CN101516448A - 基于分子印迹聚合物的化妆品制剂 - Google Patents
基于分子印迹聚合物的化妆品制剂 Download PDFInfo
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- CN101516448A CN101516448A CNA2007800345560A CN200780034556A CN101516448A CN 101516448 A CN101516448 A CN 101516448A CN A2007800345560 A CNA2007800345560 A CN A2007800345560A CN 200780034556 A CN200780034556 A CN 200780034556A CN 101516448 A CN101516448 A CN 101516448A
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Classifications
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- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8194—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
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- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8105—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- A61K8/8117—Homopolymers or copolymers of aromatic olefines, e.g. polystyrene; Compositions of derivatives of such polymers
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- A—HUMAN NECESSITIES
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- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8164—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers, e.g. poly (methyl vinyl ether-co-maleic anhydride)
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Abstract
本发明涉及包含至少一种活性成分、至少一种在该活性成分存在下分子印迹的聚合物和至少一种脂相的化妆品制剂或皮肤病制剂。
Description
本发明涉及包含至少一种活性化合物、至少一种在该活性化合物存在下分子印迹的聚合物和至少一种脂相的化妆品配制剂或皮肤病配制剂。
如果应获得化妆产品的特定活性,则成分具有决定性的重要性。在化妆品配制剂中高水平的可获取成分和原料持续扩大,这是因为消费者关心例如可抵消老化作用的苛刻的和活性的产品。在此,化妆品生产商也关心能够使皮肤新生或保护皮肤防止因光的作用而老化的活性化合物。然而,过去这类物质主要用于光滑和润湿皮肤,它们现在由大量具有生理活性的各种材料补充。这些物质的实例为维生素、果酸或神经酰胺。在此,这些活性化合物的稳定方法和方式也具有日益增加的重要性。在化妆品中,对于可以稳定方式存储在水性或含水体系中的活性化合物很关注。
为了维持不耐热的,氧化敏感的或易于挥发的化妆品或皮肤病活性化合物的活性,需要在配制剂中保护它们。
经常需要在较长时间内持续释放,即所谓的控制释放化妆品或皮肤病活性化合物。
可额外保护活性化合物的聚合物微胶囊已证明例如可用于在一些应用中的化妆品活性化合物的控制释放。
然而,理想的是,活性化合物应在配制剂的储存期间不释放,而仅在规定的作用位置释放。
聚合物类的微胶囊化已经证明在某些情况下例如可用于化妆品活性化合物的控制释放,此外,其还可保护活性化合物。
活性化合物从这类微胶囊中释放经常在使用含有它们的配制剂的过程中,通过因机械、热、化学或酶作用破坏壳而发生。这些开口的变型并不是对胶囊化的活性化合物的所需生物活性没有作用。
在用于处理皮肤,尤其是敏感性或刺激性皮肤,非常特别是婴儿护理化妆品配制剂中,然而,由于显而易见的原因,使用活性化合物的这种释放机制是有问题或不可行的。
在皮肤护理中,还必须确保皮肤的酸保护层不受不合适的添加剂破坏,而是被维持和帮助,即大部分维持“天然”环境条件。
本发明的目的是提供对特定活性化合物具有选择性亲和性的配制剂,活性化合物仅在作用位置从该配制剂中逐步且温和释放。
此外,本发明的目的是提供如下配制剂,即活性化合物受生理作用刺激,如通过与皮肤或其它器官接触而从该配制剂中释放。换言之,本发明的目的为使得可控制释放配制剂的活性化合物,其中在使用配制剂之后,皮肤或身体对于释放活性化合物的选择性有害性具有足够的缓冲能力。
上述目的通过提供包含至少一种活性化合物、至少一种在该活性化合物存在下分子印迹的聚合物和至少一种脂相的化妆品配制剂或皮肤病配制剂而实现。
本发明配制剂使得可以控制释放亲水、两性、亲油、氧化敏感性或水解敏感性活性化合物。这适用于所有常规化妆品和皮肤病形式的施用和提供。
如果化妆品活性化合物、化妆品配制剂、化妆品接受或化妆品使用详细描述在本文中,而对应的皮肤病学形式没有明确提及,则在所有情况下同样包括皮肤病活性化合物、配制剂、接受和使用。
分子印迹是一项已经广泛使用数年的技术,尤其是在色谱、固相萃取和废水处理领域中。
作为提供综述的文献,在此可提及″Molecular Imprinting-FromFundamentals to Applications(分子印迹,从原理到应用)″,Komiyama等,Wiley-VCH,ISBN 3-527-30569-6和ACS Symposium Series 703,″Molecular and Ionic Recognition with imprinted polymers(用印迹聚合物的分子和离子识别)″,编辑R.A.Bartsch and M.Maeda,ISBN0-8412-3574-0。
聚合物的分子印迹也例如由农业活性化合物分析领域已知,如J.Agric.Food Chem.1995,43,1424-1427,Journal of Physics:Conference Series 10(2005)281-284,J.Agric.Food Chem.1996,44,141-145,Chemistry Letters7(1995),491-612。
分子印迹聚合物在高压液相色谱(HPLC)中广泛用作固定相(例如参见Molecular and Ionic Recognition with imprinted polymers(用印迹聚合物的分子和离子识别),ACS Symposium Series 703,第5页)。
Kanekiyo等(Angew.Chem.Int.Ed.2003,42,3014-16)描述了分子印迹的聚合物(MIP),其中对主体分子(用其进行印迹)的亲和性是pH相关的。基于丙烯酰基-直链淀粉和含羧基单体的并用N,N-亚甲基二丙烯酰胺交联的聚合物用作MIP。双酚A用作主体分子。对于这些含COOH基团的MIP,显示了随着pH增加对双酚A的结合能力降低。
Demirel等(Macromol.Biosci.2005,5,1032-37)描述了N-叔丁基丙烯酰胺/丙烯酰胺/马来酸共聚物的水凝胶对牛血清蛋白(BSA)吸附的pH和温度依赖性。
Byrne等(Advanced Drug Delivery Reviews 54(2002)149-161)描述了来自控制释放凝胶的分子印迹水凝胶在药物中的用途。
Cunliffe等(Advanced Drug Delivery Reviews 57(2005)1836-1853)同样描述了分子印迹的水凝胶在药物活性化合物的释放中的用途。
EP-A 925776描述了具有用于至少一种器官感觉物质的结合点的分子印迹聚合物。没有描述进一步含有脂相的化妆品配制剂。
表述“至少一种活性化合物”意味着一种、两种或更多种下述化妆品活性化合物可用于制备分子印迹的聚合物,其中优选一种或两种,特别优选一种。
分子印迹的聚合物以共聚形式包含:
a)至少一种具有可借助自由基聚合而聚合的双键的化合物,和
b)至少一种具有至少两个可借助自由基聚合而聚合的非共轭双键的化合物。
就此而言,化合物a)优选选自:
a1)可借助自由基聚合而聚合的阴离子或潜阴离子化合物,
a2)α,β-烯属不饱和羧酸的酯,
a3)α,β-烯属不饱和羧酸的酰胺,
a4)乙烯基醇或烯丙基醇与C1-C30单羧酸的酯,乙烯基醚,乙烯基内酰胺,乙烯基咪唑,乙烯基芳族化合物,乙烯基卤化物,偏二卤乙烯,乙烯基吡啶,C2-C8单烯烃,具有至少2个共轭双键的非芳族烃,和
a5)它们的混合物。
化合物a1)
可借助自由基聚合而聚合的阴离子或潜阴离子化合物a1)包括具有3-25个,优选3-6个C原子的单烯属不饱和单羧酸和二羧酸,所述羧酸也可以以它们的盐或酸酐形式使用。其实例是丙烯酸、甲基丙烯酸、乙基丙烯酸、α-氯丙烯酸、巴豆酸、马来酸、马来酸酐、衣康酸、柠康酸、中康酸、戊烯二酸、乌头酸和富马酸。化合物a1)还包括含有4-10个,优选4-6个碳原子的单烯属不饱和二羧酸的半酯,例如马来酸的半酯,如马来酸单甲酯。
化合物a1)还包括单烯属不饱和磺酸和膦酸,例如乙烯基磺酸、烯丙基磺酸、丙烯酸磺基乙酯、甲基丙烯酸磺基乙酯、丙烯酸磺基丙酯、甲基丙烯酸磺基丙酯、2-羟基-3-丙烯酰氧基丙基磺酸、2-羟基-3-甲基丙烯酰氧基丙基磺酸、苯乙烯磺酸、2-丙烯酰胺基-2-甲基丙烷磺酸、乙烯基膦酸和烯丙基膦酸。
化合物a1)还包括上述酸的盐,特别是钠盐、钾盐和铵盐,以及包括与化妆品可接受胺的盐。化合物a1)可以单独使用或者以彼此的混合物使用。
优选化合物a1)选自丙烯酸、甲基丙烯酸、乙基丙烯酸、α-氯丙烯酸、巴豆酸、马来酸、马来酸酐、富马酸、衣康酸、柠康酸、中康酸、戊烯二酸、乌头酸和它们的混合物,特别优选丙烯酸、甲基丙烯酸和它们的混合物,尤其是甲基丙烯酸。
化合物a2)
化合物a2)例如选自(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸2-戊酯、(甲基)丙烯酸3-戊酯、(甲基)丙烯酸异戊酯、(甲基)丙烯酸新戊酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸1,1,3,3-四甲基丁酯、(甲基)丙烯酸乙基己基酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸正十一烷基酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸肉豆蔻基酯、(甲基)丙烯酸十五烷酯、(甲基)丙烯酸棕榈基酯、(甲基)丙烯酸十七烷酯、(甲基)丙烯酸十九烷酯、(甲基)丙烯酸二十烷酯、(甲基)丙烯酸山萮醇酯、(甲基)丙烯酸二十四碳烯基(lignocerenyl)酯、(甲基)丙烯酸二十六碳基(cerotinyl)酯、(甲基)丙烯酸三十碳基(melissinyl)酯、(甲基)丙烯酸十六碳烯基(palmitoleinyl)酯、(甲基)丙烯酸油基酯、(甲基)丙烯酸亚油基酯、(甲基)丙烯酸亚麻基酯、(甲基)丙烯酸硬脂基酯、(甲基)丙烯酸月桂酯、丙烯酸苯氧基乙基酯、丙烯酸4-叔丁基环己基酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸脲基酯、(甲基)丙烯酸四氢糠基酯及其混合物。
化合物a2)优选选自(甲基)丙烯酸的酯。
化合物a2)特别优选选自甲基丙烯酸酯和丙烯酸酯。优选(甲基)丙烯酸酯为(甲基)丙烯酸C1-C10烷基酯,尤其是上述(甲基)丙烯酸C1-C4烷基酯。
合适的化合物a2)还有α,β-烯属不饱和一元羧酸和α,β-烯属不饱和二元羧酸与氨基醇的酯。优选的氨基醇为在胺氮原子上C1-C8单烷基化或二烷基化的C2-C12氨基醇。这些酯的合适酸组分例如为丙烯酸、甲基丙烯酸、富马酸、马来酸、衣康酸、巴豆酸、马来酸酐、马来酸一丁酯及其混合物。优选使用丙烯酸、甲基丙烯酸及其混合物作为酸组分。
优选单体a3)为(甲基)丙烯酸N-(叔丁基)氨基乙酯、(甲基)丙烯酸N,N-二甲氨基甲酯、(甲基)丙烯酸N,N-二甲氨基乙酯、(甲基)丙烯酸N,N-二乙氨基乙酯、(甲基)丙烯酸N,N-二甲氨基丙酯、(甲基)丙烯酸N,N-二乙氨基丙酯和(甲基)丙烯酸N,N-二甲氨基环己酯。特别优选(甲基)丙烯酸酯N-(叔丁基)氨基乙酯和(甲基)丙烯酸N,N-二甲氨基乙酯。
合适的化合物a3)还有α,β-烯属不饱和单-和二羧酸与二醇的酯,如丙烯酸2-羟乙酯、甲基丙烯酸2-羟乙酯、乙基丙烯酸2-羟乙酯、丙烯酸2-羟丙酯、甲基丙烯酸2-羟丙酯、丙烯酸3-羟丙酯、甲基丙烯酸3-羟丙酯、丙烯酸3-羟丁酯、甲基丙烯酸3-羟丁酯、丙烯酸4-羟丁酯、甲基丙烯酸4-羟丁酯、丙烯酸6-羟己酯、甲基丙烯酸6-羟己酯、丙烯酸3-羟基-2-乙基己酯和甲基丙烯酸3-羟基-2-乙基己酯。
化合物a3)
化合物a3)可优选选自丙烯酰胺、甲基丙烯酰胺、N-甲基(甲基)丙烯酰胺、N-乙基(甲基)丙烯酰胺、N-丙基(甲基)丙烯酰胺、N-(正丁基)(甲基)丙烯酰胺、N-(叔丁基)(甲基)丙烯酰胺、N,N-二甲基(甲基)丙烯酰胺、N,N-二乙基(甲基)丙烯酰胺、哌啶基(甲基)丙烯酰胺和吗啉基(甲基)丙烯酰胺、N-(正辛基)(甲基)丙烯酰胺、N-(1,1,3,3-四甲基丁基)(甲基)丙烯酰胺、N-乙基己基(甲基)丙烯酰胺、N-(正壬基)(甲基)丙烯酰胺、N-(正癸基)(甲基)丙烯酰胺、N-(正十一烷基)(甲基)丙烯酰胺、N-十三烷基(甲基)丙烯酰胺、N-肉豆蔻基(甲基)丙烯酰胺、N-十五烷基(甲基)丙烯酰胺、N-棕榈基(甲基)丙烯酰胺、N-十七烷基(甲基)丙烯酰胺、N-十九烷基(甲基)丙烯酰胺、N-二十烷基(甲基)丙烯酰胺、N-山萮基(甲基)丙烯酰胺、N-二十四碳烯基(甲基)丙烯酰胺、N-二十六碳基(甲基)丙烯酰胺、N-三十碳基(甲基)丙烯酰胺、N-十六碳烯基(甲基)丙烯酰胺、N-油基(甲基)丙烯酰胺、N-亚油基(甲基)丙烯酰胺、N-亚麻基(甲基)丙烯酰胺、N-硬脂基(甲基)丙烯酰胺和N-月桂基(甲基)丙烯酰胺。
合适的单体a3)还有上述α,β-烯属不饱和一元羧酸和二元羧酸与具有至少一个伯氨基或仲氨基的二胺的酰胺。优选具有一个叔氨基和一个伯氨基或仲氨基的二胺。
合适的单体a3)例如为N-叔丁基氨基乙基(甲基)丙烯酰胺、N-[2-(二甲基氨基)乙基]丙烯酰胺、N-[2-(二甲基氨基)乙基]甲基丙烯酰胺、N-[3-(二甲基氨基)丙基]丙烯酰胺、N-[3-(二甲基氨基)丙基]甲基丙烯酰胺、N-[4-(二甲基氨基)丁基]丙烯酰胺、N-[4-(二甲基氨基)-丁基]甲基丙烯酰胺、N-[2-(二乙氨基)乙基]丙烯酰胺、N-[4-(二甲基氨基)环己基]丙烯酰胺和N-[4-(二甲基氨基)环己基]甲基丙烯酰胺。
合适的单体a3)还有上述α,β-烯属不饱和一元羧酸和二元羧酸的羟基烷基酰胺,如2-羟基乙基丙烯酰胺、2-羟基乙基甲基丙烯酰胺、2-羟基乙基乙基丙烯酰胺、2-羟基丙基丙烯酰胺、2-羟基丙基甲基丙烯酰胺、3-羟基丙基丙烯酰胺、3-羟基丙基甲基丙烯酰胺、3-羟基丁基丙烯酰胺、3-羟基丁基甲基丙烯酰胺、4-羟基丁基丙烯酰胺、4-羟基丁基甲基丙烯酰胺、6-羟基己基丙烯酰胺、6-羟基己基甲基丙烯酰胺、3-羟基-2-乙基己基丙烯酰胺和3-羟基-2-乙基己基甲基丙烯酰胺。
化合物a4)
合适的化合物a4)例如为N-乙烯基内酰胺及其衍生物,其例如可具有一个或多个C1-C6烷基取代基如甲基、乙基、正丙基、异丙基、正丁基、仲丁基、叔丁基等。这些化合物例如包括N-乙烯基吡咯烷酮、N-乙烯基哌啶酮、N-乙烯基己内酰胺、N-乙烯基-5-甲基-2-吡咯烷酮、N-乙烯基-5-乙基-2-吡咯烷酮、N-乙烯基-6-甲基-2-哌啶酮、N-乙烯基-6-乙基-2-哌啶酮、N-乙烯基-7-甲基-2-己内酰胺和N-乙烯基-7-乙基-2-己内酰胺。特别优选使用N-乙烯基吡咯烷酮和/或N-乙烯基己内酰胺。
合适的化合物a4)例如还有通式(II)的N-乙烯基咪唑化合物:
其中R5-R7相互独立地为氢、C1-C4烷基或苯基。
通式(II)的化合物的实例如下表1所示:
表1
R5 | R6 | R7 |
H | H | H |
Me | H | H |
H | Me | H |
H | H | Me |
Me | Me | H |
H | Me | Me |
Me | H | Me |
Ph | H | H |
H | Ph | H |
H | H | Ph |
Ph | Me | H |
Ph | H | Me |
Me | Ph | H |
H | Ph | Me |
H | Me | Ph |
Me | H | Ph |
Me=甲基
Ph=苯基
1-乙烯基咪唑(N-乙烯基咪唑)优选为单体b)。
化合物b)
化合物b)为具有至少两个可借助自由基聚合而聚合的非共轭双键的化合物。这些化合物b)通常并且在下文中也称作交联剂。
合适的化合物b)例如为至少二元醇的丙烯酸酯、甲基丙烯酸酯、烯丙基醚或乙烯基醚。就此而言,母体醇的OH基可被部分或完全醚化或酯化;然而,交联剂包含至少两个烯属不饱和基团。
母体醇的实例为二元醇如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、2,3-丁二醇、1,4-丁二醇、丁-2-烯-1,4-二醇、1,2-戊二醇、1,5-戊二醇、1,2-己二醇、1,6-己二醇、1,10-癸二醇、1,2-十二烷二醇、1,12-十二烷二醇、新戊二醇、3-甲基-1,5-戊二醇、2,5-二甲基-1,3-己二醇、2,4,4-三甲基-1,3-戊二醇、1,2-环己二醇、1,4-环己二醇、1,4-二(羟甲基)环己烷、新戊二醇与羟基新戊酸的单酯、2,2-二(4-羟苯基)丙烷、2,2-二[4-(2-羟丙基)苯基]丙烷、二甘醇、三甘醇、四甘醇、双丙二醇、三丙二醇、四丙二醇、3-硫代戊烷-1,5-二醇以及各自分子量为200-10000的聚乙二醇、聚丙二醇和聚四氢呋喃。除氧化乙烯或氧化丙烯的均聚物外,还可以使用氧化乙烯或氧化丙烯的嵌段共聚物或包含掺入的氧化乙烯和氧化丙烯基团的共聚物。具有两个以上OH基的母体醇的实例为三羟甲基丙烷,甘油,季戊四醇,1,2,5-戊三醇,1,2,6-己三醇,三乙氧基氰尿酸,脱水山梨醇,糖如蔗糖、葡萄糖和甘露糖。当然,也可以使用在与氧化乙烯和氧化丙烯反应后的以对应乙氧基化物和丙氧基化物形式的多元醇。也可以首先使多元醇与表氯醇反应而转化为对应的缩水甘油醚。优选乙二醇二(甲基)丙烯酸酯和聚乙二醇二(甲基)丙烯酸酯。
其它合适的化合物b)为不饱和一元醇的乙烯基酯或者不饱和一元醇与烯属不饱和C3-C6羧酸如丙烯酸、甲基丙烯酸、衣康酸、马来酸或富马酸的酯。这类醇的实例为烯丙醇、1-丁烯-3-醇、5-己烯-1-醇、1-辛烯-3-醇、9-癸烯-1-醇、二环戊烯基醇、10-十一碳烯-1-醇、肉桂醇、香茅醇、巴豆醇或顺-9-十八碳烯-1-醇。然而,也可以用多元羧酸如丙二酸、酒石酸、偏苯三酸、邻苯二甲酸、对苯二甲酸、柠檬酸或琥珀酸使不饱和一元醇酯化。
其它合适的化合物b)为不饱和羧酸与上述多元醇的酯,如油酸、巴豆酸、肉桂酸或10-十一碳烯酸的酯。
其它合适的化合物b)为具有至少两个双键的直链或支化、线性或环状、脂族或芳族烃,在脂族烃的情况下,所述双键不应共轭,如二乙烯基苯、二乙烯基甲苯、1,7-辛二烯、1,9-癸二烯、4-乙烯基-1-环己烯、三乙烯基环己烷或分子量为200-20000的聚丁二烯。
