CN104684541A - 具有碳硅氧烷树枝状结构和亲水性基团的共聚物 - Google Patents
具有碳硅氧烷树枝状结构和亲水性基团的共聚物 Download PDFInfo
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- CN104684541A CN104684541A CN201380051981.6A CN201380051981A CN104684541A CN 104684541 A CN104684541 A CN 104684541A CN 201380051981 A CN201380051981 A CN 201380051981A CN 104684541 A CN104684541 A CN 104684541A
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Abstract
本发明公开了一种共聚物,其包含:(A)具有碳硅氧烷树枝状结构的不饱和单体;以及(B)在所述分子中具有至少一个亲水性基团的不饱和单体。所述具有所述碳硅氧烷树枝状结构的不饱和单体的含量在所述共聚物的总单体单元的35至50质量%的范围内。本发明也为包含所述共聚物的液体组合物、表面处理剂和粉末组合物,以及包含此类组分的化妆品原材料。
Description
技术领域
本发明涉及在分子中具有碳硅氧烷树枝状结构和亲水性基团的共聚物。所述共聚物还可在分子中具有含氟的有机基团。此外,本发明还涉及包含该共聚物的液体组合物、表面处理剂和粉末组合物。本发明还涉及包含该液体组合物、表面处理剂或粉末组合物的化妆品原材料。
背景技术
甲基氢聚硅氧烷广泛用作用于化妆品的各种类型的表面处理剂。使用甲基氢聚硅氧烷处理过的粉末高度斥水,并且因此被表征为改善防止化妆品变花的能力。然而,除了在表面处理时与粒子表面反应之外,甲基氢聚硅氧烷还触发分子之间的交联反应。因此与表面反应的百分比较低,这导致表面处理过的粉末中产生剩余的未反应Si-H键。因此,根据条件,有可能产生氢气,并且此氢气在存在火等的情况下是危险的。此外,已因使用甲基氢聚硅氧烷而出现各种类型的问题,诸如化妆品容器膨胀、美妆模糊等等。已提出各种方法以使得不产生剩余的Si-H键。此类方法包括如日本未经审查的专利申请公布No.H07-196946中所述的使用单端烷氧基改性有机硅进行表面处理的方法,以及如WO 2002/100356中所述的使用具有烷氧基甲硅烷基基团的丙烯酸改性有机硅进行表面处理的方法。然而,当使用单端烷氧基改性有机硅时,烷氧基基团含量较低,并且因此使用单端烷氧基改性有机硅的方法具有与粉末的低反应性的问题。另一方面,使用具有烷氧基甲硅烷基基团的丙烯酸改性有机硅进行表面处理的方法使用通过将直链有机硅接枝到丙烯酸主链而制备的丙烯酸改性有机硅,并且因此具有不足的抗皮脂性等等的问题。此外,已使用具有烷氧基甲硅烷基基团的丙烯酸改性有机硅表面处理过的粉末具有的问题在于与其他化妆品原材料的相容性较低,并且化妆品的配混稳定性较差。
已提出了这样的化妆品原材料:其具有作为主要试剂的具有碳硅氧烷树枝状结构的基于乙烯基的聚合物、或者具有碳硅氧烷树枝状结构和含氟的有机基团两者的基于乙烯基的聚合物(参见日本未经审查的专利申请公布No.2000-063225和日本未经审查的专利申请公布No.2003-226611)。然而,在日本未经审查的专利申请公布No.2000-063225和日本未经审查的专利申请公布No.2003-226611中,未提及在表面处理中使用各种类型的粉末。此外,日本未经审查的专利申请公布No.H09-136812提出了这样的共聚物:其通过自由基可聚合单体、在一个分子链末端具有自由基可聚合基团的有机聚硅氧烷化合物、和N-乙烯基吡咯烷酮的共聚而获得。然而,该共聚物不具有亲水性基团,特别是该共聚物不具有醇式羟基基团,并且未描述在表面处理中使用各种类型的粉末。
