CN1100525C - 头发定型剂 - Google Patents

头发定型剂 Download PDF

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CN1100525C
CN1100525C CN96105533A CN96105533A CN1100525C CN 1100525 C CN1100525 C CN 1100525C CN 96105533 A CN96105533 A CN 96105533A CN 96105533 A CN96105533 A CN 96105533A CN 1100525 C CN1100525 C CN 1100525C
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CN1138451A (zh
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R·布兰肯堡
K·施佩林
A·桑纳
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    • A61K8/8147Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
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    • A61K8/8164Compositions 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

一种头发定型剂,包括A)0.5-20%重量的N-乙烯基己内酰胺均聚物或至少70%重量的N-乙烯基己内酰胺的阴离子或非离子共聚物(聚合物A),和B)0.5-20%重量的后成膜聚合物(聚合物B),是从下组中选出:聚酰胺类、聚氨酯类和单烯基类不饱和的单体的均聚合物和共聚合物。

Description

头发定型剂
本发明涉及新颖的头发定型剂,它含有聚合物混合物作为成膜剂。
含有一种聚酯和一种水容性聚合物的喷发胶组合物,例如一种N-乙烯基己内酰胺和N-乙烯基吡咯烷酮的共聚物,在WO-93/17658中公开过。
不过,这类喷发胶对水解作用敏感因而只能以受限制的方式使用和处理。
本发明的目的是开发头发定型剂,它有良好的定型性和水可洗去性以及低的粘性,没有上述的水解敏感性。
我们发现本发明的这个目的使用有下述组分的头发定型剂达到了:A)0.5-20%重量的至少有70%重量的N-乙烯基己内酰胺的均-或共聚物(聚合物A),和B)0.5-20%重量的后成膜聚合物(聚合物B),从下组中选出:聚酰胺类、聚氨酯类,和单烯类不饱和的单体的均-和共聚物。
适用的聚合物A为N-乙烯基己内酰胺的均聚物,本领域的技术人员都知道它可以用例如US-3145147中描述的方法制备。
更适用的聚合物A为N-乙烯基己内酰胺的共聚物和可再聚合的单体,该共聚物含有至少70%重量,优选85%重量的N-乙烯基己内酰胺。
聚合物A的适用的可再聚合的单体有:
具有酸功能的单体,诸如丙烯酸、甲基丙烯酸、丙烯酰氨基甲丙基磺酸(AMPS)、(甲基)丙烯酸3-磺丙基酯,如果要求的话,也可以采用全或部分中和的形式;
(甲基)丙烯酸C1-C18烷基酯类,诸如丙烯酸叔丁酯、丙烯酸乙酯、甲基丙烯酸异丁酯、甲基丙烯酸正丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯和(甲基)丙烯酸羟烷基酯类;
C2-C10脂肪酸的乙烯酯类,诸如乙酸乙烯酯,丙酸乙酯和较长链和/或支链脂肪酸的乙烯酯,例如有支链的烷烃羧酸。
C3-C8N-烷基(甲基)丙烯酰胺类,诸如甲基丙烯酰胺、N,N-二甲基丙烯酰胺、N-叔-丁基丙烯酰胺和N-叔-辛基丙烯酰胺;
N-乙烯基吡咯烷酮和N-乙烯基哌啶酮。
其他单体可以以单独的化合物或以混合物的形式用于共聚物A。
这类聚合物是已知的,或能够用传统的聚合方法制备。
例如,EP-455081描述了N-乙烯基吡咯烷酮、N-乙烯基己内酰胺和N-乙烯基咪唑共聚物。EP-74191公开了N-乙酰基吡咯烷酮、N-乙烯基己内酰胺和甲丙烯酸二甲基氨基乙酯的共聚物。
N-乙烯基己内酰胺的均聚物优选用于依据本发明的头发定型剂。
依据本发明的头发定型剂含有聚合物A量为0.5-20,优选为1-10%重量,以制成的定型剂的重量为基计。
作为聚合物B),可以使用在美发品中已经使用的多种多样的聚合物。
适用的聚合物B),依据本发明,除了A)之外的其他成膜聚合物,从下组中选出:聚酰胺类、聚氨酯类和单烯类不饱和单体的均-和共聚物。依据本发明,成膜剂聚合物可以是传统的头发定型聚合物,但也可以是工业用涂覆剂和粘结剂的成膜剂。
特别适用的单烯类不饱和单体的均-和共聚物有丙烯酸和甲基丙烯酸的C1-C12-烷基酯类,单烯类不饱和的C3-C5-一元羰酸和它们的乙烯酯类,马来酸和它的半酯类,甲基乙烯基醚,丙烯酰胺类,甲基丙烯酰胺类,N-烷基取代的(甲基)丙烯酰胺类,N-乙烯基吡咯烷酮,N-乙烯基咪唑和苯乙烯。