其它合适的化合物b)为至少双官能胺的丙烯酰胺、甲基丙烯酰胺和N-烯丙胺。这类胺例如为1,2-二氨基甲烷、1,2-二氨基乙烷、1,3-二氨基丙烷、1,4-二氨基丁烷、1,6-二氨基己烷、1,12-十二烷二胺、哌嗪、二亚乙基三胺或异佛尔酮二胺。烯丙胺与不饱和羧酸如丙烯酸、甲基丙烯酸、衣康酸、马来酸或上述至少二元二羧酸的酰胺也是合适的。
此外,三烯丙胺和三烯丙基单烷基铵盐如三烯丙基甲基氯化铵或者硫酸甲酯三烯丙基甲基铵适合作为化合物b)。
脲衍生物、至少双官能的酰胺、氰尿酸酯或尿烷的N-乙烯基化合物,例如脲、亚乙基脲、亚丙基脲或酒石酸二酰胺的N-乙烯基化合物,例如N,N′-二乙烯基亚乙基脲或N,N′-二乙烯基亚丙基脲也是合适的。
其它合适的化合物b)为二乙烯基二噁烷、四烯丙基硅烷或四乙烯基硅烷。
当然,也可以使用上述化合物b)的混合物。
非常特别优选作为化合物b)的例如为乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、季戊四醇三烯丙基醚、亚甲基双丙烯酰胺、N,N′-二乙烯基亚乙基脲、三烯丙基胺、三羟甲基丙烷三(甲基)丙烯酸酯和三烯丙基单烷基铵盐。
化合物a)与化合物b)的摩尔比通常为1∶2-1∶10,优选1∶2-1∶4,非常特别优选1∶2.5-1∶3.5,尤其是1∶2.8-1∶3.2。
本文所述的本发明聚合物在活性化合物(模板)存在下在大大过量溶剂中(溶剂与活性化合物的重量比为100∶1-5∶1,优选100∶1-50∶1,特别优选59∶1)经由沉淀聚合以分批法或半分批法制备。所得聚合物颗粒通过索氏萃取法提纯。在活性连接位置(分子印迹)又加载模板之后(或者如果在聚合物合成之后省略模板萃取),可使用聚合物从而以受控或延缓方式释放化妆品活性化合物。
本发明配制剂的显著之处在于活性化合物从聚合物-活性化合物复合物中的释放速率在pH 5下比pH 7下高。
当用活性化合物印迹聚合物并然后除去未键接的活性化合物,或使已经不含键接的活性化合物的之前印迹的聚合物再次装载活性化合物时,得到聚合物-活性化合物复合物。
释放速率理解为指每单位时间从聚合物-活性化合物复合物中释放的活性化合物量;例如该速率可以μg*min-1表述。
释放速率如下测定:向超滤池中填充在(具有调节的pH)100ml水中的100mg分子印迹聚合物分散体并将混合物搅拌15分钟直至均化。经由借助软管泵的进料将萃取剂(同样具有相同调节的pH的水)从储存罐通入超滤池。将从超滤池中排出的萃取物通入在超滤池下面的收集容器。试验操作时间:12小时;更换收集容器:每60分钟;因此在试验时间内收集了12个级分。测定了各级分的体积、重量和取出时间并从各级分中取出2ml样品。将这些样品经0.45μl过滤器过滤,转移入注射瓶中并用于借助HPLC的生育酚测定。
本发明还涉及制备分子印迹聚合物的方法,其包括在活性化合物存在下通过沉淀聚合制备聚合物。
沉淀聚合的基本原理对本领域熟练技术人员是已知的且例如描述于Guyot,A.(1989),Comprehensive Polymer Science,第4卷:Eastmond,G.C.,Ledwith,A.,Russo,S.,Sigwalt,P.(编辑).Oxford:Pergamon,第261-273页。
在优选实施方案中,可通过一种如下方法制备分子印迹聚合物,其中:
(a)将至少一种化合物a)与至少一种活性化合物在合适溶剂中混合,加入至少一种化合物b)并启动聚合,其中化合物b)优选已经预先溶于溶剂中,在非常特别优选的实施方案中,该溶剂对应于溶解化合物a)的溶剂,或
(b)将至少一种化合物a)与至少一种活性化合物和至少一种化合物b)在合适溶剂中混合,然后启动聚合。
聚合可以自由基、阴离子、阳离子或配位机理或根据缩聚或加聚原理进行。聚合优选经由自由基机理进行。就此而言,可使用各种引发剂和/或催化剂,并任选与供应热量结合。
对于阳离子聚合,例如可使用如下引发剂:
质子酸、具有或不具有共引发剂的路易斯酸、碳鎓离子、碘鎓离子和/或离子化辐射。
对于阴离子聚合,可使用如下引发剂:碱、路易斯碱、有机金属化合物和/或电子转移剂如碱金属、碱金属芳族化合物配合物或金属羰基游离基。
对于配位聚合,可使用如下引发剂/催化剂:
有机金属混合催化剂(齐格-纳塔催化剂),具有过渡金属的π配合物如茂金属,和/或活化的过渡金属氧化物。
适用于优选的自由基聚合的引发剂例如为过氧化物或偶氮化合物,取代的乙烷(如苯频哪醇),具有无机和有机组分的氧化还原体系,热,UV光和其它高能辐射,氢过氧化物、过酸酯(perester)和过硫酸盐如过二硫酸钾,优选偶氮化合物。
合适的偶氮化合物为2,2′-偶氮二异丁腈、2,2′-偶氮二(2-甲基丁腈)、2,2′-偶氮二(2,4-二甲基戊腈)、2,2′-偶氮二(4-甲氧基-2,4-二甲基戊腈)、1,1′-偶氮二(1-环己烷甲腈)、2,2′-偶氮二(异丁酰胺)二水合物、2-苯基偶氮-2,4-二甲基-4-甲氧基戊腈、2,2′-偶氮二异丁酸二甲酯、2-(氨基甲酰基偶氮)异丁腈、2,2′-偶氮二(2,4,4-三甲基戊烷)、2,2′-偶氮二(2-甲基丙烷)、作为游离碱或作为盐酸盐的2,2′-偶氮二(N,N′-二亚甲基异丁脒)、作为游离碱或作为盐酸盐的2,2′-偶氮二(2-脒基丙烷)、2,2′-偶氮二(2-甲基-N-[1,1-二(羟基甲基)乙基]丙酰胺或2,2′-偶氮二(2-甲基-N-[1,1-二(羟基甲基)-2-羟基乙基]丙酰胺。
合适的过氧化物例如为乙酰基环己烷磺酸过氧化物、过二碳酸二异丙酯、过新癸酸叔戊酯、过新癸酸叔丁酯、过新戊酸叔丁酯、过新戊酸叔戊酯、过氧化二(2,4-二氯苯甲酸)、过氧化二异壬酸、过氧化二癸酸、过氧化二辛酸、过氧化二月桂酸、过氧化二(2-甲基苯甲酸)、过氧化二琥珀酸、过氧化二乙酰、过氧化二苯甲酸、过2-乙基己酸叔丁酯、过氧化二(4-氯苯甲酸)、过异丁酸叔丁酯、过马来酸叔丁酯、1,1-二(叔丁基过氧)-3,5,5-三甲基-环己烷、1,1-二(叔丁基过氧)环己烷、过氧异丙基碳酸叔丁酯、过异壬酸叔丁酯、过乙酸叔丁酯、过苯甲酸叔戊酯、过苯甲酸叔丁酯、2,2-二(叔丁基过氧)丁烷、2,2-二-10-(叔丁基过氧)丙烷、过氧化二枯基、2,5-二甲基己烷-2,5-二-叔丁基过氧化物、3-叔丁基过氧-3-苯基苯并呋喃酮、过氧化二叔戊基、α,α′-二(叔丁基过氧异丙基)苯、3,5-二(叔丁基过氧)-3,5-二甲基-1,2-二氧戊环、过氧化二-叔丁基、2,5-二甲基己炔-2,5-二-叔丁基过氧化物、3,3,6,6,9,9-六甲基-1,2,4,5-四氧杂环壬烷、对萜烷过氧化氢、蒎烷过氧化氢、二异丙苯单过氧化氢、氢过氧化枯烯或氢过氧化叔丁基。
取决于聚合状态,可将交联剂以固体或液体形式加入反应混合物中,或以在溶剂中的溶解或分散(即乳化或悬浮)形式,优选以溶解形式加入。优选将液体交联剂或溶解(或分散/混合)在溶剂中的交联剂加入反应混合物中,特别优选将溶解(或分散/混合)在溶剂中的交联剂加入反应混合物中。在非常特别优选的实施方案中,将交联剂溶解在与官能单体或交联剂相同的溶剂中。
可使用的溶剂为有机溶剂,如二甲基甲酰胺、乙醇、甲醇、异丙醇、氯仿、二氯甲烷、甲苯、二甲亚砜、己烷和乙腈,优选甲苯和乙腈。也可使用上述溶剂的混合物。
在另一实施方案中,可向溶剂或溶剂混合物中加入比例至多为50重量%的水。
通常而言,取决于溶剂,聚合在40-120℃的温度下进行。
上述颗粒的所有实施方案在下文中称作“MIP”。
在聚合过程中得到的颗粒或者可直接用于配制剂,或者可向其中加入配制助剂,从而可将它们配制。
本发明还提供了分子印迹聚合物在化妆品配制剂,尤其是皮肤化妆品配制剂中的用途。
本发明还提供了一种处理角质表面的方法,其包括使角质表面与分子印迹聚合物接触。
活性化合物
本发明配制剂包含化妆品可接受的活性化合物。这些活性化合物尤其在5-7的pH下以受控的方式从与该活性化合物分子印迹的聚合物的组合中释放。
根据本发明,活性化合物(一种或多种化合物)可有利地选自乙酰基水杨酸、阿托品、甘菊环、氢化可的松及其衍生物(如氢化可的松17-戊酸酯)、维生素B和D系列,尤其是维生素B1、维生素B12、维生素D、维生素A或其衍生物(如棕榈酸视黄基酯)、维生素E或其衍生物(如乙酸生育基酯)、维生素C及其衍生物,例如抗坏血酸葡糖苷,以及还有烟酰胺、泛醇、红没药醇、表面麻醉剂(polydocanol)、不饱和脂肪酸(例如基本上是脂肪酸(通常称作维生素F),尤其是γ-亚麻酸、油酸、二十碳五烯酸、二十二碳六烯酸及其衍生物)、氯霉素、咖啡因、前列腺素、百里酚、樟脑、角鲨烯、其它植物和动物来源的产品的提取物,如月见草油、琉璃苣油或黑醋栗籽油、鱼油、鳕鱼肝油,以及还有神经酰胺和神经酰胺类化合物、乳香提取物、绿茶提取物、水百合提取物、甘草提取物、金缕梅、去头皮屑活性化合物(如二硫化硒、1-氧-2-巯基吡啶锌、吡罗克酮、油胺(olamine)、同菌唑、羟甲辛吡酮、表面麻醉剂及其组合)、配合物活性化合物,例如γ-米谷酚和钙盐如泛酸钙、氯化钙和乙酸钙的那些。
活性化合物也可选自NO合成酶抑制剂,尤其是如果本发明组合物用于治疗和预防皮肤内因和/或外因老化的症状以及用于治疗和预防紫外辐射对皮肤和毛发的有害作用。NO合成酶抑制剂优选硝基精氨酸。
此外,活性化合物还有利地选自:儿茶酚和儿茶酚的胆汁酸酯以及含有儿茶酚或儿茶酚的胆汁酸酯的植物或植物部分(例如茶科植物的叶子,尤其是山茶(绿茶)叶子)的含水或有机提取物。其典型的成分(如多酚或儿茶酚、咖啡因、维生素、糖、矿物质、氨基酸、类脂)是特别有利的。
儿茶酚是被认为是氢化黄酮或花色素和“儿茶酚”衍生物的一组化合物(儿茶酚、3,3′,4′,5,7-黄烷五醇、2-(3,4-二羟基苯基)苯并二氢吡喃-3,5,7-三醇)。表儿茶酚((2R,3R)-3,3′,4′,5,7-黄烷五醇)在本发明的上下文中也是有利的活性化合物。
还有利的是含有一定量儿茶酚的植物提取物,尤其是绿茶提取物,例如山茶属植物的叶提取物,非常特别是如下植物的叶子提取物:茶(Camelliasinensis),苦茶(Camellia assamica)、大理茶(Camellia taliensis)或滇缅茶(Camellia inawadiensis),以及这些与例如山茶(Camellia japonica)的单树杂交的植物的叶子提取物。
优选的活性化合物还有选自如下的多酚或儿茶酚:(-)-儿茶酚、(+)-儿茶酚、(-)-儿茶酚没食子酸酯、(-)-没食子酸没食子儿茶酚酯、(+)-表儿茶酚、(-)-表儿茶酚、(-)-没食子酸表儿茶酚酯、(-)-表没食子儿茶酚(epigallocatechol)或(-)-没食子酸表没食子儿茶酚酯。
黄酮和它的衍生物(经常也一起统称作“黄酮”)在本发明的上下文中也是有利的活性化合物。它们的特征在于下述基本结构(取代位置示出):
也可优选用于本发明组合物的一些更重要的黄酮在下表2中示出。
表2:黄酮
芹菜配基 | - | + | + | - | - | - | + | - |
非瑟酮 | + | - | + | - | - | + | + | - |
藤黄菌素 | - | + | + | - | - | + | + | - |
山奈酚 | + | + | + | - | - | - | + | - |
栎精 | + | + | + | - | - | + | + | - |
桑色素 | + | + | + | - | + | - | + | - |
刺槐亭 | + | - | + | - | - | + | + | + |
棉黄素 | + | + | + | + | - | + | + | - |
杨梅酮 | + | + | + | - | - | + | + | + |
本质上黄酮通常以苷化形式出现。
根据本发明,类黄酮优选选自下述通式物质:
其中Z1-Z7彼此独立地选自H、OH、烷氧基和羟基烷氧基,其中该烷氧基和/或羟基烷氧基可以为支化或未支化的并可具有1-18个碳原子,并且其中Gly选自单-和低聚苷基团。
然而,根据本发明,类黄酮也可以有利地选自下述通式物质:
其中Z1-Z6彼此独立地选自H、OH、烷氧基和羟基烷氧基,其中该烷氧基和/或羟基烷氧基可以为支化或未支化的并可具有1-18个碳原子,并且其中Gly选自单-和低聚苷基团。
该类结构优选可以选自下述通式物质:
其中Z1-Z6彼此独立地如上所定义,Gly1、Gly2和Gly3彼此独立地是单苷基团或低聚苷基团。Gly2和Gly3也可以单独地或共同通过氢原子饱和。
Gly1、Gly2和Gly3优选彼此独立地选自:己糖基,特别是鼠李糖基和葡糖基。然而,任选也可以有利地使用其它己糖基,例如阿洛糖基、阿卓糖基、半乳糖基、古洛糖基、艾杜糖基、甘露糖基和塔罗糖基。
根据本发明也可以有利地使用戊糖基团。
有利的是,Z1-Z5彼此独立地选自H、OH、甲氧基、乙氧基和2-羟基乙氧基,以及黄酮苷对应于下述通式:
黄酮苷特别有利地选自下述结构表示的那些:
其中Gly1、Gly2和Gly3彼此独立地是单苷基团或低聚苷基团。Gly2和Gly3也可以单独地或共同通过氢原子饱和。
Gly1、Gly2和Gly3优选彼此独立地选自:己糖基,特别是鼠李糖基和葡糖基。然而,任选也可以有利地使用其它己糖基,例如阿洛糖基、阿卓糖基、半乳糖基、古洛糖基、艾杜糖基、甘露糖基和塔罗糖基。
根据本发明还可以有利地使用戊糖基。
在本发明的上下文中,特别有利的是选择黄酮苷或选自α-葡糖基芦丁、α-葡糖基杨梅酮、α-葡糖基异栎素、α-葡糖基异栎精和α-葡糖基栎素的黄酮苷。
其它有利的活性化合物是sericoside、吡哆醇、维生素K、生物素和芳香物质。
此外,活性化合物(一种或多种化合物)还可以非常有利地选自亲水性活性化合物,尤其选自:α-羟基酸,如乳酸或水杨酸或其盐,例如乳酸钠、乳酸钙、乳酸三乙醇胺、尿、尿囊素、丝氨酸、山梨糖醇、甘油、奶蛋白质、泛醇或壳聚糖。
活性化合物(一种或多种化合物)还可非常有利地选自光过滤活性化合物。
合适的光过滤活性化合物为吸收在UV-B和/或UV-A范围的紫外线的物质。这些应理解为能够吸收紫外线并以长波辐射形式,如热量再次释放所吸收的能量的有机物质。有机物质可以是油溶性或水溶性的。合适的UV过滤剂例如为2,4,6-三芳基-1,3,5-三嗪,其中芳基在每种情况下可以带有至少一个取代基,其优选选自羟基,烷氧基,尤其是甲氧基,烷氧基羰基,尤其是甲氧基羰基和乙氧基羰基。此外合适的是对氨基苯甲酸酯,肉桂酸酯,二苯甲酮,樟脑衍生物和遮蔽紫外线的颜料如二氧化钛、滑石和氧化锌。特别优选基于二氧化钛的颜料。
可使用的油溶性UV-B过滤剂例如为如下物质:
3-亚苄基樟脑及其衍生物,如3-(4-甲基亚苄基)樟脑;
4-氨基苯甲酸衍生物,优选4-(二甲氨基)苯甲酸2-乙基己酯、4-(二甲氨基)苯甲酸2-辛酯和4-(二甲氨基)苯甲酸戊酯
肉桂酸酯,优选4-甲氧基肉桂酸2-乙基己基酯、4-甲氧基肉桂酸丙基酯、4-甲氧基肉桂酸异戊基酯、4-甲氧基肉桂酸异戊基酯和2-氰基-3-苯基-肉桂酸2-乙基己基酯(2-氰基-3,3-二苯基丙烯酸-2-乙基己酯);
水杨酸酯,优选水杨酸2-乙基己基酯、水杨酸4-异丙基苄基酯和水杨酸胡莫柳酯酯(salicylic acid homomenthyl ester);
二苯甲酮衍生物,优选2-羟基-4-甲氧基二苯甲酮、2-羟基-4-甲氧基-4′-甲基二苯甲酮和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-乙基己基)酯;
丙烷-1,3-二酮,如1-(4-叔丁基苯基)-3-(4′-甲氧基苯基)丙烷-1,3-二酮。
可行的水溶性物质为:
2-苯基苯并咪唑-5-磺酸及其碱金属盐、碱土金属盐、铵盐、烷基铵盐、链烷醇铵盐和葡糖铵(glucammonium)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-亚苯基樟脑的磺酸衍生物如4-(2-氧代-3-亚冰片基(bornylidene)甲基)苯磺酸和2-甲基-5-(2-氧代-3-亚冰片基)磺酸及其盐。
特别优选使用肉桂酸酯,4-甲氧基肉桂酸2-乙基己基酯、4-甲氧基肉桂酸异戊基酯和2-氰基-3-苯基-肉桂酸2-乙基己基酯(2-氰基-3,3-二苯基丙烯酸-2-乙基己酯)。
此外,优选使用二苯甲酮衍生物,尤其是2-羟基-4-甲氧基二苯甲酮、2-羟基-4-甲氧基-4′-甲基二苯甲酮和2,2′-二羟基-4-甲氧基二苯甲酮,以及使用丙烷-1,3-二酮,如1-(4-叔丁基苯基)-3-(4′-甲氧基苯基)丙烷-1,3-二酮。
可行的典型UV-A过滤剂为:
苯甲酰基甲烷衍生物,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或1-苯基-3-(4′-异丙基苯基)-丙烷-1,3-二酮;
二苯甲酮的氨基-羟基取代的衍生物,如N,N-二乙氨基-羟基苯甲酰基-正己基-苯甲酸酯。
UV-A和UV-B过滤剂当然也可以混合物使用。
其他合适的UV过滤剂物质在下表3中提及。
表3:合适的防晒剂
编号 | 物质 | CAS编号(=酸) |
1 | 4-氨基苯甲酸 | 150-13-0 |
2 | 3-(4’-三甲基铵)亚苄基莰烷-2-酮硫酸甲酯 | 52793-97-2 |
3 | 水杨酸3,3,5-三甲基环己酯(胡莫柳酯) | 118-56-9 |
4 | 2-羟基-4-甲氧基二苯甲酮(羟苯甲酮) | 131-57-7 |
5 | 2-苯基苯并咪唑-5-磺酸及其钾盐、钠盐和三乙醇胺盐 | 27503-81-7 |
6 | 3,3’-(1,4-亚苯基二次甲基)二(7,7-二甲基-2-氧代双环[2.2.1]庚烷-1-甲磺酸)及其盐 | 90457-82-2 |
7 | 4-二(聚乙氧基)氨基苯甲酸聚乙氧基乙酯 | 113010-52-9 |
8 | 4-二甲氨基苯甲酸2-乙基己酯 | 21245-02-3 |
9 | 水杨酸2-乙基己酯 | 118-60-5 |
10 | 4-甲氧基肉桂酸2-异戊酯 | 71617-10-2 |
11 | 4-甲氧基肉桂酸2-乙基己酯 | 5466-77-3 |
12 | 2-羟基-4-甲氧基二苯甲酮-5-磺酸(舒利苯酮(sulisobenzone))和钠盐 | 4065-45-6 |
13 | 3-(4’-磺基)亚苄基莰烷-2-酮和盐 | 58030-58-6 |
14 | 3-亚苄基莰烷-2-酮 | 16087-24-8 |
15 | 1-(4’-异丙基苯基)-3-苯基丙烷-1,3-二酮 | 63260-25-9 |
16 | 水杨酸4-异丙基苄酯 | 94134-93-7 |
17 | 3-咪唑-4-基丙烯酸及其乙酯 | 104-98-3 |
18 | 2-氰基-3,3-二苯基丙烯酸乙酯 | 5232-99-5 |
19 | 2-氰基-3,3-二苯基丙烯酸2’-乙基己基酯 | 6197-30-4 |
20 | 邻氨基苯甲酸薄荷酯或:5-甲基-2-(1-甲基乙基)-2-氨基苯甲酸酯 | 134-09-8 |
21 | 甘油对氨基苯甲酸酯或1-甘油基4-氨基苯甲酸酯 | 136-44-7 |
22 | 2,2’-二羟基-4-甲氧基二苯甲酮(双羟苯甲酮) | 131-53-3 |
23 | 2-羟基-4-甲氧基-4-甲基二苯甲酮(美可西酮) | 1641-17-4 |
24 | 三乙醇胺水杨酸盐 | 2174-16-5 |
25 | 二甲氧基苯基乙醛酸或:3,4-二甲氧基苯基乙醛酸钠 | 4732-70-1 |
26 | 3-(4’磺基)亚苄基莰烷-2-酮及其盐 | 56039-58-8 |
27 | 4-叔丁基-4’-甲氧基二苯甲酰基甲烷 | 70356-09-1 |
28 | 2,2’,4,4’-四羟基二苯甲酮 | 131-55-5 |
29 | 2,2’-亚甲基双[6(2氢-苯并三唑-2-基)-4-(1,1,3,3,-四甲基 | 103597-45-1 |
编号 | 物质 | CAS编号(=酸) |
丁基)苯酚] | ||
30 | 2,2’-(1,4-亚苯基)双-1氢-苯并咪唑-4,6-二磺酸,Na盐 | 180898-37-7 |
31 | 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 | 187393-00-6 |
32 | 3-(4-甲基亚苄基)樟脑 | 36861-47-9 |
