CN1293215A - 含硅氧烷的聚合物、它们的制备方法和用途 - Google Patents
含硅氧烷的聚合物、它们的制备方法和用途 Download PDFInfo
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- CN1293215A CN1293215A CN00126341A CN00126341A CN1293215A CN 1293215 A CN1293215 A CN 1293215A CN 00126341 A CN00126341 A CN 00126341A CN 00126341 A CN00126341 A CN 00126341A CN 1293215 A CN1293215 A CN 1293215A
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- polymkeric substance
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- iee
- methyl
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- 238000002360 preparation method Methods 0.000 title claims description 30
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- 125000001931 aliphatic group Chemical group 0.000 claims description 2
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- UNBDCVXGGDKSCP-UHFFFAOYSA-N methyl 2-methylidenetetradecanoate Chemical compound CCCCCCCCCCCCC(=C)C(=O)OC UNBDCVXGGDKSCP-UHFFFAOYSA-N 0.000 claims 1
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Abstract
本发明涉及一种水溶性或可再分散性聚合物,可通过在至少一种含聚烯化氧的硅氧烷衍生物B存在下,由烯属不饱和单体A的自由基聚合反应而获得,其中下面表示聚合物的离子交换剂当量IEEE和K值的乘积,K值×IEE≥150mmolg-1且IEE>2.7mmolg-1,且其中IEE是基于羧酸基团或羧酸酯基团,涉及所述聚合物的制备方法,并涉及作为美容用制剂、皮肤科制剂、卫生保健用制剂和/或药物制剂的添加剂的用途。
Description
本发明涉及含硅氧烷的聚合物、它们的制备方法和它们的用途,也涉及包含这些聚合物的美容用制剂、皮肤科制剂、卫生保健用制剂和/或药物制剂。
作为美容、皮肤科、卫生保健和/或药物配方用成膜剂,具有成膜性能的聚合物被用于化妆品中,且特别适合用作美发和护肤用品的添加剂。
在皮肤用化妆品或皮肤科制剂中,本发明的聚合物能够表现出特殊的活性。所述聚合物特别能够有助于水分保持和皮肤调理并能够改进肤感。于是皮肤变得更光滑、更柔软。
聚合物优选被用于固定、成形和改善头发的结构。它们提高了可梳理性并改进了发感。这些滋发剂组合物一般包含成膜剂在醇或醇与水的混合物中所形成的溶液。
对于滋发剂组合物的要求是,它们特别能够赋予头发光泽、柔韧性和自然愉快的感觉。
已知的是使用乙烯基内酰胺均聚物和共聚物或含羧酸酯的聚合物。所需的性能型式例如在高的空气湿度下的强保持性、弹性、从头发中的洗净性能和与其它配制组分的相容性,通过疏水性、弹性化、含羧基单体混合物的共聚合反应而实现。
然而,使用这些聚合物固定发型的感觉是不合意地粗糙和不自然。虽然柔软剂的加入改进了此类发型的感觉,但是这也降低了定型作用。
通常使用聚硅氧烷,虽然这些与极性聚合物是不相容的,且经常需要另外的添加剂以便它们能够真正被配制出来。
在配方贮存过程中和在使用过程中,分离都会产生一些问题。
EP-A 670342描述了烷氧基化的硅氧烷在护发组合物中的用途。但没有公开包含不饱和化合物的聚合物在护发组合物中的用途。虽然烷氧基化硅氧烷作为添加剂用于可商购头发定型聚合物确实改善了其感觉,但是这也导致降低的定型作用。
欧洲专利EP-A 412704和EP-A 412707描述了呈摩尔质量为1000~50,000的大单体形式的聚硅氧烷类,其与常规疏水性和亲水性单体聚合。这些单体的合成是非常复杂的。由于它们的高分子量,从聚合物中分离出未反应大单体和未反应杂质实际上是不可能的。这些表示毒性和过敏性的风险。而且,为了获得良好的作用,所得共聚物通常必须仅与其它聚合物、载体和其它助剂一起配制,如上述专利所教导。
DE-A 19731529描述了硅氧烷表面活性剂/丙烯酸酯共聚物。其中所述的实施例显示出对于反应混合物中具有游离羧酸酯基团的单体的比例的限制。
EP-A 614924描述了硅氧烷大单体的共聚物。然而,在合成过程中硅氧烷大单体与其它单体的不足相容性导致不需要的凝聚。
DE-A 2917504和EP-A 832638描述了具有高比例羧酸酯基团的聚合物。在此类聚合物的情况中,醇/烃防护剂中的溶解度大大降低。
由现有技术中已知的在乳液法中由烯属不饱和单体制备共聚物的方法具有许多缺点。例如设定高分子量(例如特征在于>50的K值)的尝试导致乳液的凝聚。聚合反应不得不终止,而无法获得所需的产物。
即使在具有低HLB值的硅氧烷存在下进行聚合反应也导致轻微的凝聚;同样,在硅氧烷存在下,相对大量的烯属不饱和羧酸(一般是丙烯酸、甲基丙烯酸和丁烯酸,其量应当使得所得聚合物的IEE大于4mmol g-1)被用于聚合反应。
因此本发明的目的是提供没有所述缺点的用于美容、卫生保健和/或药物配方的新型聚合物。本发明的聚合物是成膜的、可溶的和非粘性的,且根据应用,产生低表面粗糙度或高平滑度的感官印象,以便在同时存在的水中可溶性或可再分散性和醇/烃防护剂中的可溶性的情况下,它们能够被理想地用于美容、皮肤科、卫生保健和/或药物配方中。
为了制备所述聚合物,使用一种经济的方法,其不会导致无用的副产物(例如乳液聚合反应情况下的凝结物)的形成。
对于美发配方,其目的也是提供一种聚合物,由其能够获得良好的可梳理性、强的保持力和良好的感觉。
