CN1492754A - 化妆品或药物组合物 - Google Patents
化妆品或药物组合物 Download PDFInfo
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- CN1492754A CN1492754A CNA028052110A CN02805211A CN1492754A CN 1492754 A CN1492754 A CN 1492754A CN A028052110 A CNA028052110 A CN A028052110A CN 02805211 A CN02805211 A CN 02805211A CN 1492754 A CN1492754 A CN 1492754A
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- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
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Abstract
本发明涉及化妆品或药物,它具有液体或凝胶稠度,含有至少一种共聚物,后者含有至少一种N-乙烯基内酰胺和至少一种具有长链烷基原子团或链烯基基团的烯属不饱和单体,所述N-乙烯基内酰胺和单体是通过聚合作用结合在共聚物中的。本发明还涉及上述类型共聚物在化妆品或药物组合物中的用途。
Description
本发明涉及具有液体至凝胶样稠度的化妆品或药物组合物,它包含至少一种共聚物,该共聚物包含至少一种N-乙烯基内酰胺和至少一种烯属不饱和单体,该单体具有共聚方式的长链烷基或亚烷基。本发明进一步涉及这类共聚物在化妆品或药物组合物中的用途。
对于用于皮肤和头发处理的化妆品,有很多要求。非常普遍的是,它们不仅应当在制备期间和面临终端用户的操控性和应用性方面具有良好的性质,而且应当在由此所达到的效果方面也具有良好的性质。例如,皮肤和头发的化妆品与皮肤病学组合物应当存在于这样的制剂中,该制剂允许活性成分容易在作用部位发挥它们的作用。它们应当被皮肤良好地耐受,并在皮肤或头发的情况下,还应当有进一步的有益效果,例如清洁、护理、保护、保湿、调节等。所述对于用户的有益效果通常伴有肯定性的主观感觉,感觉对皮肤或头发具有全面的保健和护理效果。
为了制备化妆品和药物产品,经常使用具有非固体稠度的疏水性物质,例如油类、脂肪、蜡类等,它们仅在微小的程度上可溶于水,如果可溶的话。疏水性物质、例如油类,它们在室温下是液体,在操控和应用上经常是不切实际的和困难的。为此,对于化妆品和药物组合物的流变性质经常有特殊的要求。它们经常仅能配制成所需的应用形式,例如凝胶、霜剂或乳剂,所使用的添加剂即所谓的增稠剂。惯用的小分子增稠剂的实例例如有脂肪酸、脂肪醇或蜡的碱金属与铝盐。不过,已知增稠剂的使用经常带来一些缺点,这取决于所要增稠的制品的应用领域。例如,要么增稠剂的增稠作用可能是令人不满意的,要么它们的应用可能是所不需要的,要么向所要增稠的制品掺入它们会受到阻碍或者完全是不可能的,因为它们与所要增稠的水不溶性化合物是不相容的。为了达到所需的粘度,经常需要增稠剂的比例至少是50重量%,基于全体制剂而言。另外,很多传统的增稠剂、主要是蜡类,在皮肤上产生令人不快的粘着感。
除了疏水性组分以外或者取而代之,具有至少一种亲水性组分和/或水的化妆品和药物组合物也有特殊的要求。例如包括流变性质和配制稳定的W/O与O/W乳剂的可能性。在凝胶形式的这类产品的情况下,消费者逐渐偏爱清洁的、不透明的制剂。
目前对化妆品和药物组合物的另一个要求是保持非活性物质、例如增稠剂的比例尽可能的低。因此需要这样的添加剂或助剂,它们即使少量使用也能发挥作用,和/或尽可能对两种或多种上述产品性质具有积极影响。
使用聚合物来调整本质上水不溶性液体的流变性质是已知的。它们的优点在于,在它们可溶于疏水性物质的前提下,一般可以对作为分子量函数的粘度加以调节。
DE-A-2833711描述了防晒制剂,它们包含油溶性丙烯酸酯聚合物,以增加耐水性。
US 5,318,995描述了化妆品组合物,它包含W/O乳剂,该乳剂包含增稠剂,该增稠剂是一种共聚物,具有从(甲基)丙烯酸酯或(甲基)丙烯酰胺衍生的单元和具有末端羧酸或磺酸基团的单元。
WO-A-93/01797描述了包含油相的化妆品组合物,该油相包含两种共聚物的组合作为增稠剂。这里,第一种共聚物具有从亲油性单体和亲水性单体衍生的单元,后者包含至少一个羧酸和/或磺酸基团。第二种共聚物具有从至少一种亲油性单体和至少一种亲水性单体衍生的单元,后者具有至少一个胺、酰胺、醇或醚基团。
WO-A-98/30194描述了包含油相和聚合物增稠剂的组合物,该增稠剂具有适合于赋予至少部分油溶解性的疏水性官能度,还具有引起增稠的亲水性官能度,引入这些亲水性官能度的单体选自C3-C6-α,β-烯属不饱和一元羧酸、C4-C6-α,β-烯属不饱和二元羧酸及其单酯和单酰胺。
DE-A-19627204描述了具有高耐水性的化妆品或药物组合物,它们包含至少一种来自至少20重量%(甲基)丙烯酸酯的聚合物。这些聚合物包含至多30重量%水溶性单体。
DE-A-19815127描述了包含至少一种水不溶性成分和至少一种共聚物的组合物,该共聚物是
A)5-99重量%至少一种N-乙烯基酰胺,它不是内酰胺,
B)1-95重量%至少一种疏水性单体,和可选的
C)0-94重量%另一种单体,它尤其可以是α,β-烯属不饱和羧酸或N-乙烯基内酰胺。
DE-A-19753298描述了固体剂型的制备方法,该方法将至少一种聚合粘合剂与至少一种活性成分混合,形成可塑性混合物,然后成型,所用聚合粘合剂是N-乙烯基内酰胺与含有可与N-乙烯基内酰胺共聚的疏水性基团的单体的共聚物,还描述了通过这种方法得到的剂型。
EP-A-0953358描述了共聚物的用途,该共聚物包含50-99重量%至少一种N-乙烯基内酰胺或N-乙烯基胺和1-50重量%至少一种含有疏水性基团的单体,该共聚物作为基质用于制备固体药物和化妆品给药剂型。
未公布的德国专利申请P 100 22 247.1和P 199 41 365.7描述了聚氨酯的用途,用于调整疏水性液体的流变性质。
本发明的目的是提供具有液体至凝胶样稠度的化妆品或药物组合物,它们具有良好的施用性质。它们应当优选地适合于皮肤和/或头发的化妆品与皮肤病学处理。确切而言,应当有可能在尽可能宽的范围内调节它们的流变性质和稠度。
我们已经发现,一种化妆品组合物达到了该目的,该组合物包含至少一种共聚物,该共聚物包含共聚形式的60-99重量%至少一种亲水性单体和1-40重量%至少一种疏水性单体,该亲水性单体至少有65重量%包含至少一种N-乙烯基内酰胺。
本发明因此提供具有液体至凝胶样稠度的化妆品或药物组合物,该组合物包含:
A)至少一种共聚物,基于单体的总量而言,该共聚物包含共聚形式的:
a)60-99重量%至少一种亲水性单体,其中至少有65重量%包含至少
一种N-乙烯基内酰胺,和
b)1-40重量%至少一种疏水性单体,选自
b1)式I化合物
其中
R1是H、甲基或乙基,
X是O、NH或NR3,
R2是C8-C30-烷基、C8-C30-链烯基、环烷基-C2-C22-烷基、环烷基
-C2-C22-链烯基、芳基-C2-C22-烷基或芳基-C2-C22-链烯基,和
R3是C1-C7-烷基、环烷基、芳基或R2的含义之一,
b2)脂族C8-C30-羧酸的乙烯基酯,
b3)C8-C30-烷基乙烯基醚,
及其混合物,和
B)至少一种化妆品学上可接受的添加剂。