此外,虽然公开了共聚物在化妆品中共混成成膜剂,但共聚物具有的问题在于分散性和配混稳定性不足,特别是当共聚物与用于化妆品的粉末一起使用时。为了解决此类问题,本申请的作者在日本未经审查的专利申请公布No.2011-149017和日本未经审查的专利申请公布No.2011-148784中提出使用具有碳硅氧烷树枝状结构的特定聚合物的化妆品原材料和粉末处理。与之前存在的粉末处理剂相比,这些聚合物在化妆品中具有非常出色的分散性、配混稳定性等等。然而,这些聚合物仍有改善分散性能的余地,特别是当氟处理过的粉末等等共混于化妆品中时。另外在将包含粉末的化妆品涂覆在皮肤上后,有时在皮肤上会出现分散失效,即由于液体油剂等等的挥发使粉末结块。此外,既未提及也未建议关于构成共聚物的指定碳硅氧烷树枝状结构的相对比例。另外既未提及也未建议关于与具有亲水性官能团的单体的组合使用。
发明内容
考虑到常规技术的上述情况,本发明的目标是提供安全且不产生氢气、具有与其他化妆品原材料的良好相容性的共聚物,使得可以改善化妆品中的配混稳定性,并且使得可以为化妆品赋予良好抗水性、抗皮脂性、光泽、感觉、对毛发和皮肤的附着等等,以及能够使用该共聚物处理用于化妆品的广泛粉末,并使用该共聚物作为在施用于皮肤上时能够几乎完全抑制分散失效的表面处理剂。本发明的另一个目标是提供包含该共聚物的表面处理剂和已使用该共聚物等等进行表面处理的粉末组合物。本发明的又一个目标是通过共混此类共聚物等等来提供化妆品原材料。
本发明的目标通过共聚物而实现,该共聚物包含:
(A)具有由下式(1)表示的碳硅氧烷树枝状结构的不饱和单体:
[式1]
在该式中,
Z为二价有机基团;
p为0或1;
R1和R2各自独立地表示选自烷基基团、芳基基团和芳烷基基团的基团,其具有1至10个碳原子;且
L1为甲硅烷基烷基基团,在i=1的情况下,由下式(2)表示:
[式2]
在该式中,
Z和p与上文定义相同;
R1和R2与上文定义相同;
i为1至10范围内的整数,指示甲硅烷基烷基基团的总代数;
Li+1为选自氢原子,具有1至10个碳原子的烷基基团、芳基基团和芳烷基基团,以及甲硅烷基烷基基团的基团;然而,在i=c(c为1至10范围内的整数,指示甲硅烷基烷基基团的代数)的情况下,Li+1为选自氢原子,具有1至10个碳原子的烷基基团、芳基基团和芳烷基基团的基团;并且在i<c的情况下,Li+1为甲硅烷基烷基基团;且
ai为0至3范围内的整数;和
(B)在分子中具有至少一个亲水性基团的不饱和单体;
具有碳硅氧烷树枝状结构的不饱和单体的含量为总单体的35至50质量%。
此外,发明人发现通过共聚如下物质获得的共聚物能够较好解决上述问题而得到了本发明:(A)具有碳硅氧烷树枝状结构的不饱和单体、
(B)在分子中具有至少一个亲水性基团的不饱和单体、以及
(C)在分子中具有至少一个含氟的有机基团的不饱和单体,
它们以一定质量比率范围共聚使得{组分(A)质量含量/总单体质量含量}:{组分(B)质量含量/总单体质量含量}:{组分(C)质量含量/总单体质量含量}分别在[0.35至0.50:0.01至0.40:0.00至0.60]的范围内;
并且满足下列条件:{组分(A)质量含量/总单体质量含量}≥{组分(B)质量含量/总单体质量含量}。
具体地讲,本发明的发明人发现通过共聚如下物质获得的共聚物能够特别好地解决上述问题而得到了本发明:(A)具有碳硅氧烷树枝状结构的不饱和单体、
(B1)在分子中具有至少一个一元或多元醇式羟基基团的不饱和单体、以及
(C1)由如下通式表示的不饱和单体:
CH2=CR15COORf