令人惊奇的是,我们已经发现通过一种水溶性或可再分散性聚合物可实现该目的,所述聚合物可通过在具有轻微亲水特性的含烯化氧的硅氧烷衍生物B存在下,由烯属不饱和单体A的自由基聚合反应而获得,其中下面表示聚合物的离子交换剂当量IEE和K值的乘积,K值×IEE≥150mmol g-1且IEE>2.7mmol g-1,且其中IEE是基于羧酸基团或羧酸酯基团。单体A优选由烯属不饱和单体M和具有游离羧酸酯基团的烯属不饱和单体C构成。
在化妆品配方中,本发明聚合物的理想性能导致成膜、水溶性、可溶于常规推进剂/乙醇混合物、非粘性和非常平滑的性能的所需结合(根据应用)。这些性能对于由现有技术的IEE≥3.5mmol g-1的聚合物特别是对于美发用品来说不是已知的,且无法预期,因为与梳型接枝共聚物(在含烯化氧的硅氧烷衍生物B存在下,通过烯属不饱和单体A的聚合反应形成)相比,更期望线性聚合物(其容易地形成联锁网络)具有由于高机械强度的强保持力。另外,对于本领域熟练人员来说,由于上面特征K值获得的高分子量与良好的可梳理性不一致。而且一般地,羧酸酯基团的浓度增加。在聚合物中,尽管产生更高的力学刚性,却导致较低的机械强度。就此而论,本发明的高比例羧酸酯基团和高分子量的结合对于头发定型配方来说无法预期任何使用优势。
如果在聚合反应过程中不存在硅氧烷衍生物B,而在聚合反应后混合,则通常获得非常柔软的粘性膜,其不适于本发明在皮肤和头发化妆品方面的用途。这表明在聚合反应过程中,能够发生聚合物在硅氧烷化合物上的可能接枝,有助于良好的膜性能,例如没有粘性、高的表面平滑度和硬度。然而,除了接枝外的机理是可想像的,借助于此,本发明的聚合物能够实现它们的理想性能。
本发明也涉及本发明聚合物作为添加剂在美容用制剂、皮肤科制剂、卫生保健用制剂和/或药物制剂中的用途,并涉及包含本发明聚合物的美容用制剂、皮肤科制剂、卫生保健用制剂和/或药物制剂,其制备根据本领域熟练人员熟知的常规方法进行。
术语“离子交换剂当量”(缩写为IEE)这里指的是聚合物中离子基团的含量。例如,纯的聚甲基丙烯酸的IEE是10mmol g-1。
对于本发明来说,“可再分散性”聚合物是通过与水接触在有限时间段内(使得任何固体颗粒在没有光学设备的情况下无法用肉眼检测出来)形成流体的那些。为了检查聚合物是否可再分散于水中,将呈100μm厚的膜形式的100mg聚合物加入到100ml水中(20℃),并在可商购摇床上摇动24小时。摇动后,如果不再能够感觉到固体颗粒,而流体仍然混浊,则聚合物是可再分散于水中的;如果不存在混浊,则将其称为水溶性的。
HLB值是主要地非离子表面活性剂的水溶性或油溶性的量度。具有HLB<10的物质基本上是良好的W/O乳化剂,而具有较高HLB值的物质是O/W乳化剂。具有HLB值小于10~13的物质在水中不会形成透明溶液。实验测定HLB值的方法描述于Kirk-Othmer,Encyclopedia of Chemical Technology,第三版,Wiley_纽约1965年,第8卷,第132页。
本发明的聚合物优选具有K值(也称为Fikentscher常数,参见H.-G.Elias,Makromoleküle[Macromolecules],vol.1,Hüthig &Wepf,Heidelberg 1990,p.98以及下列等等)大于45,通过乙醇中聚合物的溶液浓度为0.5~10wt%、优选0.5~1.5wt%时测定(T=23℃)。
合适的可聚合单体A优选是具有下面特征的聚合物:聚合物的K值≥45,聚合物的IEE≥3.5mmol g-1,且视具体情况而定硅氧烷的HLB≤13。本发明的聚合物也是下面要求的那些:
IEE×K值≥l50mmol g-1且特别是
IEE×K值/HLB值≥12mmol g-1。
特别优选的是下面要求的聚合物:聚合物的K值≥50,聚合物的IEE≥6mmol g-1。
本发明优选通过在B存在下聚合M和C的混合物而进行,其中下面表示相对的质量比例(基于M、C和B的总量):
M:≤56wt%
C:≥40wt%
B:≥4wt%
特别地,使用下面的相对质量比例:
M:30-50wt%
C:45-70wt%
B:4-15wt%
在本发明特别优选的实施方案中,在含聚烯化氧的硅氧烷衍生物存在下,(甲基)丙烯酸酯在丙烯酸、甲基丙烯酸或丁烯酸存在下用乳液方法聚合。
单体M(作为均聚物具有玻璃化转变温度<25℃)的使用,特别是丙烯酸乙酯、丙烯酸甲酯、丙烯酸羟乙酯、丙烯酸正丁酯和丙烯酸十二烷基酯的使用,已经证明是特别理想的。如果使用该类型的(甲基)丙烯酸酯M,则能够在实际上没有凝聚的情况下获得其中C≥45wt%的共聚物。
合适的可聚合单体M和C优选是烯属不饱和单体。就此而论,可能使用或是单一的单体或是两种或多种单体的混合物。术语“可聚合的”指的是能够使用任何惯用合成方法聚合所用单体。
例如,其能够是溶液聚合、乳液聚合、反乳液聚合、悬浮聚合、反悬浮聚合或沉淀聚合,在不限制能够用于这些的方法的情况下。在溶液聚合中,可能使用水、常规有机溶剂或本身用作溶剂的本发明的硅氧烷衍生物。然而乳液方法是优选的。
能够通过由自由基引发的反应而聚合的单体是优选的。术语“烯属不饱和”指的是具有至少一个可聚合碳-碳双键的单体,其可以被单、二、三或四取代。
优选的烯属不饱和单体能够由下式描述:
X-C(O)CR7=CHR6其中X选自于-OH、-OM、-OR8、-NH2、-NHR8、N(R8)2;
M是选自于Na+、K+、Mg++、Ca++、Zn++、NH4 +、烷基铵、二烷基铵、三烷基铵和四烷基铵的阳离子;
基团R8可以相同或不同,并选自于-H、C1-C40线性或支化链烷基、N,N-二甲基氨基乙基、2-羟基乙基、2-甲氧基乙基、2-乙氧基乙基、羟基丙基、甲氧基丙基或乙氧基丙基;
R7和R6相互独立地选自于:-H、C1-C8线性或支化链烷基链、甲氧基、乙氧基、2-羟基乙氧基、2-甲氧基乙氧基和2-乙氧基乙基。
合适单体的代表性而非限制性的例子例如是,丙烯酸及其盐类、酯类和酰胺类。所述盐类能够由任何无毒金属、铵或取代的铵平衡离子得到。
所述酯类能够由C1-C40线性、C3-C40支化链或C3-C40碳环醇类得到,由具有2~约8个羟基的多官能醇类例如乙二醇、己二醇、甘油和1,2,6-己烷三醇得到,由氨基醇类或由醇醚类例如甲氧基乙醇和乙氧基乙醇或聚乙二醇得到。
R9是H,具有1~8个碳原子的烷基,
R10是H、甲基,
R11是具有1~24个碳原子的亚烷基,视具体情况而定被烷基取代,
R12、R13是C1-C40烷基,和
当x=1时,Z是氮,或当x=0时,Z是氧。
酰胺类能够是未取代的、N-烷基或N-烷基氨基单取代的、或N,N-二烷基取代的或N,N-二烷基氨基二取代的,其中烷基或烷基氨基由C1-C40线性、C3-C40支化链或C3-C40碳环单元得到。另外,烷基氨基能够被季化。