出于本发明的目的,表达方式C8-C30-烷基、C2-C22-烷基和C1-C7-烷基包括直链和支链烷基。适合的短链烷基例如是直链或支链C1-C7-烷基,优选C1-C6-烷基,特别优选C1-C4-烷基。它们具体地包括甲基、乙基、丙基、异丙基、正丁基、2-丁基、仲丁基、叔丁基、正戊基、2-戊基、2-甲基丁基、3-甲基丁基、1,2-二甲基丙基、1,1-二甲基丙基、2,2-二甲基丙基、1-乙基丙基、正己基、2-己基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,2-二甲基丁基、1,3-二甲基丁基、2,3-二甲基丁基、1,1-二甲基丁基、2,2-二甲基丁基、3,3-二甲基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基丁基、2-乙基丁基、1-乙基-2-甲基丙基、正庚基、2-庚基、3-庚基、2-乙基戊基、1-丙基丁基、辛基等。
适合的长链C8-C30-烷基和C8-C30-链烯基是直链和支链的烷基和链烯基。它们主要优选为直链烷基,也存在天然或合成的脂肪酸和脂肪醇,和羰基合成醇,它们可以另外是单-、二-或多不饱和的。它们例如包括正己(烯)基、正庚(烯)基、正辛(烯)基、正壬(烯)基、正癸(烯)基、正十一(烯)基、正十二(烯)基、正十三(烯)基、正十四(烯)基、正十五(烯)基、正十六(烯)基、正十七(烯)基、正十八(烯)基、正十九(烯)基等。
环烷基优选为C5-C8-环烷基,例如环戊基、环己基、环庚基或环辛基。
芳基优选为苯基、甲苯基、二甲苯基或萘基。
可以从丙烯酸和甲基丙烯酸衍生的化合物有时以缩写形式表示为向从丙烯酸衍生的化合物加入字节“(甲基)”。
根据本发明的组合物在标准条件(20℃)下具有液体至凝胶样稠度。这一般被理解为表示从稀液体经由糊/软膏样至凝胶样的流变性质。液体组合物的粘度优选在约1-6000mPas范围内。“凝胶样稠度”是由这样的组合物所显示的,它们具有比液体更高的粘度,并且是自我支撑的,也就是说,它们保留赋予它们的形状,无需形状稳定性包衣。不过与固体制剂相反,凝胶样制剂容易在重力作用下变形。凝胶样组合物的粘度优选在大于600至约60000mPas范围内。
共聚物A)包含共聚形式的60-99重量%、优选65-95重量%至少一种亲水性单体。出于本发明的目的,术语“亲水性单体”表示20℃下的水溶解度为至少10g/l、优选为至少50g/l的单体。组分a)化合物的至少65重量%选自N-乙烯基内酰胺,优选N-乙烯基吡咯烷酮、N-乙烯基哌啶酮、N-乙烯基己内酰胺及其混合物。
除了N-乙烯基内酰胺以外,组分a)还可以具有至少一种其他亲水性单体。组分a)的额外亲水性单体优选地包含至少一种α,β-烯属不饱和一元和/或二元羧酸。特别优选具有3-8个碳原子的一元烯属不饱和羧酸,例如丙烯酸、甲基丙烯酸、二甲基丙烯酸、乙基丙烯酸、马来酸、柠康酸、亚甲基丙二酸、烯丙基乙酸、乙烯基乙酸、巴豆酸、富马酸、中康酸、衣康酸及其混合物。确切而言,使用丙烯酸、甲基丙烯酸、马来酸及其混合物、更确切为丙烯酸作为组分a)。上述羧酸可以使用游离酸的形式,如果有的话,还有酸酐或者部分或完全中和的形式。可以用于中和羧酸的碱是碱金属碱,例如氢氧化钠溶液、氢氧化钾溶液、碳酸钠、碳酸氢钠、碳酸钾或碳酸氢钾;碱土金属碱,例如氢氧化钙、氧化钙、氢氧化镁或碳酸镁,氨和胺类。适合的胺例如有C1-C6-烷基胺,优选正丙胺和正丁胺;二烷基胺;三烷基胺,优选二乙基丙胺、二丙基甲胺、三乙胺和三异丙胺;氨基醇,优选乙醇胺、甲基乙醇胺、乙基乙醇胺、二乙醇胺、三乙醇胺、2-氨基-2-甲基-1-丙醇、三异丙醇胺和吗啉、二乙氨基丙胺、二亚乙基三胺、四亚乙基五胺、葡糖胺、甲基葡糖胺及其混合物。
进一步适合的亲水性组分a)例如有上述α,β-烯属不饱和一元和/或二元羧酸与C1-C4-醇的酯,例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、马来酸一甲酯、马来酸二甲酯、马来酸一乙酯、马来酸二乙酯等。
进一步适合的组分a)例如有上述α,β-烯属不饱和一元和/或二元羧酸与至少二元醇——优选C2-C30-链烷二醇——及其烷氧基化物的酯。它们例如包括(甲基)丙烯酸2-羟基乙基酯、(甲基)丙烯酸3-羟基正丙基酯、(甲基)丙烯酸羟基异丁基酯、(甲基)丙烯酸4-羟基正丁基酯、(甲基)丙烯酸羟基叔丁基酯、(甲基)丙烯酸3-羟基-2-乙基己基酯等。
进一步适合的组分a)是上述α,β-烯属不饱和一元和/或二元羧酸的酰胺和腈,例如(甲基)丙烯酰胺、N,N-二甲基(甲基)丙烯酰胺、N-叔丁基(甲基)丙烯酰胺、(甲基)丙烯腈等。
进一步适合的组分a)是乙烯基和烯丙基取代的杂芳族化合物,例如N-乙烯基咪唑、N-乙烯基-2-甲基咪唑、2-和4-乙烯基吡啶、-烯丙基吡啶等。
进一步适合的组分a)是无环的N-乙烯基酰胺,例如N-乙烯基甲酰胺、N-乙烯基乙酰胺、N-乙烯基丙酰胺、N-乙烯基丁酰胺等。
进一步适合的组分a)是(甲基)丙烯酰氨基乙醇酸、乙烯基磺酸、(甲基)烯丙基磺酸、苯乙烯磺酸、(甲基)丙烯酸3-磺基丙基酯、(甲基)丙烯酰氨基甲基丙磺酸、含有膦酸基团的单体,例如乙烯基膦酸、烯丙基膦酸和丙烯酰氨基甲基丙烷膦酸等。
上述组分a)化合物可以单独使用,也可以混合使用。
共聚物A)的疏水性单体组分b)优选地包含至少一种如上所定义的式I化合物b1)。它们优选地包括丙烯酸、甲基丙烯酸或乙基丙烯酸与饱和的或者单或多不饱和C8-C18-醇的酯,例如(甲基)丙烯酸辛基酯、(甲基)丙烯酸2-乙基己基酯、(甲基)丙烯酸壬基酯、(甲基)丙烯酸癸基酯、(甲基)丙烯酸月桂基酯、(甲基)丙烯酸十五基酯、(甲基)丙烯酸棕榈基酯、(甲基)丙烯酸花生碱基酯、(甲基)丙烯酸肉豆蔻基酯、(甲基)丙烯酸鲸蜡基酯、(甲基)丙烯酸硬脂基酯、(甲基)丙烯酸木蜡基酯、(甲基)丙烯酸蜡基酯、(甲基)丙烯酸蜂花基酯、(甲基)丙烯酸棕榈烯基酯、(甲基)丙烯酸油基酯、(甲基)丙烯酸山萮基酯、(甲基)丙烯酸环己基乙基酯、(甲基)丙烯酸环己基叔丁基酯等。
适合的单体b1)还有丙烯酸、甲基丙烯酸或乙基丙烯酸的酰胺,在酰胺氮原子上具有至少一个如上所定义的基团R3。它们例如包括正辛基(甲基)丙烯酰胺、1,1,3,3-四甲基丁基(甲基)丙烯酰胺、乙基己基(甲基)丙烯酰胺、正壬基(甲基)丙烯酰胺、正癸基(甲基)丙烯酰胺、正十一基(甲基)丙烯酰胺、十三基(甲基)丙烯酰胺、肉豆蔻基(甲基)丙烯酰胺、十五基(甲基)丙烯酰胺、棕榈基(甲基)丙烯酰胺、十七基(甲基)丙烯酰胺、十九基(甲基)丙烯酰胺、花生碱基(甲基)丙烯酰胺、山萮基(甲基)丙烯酰胺、木蜡基(甲基)丙烯酰胺、蜡基(甲基)丙烯酰胺、蜂花基(甲基)丙烯酰胺、棕榈烯基(甲基)丙烯酰胺、油基(甲基)丙烯酰胺、亚油基(甲基)丙烯酰胺、亚麻基(甲基)丙烯酰胺、硬脂基(甲基)丙烯酰胺、月桂基(甲基)丙烯酰胺及其混合物。适合的单体b1)还有马来酸的N-烷基酰胺、N,N’-二烷基酰胺、N-烷基二酰胺和N,N’-二烷基二酰胺。
特别优选的单体b1)是(甲基)丙烯酸2-乙基己基酯、(甲基)丙烯酸月桂基酯、(甲基)丙烯酸肉豆蔻基酯、(甲基)丙烯酸鲸蜡基酯、(甲基)丙烯酸硬脂基酯、(甲基)丙烯酸油基酯、(甲基)丙烯酸山萮基酯及其混合物。
优选的单体b2)是脂族C8-C18-羧酸的乙烯基酯。它们包括癸酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、油酸和山萮酸的乙烯基酯。
优选的单体b3)是C8-C18-烷基乙烯基醚。它们例如包括正辛基、2-乙基己基、正壬基、正癸基、正十一基、正十二基、正十三基、正十四基、正十五基、正十六基、正十七基、正十八基乙烯基醚及其混合物。
根据本发明的化妆品或药物组合物优选地包含至少一种共聚物A),它由下列共聚的单体单元组成:
-60-99重量%至少一种N-乙烯基内酰胺,和
-1-40重量%至少一种如上所定义的单体b)。
共聚物A)的制备是按照本领域技术人员已知的惯用方法进行的,例如溶液聚合、沉淀聚合、乳液聚合或反相悬液聚合。
聚合温度优选地在约30-200℃范围内,特别优选40-110℃。适合的引发剂例如有偶氮和过氧化合物,和惯用的氧化还原引发剂系统,例如过氧化氢与还原性化合物的组合,后者例如亚硫酸钠、亚硫酸氢钠、甲醛钠、亚砜化物和肼。
共聚物A)的K值优选为至少20。特别优选地在20-100范围内,特别是20-80。K值是这样测定的,按照H.Fikentscher,Cellulosechemie(纤维素化学),13卷,pp.58-64,71-74(1932),在25℃水溶液或醇溶液中,浓度在0.1%与5%之间,这取决于K值的范围。
