用是个人护理和制药领域中的增溶和活性释放控制。一些现有技术还关注于含聚环氧乙烷和聚环氧丙烷的水溶性嵌段共聚物的水凝胶组合物,该组合物在室温或低于室温下呈液态,随后在施加之后升温至体温时转变为凝胶形式。
US 4188373 A披露了聚环氧乙烷和聚环氧丙烷的非离子嵌段共聚物在水性药物组合物中的用途。在这些体系中,调节聚合物的浓度以得到期望的溶胶-凝胶转变温度。
US 8865143 B披露了逆向热可逆水凝胶组合物,其在约4℃至50℃的温度范围内具有凝胶形式。
然而,聚环氧乙烷和聚环氧丙烷的水溶性嵌段共聚物在乳液体系中的热敏应用在市场上还很少见。在凝胶型形式中,通常需要高含量的聚环氧乙烷和聚环氧丙烷的水溶性嵌段共聚物来提供热敏行为,这导致令人不愉快的感觉、较高的成本和较低的配方相容性。
发明内容
本发明的目的是通过选择特定的润肤剂来提供一种优化的配制品体系,以在组合物中具有较少含量的聚环氧乙烷和聚环氧丙烷的水溶性嵌段共聚物的情况下获得预期的热敏行为。
已经发现,本发明的目的可以通过包含以下的热敏组合物来实现:(a)包含至少两个聚环氧乙烷嵌段和至少一个聚环氧丙烷嵌段的水溶性嵌段共聚物;(b)至少一种基于酯的润肤剂和/或基于烷烃的润肤剂;以及(c)至少一种乳化剂,其中所述组合物具有5℃至40℃的质地转变温度。
特别地,本发明涉及以下方面。
在第一方面,本发明提供了一种热敏组合物,其包含:(a)包含至少两个聚环氧乙烷嵌段和至少一个聚环氧丙烷嵌段的水溶性嵌段共聚物;(b)至少一种基于酯的润肤剂和/或基于烷烃的润肤剂;以及(c)至少一种乳化剂,其中所述组合物具有5℃至40℃的质地转变温度。
在第二方面,本发明提供了一种用于制备根据本发明的热敏组合物的方法,该方法包括将该热敏组合物的组分混合。
在第三方面,本发明提供了根据本发明的热敏组合物作为用于化妆品活性成分的递送系统的用途。
具体实施方式
现在将在下文中详细描述本发明。应当理解,本发明可以以许多不同的方式来实施并且不应被解释为限于本文所阐述的实施例。除非另外提及,否则本文使用的所有技术和科学术语具有与由本发明所属领域的普通技术人员通常所理解的相同的含义。
如本文所用的,单数形式“一种/一个(a/an)”,和“该(the)”包括复数个指示物,除非上下文中另外明确指明。
如本文所用的,术语“包含(comprise/comprising)”等与“含有(contain/containing)”等可互换使用并应以非限制性、开放的方式进行解释。也就是说,例如,可以存在另外的组分或元素。表述“由……组成”或“基本上由……组成”或同源词可以包括在“包含(comprises)”或同源词中。
本发明的第一方面提供了一种热敏组合物,其包含:(a)包含至少两个聚环氧乙烷嵌段和至少一个聚环氧丙烷嵌段的水溶性嵌段共聚物;(b)至少一种基于酯的润肤剂和/或基于烷烃的润肤剂;以及(c)至少一种乳化剂,其中所述组合物具有5℃至40℃的质地转变温度。特别地,例如,质地转变是从液体质地到半固体或固体质地。更特别地,例如,质地转变是从乳剂或流动乳液质地到乳霜质地。
优选地,根据本发明的热敏组合物具有6℃至40℃的质地转变(例如从乳剂到乳霜)温度,例如10℃、15℃、20℃、25℃、30℃、35℃,更优选15℃至40℃。
水溶性嵌段共聚物(a)
在本发明的上下文中,热敏组合物包含水溶性嵌段共聚物作为组分(a),该水溶性嵌段共聚物包含至少两个聚环氧乙烷嵌段和至少一个聚环氧丙烷嵌段。
术语“聚环氧乙烷”、“PEO”、“EO”、“聚乙二醇”和“PEG”可互换使用来描述本发明,并且是指由以下化学结构表示的环氧乙烷的合成聚合物:
其中a是表示单体重复单元的平均数的整数。
术语“聚环氧丙烷”、“PPO”、“PO”、“聚丙二醇”和“PPG”可互换使用来描述本发明,并且是指由以下化学结构表示的环氧丙烷的合成聚合物:
其中b是表示单体重复单元的平均数的整数。
聚环氧乙烷和聚环氧丙烷的嵌段共聚物是指聚环氧乙烷嵌段(式1)和聚环氧丙烷嵌段(式2)的合成共聚物,该共聚物具有可变的分子量和不同的类型,包括直链多嵌段共聚物、侧链接枝嵌段共聚物、和超支化嵌段共聚物以及星形嵌段共聚物;聚环氧乙烷和聚环氧丙烷的嵌段共聚物还包括不同类型的末端改性和扩链的嵌段共聚物。
特别感兴趣的本发明的水溶性嵌段共聚物是包含至少两个具有式-[CH2CH2O]a-的聚环氧乙烷嵌段和至少一个具有式-[CH2CH(CH3)O]b-的聚环氧丙烷嵌段的嵌段共聚物,其中a表示约10至160、优选约40至160、更优选约50至150、最优选约55至145的数,并且b表示约10至160、优选约30至80、更优选约35至70、最优选约40至60的数。
本发明的包含至少两个聚环氧乙烷嵌段和至少一个聚环氧丙烷嵌段的示例性水溶性嵌段共聚物是以商品名(也称为泊洛沙姆(Poloxamer))从新泽西州芒特奥利夫的巴斯夫公司(BASF)可商购的三嵌段共聚物。具有通式HO-(EO)a(PO)b(EO)a-H的优选的泊洛沙姆聚合物分别是/>F127(也称为泊洛沙姆407)--其中a的平均值为约101并且b的平均值为约56,以及/>F108(也称为泊洛沙姆338)--其中a的平均值为约141并且b的平均值为约44。
本发明的包含至少两个聚环氧乙烷嵌段和至少一个聚环氧丙烷嵌段的其他示例性水溶性嵌段共聚物是具有通式HO-[(PO)b(EO)a]m(PO)c[(EO)a(PO)b]m-H的直链多嵌段共聚物,其中(EO)a是聚环氧乙烷嵌段,并且(PO)b或(PO)c是聚环氧丙烷嵌段,a、b和c各自表示约10-160的数,并且m是大于0的整数值。
本发明的其他水溶性多嵌段共聚物是具有式{[An(EO)a(PO)b(EO)aAn]E}m的扩链、超支化或星形嵌段共聚物,其中(EO)a是聚环氧乙烷嵌段,并且(PO)b是聚环氧丙烷嵌段,A是单体重复单元,E是扩链剂或交联剂,n是范围为0至50、优选1至20(在非可生物降解的材料的情况下为0至20)、甚至更优选2至16(在非可生物降解的材料的情况下为0至16)的整数,并且m是聚合物分子中的重复单元的数目并且是等于或大于2的整数(在实际限制内,最高达约100,000或更大),优选范围为约2至约500、更优选约3至100。因此,在n为0的情况下,本发明考虑具有结构{[(EO)a(PO)b(EO)a]E}m的聚合物。