式Ⅱ的优选单体是N,N-二甲基氨基甲基(甲基)丙烯酸酯、N,N-二乙基氨基甲基(甲基)丙烯酸酯、N,N-二甲基氨基乙基(甲基)丙烯酸酯、N,N-二乙基氨基乙基(甲基)丙烯酸酯。
能够使用的其它单体是取代的丙烯酸类及其盐类、酯类和酰胺类,其中碳原子上的取代基是在丙烯酸的二位置或三位置,且相互独立地选自于C1-C4烷基、-CN、COOH,特别优选甲基丙烯酸、乙基丙烯酸和3-氰基丙烯酸。这些取代的丙烯酸的这些盐类、酯类、酰胺类能够选自于如上所述的丙烯酸的盐类、酯类和酰胺类。
其它合适的单体是C1-C40线性、C3-C40支化链或C3-C40碳环羧酸的乙烯基和烯丙基酯类(例如乙酸乙烯酯、丙酸乙烯酯、新壬酸乙烯酯、新十一烷酸乙烯酯或叔丁基苯甲酸乙烯酯);乙烯基或烯丙基卤化物优选氯乙烯和烯丙基氯,乙烯基醚类,优选甲基、乙基、丁基或十二烷基乙烯基醚,乙烯基甲酰胺,乙烯基甲基乙酰胺,乙烯基胺;乙烯基内酰胺,优选乙烯基吡咯烷酮和乙烯基己内酰胺,乙烯基或烯丙基取代的杂环化合物,优选乙烯基吡啶、乙烯基噁唑啉和烯丙基吡啶。
也合适的是式Ⅲ的N-乙烯基咪唑,其中R14~R16相互独立地是氢、C1-C4烷基或苯基:
还合适的单体(a)是式(Ⅳ)的二烯丙基胺:其中R17是C1~C24烷基。
其它合适的单体是1,1-二氯乙烯;和具有至少一个碳-碳双键的烃类,优选苯乙烯、α-甲基苯乙烯、叔丁基苯乙烯、丁二烯、异戊二烯、环己二烯、乙烯、丙烯、1-丁烯、2-丁烯、异丁烯、乙烯基甲苯和这些单体的混合物。
特别合适的单体是丙烯酸、甲基丙烯酸、乙基丙烯酸、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸叔丁酯、丙烯酸2-乙基己基酯、丙烯酸癸酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸2-乙基己基酯、甲基丙烯酸癸酯、乙基丙烯酸甲酯、乙基丙烯酸乙酯、乙基丙烯酸正丁酯、乙基丙烯酸异丁酯、乙基丙烯酸叔丁酯、乙基丙烯酸2-乙基己基酯、乙基丙烯酸癸酯、2,3-二羟基丙基丙烯酸酯、2,3-二羟基丙基甲基丙烯酸酯、2-羟基乙基丙烯酸酯、羟基丙基丙烯酸酯类、2-羟基乙基甲基丙烯酸酯、2-羟基乙基乙基丙烯酸酯、2-甲氧基乙基丙烯酸酯、2-甲氧基乙基甲基丙烯酸酯、2-甲氧基乙基乙基丙烯酸酯、2-乙氧基乙基甲基丙烯酸酯、2-乙氧基乙基乙基丙烯酸酯、羟基丙基甲基丙烯酸酯类、一丙烯酸甘油酯、一甲基丙烯酸甘油酯、聚(甲基)丙烯酸亚烷基二醇酯,不饱和的磺酸例如丙烯酰氨基丙烷磺酸;丙烯酰胺,甲基丙烯酰胺,乙基丙烯酰胺、N-甲基丙烯酰胺、N,N-二甲基丙烯酰胺、N-乙基丙烯酰胺、N-异丙基丙烯酰胺、N-丁基丙烯酰胺、N-叔丁基丙烯酰胺、N-辛基丙烯酰胺、N-叔辛基丙烯酰胺、N-十八烷基丙烯酰胺、N-苯基丙烯酰胺、N-甲基甲基丙烯酰胺、N-乙基甲基丙烯酰胺、N-十二烷基甲基丙烯酰胺、1-乙烯基咪唑、1-乙烯基-2-甲基咪唑、N,N-二甲基氨基甲基(甲基)丙烯酸酯、N,N-二乙基氨基甲基(甲基)丙烯酸酯、N,N-二甲基氨基乙基(甲基)丙烯酸酯、N,N-二乙基氨基乙基(甲基)丙烯酸酯、N,N-二甲基氨基丁基(甲基)丙烯酸酯、N,N-二乙基氨基丁基(甲基)丙烯酸酯、N,N-二甲基氨基己基(甲基)丙烯酸酯、N,N-二甲基氨基辛基(甲基)丙烯酸酯、N,N-二甲基氨基十二烷基(甲基)丙烯酸酯、N-[3-(二甲基氨基)丙基]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)丁基]甲基丙烯酰胺、N-[8-(二甲基氨基)辛基]甲基丙烯酰胺、N-[12-(二甲基氨基)十二烷基]甲基丙烯酰胺、N-[3-(二乙基氨基)丙基]甲基丙烯酰胺、N-[3-(二乙基氨基)丙基]丙烯酰胺;马来酸、富马酸、马来酸酐及其一酯,巴豆酸,衣康酸,二烯丙基二甲基氯化铵,乙烯基醚类(例如甲基、乙基、丁基或十二烷基乙烯基醚),乙烯基甲酰胺,乙烯基甲基乙酰胺,乙烯基胺;甲基乙烯基酮,马来酰亚胺,乙烯基吡啶,乙烯基咪唑,乙烯基呋喃,苯乙烯,苯乙烯磺酸盐,烯丙基醇,和它们的混合物。
这些之中,特别优选的是丙烯酸、甲基丙烯酸、马来酸、富马酸、巴豆酸、马来酸酐和其一酯、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸叔丁酯、甲基丙烯酸叔丁酯、丙烯酸异丁酯、甲基丙烯酸异丁酯、丙烯酸2-乙基己基酯、N-叔丁基丙烯酰胺、N-辛基丙烯酰胺、丙烯酸2-羟基乙基酯、丙烯酸羟基丙基酯、甲基丙烯酸2-羟基乙基酯、甲基丙烯酸羟基丙基酯、(甲基)丙烯酸亚烷基二醇酯、不饱和磺酸例如丙烯酰氨基丙烷磺酸、乙烯基吡咯烷酮、乙烯基己内酰胺、乙烯基醚(例如甲基、乙基、丁基或十二烷基乙烯基醚)、乙烯基甲酰胺、乙烯基甲基乙酰胺、乙烯基胺、1-乙烯基咪唑、1-乙烯基-2-甲基咪唑、N,N-二甲基氨基甲基甲基丙烯酸酯和N-[3-(二甲基氨基)丙基]甲基丙烯酰胺;氯化3-甲基-1-乙烯基咪唑鎓盐、甲基硫酸3-甲基-1-乙烯基咪唑鎓盐、N,N-二甲基氨基乙基甲基丙烯酸酯、用氯代甲烷、硫酸甲酯或硫酸二乙酯季化的N-[3-(二甲基氨基)丙基]甲基丙烯酰胺。
含有碱性氮原子的单体能够以下面方式被季化:对于季化胺类,例如烷基中具有1~24个碳原子的烷基卤是合适的,例如氯代甲烷、溴代甲烷、碘代甲烷、氯代乙烷、溴代乙烷、氯代丙烷、氯代己烷、氯代十二烷、月桂基氯和苄基卤,特别是苄基氯和苄基溴。其它合适的季化试剂是硫酸二烷基酯,特别是硫酸二甲酯或硫酸二乙酯。碱性胺类的季化也能够用烯化氧例如环氧乙烷或环氧丙烷在酸存在下进行。优选的季化试剂是:氯代甲烷、硫酸二甲酯或硫酸二乙酯。
其例子是:(甲基)丙烯酰氧基羟基丙基三甲基氯化铵和(甲基)丙烯酰氧基羟基丙基三乙基氯化铵。
碱性单体也能够通过用无机酸或有机酸中和它们而被阳离子化,所述无机酸例如是硫酸、盐酸、氢溴酸、氢碘酸、磷酸或硝酸,所述有机酸例如是甲酸、乙酸、乳酸或柠檬酸。
除了上述单体,也可能使用作为单体的所谓大单体,例如含有一个或多个可自由基聚合的基团的含硅氧烷大单体,或如例如在EP408311中所述的烷基噁唑啉大单体。
另外,也可能使用如例如在EP 558423中所述的含氟单体,或结合或单独使用的具有交联作用或调节分子量的化合物。
能够使用的调节剂是本领域熟练人员已知的惯用化合物,例如硫化合物(例如巯基乙醇、2-乙基己基巯基乙酸酯、巯基乙酸或十二烷基硫醇)和三溴氯代甲烷或对所得聚合物的分子量具有调节作用的其它化合物。如果合适,也可能使用含硫醇的硅氧烷化合物。优选使用无硅氧烷调节剂。