33 | 4-二(聚乙氧基)对氨基苯甲酸聚乙氧基乙酯 | 113010-52-9 |
34 | 2,4-二羟基二苯甲酮 | 131-56-6 |
35 | 2,2’-二羟基-4,4’-二甲氧基二苯甲酮-5,5’-二磺酸钠 | 3121-60-6 |
36 | 2-[4-(二乙基氨基)-2-羟基苯甲酰基]苯甲酸己基酯 | 302776-68-7 |
37 | 2-(2H-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]苯酚 | 155633-54-8 |
38 | 1,1-[(2,2′-二甲基丙氧基)羰基]-4,4-二苯基-1,3-丁二烯 | 363602-15-7 |
除上述两组主要防晒物质外,还可使用抗氧化剂类型的第二防晒剂,其阻断在UV辐射穿入皮肤时引发的光化学反应链。它们的典型实例为超氧化物岐化酶、过氧化氢酶、生育酚(维生素E)和抗坏血酸(维生素C)。
另一组为抗刺激剂,其对由UV光损伤的皮肤具有消炎作用。这类物质例如为红没药醇、植醇和植烷三醇。
可用于本发明组合物中的如上所列的活性化合物和活性化合物组合当然不是用来限制。活性化合物可单独使用或以相互间的任何所需组合使用。
这类活性化合物(一种或多种化合物)在本发明组合物中的量基于组合物的总重量优选为0.001-30重量%,特别优选0.05-20重量%,尤其是1-10重量%。
可用于本发明组合物中的所述活性化合物和其它活性化合物在DE103 18 526 A1第12-17页中提及,此处将其完全引入作为参考。
在本发明配制剂中,用活性化合物分子印迹的聚合物与活性化合物的重量比为1∶10-100∶1,优选1∶1-10∶1,特别优选4∶1-5∶1,尤其是4∶1。脂相
本发明配制剂包括至少一种脂相。脂相应理解为指所有化妆品可接受的油、脂肪和/或蜡。
本发明化妆品配制剂的成分
这些成分优选选自天然或合成聚合物、颜料、保湿剂、油、蜡、酶、矿物质、维生素、防晒剂、染料、颜料、香料、抗氧化剂、防腐剂和/或药物活性化合物。
适用于制备皮肤化妆品配制剂的助剂和添加剂对本领域熟练技术人员是熟知的并可在化妆品手册,如Schrader,Grundlagen und Rezepturen derKosmetika[化妆品原理和配方],Hüthig Verlag,Heidelberg,1989,ISBN 3-7785-1491-1,或Umbach,Kosmetik:Entwicklung,Herstellung undAnwendung kosmetischer Mittel[化妆品:化妆品制剂的开发、生产和用途],第2版扩展版,1995,Georg Thieme Verlag,ISBN 3 13 712602 9中找到。
用活性化合物分子印迹的本发明聚合物优选与至少一种与之不同并选自下列的物质结合用于皮肤化妆品:化妆品活性化合物、乳化剂、表面活性剂、防腐剂、芳香油、增稠剂、发用聚合物、毛发和皮肤调理剂、接枝聚合物、水溶性或水分散性含聚硅氧烷聚合物、防晒剂、漂白剂、胶凝剂、护理剂、着色剂、调色剂、晒黑剂、染料、颜料、赋予稠度的试剂、保湿剂、再加油剂(re-oiling agent)、胶原、蛋白质水解产物、类脂、抗氧化剂、消泡剂、抗静电剂、柔润剂和软化剂。
抗氧化剂有利地选自:氨基酸(如甘氨酸、组氨酸、酪氨酸、色氨酸)及其衍生物,咪唑(如尿刊酸)及其衍生物,肽如D,L-肌肽、D-肌肽、L-肌肽及其衍生物(如鹅肌肽),类胡萝卜素,胡萝卜素(如β-胡萝卜素、番茄红素)及其衍生物,绿原酸及其衍生物,硫辛酸及其衍生物(如二氢硫辛酸),金硫葡糖(aurothioglucose),丙硫氧嘧啶和其它硫醇(如硫氧还蛋白(thiorodoxin)、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、γ-亚油酸基、胆甾烯基和甘油基酯)及其盐,硫代二丙酸二月桂酯,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、核苷及盐),以及非常低耐受剂量(如pmol至μmol/kg)的磺酰亚胺(sulfoximine)化合物(如丁硫堇(buthionine)磺酰亚胺,高半胱氨酸磺酰亚胺,丁硫堇砜,五-、六-、七硫堇磺酰亚胺),以及(金属)螯合剂(如α-羟基脂肪酸、棕榈酸、肌醇六磷酸、乳铁蛋白),α-羟基酸(如柠檬酸、乳酸、苹果酸),腐殖酸,胆汁酸、胆汁萃取物,胆红素,胆绿素,EDTA及其衍生物,不饱和脂肪酸及其衍生物(如γ-亚麻酸、亚油酸、油酸),叶酸及其衍生物,泛醌和泛醌醇及其衍生物,维生素C及衍生物(如抗坏血酸钠、棕榈酸抗坏血酸酯、抗坏血酸磷酸镁,乙酸抗坏血酸酯),生育酚及衍生物(如维生素E乙酸酯,生育酚三烯醇),维生素A及衍生物(维生素A棕榈酸酯),以及苯偶姻树脂的松柏基苯甲酸酯,芸香亭酸及其衍生物,α-糖基芸香苷,阿魏酸,亚糠基葡萄糖醇,肌肽,丁羟基甲苯,丁羟基茴香醚,去甲二氢愈创木树酯酸,去甲二氢愈创木酸,三羟基丙基苯基酮,尿酸及其衍生物,甘露糖及其衍生物,锌及其衍生物(如ZnO、ZnSO4),硒及其衍生物(如硒代甲硫氨酸),均二苯代乙烯及其衍生物(如均二苯代乙烯氧化物,反式均二苯代乙烯氧化物)。
根据本发明优选使用的维生素B组的维生素、微生物原或维生素前体,或其衍生物或2-呋喃酮的衍生物尤其为:
维生素B1,俗名硫胺素,化学名3-[(4′-氨基-2′-甲基-5′-嘧啶基)甲基]-5-(2-羟乙基)-4-甲基噻唑鎓氯化物。
维生素B2,俗名核黄素,化学名7,8-二甲基-10-(1-D-核糖基)-苯并[g]喋啶-2,4(3H,10H)-二酮。核黄素例如在乳清中以游离形式出现,且其它核黄素衍生物可从细菌和酵母中分离。根据本发明同样合适的核黄素立体异构体为可从鱼肉或肝脏分中离出的来苏黄素,其具有D-阿拉伯糖基而不是D-核糖基。
维生素B3。此命名通常用于化合物烟酸和烟酰胺。根据本发明优选烟酰胺。
维生素B5(泛酸和泛醇),优选使用泛醇。根据本发明可使用的泛醇衍生物尤其为泛醇的酯和醚和阳离子衍生泛醇。在本发明的另一优选实施方案中,除泛酸或泛醇外,也可使用2-呋喃酮的衍生物。特别优选衍生物为市售物质二氢-3-羟基-4,4-二甲基-2(3H)-呋喃酮(Merck),其俗名为泛酸内酯;4-羟甲基-γ-丁内酯(Merck);3,3-二甲基-2-羟基-γ-丁内酯(Aldrich)和2,5-二氢-5-甲氧基-2-呋喃酮(Merck),明确包括其所有立体异构体。
有利的是这些化合物赋予本发明化妆品组合物保水和皮肤光滑性能。
维生素B6,其不应理解为同一物质,而是已知俗名为吡哆素、吡哆胺和吡哆醇的5-羟甲基-2-甲基吡啶-3-醇的衍生物。
维生素B7(生物素)也称为维生素H或″皮肤维生素″。生物素是(3aS,4S,6aR)-2-氧代六氢噻吩并[3,4-d]咪唑-4-戊酸。
根据本发明,特别优选泛醇、泛酸内酯、烟酰胺和生物素。
染料
可使用的染料为证明适用于化妆品目的的物质,例如总结在出版物″Kosmetische[化妆品着色剂]of the Dyestuffs Commission ofthe Deutsche Forschungsgemeinschaft,Verlag Chemie出版,Weinheim、1984。这些染料基于全部混合物通常以0.001-0.1重量%的浓度使用。
颜料
在优选实施方案中,本发明组合物包含至少一种颜料。颜料以未溶解形式存在于产品中并且存在量可为0.01-25重量%,特别优选5-15重量%。优选粒度为1-200μm,尤其是3-150μm,特别优选10-100μm。颜料为事实上不溶于应用介质的着色剂且可为无机或有机的。无机-有机混合颜料也是可以的。优选无机颜料。无机颜料的优点为它们对光、气候和热的优异牢度。无机颜料可以是天然源的,例如由白垩、赭石、棕土、绿土、煅黄土或石墨制备。颜料可为白色颜料如二氧化钛或氧化锌,黑色颜料如氧化铁黑,彩色颜料如群青或氧化铁红,光泽颜料,金属效果颜料,珠光颜料和荧光或磷光颜料,其中优选至少一种颜料为彩色的非白色颜料。金属氧化物、氢氧化物和氧化物水合物,混合相颜料,含硫硅酸盐,金属硫化物,复合金属氰化物,金属硫酸盐、铬酸盐和钼酸盐,以及金属本身(青铜粉颜料)是合适的。特别合适的是二氧化钛(CI 77891)、氧化铁黑(CI 77499)、氧化铁黄(CI 77492)、氧化铁红和氧化铁棕(CI 77491)、锰紫(CI 77742)、群青(磺基硅酸钠铝,CI77007,颜料蓝29)、氧化铬水合物(CI 77289)、铁蓝(亚铁氰化铁,CI7751 0)和洋红(胭脂虫红)。特别优选基于云母并涂覆金属氧化物或金属氧氯化物(如二氧化钛或氧氯化铋)的珠光颜料和着色颜料,任选赋予颜色的其它物质如铁氧化物、铁蓝、群青、洋红等,其中颜色可通过改变层厚度而确定。这类颜料例如以商品名 和(Merk)销售。有机颜料例如为天然颜料乌贼墨、藤黄、木炭、卡塞尔棕、靛蓝、叶绿素和其它植物颜料。合成有机颜料例如为偶氮颜料、蒽醌(anthraquinoid)、(硫)靛蓝、二噁嗪、喹吖啶酮、酞菁、异吲哚啉酮、苝、紫环酮(perinone)、金属配合物、碱性蓝和二酮吡咯并吡咯颜料。
在一个实施方案中,本发明聚合物或通过本发明方法用活性化合物分子印迹而制备的聚合物与至少一种粒状物质一起使用,该粒状物质以0.01-10重量%,优选0.05-5重量%的含量存在于组合物中。合适的物质例如为在室温(25℃)下为固体且以颗粒形式存在的物质。例如硅石、硅酸盐、铝酸盐、矾土、云母,盐,尤其是无机金属盐,金属氧化物如二氧化钛,矿物和聚合物颗粒是合适的。颗粒以未溶解,优选稳定分散形式存在于组合物中,并且在施加至应用表面上和溶剂蒸发之后可以以固体形式沉积。优选的粒状物质为硅石(硅胶、二氧化硅)和金属盐,尤其是无机金属盐,其中特别优选硅石。金属盐例如为碱金属或碱土金属卤化物如氯化钠或氯化钾;碱金属或碱土金属硫酸盐如硫酸钠或硫酸镁。
珠光剂
可行的珠光剂例如是:亚烷基二醇酯,特别是二硬脂酸乙二醇酯;脂肪酸链烷醇酰胺,特别是椰子脂肪酸二乙醇酰胺;部分甘油酯,特别是硬脂酸单甘油酯;任选羟基取代的羧酸与具有6-22个碳原子的脂肪醇的酯,特别是酒石酸的长链酯;脂肪物质(如脂肪醇、脂肪酮、脂肪醛、脂肪醚和脂肪碳酸酯),其中每种脂肪物质总共具有至少24个碳原子,特别是月桂酮和二硬脂基醚;脂肪酸,如硬脂酸、羟基硬脂酸或二十二碳烷酸,具有12-22个碳原子的烯烃环氧化物与具有12-22个碳原子的脂肪醇和/或具有2-15个碳原子和2-10个羟基的多元醇的开环产物及其混合物。
在这类配制剂中的常用增稠剂是交联的聚丙烯酸及其衍生物,多糖及其衍生物,如黄原胶、琼脂、藻酸盐或纤基乙酸钠,纤维素衍生物,如羧甲基纤维素或羟基羧甲基纤维素,脂肪醇、甘油单酯和脂肪酸,聚乙烯醇和聚乙烯吡咯烷酮。优选使用非离子增稠剂。
合适的化妆品和/或皮肤化妆品活性化合物例如为着色活性化合物、皮肤和毛发着色剂、调色剂、晒黑剂、漂白剂、角蛋白硬化物质、抗微生物活性化合物、滤光活性化合物、驱除剂活性化合物(repellent activeingredients)、具有充血作用的物质、具有溶角蛋白和角质增生(keratoplastic)作用的物质、去头屑活性化合物、消炎剂、具有角质化作用的化合物、具有抗氧化作用或自由基清除作用的活性化合物、使皮肤湿润或使其保持湿润的物质、再加油活性化合物、抗红斑(antierythematously)或抗过敏活性化合物、支化脂肪酸如18-甲基二十烷酸及其混合物。
产生人工晒黑并适用于晒黑皮肤而无需自然或人工暴露于紫外线的活性化合物例如为二羟基丙酮、阿脲(alloxan)和胡桃壳提取物。合适的角蛋白硬化物质通常为也用于防汗剂的活性化合物,例如硫酸铝钾、碱式氯化铝、乳酸铝等。
抗微生物活性化合物用于消灭微生物或用于抑制它们生长,因此同时用作防腐剂和减少体臭的形成及强度的除臭物质。这些例如包括本领域熟练技术人员已知的常规防腐剂如对羟基苯甲酸酯、咪唑烷基脲、甲醛、山梨酸、苯甲酸、水杨酸等。这类具有除臭作用物质例如为蓖麻酸锌、玉洁纯(triclosan)、十一碳烯酸链烷醇酰胺、柠檬酸三乙酯、洗必泰(chlorhexidine)等。
根据本发明有利地使用的合适防腐剂为:
表4合适的防腐剂。
E 200 | 山梨酸 | E 227 | 亚硫酸氢钙 |
E 201 | 山梨酸钠 | E 228 | 亚硫酸氢钾 |
E 202 | 山梨酸钾 | E 230 | 联苯 |
E 203 | 山梨酸钙 | E 231 | 邻苯基苯酚 |
E 210 | 苯甲酸 | E 232 | 邻苯基苯酚钠 |
E 211 | 苯甲酸钠 | E 233 | 涕必灵 |
E 212 | 苯甲酸钾 | E 235 | 多马霉素 |
E 213 | 苯甲酸钙 | E 236 | 甲酸 |
E 214 | 对羟基苯甲酸乙酯 | E 237 | 甲酸钠 |
E 215 | 对羟基苯甲酸乙酯钠盐 | E 238 | 甲酸钙 |
E 216 | 对羟基苯甲酸正丙酯 | E 239 | 六亚甲基四胺 |
E 217 | 对羟基苯甲酸正丙酯钠盐 | E 249 | 亚硝酸钾 |
E 218 | 对羟基苯甲酸甲酯 | E 250 | 亚硝酸钠 |
E 219 | 对羟基苯甲酸甲酯钠盐 | E 251 | 硝酸钠 |
E 220 | 二氧化硫 | E 252 | 硝酸钾 |
E 221 | 亚硫酸钠 | E 280 | 丙酸 |
E 222 | 亚硫酸氢钠 | E 281 | 丙酸钠 |
E 223 | 焦亚硫酸钠 | E 282 | 丙酸钙 |
E 224 | 焦亚硫酸钾 | E 283 | 丙酸钾 |
E 226 | 亚硫酸钙 | E 290 | 二氧化碳 |
上表中所列的E数字是Directive 95/2/EEC中常用的名称。
此外,化妆品领域中常用的防腐剂或防腐剂助剂,如二溴二氰基丁烷(2-溴-2-溴甲基戊二腈)、氨基甲酸3-碘-2-丙炔基丁酯、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、杀藻胺(benzalkonium chloride)和苄醇也适合本发明。此外,苯基羟基烷基醚,尤其是以苯氧基乙醇已知的化合物基于它们对许多微生物的杀菌和杀真菌作用也适合用作防腐剂。
其它抑菌剂同样适合掺入本发明配制剂。有利的物质例如为2,4,4′-三氯-2′-羟基二苯醚(三氯生),1,6-二-(4-氯苯基双胍)-己烷(氯己定(chlorhe-xidine)),3,4,4′-三氯对称二苯脲,季铵化合物,丁香油,薄荷油,百里香,柠檬酸三乙酯,金合欢醇(3,7,11-三甲基-2,6,10-十二烷三烯-1-醇),以及在如下专利说明书中描述的活性化合物和活性化合物组合DE-37 40 186、DE-39 38 140、DE-42 04 321、DE-42 29 707、DE-43 09 372、DE-44 11 664、DE-195 41 967、DE-195 43 695、DE-195 43 696、DE-195 47 160、DE-196 02108、DE-196 02 110、DE-196 02 111、DE-196 31 003、DE-196 31 004和DE-196 34 019和专利说明书DE-42 29 737、DE-42 37 081、DE-43 24 219、DE-44 29 467、DE-44 23 410和DE-195 16 705。使用碳酸氢钠也是有利的。同样可使用微生物多肽。
芳香油
化妆品组合物可任选包含芳香油。可以提及的芳香油例如为天然和合成香料物质的混合物。天然香料物质为来自如下原料的提取物:花(百合、熏衣草、玫瑰、茉莉、苦橙花、依兰),茎和叶(老鹳草、广藿香、苦橙叶(petitgrain)),果实(茴香、芫荽、芡蒿子、刺柏),果皮(香柠檬、柠檬、橙),根(肉豆蔻、当归、芹菜、小豆蔻、广木香、鸢尾、菖蒲),木(松木、檀香木、愈创木、雪松木、蔷薇木),香草和草(龙蒿、香茅草、鼠尾草、百里香),针和枝(云杉、冷杉、松树、矮松),树脂和香脂(古蓬香脂、榄香脂、安息香、没药、乳香、红没药)。动物原料也是合适的,例如麝猫香和海狸香。典型的合成香料化合物为酯类、醚类、醛类、酮类、醇类和烃类产品。酯类香料化合物例如为乙酸苄酯、异丁酸苯氧基乙酯、乙酸4-叔丁基环己酯、乙酸芳樟酯、乙酸二甲基苄基原酯、乙酸苯乙酯、苯甲酸芳樟酯、甲酸苄酯、氨基乙酸乙基甲基苯酯、环己基丙酸烯丙基酯、丙酸苏合香酯和水杨酸苄酯。醚类例如包括苯基乙基醚,醛类例如包括具有8-18个碳原子的线性链烷醛、柠檬醛、香茅醛、香茅基氧基乙醛、仙客来醛、羟基香茅醛、铃兰醛和波洁红醛(bourgeonat),酮类例如包括芷香酮、cc-异甲基紫罗兰酮和甲基柏木酮,醇包括茴香脑、香茅醇、丁子香酚、异丁子香酚、香叶醇、芳樟醇、苯乙醇和松油醇,以及烃类主要包括萜类和香脂。然而,优选使用一起产生令人愉悦香味的不同香料的混合物。通常用作香料组分的低挥发性精油也适合用作芳香油,例如鼠尾草油、春黄菊油、丁香油、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。优选单独或混合使用如下物质: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、Forte、龙涎呋喃(ambroxan)、吲哚、二氢茉莉酮酸甲酯(hedione)、sandelice、柠檬油、橘子油、橙油、戊基甘醇酸烯丙基酯、cyclovertal、杂熏衣草油、鼠尾草油、β-突厥酮、波旁香叶油、水杨酸环己酯、coeur、iso-E- NP、evernyl、iraldein gamma、苯乙酸、乙酸香叶酯、乙酸苄酯、氧化玫瑰、romillat、irotyl和floramat。
油、脂肪和蜡
本发明组合物包含至少一种脂相。脂相应理解为指油、脂肪和/或蜡。本发明组合物的油相和/或脂相的成分有利地选自卵磷脂和脂肪酸甘油三酯,即链长为8-24个,尤其是12-18个碳原子的饱和和/或不饱和、支化和/或未支化链烷羧酸的甘油三酯。脂肪酸甘油三酯例如可有利地选自合成、半合成和天然的油如橄榄油、葵花油、大豆油、花生油、菜籽油、杏仁油、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、澳洲坚果油等等。其它极性油组分可选自链长为3-30个碳原子的饱和和/或不饱和、支化和/或未支化链烷羧酸与链长为3-30个碳原子的饱和和/或不饱和、支化和/或未支化醇的酯,芳族羧酸与链长为3-30个碳原子的饱和和/或不饱和、支化和/或未支化醇的酯。因此这类酯油可有利地选自: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、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、硬脂酸2-己基癸酯、棕榈酸2-辛基十二烷基酯、油酸油酯、芥酸油酯、油酸瓢儿菜酯、芥酸瓢儿菜酯、碳酸二辛酯(Cetiol CC)和椰油甘油酯(Myritol 331)、丁二醇二辛酸酯/二癸酸酯和己二酸二丁酯以及所述酯的合成、半合成和天然混合物,如霍霍巴油。
此外,一种或多种油组分可有利地选自支化和未支化烃和烃蜡、硅油、二烷基醚,饱和或不饱和、支化或未支化醇。对本发明而言,有利的是使用这类油和蜡组分的任何所需混合物。合适的话,也任选可有利地使用蜡如棕榈酸鲸蜡酯作为油相的唯一类脂组分。根据本发明,有利的是油组分选自异硬脂酸2-乙基己酯、辛基十二醇、异壬酸异十三烷基酯、异二十碳烷、椰油酸2-乙基己酯、苯甲酸C12-15烷基酯、甘油三(辛酸/癸酸)酯、二辛酰醚。根据本发明,有利的是苯甲酸C12-C15烷基酯和异硬脂酸2-乙基己酯的混合物,苯甲酸C12-15烷基酯和异壬酸异十三烷基酯的混合物,以及苯甲酸C12-15烷基酯、异硬脂酸2-乙基己酯和异壬酸异十三烷基酯的混合物。根据本发明,脂肪酸甘油三酯,尤其是大豆油和/或杏仁油特别优选用作具有极性为5-50mN/m的油。在烃中,石蜡油、角鲨烷和角鲨烯有利地用于本发明的上下文中。
而且,油相可有利地选自格尔伯特(Guerbet)醇。格尔伯特醇按MacrcelGuerbet命名,他首次描述了它们的制备。格尔伯特醇根据下列反应方程式:
通过将醇氧化成醛,通过该醛的醇醛缩合,从醇醛中除去水并将烯丙基醛氢化而形成。格尔伯特醇甚至在较低温度下也是液体并基本上不会引起皮肤刺激。它们在化妆品组合物中可有利地用作具有加油、富油(super-oiling)和再加油作用的组分。
格尔伯特醇在化妆品中的使用本身是已知的。该类醇在次情况下特征在于具有如下结构:
此处R1和R2通常是未支化烷基。
根据本发明,格尔伯特醇有利地选自这样的一组:其中
R1=丙基、丁基、戊基、己基、庚基或辛基,和
R2=己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基或十四烷基。
根据本发明格尔伯特醇优选是2-丁基辛醇(例如商业上可得的12(Condea))和2-己基癸醇(例如商业上可得的16(Condea))。根据本发明格尔伯特醇的混合物也可有利地使用,例如2-丁基辛醇和2-己基癸醇的混合物(例如商业上可得的14(Condea))。
该类油和蜡组分的任何所需混合物也可有利地用于本发明上下文中。在聚烯烃中,聚癸烯是优选物质。
油组分此外还可有利地含有环状或线性硅油,或完全由该类油组成,但除了硅油以外,优选使用额外量的其它油相组分。低分子量聚硅氧烷或硅油通常由下述通式所定义:
高分子量聚硅氧烷或硅油通常由下述通式所定义:
其中硅原子可以被相同或不同的烷基和/或芳基取代,该烷基和芳基此处通常由基团R1-R4代表。然而不同基团的数量不必须限定为至多4。m此处可采用2-200 000的值。
根据本发明有利地使用的环状聚硅氧烷通常由下述通式所定义:
其中硅原子可以被相同或不同的烷基和/或芳基取代,该烷基和芳基此处通常由基团R1-R4代表。然而不同基团的数量不必须限定为至多4。n此处可采用3/2-20的值。考虑到环中可能存在奇数个硅氧基的事实,因此n存在分数值。
聚苯基三甲基硅氧烷有利地选作硅油。其它硅油,例如聚二甲基硅氧烷、六甲基环三硅氧烷、聚苯基二甲基硅氧烷、环状聚二甲基硅氧烷(八甲基环五硅氧烷)、六甲基环三硅氧烷、聚二甲基硅氧烷、聚(甲基苯基硅氧烷)、十六烷基聚二甲基硅氧烷和二十二烷基氧基聚二甲基硅氧烷也可有利地用于本发明的上下文中。而且环状聚二甲基硅氧烷和异壬酸异十三烷基酯的混合物以及环状聚二甲基硅氧烷和异硬脂酸2-乙基己基酯的混合物也是有利的。然而,还有利的是选择成分与上述化合物的成分类似但是其有机侧链被衍生(例如聚乙氧基化和/或聚丙氧基化)的硅油。这些例如包括聚硅氧烷聚烷基-聚醚共聚物,例如含聚氧乙烯或聚氧丙烯侧链的十六烷基聚二甲基硅氧烷。环状聚二甲基硅氧烷(八甲基环四硅氧烷)有利地用作根据本发明使用的硅油。根据本发明有利地使用的脂肪和/或蜡组分可选自:植物蜡、动物蜡、矿物蜡和石化蜡(Petrochemical wax)。例如有利的是小烛树蜡、巴西棕榈蜡、日本蜡、西班牙针草蜡、软木蜡、瓜耳胶蜡、米胚油蜡、甘蔗蜡、浆果蜡、小冠椰子蜡、褐煤蜡、霍霍巴蜡、牛油树脂、蜂蜡、虫胶蜡、鲸油、羊毛脂(羊毛蜡)、尾臀油脂、纯地蜡(ceresin)、地蜡(earthwax)、石蜡和微晶蜡。
其它有利的脂肪和/或蜡组分是化学改性的蜡和合成蜡,例如HRC(三-二十二烷酸甘油酯)和AW1 C(C18-36脂肪酸)和褐煤酯蜡,Sasol蜡,氢化霍霍巴蜡,合成或改性的蜂蜡(如含聚氧乙烯或聚氧丙烯侧链的聚二甲基硅氧烷蜂蜡和/或C30-50烷基蜂蜡),蓖麻油酸十六烷基酯,例如CR,聚亚烷基蜡,聚乙二醇蜡,但还有化学改性的脂肪,例如氢化植物油(例如氢化蓖麻油和/或氢化椰子脂肪甘油酯),甘油三酯,如大豆甘油酯、三羟基三硬脂酸甘油酯,脂肪酸、脂肪酸酯和乙二醇酯,例如C20-40烷基硬脂酸酯、C20-40烷基羟基硬脂酰基硬脂酸酯和/或褐煤酸乙二醇酯。此外还有利的是具有类似于所述脂肪和/或蜡组分的物理性能的某些有机硅化合物,例如硬脂氧基三甲基硅烷。根据本发明,脂肪和/或蜡组分在组合物中可单独或者混合使用。这些油和蜡组分的任何所需混合物也可有利地用于本发明上下文中。油相有利地选自:异硬脂酸2-乙基己基酯、辛基十二烷醇、异壬酸异十三烷基酯、丁二醇二辛酸酯/二癸酸酯、椰油酸2-乙基己基酯、苯甲酸C12-15烷基酯、甘油三(辛酸/己酸)酯、二辛基醚。特别有利的是辛基十二烷醇、甘油三(辛酸/己酸)酯、二辛基醚、碳酸二辛基酯、椰油甘油酯的混合物,或苯甲酸C12-15烷基酯和异硬脂酸2-乙基己基酯的混合物,苯甲酸C12-15烷基酯和丁二醇二辛酸酯/二癸酸酯的混合物,以及苯甲酸C12-15烷基酯、异硬脂酸2-乙基己基酯和异壬酸异十三烷基酯的混合物。在烃中,石蜡油、环状蜡、角鲨烷、角鲨烯、氢化聚异丁烯和聚癸烯有利地用于本发明的上下文中。
油组分此外还有利地选自磷脂。磷脂是酰化甘油的磷酸酯。在磷脂酰胆碱类中最重要的例如是具有如下通式结构特征的卵磷脂:
其中R’和R”典型的为具有15或17个碳原子且至多4个顺式双键的未支化脂族基团。
根据本发明,得自Merkur Vaseline的Merkur White oil Pharma 40,得自Shell & DEA Oil的Shell917、Shell927、ShellOil 4222、Shell933,6301 S、2071(Hansen &Rosenthal)可用作对本发明有利的石蜡油。合适的化妆品相容的油和脂肪组分描述在Karl-Heinz Schrader,Grundlagen und Rezepturen derKosmetika[化妆品原料和配方],第二版,Verlag Hüthig,Heidelberg,第319-355页中,该文献全部引入本文作为参考。
溶剂
如果将本发明聚合物或通过本发明方法用活性化合物分子印迹而制备的聚合物用于溶液或乳液或分散体形式的化妆品配制剂或皮肤病配制剂,则可使用的溶剂为:
水或水溶液;油,如癸酸或辛酸甘油三酯,但优选蓖麻油;脂肪、蜡和其它天然和合成脂肪物质,优选脂肪酸与低碳原子数醇的酯,如与异丙醇、丙二醇或甘油的酯,或脂肪醇与低碳原子数链烷酸或与脂肪酸的酯;低碳原子数的醇、二醇或多元醇,及其醚,优选乙醇、异丙醇、丙二醇、甘油、乙二醇、乙二醇单乙醚或单丁醚,丙二醇单甲醚、单乙醚或单丁醚,二甘醇单甲醚或单乙醚和类似产物。尤其可使用上述溶剂的混合物。在醇类溶剂的情况下,水可以是另一组分。
表面活性剂
根据本发明,除了本发明聚合物或通过本发明方法用活性化合物分子印迹而制备的聚合物外,组合物也可包含表面活性剂。这类表面活性剂例如为:
-磷酸酯和盐,如油基聚氧乙烯(10)醚磷酸二乙醇胺和二[月桂基聚氧乙烯(10)醚]磷酸酯,
-烷基磺酸盐,例如例如椰油甘油一硫酸酯钠、C12-14烯烃磺酸钠、月桂基磺基乙酸钠和PEG-3椰油酰胺硫酸镁,
-羧酸及衍生物,例如月桂酸、硬脂酸铝、链烷酸镁和十一烯酸锌,和酯-羧酸,例如硬脂酰乳酸钙、月桂基聚氧乙烯(6)醚柠檬酸酯和PEG-4月桂酰胺羧酸钠,
-通过羧酸和氧化乙烯、甘油、失水山梨醇和其它醇的酯化形成的酯
-醚,例如乙氧基化醇、乙氧基化羊毛脂、乙氧基化聚硅氧烷、丙氧基化POE醚和烷基多苷,如十二烷基葡糖苷、癸基糖苷和椰油基糖苷。
失水山梨醇聚氧乙烯醚酯
根据本发明,除了本发明聚合物或通过本发明方法用活性化合物分子印迹而制备的聚合物外,组合物也可包含失水山梨醇聚氧乙烯醚酯。
对本发明而言,有利的失水山梨醇聚氧乙烯醚酯是:
-聚氧乙烯(4)失水山梨醇单月桂酸酯(21,CAS-No.9005-64-5)
-聚氧乙烯(20)失水山梨醇三硬脂酸酯(65,CAS-No.9005-71-4)
特别有利的是:
-聚氧乙烯(20)失水山梨醇单硬脂酸酯(Tween60,CAS-No.9005-67-8)。
根据本发明,失水山梨醇聚氧乙烯醚酯有利的使用浓度基于组合物的总重量为0.1-5重量%,特别为1.5-2.5重量%,其中它们单独或作为多种失水山梨醇聚氧乙烯醚酯的混合物使用。
调理剂
在优选实施方案中,组合物还含有调理剂。
根据本发明,调理剂优选例如是在International Cosmetic lngredientDictionary and Handbook(国际化妆品成分词典和手册)第4部分中提到的所有化合物(第4卷,编辑:R.C.Pepe,J.A.Wenninger,G.N.McEwen,The Cosmetic,Toiletry and Fragrance Association,第9版,2002),其关键词是毛发调理剂、保湿剂、皮肤调理剂、皮肤调理剂-润肤剂、皮肤调理剂-保湿剂、皮肤调理剂-混合型、皮肤调理剂-吸留性和皮肤保护剂,以及调理剂还包括在EP-A 934 956中(第11-13页)在“水溶性调理剂”和“油溶性调理剂”下提到的所有化合物。其它有利的调理剂例如是根据INCI命名为聚季铵盐(Polyquaternium)(尤其是聚季铵盐-1至聚季铵盐-56)的化合物。
合适的调节剂也例如包括聚合的季铵化合物、阳离子纤维素衍生物和多糖。
就此而言,根据本发明有利的调节剂可选自下表中示出的化合物。
表5:有利地使用的调理剂
根据本发明有利的其它调理剂是纤维素衍生物和季铵化瓜耳胶衍生物,尤其是瓜耳羟基丙基氯化铵(如Excel和C 162,CAS65497-29-2,CAS 39421-75-5)。根据本发明,非离子的聚-N-乙烯基吡咯烷酮/聚乙酸乙烯酯共聚物(如VA 64(BASF Aktiengesellschaft))、阴离子的丙烯酸酯共聚物(如Soft(BASF Aktiengesellschaft))和/或两性的酰胺/丙烯酸酯/甲基丙烯酸酯共聚物(如(NationalStarch))也可有利地用作调理剂。
粉末原料
加入粉末原料通常是有利的。特别优选使用滑石。
乙氧基化甘油脂肪酸酯
根据本发明,除了分子印迹聚合物外,组合物还可包含选自下述的乙氧基化油:乙氧基化甘油脂肪酸酯,特别优选PEG-10橄榄油甘油酯、PEG-11鳄梨油甘油酯、PEG-11椰油黄油甘油酯、PEG-13向日葵油甘油酯、PEG-15甘油基异硬脂酸酯、PEG-9椰子脂肪酸甘油酯、PEG-54氢化蓖麻油、PEG-7氢化蓖麻油、PEG-60氢化蓖麻油、霍霍巴油乙氧化物(PEG-26霍霍巴脂肪酸、PEG-26霍霍巴醇)、甘油聚氧乙烯(5)醚椰油酸酯、PEG-9椰子脂肪酸甘油酯、PEG-7甘油基椰油酸酯、PEG-45棕榈仁油甘油酯、PEG-35蓖麻油、橄榄油-PEG-7酯、PEG-6辛酸/癸酸甘油酯、PEG-10橄榄油甘油酯、PEG-13向日葵油甘油酯、PEG-7氢化蓖麻油、氢化棕榈仁油甘油酯-PEG-6酯、PEG-20玉米油甘油酯、PEG-18甘油基油酸酯椰油酸酯、PEG-40氢化蓖麻油、PEG-40蓖麻油、PEG-60氢化蓖麻油、PEG-60玉米油甘油酯、PEG-54氢化蓖麻油、PEG-45棕榈仁油甘油酯、PEG-35蓖麻油、PEG-80甘油基椰油酸酯、PEG-60杏仁油甘油酯、PEG-60“月见草”甘油酯、PEG-200氢化甘油基棕榈酸酯、PEG-90甘油基异硬脂酸酯。
优选的乙氧基化油是PEG-7甘油基椰油酸酯、PEG-9椰子甘油酯、PEG-40氢化蓖麻油、PEG-200氢化甘油基棕榈酸酯。乙氧基化甘油脂肪酸酯由于不同目的用于含水清洁配制剂。低乙氧基化程度(3-12个氧化乙烯单元)的甘油脂肪酸酯通常用作再加油剂以改善在皮肤上干燥后的感觉,乙氧基化度为大约30-50的甘油脂肪酸酯用作非极性物质,如芳香油的加溶剂。高度乙氧基化的甘油脂肪酸酯用作增稠剂。所有这些物质的共同特征在于当用水稀释使用时它们在皮肤上产生特别的感觉。
防晒剂
本发明还提供了本发明聚合物或通过本发明方法用活性化合物分子印迹而制备的聚合物与防晒剂结合用于皮肤化妆品配制剂中的用途。
这些化妆品和/或皮肤病防晒组合物用于防止光的化妆和/或皮肤病学保护,此外用于处理和护理皮肤和/或毛发以及在装饰性化妆品中作为化妆产品。它们例如包括防晒霜、洗剂、乳、油、香液和凝胶,唇护理产品和唇膏,遮盖霜(covering cream)和棒,润湿霜,洗剂和乳液,面、体和手霜,毛发处理和调理剂,毛发定型组合物,定型凝胶,喷发胶,滚球式除臭剂(roll-on deodorant)或眼用防皱霜(eye wrinkle cream)、热带防晒霜(tropicals,sunblock)和晒后用制剂。所有制剂包含至少一种用活性化合物分子印迹的聚合物和一种所述UV过滤剂物质。
防晒油通常为各种油与一种或多种防晒过滤剂和芳香油的混合物。油组分根据各种化妆品性能选择。将上油良好并赋予柔软皮肤感觉的油如矿物油(如石蜡油)和脂肪酸甘油三酯(如花生油、芝麻油、鳄梨油、中链甘油三酯与改善防晒油分布容易性和被皮肤吸收,降低粘性并使得油膜能被空气和蒸气透过(排汗)的油混合。这些例如包括支链脂肪酸酯(如棕榈酸异丙酯)和硅油(如聚二甲基硅氧烷)。如果使用基于不饱和脂肪酸的油,则加入抗氧化剂如生育酚以防止它们变臭。作为不含水的配制剂,防晒油通常不含防腐剂。将防晒乳和防晒霜制备为水包油(O/W)乳液和油包水(W/O)乳液。制剂的性能取决于乳液类型而非常不同。O/W乳液可易于在皮肤上分布,它们通常被快速吸收并且几乎总是可以易于用水洗掉。W/O乳液较难擦入,它们对皮肤上油更深入,因此具有一定的粘性作用,但另一方面可更好的防止皮肤变干。W/O乳液通常为耐水的。在O/W乳液的情况下,耐水程度取决于乳液基质、合适的防晒物质的选择以及合适的话助剂(如聚合物)的使用。液体和霜状O/W乳液的基质的组成与常用于护肤的乳液类似。防晒乳应对被太阳、水和风干燥的皮肤充分上油。它们不应是粘性的,因为这在热的时候以及在与沙接触的时候感觉特别不舒服。防晒组合物通常基于含有至少一个油相的载体。然而,仅基于水的组合物也是可能的。因此,油,水包油和油包水乳液,霜和糊,唇膏保护组合物或不含脂肪的凝胶是可能的。可能的乳液尤其为具有以分散形式存在的表面涂覆的二氧化钛颗粒的O/W粗乳液,O/W微乳液或O/W/O乳液,其中乳液可通过相反转技术根据DE-A-197 26 121得到。
作为可行的添加剂的常规化妆品助剂例如为(辅助)乳化剂、脂肪和蜡,稳定剂,增稠剂,生物活性化合物,成膜剂,香料,染料,珠光剂,防腐剂,颜料,电解质(如硫酸镁)和pH调节剂。可使用的稳定剂为脂肪酸金属盐,如硬脂酸镁、硬脂酸铵和/或硬脂酸锌。生物活性化合物应理解为指例如植物提取物、蛋白质水解物和维生素复合物。常用的成膜剂例如为水凝胶如壳聚糖、微晶壳聚糖或季铵化壳聚糖,聚乙烯基吡咯烷酮,乙烯基吡咯烷酮/乙酸乙烯酯共聚物,丙烯酸类聚合物,季铵化纤维素衍生物和类似化合物。
合适的光过滤活性化合物为吸收在UV-B和/或UV-A范围的紫外线的物质。这些应理解为能够吸收紫外线并以长波辐射形式,如热量再次释放所吸收的能量的有机物质。有机物质可以是油溶性或水溶性的。合适的UV过滤剂例如为2,4,6-三芳基-1,3,5-三嗪,其中芳基在每种情况下可以带有至少一个取代基,其优选选自羟基,烷氧基,尤其是甲氧基,烷氧基羰基,尤其是甲氧基羰基和乙氧基羰基。此外合适的是对氨基苯甲酸酯,肉桂酸酯,二苯甲酮,樟脑衍生物和遮蔽紫外线的颜料如二氧化钛、滑石和氧化锌。特别优选基于二氧化钛的颜料。
可使用的油溶性UV-B过滤剂例如为如下物质:
3-亚苄基樟脑及其衍生物,如3-(4-甲基亚苄基)樟脑;
4-氨基苯甲酸衍生物,优选4-(二甲氨基)苯甲酸2-乙基己酯、4-(二甲氨基)苯甲酸2-辛酯和4-(二甲氨基)苯甲酸戊酯
肉桂酸酯,优选4-甲氧基肉桂酸2-乙基己基酯、4-甲氧基肉桂酸丙基酯、4-甲氧基肉桂酸异戊基酯、4-甲氧基肉桂酸异戊基酯和2-氰基-3-苯基-肉桂酸2-乙基己基酯(2-氰基-3,3-二苯基丙烯酸-2-乙基己酯);
水杨酸酯,优选水杨酸2-乙基己基酯、水杨酸4-异丙基苄基酯和水杨酸胡莫柳酯酯;
二苯甲酮衍生物,优选2-羟基-4-甲氧基二苯甲酮、2-羟基-4-甲氧基-4′-甲基二苯甲酮和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-乙基己基)酯;
丙烷-1,3-二酮,如1-(4-叔丁基苯基)-3-(4′-甲氧基苯基)丙烷-1,3-二酮。
可行的水溶性物质为:
2-苯基苯并咪唑-5-磺酸及其碱金属盐、碱土金属盐、铵盐、烷基铵盐、链烷醇铵盐和葡糖铵盐;
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-亚苯基樟脑的磺酸衍生物如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。
特别优选使用肉桂酸酯,4-甲氧基肉桂酸2-乙基己基酯、4-甲氧基肉桂酸异戊基酯和2-氰基-3-苯基-肉桂酸2-乙基己基酯(2-氰基-3,3-二苯基丙烯酸-2-乙基己酯)。
此外,优选使用二苯甲酮衍生物,尤其是2-羟基-4-甲氧基二苯甲酮、2-羟基-4-甲氧基-4′-甲基二苯甲酮和2,2′-二羟基-4-甲氧基二苯甲酮,以及使用丙烷-1,3-二酮,如1-(4-叔丁基苯基)-3-(4′-甲氧基苯基)丙烷-1,3-二酮。
可行的典型UV-A过滤剂为:
苯甲酰基甲烷衍生物,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或1-苯基-3-(4′-异丙基苯基)-丙烷-1,3-二酮;
二苯甲酮的氨基-羟基取代的衍生物,如N,N-二乙氨基-羟基苯甲酰基-正己基-苯甲酸酯。
UV-A和UV-B过滤剂当然也可以混合物使用。
其他合适的UV过滤剂物质在下表中提及。
表6:合适的防晒剂
编号 | 物质 | CAS编号(=酸) |
1 | 4-氨基苯甲酸 | 150-13-0 |
2 | 3-(4’-三甲基铵)亚苄基莰烷-2-酮硫酸甲酯 | 52793-97-2 |
3 | 水杨酸3,3,5-三甲基环己酯(胡莫柳酯) | 118-56-9 |
4 | 2-羟基-4-甲氧基二苯甲酮(羟苯甲酮) | 131-57-7 |
5 | 2-苯基苯并咪唑-5-磺酸及其钾盐、钠盐和三乙醇胺盐 | 27503-81-7 |
6 | 3,3’-(1,4-亚苯基二次甲基)二(7,7-二甲基-2-氧代双环[2.2.1]庚烷-1-甲磺酸)及其盐 | 90457-82-2 |
7 | 4-二(聚乙氧基)氨基苯甲酸聚乙氧基乙酯 | 113010-52-9 |
8 | 4-二甲氨基苯甲酸2-乙基己酯 | 21245-02-3 |
9 | 水杨酸2-乙基己酯 | 118-60-5 |
10 | 4-甲氧基肉桂酸2-异戊酯 | 71617-10-2 |
编号 | 物质 | CAS编号(=酸) |
11 | 4-甲氧基肉桂酸2-乙基己酯 | 5466-77-3 |
12 | 2-羟基-4-甲氧基二苯甲酮-5-磺酸(舒利苯酮(sulisobenzone))和钠盐 | 4065-45-6 |
13 | 3-(4’-磺基)亚苄基莰烷-2-酮和盐 | 58030-58-6 |
14 | 3-亚苄基莰烷-2-酮 | 16087-24-8 |
15 | 1-(4’-异丙基苯基)-3-苯基丙烷-1,3-二酮 | 63260-25-9 |
16 | 水杨酸4-异丙基苄酯 | 94134-93-7 |
17 | 3-咪唑-4-基丙烯酸及其乙酯 | 104-98-3 |
18 | 2-氰基-3,3-二苯基丙烯酸乙酯 | 5232-99-5 |
19 | 2-氰基-3,3-二苯基丙烯酸2’-乙基己基酯 | 6197-30-4 |
20 | 邻氨基苯甲酸薄荷酯或:5-甲基-2-(1-甲基乙基)-2-氨基苯甲酸酯 | 134-09-8 |
21 | 甘油对氨基苯甲酸酯或1-甘油基4-氨基苯甲酸酯 | 136-44-7 |
22 | 2,2’-二羟基-4-甲氧基二苯甲酮(双羟苯甲酮) | 131-53-3 |
23 | 2-羟基-4-甲氧基-4-甲基二苯甲酮(美可西酮) | 1641-17-4 |
24 | 三乙醇胺水杨酸盐 | 2174-16-5 |
25 | 二甲氧基苯基乙醛酸或:3,4-二甲氧基苯基乙醛酸钠 | 4732-70-1 |
26 | 3-(4’磺基)亚苄基莰烷-2-酮及其盐 | 56039-58-8 |
27 | 4-叔丁基-4’-甲氧基二苯甲酰基甲烷 | 70356-09-1 |
28 | 2,2’,4,4’-四羟基二苯甲酮 | 131-55-5 |
29 | 2,2’-亚甲基双[6(2氢-苯并三唑-2-基)-4-(1,1,3,3,-四甲基丁基)苯酚] | 103597-45-1 |
30 | 2,2’-(1,4-亚苯基)双-1氢-苯并咪唑-4,6-二磺酸,Na盐 | 180898-37-7 |