本发明的其他水溶性嵌段共聚物是具有通式R-G-(EO)a(PO)b(EO)a-G-R的末端改性嵌段共聚物,其中(EO)a是聚环氧乙烷嵌段,并且(PO)b是聚环氧丙烷嵌段,G选自由C-C、C-O、C(O)NH、S-C、C(O)-O和Si-O组成的组,R是具有在C6-C36范围内的烷基链长度的烷基或芳基烷基,a是范围为50至150的整数,b是范围为35至70的整数。
示例性的水溶性嵌段共聚物是包含至少两个聚环氧乙烷嵌段和至少一个聚环氧丙烷嵌段的烷基或芳基烷基末端改性剂嵌段共聚物,其是醇与末端烷基或芳基烷基的缩合反应的产物。烷基应具有疏水特征,如丁基、己基等。烷基泊洛沙姆可以具有通式R-[(EO)a(PO)b(EO)a]m-R′,其中(EO)a是聚环氧乙烷嵌段,(PO)b是聚环氧丙烷嵌段,R和R′为非极性基团,如具有在C6-C36范围内的烷基链长度的烷基和芳基烷基,并且m是范围为1至10的整数。
本发明的其他示例性水溶性嵌段共聚物是包含至少两个聚环氧乙烷嵌段和至少一个聚环氧丙烷嵌段的接枝侧链的接枝嵌段共聚物,其具有通式[A(EO)a(PO)b(EO)a]m,其中(EO)a是聚环氧乙烷嵌段,(PO)b是聚环氧丙烷嵌段,a和b各自独立地表示约10至150的数。A是由以下组成的共聚物的主链的单体重复单元:乙烯基、酯、酰胺、酰亚胺、醚、硅氧烷键等,m是聚合物分子中重复单元的数目并且是等于或大于2的整数。
本发明的其他水溶性多嵌段共聚物是具有式{[An(EO)a(PO)b(EO)aAn]E}m的聚酯扩链嵌段共聚物,其中(EO)a是聚环氧乙烷嵌段,(PO)b是聚环氧丙烷嵌段,A是单体重复单元,(EO)a是聚环氧乙烷嵌段,并且(PO)b是如先前定义的聚环氧丙烷嵌段,E是扩链剂或交联剂,n是范围为0至50、优选1至20(在非可生物降解的材料的情况下为0至20)、甚至更优选2至16(在非可生物降解的材料的情况下为0至16)的整数,并且m是聚合物分子中的重复单元的数目并且是等于或大于2的整数(在实际限制内,最高达约100,000或更大),优选范围为约2至约500、更优选约3至100。因此,在n为0的情况下,本发明考虑具有结构{[(EO)a(PO)b(EO)a]E}m的聚合物。
单体重复单元可以衍生自脂肪族羟基羧酸或相关酯、内酯、二聚酯、碳酸酯、酸酐、二氧环己酮、酰胺或相关单体,并且优选衍生自脂肪族α-羟基羧酸或相关酯,此类单元衍生自以下项:包括例如,乳酸、丙交酯、乙醇酸、乙交酯,或相关的脂肪族羟基羧酸、酯(内酯)、二聚酸或相关的化合物例如像β-丙内酯、ε-己内酯、δ-戊二醇内酯、δ-戊内酯、β-丁内酯、新戊内酯、α,α-二乙基丙内酯、碳酸亚乙酯、碳酸三亚甲基酯、γ-丁内酯、对二氧环己酮、1,4-二氧杂环庚烷-2-酮、3-甲基-1,4-二氧杂环己-2,5-二酮、3,3,-二甲基-1-4-二氧杂环己-2,5-二酮,α-羟基丁酸、α-羟基戊酸、α-羟基异戊酸、α-羟基己酸、α-羟基-α-乙基丁酸、α-羟基异己酸、α-羟基-α-甲基戊酸、α-羟基庚酸、α-羟基硬脂酸、α-羟基二十四烷酸、水杨酸及其混合物的环状酯。优选在本发明中使用α-羟基酸及其相应的环状二聚酯,尤其是丙交酯、乙交酯和己内酯。值得注意的是,在使用根据本发明的某些所述单体时,产生的单体单元并不具体是酯基团,而是可以包括这样的基团,如衍生自上述单体或者含有亲核基团和亲电基团并且可以聚合的碳酸酯基团(聚碳酸酯)、氨基酸(其产生聚酰胺)和相关的基团。应当理解的是,术语聚酯应当涵盖衍生自所有上述单体的聚合物,其中优选实际产生酯单元的那些。
术语“聚(羟基羧酸)”或“聚(α-羟基羧酸)”是用于描述根据本发明使用的{[An(BCB)An]E}m多嵌段的某些聚酯A嵌段的术语,其中A是衍生自脂肪族羟基羧酸或相关的酯或二聚酯、并且优选衍生自脂肪族α-羟基羧酸或相关的酯的聚合物聚酯单元,包括环状二聚酯例如像乳酸、丙交酯、乙醇酸、乙交酯,或相关的脂肪族羟基羧酸或酯(内酯)例如像ε-己内酯、δ-戊二醇内酯、δ-戊内酯、γ-丁内酯及其混合物,以及如本文所述的许多其他物质。优选在本发明中使用α-羟基酸及其相应的环状二聚酯,尤其是丙交酯和乙交酯。
在一个优选的实施例中,本发明的水溶性嵌段共聚物是三嵌段EO-PO-EO共聚物,其可以由以下通式表示:
其中a表示40至160、优选50至150、更优选55至145的数,并且b表示30至80、优选35至70、更优选40至60的数。
优选地,根据本发明的热敏组合物可以包含基于热敏组合物的总重量大于或等于按重量计5%、优选按重量计5%至20%、更优选按重量计6%至18%、最优选按重量计7%至15%、尤其是按重量计8%至13%的组分(a)。
基于酯/烷烃的润肤剂(b)
在本发明的上下文中,热敏组合物包含至少一种基于酯的润肤剂和/或基于烷烃的润肤剂作为组分(b)。
本文使用的术语“润肤剂”是指可用于预防或缓解干燥以及用于保护皮肤的材料。
在基于酯的润肤剂中,酯由至少一种酸和至少一种醇形成,并且各种酸和各种醇的碳原子总数小于或等于42、优选小于或等于28、更优选小于或等于22,并且各种酸和各种醇的碳原子数之差的绝对值小于或等于15、优选小于或等于10、更优选小于或等于8。
在酯中,酸部分可以衍生自一元羧酸、二元羧酸、包含至少3个羧基的多元羧酸、或碳酸。
一元羧酸可以是饱和或不饱和的,或者甚至是芳族、直链或支链的,其包含5至26个碳原子、优选6至22个碳原子、更优选6至18个碳原子。
在可以使用的一元羧酸中,可以单独或混合地提及以下项:
饱和一元羧酸,如己酸、异庚酸、4-乙基戊酸、2-乙基己酸、4,5-二甲基己酸、2-庚基庚酸、3,5,5-三甲基己酸、辛酸、异辛酸、壬酸、异壬酸、癸酸、月桂酸、十三烷酸、肉豆蔻酸、棕榈酸、硬脂酸、异硬脂酸、花生酸、山萮酸、蜡酸、椰油酸;以及
不饱和一元羧酸,如癸烯酸、十碳烯酸、十一碳烯酸、十二碳烯酸、林德酸、肉豆蔻脑酸、油酸、芥酸;以及芳族一元羧酸,如苯甲酸、邻甲基苯甲酸、间甲基苯甲酸、对甲基苯甲酸、4-叔丁基苯甲酸。