特别优选的聚合物B)是丙烯酸酯聚合物,例如丙烯酸/丙烯酸乙酯/N-叔丁基-丙烯酰胺的共聚物,甲基丙烯酸/丙烯酸叔丁酯/N-乙烯基吡咯烷酮的共聚物,以丙烯酸和乙酸乙烯酯为基础的共聚物,辛基丙烯酰胺/丙烯酸酯/甲基丙烯酸丁氨乙酯的共聚物,辛基丙烯酰胺/丙烯酸酯的共聚物,甲基丙烯酸乙酯/甲基丙烯酸/N-乙烯基吡咯烷酮的共聚物或丙烯酸酯与丙烯酸羟烷基酯的共聚物。这些共聚物市场有售,例如,按以下的商品名标出售:Amerhold,Ultrahold8,Ultrahold Strong,LuviflexVBM,Luvimer100P,Luvimer36D,LuvimerMAE30D,Acronal500D,Acudyne255,Stepanhold,LovocrylVersatyl和Amphomer。
优选的聚合物B是含磺酸酯的聚酰胺类,包括:-   从20至99%摩尔的含有2至12个碳原子的一氨基羧酸或其内酰胺,-   从0.5至40%摩尔的含有2至18个碳原子的二胺,-   从0.5至25%摩尔的含有4至12个碳原子的含磺酸酯的二羧酸,和-   从0至35%摩尔的含有2至16个碳原子的另一种二羧酸。
优选的聚合物B)还有含磺酸酯的丙烯酸酯,包括:-   从50至90%重量的一种或多种单体,从下组中选出:丙烯酸的或甲基丙烯酸的C1-C18烷基酯类,以及饱和的C2-C10-一元羧酸的乙烯基酯,-   从10至25%重量含有磺酸的乙烯基单体,和-   从0至40%重量的另一种单体,从下组中选出:丙烯酸、甲基丙烯酸、
丙烯酰胺、甲基丙烯酰胺、C3-C8-N-烷基丙烯酰胺和N,N-二甲基丙烯酰胺。
同样优选的聚合物B)还有依据DE-A4327514的微分散方式得到的共聚物,它们是下组中的物质通过自由基引发的共聚合反应或通过使用电离辐射引发的共聚合反应获得:-   从40至99%重量的一种或多种非水溶的单乙烯基不饱和的单体,-   从1至60%重量的一种或多种水溶的单乙烯基不饱和的单体和-   从0至30%重量的一种或多种多在水介质中的乙烯基不饱和的单体,在从2至20%重量(以单体的总重量计)作为乳化剂的表面活性剂化合物存在的条件下,在水介质中以光学扫描测定,平均粒径为5至37nm。
适用的聚合物B)还有N-乙烯基吡咯烷酮的均-和共聚物,例如在市场上可买到的,诸如BASF公司以Luviskol命名的。这类聚合物通过N-乙烯基吡咯烷酮与乙酸乙烯酯和/或丙酸乙烯酯以各种比例聚合而获得,这类聚合物的例子有:
LuviskolK17,LuviskolK30,LuviskolK60,LuviskolK80,LuviskolK90(适当的K值的聚乙烯基吡咯烷酮表示为一种粉剂或溶液(水的或水/乙醇的))。
LuviskolVA=乙烯基吡咯烷酮/乙酸乙烯酯共聚物,具体的为:LuviskolVA73,LuviskolVA64,LuviskolVA55,LuviskolVA37和LuviskolVA28。
其他适用的聚合物B)为乙烯基吡咯烷酮、乙酸乙烯酯和丙酸乙烯酯的三元聚合物,例如LuviskolVAP 343。
同样适用的还有乙酸乙烯酯与巴豆酸的共聚物;例如产品LuvisetCA,LuvisetCAP和National28-2930。
季铵化的聚季铵-4、聚季铵-6、聚季铵-7、聚季铵-10、聚季铵-11或聚季铵-16也可以使用。
其他适用的聚合物B)有甲基乙烯基醚(MVE)和马来酸酯的共聚物,例如MVE/马来酸一乙基酯、MVE/马来酸一异丙基酯或MVE/马来酸一丁基酯的共聚物,例如产品Gantrez  ES-225,Gantrez  ES-335,Gantrez  ES-425,Gantrez  ES-435和Gantrez  SP-215。
聚氨酯类,例如在WO 94/03510中所描述的,也可以用作聚合物B。聚苯乙烯磺酸的钠盐,例如以商品名Flexan130出售的,亦同样适用。
如果它们是由含酸的单体合成的,依据本发明,聚合物A和B可以采取酸的形式或部分或全部中和的形式用于头发定型剂。碱金属的氢氧化物类,氨和有机胺类,特别是氨基醇类,适于该中和反应,特别推荐2-氨基-2-甲基-1-丙醇。
聚合物A和B是在一种溶剂中,所用的溶剂优选水或醇类或水与低级醇的混合物。溶剂在头发定型剂中的比例通常为25~98%重量。
聚合物A和B能够通过把A和B溶解在一种溶剂中混合在一起成为粉剂,或通过,把另一种聚合物,一般总是呈固体,或也可以呈为溶液,混合加人到一种聚合物溶液中。聚合物B也可以呈为一种分散剂存在,聚合物A能够以粉或剂水溶液或水-醇溶液的形式加入。
依据本发明的头发定型剂的聚合物B的含量为0.5-20.0%,优选为1-5%,以制成的定型剂的重量计。
除了聚合物A和B以及一种溶剂外,依据本发明的头发定型剂,根据预订的用途,还可以含有惯用的美发添加剂,例如香精油、乳化剂、防腐剂,保养物质诸如泛醇、胶原、维生素、蛋白水解产物,稳定剂、pH调节剂,着色剂和其他惯用添加剂。
如果依据本发明的头发定型剂要作为喷发胶使用,一般要加入推进剂。惯用的推进剂是低级链烷烃类,例如丙烷或丁烷,二乙醚,氮气,氧化亚氮或二氧化碳或这些物质的混合物。依据本发明的头发定型剂也可以用含卤烃作为推进剂。当使用机械装置时,例如喷射泵,可以不要推进剂。