31 | 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 | 187393-00-6 |
32 | 3-(4-甲基亚苄基)樟脑 | 36861-47-9 |
33 | 4-二(聚乙氧基)对氨基苯甲酸聚乙氧基乙酯 | 113010-52-9 |
34 | 2,4-二羟基二苯甲酮 | 131-56-6 |
35 | 2,2’-二羟基-4,4’-二甲氧基二苯甲酮-5,5’-二磺酸钠 | 3121-60-6 |
36 | 2-[4-(二乙基氨基)-2-羟基苯甲酰基]苯甲酸己基酯 | 302776-68-7 |
37 | 2-(2H-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]苯酚 | 155633-54-8 |
38 | 1,1-[(2,2′-二甲基丙氧基)羰基]-4,4-二苯基-1,3-丁二烯 | 363602-15-7 |
除上述两组主要防晒物质外,还可使用抗氧化剂类型的第二防晒剂,其阻断在UV辐射穿入皮肤时引发的光化学反应链。它们的典型实例为超氧化物歧化酶、过氧化氢酶、生育酚(维生素E)和抗坏血酸(维生素C)。
另一组为抗刺激剂,其对由UV光损伤的皮肤具有消炎作用。这类物质例如为红没药醇、植醇和植烷三醇。
本发明还提供了本发明聚合物或通过本发明方法用活性化合物分子印迹而制备的聚合物与防止UV光的无机颜料结合用于皮肤化妆品配制剂中的用途。优选存在基于不溶于水或微溶于水的金属氧化物和/或其它金属化合物的颜料,其选自:锌氧化物(ZnO),钛氧化物(TiO2),铁氧化物(如Fe2O3),锆氧化物(ZrO2)、硅氧化物(SiO2),锰氧化物(如MnO),铝氧化物(Al2O3),铈氧化物(如Ce2O3),相应金属的混合氧化物以及这些氧化物的共混物。
此处无机颜料可以以涂覆形式存在,即将它们表面处理。所述表面处理例如包括通过本身已知的如描述于DE-A-33 14 742中方法对颜料提供疏水性薄层。
合适的驱除剂活性化合物为能够使某些动物,尤其是昆虫远离人类或驱赶它们的化合物。这些化合物例如包括2-乙基-1,3-己二醇、N,N-二乙基-间甲苯酰胺等。刺激皮肤血液循环的合适的充血作用物质例如为精油如矮松针提取物、薰衣草提取物、迷迭香提取物、刺柏提取物、马栗提取物、白桦叶提取物、干草种子提取物、乙酸乙酯、樟脑、薄荷醇、薄荷油、迷迭香提取物、桉叶油等。合适的溶角蛋白剂和角质增生作用物质例如为水杨酸、巯基乙酸钙、巯基乙酸及其盐、硫等。合适的去头屑活性化合物例如为硫、磺基聚乙二醇脱水山梨醇单油酸酯、磺基蓖麻醇聚乙氧基化物、1-氧2-巯基吡啶锌、1-氧2-巯基吡啶铝等。抵消皮肤刺激的合适的消炎剂例如为尿囊素、红没药醇、α-红没药醇(dragosantol)、白花母菊提取物、泛醇等。
本发明还提供了本发明聚合物或通过本发明方法用活性化合物分子印迹而制备的聚合物与至少一种化妆品或药物可接受聚合物结合的用途。
合适的聚合物例如是INCI名称为聚季铵盐(Polyquaternium)的其它阳离子聚合物,例如乙烯基吡咯烷酮/N-乙烯基咪唑鎓盐的共聚物(LuviquatFC、Luviquat HM、Luviquat MS、Luviquat&commat Care),用硫酸二乙酯季铵化的N-乙烯基吡咯烷酮/甲基丙烯酸二甲氨基乙酯的共聚物(Luviquat PQ 11)、N-乙烯基己内酰胺/N-乙烯基吡咯烷酮/N-乙烯基咪唑鎓盐的共聚物(Luviquat Hold);阳离子纤维素衍生物(聚季铵盐-4和-10)、丙烯酰胺基共聚物(聚季铵盐-7),和壳聚糖。
合适的阳离子(季铵化)聚合物还有Merquat(基于二甲基二烯丙基氯化铵的聚合物)、Gafquat(由聚乙烯基吡咯烷酮与季铵化合物反应形成的季铵聚合物)、聚合物JR(具有阳离子基团的羟乙基纤维素)和基于植物的阳离子聚合物,例如瓜尔胶聚合物如得自Rhodia的Jaguar牌。
其它合适的聚合物还有中性聚合物,如聚乙烯基吡咯烷酮,N-乙烯基吡咯烷酮和乙酸乙烯酯和/或丙酸乙烯酯的共聚物,聚硅氧烷,聚乙烯基己内酰胺以及与N-乙烯基吡咯烷酮的其它共聚物,聚乙烯亚胺及其盐、聚乙烯基胺及其盐、纤维素衍生物,聚天冬氨酸盐和衍生物。这些包括例如Luviflex 0 Swing(聚乙酸乙烯酯和聚乙二醇的部分皂化共聚物,BASFAktiengesellschaft)。
合适的聚合物还有非离子的水溶性或水分散性聚合物或低聚物,如聚乙烯基己内酰胺,例如Luviskol 0 Plus(BASF)或聚乙烯基吡咯烷酮和其共聚物,尤其是与乙烯酯如乙酸乙烯酯的共聚物,例如Luviskol 0 VA64(BASF);聚酰胺,例如基于衣康酸和脂族二胺的聚酰胺,例如如DE-A-4333 238中所述。
合适的聚合物还有两性聚合物或两性离子聚合物,如辛基丙烯酰胺/甲基丙烯酸甲酯/甲基丙烯酸叔丁基氨基乙酯/甲基丙烯酸羟丙酯共聚物,其可以商品名Amphomer(National Starch)获得,以及两性离子聚合物,例如公开于德国专利申请DE 39 29 973、DE 21 50 557、DE 28 17 369和DE 3708 451中。丙烯酰胺基丙基三甲基氯化铵/丙烯酸或甲基丙烯酸共聚物及其碱金属盐和铵盐是优选的两性离子聚合物。此外,合适的两性离子聚合物是甲基丙烯酰基乙基甜菜碱/甲基丙烯酸酯共聚物,其以商品名Amersette(AMERCHOL)市售,以及甲基丙烯酸羟乙酯、甲基丙烯酸甲酯、甲基丙烯酸N,N-二甲氨基乙酯和丙烯酸的共聚物(Jordapon(D))。
合适的聚合物还有非离子的含有硅氧烷的水溶性或水分散性聚合物,例如聚醚硅氧烷,如Tegopren 0(Goldschmidt)或Belsil&commat(Wacker)。
本发明还提供了分子印迹聚合物与皮肤化妆品活性化合物(一种或多种化合物)结合的用途,该皮肤化妆品活性化合物有利地选自乙酰基水杨酸、阿托品、甘菊环、氢化可的松及其衍生物(如氢化可的松17-戊酸酯)、维生素B和D系列,尤其是维生素B1、维生素B12、维生素D、维生素A或其衍生物(如棕榈酸视黄基酯)、维生素E或其衍生物(如乙酸生育基酯)、维生素C及其衍生物,例如抗坏血酸葡糖苷,以及还有烟酰胺、泛醇、红没药醇、表面麻醉剂(polydocanol)、不饱和脂肪酸(例如基本上是脂肪酸(通常称作维生素F),尤其是γ-亚麻酸、油酸、二十碳五烯酸、二十二碳六烯酸及其衍生物)、氯霉素、咖啡因、前列腺素、百里酚、樟脑、角鲨烯、其它植物和动物来源的产品的提取物,如月见草油、琉璃苣油或黑醋栗籽油、鱼油、鳕鱼肝油,以及还有神经酰胺和神经酰胺类化合物、乳香提取物、绿茶提取物、水百合提取物、甘草提取物、金缕梅、去头皮屑活性化合物(如二硫化硒、1-氧-2-巯基吡啶锌、吡罗克酮、油胺(olamine)、同菌唑、羟甲辛吡酮、表面麻醉剂及其组合)、配合物活性化合物,例如γ-米谷酚和钙盐如泛酸钙、氯化钙和乙酸钙的那些。还有利的是活性化合物选自再加油物质,例如普赛林油(purcellin oil)、和活性化合物特别有利地还选自NO合成酶抑制剂,尤其是如果本发明组合物用于治疗和预防内因和/或外因老化的症状以及用于治疗和预防紫外辐射对毛发的有害作用。NO合成酶抑制剂优选硝基精氨酸。此外,活性化合物还有利地选自:儿茶酚和儿茶酚的胆汁酸酯以及含有儿茶酚或儿茶酚的胆汁酸酯的植物或植物部分(例如茶科植物的叶子,尤其是山茶(绿茶)叶子)的含水或有机提取物。其典型的成分(如多酚或儿茶酚、咖啡因、维生素、糖、矿物质、氨基酸、类脂)是特别有利的。儿茶酚是被认为是氢化黄酮或花色素和“儿茶酚”衍生物的一组化合物(儿茶酚、3,3′,4′,5,7-黄烷五醇、2-(3,4-二羟基苯基)苯并二氢吡喃-3,5,7-三醇)。表儿茶酚((2R,3R)-3,3′,4′,5,7-黄烷五醇)在本发明的上下文中也是有利的活性化合物。还有利的是含有一定量儿茶酚的植物提取物,尤其是绿茶提取物,例如山茶属植物的叶提取物,非常特别是如下植物的叶子提取物:茶(Camellia sinensis),苦茶(Camellia assamica)、大理茶(Camellia taliensis)或滇缅茶(Camellia inawadiensis),以及这些与例如山茶(Camellia japonica)的单树杂交的植物的叶子提取物。优选的活性化合物还有选自如下的多酚或儿茶酚:(-)-儿茶酚、(+)-儿茶酚、(-)-儿茶酚没食子酸酯、(-)-没食子酸没食子儿茶酚酯、(+)-表儿茶酚、(-)-表儿茶酚、(-)-没食子酸表儿茶酚酯和(-)-表没食子儿茶酚(epigallo catechol)、(-)-没食子酸表没食子儿茶酚酯。
黄酮和它的衍生物(经常也一起统称作“黄酮”)在本发明的上下文中也是有利的活性化合物。它们的特征在于下述基本结构(取代位置示出):
也可优选用于本发明组合物的一些更重要的黄酮在下表8中示出。
表8:黄酮
芹菜配基 | - | + | + | - | - | - | + | - |
非瑟酮 | + | - | + | - | - | + | + | - |
藤黄菌素 | - | + | + | - | - | + | + | - |
山奈酚 | + | + | + | - | - | - | + | - |
栎精 | + | + | + | - | - | + | + | - |
桑色素 | + | + | + | - | + | - | + | - |
刺槐亭 | + | - | + | - | - | + | + | + |
棉黄素 | + | + | + | + | - | + | + | - |
杨梅酮 | + | + | + | - | - | + | + | + |
本质上黄酮通常以苷化形式出现。根据本发明,类黄酮优选选自下述通式物质:
其中Z1-Z7彼此独立地选自H、OH、烷氧基和羟基烷氧基,其中该烷氧基和/或羟基烷氧基可以为支化或未支化的并可具有1-18个碳原子,并且其中Gly选自单-和低聚苷基团。
此外,活性化合物(一种或多种化合物)还可以非常有利地选自亲水性活性化合物,尤其选自:α-羟基酸,如乳酸或水杨酸及其盐,例如乳酸钠、乳酸钙、乳酸三乙醇胺、尿、尿囊素、丝氨酸、山梨糖醇、甘油、奶蛋白质、泛醇或壳聚糖。
这些活性化合物(一种或多种化合物)在本发明配制剂中的用量基于该配制剂的总重量优选为0.001-30重量%,特别优选0.05-20重量%,尤其是1-10重量%。可用于本发明配制剂中的所述和其它活性化合物描述在DE 103 18 526 A1第12-17页,该文献就此全部引入本文作为参考。
此外,本发明涉及上述配制剂在防止皮肤特性不希望的变化中的用途,所述变化例如为粉刺或油性皮肤、角质化、红斑粉刺或光敏、发炎、红斑、过敏或免疫反应性反应。
取决于应用领域,本发明组合物优选为皮肤保护组合物、护肤组合物、皮肤清洁组合物、毛发保护组合物、护发组合物、毛发清洁组合物、毛发着色组合物、漱口剂和口腔冲洗剂,或装饰化妆品用配制剂,其优选以膏、霜、乳液、悬浮液、洗剂、乳、糊、凝胶、泡沫或喷雾剂的形式使用。
除了本发明聚合物或通过本发明方法用活性化合物分子印迹而制备的聚合物外,本发明皮肤化妆品还可包含所有如上所列的聚合物、颜料、保湿剂、油、蜡、酶、矿物质、维生素、防晒剂、染料、香料、抗氧化剂、防腐剂和/或药物活性化合物。
此外,下列适用于本发明皮肤化妆品:本发明组合物的配制基质优选包含化妆品或皮肤化妆品/药物可接受的助剂。已知可用于药物、食品技术和相关领域的助剂尤其是在相关药典(如DAB Ph.Eur.BP NF)中所列的那些和其性能不排除生理学应用的其它助剂。
合适的助剂可以为:润滑剂、润湿剂、乳化剂和悬浮剂、防腐剂、抗氧化剂、抗刺激物质、螯合剂、乳液稳定剂、成膜剂、胶凝剂、臭味遮蔽剂、树脂、水胶体、溶剂、加溶剂、中和剂、渗透促进剂、颜料、季铵化合物、加油剂、富油剂、软膏基、霜基、油基、聚硅氧烷衍生物、稳定剂、杀菌剂、推进剂、干燥剂、遮光剂、增稠剂、蜡、软化剂和白油。相关配制基于本领域熟练技术人员的知识,例如描述于Fielder,H.P.Lexikon derHilfsstoffe für Pharmazie,Kosmetik und angrenzende Gebiete,[药物、化妆品和相关领域的助剂词典]第4版,Aulendorf:ECV-Editio-Kantor-Verlag,1996中。
为制备本发明皮肤化妆品组合物,可将活性化合物与合适助剂混合或用其稀释(赋形剂)。赋形剂可以为固体、半固体或液体材料,其可作为活性化合物用媒介物、载体或介质。如果需要的话,以本领域熟练技术人员已知的方式混入其它助剂。此外,聚合物和分散剂适合作为助剂用于药物,优选以涂覆组合物或者粘合剂用于固体药剂形式。它们也可以用于霜和用作片涂覆组合物以及片粘合剂。
根据另一优选实施方案,本发明组合物为皮肤和毛发护理和防护用化妆品组合物、指甲护理组合物以及装饰化妆品用配制剂。
合适的皮肤化妆品组合物例如为洗面奶、面膜、除臭剂和其它化妆水。用于装饰化妆品的组合物例如包括遮盖棒、舞台彩妆、睫毛油、眼影、唇膏、眼线水笔(kajal stick)、眼线笔、胭脂、底粉和眉笔。
此外,分子印迹聚合物可用于毛孔清洁用鼻贴(nose strips),用于防粉刺组合物、驱除剂、剃须组合物、剃须后和剃须前护理组合物、日晒后护理组合物、脱毛组合物、毛发着色组合物、个人卫生护理组合物和足护理组合物以及用于婴儿护理。
本发明护肤组合物尤其为W/O或O/W护肤霜、日霜、晚霜、眼霜、面霜、防皱霜、防晒霜、保湿霜、润肤膏霜、漂白霜、自晒黑霜、维生素霜、润肤液、护理液和润湿液。
除了本发明聚合物或通过本发明方法用活性化合物分子印迹而制备的聚合物外,本发明皮肤化妆品和皮肤病组合物还可包含破坏自由基的活性化合物,用于皮肤和/或毛发中或者对皮肤和/或毛发的损害的氧化过程和相关的老化过程的保护。这些活性化合物优选为在专利申请WO/0207698和WO/03059312中所述的物质,此处明确参考这些文献的内容,优选其中所述的含硼化合物,其可将过氧化物或氢过氧化物还原为相应的醇,而不形成自由基第二段。为此可进一步使用如下通式的空间位阻胺:
其中基团Z具有如下含义:H,C1-C22烷基,优选C1-C12烷基,如甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、戊基、异戊基、新戊基、叔戊基、己基、庚基、辛基、壬基、癸基、十一烷基或十二烷基,C1-C22烷氧基,优选C1-C12烷氧基,如烷氧基-甲基、烷氧基-乙基、烷氧基-丙基、烷氧基-异丙基、烷氧基-丁基、烷氧基-异丁基、烷氧基-仲丁基、烷氧基-叔丁基、烷氧基-戊基、烷氧基-异戊基、烷氧基-新戊基、烷氧基-叔戊基、烷氧基-己基、烷氧基-庚基、烷氧基-辛基、烷氧基-壬基、烷氧基-癸基、烷氧基-十一烷基或烷氧基-十二烷基、C6-C10芳基,如苯基和萘基,其中苯基可被C1-C4烷基取代,或C6-C10 O-芳基,其可被上述C1-C22烷基或C1-C22烷氧基,优选C1-C12烷基或C1-C12烷氧基取代,和
基团R1-R6相互独立地具有如下含义:H,OH,O,C1-C22烷基,优选C1-C12烷基,如甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、戊基、异戊基、新戊基、叔戊基、己基、庚基、辛基、壬基、癸基、十一烷基或十二烷基,C1-C22烷氧基,优选C1-C12烷氧基,如烷氧基-甲基、烷氧基-乙基、烷氧基-丙基、烷氧基-异丙基、烷氧基-丁基、烷氧基-异丁基、烷氧基-仲丁基、烷氧基-叔丁基、烷氧基-戊基、烷氧基-异戊基、烷氧基-新戊基、烷氧基-叔戊基、烷氧基-己基、烷氧基-庚基、烷氧基-辛基、烷氧基-壬基、烷氧基-癸基、烷氧基-十一烷基或烷氧基-十二烷基、C6-C10芳基,如苯基和萘基,其中苯基可被C1-C4烷基取代,或C6-C10 O-芳基,C6-C10 O-芳基可被上述C1-C22烷基或C1-C22烷氧基,优选C1-C12烷基或C1-C12烷氧基取代。
特别优选使用空间位阻胺3-十二烷基-N-(2,2,6,6-四甲基-4-哌啶基)琥珀酰亚胺、3-十二烷基-N-(1,2,2,6,6-五甲基-4-哌啶基)琥珀酰亚胺、3-辛基-N-(2,2,6,6-四甲基-4-哌啶基)琥珀酰亚胺、3-辛基-N-(1,2,2,6,6-五甲基-4-哌啶基)琥珀酰亚胺、3-辛烯基-N-(2,2,6,6-四甲基-4-哌啶基)琥珀酰亚胺、3-辛烯基-N-(1,2,2,6,6-五甲基-4-哌啶基)琥珀酰亚胺和/或5050H,其含量基于组合物总重量为0.001-1重量%,优选0.01-0.1重量%,0.1-1重量%。
除上述本发明化合物和合适的载体之外,皮肤化妆品配制剂也可包含上述常用于皮肤化妆品中的其它活性化合物和助剂。这些物质优选包括乳化剂,防腐剂,芳香油,化妆品活性化合物如植烷三醇、维生素A、维生素E、维生素C、视黄醇、红没药醇、泛醇,防晒剂,漂白剂,着色剂,调色剂,晒黑剂,胶原,蛋白质水解产物,稳定剂,pH调节剂,染料,盐,增稠剂,凝胶剂,赋予稠度的试剂,聚硅氧烷,保湿剂,再加油剂以及其它常规添加剂。
优选的皮肤化妆品和皮肤化妆品组合物的油和脂组分为上述矿物油和合成油如石蜡,硅油和具有超过8个碳原子的脂族烃,动物油和植物油如葵花油、椰子油、鳄梨油、橄榄油、羊毛脂,或者蜡,脂肪酸,脂肪酸酯如C6-C30脂肪酸的甘油三酯,蜡酯如霍霍巴油,脂肪醇,凡士林,氢化羊毛脂和乙酰化羊毛脂及其混合物。
为建立特定性能,例如改进触觉、铺展性能、耐水性能和/或活性化合物与助剂如颜料的粘结,皮肤化妆品和皮肤化妆品配制剂可另外包含基于聚硅氧烷化合物的调理物质。
合适的聚硅氧烷化合物例如为聚烷基硅氧烷、聚芳基硅氧烷、聚芳基烷基硅氧烷、聚醚硅氧烷或有机硅树脂。
化妆品或皮肤化妆品配制剂通过本领域熟练技术人员已知的常规方法制备。
化妆品和皮肤化妆品组合物优选呈乳液,尤其是油包水(W/O)或水包油(O/W)乳液形式。
然而,也可选择其它类型的配制剂,如凝胶,油,油凝胶,多相乳液,如以W/O/W或O/W/O乳液形式,无水膏基质等。不含乳化剂的配制剂,如水分散体、水凝胶或Pickering乳液也是有利的实施方案。
乳液的制备通过已知的方法进行。除了至少一种分子印迹的聚合物之外,乳液通常在水存在下含有常规成分,如脂肪醇,脂肪酸酯,尤其是脂肪酸甘油三酯,脂肪酸,羊毛脂及其衍生物,天然或合成油或蜡和乳化剂。针对乳液类型和合适乳液制备的具体添加剂的选择例如描述于Schrader,Grundlagen und Rezepturen der Kosmetika[化妆品原理和配方],HüthigBuch Verlag,Heidelberg,第2版,1989,第3部分,或Umbach,Kosmetik:Entwicklung,Herstellung und Anwendung kosmetischer Mittel[化妆品:化妆品制剂的开发、生产和用途],第2版扩展版,1995,Georg ThiemeVerlag,ISBN 3 13 712602 9,第122页及随后各页,此处明确对其参考。
适合作为W/O乳液的乳液,如用于护肤霜等的乳液通常含有水相,水相借助合适的乳化剂体系乳化在油相或脂相中。聚电解质配合物可用于提供水相。
优选可包含在乳液的脂相中的脂肪组分为烃油如石蜡油、purcellin油、全氢化角鲨烯和微晶蜡在这些油中的溶液,动物油或植物油如甜杏仁油、鳄梨油、海棠木(calophylum)油、羊毛脂及其衍生物、蓖麻油、芝麻油、橄榄油、霍霍巴油、Karite油、胸棘鲷(hoplostethus)油,在大气压力和约250℃下开始蒸馏,蒸馏终点温度为约410℃的矿物油如凡士林油,饱和脂肪酸或不饱和脂肪酸的酯,例如肉豆蔻酸烷基酯如肉豆蔻酸异丙酯、肉豆蔻酸丁酯或肉豆蔻酸鲸蜡酯,硬脂酸十六烷基酯,棕榈酸乙酯或棕榈酸异丙酯,甘油三辛酸酯,甘油三癸酸酯和蓖麻酸鲸蜡酯。
脂相也可以包含可溶于其它油的硅油,例如聚二甲基硅氧烷、聚(甲基苯基硅氧烷)和硅氧烷/乙二醇共聚物、脂肪酸和脂肪醇。
除上述本发明聚合物外,护肤组合物还可以包含蜡如巴西棕榈蜡、小烛树蜡、蜂蜡、微晶蜡、地蜡以及油酸钙、油酸镁、油酸铝、肉豆蔻酸钙、肉豆蔻酸镁、肉豆蔻酸铝、亚油酸钙、亚油酸镁、亚油酸铝、硬脂酸钙、硬脂酸镁和硬脂酸铝。