优选地,可以使用以下项:2-乙基己酸、辛酸、异辛酸、癸酸、月桂酸、肉豆蔻酸、异庚酸、异壬酸、壬酸、棕榈酸、硬脂酸、油酸、芥酸、椰油酸、苯甲酸、邻甲基苯甲酸、间甲基苯甲酸或其组合。
二元羧酸可以是饱和或不饱和的,或者甚至是芳族、直链或支链的,其包含5至15个碳原子、优选6至12个碳原子、更优选6至10个碳原子。
优选地,所述二元羧酸是脂肪族的并且包含5至15个碳原子、优选6至12个碳原子、更优选6至10个碳原子。
在可以使用的二元羧酸中,可以单独或混合地提及以下项:
癸二酸、十二烷二酸、辛二酸、草酸、丙二酸、琥珀酸、邻苯二甲酸、对苯二甲酸、间苯二甲酸、庚二酸、癸二酸、壬二酸、戊二酸、己二酸、富马酸、马来酸、衣康酸。
多元羧酸可以是饱和或不饱和的,或者甚至是芳族、直链或支链的,其包含至少3个羧基、优选3至4个羧基、更优选3个羧基。
所述多元羧酸可以包含5至15个碳原子、优选6至12个碳原子、更优选6至10个碳原子。
优选地,所述多元羧酸是脂肪族的并且包含5至15个碳原子、优选6至12个碳原子、更优选6至10个碳原子。优选地,其包含3个羧基。
在可以使用的多元羧酸中,可以单独或混合地提及以下项:
三羧酸,如偏苯三酸、1,2,3-苯三甲酸、1,3,5-苯三甲酸;以及
四羧酸,如丁烷四羧酸和苯均四酸。
在酯中,醇部分可以衍生自一元醇、二元醇或多元醇。
一元醇可以是非支链或支链的脂肪族C1-C25-醇、优选C2-C22-醇、更优选C4-C20-醇,如乙醇、丙醇、异丙醇、正丁醇、仲丁醇、异丁醇、叔丁醇、正戊醇、异戊醇、叔戊醇、正己醇、甲基-2-丁醇、3-甲基-3-戊醇、2-乙基己醇、正庚醇、正辛醇、异辛醇、2-乙基己醇、正壬醇、异壬醇、2-丙基己醇、正癸醇、异癸醇、2-丙基庚醇、正十一烷醇、正十二烷醇、正十三烷醇、正十四烷醇、正十五烷醇或其组合。
优选的一元醇是异丙醇、正丁醇、正己醇、正辛醇、异辛醇、正壬醇、异壬醇、正十二烷醇、正十三烷醇、正十四烷醇、正十五烷醇、鲸蜡硬脂醇、油醇、辛基十二烷醇、癸醇或其组合。
二元醇可以是非支链或支链的脂肪族C2-C8-烷二醇,更优选非支链或支链的C2-C6-烷二醇,如1,2-乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、1,2-戊二醇、1,3-戊二醇、2-甲基-1,3-戊二醇、2,2-二甲基-1,3-戊二醇、1,4-戊二醇、1,5-戊二醇、1,2-己二醇、1,3-己二醇、1,4-己二醇、1,5-己二醇、1,6-己二醇或这些二元醇的混合物。更特别地,用于制备具有通式(I)的聚酯增塑剂的二元醇是1,2-丙二醇、1,3-丁二醇、1,4-丁二醇、2,2-二甲基-1,3-丙二醇、或其混合物。
多元醇可以是非支链或支链脂肪族的,其包含3至4个羟基。
所述多元醇优选包含3至15个碳原子、优选3至12、更优选4至10个碳原子。
在可以使用的多元醇中,可以单独或混合地提及以下项:
三醇,如甘油、三羟甲基乙烷、三羟甲基丙烷、1,2,4-丁三醇、1,2,6-己三醇;以及
四醇,如季戊四醇(四羟甲基甲烷)、赤藓醇、二甘油或双三羟甲基丙烷。
在一个优选的实施例中,酯由至少一种选自由辛酸、异壬酸、癸酸、月桂酸、2-乙基己酸、苯甲酸、己二酸、碳酸或其组合组成的组的酸,以及至少一种选自由正丁醇、正己醇、正辛醇、异壬醇、正十二烷醇、正十三烷醇、正十四烷醇、正十五烷醇、甘油、季戊四醇或其组合组成的组的醇形成。
在一个特别优选的实施例中,酯选自由以下组成的组:己二酸二丁酯、月桂酸己酯、C12-15-烷基苯甲酸酯、季戊四醇四乙基己酸酯、三乙基己酸甘油酯、碳酸二辛酯、异壬酸异壬酯、辛酸/癸酸甘油三酯或其组合。
作为基于烷烃的润肤剂,选自由直链烷烃、石蜡油和氢化聚异丁烯组成的组中的至少一种适用于本发明。
作为适用于本发明的烷烃的实例,可以提及正庚烷(C7)、正辛烷(C8)、正壬烷(C9)、正癸烷(C10)、正十一烷(C11)、正十二烷(C12)、正十三烷(C13)和正十四烷(C14)、正十五烷(C15)及其混合物。根据一个具体实施例,直链烷烃选自正壬烷、正十一烷、正十二烷、正十三烷、正十四烷和正十五烷、及其混合物。
根据一个优选的实施例,可以提及正十一烷(C11)和正十三烷(C13)的混合物(作为ULTIMATE从巴斯夫公司可商购)。
根据本发明,可以使用的根据本发明有利的石蜡油是来自默克凡士林公司(Merkur Vaseline)的Merkur white oil Pharma 40,来自壳牌DEA油气公司(Shell&DEAOil)的Shell Ondina 917、Shell Ondina 927、Shell Oil 4222、Shell Ondina 933,Pionier 6301S、Pionier 2071(汉圣公司(Hansen&Rosenthal))。
根据本发明,可以使用的根据本发明有利的氢化聚异丁烯是从巴斯夫公司可商购的LITE EM。
优选地,根据本发明的热敏组合物可以包含基于该热敏组合物的总重量按重量计大于0%至小于或等于60%、优选按重量计4%至55%、更优选按重量计5%至50%、最优选按重量计10%至45%、尤其是按重量计25%至45%的组分(b)。
在一个实施例中,组分(a)和(b)按重量计%的量满足以下等式:(a)+(b)/9≥11.5,优选25.0≥(a)+(b)/9≥11.5,更优选15.0≥(a)+(b)/9≥11.5。
在一个优选的实施例中,根据本发明的热敏组合物可以包含基于该热敏组合物的总重量按重量计大于或等于5%、优选按重量计5%至20%、更优选按重量计6%至18%、最优选按重量计7%至15%、尤其是按重量计8%至13%的组分(a),以及按重量计大于0%至小于或等于60%、优选按重量计4%至55%、更优选按重量计5%至50%、最优选按重量计10%至45%、尤其是按重量计25%至45%的组分(b),并且组分(a)和(b)按重量计%的量满足以下等式:(a)+(b)/9≥11.5,优选25.0≥(a)+(b)/9≥11.5,更优选15.0≥(a)+(b)/9≥11.5。