能够使用的交联单体是具有至少两个烯属不饱和双键的化合物,例如烯属不饱和羧酸如丙烯酸或甲基丙烯酸的酯类,和多羟基醇类,至少二羟基醇类的醚例如乙烯基醚或烯丙基醚。也合适的是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类,其中在脂族烃类的情况下,必须不是共轭的。也合适的是丙烯酸和甲基丙烯酸的酰胺类和至少双官能胺类的N-烯丙基胺例如1,2-二氨基乙烷和1,3-二氨基丙烷。也合适的是三烯丙基胺或相应的铵盐,脲衍生物的N-乙烯基化合物,至少双官能的酰胺类,氰尿酸酯或氨基甲酸酯类。其它合适的交联剂是二乙烯基二氧杂环己烷、四烯丙基硅烷或四乙烯基硅烷。
特别优选的交联剂例如是亚甲基双丙烯酰胺、三烯丙基胺和三烯丙基铵盐、二乙烯基咪唑、N,N′-二乙烯基亚乙基脲、多羟基醇类与丙烯酸或甲基丙烯酸的反应产物,聚烯化氧或已与环氧乙烷和/或环氧丙烷和/或表氯醇反应的多羟基醇的甲基丙烯酸酯类和丙烯酸酯类。
合适的硅氧烷衍生物B特别是以硅氧烷表面活性剂或以INCI名Dimethicone Copolyols或Dimethicone Copolyol Acetates已知的化合物。合适的硅氧烷衍生物B包括CAS号为64365-23-7;67762-85-0;68440-66-4;68554-65-4;68937-54-2;68937-55-3;68938-54-5;71965-38-3的化合物。这些可例如以商标名AbilTM(T.Goldschmidt)、AlkasilTM(Rh_ne-Puolenc)、Silicone PolyolCopolymerTM(Genesee)、BelsilTM(Wacker)、SilwetTM和SilsoftTM(Witco)或Dow Corning Silicones DC(Dow Corning)得到。
R6是具有1~40个碳原子的有机基团,其能够含有氨基、羧酸或磺酸酯基团,或对于c=0,也是无机酸的阴离子,
且其中基团R1可以相同或不同,或是来自于具有1~20个碳原子的脂族烃,或是具有3~20个碳原子的环脂族烃,具有芳香特性或等于R5,其中:
条件是基团R1、R2或R3中的至少一个是根据上述定义的含聚烯化氧的基团,
n是1~6的整数,
x和y是使得聚硅氧烷嵌段的分子量介于150~30,000g/mol的整数,
a、b能够是0~50之间的整数,条件是a+b之和大于0,且c是0或1。
优选的基团R2和R5是其中a+b之和介于5~30之间的那些。
基团R1优选选自于下面的基团:甲基、乙基、丙基、丁基、异丁基、戊基、异戊基、己基、辛基、癸基、十二烷基和十八烷基,环脂族基团特别是环己基,芳香基团特别是苯基或萘基,混合的芳香-脂族基团例如苄基或苯基乙基,和甲苯基和二甲苯基和R5。
特别合适的基团R4是其中R4=-(CO)c-R6的那些,其中R6是具有1~40个碳原子并能够带有另外的可离子化基团例如NH2、COOH、SO3H的任何烷基、环烷基或芳基。
优选的无机基团R6是当c=0时的磷酸酯和硫酸酯基团。
就此而论,特别优选的是在基团R5上具有作为端基R4的氢、正丁基、甲基或乙酰基且其中R1是甲基的那些化合物。
在单体A的聚合反应过程中,如果合适,也可能存在其它聚合物,例如聚酰胺类、聚氨酯类、聚酯类、烯属不饱和单体的均聚物和共聚物。
此类聚合物(其中一些也被用于化妆品中)的例子是以商标名AmerholdTM、UltraholdTM、Ultrahold StrongTM、LuviflexTM VBM、LuvimerTM、AcronalTM、AcudyneTM、StepanholdTM、LovocrylTM、VersatylTM、AmphomerTM或Eastman AQTM已知的聚合物。
按照聚合反应,也可能向本发明的聚合物制剂中加入其它聚合物,如果本发明要设定特殊的性能的话。
适合于此目的的惯用聚合物例如是阴离子、阳离子、两性或中性聚合物。
阴离子聚合物的例子是丙烯酸和丙烯酰胺及其盐的均聚物和共聚物,多羟基羧酸的钠盐,水溶性或水分散性聚酯,聚氨酯和聚脲。特别合适的聚合物是丙烯酸叔丁酯、丙烯酸乙酯、甲基丙烯酸的共聚物(例如LuvimerTM 100 P),丙烯酸乙酯和甲基丙烯酸的共聚物(例如LuvimerTM MAE),N-叔丁基丙烯酰胺、丙烯酸乙酯、丙烯酸的共聚物(例如Ultrahold StrongTM),乙酸乙烯酯、丁烯酸和如果合适另外的乙烯基酯类的共聚物(例如Luviset CA66TM、Luviset CAPTM级),马来酸酐共聚物,视具体情况而定与醇类、阴离子聚硅氧烷反应,例如乙烯基吡咯烷酮、丙烯酸叔丁酯、甲基丙烯酸的羧基官能化共聚物(例如LuviskolTM VBM),丙烯酸和甲基丙烯酸与疏水性单体例如(甲基)丙烯酸的C4-C30烷基酯类、C4-C30烷基乙烯基酯类、C4-C30烷基乙烯基醚类和透明质酸的共聚物,和以商标名AmerholdTM、UltraholdTM、LuviflexTM VBM 35、LuvisetTM P.U.R.、AcronalTM、AcudyneTM、StepanholdTM、LovocrylTM、VersatylTM、AmphomerTM(28-4910,LV-71,HC 28-4942)、PlaciseTM L53、GantrezTM ES 425、Advantage PlusTM(CP,V)、OmnirezTM 2000、ResynTM 28-1310、ResynTM 28-2930、BalanceTM(0/55,47)、AcudyneTM 255、AristoflexTM或Eastman AQTM已知的其它聚合物。
其它合适的聚合物是具有INCI名为Polyquaternium的阳离子聚合物,例如乙烯基吡咯烷酮/N-乙烯基咪唑鎓盐的共聚物(LuviquatTMFC、LuviquatTM HM、LuviquatTM MS、LuviquatTM Care),用硫酸二乙酯季化的N-乙烯基吡咯烷酮/二甲基氨基乙基甲基丙烯酸酯的共聚物(LuviquatTM 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(LuviquatTM Hold);阳离子纤维素衍生物(Polyquaternium-4和-10),丙烯酰胺共聚物(Polyquaternium-[lacuna]),StyleezeTM CC-10,AquaflexTM SF-40和脱乙酰壳多糖衍生物。