本发明乳液也可呈O/W乳液形式。这种乳液通常含有油相,乳化剂和通常呈增稠形式的水相,其中乳化剂稳定在水相中的油相。可行的乳化剂优选为O/W乳化剂,如聚甘油酯、脱水山梨醇酯或部分酯化的甘油酯。
根据另一优选实施方案,本发明组合物为防晒组合物、沐浴凝胶、吸附剂配制剂和盆浴制剂,其中特别优选防晒制剂。
这类配制剂包含至少一种本发明聚合物或通过本发明方法用活性化合物分子印迹的聚合物和作为基础表面活性剂的常规阴离子表面活性剂以及作为辅助表面活性剂的两性和/或非离子表面活性剂。其它合适的活性化合物和/或助剂通常选自类脂、芳香油、染料、有机酸、防腐剂和抗氧化剂和增稠剂/胶凝剂、皮肤调理剂和保湿剂。
这些配制剂基于配制剂总重量优选包含2-50重量%,优选5-40重量%,特别优选8-30重量%表面活性剂。
所有常用于身体清洁组合物中的阴离子的、中性的、两性的或阳离子表面活性剂均可用于洗涤、沐浴和盆浴制剂中。
合适的阴离子表面活性剂例如为烷基硫酸盐、烷基醚硫酸盐、烷基磺酸盐、烷基芳基磺酸盐、烷基琥珀酸盐、烷基磺基琥珀酸盐、N-烷酰基肌氨酸盐、酰基牛磺酸盐、酰基羟乙基磺酸盐、烷基磷酸盐、烷基醚磷酸盐、烷基醚羧酸盐、α-烯烃磺酸盐,特别是碱金属盐和碱土金属盐,例如钠、钾、镁、钙盐以及铵盐和三乙醇胺盐。烷基醚硫酸盐、烷基醚磷酸盐和烷基醚羧酸盐可以在其分子中具有1-10个氧化乙烯或氧化丙烯单元,优选1-3个氧化乙烯单元。
这些例如包括月桂基硫酸钠、月桂基硫酸铵、月桂基醚硫酸钠、月桂基醚硫酸铵、月桂基肌氨酸钠、油基琥珀酸钠、月桂基磺基琥珀酸铵、十二烷基苯磺酸钠、十二烷基苯磺酸三乙醇胺。
合适的两性表面活性剂例如为烷基甜菜碱、烷基酰氨基丙基甜菜碱、烷基磺基甜菜碱、烷基氨基乙酸盐、烷基羧基氨基乙酸盐、N-(烷基酰氨基乙基)-N-(羟乙基)氨基乙酸盐(alkyl amphoacetates)、N-(烷基酰氨基乙基)-N-(羟乙基)氨基丙酸盐、N-(烷基酰氨基乙基)-N-(羟乙基)氨基二乙酸盐和N-(烷基酰氨基乙基)-N-(羟乙基)氨基二丙酸盐。
例如,也可以使用椰油基二甲基磺基丙基甜菜碱、月桂基甜菜碱、椰油酰氨基丙基甜菜碱或N-(椰油酰氨基乙基)-N-(羟乙基)氨基丙酸钠。
合适的非离子表面活性剂例如为脂族醇或者在可为线性或支化的烷基链上具有6-20个碳原子的烷基酚与氧化乙烯和/或氧化丙烯的反应产物。氧化烯的量为每摩尔醇约6至60摩尔。此外,烷基胺氧化物、单烷基链烷醇酰胺、二烷基链烷醇酰胺、聚乙二醇的脂肪酯、乙氧基化脂肪酰胺、烷基聚糖苷或脱水山梨醇醚酯也是合适的。
此外,洗涤制剂、淋浴制剂和盆浴制剂可以包含常规的阳离子表面活性剂,例如季铵化合物如鲸蜡基三甲基氯化铵。
此外,淋浴凝胶/洗发配制剂可以包含增稠剂,例如氯化钠、PEG-55、丙二醇油酸酯、PEG-120甲基葡萄糖二油酸酯和其它,以及防腐剂,其它活性化合物和赋形剂以及水。
毛发处理组合物
根据另一优选的实施方案,本发明皮肤化妆品为毛发处理组合物。
本发明毛发处理组合物优选呈泡沫定型组合物、发用摩丝、发用凝胶、洗发剂、喷发胶、发用泡沫、喷雾液体,以及用于长效卷发剂、染发剂和漂白组合物或焗油处理的匀染组合物的形式。取决于应用领域,毛发化妆品配制剂可以以(气溶胶型)喷雾剂、(气溶胶)泡沫、凝胶、凝胶喷雾剂、霜、洗剂或蜡的形式使用。
就此而言,喷发胶同时包括气溶胶型喷雾剂和不含推进剂气体的手按泵型喷雾剂。发用泡沫同时包括气溶胶泡沫和不含推进剂气体的手按泵型泡沫。喷发胶和发用泡沫优选主要或仅包含水溶性或水分散性组分。如果用于本发明喷发胶和发用泡沫的化合物为水分散性,则它们可以以粒径通常为1-350nm,优选1-250nm的含水微分散体的形式使用。就此而言,这些制剂的固含量通常为约0.5至20重量%。通常而言,这些微分散体不需要乳化剂或表面活性剂来使它们稳定。
其它组分的含义应理解为在化妆品中的所有常规添加剂,例如推进剂、消泡剂、表面活性化合物即表面活性剂、乳化剂、起泡剂和加溶剂。使用的表面活性化合物可以为阴离子、阳离子、两性或中性。此外,常规组分例如还可以为防腐剂,芳香油,遮光剂,活性物质,UV过滤剂,护理物质如泛醇、胶原、维生素、蛋白质水解产物、α-羟基羧酸、β-羟基羧酸,稳定剂,pH调节剂,染料,粘度调节剂,胶凝剂,盐,保湿剂,再加油剂、配合剂和其它常规添加剂。
此外,这些包括已知在化妆品中的所有定型和调理聚合物,如果要建立非常特殊的性能,则可将其与分子印迹聚合物组合使用。
合适的毛发化妆品的常规聚合物例如为上述阳离子、阴离子、中性、非离子和两性聚合物,此处对其进行参考。
为建立特殊性能,配制剂可另外包含基于聚硅氧烷化合物的调理物质。合适的聚硅氧烷化合物例如为聚烷基硅氧烷、聚芳基硅氧烷、聚芳基烷基硅氧烷、聚醚硅氧烷、有机硅树脂或含聚氧乙烯或聚氧丙烯侧链的聚二甲基硅氧烷(CTFA)以及氨基官能聚硅氧烷化合物如氨基封端的聚二甲基硅氧烷(CTFA)。
推进剂为通常用于喷发胶或气溶胶泡沫的推进剂。优选丙烷/丁烷的混合物、戊烷、二甲醚、1,1-二氟乙烷(HFC-152 a)、二氧化碳、氮气或压缩空气。
可以使用的乳化剂为通常用于发用泡沫的所有乳化剂。合适的乳化剂可以是非离子、阳离子或阴离子或两性乳化剂。非离子乳化剂(INCI命名)的实例为月桂基聚氧乙烯醚类如月桂基聚氧乙烯(4)醚;十六烷基聚氧乙烯醚如十六烷基乙二醇醚、聚乙二醇鲸蜡基醚;十六/十八醇聚氧乙烯醚类如十六/十八醇聚氧乙烯(25)醚,聚乙二醇脂肪酸甘油酯,羟基化卵磷脂,脂肪酸的乳酰酯,烷基聚糖苷。
阳离子乳化剂的实例为鲸蜡基二甲基-2-羟乙基磷酸二氢铵、鲸蜡基三甲基氯化铵、鲸蜡基三甲基溴化铵、硫酸甲酯椰油三甲基铵,Quaternium-1至Quaternium-x(INCI)。
阴离子乳化剂例如可以选自烷基硫酸盐、烷基醚硫酸盐、烷基磺酸盐、烷基芳基磺酸盐、烷基琥珀酸盐、烷基磺基琥珀酸盐、N-烷酰基肌氨酸盐、酰基牛磺酸盐、酰基羟乙磺酸盐、烷基磷酸盐、烷基醚磷酸盐、烷基醚羧酸盐、α-烯烃磺酸盐,尤其是碱金属盐和碱土金属盐如钠盐、钾盐、镁盐和钙盐以及铵盐和三乙醇胺盐。烷基醚硫酸盐、烷基醚磷酸盐和烷基醚羧酸盐可以在分子中具有1-10个氧化乙烯或氧化丙烯单元,优选1-3个氧化乙烯单元。
可以使用的胶凝剂为在化妆品中的所有常规胶凝剂。这些包括微交联的聚丙烯酸如卡波姆(Carbomer)(INCI),纤维素衍生物如羟丙基纤维素、羟乙基纤维素、阳离子改性纤维素,多糖如黄原胶,甘油三辛酸/癸酸酯,丙烯酸钠共聚物,聚季铵盐-32(和)液态石蜡(Paraffinum Liquidum)(INCI),丙烯酸钠共聚物(和)液态石蜡(和)PPG-1十三烷基聚氧乙烯(6)醚,丙烯酰氨基丙基三甲基氯化铵/丙烯酰胺共聚物,硬脂基聚氧乙烯(10)醚烯丙基醚,丙烯酸酯共聚物,聚季铵盐-37(和)液态石蜡(和)PPG-1十三烷基聚氧乙烯(6)醚,聚季铵盐-37(和)丙二醇二癸酸酯二辛酸酯(和)PPG-1十三烷基聚氧乙烯(6)醚,聚季铵盐-7,聚季铵盐-44。
在洗发配制剂中,可以使用通常用于洗发剂的所有阴离子、中性、两性或阳离子表面活性剂。
合适的阴离子表面活性剂例如为烷基硫酸盐、烷基醚硫酸盐、烷基磺酸盐、烷基芳基磺酸盐、烷基琥珀酸盐、烷基磺基琥珀酸盐、N-烷酰基肌氨酸盐、酰基牛磺酸盐、酰基羟乙磺酸盐、烷基磷酸盐、烷基醚磷酸盐、烷基醚羧酸盐、α-烯烃磺酸盐,尤其是碱金属盐和碱土金属盐如钠盐、钾盐、镁盐和钙盐以及铵盐和三乙醇胺盐。烷基醚硫酸盐、烷基醚磷酸盐和烷基醚羧酸盐可以在分子中具有1-10个氧化乙烯或氧化丙烯单元,优选1-3个氧化乙烯单元。
例如,合适的是月桂基硫酸钠、月桂基硫酸铵、月桂基醚硫酸钠、月桂基醚硫酸铵、月桂酰基肌氨酸钠、油基琥珀酸钠、月桂基磺基琥珀酸铵、十二烷基苯磺酸钠、十二烷基苯磺酸三乙醇胺。
合适的两性表面活性剂例如为烷基甜菜碱、烷基酰氨基丙基甜菜碱、烷基磺基甜菜碱、烷基氨基乙酸盐、烷基羧基氨基乙酸盐、N-(烷基酰氨基乙基)-N-(羟乙基)氨基乙酸盐、N-(烷基酰氨基乙基)-N-(羟乙基)氨基丙酸盐、N-(烷基酰氨基乙基)-N-(羟乙基)二乙酸盐和N-(烷基酰氨基乙基)-N-(羟乙基)氨基二丙酸盐。
例如,可以使用椰油基二甲基磺基丙基甜菜碱、月桂基甜菜碱、椰油酰氨基丙基甜菜碱或N-(椰油酰氨基乙基)-N-(羟乙基)氨基丙酸钠。
合适的非离子表面活性剂例如为脂族醇或者在可为线性或支化的烷基链上具有6-20个碳原子的烷基酚与氧化乙烯和/或氧化丙烯的反应产物。氧化烯的量为每摩尔醇约6至60摩尔。此外合适的是,烷基胺氧化物、单烷基链烷醇酰胺、二烷基链烷醇酰胺、聚乙二醇的脂肪酯、烷基聚糖苷或脱水山梨醇醚酯。
此外,洗发配制剂可以包含常规阳离子表面活性剂,例如季铵化合物如鲸蜡基三甲基氯化铵。
可将常规调理剂与分子印迹聚合物组合用于洗发配制剂中以获得特殊效果。
这些调理剂例如包括上述根据INCI名为聚季铵盐的阳离子聚合物,尤其是乙烯基吡咯烷酮/N-乙烯基咪唑鎓盐共聚物(Luviquat FC、LuviquatHM、Luviquat MS、Luviquat&commat Care)、用硫酸二乙酯季铵化的N-乙烯基吡咯烷酮/甲基丙烯酸二甲氨基乙酯共聚物(Luviquat D PQ 11)、N-乙烯基己内酰胺/N-乙烯基吡咯烷酮/N-乙烯基咪唑鎓盐共聚物(LuviquatD Hold);阳离子纤维素衍生物(聚季铵盐-4和聚季铵盐-10)、丙烯酰氨共聚物(聚季铵盐-7)。还可以使用蛋白质水解产物以及基于聚硅氧烷化合物例如聚烷基硅氧烷、聚芳基硅氧烷、聚芳基烷基硅氧烷、聚醚硅氧烷或有机硅树脂的调理物质。其它合适的聚硅氧烷化合物为含聚氧乙烯或聚氧丙烯侧链的聚二甲基硅氧烷(CTFA)以及氨基官能聚硅氧烷化合物如氨基封端的聚二甲基硅氧烷(CTFA)。此外,可以使用阳离子瓜耳胶衍生物如瓜耳胶羟丙基三甲基氯化铵(INCI)。
根据另一实施方案,该毛发化妆品或皮肤化妆品配制剂用于护理或保护皮肤或毛发并且呈乳液、分散体、悬浮液、含水表面活性剂配制剂、乳剂、洗剂、霜、香液、膏、凝胶、颗粒、粉末、棒状制剂如唇膏、泡沫、气溶胶或喷雾剂形式。这类配制剂特别适用于局部制剂。可能的乳液为水包油乳液和油包水乳液或微乳液。
通常而言,将毛发化妆品或皮肤化妆品配制剂用于施加至皮肤(局部)或毛发。就此而言,局部配制剂应理解为指适合将活性化合物以精细分布,优选以可通过皮肤吸收的形式施加至皮肤的那些配制剂。例如,水性和水-醇溶液、喷雾剂、泡沫、泡沫气溶胶、膏、水凝胶、O/W或W/O型乳液、微乳液或化妆品棒状制剂适合于此。
根据本发明化妆品组合物的优选实施方案,组合物包含载体。优选将水、气体、水基液体、油、凝胶、乳液或微乳液、分散体或其混合物作为载体。所述载体显示良好的皮肤耐受性。水凝胶、乳液或微乳液特别有利于局部配制剂。
非离子表面活性剂、两性离子表面活性剂、两性表面活性剂或阴离子乳化剂可用作乳化剂。本发明组合物可基于组合物以0.1-10重量%,优选1-5重量%的量包含乳化剂。
至少一种下组的表面活性剂例如可用作非离子性表面活性剂:
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的加合产物,在具有12-22个碳原子的脂肪酸上的加合产物以及在烷基上具有8-15个碳原子的烷基酚上的加合产物;
1-30摩尔氧化乙烯在甘油上的加合产物的C12/18脂肪酸单酯和二酯;具有6-22个碳原子的饱和脂肪酸和不饱和脂肪酸的甘油单酯和甘油二酯以及脱水山梨醇单酯和脱水山梨醇二酯及其氧化乙烯加合产物;烷基上具有8-22个碳原子的烷基单糖苷和烷基低聚糖苷及其乙氧基化的类似物;15-60摩尔氧化乙烯在蓖麻油和/或氢化蓖麻油上的加合产物;聚醇,尤其是聚甘油酯,例如聚甘油聚蓖醇酸酯、聚甘油聚12-羟基硬脂酸酯或聚甘油二聚酯。同样适合的是来自这类物质的化合物的混合物;2-15摩尔氧化乙烯在蓖麻油和/或氢化蓖麻油上的加合产物;
基于线性、支化、不饱和或饱和C6/22脂肪酸,蓖麻醇酸和12-羟基硬脂酸与甘油、聚甘油、季戊四醇、二季戊四醇、糖醇(如山梨醇)、烷基葡糖苷(如甲基葡糖苷、丁基葡糖苷、月桂基葡糖苷)和聚葡糖苷(如纤维素)的偏酯;磷酸单烷基酯、磷酸二烷基酯和磷酸三烷基酯以及磷酸单聚乙二醇烷基酯、磷酸二聚乙二醇烷基酯和/或磷酸三聚乙二醇烷基酯及其盐;
羊毛蜡醇;
聚硅氧烷/聚烷基/聚醚共聚物和对应的衍生物;
根据DE-PS 1165574的季戊四醇、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,和聚亚烷基二醇。
此外可将两性离子表面活性剂用作乳化剂。两性离子表面活性剂是用来指那些在分子中具有至少一个季铵基团和至少一个羧酸根和/或一个磺酸根的那些表面活性化合物。特别适合的两性离子表面活性剂为所谓的内铵盐类,例如N-烷基-N,N-二甲基铵氨基乙酸盐如椰油烷基二甲基铵氨基乙酸盐,N-酰氨基丙基-N,N-二甲基铵氨基乙酸盐如椰油酰氨基丙基二甲基铵氨基乙酸盐,以及在烷基或酰基上各具有8-18个碳原子的2-烷基-3-羧甲基-3-羟乙基咪唑啉,和椰油酰氨基乙基羟乙基羧甲基氨基乙酸盐。特别优选以CTFA名椰油酰胺丙基甜菜碱已知的脂肪酰胺衍生物。
同样适合的乳化剂为两性表面活性剂。两性表面活性剂的含义理解为那些在分子中除C8,18烷基或C8,18酰基外,还含有至少一个游离氨基和至少一个-COOH和/或-SO3H基团并且可形成内盐的表面活性化合物。合适的两性表面活性剂的实例为N-烷基甘氨酸、N-烷基丙酸、N-烷基氨基丁酸、N-烷基亚胺二丙酸、N-羟乙基-N-烷基酰氨基丙基甘氨酸、N-烷基牛磺酸、N-烷基肌氨酸、在每种情况下在烷基上具有约8至18个碳原子的2-烷基氨基丙酸和烷基氨基乙酸。
特别优选的两性表面活性剂为N-椰油烷基氨基丙酸盐、椰油酰氨基乙氨基丙酸盐和C12/18酰基肌氨酸。除两性乳化剂外,季铵乳化剂也是可以的,特别优选那些酯季铵型,优选甲基季铵化的二脂肪酸三乙醇胺酯盐。此外,可将烷基醚硫酸盐、甘油单酯硫酸盐、脂肪酸硫酸盐、磺基琥珀酸盐和/或醚羧酸用作阴离子乳化剂。
可行的油物质例如为基于具有6-18个,优选8-10个碳原子的脂肪醇的格尔伯特醇,线性C6-C22脂肪酸与线性C6-C22脂肪醇的酯,支化C6-C13羧酸与线性C6-C22脂肪醇的酯,线性C6-C22脂肪酸与支化醇,尤其是2-乙基己醇的酯,线性和/或支化脂肪酸与多元醇(如丙二醇、二聚二醇或三聚三醇)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脂肪酸的液态甘油单酯/甘油二酯/甘油三酯混合物,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羧酸与具有1-22个碳原子的线性或支化醇或具有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,线性C6-C22脂肪醇碳酸酯,格尔伯特碳酸酯,苯甲酸与线性和/或支化C6-C22醇的酯(如TN),二烷基醚,环氧化脂肪酸酯与多元醇的开环产物,硅油和/或脂族烃或环烷烃。此外,聚硅氧烷化合物也适合用作油物质,例如聚二甲基硅氧烷,聚甲基苯基硅氧烷,环状聚硅氧烷和氨基-、脂肪酸-、醇-、聚醚-、环氧基-、氟-、烷基-和/或糖苷改性的聚硅氧烷化合物,其在室温下可为液体或树脂。本发明组合物可基于组合物以1-90重量%,优选5-80重量%,尤其是10-50重量%的量包含油物质。
所列出的所述组分当然不应认为是结论性的或限制。组分可单独使用或以相互间的任何所需组合使用。
实施例
实施例1合成用α-生育酚作为模板分子而分子印迹的聚合物
使2L HWS反应器配有冷凝器、搅拌器马达、锚式搅拌器、具有玻璃料的氮气入口管、具有2-PT-100热传感器的Julabo LC 3实验室调节器、具有浸没的加热器的油浴和磁力搅拌器,以及2个各自具有泵头(0-1ml/min)的HPLC泵(Bischoff)以用于计量加入引发剂和单体。在开始试验之前,用氮气吹扫装置。在整个试验过程中,使氮气流过溶液,体积流量为约10l/h。首先将800ml溶剂乙腈(AcN)引入反应容器中,并将17.25gα-生育酚(模板)溶于其中。
制备了6.12g甲基丙烯酸和73.51g三羟甲基丙烷三甲基丙烯酸酯(TRIM)在250ml乙腈中的另外溶液(溶液1)。从溶液1中取出1ml用于后面的HPLC分析。将剩余溶液1的一半加入反应器的起始混合物中并与之在搅拌(100min-1)下混合。从反应器中取出1ml样品用于HPLC分析。
将四分之一量的引发剂,即0.532g加入反应器中,在通过剧烈搅拌促进引发剂溶解之后,取出1ml样品用于随后HPLC分析。
将反应器中的起始混合物搅拌加热至75℃,并又取出1ml样品。
制备了另一溶液(溶液2),其具体通过将剩余的3/4的引发剂(对应于1.594g)溶解在250ml乙腈中而制备。
将溶液1的另一半和溶液2借助两个HPLC泵经18小时计量加入反应器中。计量加入速率对于溶液1为0.153ml/min,对于溶液2为0.232ml/min。
随后的后反应时间为6小时,总反应时间因此为24小时。在每个小时结束后,从反应混合物中取出1ml样品,并且在过滤之后进行HPLC分析。
在聚合结束之后,从反应器中取出聚合物悬浮液并使用吸滤器过滤。用每次用100ml乙腈将滤饼洗涤三次并在50℃下真空干燥。
实施例b)
使2L HWS反应器配有冷凝器、搅拌器马达、锚式搅拌器、具有玻璃料的氮气入口管、具有2-PT-100热传感器的Julabo LC 3实验室调节器、具有浸没的加热器的油浴和磁力搅拌器。在开始试验之前,用氮气吹扫装置。在整个试验过程中,使氮气流过溶液,体积流量为约10l/h。首先将1000ml溶剂乙腈(AcN)引入反应容器中,并将17.25gα-生育酚(模板)、6.12g甲基丙烯酸和76.32g三羟甲基丙烷三甲基丙烯酸酯溶于其中。将混合物在搅拌(100min-1)下加热至65℃,并取样用于HPLC分析。最后将0.564g 2,2′-偶氮二(2-甲基丁腈)(引发剂)溶于5ml乙腈中。将该溶液缓慢注射入反应器内容物中。在每个小时结束后,从反应混合物中取出10ml样品,并且在过滤之后进行HPLC分析。总反应时间为5小时。在聚合结束之后,从反应器中取出聚合物悬浮液并使用吸滤器过滤。用每次用100ml乙腈将滤饼洗涤三次并在50℃下真空干燥。
实施例2:从聚合物中萃取活性化合物
向500ml圆底烧瓶装配索氏萃取装置、冷凝器、磁力搅拌器和实验室调节器(具有2 PT 100的Julabo LC 3)并将其浸入油浴中。将8g聚合物在索氏萃取装置中用400ml甲醇/冰醋酸(7∶1,v/v)(萃取剂1)萃取6-8小时,然后用400ml甲醇(萃取剂2)萃取6小时。收集萃取液,测定其体积,在每种情况下将2ml样品储存于4℃的冰箱中,以用于借助HPLC测定α-生育酚浓度。
实施例3:用化妆品活性化合物加载聚合物
在由索氏萃取得到的聚合物干燥之后,将1g聚合物与10ml 0.14mol/l的锐劲特(Fipronil)溶液混合。(0.14mol/lα-生育酚溶液的制备:将3g α-生育酚溶于50ml乙腈中)。在3小时的作用时间之后,借助离心(在3,800rpm下15分钟)和滗析将液体与聚合物分离。将聚合物在50℃下真空干燥。
实施例4:化妆品活性化合物从分子印迹聚合物中的控制释放
将Millipore超滤池(型号8400)与作为储存容器的5L塑料罐(内容物:水)连接。用100mg聚合物在100ml水中的分散体填充该池,将分散体用结合入超滤池的磁力搅拌器搅拌15分钟,直至均化。将萃取剂(水)经由使压力不增加的进料从储存容器通入池中。将从池中排出的萃取液通入在池下面的收集容器中。最后,测定各级分的体积、重量和时间,并从各级分中取出2ml样品。在试验时间中收集了数个级分。将这些样品在0.45μl的过滤器上过滤并储存于4℃的冰箱中,以用于借助HPLC测定α-生育酚浓度。在试验结束后,从超滤容器中取出分散体并转移至容器。
实施例5:化妆品活性化合物从分子印迹聚合物中的控制释放
首先将100mg分子印迹聚合物引入250ml的锥形瓶中。然后加入100ml萃取剂(调节pH的水),将瓶密闭并将悬浮液在室温下搅拌6小时。取样:每30分钟;样品体积:在每种情况下1ml。最后,将产物吸滤,并从滤液中取出1ml样品用于HPLC。这样在试验时间中收集了13个样品(包括在时间t=0时的样品)。将这些样品在0.45μl的过滤器上过滤,转移入注射瓶中并用于借助HPLC测定生育酚。