乳化剂(c)
在本发明的上下文中,热敏组合物包含至少一种乳化剂作为组分(c)。
化妆品应用或个人护理应用中任何常规使用的乳化剂均可用于本发明的组合物。
乳化剂可以包含例如:
羧酸及其盐:钠、钾和铵的碱性皂,钙或镁的金属皂,有机基皂如月桂酸、棕榈酸、硬脂酸和油酸等。烷基磷酸酯或磷酸酯、酸式磷酸盐、磷酸二乙醇胺、鲸蜡醇磷酸酯钾。乙氧基化羧酸或聚乙二醇酯,PEG-n酰化物。具有8至22个碳原子的直链脂肪醇,用具有12至22个碳原子的脂肪酸和烷基中具有8至15个碳原子的烷基酚支化的2至30mol环氧乙烷和/或0至5mol环氧丙烷。脂肪醇聚乙二醇醚如山嵛醇聚醚-n(例如山嵛醇聚醚-25(BA25))、月桂醇聚醚-n、鲸蜡硬脂醇聚醚-n、硬脂醇聚醚-n、油醇聚醚-n。脂肪酸聚乙二醇醚如PEG-n硬脂酸酯、PEG-n油酸酯、PEG-n椰油酸酯。甘油单酯和多元醇酯。1至30mol环氧乙烷与多元醇的加成产物的C12-C22脂肪酸单酯和二酯。脂肪酸和聚甘油酯如单硬脂酸甘油酯、二异硬脂酰基聚甘油基-3-二异硬脂酸酯、聚甘油基-3-二异硬脂酸酯、三甘油二异硬脂酸酯、聚甘油基-2-倍半异硬脂酸酯、聚甘油基-2-二聚羟基硬脂酸酯或聚甘油基二聚酸酯。来自多个那些物质类别的化合物的混合物也是适合的。脂肪酸聚乙二醇酯如二甘醇单硬脂酸酯、脂肪酸和聚乙二醇酯,脂肪酸和蔗糖(saccharose)酯如蔗糖(sucro)酯(例如蔗糖聚硬脂酸酯(/>Sucro)),甘油和蔗糖酯如蔗糖甘油酯。山梨糖醇和脱水山梨糖醇,具有6至22个碳原子的饱和及不饱和脂肪酸和环氧乙烷加成产物的脱水山梨糖醇单酯和二酯。聚山梨醇酯-n系列,脱水山梨糖醇酯如倍半异硬脂酸酯、脱水山梨糖醇、PEG-(6)-脱水山梨糖醇异硬脂酸酯、PEG-(10)-脱水山梨糖醇月桂酸酯、PEG-17-脱水山梨糖醇二油酸酯。葡萄糖衍生物,C8-C22烷基-单和寡糖苷以及乙氧基化类似物,其中葡萄糖优选作为糖组分。O/W乳化剂如甲基葡糖醇聚醚-20-倍半硬脂酸酯、脱水山梨糖醇硬脂酸酯/蔗糖椰油酸酯、甲基葡萄糖倍半硬脂酸酯、鲸蜡硬脂醇/鲸蜡硬脂基葡糖苷。W/O乳化剂如甲基葡萄糖二油酸酯/甲基葡萄糖异硬脂酸酯。硫酸盐和磺化衍生物、二烷基磺基琥珀酸盐、二辛基琥珀酸盐、烷基月桂基磺酸盐、直链磺化石蜡、磺化四丙烯磺酸盐、月桂基硫酸钠、月桂基硫酸铵和月桂基硫酸乙醇胺、月桂基醚硫酸盐、月桂醇醚硫酸钠、磺基琥珀酸盐、乙酰基异硫磺酸盐、烷醇酰胺硫酸盐、牛磺酸、甲基牛磺酸、咪唑硫酸盐;聚硅氧烷/聚烷基/聚醚共聚物和衍生物、聚二甲基硅氧烷、共聚多元醇、硅酮聚环氧乙烷共聚物、硅酮二醇共聚物;丙氧基化或POE-n醚(Meroxapols);分子中携带至少一个季铵基团和至少一个羧酸和/或磺酸基团的两性离子表面活性剂。特别合适的两性离子乳化剂为甜菜碱,如N-烷基-N,N-二甲基甘氨酸铵、椰油烷基二甲基甘氨酸铵、N-酰基氨基丙基-N,N-二甲基甘氨酸铵、椰油酰基氨基丙基二甲基甘氨酸铵和2-烷基-3-羧基甲基-3-羟基乙基咪唑啉,其各自在烷基或酰基中具有8至18个碳原子,以及还有椰油酰基氨基乙基羟基乙基羧基甲基甘氨酸盐、N-烷基甜菜碱、N-烷基氨基甜菜碱;烷基咪唑啉、烷基肽、脂基氨基酸、自乳化碱和如在K.F.DePolo,A shorttextbook of cosmetology[美容学短篇教材],第8章,表8-7,第250-251页中所述的化合物。
在一个实施例中,乳化剂可以包括例如非离子乳化剂,如
(1)2至50mol环氧乙烷和/或1至20mol环氧丙烷与含有8至40个碳原子的直链脂肪醇、与含有12至40个碳原子的脂肪酸、以及与在烷基中含有8至15个碳原子的烷基苯酚的加成产物;
(2)1至50mol环氧乙烷与甘油的加成产物的C12-18脂肪酸单酯和二酯;
(3)含有6至22个碳原子的饱和和不饱和脂肪酸的脱水山梨糖醇单酯和二酯及其环氧乙烷加合物;
(4)在烷基中含有8至22个碳原子的烷基单糖苷和寡糖苷及其乙氧基化类似物;
(5)7至60mol环氧乙烷与蓖麻油和/或氢化蓖麻油的加成产物;
(6)多元醇酯,并且特别是聚甘油酯,例如像多元醇聚-12-羟基硬脂酸酯、聚甘油聚蓖麻油酸酯、聚甘油基-4-月桂酸酯、聚甘油二异硬脂酸酯或聚甘油二聚酸酯。来自这些类别中的几种的化合物的混合物也是适合的;
(7)2至15mol环氧乙烷与蓖麻油和/或氢化蓖麻油的加成产物;
(8)基于直链、支链、不饱和或饱和C6-22脂肪酸、蓖麻油酸以及12-羟基硬脂酸和聚甘油、季戊四醇、二季戊四醇、糖醇(例如山梨糖醇)、烷基葡糖苷(例如甲基葡糖苷、丁基葡糖苷、月桂基葡糖苷)和多葡糖苷(例如纤维素)的偏酯或混合酯,以及蔗糖脂肪酸聚酯(例如用C8-C20、或C12-C18、或C14-C18脂肪酸酯化的蔗糖),例如蔗糖聚硬脂酸酯(作为SUCRO从巴斯夫公司可商购);
(9)聚硅氧烷/聚烷基/聚醚共聚物和相应的衍生物;以及
(10)季戊四醇、脂肪酸、柠檬酸和脂肪醇的混合酯和/或含有6至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。
在一个实施例中,乳化剂可以包括例如阴离子乳化剂,如PEG-2硬脂酸酯SE、硬脂酸甘油酯SE、硬脂酸丙二醇酯。阴离子酸性基体,如鲸蜡硬脂醇和鲸蜡硬脂基硫酸钠,鲸蜡硬脂醇和月桂基硫酸钠,三烷醇聚醚-4磷酸酯和乙二醇硬脂酸酯和PEG-2硬脂酸酯,硬脂酸甘油酯和月桂基硫酸钠,硬脂酰谷氨酸钠(例如SG)。阳离子酸性基体,如鲸蜡硬脂醇和十六烷基三甲基溴化铵。
在一个优选的实施例中,组合物包含至少一种非离子乳化剂,其中至少一种非离子表面活性剂可以是烷氧基化非离子表面活性剂或非烷氧基化非离子表面活性剂,优选烷氧基化非离子表面活性剂是C12-C24脂肪酸乙氧基化物,更优选C16-C22脂肪酸乙氧基化物,其中非烷氧基化非离子乳化剂是蔗糖脂肪酸酯。