其中,R15为氢原子或甲基基团;Rf为氟代烷基基团或氟代烷氧基氟代亚烷基基团,
它们以一定质量比率范围共聚使得{组分(A)质量含量/总单体质量含量}:{组分(B)质量含量/总单体质量含量}:{组分(C1)质量含量/总单体质量含量}分别在[0.35至0.50:0.10至0.40:0.10至0.50]的范围内;
并且满足下列条件:{组分(A)质量含量/总单体质量含量}≥{组分(B)质量含量/总单体质量含量}。
本发明的目标最终通过使用包含上述共聚物的表面处理剂、通过使用已用上述共聚物进行表面处理的粉末、以及通过使用此类组分作为化妆品原材料来实现。
该共聚物还优选地以包含(D)至少一种类型的油剂的液体组合物的形式使用。该油剂还优选地为在25℃下具有0.65至100,000mm2/s的粘度的疏水有机硅油。该共聚物特别优选地以包含挥发性有机硅油(例如,十甲基环五硅氧烷等等)或烃油诸如异十二烷等等的液体组合物的形式使用。
该共聚物或液体组合物可用作粉末等等的表面处理剂。具体地讲,优选地使用包含该共聚物和(E)至少一种类型的粉末或染色剂的粉末组合物形式。该粉末等等可为选自具有1nm至20μm范围内的平均粒径的无机颜料粉末、有机颜料粉末和树脂粉末的至少一种类型。可通过除本发明共聚物之外的表面处理剂对粉末和/或染色剂的至少一部分进行防水处理。上述粉末或染色剂优选地为(E1)斥水性处理过的粉末或染色剂。
当本发明的聚合物用作表面处理剂或化妆品原材料时,可有利地使用本发明的聚合物为粉末等等的表面赋予斥水性,并且由于不产生氢气,安全性极佳。此外,本发明的共聚物用作具有亲水性基团且具有多元接枝到主链的非直链的(即高度支化的)树枝状有机硅的共聚物。因此,与各种类型的其他化妆品原材料的相容性是良好的,并且因此化妆品等等的配混稳定性是优异的。此外,本发明的共聚物能够用于处理化妆品中所用的广泛粉末等等。此外,当施用于皮肤时,本发明的共聚物能够在油剂挥发后几乎完全抑制粉末等等的分散失效。因此可以提供包含该共聚物的表面处理剂并且提供通过使用该共聚物等等进行表面处理所制备的粉末组合物。
本发明的共聚物可用作化妆品原材料。另外通过共混到其他化妆品原材料(诸如各种类型的粉末、油剂等等)的化妆品中,可以提供从抗水性、抗皮脂性、光泽、感觉、对毛发的附着性、对皮肤的附着性等等的角度看更优异的表面保护特性、外观和使用感觉。
具体实施方式
本发明的共聚物为包含如下物质的共聚物:
(A)具有由下式(1)表示的碳硅氧烷树枝状结构的聚合物:
[式3]
在该式中,
Z为二价有机基团;
p为0或1;
R1和R2各自独立地表示选自烷基基团、芳基基团和芳烷基基团的基团,其具有1至10个碳原子;且
L1为甲硅烷基烷基基团,在i=1的情况下,由下式(2)表示:
[式4]
在该式中,
Z和p与上文定义相同;
R1和R2与上文定义相同;
i为1至10范围内的整数,指示甲硅烷基烷基基团的总代数,并且i优选地为1至5,更优选地为1至3,并且进一步优选地为1或2;
Li+1为选自氢原子,具有1至10个碳原子的烷基基团、芳基基团和芳烷基基团,以及甲硅烷基烷基基团的基团;然而,在i=c(c为1至10范围内的整数,指示甲硅烷基烷基基团的代数,并且c优选地为1至5,更优选地为1至3,并且进一步优选地为1或
2)的情况下,Li+1为选自氢原子,具有1至10个碳原子的烷基基团、芳基基团和芳烷基基团的基团;并且在i<c的情况下,Li+1为甲硅烷基烷基基团;且
ai为0至3范围内的整数,优选地为0至2,更优选地为0至1,并且进一步优选地为0;和
(B)在分子中具有至少一个亲水性基团的不饱和单体;
具有碳硅氧烷树枝状结构的不饱和单体的含量为总单体的35至50质量%。此外,本发明的共聚物优选地为包含(C)在分子中具有至少一个含氟的有机基团的不饱和单体的共聚物。