其它合适的聚合物也是中性聚合物,例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,聚乙烯基己内酰胺和与N-乙烯基吡咯烷酮的共聚物,聚乙烯亚胺及其盐类,聚乙烯基胺类及其盐类,纤维素衍生物,聚天冬氨酸盐类和衍生物。这些包括以商标名LuviskolTM(K、VA、Plus)、PVP K、PVP/VA AdvantageTM HC和H2Old EP-1已知的聚合物。
另外,也合适的是生物聚合物,即由天然可再生原料获得并由天然单体结构单元构成的聚合物,例如纤维素衍生物,和壳多糖、脱乙酰壳多糖、DANN、透明质酸和RNA的衍生物。
其它聚合物也是betainic聚合物,例如yukaformers(R205,SM)和diaformers。
本发明的单体C能够使用酸或碱在聚合反应之前或之后被部分或完全中和,以便例如将水中溶解度或分散能力调节到所需水平。
能够使用的用于带有酸性基团的单体的中和试剂例如是无机碱类,诸如碳酸钠、碱金属氢氧化物和氨,有机碱类,诸如氨基醇类,特别是2-氨基-2-甲基-1-丙醇、单乙醇胺、二乙醇胺、三乙醇胺、三异丙醇胺、三[(2-羟基)-1-丙基]胺、2-氨基-2-甲基-1,3-丙二醇、2-氨基-2-羟基甲基-1,3-丙二醇,和二胺类,诸如赖氨酸。
能够使用的用于带有可阳离子化基团的单体的中和试剂例如是,无机酸类,诸如盐酸、硫酸或磷酸,和有机酸类,诸如羧酸、乳酸、柠檬酸等等。
也可能存在助剂,例如柔软剂、成膜助剂、颜料、香料、增稠剂、表面活性剂、防腐剂、美容活性成分,例如植烷三醇、维生素和维生素原,例如维生素A、E和C,维生素A醇,红没药醇,泛醇,天然和合成防晒剂,天然物质,推进剂,增溶剂,防护剂,漂白剂,着色剂,调色剂,鞣剂,反射剂,蛋白质,神经酰胺,AHA酸,果酸,骨胶原,蛋白质水解产物,稳定剂,pH调节剂,乳化剂,胶凝剂,增稠剂,硅氧烷,保湿剂,加脂剂或其它惯用添加剂,它们单独或结合使用,在聚合反应过程中存在和/或在聚合反应之后加入。
另外,也可能使用抗菌剂。这些一般包括具有抗革兰氏阳性菌的特殊作用的所有合适的防腐剂,例如三氯羟基二苯醚(2,4,4'-三氯-2'-羟基二苯醚)、双氯苯双胍己烷(1,1'-六亚甲基双[5-(4-氯苯基)]双胍)和TTC(3,4,4′-三氯对称二苯脲)。季铵化合物一般也是合适的,但是其被优选用于消毒皂和洗液。大量的日用香料也具有抗菌性能。具有抗革兰氏阳性菌的特殊功效的特定结合物被用于所谓祛臭香料的组合物。同时,大量的芳香油或其特性成分例如丁子香油(丁子香酚)、薄荷油(薄荷醇)或百里香油(百里酚),表现出显著的抗菌功效。
使用抗菌活性物质的浓度是约0.1-0.3wt%。
本发明还涉及包含本发明聚合物的美容、皮肤科、卫生保健和/或药物组合物。本发明的聚合物优选用作或用于角质表面例如头发、皮肤和指甲的涂饰剂。
如果本发明的聚合物被用于美发用品中,特别是在用作定型剂的情况中,则理想的是通过烯属不饱和单体的适当结合将聚合物的玻璃化转变温度调节到大于20℃的数值。
特别合适的单体是水溶性或其水分散能力足够大到它们可溶于50∶50(vol%∶vol%)水∶乙醇溶剂混合物中(其量大于0.1g/l、优选大于0.2g/l)的那些。
如果聚合物由带有可中和基团的单体构成,则优选以中和形式可溶于50∶50(vol%∶vol%)水∶乙醇溶剂混合物中(其量大于0.1g/l、优选大于0.2g/l)的聚合物。
本发明的聚合物例如被用于化妆品组合物中,以清洗皮肤。此类化妆品清洗组合物选自于皂条,例如香皂、酪状皂、透明皂、高级香皂、祛臭皂、乳脂皂、婴儿皂、护肤皂、擦洗皂和合成洗涤剂,液体皂,例如膏状皂、软皂和洗涤膏,和液体洗涤剂,浴室用品,例如洗涤膏,淋浴用品和凝胶,泡沫浴,浴油和擦洗用品,剃须泡沫体,洗液,洗膏。
它们特别适合于美发用品,优选用于制剂中,例如滋发剂、美发乳、护发素、发乳、防末端分叉液、长效卷发剂的中和剂、锔油处理剂、调理剂、定型液、香波、染发剂或发胶,处理头皮屑和脱发的组合物,和用于生发组合物中。
护肤组合物特别呈W/O或O/W护肤膏、日妆和晚妆霜、眼霜、面霜、抗皱霜、保湿霜、漂白霜、维生素霜剂、护肤液、保养液和保温液、润手香脂和护肤膏、软膏和防晒霜的形式。
取决于应用领域,美容用制剂、卫生保健用制剂、皮肤科制剂和/或药物制剂能够被用作喷洒剂(泵喷剂或气雾剂)、泡沫体、凝胶、凝胶喷雾剂、露或摩丝。
它们也适合于肤用化妆品制剂,例如润面露、面膜、祛臭剂和其它化妆液,且适合用于美饰化妆品,例如用作遮盖棒、舞台彩妆品,用于睫毛油和眼影膏,口红,眼圈墨笔、眼线膏、胭脂和底粉和画眉笔,也用作漱口剂、牙膏或用于皮肤药用制剂。
另外,本发明的聚合物能够用作鼻用条物,用于清洗鼻孔,用于防痤疮组合物、防护剂、剃须用组合物、脱毛剂、个人保健用组合物、护脚组合物和用于婴儿护肤用品。
本发明的聚合物也适合用作药用助剂,优选用作或用于固体药物形式的覆盖层或粘合剂。它们也能够被用于膏剂和用作片剂覆盖层和片剂粘合剂。
本发明的共聚物在美容用制剂、皮肤科制剂、卫生保健用制剂和/或药物制剂中存在的量是基于组合物总重量的约0.001~20wt%,优选0.1~10wt%。
能够特别提及的合适的溶剂是水和低级一元醇类或具有1~6个碳原子的多元醇类及其混合物;优选的一元醇类或多元醇类是乙醇、异丙醇、丙二醇、甘油和山梨糖醇。
可以存在的其它惯用添加剂是脂类物质,例如矿物油和合成油,诸如烷属烃、硅油和具有多于8个碳原子的脂族烃类,动物和植物油类,诸如葵花油、椰子油、鳄梨油、橄榄油、羊毛脂,或蜡,脂肪酸,脂肪酸酯,诸如C6-C30脂肪酸的三甘油酯,蜡酯,诸如西蒙得木油,脂肪醇类,凡士林,氢化羊毛脂。当然也可能使用它们的混合物。
此类配方中的惯用增稠剂是交联的聚丙烯酸类及其衍生物,多糖,例如黄原胶、琼脂、藻酸盐或纤基乙酸钠,纤维素衍生物,例如羧甲基纤维素或羟基羧甲基纤维素,脂肪醇类,单酸甘油酯类和脂肪酸类,聚乙烯醇和聚乙烯基吡咯烷酮。
可被用于上述美容用制剂、皮肤科制剂、卫生保健用制剂和/或药物制剂中的其它添加剂是UV-A和UV-B滤过物质。其例子包括:
号码 | 物质 | CAS号(=酸) |
1 | 4-氨基苯甲酸 | 150-13-0 |
2 | 3-(4′-三甲基氨合)亚苄基-2-莰烷酮甲基硫酸 | 52793-97-2 |
3 | 3,3,5-三甲基环己基水杨酸酯(高水杨酸酯) | 118-56-9 |
4 | 2-羟基-4-甲氧基二苯酮(羟苯甲酮) | 131-57-7 |
5 | 2-苯基苯并咪唑-5-磺酸及基钾、钠和三乙醇胺 | 27503-81-7 |
最后,也可以提及的是微粉化的颜料,例如二氧化钛和氧化锌。
图1为实施例H1的配方,比较例HVl的配方和比较例HV2的配方作为发胶的应用性能(半头试验)的比较图。