根据本发明的化妆品或药物组合物包含至少一种化妆品或药学上可接受的添加剂作为组分B)。优选这样的组合物,其中组分B)包含至少一种本质上水不溶性(疏水性)化合物,它在20℃下是液体(油或脂肪组分)。这里,根据本发明的组合物可以包含油或脂肪组分作为化妆品或药物活性成分、作为载体、作为助剂或其组合。根据本发明的含油或脂肪的组合物的流变性质和稠度一般可以设置在宽泛的范围内。“流变性质的调整”在这里出于本发明的目的被广义地理解。用在根据本发明的组合物中的聚合物A)一般适合于增稠广泛的疏水性化合物的稠度。根据疏水性液体化合物的基本稠度,一般有可能实现从稀液体到固体(在“不再可流动”的意义上)的流动性质,这取决于所用聚合物的量。“流变性质的调整”因而被理解为尤其表示液体粘度的增加、凝胶触变性质的提高、凝胶和蜡的固化等。根据本发明的组合物因而优选地适合于配制含有油和脂肪的化妆品和药物产品。根据组分B)化合物的基本稠度,性质一般可以从稀液体稠度变为凝胶样稠度,这取决于所用聚合物A)的量。优选地,聚合物A)在油或脂肪组分B)中的溶液一般是澄清的。因而有利的是,有可能将制剂、特别是化妆品制剂染色,而不会削弱根据本发明的组合物的固有颜色。此外,根据本发明的组合物可以配制成不透明至澄清的凝胶。
包含至少一种油或脂肪组分B)的根据本发明的组合物可以是均相或非均相制剂的形式。“均相制剂”仅具有单一的相,与其构成物的数量无关。“非均相组合物”是两种或多种不可混溶的组分的分散体系。它们优选地包括乳剂,例如O/W和W/O制剂,它们具有至少一种油或脂肪组分和水作为不可混溶的相,前者在下面有详细描述。在这一点上,根据本发明使用的聚合物A)一般用在水相或者油相中。有利的是,根据本发明使用的共聚物A)通常能够在油和/或脂肪组分的基础上容易搅拌形成制剂,无需加入溶剂。在这一点上,可能有利的是加热各组分至温度>40℃进行配制。
根据本发明的组合物优选包含约0.001-50重量%的聚合物组分A),特别优选0.01-30重量%、特别是0.1-20重量%,基于组合物的总重量计。
如果根据本发明的组合物包含至少一种疏水性组分B),那么它优选地选自
i)油,
ii)脂肪,
iii)蜡,
iv)C6-C30-一元羧酸与一元、二元或三元醇的酯,它们不同于i)至iii),
v)饱和的无环和环状烃,
vi)脂肪酸,
vii)脂肪醇,
及其混合物。
根据本发明的组合物例如具有油或脂肪组分B),选自:低极性烃,例如矿物油;直链饱和烃,优选地具有8个以上碳原子,例如十四烷、十六烷、十八烷等;环状烃,例如十氢萘;支链烃、动物和植物油;蜡;蜡酯;凡士林;酯,优选脂肪酸的酯,例如C1-C24-一元醇与C1-C22-一元羧酸的酯,例如异硬脂酸异丙酯、肉豆蔻酸正丙酯、肉豆蔻酸异丙酯、棕榈酸正丙酯、棕榈酸异丙酯、棕榈酸二十六烷基酯、棕榈酸二十八烷基酯、棕榈酸三十烷基酯、棕榈酸三十二烷基酯、棕榈酸三十四烷基酯、硬脂酸二十六烷基酯、硬脂酸二十八烷基酯、硬脂酸三十烷基酯、硬脂酸三十二烷基酯、硬脂酸三十四烷基酯;水杨酸酯,例如C1-C10-水杨酸酯,例如水杨酸辛基酯;苯甲酸酯,例如C10-C15-烷基苯甲酸酯、苯甲酸苄基酯;其他化妆品酯,例如脂肪酸甘油三酯、丙二醇单月桂酸酯、聚乙二醇单月桂酸酯、C10-C15-烷基乳酸酯等及其混合物。
适合的硅油B)例如有线性聚二甲基硅氧烷、聚(甲基苯基硅氧烷)、环状硅氧烷及其混合物。聚二甲基硅氧烷和聚(甲基苯基硅氧烷)的数均分子量优选地在约1000-150000g/mol范围内。优选的环状硅氧烷具有4-8元环。适合的环状硅氧烷例如有商业上可得到的环甲基硅酮。
优选的油和脂肪组分B)选自石蜡和石蜡油;凡士林;天然脂肪和油,例如蓖麻油、大豆油、花生油、橄榄油、向日葵油、芝麻油、鳄梨油、可可脂、杏仁油、桃仁油、蓖麻油、鱼肝油、猪油、鲸蜡、鲸蜡油、鲸油、麦胚油、澳洲坚果油、月见草油、霍霍巴油;脂肪醇,例如月桂醇、肉豆蔻醇、鲸蜡醇、硬脂醇、油醇、鲸蜡醇;脂肪酸,例如肉豆蔻酸、硬脂酸、棕榈酸、油酸、亚油酸、亚麻酸和与之不同的饱和、不饱和与取代的脂肪酸;蜡,例如蜂蜡、巴西棕榈蜡、小烛树蜡、鲸蜡、和上述油和脂肪组分的混合物。
适合的化妆品学上和药学上可相容的油和脂肪组分B)参见Karl-HeinzSchrader,Grundlagen und Rezepturen der Kosmetika(化妆品基质和制剂),第2版,Verlag Hüthig,Heidelberg,pp.319-355,这里参照其内容。
适合的化妆品学和/或皮肤病学活性成分B1)例如有鞣酸活性成分、皮肤和头发染色剂、调色剂、着色剂、漂白剂、角蛋白硬化物、抗微生物活性成分、滤光活性成分、驱避活性成分、具有充血活性的物质、具有角质层溶解与角质层成形活性的物质、抗头皮屑活性物质、消炎剂、具有角化作用的物质、充当抗氧化剂或自由基清除剂的物质、皮肤保湿剂或湿润剂、再加脂性活性成分、抗红斑或抗变态反应活性成分及其混合物。
人工晒黑皮肤并且适合于无需天然或人工UV光线照射即可晒黑皮肤的鞣酸活性成分例如有二羟丙酮、四氧嘧啶和胡桃壳提取物。适合的角蛋白硬化物通常是也用在止汗剂中的活性成分,例如硫酸铝钾、碱式氯化铝、乳酸铝等。使用抗微生物活性成分B1)的目的是破坏微生物或者抑制它们的生长,因而既充当防腐剂,也充当除臭物,后者防止体臭的形成或强化。它们例如包括本领域技术人员已知的惯用防腐剂,例如对-羟基苯甲酸酯、咪唑烷基脲、甲醛、山梨酸、苯甲酸、水杨酸等。这类除臭物例如有蓖麻油酸锌、三氯生、十一碳烯酸烷醇胺、柠檬酸三乙酯、氯己定等。适合的滤光活性物质B1)是吸收UV-B和/或UV-A区域中的UV光线的物质。适合的UV过滤剂例如有2,4,6-三芳基-1,3,5-三嗪,其中芳基可以各自携带至少一个取代基,取代基优选地选自羟基;烷氧基,具体为甲氧基;烷氧基羰基,具体为甲氧羰基和乙氧羰基;及其混合物。适合的还有对-氨基苯甲酸酯、肉桂酸酯、二苯酮、樟脑衍生物、和隔绝UV光线的色素,例如二氧化钛、滑石和氧化锌。适合的驱避活性成分B1)是能够从人驱赶或驱除开某些动物、确切为昆虫的化合物。它们例如包括2-乙基-1,3-己二醇、N,N-二乙基间甲苯甲酰胺等。适合的具有充血活性的物质B1)刺激血液流经皮肤,例如有精油,例如矮松、熏衣草、迷迭香、杜松子、马栗提取物、桦叶提取物、干草籽提取物、乙酸乙酯、樟脑、薄荷醇、薄荷油、迷迭香提取物、桉油等。适合的角质层溶解与角质层形成物B1)例如有水杨酸、巯基乙酸钾、巯基乙酸及其盐、硫磺等。适合的抗头皮屑活性物质B1)例如有硫磺、聚乙二醇脱水山梨醇单油酸硫、硫磺、蓖麻醇聚乙氧基化物、吡硫鎓锌、吡硫鎓铝等。适合的消炎剂B1)对抗皮肤刺激,例如有尿囊素、红没药醇、Dragosantol、春黄菊提取物、泛醇等。
根据本发明的化妆品组合物可以包含至少一种化妆品学上或药学上可接受的不同于组分A)化合物的聚合物,作为化妆品和/或药物活性成分B1)(以及可选地作为助剂B3))。非常普遍地,它们包括阴离子、阳离子、两性和中性的聚合物。
阴离子聚合物的实例是丙烯酸与甲基丙烯酸或其盐的均聚物与共聚物、丙烯酸与丙烯酰胺及其盐的共聚物;多羟基羧酸的钠盐、水溶性或水可分散性聚酯、聚氨酯和聚脲。特别适合的聚合物是丙烯酸叔丁酯、丙烯酸乙酯与甲基丙烯酸的共聚物(例如Luvimer100P)、丙烯酸乙酯与甲基丙烯酸的共聚物(例如LuvimerMAE),N-叔丁基丙烯酰胺、丙烯酸乙酯与丙烯酸的共聚物(Ultrahold8,强),乙酸乙烯酯、巴豆酸与可选的其他乙烯基酯的共聚物(例如Luviset级),马来酸酐共聚物(可选地与醇、阴离子聚硅氧烷(例如羧基官能的)、丙烯酸叔丁酯、甲基丙烯酸反应)(例如LuviskolVBM),具有疏水性单体的丙烯酸与甲基丙烯酸的共聚物,例如甲基(丙烯酸)的C4-C30-烷基酯、C4-C30-烷基乙烯基酯、C4-C30-烷基乙烯基醚和透明质酸。阴离子聚合物的实例还有乙酸乙烯酯/巴豆酸共聚物,它们是商业上可得到的,例如Resyn(National Starch)和Gafset(GAF),和乙烯吡咯烷酮/丙烯酸乙烯酯共聚物,例如Luviflex(BASF)。其他适合的聚合物有乙烯基吡咯烷酮/丙烯酸酯三元共聚物,例如LuviflexVBM-35(BASF),和含有磺酸钠的聚酰胺或含有磺酸钠的聚酯。