图1:DL-α-生育酚从装载的三羟甲基丙烷三甲基丙烯酸酯MIP颗粒中的控制释放-在超滤池中用具有各种pH值的水从聚合物中连续萃取DL-α-生育酚-释放的DL-α-生育酚的绝对累积重量相对于时间的曲线。
图2:DL-α-生育酚从装载的甲基丙烯酸/三羟甲基丙烷三甲基丙烯酸酯MIP颗粒中的控制释放-在分批反应器中用具有各种pH值的水从聚合物中萃取DL-α-生育酚-在分批反应器中DL-α-生育酚的浓度相对于时间的曲线。
图3:三氯异氰脲酸从甲基丙烯酸/三羟甲基丙烷三甲基丙烯酸酯MIP颗粒中的控制释放-在超滤池中用具有各种pH值的水从聚合物中连续萃取三氯异氰脲酸-释放的三氯异氰脲酸的绝对累积重量相对于时间的曲线。
皮肤化妆品配制剂的实施例
在下文中描述包含根据实施例1制备的用α-生育酚作为模板化合物分子印迹的聚合物的本发明皮肤化妆品配制剂。所述用α-生育酚作为模板化合物分子印迹的聚合物在如下实施例中称作MIP。在如下实施例中提及的用α-生育酚作为模板化合物分子印迹的聚合物为用所述活性化合物分子印迹的所有其它聚合物的代表。对本领域熟练技术人员不言而喻的是,所有其它所述活性化合物可根据实施例1制备并用于下述配制剂中。
实施例8:MIP在面部清洁液中的用途-O/W类型
AC 1%:
% 成分(INCI)
A 10.0 乙基己酸十六/十八烷基酯
10.0 三(辛酸/癸酸)甘油酯
1.5 环五硅氧烷,环六硅氧烷
2.0 聚氧乙烯(40)氢化蓖麻油
B 3.5 三(辛酸/癸酸)甘油酯,丙烯酸钠共聚物
C 1.0 生育酚乙酸酯
0.2 红没药醇
适量 防腐剂
适量 芳香油
D 3.0 聚季铵盐-44
0.5 椰油基三甲基硫酸甲酯铵
0.5 十六/十八醇聚氧乙烯(25)醚
2.0 泛醇,丙二醇
4.0 丙二醇
0.1 EDTA二钠
1.0 具有约5%MIP的水溶液
60.7软化水
AC 5%:
% 成分(INCI)
A 10.0 基己酸十六/十八烷基酯
10.0 三(辛酸/癸酸)甘油酯
1.5 环五硅氧烷,环六硅氧烷
2.0 聚氧乙烯(40)氢化蓖麻油
B 3.5 三(辛酸/癸酸)甘油酯,丙烯酸钠共聚物
C 1.0 生育酚乙酸酯
0.2 红没药醇
适量 防腐剂
适量 芳香油
D 3.0 聚季铵盐-44
0.5 椰油基三甲基硫酸甲酯铵
0.5 十六/十八醇聚氧乙烯(25)醚
2.0 泛醇,丙二醇
4.0 丙二醇
0.1 EDTA二钠
5.0 具有约5%MIP的水溶液
56.7 软化水
制备:溶解相A。将相B搅拌入相A中,将相C引入合并的相A和B中。溶解相D,并将其搅拌入合并的相A、B和C并均化。后搅拌15分钟。
实施例9:MIP在日用护体喷雾剂中的用途
AC 1%:
% 成分(INCI)
A 3.0 甲氧基肉桂酸乙基己基酯
2.0 二乙氨基羟基苯甲酰基己基苯甲酸酯
1.0 聚季铵盐-44
3.0 丙二醇
2.0 泛醇,丙二醇
1.0 环五硅氧烷,环六硅氧烷
10.0 辛基十二烷醇
0.5 PVP
10.0 三(辛酸/癸酸)甘油酯
3.0 苯甲酸C12-15烷基酯
3.0 甘油
1.0 生育酚乙酸酯
0.3 红没药醇
1.0 具有约5%MIP的水溶液
59.2 乙醇
AC 5%:
% 成分(INCI)
A 3.0 甲氧基肉桂酸乙基己基酯
2.0 二乙氨基羟基苯甲酰基己基苯甲酸酯
1.0 聚季铵盐-44
3.0 丙二醇
2.0 泛醇,丙二醇
1.0 环五硅氧烷,环六硅氧烷
10.0 辛基十二烷醇
0.5 PVP
10.0 三(辛酸/癸酸)甘油酯
3.0 苯甲酸C12-15烷基酯
3.0 甘油
1.0 生育酚乙酸酯
0.3 红没药醇
5.0 具有约5%MIP的水溶液
55.2 乙醇
制备:称重相A的组分并将其溶解得到清澈溶液。
实施例17:MIP在具有红没药醇W/O乳液中的用途
AC 1%:
% 成分(INCI)
A 6.0 聚氧乙烯(7)氢化蓖麻油
8.0 乙基己酸十六/十八烷基酯
5.0 肉豆蔻酸异丙酯
15.0 矿物油
0.3 硬脂酸镁
0.3 硬脂酸铝
2.0 PEG-45/十二烷基乙二醇共聚物
B 5.0 甘油
0.7 硫酸镁
55.6 软化水
C 1.0 具有约5%MIP的水溶液
0.5 生育酚乙酸酯
0.6 红没药醇
AC 5%:
% 成分(INCI)
A 6.0 聚氧乙烯(7)氢化蓖麻油
8.0 乙基己酸十六/十八烷基酯
5.0 肉豆蔻酸异丙酯
15.0 矿物油
0.3 硬脂酸镁
0.3 硬脂酸铝
2.0 PEG-45/十二烷基乙二醇共聚物
B 5.0 甘油
0.7 硫酸镁
51.6 软化水
C 5.0 具有约5%MIP的水溶液
0.5 生育酚乙酸酯
制备:将相A和B相互分开地加热至约85℃。将相B搅拌入相A中并均化。在搅拌下冷却至约40℃,加入相C并又简单均化。在搅拌下冷却至室温。
实施例24:定型泡沫
AC 1%
% 成分(INCI)
A 2.00 椰油基三甲基硫酸甲酯铵
适量 芳香油
B 72.32 软化水
2.00 VP/丙烯酸酯/甲基丙烯酸月桂酯共聚物
0.53 AMP
1.00 具有约5%MIP的水溶液
0.20 十六/十八醇聚氧乙烯(25)醚
0.50 泛醇
0.05 二苯甲酮-4
0.20 氨基封端的聚二甲基硅氧烷,十六烷基三甲基氯化铵,十三烷基聚氧乙烯(12)醚
15.00 乙醇
C 0.20 羟乙基纤维素
D 6.00 丙烷/丁烷
AC 5%
% 成分(INCI)
A 2.00 椰油基三甲基硫酸甲酯铵
适量 芳香油
B 68.32 软化水
2.00 VP/丙烯酸酯/甲基丙烯酸月桂酯共聚物
0.53 AMP
5.00 具有约5%MIP的水溶液
0.20 十六/十八醇聚氧乙烯(25)醚
0.50 泛醇
0.05 二苯甲酮-4
0.20 氨基封端的聚二甲基硅氧烷,十六烷基三甲基氯化铵,十三烷基聚氧乙烯(12)醚
15.00 乙醇
C 0.20 羟乙基纤维素
D 6.00 丙烷/丁烷
制备:混合相A的组分。依次加入相B的组分并溶解。将相C溶解入A和B的混合物中,然后将pH调节至6-7。转移入具有相D的容器中。
实施例36:液体化妆品-O/W类型
AC 1%
% 成分(INCI)
A 2.0 十六/十八醇聚氧乙烯(6)醚,硬脂醇
2.0 十六/十八醇聚氧乙烯(25)醚
6.0 硬脂酸甘油酯
1.0 鲸蜡醇
8.0 矿物油
7.0 乙基己酸十六/十八烷基酯
0.2 聚二甲基硅氧烷
B 3.0 丙二醇
1.0 泛醇
适量 防腐剂
61.9 软化水
C 0.1 红没药醇
1.0 具有约5%MIP的水溶液
适量 芳香油
D 5.7 C.I.77 891.二氧化钛
1.1 氧化铁
AC 5%
% 成分(INCI)
A 2.0 十六/十八醇聚氧乙烯(6)醚,硬脂醇
2.0 十六/十八醇聚氧乙烯(25)醚
6.0 硬脂酸甘油酯
1.0 鲸蜡醇
8.0 矿物油
7.0 乙基己酸十六/十八烷基酯
0.2 聚二甲基硅氧烷
B 3.0 丙二醇
1.0 泛醇
适量 防腐剂
57.9 软化水
C 0.1 红没药醇
5.0 具有约5%MIP的水溶液
适量 芳香油
D 5.7 C.I.77 891.二氧化钛
1.1 氧化铁
制备:将相A和B分开地加热至约80℃。将相B搅拌入相A中并均化。在搅拌下冷却至约40℃,加入相C和D并又充分均化。在搅拌下冷却至室温。
实施例37:
在下文中描述包含根据实施例1制备的用α-生育酚作为模板化合物分子印迹的聚合物的本发明皮肤化妆品配制剂。所述用α-生育酚作为模板化合物分子印迹的聚合物在如下实施例中称作MIP。在如下实施例中提及的用α-生育酚作为模板化合物分子印迹的聚合物为用所述活性化合物分子印迹的所有其它聚合物的代表。对本领域熟练技术人员不言而喻的是,所有其它所述活性化合物可根据实施例1制备并用于下述配制剂中。
用所述活性化合物分子印迹的聚合物以固体使用。下列数据为重量份。
清澈洗发剂
洗发剂
成分(INCI) | 1 | 2 | 3 | 4 | 5 |
月桂基聚氧乙烯醚硫酸钠 | 35.00 | 40.00 | 30.00 | 45.00 | 27.00 |
癸基葡糖苷 | 5.00 | 5.50 | 4.90 | 3.50 | 7.00 |
椰油酰胺基丙基甜菜碱 | 10.00 | 5.00 | 12.50 | 7.50 | 15.00 |
芳香油 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 |
MIP | 1.0 | 5.0 | 0.1 | 0.5 | 10.0 |
D-泛醇USP | 0.50 | 1.00 | 0.80 | 1.50 | 0.50 |
防腐剂 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 |
柠檬酸 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 |
月桂基聚氧乙烯(3)醚 | 0.50 | 2.00 | 0.50 | 0.50 | 2.00 |
氯化钠 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 |
软化水 | 至100 | 至100 | 至100 | 至100 | 至100 |
清澈调理剂洗发剂
泡沫O/W乳液
乳液1 | 乳液2 | |||
重量% | 体积% | 重量% | 体积% | |
硬脂酸 | 5.00 | 1.00 | ||
鲸蜡醇 | 5.50 | |||
十六/十八醇 | 2.00 | |||
硬脂酸聚乙二醇(40)酯 | 8.50 | |||
硬脂酸聚乙二醇(20)酯 | 1.00 | |||
三(辛酸/癸酸)甘油酯 | 4.00 | 2.00 | ||
苯甲酸C12-15烷基酯 | 10.00 | 15.00 | ||
环状聚二甲基硅氧烷 | 4.00 | |||
聚二甲基硅氧烷 | 0.50 | |||
MIP | 5.0 | 10.0 | ||
异硬脂酸乙基己基酯 | 5.00 | |||
肉豆蔻酸肉豆蔻酯 | 2.00 | |||
纯地蜡 | 1.50 |
甘油 | 3.00 | |||
羟基丙基淀粉磷酸盐 | 1.00 | 3.50 | ||
BHT | 0.02 | |||
EDTA二钠 | 0.50 | 0.10 | ||
芳香油,防腐剂 | 适量 | 适量 | ||
着色剂 | 适量 | 适量 | ||
氢氧化钾 | 适量 | 适量 | ||
软化水 | 至100 | 至100 | ||
将pH调至6.5-7.5 | 将pH调至5.0-6.0 | |||
乳液1 | 70 | |||
乳液2 | 35 | |||
氮气 | 30 | |||
丙烷/丁烷 | 65 |
具有珠光的调理剂洗发剂
将pH调至6.0
清澈调理剂洗发剂
将pH调至6.0
具有体积效果的清澈调理剂洗发剂
将pH调至6.0
凝胶霜
O/W防晒配制剂
水分散体
W/O防晒乳液
棒
PIT乳液
凝胶霜
O/W配制剂
自晒黑剂
1 | 2 | 3 | 4 | 5 | 6 | 7 | |
甘油单硬脂酸酯SE | 0.50 | 1.00 | 3.00 | 1.50 | |||
甘油硬脂酸酯柠檬酸酯 | 2.00 | 1.00 | 2.00 | 4.00 | |||
硬脂酸 | 3.00 | 2.00 | |||||
硬脂酸聚乙二醇(40)酯 | 0.50 | 2.00 | |||||
磷酸十六烷酯 | 1.00 | ||||||
硫酸十六/十八烷酯 | 0.75 | ||||||
硬脂醇 | 3.00 | 2.00 | 0.60 | ||||
鲸蜡醇 | 2.50 | 1.10 | 1.50 | 0.60 | 2.00 | ||
MIP | 0.1 | 0.5 | 0.025 | 5.0 | 3.0 | 10.0 | 1.0 |
二羟基丙酮 | 3.00 | 5.00 | 4 | ||||
二氧化钛-超细 | 1.00 | 1.50 | 1.50 | ||||
氧化锌-超细 | 0.25 | 2.00 | |||||
苯甲酸C12-15烷基酯 | 0.25 | 4.00 | 7.00 | ||||
二辛基醚 | 3.50 | 2.00 | |||||
丁二醇二辛酸酯/二癸酸酯 | 5.00 | 6.00 | |||||
椰油单、双、三甘油酯 | 6.00 | 2.00 | |||||
聚二甲基硅氧烷 | 0.50 | 1.00 | 2.00 | ||||
环状聚二甲基硅氧烷 | 2.00 | 0.50 | 0.50 | ||||
牛油果(牛油树脂) | 2.00 | ||||||
VP/十六碳烯共聚物 | 0.20 | 0.50 | 1.00 | ||||
甘油 | 3.00 | 7.50 | 7.50 | 5.00 | 2.50 | ||
黄原胶 | 0.15 | 0.05 | 0.30 | ||||
卡波姆钠 | 0.20 | 0.15 | 0.25 |
维生素E乙酸酯 | 0.60 | 0.23 | 0.70 | 1.00 | |||
生物糖胶-1 | 3.00 | 10.00 | |||||
野生大豆(大豆)油 | 0.50 | 1.50 | 1.00 | ||||
乙基己基甘油 | 0.30 | ||||||
二甲基二羟甲基乙内酰脲 | 0.60 | 0.40 | 0.20 | ||||
丁基氨基甲酸碘丙炔基酯 | 0.18 | 0.20 | |||||
对羟基苯甲酸甲酯 | 0.15 | 0.25 | 0.50 | ||||
苯氧基乙醇 | 1.00 | 0.40 | 0.40 | 0.50 | 0.40 | ||
EDTA三钠 | 0.02 | 0.05 | |||||
亚氨基二琥珀酸四钠 | 0.25 | 1.00 | |||||
乙醇 | 2.00 | 1.50 | 3.00 | 1.20 | 5.00 | ||
芳香油 | 0.10 | 0.25 | 0.30 | 0.40 | 0.20 | ||
软化水 | 至100 | 至100 | 至100 | 至100 | 至100 | 至100 | 至100 |
O/W化妆品
1 | 2 | 3 | 4 | 5 | 6 | 7 | |
甘油单硬脂酸酯SE | 0.50 | 1.00 | 3.00 | 1.50 | |||
甘油硬脂酸酯柠檬酸酯 | 2.00 | 1.00 | 2.00 | 4.00 | |||
硬脂酸 | 3.00 | 2.00 | |||||
硬脂酸聚乙二醇(40)酯 | 0.50 | 2.00 | |||||
磷酸十六烷酯 | 1.00 | ||||||
硫酸十六/十八烷酯 | 0.75 | ||||||
硬脂醇 | 3.00 | 2.00 | 0.60 | ||||
鲸蜡醇 | 2.50 | 1.10 | 1.50 | 0.60 | 2.00 | ||
MIP | 3.0 | 5.0 | 2.0 | 0.5 | 1.0 | 5.0 | 10.0 |
二氧化钛 | 10.00 | 12.00 | 9.00 | 8.50 | 11.00 | 9.50 | 10.00 |
氧化铁 | 2.00 | 4.00 | 3.00 | 5.00 | 3.40 | 6.00 | 4.40 |
氧化锌 | 4.00 | 2.00 | 3.00 | ||||
苯甲酸C12-15烷基酯 | 0.25 | 4.00 | 7.00 | ||||
二辛基醚 | 3.50 | 2.00 | |||||
丁二醇二辛酸酯/二癸酸酯 | 5.00 | 6.00 | |||||
椰油单、双、三甘油酯 | 6.00 | 2.00 |
聚二甲基硅氧烷 | 0.50 | 1.00 | 2.00 | ||||
环状聚二甲基硅氧烷 | 2.00 | 0.50 | 0.50 | ||||
牛油果(牛油树脂) | 2.00 | ||||||
VP/十六碳烯共聚物 | 0.20 | 0.50 | 1.00 | ||||
甘油 | 3.00 | 7.50 | 7.50 | 5.00 | 2.50 | ||
黄原胶 | 0.15 | 0.05 | 0.30 | ||||
卡波姆钠 | 0.20 | 0.15 | 0.25 | ||||
维生素E乙酸酯 | 0.60 | 0.23 | 0.70 | 1.00 | |||
野生大豆(大豆)油 | 0.50 | 1.50 | 1.00 | ||||
乙基己基甘油 | 0.30 | ||||||
二甲基二羟甲基乙内酰脲 | 0.60 | 0.40 | 0.20 | ||||
丁基氨基甲酸碘丙炔基酯 | 0.18 | 0.20 | |||||
对羟基苯甲酸甲酯 | 0.15 | 0.25 | 0.50 | ||||
苯氧基乙醇 | 1.00 | 0.40 | 0.40 | 0.50 | 0.40 | ||
EDTA三钠 | 0.02 | 0.05 | |||||
亚氨基二琥珀酸四钠 | 0.25 | 1.00 | |||||
乙醇 | 2.00 | 1.50 | 3.00 | 1.20 | 5.00 | ||
芳香油 | 0.10 | 0.25 | 0.30 | 0.40 | 0.20 | ||
软化水 | 至100 | 至100 | 至100 | 至100 | 至100 | 至100 | 至100 |
水分散体自晒黑剂
晒后用水分散体
WO乳液
固体稳定的乳液
(Pickering乳液)
1 | 2 | 3 | 4 | 5 | |
矿物油 | 16.00 | 16.00 | |||
辛基十二烷醇 | 9.00 | 9.00 | 5.00 | ||
三(辛酸/癸酸)甘油酯 | 9.00 | 9.00 | 6.00 | ||
苯甲酸C12-15烷基酯 | 5.00 | 8.00 | |||
丁二醇二辛酸酯/二癸酸酯 | 8.00 | ||||
二辛基醚 | 9.00 | 4.00 | |||
碳酸二辛酯 | 9.00 | ||||
羟基二十八烷基羟基硬脂酸酯 | 2.00 | 2.00 | 2.20 | 2.50 | 1.50 |
二硬脂基二甲基胺锂皂石 | 1.00 | 0.75 | 0.50 | 0.25 | |
蜂蜡微晶+液态石蜡 | 0.35 | 5.00 | |||
羟基丙基甲基纤维素 | 0.10 | 0.05 | |||
聚二甲基硅氧烷 | 3.00 | ||||
MIP | 1.0 | 0.5 | 0.1 | 3.0 | 5.0 |
二氧化钛+矾土+二甲基硅氧烷链长200-350的聚二甲基硅氧烷和硅胶的混合物+水 | 3.00 | ||||
二氧化钛+三甲氧基辛酰基硅烷 | 2.00 | 4.00 | 2.00 | 4.00 | |
硅石二甲基水杨酸酯 | 2.50 | 6.00 | 2.50 | ||
氮化硼 | 1.00 | ||||
淀粉/偏磷酸钠聚合物 | 2.00 | ||||
木薯淀粉 | 0.50 | ||||
氯化钠 | 5.00 | 7.00 | 8.50 | 3.00 | 4.50 |
甘油 | 1.00 | ||||
EDTA三钠 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
维生素E乙酸酯 | 5.00 | 10.00 | 3.00 | 6.00 | 10.00 |
棕榈酸抗坏血酸酯 | 1.00 | 1.00 | 1.00 | ||
对羟基苯甲酸甲酯 | 0.60 | 0.20 | |||
对羟基苯甲酸丙酯 | 0.20 | ||||
苯氧基乙醇 | 0.20 | ||||
二羟乙磺酸己脒定 | 0.40 | 0.50 | 0.40 | ||
N-(羟甲基)-N-(1,3-双羟甲基-2,5-二氧-4-咪唑烷基)-N’-(羟甲基)脲 | 0.08 | ||||
乙醇 | 0.23 | 0.20 | |||
芳香油 | 5.00 | 3.00 | 4.00 | ||
软化水 | 0.20 | 0.30 | 0.10 | ||
至100 | 至100 | 至100 | 至100 | 至100 |
油凝胶
1 | 2 | 3 | 4 | |
三(辛酸/癸酸)甘油酯 | 12.00 | 10.00 | 6.00 | |
辛基十二烷醇 | 7.00 | 14.00 | 8.00 | 3.00 |