图2为实施例M1的配方,比较例MVl的配方作为定型泡沫体的应用性能(半头试验)的比较图。
下面的实施例用于更详细地说明本发明:
实施例
聚合物的合成
(各聚合物的K值是在乙醇溶液中聚合物的浓度为1wt%时测定)
实施例S1
将380g水、1g十二烷基硫酸钠、30.5g的Belsil DMC 6031(Wacker,CAS号71965-38-3)和45g的物料1加热到80℃。然后加入8g的7%的过硫酸钠水溶液。15分钟后,在两小时内计量物料1。然后在80℃将混合物后聚合2小时。
物料1:181.5g水
2g十二烷基硫酸钠
135g丙烯酸乙酯
140g甲基丙烯酸
1g巯基乙酸乙基己基酯(EHTG)。
产物的K值是51.3。酸值是387mg KOH;这对应于IEE为6.9mmolg-1。固体含量是32.6wt%。凝结物的量低于基于固体量的0.5wt%。聚合物被用作乳液,或在干燥(如果合适,喷雾干燥或在流化床中干燥)后用作粉末。
实施例S2
如实施例S1,只是仅使用0.25g的EHTG。产物的K值是67.5。IEE是6.9mmolg-1。固体含量是35.2wt%。凝结物的量低于基于固体量的1wt%。
实施例S3
如实施例S1,只是不使用EHTG。产物的K值是96。IEE是6.9mmolg-1。凝结物的量低于基于固体量的2wt%。
实施例S4
如实施例S1,只是使用Silwet L 7500(Witco;CAS号68440-66-4,与聚环氧丙烷侧链的硅氧烷接枝共聚物)代替Belsil DMC6031。凝结物<0.5wt%。K值是50.5。
实施例S5
如实施例S1,只是使用Silicones DC 5200(来自Dow Corning的二甲聚硅氧烷共聚多元醇)代替Belsil DMC 6031。没有凝结物。
实施例S6
如实施例S1,只是使用Belsil DMC 6032(来自Wacher-Chemie的二甲聚硅氧烷共聚多元醇乙酸酯)代替Belsil DMC 6031。没有凝结物。
实施例S7
如实施例S1,只是使用Silwet L 7064(Witco;CAS号68937-54-2,具有环氧乙烷侧链的硅氧烷接枝共聚物)代替Belsil DMC6031。没有凝结物。
比较例SV1
将50g的物料1和3.75g的物料2逐滴加入到搅拌的起始物料中。然后将混合物加热到78℃。然后在1.5小时内逐滴加入物料1的剩余部分,和在2小时内加入物料2的剩余部分。将混合物搅拌另外的2小时。然后在15分钟内逐滴加入物料3,在78℃将混合物搅拌另外的2小时。起始物料: 45g的Belsil DMC 6031,150g的乙醇物料1: 281g丙烯酸叔丁酯,93.8g甲基丙烯酸,75g乙醇物料2: 1.5g的过新戊酸叔丁酯(在异十二烷中的浓度为
75%),100g乙醇物料3: 0.5g的过新戊酸叔丁酯,57.5g的乙醇
产物的K值是39.2。固体含量是50.1wt%。
应用性能的试验
发胶
实施例H1
配方
4.00%的来自实施例A1的聚合物
0.40%的氨基甲基丙醇
35.00%的二甲基醚
100%的乙醇
比较例HV1
配方
4.00%的来自BASF的聚合物Luviflex Soft
50%甲基丙烯酸和50%丙烯酸乙酯的共聚物
0.40%的氨基甲基丙醇
35.00%的二甲基醚
100%的乙醇
比较例HV2
配方
4.00%的来自比较例SV1的聚合物
0.40%的氨基甲基丙醇
35.00%的二甲基醚
100%的乙醇
作为发胶的应用性能(半头试验)参见图1
定型泡沫体
实施例M1
配方
2.00%的来自实施例S1的聚合物
0.20%的氨基甲基丙醇
2.20%的Luviquat Mono LS(cocotrimonium甲基硫酸盐)和适量芳香油
0.10%的防腐剂
10.00%的丙烷/丁烷
100.00%的蒸馏水。
比较例MV1
配方
2.00%的来自BASF的聚合物Luviflex Soft,50%甲基丙烯酸和50%丙烯酸乙酯的共聚物
0.20%的氨基甲基丙醇
2.20%的Luviquat Mono LS(cocotrimonium甲基硫酸盐)和适量芳香油
0.10%的防腐剂
10.00%的丙烷/丁烷
100.00%的蒸馏水。
作为定型泡沫体的应用性能(半头试验)参见图2
配方
实施例F1:发胶来自实施例S1的聚合物 1g水 100gMirapol 550(CAS号26590-05-6) 3g丙二醇 2gAlkamuls EL 719(来自Rhodia的TM,CAS号61791- 2g12-6)Gluadin AGP(来自Henkel的TM,水解的麦蛋白, 2gCAS号70084-87-6)Mirasil DMCO(来自Rhodia的TM,CAS号64365-23-7) 0.5gUV吸收剂 适量防腐剂 适量芳香油 适量染料 适量
实施例F2:防晒凝胶来自实施例S1的聚合物 1.2g)1水 ad 80.4gCarbopol 980(来自B.F.Goodrich,CTFA名Carbomer) 1.2g乙醇,98%,变性 4.0gUvinul MS 40(BASF) 3.0g2-氨基-2-(羟基甲基)-1,3-丙二醇 4.0gTrilon B液(来自BASF的TM,EDTA四钠溶液) 0.3g库拉索芦荟凝胶提浓物,10∶1 0.5gd-泛醇 0.5g芳香油 0.2g没药醇 0.1gCremophor A 25(来自BASF的TM,CTFA名Ceteareth- 1.2g25)
)1给出的是基于固体树脂的量
实施例F3:防晒喷洒剂环二甲聚硅氧烷(cyclomethicone)DC 345(来自Dow 55.60gCorning的TM,环低聚二甲基硅氧烷)Polysynlane(来自Polyesther的TM,CAS号61693- 8.00g08-1)来自实施例S1的聚合物,喷雾干燥,无水乙醇中的浓 3g度为50%葵花油 3.50g维生素E乙酸乙酯 0.25gTenox 6(来自Eastman Chemical的TM,玉米油、油酸 0.15g甘油酯、丙二醇、苯酚衍生物、棓酸丙酯、柠檬酸的混合物)日用香料 0.50g己二酸二异丙酯 5.00g甲氧基肉桂酸辛酯 7.50g羟苯甲酮(CAS号131-57-7) 4.00g水杨酸辛酯 5.00g乙氧基二甘醇(CAS号111-90-0) 7.50g