在一个更优选的实施例中,组合物包含至少一种阴离子乳化剂和至少一种非离子乳化剂,其中该至少一种阴离子乳化剂为基于N-酰基氨基酸的表面活性剂。基于N-酰基氨基酸的表面活性剂的实例包括但不限于N-酰化丙氨酸、N-酰基谷氨酸、N-酰基甘氨酸、N-酰化肌氨酸、及其盐。特别地,基于氨基酸的表面活性剂可以是C8-C16酰基肌氨酸盐、C8-C16酰基谷氨酸盐、C8-C16酰基甘氨酸盐、或其组合。C8-C16酰基肌氨酸盐、C8-C16酰基谷氨酸盐和/或C8-C16酰基甘氨酸盐是分别衍生自氨基酸肌氨酸、谷氨酰胺或甘氨酸和相应的C8-C16脂肪酸的阴离子表面活性剂。合适的C8-C16酰基肌氨酸盐包括但不限于:月桂酰肌氨酸钠、椰油酰肌氨酸钠(其是C8-C16酰基肌氨酸钠的混合物)、肉豆蔻酰肌氨酸钠、月桂酰肌氨酸铵、椰油酰肌氨酸铵、月桂酰肌氨酸异丙酯、椰油酰肌氨酸钾、月桂酰肌氨酸钾及其组合;合适的C8-C16谷氨酸盐包括但不限于:月桂酰谷氨酸钠、椰油酰谷氨酸钠(其是C8-C16酰基谷氨酸钠的混合物)、肉豆蔻酰谷氨酸钠、月桂酰谷氨酸铵、椰油酰谷氨酸铵、月桂酰谷氨酸异丙酯、椰油酰谷氨酸钾、月桂酰谷氨酸钾及其组合;合适的C8-C16酰基甘氨酸盐包括但不限于:月桂酰甘氨酸钠、椰油酰甘氨酸钠(其是C8-C16酰基甘氨酸钠的混合物)、肉豆蔻酰甘氨酸钠、月桂酰甘氨酸铵、椰油酰甘氨酸铵、月桂酰甘氨酸异丙酯、椰油酰甘氨酸钾、月桂酰甘氨酸钾及其组合。还可以使用一种或多种C8-C16酰基肌氨酸盐、C8-C16酰基谷氨酸盐、和/或C8-C16酰基甘氨酸盐的组合。
优选地,根据本发明的热敏组合物可以包含基于该热敏组合物的总重量按重量计0.1%至30%、优选按重量计0.5%至25%、更优选按重量计1%至20%、最优选按重量计2%至15%、尤其是按重量计3%至10%的乳化剂。
在其他优选的实施例中,根据本发明的热敏组合物进一步包含以下其他成分。
增稠剂
适合用于根据本发明的热敏组合物的增稠剂是多糖,优选黄原胶(例如XGN(从巴斯夫公司可商购))、瓜尔胶、琼脂、藻酸盐或侵填体,纤维素衍生物,例如羟烷基纤维素,其中烷基是C1-C4-烷基,特别是羟乙基纤维素,优选NatrosolTM商品名、尤其优选赫克力士公司(Herkules Incorporated)的NatrosolTM250(CAS号9004-62-0),羧甲基纤维素或羟基羧甲基纤维素,淀粉,优选商品名National 465、Purity W或淀粉B990,以及还有脂肪酸的相对高分子量聚乙二醇单-和二酯,脂肪醇,甘油单酯和脂肪酸。
合适的增稠剂还有聚丙烯酸酯、交联的聚丙烯酸及其衍生物,如CD、和TTA(从巴斯夫公司可商购)、/>(从路博润公司(Lubrizol)可商购)、(从路博润公司可商购)、/>EM(从巴斯夫公司可商购)、/>SP(从巴斯夫公司可商购)、/>GTC UP(从巴斯夫公司可商购)、/>98(从赛比克公司(Seppic)可商购)、/>(从西格玛公司(Sigma)可商购)、来自罗门哈斯公司(Rohm and Haas)的/>等级,如/>22(丙烯酸酯和具有硬脂基的甲基丙烯酸乙氧基化物的共聚物(20个环氧乙烷(EO)单元))和/>28(丙烯酸酯和具有山萮基的甲基丙烯酸乙氧基化物的共聚物(25个EO单元))。
此外,合适的增稠剂是例如气溶胶等级(亲水性二氧化硅),聚丙烯酰胺,聚乙烯醇和聚乙烯基吡咯烷酮,乙氧基化脂肪酸甘油酯,脂肪酸与多元醇、例如像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萄糖苷,以及还有电解质如氯化钠和氯化铵。
增稠剂可以以本领域常规的量存在并且取决于它们的类型。本领域技术人员将能够为本发明选择合适的增稠剂和量。
在本发明的上下文中,增稠剂可以以基于热敏组合物的总重量0.01至3wt%、优选0.05至2.0wt%、更优选0.2至1.0wt%的量存在。
防腐剂
根据本发明的热敏组合物可以有利地包含一种或多种防腐剂。
在本发明的上下文中有利的防腐剂是例如甲醛供体(例如像DMDM乙内酰脲,其例如以商品名可商购(从龙沙公司(Lonza)可商购)),碘丙基丁基氨基甲酸酯(例如/>(从龙沙公司可商购),/>LMB(从简达克公司(Jan Dekker))可商购),对羟基苯甲酸酯(对羟基苯甲酸烷基酯,例如像对羟基苯甲酸甲酯、对羟基苯甲酸乙酯、对羟基苯甲酸丙酯和/或对羟基苯甲酸丁酯),脱氢乙酸(/>K702(从舒美公司(Schülke&Mayr)可商购)),苯氧基乙醇,乙醇,苯甲酸,或其组合。还有利地使用所谓的防腐助剂,例如像辛氧基甘油、甘氨酸、大豆等。
还有利的是化妆品中常用的防腐剂或防腐助剂,如二溴二氰基丁烷(2-溴-2-溴甲基戊二腈)、苯氧基乙醇、3-碘-2-丙炔基丁基氨基甲酸酯、2-溴-2-硝基丙烷-1,3-二醇、咪唑烷基脲、5-氯-2-甲基-4-异噻唑啉-3-酮、2-氯乙酰胺、苯甲醇、水杨酸和水杨酸盐。
防腐剂可以以基于热敏组合物的总重量0.01至5wt%、优选0.1至2wt%、更优选0.2至1wt%的量存在。
香水油
合适的话,根据本发明的热敏组合物可以包含香水油。可以提及的香水油是例如天然和合成香料的混合物。天然香料是来自花(百合、薰衣草、玫瑰、茉莉、橙花、依兰花),茎和叶(天竺葵、广藿香、苦橙叶),果实(茴香、芫荽、香菜、杜松),果皮(佛手柑、柠檬、橙),根(肉豆蔻、当归、芹菜、小豆蔻、闭鞘姜、鸢尾、菖蒲),木材(松木、檀香木、愈创木、杉木、黄檀木),药草和禾草(龙蒿、柠檬草、鼠尾草、百里香),针叶和细枝(云杉、冷杉、松树、矮生松),树脂和香脂(白松香、榄香脂、安息香、没药、乳香、红没药)的提取物。还合适的是动物原料,例如像麝猫和海狸。典型的合成香料化合物是酯、醚、醛、酮、醇和烃类型的产物。酯类型的香料化合物是例如乙酸苄酯、异丁酸苯氧基乙酯、4-叔丁基环己基乙酸酯、乙酸芳樟酯、乙酸二甲基苄基甲醇酯、乙酸苯乙酯、苯甲酸芳樟酯、甲酸苄酯、苯基甘氨酸乙基甲基酯、环己基丙酸烯丙酯、丙酸苏合香酯和水杨酸苄酯。醚类包括例如苄基乙基醚,醛类包括例如具有8至18个碳原子的直链烷醛、柠檬醛、香茅醛、香茅基氧基乙醛、兔耳草醛、羟基香茅醛、铃兰醛和波洁红醛,酮类包括例如紫罗兰酮类,cc-异甲基紫罗兰酮和甲基柏木酮,醇类包括茴香脑、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,并且烃类主要包括萜烯和香脂。然而,优选使用一起产生令人愉悦的香味的不同香料的混合物。最常用作芳香组分的具有较低挥发性的精油也适合作为香水油,例如鼠尾草油、春黄菊油、丁香油、蜂花油、薄荷油、肉桂叶油、菩提花油、杜松子油、香根油、乳香油、格蓬油、岩蔷薇油和杂熏衣草油。优选单独或者以混合物使用佛手柑油、二氢月桂烯醇、铃兰醛、新铃兰醛、香茅醇、苯乙醇、α-己基肉桂醛、香叶醇、苄基丙酮、兔耳草醛、芳樟醇、Forte、降龙涎香醚、吲哚、二氢茉莉酮酸甲酯、三香草(sandelice)、柠檬油、橘油、橙油、乙醇酸烯丙基戊基酯、cyclovertal、杂熏衣草油、香紫苏油、β-突厥酮、波旁香叶油、水杨酸环己酯、Coeur、iso/>NP、埃弗尼(evernyl)、γ-甲基紫罗兰酮、苯乙酸、乙酸香叶酯、乙酸苄酯、玫瑰醚、romillat、依罗酯(irotyl)和2-叔丁基环己基乙基碳酸酯(floramat)。