依据本发明头发定型剂有突出的应用性能,它们形成透明膜并在水/醇溶液中有低的粘度,因而它们即使采用在较高浓度仍有良好的推进性。令人惊异的是,非水容性成膜聚合物也可以与聚乙烯基己内酰胺结合加工制成能容易洗掉的头发定型剂。
在下面各实施例中所用的聚乙烯基己内酰胺溶液按在乙烯醇溶液中的重量计浓度为50%。依据Fikentscher的聚合物的K值为40(在乙烯醇中为1%)。
                      实施例1
一种头发定型剂的制备与性质4.0%重量的Luvimer36D(丙烯酸叔-丁基酯、丙烯酸乙酯和甲基丙烯酸的共聚物的水分散剂,36%重量浓度)7.0%重量的聚乙烯基己内酰胺溶液89.0%重量的蒸馏水+)K值40
在室温下溶解并灌入喷射泵内。喷射两个模特的头发后,得到如下的定型剂评价:被处理的头发定形既好又有光泽且头发不粘黏。手握感松软,梳理性和水洗性亦佳。
                实施例2-9
测定经处理的发丝的外观和性质以及下文中提到的各种配方的组合物的粘着性,结果列于表中。
发丝在各种配方中蘸过后,在滤纸上轻轻挤压、干燥并测量其韧性。
通过在10%重量浓度的十二烷基醚磺酸钠水溶液洗涤上述被处理的发丝测定洗掉性,在37℃在30秒钟内,浸没五次并挤干。然后用清水漂洗发丝,重复洗掉的过程并在滤纸上挤压发丝,干燥一整夜。然后测定发丝的残留量。
              粘着性的评价
各种配制好的试样用缝宽120μm的刮浆刀涂覆在玻璃板上。湿膜在室温下干燥然后贮藏在75%相对湿度和20℃的空调柜中一整夜。为了测试,用一圆橡皮戳子(40mmShoreA硬度60±5)以250N把一塑性碳带压在聚合物膜上10秒钟。碳带的印迹粘附到聚合物膜上保持的程度是聚合物表面的粘着性。黏性1表示印痕保持黏附到聚合物膜上的程度为最小。
                实施例25%重量的聚乙烯基己内酰胺溶液10.0%重量的依据WO/03510中实施例3的聚氨酯,25%的重量浓度的微分散水溶液85.0%重量的分散剂水
               实施例35%重量的聚乙烯基己内酰胺溶液2.5%重量的由20%摩尔-己内酰胺、34%摩尔六亚甲基二胺、17%摩尔5-磺异苯二甲酸的钠盐和17%摩尔的异苯二甲酸构成的聚酰胺92.5%重量的分散剂水
               实施例45%重量的聚乙烯基己内酰胺10%重量的丙烯酸酯微分散剂,依据DE-A 4327514实施例10(20%重量的固体含量)85%重量的分散剂水
               实施例55.0%重量的聚乙烯基己内酰胺溶液2.5%重量的Luviskol VA 64P,N-乙烯基吡咯烷酮/乙酸乙烯酯的粉状共聚物52.5%重量的无水乙醇40.0%重量的蒸馏水
               实施例65%重量的聚乙烯基己内酰胺溶液2.5%重量的Luvimer 100P,丙烯酸N-叔丁基酯/丙烯酸乙酯/甲基丙烯酸酯的粉状共聚物0.58%重量的2-氨基-2-甲基丙醇(AMP)52.50%重量的无水乙醇39.42%重量的蒸馏水
               例75%重量的聚乙烯基己内酰胺溶液2.5%重量的Luviset CAP,乙酸乙烯酯/丙酸乙烯酯/巴豆酸的粉状三元共聚物0.19%重量的AMP52.50%重量的吸收剂乙醇39.81%重量的分散剂水
               实施例85%重量的聚乙烯基己内酰胺溶液2.5%重量的Ultrahold 8,N-叔丁基丙烯酰胺、丙烯酸乙酯和丙烯酸的粉状三元共聚物0.23%重量的AMP52.50%重量的无水乙醇39.77%重量的蒸馏水
               实施例95%重量的聚乙烯基己内酰胺溶液2.5%重量的Amphomer,烷基丙烯酸酰胺/丙烯酸酯共聚物0.41%重量的AMP52.50%重量的无水乙醇39.59%重量的蒸馏水
               实施例106.8%重量的聚乙烯基己内酰胺溶液3.4%重量的Acronal 500D,50%重量浓度的丙烯酸酯/乙酸乙烯酯共聚物的一种阴离子共聚物水分散剂89.8%重量的蒸馏水
        表1
试验序号     外观溶液    在玻璃 被处理的发丝 20℃,80%相对湿度下,5%重量浓
板上的膜 变硬    洗去效果    能力 度时溶液的粘性
  2   透明      透明 很好    好   1
  3   透明      透明 很好    好   1
  4   不透明    透明 很好    好   1
  5   透明      透明 很好    好   1
  6   透明      透明 很好    好   1
  7   透明      透明 很好    好   1
  8   透明      透明 很好    好   1
  9   透明      几呼透明 很好    好   1
  10   乳色      几呼透明 很好    仍好   1
实施例115%重量的聚乙烯基己内酰胺溶液2.5%重量的Luvimer100p0.58%重量的AMP52.50%重量的乙醇39.42%重量的丙烷与丁烷50∶50的混合物
实施例125%重量的聚乙烯基己内酰胺2.5%重量的Ultrahold 8溶液2.5%重量的AMP37.27%重量的乙醇60%重量的丙烷、丁烷、和n-戊烷30∶50∶20的混合物