实施例F4:日晒后水分喷洒剂来自实施例S1的聚合物,36%的水分散体 3.00g)12-氨基-2-甲基-1-丙醇 1.50g去离子水 ad 84.60gLuviquat mono CP(来自BASF的TM,CTFA名:羟基乙 2.00g基十六烷基二镆(Cetyldimonium)磷酸酯)D-泛醇 0.50g丙二醇 5.00gSilicones DC 190(来自Dow Corning的TM,CTFA名 0.50g二甲聚硅氧烷共聚多元醇乙酸酯)Prodew 200(来自Ajinomoto的TM,乳酸钠、吡咯烷酮 2.00g羧酸钠盐、山梨糖醇、水解的胶原蛋白、脯氨酸的混合物)二羟甲基二甲基乙内酰脲(CAS号6440-58-0) 0.50gCremophor RH 40(来自BASF的TM,CAS号61788-85-0) 0.30g日用香料 0.10g
)1给出的是基于固体树脂的量
实施例F5:口红Candelilla(Euphorbia Cerifera)蜡(CAS号8006-44- 4.75g8)蜂蜡 1.20g地蜡 7.20g来自实施例S1的聚合物,喷雾干燥 3.40g微晶蜡SP 96(来自Strahl & Pitsch的TM, 7.00gCAS号63231-60-7)Abil蜡2440(来自Goldschmidt的TM,CTFA名山嵛氧 3.40g基二甲聚硅氧烷)羊毛异丙酯(isopropyl lanolate) 3.40g羊毛脂 5.75g山嵛酸异十八烷基酯 2.30gCetiol LC(来自Henkel的TM,CTFA名椰子辛酸酯/癸 12.45g酸酯)池花属植物种子油 15.4g肉豆蔻酸十四烷基酯 7.60gPPG-2十四烷基醚丙酸酯(CAS号74775-06-7) 9.55gMicapolv UV Shadow(来自Centerchem的TM,云母、 3.00g二氧化钛、环二甲聚硅氧烷、二甲聚硅氧烷醇、异十二烷、乙烯/乙酸乙烯酯共聚物、氧化铁的混合物)羊毛脂 4.00g全氟萘烷(CAS号306-94-5) 3.00g颜料 适量
实施例F6:发脂凡士林(CAS号8009-03-8) 66.2g来自实施例S1的聚合物,喷雾干燥 1.4gSchercemol DID(来自Scher Chemicals的TM, 20.0g二亚油酸二异丙酯)Schercemol BE(来自Scher Chemicals的TM, 9.0g芥酸二十二烷酯,CAS号18312-32-8)十六醇 4.2g对羟苯甲酸丙酯 0.1g芳香油 0.5g染料 适量
实施例F7:睫毛油(hair mascara)
由组分A、B、C、D组成
组分ACrodafos CES(来自Croda的TM,cetearyl醇、磷酸二(十 4.00g六烷基)酯、磷酸ceteth-10酯的混合物)Volpo S-2(来自Croda的TM,CTFA名Steareth-2) 0.50gVolpo S-10(来自Croda的TM,CTFA名Steareth-10) 1.00g蜂蜡 6.50g巴西棕榈蜡 1.25gPolychol 5(来自Croda,CTFA名Laneth-5) 0.50g十八烷醇 1.00g
组分B来自实施例S1的聚合物,36%的水分散体 3.00g)1水 57.81g聚乙烯基吡咯烷酮K-30 1.00gNatrolsol 250HHR(来自Aqualon的TM,羟乙基纤维素) 0.10g氢氧化钾 0.19gNa2EDTA 0.10gColorona Bordeaux(来自Rona/E.Merck的TM, 12.00g云母和氧化铁的混合物)丙二醇 6.00g
组分CHydrotriticum PVP(来自Croda的TM, 4.00gPVP和水解的麦蛋白的共聚物)氢氧化钾 0.05g
组分DGermaben Ⅱ(来自Sutton的TM,丙二醇、二偶氮烷基脲、 1.00g)1甲基脲、甲基对羟基苯甲酸酯和苯基对羟基苯甲酸酯的混合物)
)1基于固体树脂
实施例F8:水性发胶Ultrahold Strong(来自BASF的TM,丙烯酸、丙烯酸乙酯、 4g)1N-叔丁基丙烯酰胺的共聚物)Luvimer 100P(来自Amerchol的TM, 0.5g丙烯酸乙酯、丙烯酸叔丁酯和甲基丙烯酸的共聚物)来自实施例S1的聚合物 3.5g)12-氨基-2-甲基-1-丙醇 pH 9水 100g芳香油 适量
)1给出的量是基于固体树脂
实施例F9:醇性发胶来自实施例S1的聚合物,喷雾干燥 3g2-氨基-2-甲基-1-丙醇 1.5g乙醇 ad 50g丙烷/丁烷 ad 100g芳香油 适量
实施例F10:发胶(聚合物混合物)来自实施例S1的聚合物,喷雾干燥 1g2-氨基-2-甲基-1-丙醇 0.5gLuviskol VA 37(来自BASF的TM, 8g乙烯基吡咯烷酮和乙酸乙烯酯的共聚物)水 5.5g乙醇 37.5g二甲醚 100g芳香油 适量
实施例F11:护理泡沫体(care foam)来自实施例S1的聚合物,喷雾干燥 5g)12-氨基-2-甲基-1-丙醇 2.5gCremophor A 25(来自BASF的TM,CTFA名Ceteareth-25) 0.2gLuviquat Mono CP(来自BASF的TM, 0.5gCTFA名:羟基乙基十六烷基二镆(cetyldimonium)磷酸酯)芳香油 适量防腐剂 适量UV吸收剂 适量水 ad 90g丙烷/丁烷 ad 100g
)1给出的量是基于固体树脂
实施例F12:指甲油(聚合物混合物)来自实施例S1的聚合物,喷雾干燥 4gGantrez ES-435(来自ISP的TM, 44g)1乙烯基甲基醚和马来酸二丁酯的共聚物,50%的乙醇溶液)蓖麻油 2g乙醇 47.5g邻苯二甲酸二乙酯 2g9,10-蒽二酮(CAS号81-48-1) 0.5g芳香油 适量
)1给出的量是基于固体树脂
实施例F13:指甲油(聚合物混合物)来自实施例S1的聚合物,喷雾干燥 4gAntaron WP-660(来自ISP的TM, 44g乙烯基吡咯烷酮和C30烯烃的共聚物)蓖麻油 2g乙醇 47.5g邻苯二甲酸二乙酯 2g9,10-蒽二酮(CAS号81-48-1) 0.5g芳香油 适量
Claims (31)
1、一种水溶性或可再分散性聚合物,可通过在至少一种含聚烯化氧的硅氧烷衍生物B存在下,由烯属不饱和单体A的自由基聚合反应而获得,其中下面表示聚合物的离子交换剂当量IEE和K值的乘积,
K值×IEE≥150mmol g-1,
且IEE>2.7mmol g-1,且其中IEE是基于羧酸基团或羧酸酯基团。
2、权利要求1的聚合物,其中下面表示聚合物的离子交换剂当量IEE和K值与硅氧烷衍生物的HLB值之间的关系式
IEE×K值/HLB值≥12mmol g-1。
3、权利要求1或2的聚合物,其中IEE大于3.5mmol g-1。
4、权利要求1~3中任一的聚合物,其中K值大于45。
5、权利要求1~4中任一的聚合物,其中聚合物的K值大于45,且其中占40-100wt%的不饱和单体A包含不饱和羧酸或其盐类。