进一步适合的聚合物是阳离子聚合物,INCI名称为Polyquaternium,例如乙烯基吡咯烷酮/N-乙烯基咪唑鎓盐的共聚物(LuviquatFC,LuviquatHM,LuviquatMS,LuviquatCare)、N-乙烯基吡咯烷酮/甲基丙烯酸二甲氨基乙基酯的共聚物(用硫酸二乙酯季铵化)(LuviquatPQ11)、N-乙烯己内酰胺/N-乙烯基吡咯烷酮/N-乙烯咪唑鎓盐的共聚物(LuviquatHold);阳离子纤维素衍生物(Polyquaternium-4和-10)、丙烯酰氨基共聚物(Polyquaternium-7)和壳聚糖。适合的阳离子(季铵化)聚合物还有Merquat(基于氯化二甲基二烯丙基铵的聚合物)、Gafquat(通过聚乙烯基吡咯烷酮与季铵化合物的反应所生成的季铵聚合物)、JR聚合物(具有阳离子基团的羟乙基纤维素)和植物类阳离子聚合物,例如瓜尔豆聚合物,例如来自Rhodia的Jaguar级。
进一步适合的聚合物还有中性聚合物,例如聚乙烯基吡咯烷酮,N-乙烯基吡咯烷酮与乙酸乙烯酯和/或丙酸乙烯酯的共聚物,聚硅氧烷,聚乙烯基己内酰胺和其他与N-乙烯基吡咯烷酮的共聚物,聚乙烯亚胺及其盐,聚乙烯胺及其盐,纤维素衍生物,聚天冬氨酸盐与衍生物。
适合的聚合物还有非离子的、水溶性或水可分散性聚合物或低聚物,例如聚乙烯基己内酰胺,例如LuviskolPlus(BASF),或聚乙烯基吡咯烷酮及其共聚物,特别是乙烯基酯、例如乙酸乙烯酯的共聚物,例如LuviskolVA37(BASF);聚酰胺,例如基于衣康酸和脂族二胺的那些,例如DE-A-4333 238所述。
适合的聚合物还有两性或两性离子聚合物,例如辛基丙烯酰胺/甲基丙烯酸甲酯/甲基丙烯酸叔丁氨基乙酯/甲基丙烯酸2-羟基丙基酯共聚物,例如Amphomer(National Starch),和两性离子聚合物,例如公开在德国专利申请DE 39 29 973、DE 21 50 557、DE 28 17 369和DE 37 08 451中。氯化芳酰氨基丙基三甲铵/丙烯酸或甲基丙烯酸共聚物及其碱金属与铵盐是优选的两性离子聚合物。其他适合的两性离子聚合物有甲基丙烯酰乙基内铵盐/甲基丙烯酸酯共聚物,它们是商业上可得到的Amersette(AMERCHOL),和甲基丙烯酸羟乙酯、甲基丙烯酸甲酯、甲基丙烯酸N,N-二甲氨基乙基酯与丙烯酸的共聚物(Jordapon)。
适合的聚合物还有非离子的、含有硅氧烷的、水溶性或水可分散性聚合物,例如聚醚硅氧烷,例如Tegopren(Goldschmidt)或Belsil(Wacker)。
载体组分B2)优选地选自水、亲水性组分、疏水性组分及其混合物。
适合的亲水性载体B2)例如有一元、二元或多元醇,优选地具有1-8个碳原子,例如乙醇、正丙醇、异丙醇、丙二醇、甘油、山梨醇等。
适合的疏水性载体B2)例如有上述油和脂肪组分,这里参照其内容。
根据本发明的化妆品学或药学活性组合物还可以包含至少一种助剂B3)。
根据本发明的药物组合物的制剂基质优选地包含药学上可接受的助剂。药学上可接受的助剂是已知用于药学、食品技术领域和相关领域的助剂,特别是列在有关药典(例如DAB Ph.Eur.BP NF)中的助剂和其性质不会妨碍生理学应用的其他助剂。
适合的助剂B3)可以是:润滑剂、润湿剂、乳化与悬浮剂、防腐剂、抗氧化剂、抗红斑物、螯合剂、乳剂稳定剂、膜形成剂、凝胶形成剂、臭味掩蔽剂、树脂、水胶体、溶剂、溶解促进剂、中和剂、渗透加速剂、色素、季铵化合物、再加脂剂与超加脂剂、软膏基质、霜剂基质或油基质、硅酮衍生物、稳定剂、消毒剂、推进剂、干燥剂、不透明剂、增稠剂、蜡类、软化剂、白油。制剂在这点上基于专业知识,例如Fiedler,H.P.Lexikonder Hilfsstoffe für Pharmazie,Kosmetik und angrenzende Gebiete(药学、化妆品与相关领域助剂辞典),第4版,Aulendorf:ECV-Editio-Kantor-Verlag,1996。
为了制备根据本发明的皮肤病学组合物,可以将活性成分用适合的助剂(赋形剂)混合或稀释。赋形剂可以是固体、半固体或液体材料,它们还可以充当活性成分的载体或介质。如果需要的话进行进一步助剂的混合,方式是本领域技术人员已知的。
优选的化妆品和皮肤病学制剂的实例是软膏、霜剂、乳剂、悬液、洗剂、洗面奶、糊剂、凝胶、泡沫、喷雾剂等。如果需要的话,还可以使用脂质体或微球体。
根据本发明的化妆品组合物可以是皮肤化妆品、皮肤病学组合物或头发化妆品组合物。
在第一种优选的实施方式中,根据本发明的组合物是皮肤清洁组合物。
优选的皮肤清洁组合物是液体至凝胶样稠度的皂类,例如透明皂、高档皂、除臭皂、奶油皂、婴儿皂、皮肤防护皂、研磨皂与合成洗涤剂、糊状皂、软皂与洗涤糊剂、液体洗涤剂、淋浴与沐浴制品,例如洗剂、浴用凝胶、泡沫浴液、油浴液和擦洗制品。
按照进一步优选的实施方式,根据本发明的组合物是用于皮肤护理与防护的化妆品组合物、指甲护理组合物或化妆制品。
特别优选皮肤护理组合物、个人卫生组合物、足部护理组合物、光防护组合物、驱避剂、修面组合物、脱毛组合物、抗痤疮组合物、化妆品、睫毛膏、唇膏、眼影、化妆笔、眼线、腮红和眉笔。
根据本发明的皮肤护理组合物特别是W/O或O/W皮肤霜剂、日霜与晚霜、眼霜、面霜、抗皱霜、保湿霜、漂白霜、维生素霜、皮肤洗剂、护理洗剂和保湿洗剂。
基于上述聚合物A)的皮肤化妆品和皮肤病学组合物表现有益效果。聚合物尤其能够有助于皮肤的保湿和调节,有助于皮肤触感的改善。聚合物还可以在制剂中充当增稠剂。加入根据本发明的聚合物,有可能可观地提高某些制剂中的皮肤相容性。
皮肤化妆品和皮肤病学组合物优选地包含约0.001-50重量%的至少一种聚合物A),优选0.01-30重量%,特别优选0.1-20重量%,基于组合物的总重而言。
与惯用的助剂相比,例如聚乙烯基吡咯烷酮,基于共聚物A)的光防护剂特别具有增加UV吸收成分停留时间的性质。
依赖于使用领域,根据本发明的组合物能够以适合于皮肤护理的形式使用,例如霜剂、泡沫、凝胶、笔、摩丝、洗面奶、喷雾剂(泵式喷雾剂或含有推进剂的喷雾剂)或洗剂。
除了包含聚合物A)和适合的载体以外,皮肤化妆品制品还可以包含在皮肤化妆品中惯用的其他活性成分和助剂,如上所述。它们优选地包括乳化剂、防腐剂、芳香油、化妆品活性成分,例如植烷三醇、维生素A、E与C、视黄醇、红没药醇、泛醇、光防护剂、漂白剂、着色剂、调色剂、鞣剂、胶原、蛋白质水解产物、稳定剂、pH调节剂、染剂、盐、增稠剂、凝胶形成剂、稠度调节剂、硅酮、保湿剂、重置剂和其他惯用添加剂。
皮肤化妆品和皮肤病学组合物的优选的油和脂肪组分是上述矿物质和合成油,例如石蜡、硅酮油和具有8个以上碳原子的脂族烃,动物和植物油,例如向日葵油、椰子油、鳄梨油、橄榄油、羊毛脂,或蜡类、脂肪酸、脂肪酸酯,例如C6-C30-脂肪酸的甘油三酯,蜡酯,例如霍霍巴油,脂肪醇、凡士林、氢化羊毛脂和乙酰化羊毛脂,及其混合物。
如果为了获得特定的性质,根据本发明的聚合物还可以与传统的聚合物混合。
为了获得某些性质,例如改善对触摸的感觉、涂敷行为、耐水性和/或活性成分与助剂、例如色素的结合,皮肤化妆品和皮肤病学制品还可以另外包含基于硅酮化合物的调节物质。适合的硅酮化合物例如有聚烷基硅氧烷、聚芳基硅氧烷、聚芳基烷基硅氧烷、聚醚硅氧烷或硅树脂。
化妆品或皮肤病学制品是通过本领域技术人员已知的惯用方法制备的。
化妆品和皮肤病学组合物优选地是乳剂的形式,特别是油包水(W/O)型乳剂或水包油(O/W)型乳剂。不过,选择其他类型的制剂也是可能的,例如水分散系、凝胶、油、油凝胶、多重乳剂(例如W/O/W或O/W/O乳剂的形式)、无水软膏或软膏基质等。