Claims (8)

1.一种头发定型剂,包括
A)0.5-20%重量的N-乙烯基己内酰胺均聚物或至少70%重量的N-乙烯基己内酰胺的阴离子或非离子共聚物(聚合物A),该聚合物A的单体选自具有酸功能的单体、(甲基)丙烯酸C1-C18烷基酯类和(甲基)丙烯酸羟烷基酯类、C2-C20脂肪酸的乙烯酯类和较长链和/或支链脂肪酸的乙烯酯类、C3-C8N-烷基(甲基)丙烯酰胺类、N-乙烯基吡咯烷酮和N-乙烯基哌啶酮,和
B)0.5-20%重量的后成膜聚合物(聚合物B),该聚合物B选自:聚酰胺类、聚氨酯类和单烯基类不饱和的单体的均聚合物和共聚合物。
2.如权利要求1所述的头发定型剂,其中所述具有酸功能的单体为丙烯酸、甲基丙烯酸、丙烯酰氨基甲丙基磺酸、(甲基)丙烯酸3-磺丙基酯。
3.如权利要求1所述的头发定型剂,其中所述(甲基)丙烯酸C1-C18烷基酯为丙烯酸叔丁酯、丙烯酸乙酯、甲基丙烯酸异丁酯、甲基丙烯酸正丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯。
4.如权利要求1所述的头发定型剂,其中所述C2-C20脂肪酸的乙烯酯为乙酸乙烯酯、丙酸乙烯酯。
5.如权利要求1所述的头发定型剂,其中所述C3-C8N-烷基(甲基)丙烯酰胺为甲基丙烯酰胺、N,N-二甲基丙烯酰胺、N-叔丁基丙烯酰胺和N-叔辛基丙烯酰胺。
6.如权利要求1所述的头发定型剂,其中,所用的聚合物A是N-乙烯基已内酰胺的一种均聚物。
7.如权利要求1或6所述的头发定型剂,其中,聚合物A的用量为1-10%重量。
8.如权利要求7所述的头发定型剂,含有醇和低级烷烃类。
CN96105533A 1995-03-27 1996-03-27 头发定型剂 Expired - Fee Related CN1100525C (zh)

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