香水油可以以常规量存在于热敏组合物中。
活性成分
已经发现,可以将具有可变溶解性的活性成分均匀地掺入根据本发明的热敏组合物中。
根据本发明,活性成分可以有利地选自NO合酶抑制剂的组,特别是如果根据本发明的热敏组合物用于治疗和预防内源性和/或外源性老化症状以及还用于治疗和预防紫外线辐射对皮肤的有害影响。优选的NO合酶抑制剂是硝基精氨酸。
此外,活性成分有利地选自由以下项组成的组:儿茶素和儿茶素胆汁酸酯以及来自具有儿茶素或儿茶素胆汁酸酯含量的植物或植物部分的水性或有机提取物,例如像茶科植物的叶子,特别是茶树物种(绿茶)的叶子。它们的典型成分(例如多酚或儿茶素、咖啡因、维生素、糖、矿物质、氨基酸、脂质)是特别有利的。
儿茶素是被认为氢化黄酮类或花青素类并且是“儿茶素”衍生物(儿茶酚、3,3',4',5,7-黄烷戊醇、2-(3,4-二羟基苯基)色满-3,5,7-三醇)的一组化合物。表儿茶素((2R,3R)-3,3',4',5,7-黄烷戊醇)在本发明的上下文中也是有利的活性成分。
还有利的是具有儿茶素含量的植物提取物、特别是绿茶提取物,例如像来自山茶属(Camellia)物种的植物,非常特别为茶树品种山茶、大叶茶(C.assamica)、大理茶(C.taliensis)和滇缅茶(C.inawadiensis)以及这些茶树品种与例如山茶(Camelliajaponica)的杂交品种的叶子的提取物。
优选的活性成分还是来自由以下项组成的组的多酚和儿茶素:(-)-儿茶素、(+)-儿茶素、(-)-儿茶素没食子酸酯、(-)-棓儿茶素没食子酸酯、(+)-表儿茶素、(-)-表儿茶素、(-)-表儿茶素没食子酸酯、(-)-表棓儿茶素、(-)-表棓儿茶素没食子酸酯。
黄酮及其衍生物(通常也统称“黄酮类”)在本发明的上下文中也是有利的活性成分。
进一步优选的活性成分是绢毛榄仁苷、吡哆醇、维生素K、生物素和芳香物质、红没药醇(红没药醇异构体(从巴斯夫公司可商购))、生育酚(T-50C(从巴斯夫公司可商购))、视黄醇棕榈酸酯(Vitamin A-Palmitate Care(从巴斯夫公司可商购))、视黄醇(Retinol50C(从巴斯夫公司可商购))、五味子果提取物(/>LS 9905(从巴斯夫公司可商购))。
此外,活性成分还可以非常有利地选自亲水性活性成分的组,特别是选自以下组:
α-羟基酸,如乳酸或水杨酸及其盐,例如像乳酸钠、乳酸钙、乳酸TEA盐、尿素、尿囊素、丝氨酸、山梨糖醇、乳蛋白、泛醇、壳聚糖、甘油和甘油基葡萄糖苷(例如Aquaporin(从巴斯夫公司可商购))或其组合。
可用于根据本发明的热敏组合物中的特定活性成分和活性成分组合的列表当然不旨在是限制性的。活性成分可以单独或彼此任意组合使用。
活性成分可以根据其类型以本领域常规的量存在于根据本发明的热敏组合物中。本领域技术人员将能够为本发明选择合适的活性成分和量。
可用于根据本发明的热敏组合物中的具体的和另外的活性成分在DE 103 18526A1的第12至17页中给出,在此对其全文进行引用。
附加的有益试剂
本发明的组合物可以进一步包含一种或多种有益试剂,该有益试剂可以为被护理的基材例如皮肤提供积极和/或有益的效果。本领域技术人员能够根据配制化妆品组合物领域的常识以及大量相关文献来选择用于应用目的的合适的此类任选成分。
在一个实施例中,根据本发明的热敏组合物进一步包含一种或多种有益试剂,如调理剂、皮肤调理剂,如维生素或其衍生物,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、肉碱、维生素A、C、D、E、K及其衍生物,如维生素A棕榈酸酯,和前维生素,例如泛醇(前维生素B5)、泛醇三乙酸酯及其混合物;抗氧化剂;自由基清除剂;天然或合成的研磨剂;染料;头发着色剂;漂白剂;头发漂白剂;UV吸收剂,如二苯甲酮、波尼酮、PABA(对氨基苯甲酸)、丁基PABA、肉桂酸酰胺基丙基三甲基氯化铵(cinnamidopropyl trimethyl ammonium chloride)、二苯乙烯基联苯基二磺酸二钠、甲氧基肉桂酸钾;抗UV试剂,如丁基甲氧基二苯甲酰基甲烷、甲氧基肉桂酸辛酯、羟苯甲酮、奥克立林、水杨酸辛酯、苯基苯并咪唑磺酸、氨基苯甲酸乙基羟丙酯、邻氨基苯甲酸甲酯、氨基苯甲酸、西诺沙酯、二乙醇胺甲氧基肉桂酸酯、氨基苯甲酸甘油酯、二氧化钛、氧化锌、羟苯甲酮、辛基二甲基PABA(帕地马酯O)、红凡士林;抗微生物剂;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、对氯间二甲苯酚(PCMX)、三氯卡班(TCC)、葡萄糖酸氯己定(CHG)、吡硫锌、二硫化硒;抗真菌剂;黑色素调节剂;晒黑加速剂;脱色素剂,如维生素A酸类(如视黄醇)、曲酸以及其衍生物(例如像,曲酸二棕榈酸酯)、氢醌以及其衍生物(如熊果苷)、氨甲环酸、维生素(如烟酸、维生素C和其衍生物)、壬二酸、placertia、甘草、提取物(如春黄菊和绿茶),其中视黄醇、曲酸和氢醌是优选的;皮肤增亮剂,如氢醌、儿茶酚和其衍生物、抗坏血酸以及其衍生物;皮肤着色剂,如二羟基丙酮;脂肪调节剂;减重剂;抗痤疮剂;抗皮脂溢剂;抗衰老剂;