丁二醇二辛酸酯/二癸酸酯 | 12.00 | |||
季戊四醇四异硬脂酸酯 | 10.00 | 6.00 | 8.00 | 7.00 |
二异硬脂酸聚甘油(3)酯 | 2.50 | |||
双甘油多酰基己二酸酯-2 | 9.00 | 8.00 | 10.00 | 8.00 |
肉豆蔻酸肉豆蔻酯 | 3.50 | 3.00 | 4.00 | 3.00 |
二氢化牛油基二甲基氯化铵膨润土 | 5.00 | 5.00 | 6.00 | 6.00 |
4-甲基-1,3-二氧戊环-2-酮 | 15.00 | 20.00 | 18.00 | 19.50 |
MIP | 1.0 | 0.5 | 3.0 | 5.0 |
维生素E乙酸酯 | 0.50 | 1.00 | ||
棕榈酸抗坏血酸酯 | 0.05 | 0.05 | ||
Buxus Chinensis油(霍霍巴油) | 2.00 | 1.00 | 1.00 | |
芳香油,BHT | 0.10 | 0.25 | 0.35 | |
Ricinus Communis油(蓖麻油) | 至100 | 至100 | 至100 | 至100 |
实施例38:
在下列配方中描述包含如下物质的组合的化妆品防晒配制剂:至少一种无机颜料,优选氧化锌和/或二氧化钛,和有机UV-A和UV-B过滤剂和根据实施例1制备的用α-生育酚作为模板分子而分子印迹的聚合物。所述用α-生育酚作为模板化合物分子印迹的聚合物在如下实施例中称作MIP。在如下实施例中提及的用α-生育酚作为模板化合物分子印迹的聚合物为用所述活性化合物分子印迹的所有其它聚合物的代表。对本领域熟练技术人员不言而喻的是,所有其它所述活性化合物可根据实施例1制备并用于下述配制剂中。
优选在分子印迹聚合物中的模板分子为有机UV过滤剂,其经由所述释放机制释放至皮肤。
下文提及的配制剂以本领域熟练技术人员已知的常规方式制备。
用活性化合物分子印迹的聚合物的含量为100%。用活性化合物分子印迹的本发明聚合物可以纯净形式或以水溶液使用。在水溶液的情况下,水含量必须调节至适于特定配制剂。
A 7.50Uvinul MC 80 | 乙基己基肉桂酸酯 |
2.00Uvinul M 40 | 双羟基-4-甲氧基二苯甲酮 |
0.80Rylo PG 11 | 聚甘油基二聚大豆油酯 |
1.00Span 60 | 失水山梨糖醇硬脂酸酯 |
0.50维生素E乙酸酯 | 生育酚乙酸酯 |
3.00Dracorin 100SE | 硬脂酸甘油酯,硬脂酸聚乙二醇(100)酯 |
1.00Cremophor CO 410 | 聚氧乙烯(40)氢化蓖麻油 |
B 3.00T-Lite SF | 二氧化钛,水合氧化铝,聚二甲基硅氧烷/聚甲基硅氧烷共聚物 |
1.00Cetiol SB 45 | 牛油果(牛油树脂) |
6.50Finsolv TN | 苯甲酸C12-15烷基酯 |
C 5.00丁二醇 | 丁二醇 |
0.30Keltrol | 黄原胶 |
0.10Edeta BD | EDTA二钠 |
0.10尿囊素 | 尿囊素 |
66.20软化水 | 软化水 |
D 1.00Sepigel 305 | 聚丙烯酰胺,C13-14异构烷烃月桂基聚氧乙烯(7)醚 |
1%MIP | |
适量 | 防腐剂 |
A 7.50Uvinul MC 80 | 乙基己基肉桂酸酯 |
2.00Uvinul M 40 | 双羟基-4-甲氧基二苯甲酮 |
0.80Rylo PG 11 | 聚甘油基二聚大豆油酯 |
1.00Span 60 | 失水山梨糖醇硬脂酸酯 |
0.50维生素E乙酸酯 | 生育酚乙酸酯 |
3.00Dracorin 100SE | 硬脂酸甘油酯,硬脂酸聚乙二醇(100)酯 |
1.00Cremophor CO 410 | 聚氧乙烯(40)氢化蓖麻油 |
B 3.00Z-COTE MAX | 氧化锌(和)二苯基辛基聚甲基硅氧烷 |
1.00Cetiol SB 45 | 牛油果(牛油树脂) |
6.50Finsolv TN | 苯甲酸C12-15烷基酯 |
C 5.00丁二醇 | 丁二醇 |
0.30Keltrol | 黄原胶 |
0.10Edeta BD | EDTA二钠 |
0.10尿囊素 | 尿囊素 |
66.20软化水 | 软化水 |
D 2.00Simulgel NS | 丙烯酸羟乙酯/丙烯酰基二甲基牛磺酸钠共聚物,角鲨烷,失水山梨醇聚氧乙烯(20)醚硬脂酸酯 |
1%MIP | |
适量 | 防腐剂 |
A 7.50Uvinul MC 80 | 乙基己基肉桂酸酯 |
2.00Uvinul A Plus | 二乙氨基羟基苯甲酰基己基苯甲酸酯 |
0.80Rylo PG 11 | 聚甘油基二聚大豆油酯 |
1.00Span 60 | 失水山梨糖醇硬脂酸酯 |
0.50维生素E乙酸酯 | 生育酚乙酸酯 |
3.00Dracorin 100SE | 硬脂酸甘油酯,硬脂酸聚乙二醇(100)酯 |
1.00Cremophor CO 410 | 聚氧乙烯(40)氢化蓖麻油 |
B 3.00Z-COTE MAX | 氧化锌(和)二苯基辛基聚甲基硅氧烷 |
1.00Cetiol SB 45 | 牛油果(牛油树脂) |
6.50Finsolv TN | 苯甲酸C12-15烷基酯 |
C 5.00丁二醇 | 丁二醇 |
0.30Keltrol | 黄原胶 |
0.10Edeta BD | EDTA二钠 |
0.10尿囊素 | 尿囊素 |
66.20软化水 | 软化水 |
D 2.00Simulgel NS | 丙烯酸羟乙酯/丙烯酰基二甲基牛磺酸钠共聚物,角鲨烷,失水山梨醇聚氧乙烯(20)醚硬脂酸酯 |
1%MIP | |
适量 | 防腐剂 |
A 1.00Abil Care 85 | 双-聚乙二醇(16)/聚丙二醇(16)共聚物/聚乙二醇(16)/聚丙二醇(16)共聚物聚二甲基硅氧烷,三(辛酸/癸酸)甘油酯 |
3.00Cremophor CO 40 | 聚氧乙烯(40)氢化蓖麻油 |
0.30Cremophor WO 7 | 聚氧乙烯(7)氢化蓖麻油 |
2.00Parsol 1789 | 丁基甲氧基二苯甲酰基甲烷 |
2.00Mexoryl XL | 甲酚曲唑三硅氧烷 |
10.00Witconol APM | PPG-3肉豆蔻基醚 |
1.00Uvinul T 150 | 乙基己基三嗪酮 |
1.00Dow Corning 345Fluid | 环五硅氧烷,环六硅氧烷 |
5.00Uvinul N 539T | 2-氰基-3,3-二苯基丙烯酸-2-乙基己酯 |
B 3.00Z-COTE MAX | 氧化锌(和)二苯基辛基聚甲基硅氧烷 |
C 5.00 1,2-丙二醇 | 丙二醇 |
1.00Mexoryl SX | 对苯二亚甲基二樟脑磺酸 |
0.20Keltrol | 黄原胶 |
0.06Edeta BD | EDTA二钠 |
0.04TEA | 三乙醇胺 |
0.30Carbopol Ultrez 10P | 卡波姆 |
63.50软化水 | 软化水 |
1%MIP | |
D适量 芳香油 | |
0.50Glydant | 二甲基二羟甲基乙内酰脲 |
A 5.50Uvinul MC 80 | 甲氧基肉桂酸乙基己基酯 |
2.00Uvinul A Plus | 二乙氨基羟基苯甲酰基己基苯甲酸酯 |
3.00Uvinul N 539T | 2-氰基-3,3-二苯基丙烯酸-2-乙基己酯 |
3.00Emulgade PL 68/50 | 十六/十八烷基葡糖苷,十六/十八醇 |
2.00Dracorin 100SE | 硬脂酸甘油酯,硬脂酸聚乙二醇(100)酯 |
1.00Fitoderm | 角鲨烷 |
0.50Cremophor WO 7 | 聚氧乙烯(7)氢化蓖麻油 |
0.50Cremophor PS 20 | 失水山梨醇聚氧乙烯(20)月桂酸酯 |
2.00Dry Flo Pure | 辛烯基琥珀酸铝淀粉 |
B 5.00T-Lite SF-S | 二氧化钛,水合二氧化硅,水合氧化铝,聚甲基硅氧烷/聚二甲基硅氧烷共聚物 |
C 4.00 1,2-丙二醇Care | 丙二醇 |
0.20Keltrol | 黄原胶 |
2.00Simulgel NS | 丙烯酸羟乙酯/丙烯酰基二甲基牛磺酸钠共聚物,角鲨烷,失水山梨醇聚氧乙烯(20)醚硬脂酸酯 |
66.30软化水 | 软化水 |
适量 防腐剂 | |
0.50维生素E乙酸酯 | 生育酚乙酸酯 |
0.5%MIP | |
1.00RetiSTAR | 三(辛酸/癸酸)甘油酯,抗坏血酸钠,生育酚,视黄醇 |
5.00Z-COTE MAX | 氧化锌(和)二苯基辛基聚甲基硅氧烷 |
2.00Parsol 1789 | 丁基甲氧基二苯甲酰基甲烷 |
1.00Uvinul T150 | 乙基己基三嗪酮 |
5.00Uvinul MC 80 | 甲氧基肉桂酸乙基己基酯 |
2.00Uvinul T 539N | 2-氰基-3,3-二苯基丙烯酸-2-乙基己酯 |
0.50Abil 350 | 聚二甲基硅氧烷 |
2.75Carnico wax LT 20 | 巴西棕榈蜡(Copernica Cerifera,石蜡 |
3.70小烛树蜡LT 281LJ | 小烛树蜡(Euphorbia Cerifera) |
1.80蜂蜡3050PH | 蜂蜡 |
3.20TeCero wax 30445 | 微晶蜡 |
3.20TeCero wax 1030K | 微晶蜡 |
1.34Cutina CP | 棕榈酸十六烷基酯 |
6.40Vaseline | 凡士林 |
7.30Softisan 100 | 氢化椰油单、双、三甘油酯 |
10.00Luvitol EHO | 乙基己酸十六/十八烷基酯 |
0.17红没药醇 天然 | 红没药醇 |
1.84维生素E乙酸酯 | 生育酚乙酸酯 |
0.42D,L-α-生育酚 | 生育酚 |
1%MIP | |
40.38蓖麻油 | 蓖麻油(Ricinus Communis) |
5.00T-Lite SF | 二氧化钛,水合氧化铝,聚二甲基硅氧烷/聚甲基硅氧烷共聚物 |
2.00Parsol 1789 | 丁基甲氧基二苯甲酰基甲烷 |
1.00Uvinul T150 | 乙基己基三嗪酮 |
3.00Uvinul MC 80 | 甲氧基肉桂酸乙基己基酯 |
2.00Uvinul N 539T | 2-氰基-3,3-二苯基丙烯酸-2-乙基己酯 |
0.50Abil 350 | 聚二甲基硅氧烷 |
2.75Carnico wax LT 20 | 巴西棕榈蜡(Copernica Cerifera),Paraffin |
3.70小烛树蜡LT 281LJ | 小烛树蜡(Euphorbia Cerifera) |
1.80蜂蜡3050PH | 蜂蜡 |
3.20TeCero wax 30445 | 微晶蜡 |
3.20TeCero wax 1030K | 微晶蜡 |
1.34Cutina CP | 棕榈酸十六烷基酯 |
6.40Vaseline | 凡士林 |
7.30Softisan 100 | 氢化椰油单、双、三甘油酯 |
10.00Luvitol EHO | 乙基己酸十六/十八烷基酯 |
0.17红没药醇 天然 | 红没药醇 |
1.84维生素E乙酸酯 | 生育酚乙酸酯 |
0.42D,L-α-生育酚 | 生育酚 |
1%MIP | |
40.38蓖麻油 | 蓖麻油(Ricinus Communis) |
A 1.00Uvinul A Plus | 二乙氨基羟基苯甲酰基己基苯甲酸酯 |
1.00Tinosorb S | 双-乙基己氧基酚甲氧基苯基三嗪 |
3.00Uvinul MC 80 | 甲氧基肉桂酸乙基己基酯 |
8.00Miglyol 812 | 三(辛酸/癸酸)甘油酯 |
1.50Dow Corning 350Fluid | 聚二甲基硅氧烷 |
3.00Z-COTE MAX | 二氧化钛,水合氧化铝,聚二甲基硅氧烷/聚甲基硅氧烷共聚物 |
3.00Finsolv TN | 苯甲酸C12-15烷基酯 |
1.00Cremophor CO 40 | 聚氧乙烯(40)氢化蓖麻油 |
B 2.00Luvigel EM | 三(辛酸/癸酸)甘油酯,丙烯酸钠共聚物 |
C 54.80软化水 | 软化水 |
D 15.00乙醇96% | 乙醇 |
5.001,2-丙二醇Care | 丙二醇 |
0.50Cremophor A 25 | 十六/十八醇聚氧乙烯(25)醚 |
1.0%MIP | |
1.00维生素E乙酸酯 | 生育酚乙酸酯 |
0.20红没药醇 外消旋 | 红没药醇 |
A 25.00Dow Corning 345Fluid | 环五硅氧烷,环六硅氧烷 |
20.00Dow Corning 245Fluid | 环五硅氧烷 |
8.00Uvinul MC 80 | 甲氧基肉桂酸乙基己基酯 |
4.00Abil EM 90 | 十六烷基聚乙二醇(10)/聚丙二醇(1)聚二甲基硅氧烷 |
7.00T-Lite SF-S | 二氧化钛,水合二氧化硅,水合氧化铝,聚甲基硅氧烷/聚二甲基硅氧烷共聚物 |
B 17.00乙醇95% | 乙醇 |
9.99Z-COTE MAX | 氧化锌(和)二苯基辛基聚甲基硅氧烷 |
5.00软化水 | 软化水 |
3.00甘油87% | 甘油 |
0.01%MIP | |
1.00滑石 | 滑石 |
A 20.00Dow Corning 345Fluid | 环五硅氧烷,环六硅氧烷 |
10.00Dow Corning 245Fluid | 环五硅氧烷 |
7.50Uvinul MC 80 | 甲氧基肉桂酸乙基己基酯 |
2.00Uvinul T 150 | 乙基己基三嗪酮 |
12.00Cosmacol EMI | 苹果酸二C12-13烷基酯 |
4.00Abil EM 90 | 十六烷基聚乙二醇(10)/聚丙二醇(1)聚二甲基硅氧烷 |
B 7.00T-Lite SF | 二氧化钛,水合氧化铝,聚二甲基硅氧烷/聚甲基硅氧烷共聚物 |
C 15.00乙醇95% | 乙醇 |
10.00Z-COTE MAX | 氧化锌(和)二苯基辛基聚甲基硅氧烷 |
3.00甘油87% | 甘油 |
1.5%MIP | |
8.00软化水 | 软化水 |
A 10.00Uvinul A Plus B | 甲氧基肉桂酸乙基己基酯,二乙氨基羟基苯甲酰基己基苯甲酸酯 |
10.00Uvinul N 539T | 2-氰基-3,3-二苯基丙烯酸-2-乙基己酯 |
4.00Eumulgin VL 75 | 月桂基葡糖苷,聚甘油基-2二聚羟基硬脂酸酯,甘油 |
8.00Cetiol B | 己二酸二丁酯 |
8.00Finsolv TN | 苯甲酸C12-15烷基酯 |
12.00Myritol 331 | 椰油单、双、三甘油酯 |
1.00Lanette E | 十六/十八烷基硫酸钠 |
2.00Lanette O | 十六/十八醇 |
B 3.00Z-COTE MAX | 氧化锌(和)二苯基辛基聚甲基硅氧烷 |
C 35.08软化水 | 软化水 |
0.38柠檬酸 | 柠檬酸 |
2.9甘油87% | 甘油 |
0.05Edeta BD | EDTA二钠 |
0.20尿囊素 | 尿囊素 |
0.30Keltrol | 黄原胶 |
0.1%MIP | |
1.50Veegum Ultra | 硅酸铝镁 |
D 0.50Phenonip | |
1.00维生素E乙酸酯 | 生育酚乙酸酯 |
Claims (12)
1.一种化妆品配制剂或皮肤病配制剂,包含:
-至少一种活性化合物,
-至少一种在该活性化合物存在下分子印迹的聚合物,和
-至少一种脂相。
2.根据权利要求1的配制剂,其中所述活性化合物从聚合物-活性化合物复合物中的释放速率在pH 5下比pH 7下高。
3.根据权利要求1或2的配制剂,其中所述聚合物以共聚形式包含:
a)至少一种具有可借助自由基聚合而聚合的双键的化合物,和
b)至少一种具有至少两个可借助自由基聚合而聚合的非共轭双键的化合物。
4.根据权利要求1-3中任一项的配制剂,其中所述化合物a)选自:
a1)可借助自由基聚合而聚合的阴离子或潜阴离子化合物,
a2)α,β-烯属不饱和羧酸的酯,
a3)α,β-烯属不饱和羧酸的酰胺,
a4)乙烯基醇或烯丙基醇与C1-C30单羧酸的酯,乙烯基醚,乙烯基芳族化合物,乙烯基内酰胺,乙烯基咪唑,乙烯基卤化物,偏二卤乙烯,C2-C8单烯烃,具有至少2个共轭双键的非芳族烃,和
a5)它们的混合物。
5.根据权利要求1-4中任一项的配制剂,其中化合物a1)选自可借助自由基聚合而聚合的且含有任选脱质子的COOH基团的化合物。
6.根据权利要求1-5中任一项的配制剂,其中聚合物与活性化合物的重量比为1∶10-100∶1。
7.根据权利要求1-6中任一项的配制剂,其呈霜、泡沫、喷雾剂、凝胶、凝胶型喷雾剂、洗剂、油、油性凝胶或摩丝的形式。
8.分子印迹的聚合物在化妆品配制剂或皮肤病配制剂中的用途。
9.根据权利要求8的用途,其中所述配制剂为皮肤化妆品配制剂。
10.一种制备如权利要求1-7中任一项所定义的分子印迹的聚合物的方法,其包括通过在活性化合物存在下沉淀聚合而制备该聚合物。
11.根据权利要求10的方法,其中:
1)将至少一种化合物a)与至少一种活性化合物在合适溶剂中混合,加入至少一种化合物b)并启动聚合,或
2)将至少一种化合物a)与至少一种活性化合物b)在合适溶剂中混合,然后启动聚合。
12.一种处理角质表面的方法,其包括使角质表面与分子印迹的聚合物接触。
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PCT/EP2007/059683 WO2008034764A2 (de) | 2006-09-19 | 2007-09-14 | Kosmetische zubereitungen auf basis molekular geprägter polymere |
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Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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CN102648221A (zh) * | 2009-11-26 | 2012-08-22 | 弗拉梅技术公司 | 含α-生育酚接枝侧链的丙烯酸和/或甲基丙烯酸类聚合物 |
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CN114524911B (zh) * | 2022-01-20 | 2024-03-12 | 河南科技大学 | 一种葡聚糖内切印迹模拟酶、制备方法及其应用 |
CN116139833A (zh) * | 2023-02-22 | 2023-05-23 | 南通大学 | 一种含铅废水处理剂及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
KR20090073170A (ko) | 2009-07-02 |
EP2066406A2 (de) | 2009-06-10 |
WO2008034764A3 (de) | 2008-05-08 |
WO2008034764A2 (de) | 2008-03-27 |
CN101516448B (zh) | 2014-07-16 |
US20100048737A1 (en) | 2010-02-25 |
US20130085186A1 (en) | 2013-04-04 |
RU2499607C2 (ru) | 2013-11-27 |
JP2010503715A (ja) | 2010-02-04 |
CA2662911A1 (en) | 2008-03-27 |
RU2009114552A (ru) | 2010-10-27 |
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