乳剂是通过已知方法制备的。除了共聚物A)以外,乳剂通常还包含惯用的构成物,例如脂肪醇、脂肪酸酯(特别是脂肪酸甘油三酯)、脂肪酸、羊毛脂及其衍生物、天然或合成的油或蜡和——在水的存在下——乳化剂。乳剂类型专属性添加剂的选择和适合的乳剂的制备例如描述在Schrader,Grundlagen und Rezepturen der Kosmetika(化妆品基质与制剂),HüthigBuch Verlag,Heidelberg,第2版,1989第三部分,这里参照其内容。
适合于皮肤霜剂等的乳剂一般包含水相,借助适合的乳化剂系统将其乳化在油或脂肪相中。
乳化剂系统在这种类型乳剂中的比例优选为约4-35重量%,基于乳剂的总重而言。脂肪相的比例优选为约20-60重量%。水相的比例优选为约20-70%,均基于乳剂的总重而言。乳化剂是惯用在这种类型乳剂中的那些。它们例如选自:C12-C18-脱水山梨醇脂肪酸酯;羟基硬脂酸与C12-C30-脂肪醇的酯;C12-C18-脂肪酸与甘油或聚甘油的单酯与二酯;环氧乙烷与丙二醇的缩合产物;环氧丙烷化/环氧乙烷化的C12-C18-脂肪醇;多环醇,例如甾醇;高分子量脂族醇,例如羊毛脂;环氧丙烷化/聚甘油化的醇与异硬脂酸镁的混合物;聚氧乙烯化或聚氧丙烯化脂肪醇的琥珀酸酯;羊毛脂化镁、羊毛脂化钙、羊毛脂化锂、羊毛脂化锌或羊毛脂化铝与氢化羊毛脂或羊毛脂醇的混合物。
可以存在于乳剂脂肪相中的优选的脂肪组分是:烃油,例如石蜡油、PurCellin油、全氢角鲨烯和微晶蜡在这些油中的溶液;动物或植物油,例如甜杏仁油、鳄梨油、红厚壳油、羊毛脂及其衍生物、蓖麻油、芝麻油、橄榄油、霍霍巴油、牛油果油、棘胸鱼油;矿物油,它们在大气压下的蒸馏起点为约250℃,蒸馏终点为410℃,例如凡士林油;饱和或不饱和脂肪酸的酯,例如肉豆蔻酸烷基酯,例如肉豆蔻酸异丙酯、丁酯或鲸蜡基酯,硬脂酸十六基酯、棕榈酸乙酯或异丙酯、甘油三辛酸或癸酸酯和蓖麻油酸鲸蜡基酯。
脂肪相还可以包含可溶于其他油的硅酮油,例如二甲基聚硅氧烷、甲基苯基聚硅氧烷和硅酮二醇共聚物、脂肪酸和脂肪醇。
为了有利于油的保留,除了聚合物A)以外,使用蜡类也是可能的,例如巴西棕榈蜡、小烛树蜡、蜂蜡、微晶蜡、地蜡和Ca、Mg与Al的油酸盐、肉豆蔻酸盐、亚油酸盐与硬脂酸盐。
油包水型乳剂一般是这样制备的,向反应容器引入脂肪相和乳化剂。在大约50-70℃的温度下加热容器,然后加入可溶于油的活性成分和/或助剂,在搅拌下加入水,水已经预先被加热至大约相同的温度,并且可选地已经预先在其中溶解了水溶性成分。搅拌混合物,直至乳剂达到所需的细度,然后放冷至室温,如果必要的话略加搅拌。
按照进一步优选的实施方式,根据本发明的组合物是淋浴凝胶、香波制剂或沐浴制品。
这类制剂包含至少一种聚合物A)和惯用的阴离子表面活性剂作为基本表面活性剂,和两性和/或非离子表面活性剂作为辅助表面活性剂。进一步适合的活性成分和/或助剂一般选自脂质、芳香油、染剂、有机酸、防腐剂与抗氧化剂、增稠剂/凝胶形成剂、皮肤调节剂和湿润剂。
这些制剂优选地包含2-50重量%、优选5-40重量%、特别优选8-30重量%的表面活性剂,基于制剂的总重而言。
所有惯用在肌体清洁组合物中的阴离子、中性、两性或阳离子表面活性剂都可以用在洗涤、淋浴和沐浴制品中。
适合的阴离子表面活性剂例如有烷基硫酸盐、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,特别是碱金属和碱土金属盐,例如钠、钾、镁、钙、铵和三乙醇胺的盐。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个环氧乙烷或环氧丙烷单元,优选1-3个环氧乙烷单元。
它们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。
适合的两性表面活性剂例如有烷基内铵盐、烷基酰氨基丙基内铵盐、烷基磺基内铵盐、烷基甘氨酸盐、烷基羧基甘氨酸盐、烷基两性乙酸盐或两性丙酸盐、烷基两性二乙酸盐或两性二丙酸盐。
例如,可以使用椰油二甲基磺基丙基内铵盐、月桂基内铵盐、椰油酰氨基丙基内铵盐或椰油两性丙酸钠。
适合的非离子表面活性剂例如是在烷基链(可以是直链或支链的)中具有6-20个碳原子的脂族醇或烷基酚与环氧乙烷和/或环氧丙烷的反应产物。烯化氧的量是以每摩尔醇计的约6-60摩尔。适合的还有烷基胺氧化物、单或二烷基链烷醇酰胺、聚乙二醇的脂肪酸酯、乙氧基化脂肪酸酰胺、烷基聚苷或脱水山梨醇醚酯。
洗涤、淋浴和沐浴制品还可以包含惯用的阳离子表面活性剂,例如季铵化合物,例如氯化鲸蜡基三甲铵。
另外,还有可能使用其他惯用的阳离子聚合物,例如丙烯酰胺与氯化二甲基二烯丙基铵的共聚物(Polyquaternium-7)、阳离子纤维素衍生物(Polyquaternium-4,-10)、瓜尔氯化羟丙基三甲铵(INCI:氯化羟丙基瓜尔羟丙基三铵)、N-乙烯基吡咯烷酮与季铵化N-乙烯基咪唑的共聚物(Polyquaternium-16,-44,-46)、N-乙烯基吡咯烷酮/甲基丙烯酸二甲氨基乙基酯(季铵化)与硫酸二乙酯的共聚物(Polyquaternium-11)和其他。
淋浴凝胶/香波制剂可以进一步包含增稠剂,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他,和防腐剂、其他活性成分、助剂和水。
在进一步优选的实施方式中,根据本发明的组合物是头发处理组合物。
根据本发明的头发处理组合物优选地包含约0.1-30重量%的至少一种共聚物A),优选0.5-20重量%,基于组合物的总重而言。
根据本发明的头发处理组合物优选地是固定泡沫、摩丝、发胶、香波、喷发剂或发用泡沫的形式。喷发剂包括气雾剂和没有推进气体的泵式喷雾剂。发用泡沫包括气雾剂泡沫和没有推进气体的泵式泡沫。
喷发剂和发用泡沫优选地主要或者唯一包含水溶性或水可分散性组分。如果用在根据本发明的喷发剂和发用泡沫中的化合物是水可分散性的,那么它们可以是水性微分散系的形式,粒径通常为1-350nm,优选1-250nm。这些制品的固体含量习惯上在约0.5-20重量%范围内。这些微分散系一般不需要乳化剂或表面活性剂加以稳定化。
优选的头发处理组合物是水性分散系的形式或醇溶液或水-醇溶液的形式。适合的醇的实例有乙醇、丙醇、异丙醇及其混合物。
此外,根据本发明的头发处理组合物一般可以包含惯用的化妆品助剂,例如软化剂,例如甘油和乙二醇;润肤剂;香料;表面活性剂;UV吸收剂;染剂;抗静电剂;提高相容性的试剂;防腐剂;和止泡剂。
如果根据本发明的组合物被配制成喷发剂,则它们包含足量的推进剂,例如低沸点的烃或醚,例如丙烷、丁烷、异丁烷或二甲醚。可以使用的推进剂还有压缩气体,例如氮、空气或二氧化碳。推进剂的量在这里可以保持少量,目的是不会不必要地增加VOC含量。因此一般不超过55重量%,基于组合物的总重而言。不过若需要的话,更高的VOC含量如85重量%和以上也是可能的。
上述聚合物A)还可以与其他发用聚合物联合用在组合物中。适合的聚合物是上述那些。
其他发用聚合物的含量优选地高达10重量%,以组合物的总重量计。
优选的头发处理组合物包含:
a)0.5-20重量%、优选1-10重量%的至少一种如上所定义的聚合物A),
b)50-99.5重量%、优选55-99重量%载体(溶剂),选自水和水可混溶性溶剂,优选C2-C5-醇,特别是乙醇,及其混合物,
c)0-70重量%、优选0.1-50重量%推进剂,优选地选自二甲醚和烷烃,例如丙烷/丁烷混合物,
d)0-10重量%、优选0.1-10重量%至少一种不同于a)的发用聚合物,优选水溶性或水可分散性聚合物,
e)0-0.5重量%、优选0.001-2重量%至少一种水溶性或水可分散性硅化合物,
和可选的如上所定义的其他活性成分和/或助剂。
根据本发明的组合物可以包含至少一种非离子的、含有硅氧烷的水溶性或水可分散性聚合物作为组分e),特别是选自上述聚醚硅氧烷。该组分的比例一般为约0.001-2重量%,基于组合物的总重而言。