6、权利要求1~5中任一的聚合物,其中HLB值小于13。
7、权利要求1~6中任一的聚合物,其中使用至少两种烯属不饱和单体,且其中两种单体中的至少一种是不饱和羧酸或其盐类。
8、权利要求1~7中任一的聚合物,其中85-96重量份的不饱和单体A在4-15重量份硅氧烷衍生物B存在下被聚合。
9、权利要求1~8中任一的聚合物,其中定量比是
(a)烯属不饱和单体M是30-50wt%
(b)具有游离羧酸酯基团的烯属不饱和单体C是45-70wt%和
(c)含烯化氧的硅氧烷衍生物B是4-15wt%。
10、权利要求1~9中任一的聚合物,其中40-100wt%的不饱和单体A选自于丙烯酸、甲基丙烯酸、丁烯酸或其盐类。
11、权利要求1~10中任一的聚合物,其中不饱和单体A包含0.5-60wt%的呈均聚形式且具有玻璃化转变温度低于25℃的单体。
12、权利要求1~11中任一的聚合物,其中0.5-60wt%的不饱和单体A选自于丙烯酸乙酯、丙烯酸甲酯、丙烯酸羟乙酯、丙烯酸正丁酯、(甲基)丙烯酸十二烷基酯和(甲基)丙烯酸十八烷基酯。
13、权利要求1~12中任一的聚合物,其中0.5-60wt%的不饱和单体A选自于甲基丙烯酸甲酯、丙烯酸叔丁酯、苯乙烯、N-叔丁基丙烯酰胺、乙酸乙烯酯、丙酸乙烯酯、乙烯基己内酰胺、乙烯基吡咯烷酮、乙烯基咪唑和N-甲基乙烯基咪唑鎓盐。
15、权利要求14的聚合物,其中式Ⅰ具有下面的含义:
16、一种通过在至少一种含聚烯化氧的硅氧烷衍生物B存在下,由烯属不饱和单体A的自由基聚合反应制备水溶性或可再分散性聚合物的方法,其中下面表示聚合物的离子交换剂当量IEE和K值的乘积,
K值×IEE≥150mmol g-1,
且IEE>2.7mmol g-1,且其中IEE是基于羧酸基团或羧酸酯基团。
17、权利要求1-15中任一聚合物的用途,用作美容用制剂、皮肤科制剂、卫生保健用制剂和/或药物制剂中的添加剂。
18、权利要求17的聚合物的用途,其中美容用制剂选自于皮肤和/或头发处理用化妆品组合物。
19、权利要求18的用途,其中头发处理用化妆品组合物选自于护理和保护头发用化妆品组合物。
20、权利要求19的用途,其中头发处理用化妆品组合物选自于美发喷剂、定型泡沫体、摩丝、发胶、定型膏、滋发剂、美发乳、护发素、发乳、防末端分叉液、长效卷发剂的中和剂组合物、锔油处理剂、调理剂、定型液、香波或染发剂。
21、一种美容、皮肤科、卫生保健和/或药物组合物,除了惯用添加剂之外,还包含权利要求1~15中任一的聚合物。
22、一种包含权利要求1~15中任一的聚合物的美容、皮肤科、卫生保健和/或药物组合物,其中所述聚合物被用于与至少一种其它聚合物的混合物中和视具体情况而定与其它物质的混合物中。
23、一种美容、皮肤科、卫生保健和/或药物组合物,除了包含权利要求1~15中任一的聚合物外,还包含另外的阴离子聚合物,以及惯用添加剂。
24、一种美容、皮肤科、卫生保健和/或药物组合物,除了包含权利要求1~15中任一的聚合物外,还包含另外的阳离子聚合物,以及惯用添加剂。
25、一种美容、皮肤科、卫生保健和/或药物组合物,除了包含权利要求1~15中任一的聚合物外,还包含另外的中性聚合物,以及惯用添加剂。
26、一种美容、皮肤科、卫生保健和/或药物组合物,除了包含权利要求1~15中任一的聚合物外,还包含另外的中性聚合物,以及惯用添加剂。
27、一种美容、皮肤科、卫生保健和/或药物组合物,除了包含权利要求1~15中任一的聚合物外,还包含至少一种另外的生物聚合物,以及惯用添加剂。
28、权利要求17的用途,其中所述配方包含19~90wt%的水。
29、权利要求17的用途,其中所述配方包含至少一种用于聚合物的中和试剂。
30、权利要求17的用途,其中所述配方包含氨、有机碱、2-氨基-2-甲基-1-丙醇、单乙醇胺、二乙醇胺、三乙醇胺、三异丙醇胺或三[(2-羟基)1-丙基]胺。
31、权利要求17的用途,其中所述配方包含表面活性剂、表面活性物质、UV吸收剂和/或增稠剂。
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DE19951877.7 | 1999-10-28 | ||
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---|---|---|---|---|
FR2740037B1 (fr) * | 1995-10-18 | 1997-12-05 | Rhone Poulenc Chimie | Compositions cosmetiques pour le cheveu et la peau a base de polyorganosiloxanes fonctionnalises greffes |
JPH10226627A (ja) * | 1997-02-18 | 1998-08-25 | Kao Corp | 泡状毛髪化粧料 |
JPH11228362A (ja) * | 1998-02-13 | 1999-08-24 | Shiseido Co Ltd | パーマネントウェーブ剤第1剤 |
-
2000
- 2000-08-25 EP EP00118465A patent/EP1083184A3/de not_active Withdrawn
- 2000-09-04 JP JP2000267434A patent/JP2001081113A/ja not_active Withdrawn
- 2000-09-07 CN CN00126341A patent/CN1293215A/zh active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104174071A (zh) * | 2004-04-28 | 2014-12-03 | 安希奥设备国际有限责任公司 | 用于形成交联生物材料的组合物和***及关联的制备方法与用途 |
CN101263182B (zh) * | 2005-09-08 | 2011-06-15 | 瓦克化学有限公司 | 亲水性有机官能硅氧烷共聚物 |
Also Published As
Publication number | Publication date |
---|---|
EP1083184A2 (de) | 2001-03-14 |
EP1083184A3 (de) | 2002-07-17 |
JP2001081113A (ja) | 2001-03-27 |
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