构成本发明共聚物的组分(A)的质量分数(即{组分(A)的质量/所有单体的质量})必须在0.35至0.50的范围内。这意味着共聚物的(A)具有碳硅氧烷树枝状结构的不饱和单体含量在所有单体单元的35至50质量%范围内。组分(A)的质量分数优选地在所有单体单元的40至50质量%范围内,并且最优选地在所有单体单元的42至48质量%范围内。当组分(A)的质量分数超过所述上限时,斥水性变得过高,并且化妆品等等中的配混稳定性可变得不足。当组分(A)的质量分数小于所述下限时,皮肤上的粉末等等的斥水性和分散稳定性可变得不足。此外,组分(B)是用于为共聚物赋予亲水性的组分。当本发明的共聚物用作表面处理剂时,共聚物优选地具有对于整个分子而言适当程度的斥水性。因此特别优选的是{组分(A)质量含量/总单体质量含量}大于或等于{组分(B)质量含量/总单体质量含量}。
本发明的共聚物的组分(A)至(C)优选地以一定范围共聚使得{组分(A)质量含量/总单体质量含量}:{组分(B)质量含量/总单体质量含量}:{组分(C)质量含量/总单体质量含量}分别等于[0.35至0.50:0.01至0.40:0.00至0.60]。此外,组分(C)优选地为必需成分,并且这些组成范围优选地分别为[0.35至0.50:0.10至0.40:0.10至0.50]。这些组成范围特别优选地分别为[0.40至0.50:0.15至0.40:0.15至0.40]。当各种组分的聚合处于上述范围之外时,可出现问题,诸如粉末的分散性、配混稳定性等等下降(特别是当共混于最终产品中时)以及油剂挥发后皮肤上的分散失效。
组分(A)为具有在上式(1)中表示的碳硅氧烷树枝状结构的聚合物,并且该结构将在下文详细阐述。
二价有机基团不受到特别限制,并且二价有机基团的例子包括具有1至30个碳原子的取代或未取代的和直链或支链的二价烃基。具有1至30个碳原子的取代或未取代的和直链或支链的二价烃基的例子包括:具有1至30个碳原子的直链或支链的亚烷基基团,诸如亚甲基基团、二亚甲基基团、三亚甲基基团、四亚甲基基团、五亚甲基基团、六亚甲基基团、七亚甲基基团、八亚甲基基团等等;具有2至30个碳原子的亚烯基基团,诸如亚乙烯基基团、亚烯丙基基团、亚丁烯基基团、亚己烯基基团、亚辛烯基基团等等;具有6至30个碳原子的亚芳基基团,诸如亚苯基基团、二亚苯基基团等等;具有7至30个碳原子的亚烷基亚芳基基团,诸如二亚甲基亚苯基基团等等;以及其取代的基团,其中键合至所述基团的碳原子的氢原子至少部分地被卤素原子诸如氟原子等等,或者包含甲醇基团、环氧基团、缩水甘油基基团、酰基基团、羧基基团、氨基基团、甲基丙烯酰基基团、巯基基团、酰胺基团、氧化亚烷基基团等等的有机基团取代。二价烃基优选地为具有1至30个碳原子的未取代的二价饱和烃基,更优选地为具有1至6个碳原子的直链或支链的亚烷基基团,并且特别优选地为二亚甲基基团。
例如,二价有机基团可为选自下列基团的基团:
[式5]
-R3-
-R3-CO-
-R3-COO-R3-
-CO-R3-
-R3-COO-R3′-
-R3-CONH-R3′-
-R3-R3′-
在该式中,
R3为具有1至30个碳原子的取代或未取代的和直链或支链的二价烃基,其可具有如上所述的取代基;且
R3’为选自下列基团的基团:
[式6]
可通过硅键合的氢原子与烯基基团之间的反应引入的由通式-R3-或-R3-R3’-表示的二价有机基团是优选的。以与上述相同的方式,可通过硅键合的氢原子与不饱和羧酸官能团之间的反应引入的由通式-R3-COO-R3-或-R3-COO-R3’-表示的二价有机基团也是优选的。
具体地讲,Z优选地为具有1至30个碳原子的直链或支链的亚烷基基团,并且特别优选地为二亚甲基基团(亚乙基基团)。