根据本发明的组合物可以包含至少一种水不溶性硅酮作为附加组分,特别是聚二甲基硅氧烷,例如来自Goldschmidt的Abil级。该组分的比例一般为约0.0001-0-2重量%,优选0.001-0.1重量%,以组合物的总重计。
根据本发明的组合物可以另外可选地包含止泡剂,例如基于硅酮的一种。止泡剂的量一般高达约0.001重量%,基于组合物的总量而言。
本发明进一步提供至少一种共聚物的用途,该共聚物包含共聚形式的
a)60-99重量%至少一种亲水性单体,其中至少有65重量%包含至少一种N-乙烯基内酰胺,和
b)1-40重量%至少一种疏水性单体,选自
b1)式I化合物
其中
R1是H、甲基或乙基,
X是O、NH或NR3,
R2是C8-C30-烷基、C8-C30-链烯基、环烷基-C6-C22-烷基、环烷基
-C6-C22-链烯基、芳基-C6-C22-烷基或芳基-C6-C22-链烯基,和
R3是C1-C7-烷基、环烷基、芳基或R2的含义之一,
b2)脂族C8-C30-羧酸的乙烯基酯,
b3)C8-C30-烷基乙烯基醚,
及其混合物,
该共聚物用作包含至少一种疏水性组分的均相或非均相化妆品或药物组合物的组分,用于调整该组合物的流变性质。
本发明进一步提供如上所定义的共聚物在皮肤清洁组合物、用于皮肤护理与防护的组合物、指甲护理组合物、化妆制品、淋浴凝胶、香波、沐浴制品和头发处理组合物中的用途。
本发明进一步提供共聚物A)在包含水和至少一种疏水性组分的皮肤清洁组合物、用于皮肤护理与防护的组合物、指甲护理组合物、化妆制品、淋浴凝胶、香波、沐浴制品和头发处理组合物中的用途,用于皮肤保湿;用于调节皮肤,例如改善触感和平滑性;用作增稠剂;和/或用于提高皮肤相容性,例如用于减少刺激,特别是针对表面活性剂而言的;还用于实现更好的湿润效果。
在头发处理组合物中,共聚物A)优选地用作固定剂和/或调节剂。这里的组合物优选地是固定泡沫、摩丝、发胶、香波、喷发剂或发用泡沫的形式。
参照下列非限制性实施例详细阐述发明。
实施例
I.应用例
应用例1:皮肤霜剂
按照下列配方制备水/油乳剂(皮肤霜剂A):
CTFA名称 | 重量% | |
CremophorA6(BASFAG) | Ceteareth-6(硬脂醇乙氧基化物)和硬脂醇 | 2.0 |
CremophorA25(BASFAG) | Ceteareth-25(脂肪醇乙氧基化物) | 2.0 |
Lanette | 鲸蜡硬脂醇 | 2.0 |
Imwitor960K | 甘油硬脂酸酯SE | 3.0 |
石蜡油 | 5.0 | |
霍霍巴油 | 4.0 | |
LuvitolEHO(BASF AG) | 鲸蜡硬脂基辛酸酯(鲸蜡基硬脂基2-乙基己酸酯) | 3.0 |
ABIL350(Goldschmidt) | Dimethicone(聚二甲基硅氧烷) | 1.0 |
Amerchol L101(Amerchol Edison) | 矿物油和羊毛脂醇 | 3.0 |
Veegum Ultra | 硅酸铝镁 | 0.5 |
1,2-丙二醇 | 丙二醇 | 5.0 |
Abiol | 咪唑烷基脲 | 0.3 |
苯氧基乙醇 | 0.5 | |
D-泛醇USP | 1.0 | |
乙烯基吡咯烷酮/甲基丙烯酸硬脂基酯聚合物70/30重量%(K值50;1%异丙醇溶液) | 0.5 | |
水 | 加至100 |
应用例2:淋浴凝胶/香波
首先按照下列配方制备根据本发明的淋浴凝胶制剂(淋浴凝胶A):
CTFA名称 | 重量% | |
TexaponNSO(Henkel) | 月桂基醚硫酸钠 | 40.0 |
Tego BetainL7(Goldschmidt) | 椰油酰氨基丙基内铵盐 | 5.0 |
Plantacare 2000 | 癸基糖苷 | 5.0 |
香料 | 0.2 | |
乙烯基吡咯烷酮/甲基丙烯酸硬脂基酯聚合物,70/30重量%(K值50;1%异丙醇溶液) | 0.2 | |
Euxyl K100(Schülke &Mayr) | 苯甲醇、甲基氯异噻唑啉酮、甲基异噻唑啉酮 | 0.1 |
D-泛醇USP | 0.5 | |
柠檬酸(pH 6-7) | 适量 | |
NaCl | 2.0 | |
水 | 加至100 |
按相同方式制备三种对比淋浴凝胶,具体而言:
淋浴凝胶B:用等量非交联的聚合物Polyquaternium-16代替根据本发明的共聚物;
淋浴凝胶C:用等量阳离子改性的羟乙基纤维素代替根据本发明的共聚物;
淋浴凝胶D:不加入聚合物。
利用淋浴凝胶A、B、C和D进行下列对比试验,测定泡沫的乳脂性。
在每种情况下,将2.0g上述制剂放置在左手掌上,用自来水洗出泡沫,两手摩擦1分钟后,评估手掌对泡沫的感觉:
第1级:非常有乳脂性
第2级:乳脂性
第3级:钝涩感/缺乏试验物
对比试验结果(10名受试者评价平均值)
淋浴凝胶 | 10名受试者的平均值 |
A | 1.4 |
B | 2.9 |
C | 2.0 |
D | 3.0 |
应用例3:保湿制剂
制剂A
CTFA名称 | 重量% | |
CremophorA6(BASF AG) | Ceteareth-6(硬脂醇乙氧基化物)和硬脂醇 | 2.0 |
CremophorA25(BASF AG) | Ceteareth-25(脂肪醇乙氧基化物) | 2.0 |
石蜡油 | 10 | |
LanetteO | 鲸蜡硬脂醇 | 2.0 |
硬脂酸 | 3.0 | |
Nip-Nip(Nipa LaboratoriesLtd.,USA) | 4-羟基苯甲酸甲酯与丙酯(7∶3) | 0.5 |
Abiol | 咪唑烷基脲 | 0.5 |
乙烯基吡咯烷酮/甲基丙烯酸硬脂基酯聚合物,80/20重量%(K值25;1%异丙醇溶液) | 3.0 | |
水 | 加至100 |
为了制备该制剂,将两相加热至80℃,搅拌a)相和b)相,均质化,搅拌至冷却,然后用10%NaOH水溶液调节pH至6。
按照相同方式制备对比霜剂(制剂B),不加入聚合物。
使用制剂A和B对8名受试者进行试验。为此,将每种制剂涂在受试者的前臂上,用量2mg/cm2。30分钟后,利用Corneometer CM 825(Khazaka & Courage)测定皮肤的水分。涂用制剂A后,测量Corneometer单位的平均值为41,关于制剂B,平均值为35。
应用例4:用于皮肤保湿的O/W霜剂
添加剂 | 重量% |
甘油单硬脂酸酯 | 2.0 |
鲸蜡醇 | 3.0 |
亚液态石蜡油 | 15.0 |
凡士林 | 3.0 |
甘油三辛酸/癸酸酯 | 4.0 |
辛基十二烷醇 | 2.0 |
氢化椰油 | 2.0 |
磷酸鲸蜡基酯 | 0.4 |
乙烯基吡咯烷酮/丙烯酸/甲基丙烯酸硬脂基酯聚合物60/5/35重量%(K值41;1%异丙醇溶液) | 3.0 |
甘油 | 3.0 |
氢氧化钠 | 适量 |
芳香油 | 适量 |
防腐剂 | 适量 |
水 | 加至100 |
应用例5:O/W洗剂
添加剂 | 重量% |
硬脂酸 | 1.5 |
脱水山梨醇单硬脂酸酯 | 1.0 |
脱水山梨醇单油酸酯 | 1.0 |
亚液态石蜡油 | 7.0 |
鲸蜡醇 | 1.0 |
聚二甲基硅氧烷 | 1.5 |
甘油 | 3.0 |
乙烯基吡咯烷酮/丙烯酸/甲基丙烯酸硬脂基酯聚合物,50/10/40重量%(K值36;1%异丙醇溶液) | 0.5 |
芳香油 | 适量 |
防腐剂 | 适量 |
水 | 加至100 |
应用例6:W/O洗剂
添加剂 | 重量% |
PEG-7氢化蓖麻油 | 4.0 |
羊毛蜡醇 | 1.5 |
蜂蜡 | 3.0 |
液体甘油三酯 | 5.0 |
凡士林 | 9.0 |
地蜡 | 4.0 |
亚液态石蜡油 | 4.0 |
甘油 | 2.0 |
乙烯基吡咯烷酮/丙烯酸/甲基丙烯酸硬脂基酯聚合物,80/10/10重量%(K值45;1%异丙醇溶液) | 10.0 |
硫酸镁*7H2O | 0.7 |
芳香油 | 适量 |
防腐剂 | 适量 |
水 | 加至100 |
应用例7:皮肤护理用水凝胶
添加剂 | 重量% |