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、hetrophen,植物提取物如桤木、山金车、茵陈蒿、细辛根、金盏花、春黄菊、蛇床子、紫草科植物、茴香、五倍子、山楂、鱼腥草、金丝桃属植物、枣子、猕猴桃、甘草、木兰、橄榄、薄荷、喜林芋、鼠尾草、山白竹、咪唑类如酮康唑和新康唑(elubiol);清新剂;愈合剂;脉管保护剂;用于减轻头皮屑(去头皮屑剂)、脂溢性皮炎或银屑病的药剂,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及其衍生物如蒽林,吡罗克酮乙醇胺(Octopirox),硫化硒,环吡酮胺,抗银屑病剂如维生素D类似物,例如卡泊三醇、骨化三醇和大钙乐特醇(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,视黄醇和视黄酸,皮质类固醇如氢化可的松、丁酸氯倍他松、丙酸氯倍他索;止汗剂或除臭剂,如氢氧氯化铝、氢氧氯化锆铝(aluminum zirconium chlorohydrates);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;用于对抗脱发的试剂;用于烫发的还原剂;反射剂,如云母、氧化铝、硅酸钙、二醇二油酸酯、二醇二硬脂酸酯、二氧化硅、氟硅酸镁钠;精油和香料。
不用说,根据本发明的热敏组合物应该是在化妆品上或皮肤病学上可接受的,即,它应该含有无毒的生理学上可接受的介质并且应该能够施用于皮肤。出于本发明的目的,表述“化妆品上可接受的”意指具有令人愉快的外观、气味、感觉和/或味道的组合物。
可以将根据本发明的热敏组合物的pH常规地调节至例如4.0至7.0、优选4.5至6.5、更优选6.0至6.5。
在第二方面,本发明提供了一种用于制备根据本发明的热敏组合物的方法,该方法包括将该热敏组合物的组分混合。
在第三方面,本发明提供了根据本发明的热敏组合物作为用于化妆品活性成分的递送系统的用途。
已经发现,根据本发明的热敏组合物在组合物中具有较少含量的聚环氧乙烷和聚环氧丙烷的水溶性嵌段共聚物的情况下可以获得预期的热敏行为。
实例
通过以下实例更充分地说明了本发明的各方面,这些实例是为了说明本发明的某些方面而提出的,而不应被解释为对其的限制。
材料:
使用在表1中示出的材料。
表1
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根据本发明的热敏组合物的制备:
如下制备根据本发明的热敏组合物,并且材料的重量百分比在下表2至表5中示出:
1.将(a)嵌段共聚物和水在75℃-85℃下搅拌直至均匀;
2.在搅拌下,添加增稠剂;
3.将(c)乳化剂添加到(b)酯/烷烃或水相中以获得均匀的混合物;
4.将(b)酯/烷烃加热至75℃-85℃;
5.在搅拌下,将水相添加到(b)酯/烷烃中;
6.均质化几分钟;
7.在搅拌下冷却至低于50℃,添加防腐剂,并且将pH调节至6-7。
质地转变温度评估方法:
1.在测试之前将样品放入60ml塑料瓶中,在4℃冰箱中放置至少24h进行平衡;
2.将样品放入水浴中;
3.将水浴从4℃缓慢升温至40℃,缓慢搅拌样品,将样品从流动乳剂变成乳霜(在倒置下不流动)时的温度记录为转变温度。
结果在下表2至表5中示出。
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Claims (19)
1.一种热敏组合物,其包含:(a)包含至少两个聚环氧乙烷嵌段和至少一个聚环氧丙烷嵌段的水溶性嵌段共聚物;(b)至少一种基于酯的润肤剂和/或基于烷烃的润肤剂;以及(c)至少一种乳化剂,其中所述组合物具有5℃至40℃、优选6℃至40℃、更优选15℃至40℃的质地转变温度。
2.根据权利要求1所述的热敏组合物,其中,该嵌段共聚物包含至少两个具有式-[CH2CH2O]a-的聚环氧乙烷嵌段和至少一个具有式-[CH2CH(CH3)O]b-的聚环氧丙烷嵌段,其中a和b各自独立地表示10至160的数。
3.根据权利要求1或2所述的热敏组合物,其中,该嵌段共聚物是由以下通式表示的三嵌段EO-PO-EO共聚物:
其中a表示40至160、优选50至150、更优选55至145的数,并且b表示30至80、优选35至70、更优选40至60的数。
4.根据权利要求1至3中任一项所述的热敏组合物,其中,该热敏组合物包含基于该热敏组合物的总重量按重量计大于或等于5%、优选按重量计5%至20%、更优选按重量计6%至18%、最优选按重量计7%至15%、尤其是按重量计8%至13%的组分(a)。
5.根据权利要求1至4中任一项所述的热敏组合物,其中,该酯由至少一种酸和至少一种醇形成,并且各种酸和各种醇的碳原子总数小于或等于42、优选小于或等于28、更优选小于或等于22,并且各种酸和各种醇的碳原子数之差的绝对值小于或等于15、优选小于或等于10、更优选小于或等于8。
6.根据权利要求5所述的热敏组合物,其中,该酸部分衍生自一元羧酸、二元羧酸、包含至少3个羧基的多元羧酸、或碳酸。
7.根据权利要求6所述的热敏组合物,其中,该一元羧酸是饱和一元羧酸,优选己酸、异庚酸、4-乙基戊酸、2-乙基己酸、4,5-二甲基己酸、2-庚基庚酸、3,5,5-三甲基己酸、辛酸、异辛酸、壬酸、异壬酸、癸酸、月桂酸、十三烷酸、肉豆蔻酸、棕榈酸、硬脂酸、异硬脂酸、花生酸、山萮酸、蜡酸;不饱和一元羧酸,优选癸烯酸、十碳烯酸、十一碳烯酸、十二碳烯酸、林德酸、肉豆蔻脑酸、油酸、芥酸;以及芳族一元羧酸,优选苯甲酸、邻甲基苯甲酸、间甲基苯甲酸、对甲基苯甲酸、4-叔丁基苯甲酸;更优选2-乙基己酸、辛酸、异辛酸、癸酸、月桂酸、肉豆蔻酸、异庚酸、异壬酸、壬酸、棕榈酸、硬脂酸、油酸、芥酸、苯甲酸、邻甲基苯甲酸、间甲基苯甲酸、椰油酸或其组合。
8.根据权利要求6所述的热敏组合物,其中,该二元羧酸是癸二酸、十二烷二酸、辛二酸、草酸、丙二酸、琥珀酸、邻苯二甲酸、对苯二甲酸、间苯二甲酸、庚二酸、癸二酸、壬二酸、戊二酸、己二酸、富马酸、马来酸、衣康酸或其组合。