具有1至10个碳原子的烷基基团、芳基基团或芳烷基基团的例子包括:具有1至30个碳原子的直链或支链的烷基基团,诸如甲基基团、乙基基团、丙基基团、丁基基团、戊基基团、己基基团、庚基基团、辛基基团等等;具有3至10个碳原子的环烷基基团,诸如环戊基基团、环己基基团等等;具有6至10个碳原子的芳基基团,诸如苯基基团、甲苯基基团、二甲苯基基团等等;具有7至10个碳原子的芳烷基基团,诸如苄基基团等等;以及其取代的基团,其中键合至所述基团的碳原子的氢原子至少部分地被卤素原子诸如氟原子等等,或者包含甲醇基团、环氧基团、缩水甘油基基团、酰基基团、羧基基团、氨基基团、甲基丙烯酰基基团、巯基基团、酰胺基团、氧化亚烷基基团等等的有机基团取代。烷基基团、芳基基团或芳烷基基团优选地为具有1至10个碳原子的未取代的烷基基团、芳基基团或芳烷基基团,更优选地为具有1至6个碳原子的未取代的烷基基团或芳基基团,并且甚至更优选地为甲基基团、乙基基团或苯基基团。
碳硅氧烷树枝状结构为从一个硅原子处呈放射状且高度支化的化学结构。指定甲硅烷基烷基基团的总代数的“i”指示支化度。例如,在总代数i为1且Li+1为例如甲基基团的情况下,碳硅氧烷树枝状结构意指下列结构:
[式7]
在该式中,Z、p、R1和R2与上文定义相同;并且a1为0至3范围内的整数。
以上述相同的方式,在代数i为2且Li+1为例如甲基基团的情况下,碳硅氧烷树枝状结构意指下列结构(其中p=1):
[式8]
在该式中,Z、R1和R2与上文定义相同;并且a1和a2为0至3范围内的整数。
此外,在代数i为3且Li+1为例如甲基基团的情况下,碳硅氧烷树枝状结构意指下列结构(其中p=1):
[式9]
在该式中,Z、R1和R2与上文定义相同;并且a1、a2和a3为0至3范围内的整数。
下列结构特别优选地作为碳硅氧烷树枝状结构:
[式10]
在该式中,Z和R2与上文定义相同,
式11
在该式中,Z和R2与上文定义相同。
具有碳硅氧烷树枝状结构的甲硅烷基烷基基团具有这样的结构,其中碳硅氧烷单元以树枝状的形式延伸。因此,甲硅烷基烷基基团是与直链或简单支链的聚硅氧烷单元相比表现出增强的斥水性(增强的抗水性)的官能团。另外,具有碳硅氧烷树枝状结构的甲硅烷基烷基在化学上是稳定的,因此,甲硅烷基烷基是提供有利性质诸如能够结合多种多样的用于化妆品组合物的原材料一起使用的官能团。
(A)具有碳硅氧烷树枝状结构的不饱和单体例如由下式(1')表示:
[式12]
在该式中,
Y为能够自由基聚合的含不饱和基团的基团;且
Z、p、R1、R2、L1和ai与上文定义相同。
含不饱和基团的基团不受到特别限制,只要含不饱和基团的基团具有自由基可聚合的不饱和基团即可。含不饱和基团的基团被示例为乙烯基基团、烯丙基基团、(甲基)丙烯酰基基团等等。
(A)具有碳硅氧烷树枝状结构的不饱和单体优选地具有选自如下的基团:由下列通式表示的含丙烯酰基或甲基丙烯酰基基团的有机基团:
[式13]
(在该式中,R4为氢原子或甲基基团;并且R5为具有1至10个碳原子的亚烷基基团)、由下列通式表示的含丙烯酰基或甲基丙烯酰基基团的有机基团:
[式14]
(在该式中,R4和R5具有与上文定义相同的含义)、以及如下列通式表示的含烯基芳基基团的有机基团或具有2至10个碳原子的烯基基团:
[式15]
(在该式中,R6为氢原子或甲基基团;R7为具有1至10个碳原子的烷基基团;R8为具有1至10个碳原子的亚烷基基团;b为0至4范围内的整数,并且c为0或1)。
(A)具有碳硅氧烷树枝状结构的不饱和单体被示例为下式。[式16]
[式17]
(A)具有碳硅氧烷树枝状结构的不饱和单体可根据例如日本未经审查的专利申请公布No.H11-001530(日本专利申请No.H09-171154)中所述的用于制备支链硅氧烷/亚烷基硅烷(silalkylene)共聚物的方法来制备。