乙烯基吡咯烷酮/丙烯酸/甲基丙烯酸硬脂基酯聚合物,50/20/30重量%(K值36;1%异丙醇溶液) | 20.0 |
山梨醇 | 2.0 |
甘油 | 3.0 |
聚乙二醇400 | 5.0 |
乙醇 | 1.0 |
芳香油 | 适量 |
防腐剂 | 适量 |
水 | 加至100 |
应用例8:液体皂
添加剂 | 重量% |
椰子脂肪酸,钾盐 | 15 |
油酸钾 | 3 |
甘油 | 5 |
乙烯基吡咯烷酮/甲基丙烯酸硬脂基酯聚合物,70/30重量%(K值47;1%异丙醇溶液) | 2 |
甘油硬脂酸酯 | 1 |
乙二醇二硬脂酸酯 | 2 |
特定的添加剂、配合剂、香味剂、水 | 加至100 |
应用例9:W/O防晒乳剂
添加剂 | 重量% |
硬脂酸镁 | 0.5 |
硬脂酸铝 | 0.5 |
氢化蓖麻油7EO | 6.0 |
乙烯基吡咯烷酮/甲基丙烯酸硬脂基酯聚合物,70/30重量%(K值47;1%异丙醇溶液) | 5.0 |
Microwax | 1.0 |
2-乙基己酸鲸蜡硬脂基酯 | 10.0 |
2-羟基-4-甲氧基二苯酮 | 2.0 |
聚乙氧基乙基4-双(聚乙氧基)氨基苯甲酸酯 | 5.0 |
α-红没药醇 | 0.2 |
1,2-丙二醇 | 3.0 |
芳香油 | 适量 |
防腐剂 | 适量 |
水 | 加至100 |
应用例10:防晒油
添加剂 | 重量% |
乙烯基吡咯烷酮/甲基丙烯酸硬脂基酯聚合物,70/30重量%(K值45;1%异丙醇溶液) | 10.0 |
3-(4’-甲基)亚苄基萜烷-2-酮 | 2.5 |
2-羟基-4-甲氧基二苯酮 | 5.5 |
甘油三辛酸/癸酸酯 | 10.0 |
己二酸二丁酯 | 22.5 |
肉豆蔻酸异丙酯 | 7.5 |
石蜡油 | 42.0 |
Claims (15)
1.一种具有液体至凝胶样稠度的化妆品或药物组合物,该组合物包含:
A)至少一种共聚物,基于单体的总量而言,该共聚物包含共聚形式的:
a)60-99重量%的至少一种亲水性单体,其中至少有65重量%包含至少一种N-乙烯基内酰胺,和
b)1-40重量%的至少一种疏水性单体,选自
b1)式I化合物
其中
R1是H、甲基或乙基,
X是O、NH或NR3,
R2是C8-C30-烷基、C8-C30-链烯基、环烷基-C2-C22-烷基、环烷基
-C2-C22-链烯基、芳基-C2-C22-烷基或芳基-C2-C22-链烯基,和
R3是C1-C7-烷基、环烷基、芳基或R2的含义之一,
b2)脂族C8-C30-羧酸的乙烯基酯,
b3)C8-C30-烷基乙烯基醚,
及其混合物,和
B)至少一种化妆品学上可接受的添加剂。
2.如权利要求1所要求保护的组合物,其中该N-乙烯基内酰胺选自N-乙烯基吡咯烷酮、N-乙烯基哌啶酮、N-乙烯基己内酰胺及其混合物。
3.如前述权利要求任一项所要求保护的组合物,其中该组分a)包含至少一种α,β-烯属不饱和一元和/或二元羧酸。
4.如前述权利要求任一项所要求保护的组合物,其中该共聚物A)由共聚的单体单元组成,该单体单元是
-60-99重量%至少一种N-乙烯基内酰胺,和
-1-40重量%至少一种如权利要求1所定义的单体b)。
5.如前述权利要求任一项所要求保护的组合物,其中该组分B)包含至少一种在20℃下为液体的疏水性化合物。
6.如前述权利要求任一项所要求保护的组合物,其中组分B)选自
B1)化妆品和药学活性成分,
B2)载体,和
B3)助剂。
7.如权利要求6所要求保护的组合物,其中该组分B2)选自水、亲水性组分、疏水性组分及其混合物。
8.如权利要求5-7任一项所要求保护的组合物,包含至少一种疏水性组分,选自
i)油,
ii)脂肪,
iii)蜡,
iv)C6-C30-一元羧酸与一元、二元或三元醇的酯,它们不同于i)至iii),
v)饱和的无环和环状烃,
vi)脂肪酸,
vii)脂肪醇,
及其混合物。
9.如前述权利要求任一项所要求保护的组合物,它是软膏、霜剂、乳剂、悬液、洗剂、洗面奶、糊剂、凝胶、泡沫或喷雾剂的形式。
10.一种头发处理组合物,包含
a)0.5-20重量%的至少一种如权利要求1-4任一项所定义的聚合物A),
b)50-99.5重量%的载体,选自水、水可混溶性溶剂,优选C2-C5-醇,及其混合物,
c)0-70重量%的推进剂,它优选地选自二甲醚和烷烃,
d)0-10重量%的至少一种不同于a)的发用聚合物,
e)0-0.5重量%的至少一种水溶性或水可分散性硅酮化合物,
和可选的其他活性成分和/或助剂。
11.至少一种共聚物的用途,该共聚物包含共聚形式的
a)60-99重量%的至少一种亲水性单体,其中至少有65重量%包含至少一种N-乙烯基内酰胺,和
b)1-40重量%的至少一种疏水性单体,选自
b1)式I化合物
其中
R1是H、甲基或乙基,
X是O、NH或NR3,
R2是C8-C30-烷基、C8-C30-链烯基、环烷基-C6-C22-烷基、环烷基
-C6-C22-链烯基、芳基-C6-C22-烷基或芳基-C6-C22-链烯基,和
R3是C1-C7-烷基、环烷基、芳基或R2的含义之一,
b2)脂族C8-C30-羧酸的乙烯基酯,
b3)C8-C30-烷基乙烯基醚,
及其混合物,
该共聚物用作包含至少一种疏水性组分的均相或非均相化妆品或药物组合物的组分,用于改进该组合物的流变性质。
12.如权利要求11所定义的共聚物在皮肤清洁组合物、用于皮肤护理与防护的组合物、指甲护理组合物、化妆制品、淋浴凝胶、香波、沐浴制品和头发处理组合物中的用途。
13.如权利要求12所要求保护的在包含水和至少一种疏水性组分的皮肤清洁组合物、用于皮肤护理与防护的组合物、指甲护理组合物、化妆制品、淋浴凝胶、香波和沐浴制品中的用途,用于皮肤保湿、用于调节皮肤、用作增稠剂、用于提高皮肤相容性和/或用于实现更好的湿润效果。
14.如权利要求12所要求保护的在头发护理组合物中的用途,用作固定剂和/或调节剂。
15.如权利要求14所要求保护的用途,其中该组合物是固定泡沫、摩丝、发胶、香波、喷发剂或发用泡沫的形式。
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ES2536713T3 (es) * | 2003-03-12 | 2015-05-27 | Epitome Pharmaceuticals Limited | Composiciones para la piel lipófilas de rápida absorción y usos de las mismas |
DE10353030A1 (de) * | 2003-11-13 | 2005-07-07 | Beiersdorf Ag | Konservierende Wirkstoffkombination |
DE102004005095A1 (de) | 2004-01-27 | 2005-09-22 | Coty B.V. | Kosmetische Zusammensetzung mit wasserbeständiger Parfümkomponente |
US20060075923A1 (en) * | 2004-10-12 | 2006-04-13 | Richardson H W | Method of manufacture and treatment of wood with injectable particulate iron oxide |
ES2332539T3 (es) * | 2007-02-14 | 2010-02-08 | Beiersdorf Ag | Preparacion cosmetica con filtro de luz uv hidrosoluble y un copolimero de vinilpirrolidina / acido acrilico. |
US20080193395A1 (en) * | 2007-02-14 | 2008-08-14 | Beiersdorf Ag | Cosmetic preparation with vinylpyrrolidone/acrylic acid copolymer |