9.根据权利要求5至8中任一项所述的热敏组合物,其中,该醇部分衍生自一元醇、二元醇或多元醇。
10.根据权利要求9所述的热敏组合物,其中,该一元醇是异丙醇、正丁醇、正己醇、正辛醇、异辛醇、正壬醇、异壬醇、正十二烷醇、正十三烷醇、正十四烷醇、正十五烷醇、鲸蜡硬脂醇、油醇、辛基十二烷醇、癸醇或其组合。
11.根据权利要求9所述的热敏组合物,其中,该二元醇是非支链或支链的脂肪族C2-C8-烷二醇,优选非支链或支链的C2-C6-烷二醇,更优选1,2-乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、1,2-戊二醇、1,3-戊二醇、2-甲基-1,3-戊二醇、2,2-二甲基-1,3-戊二醇、1,4-戊二醇、1,5-戊二醇、1,2-己二醇、1,3-己二醇、1,4-己二醇、1,5-己二醇、1,6-己二醇或这些二元醇的混合物。
12.根据权利要求9所述的热敏组合物,其中,该多元醇是甘油、三羟甲基乙烷、三羟甲基丙烷、1,2,4-丁三醇、1,2,6-己三醇、季戊四醇、赤藓醇、二甘油或双三羟甲基丙烷。
13.根据权利要求1至12中任一项所述的热敏组合物,其中,该烷烃是选自由直链烷烃、石蜡油和氢化聚异丁烯组成的组中的至少一种。
14.根据权利要求1至13中任一项所述的热敏组合物,其中,该热敏组合物包含基于该热敏组合物的总重量按重量计大于0%至小于或等于60%、优选按重量计4%至55%、更优选按重量计5%至50%、最优选按重量计10%至45%、尤其是按重量计25%至45%的组分(b)。
15.根据权利要求1至14中任一项所述的热敏组合物,其中,组分(a)和(b)按重量计%的量满足以下等式:(a)+(b)/9≥11.5,优选25.0≥(a)+(b)/9≥11.5,更优选15.0≥(a)+(b)/9≥11.5。
16.根据权利要求1至15中任一项所述的热敏组合物,其中,该热敏组合物包含基于该热敏组合物的总重量按重量计大于或等于5%、优选按重量计5%至20%、更优选按重量计6%至18%、最优选按重量计7%至15%、尤其是按重量计8%至13%的组分(a),以及按重量计大于0%至小于或等于60%、优选按重量计4%至55%、更优选按重量计5%至50%、最优选按重量计10%至45%、尤其是按重量计25%至45%的组分(b),并且其中组分(a)和(b)按重量计%的量满足以下等式:(a)+(b)/9≥11.5,优选25.0≥(a)+(b)/9≥11.5,更优选15.0≥(a)+(b)/9≥11.5。
17.根据权利要求1至16中任一项所述的热敏组合物,其中,该乳化剂包含非离子乳化剂和阴离子乳化剂,和/或该热敏组合物包含基于该热敏组合物的总重量按重量计0.1%至30%、优选按重量计0.5%至25%、更优选按重量计1%至20%、最优选按重量计2%至15%、尤其是按重量计3%至10%的该乳化剂。
18.一种用于制备根据权利要求1至17中任一项所述的热敏组合物的方法,该方法包括将该热敏组合物的组分混合。
19.根据权利要求1至17中任一项所述的热敏组合物作为用于化妆品活性成分的递送系统的用途。
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CNPCT/CN2021/117193 | 2021-09-08 | ||
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PCT/EP2022/074206 WO2023036666A1 (en) | 2021-09-08 | 2022-08-31 | Thermo-sensitive composition and method for preparation thereof |
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KR (1) | KR20240056504A (zh) |
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US4188373A (en) | 1976-02-26 | 1980-02-12 | Cooper Laboratories, Inc. | Clear, water-miscible, liquid pharmaceutical vehicles and compositions which gel at body temperature for drug delivery to mucous membranes |
US4810503A (en) * | 1987-03-31 | 1989-03-07 | Basf Corporation | Polymers which form gels at low concentrations in water |
DE10318526A1 (de) | 2003-04-24 | 2004-11-11 | Beiersdorf Ag | Reinigungsemulsion mit hohem Fettgehalt |
FR2910321B1 (fr) * | 2006-12-21 | 2009-07-10 | Galderma Res & Dev S N C Snc | Gel creme comprenant au moins un retinoide et du peroxyde de benzole |
LT2689774T (lt) | 2011-03-21 | 2019-03-25 | Broda Technologies Co., Ltd | Atvirkščiai termiškai grįžtama hidrogelio kompozicija |
WO2020112595A1 (en) * | 2018-11-30 | 2020-06-04 | L'oreal | Thermoresponsive oil-in-water nanoemulsion |
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