DE102008006393A1 (de) * | 2008-01-28 | 2009-07-30 | Beiersdorf Ag | Verwendung von Lipidkomponenten gegen Pollenallergien |
US20110130457A1 (en) * | 2008-08-06 | 2011-06-02 | University Of Louisville Research Foundation, Inc. | Wax-Based Emulsion for the Treatment of Dry Eye Conditions |
US9364418B2 (en) * | 2010-01-14 | 2016-06-14 | Basf Se | Water-resistant cosmetic formulations comprising a hydrophobically modified vinylpyrrolidone copolymer |
MX2018006918A (es) * | 2015-12-08 | 2018-11-09 | Kemira Oyj | Composiciones polimericas liquidas. |
CN116194073A (zh) | 2020-07-21 | 2023-05-30 | 化美有限责任公司 | 二酯化妆品制剂及其用途 |
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LU58383A1 (zh) * | 1969-04-08 | 1970-11-09 | ||
LU58617A1 (zh) * | 1969-05-09 | 1971-03-09 | ||
US3910862A (en) * | 1970-01-30 | 1975-10-07 | Gaf Corp | Copolymers of vinyl pyrrolidone containing quarternary ammonium groups |
DE2161817A1 (de) * | 1970-12-14 | 1972-06-29 | Oreal | Kosmetische Zubereitungen |
US5015708A (en) * | 1989-06-26 | 1991-05-14 | Gaf Chemicals Corporation | Precipitation polymerization of terpolymers of a vinyl lactam, a polymerizable carboxylic acid and a hydrophobic monomer in an aliphatic hydrocarbon solvent |
EP0409383B1 (en) * | 1989-07-21 | 1994-04-06 | Izhak Blank | Estradiol compositions and methods for topical applications |
US5997855A (en) * | 1994-12-28 | 1999-12-07 | Isp Investments Inc. | Personal care composition containing a clear homogeneous polymer of an N-vinyl lactam |
US5686067A (en) * | 1995-01-05 | 1997-11-11 | Isp Investments Inc. | Low voc hair spray compositions |
DE19719187A1 (de) * | 1997-05-07 | 1998-11-12 | Basf Ag | Verwendung von Copolymerisaten des N-Vinyl-pyrrolidons in Zubereitungen wasserunlöslicher Stoffe |
DE19814730A1 (de) * | 1998-04-02 | 1999-10-07 | Basf Ag | Verwendung von N-Vinyllacram oder N-Vinylamin haltigen Copolymeren als Matrix zur Herstellung von festen pharmazeutischen und kosmetischen Darreichungsformen |
WO2000030595A1 (en) * | 1998-11-23 | 2000-06-02 | Isp Investments Inc. | Polymer personal care compositions |
US6479076B2 (en) * | 2001-01-12 | 2002-11-12 | Izhak Blank | Nicotine delivery compositions |
-
2001
- 2001-02-21 DE DE10108387A patent/DE10108387A1/de not_active Withdrawn
-
2002
- 2002-02-20 WO PCT/EP2002/001802 patent/WO2002072047A2/de not_active Application Discontinuation
- 2002-02-20 JP JP2002571006A patent/JP2004529903A/ja active Pending
- 2002-02-20 US US10/467,946 patent/US20040146477A1/en not_active Abandoned
- 2002-02-20 CN CNA028052110A patent/CN1492754A/zh active Pending
- 2002-02-20 EP EP02718151A patent/EP1363585A2/de not_active Withdrawn
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102113979A (zh) * | 2010-12-07 | 2011-07-06 | 江晨 | 一种洗发膏的配方 |
CN106310353A (zh) * | 2015-07-03 | 2017-01-11 | 江苏诺瓦立医疗用品有限公司 | 水胶体粘合剂、相关应用及水胶体敷料 |
CN110035735A (zh) * | 2016-07-18 | 2019-07-19 | 安瑞特研究有限公司 | 包含白桦脂醇的油包水泡沫及其组合物 |
US11826374B2 (en) | 2018-01-04 | 2023-11-28 | Amryt Research Limited | Betulin-containing birch bark extracts and their formulation |
Also Published As
Publication number | Publication date |
---|---|
WO2002072047A3 (de) | 2002-12-27 |
DE10108387A1 (de) | 2002-08-29 |
WO2002072047A2 (de) | 2002-09-19 |
EP1363585A2 (de) | 2003-11-26 |
US20040146477A1 (en) | 2004-07-29 |
JP2004529903A (ja) | 2004-09-30 |
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