(B)在分子中具有至少一个亲水性基团的不饱和单体不受到特别限制,只要(B)在分子中具有至少一个亲水性基团的不饱和单体具有直链或支链的亲水性基团和不饱和自由基可聚合基团即可。此外,组分(B)可为一种类型的不饱和单体或者两种或更多种类型的不同不饱和单体的混合物。此外,亲水性基团优选地为具有醇式羟基基团的亲水性基团。亲水性基团特别优选地为一元或多元醇式羟基基团。
(B1)在分子中具有至少一个一元或多元醇式羟基基团的不饱和单体特别优选地用作本发明的组分(B),并且具体例子包括:丙烯酸2-羟乙酯、二乙二醇丙烯酸酯、聚乙二醇丙烯酸酯、甲氧基二乙二醇丙烯酸酯、甲氧基聚乙二醇丙烯酸酯、乙氧基二乙二醇丙烯酸酯、乙氧基聚乙二醇丙烯酸酯、丙烯酸2-羟丙酯、二丙二醇丙烯酸酯、聚丙二醇丙烯酸酯、甲氧基聚丙二醇丙烯酸酯、乙氧基聚丙二醇丙烯酸酯、或类似单丙烯酸酯;二乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、或类似二丙烯酸酯;甲基丙烯酸2-羟乙酯、二乙二醇甲基丙烯酸酯、聚乙二醇甲基丙烯酸酯、甲氧基二乙二醇甲基丙烯酸酯、甲氧基聚乙二醇甲基丙烯酸酯、乙氧基二乙二醇甲基丙烯酸酯、乙氧基聚乙二醇甲基丙烯酸酯、甲基丙烯酸2-羟丙酯、二丙二醇甲基丙烯酸酯、聚丙二醇甲基丙烯酸酯、甲氧基聚丙二醇甲基丙烯酸酯、乙氧基聚丙二醇甲基丙烯酸酯、或类似单甲基丙烯酸酯;二乙二醇二甲基丙烯酸酯、聚乙二醇二甲基丙烯酸酯、二丙二醇二甲基丙烯酸酯、聚丙二醇二甲基丙烯酸酯、或类似二甲基丙烯酸酯;丙烯酸甘油酯、甲基丙烯酸甘油酯、或类似丙烯酸甘油酯;等等。具体地讲,具有2至8个碳原子的丙烯酸或甲基丙烯酸的羟烷基酯、或者丙烯酸或甲基丙烯酸的甘油酯优选作为组分(B1)。
组分(B1)特别优选地在本发明共聚物的总单体单元的1至40质量%的含量范围内共混,该范围更优选地为10至40质量%,并且该范围最优选地为15至40质量%。组分(B)是为本发明的共聚物赋予适当亲水性的组分。当聚合范围处于上述范围之外时,可出现问题,诸如在共聚物共混于最终产品中时粉末的配混稳定性、分散性等等下降,以及油剂挥发后皮肤上出现分散失效。
组分(C)为在分子中具有至少一个含氟的有机基团的不饱和单体。从改善斥水性和与斥水性处理过的粉末的相容性角度看,特别优选地使用含氟化有机基团的基于乙烯基的单体。
含氟化有机基团的基于乙烯基的单体优选地为由如下(C1)通式表示的单体:CH2=CR15COORf。在该式中,R15为氢原子或甲基基团,并且Rf为氟化有机基团。例子包括如上所述的氟代烷基基团或氟代烷氧基氟代亚烷基基团。由下式表示的化合物可被引用作为该类型的组分(C1)的例子。在下式中,z为1至4范围内的整数。
CH2=CCH3COO-CF3、CH2=CCH3COO-C2F5、CH2=CCH3COO-nC3F7、CH2=CCH3COO-CF(CF3)2、CH2=CCH3COO-nC4F9、CH2=CCH3COO-CF2CF(CF3)2、CH2=CCH3COO-nC5F11、CH2=CCH3COO-nC6F13、CH2=CCH3COO-nC8F17、CH2=CCH3COO-CH2CF3、CH2=CCH3COO-CH(CF3)2、CH2=CCH3COO-CH2CH(CF3)2、CH2=CCH3COO-CH2(CF2)2F、CH2=CCH3COO-CH2(CF2)3F、CH2=CCH3COO-CH2(CF2)4F、CH2=CCH3COO-CH2(CF2)6F、CH2=CCH3COO-CH2(CF2)8F、CH2=CCH3COO-CH2CH2CF3、CH2=CCH3COO-CH2CH2(CF2)2F、CH2=CCH3COO-CH2CH2(CF2)3F、CH2=CCH3COO-CH2CH2(CF2)4F、CH2=CCH3COO-CH2CH2(CF2)6F、CH2=CCH3COO-CH2CH2(CF2)8F、CH2=CCH3COO-CH2CH2(CF2)10F、CH2=CCH3COO-CH2CH2(CF2)12F、CH2=CCH3COO-CH2CH2(CF2)14F、CH2=CCH3COO-CH2CH2(CF2)16F、CH2=CCH3COO-CH2CH2CH2CF3、CH2=CCH3COO-CH2CH2CH2(CF2)2F、CH2=CCH3COO-CH2CH2CH2(CF2)2H、CH2=CCH3COO-CH2(CF2)4H、CH2=CCH3COO-CH2CH2(CF2)3H、CH2=CCH3COO-CH2CH2CF(CF3)-[OCF2CF(CF3)]z-OC3F7、CH2=CCH3COO-CH2CH2CF2CF2-[OCF2CF(CF3)]z-OC3F7CH2=CHCOO-CF3、CH2=CHCOO-C2F5、CH2=CHCOO-nC3F7、CH2=CHCOO-CF(CF3)2、CH2=CHCOO-nC4F9、CH2=CHCOO-CF2CF(CF3)2、CH2=CHCOO-nC5F11、CH2=CHCOO-nC6F13、CH2=CHCOO-nC8F17、CH2=CHCOO-CH2CF3、CH2=CHCOO-CH(CF3)2、CH2=CHCOO-CH2CH(CF3)2、CH2=CHCOO-CH2(CF2)2F、CH2=CHCOO-CH2(CF2)3F、CH2=CHCOO-CH2(CF2)4F、CH2=CHCOO-CH2(CF2)6F、CH2=CHCOO-CH2(CF2)8F、CH2=CHCOO-CH2CH2CF3、CH2=CHCOO-CH2CH2(CF2)2F、CH2=CHCOO-CH2CH2(CF2)3F、CH2=CHCOO-CH2CH2(CF2)4F、CH2=CHCOO-CH2CH2(CF2)6F、CH2=CHCOO-CH2CH2(CF2)8F、CH2=CHCOO-CH2CH2(CF2)10F、CH2=CHCOO-CH2CH2(CF2)12F、CH2=CHCOO-CH2CH2(CF2)14F、CH2=CHCOO-CH2CH2(CF2)16F、CH2=CHCOO-CH2CH2CH2CF3、CH2=CHCOO-CH2CH2CH2(CF2)2F、CH2=CHCOO-CH2CH2CH2(CF2)2H、CH2=CHCOO-CH2(CF2)4H、CH2=CHCOO-CH2CH2(CF2)3H、CH2=CHCOO-CH2CH2CF(CF3)-[OCF2CF(CF3)]z-OC3F7、以及CH2=CHCOO-CH2CH2CF2CF2-[OCF2CF(CF3)]z-OC3F7。其中,由下式表示的乙烯基单体是优选的。CH2=CHCOO-CH2CH2(CF2)6F、CH2=CHCOO-CH2CH2(CF2)8F、CH2=CCH3COO-CH2CH2(CF2)6F、CH2=CCH3COO-CH2CH2(CF2)8F、CH2=CHCOO-CH2CF3、以及CH2=CCH3COO-CH2CF3。由下式表示的乙烯基单体是特别优选的。CH2=CHCOO-CH2CF3、以及CH2=CCH3COO-CH2CF3。
组分(C1)在本发明共聚物的总单体单元中的共混量优选地在1至50质量%的范围内,进一步优选地在10至50质量%的范围内,并且最优选地在15至40质量%的范围内。
自由基聚合方法或离子聚合方法可用作共聚方法。在这些方法中,自由基聚合方法是优选的,并且特别优选地使用溶液聚合方法。溶液聚合方法通过使溶剂中的每种不饱和单体在存在自由基引发剂的情况下在50至150℃范围内的温度条件下反应3至20小时来进行。此类反应期间所用的溶剂被示例为脂族烃,诸如己烷、辛烷、癸烷、环己烷等等;芳族烃,诸如苯、甲苯、二甲苯等等;醚,诸如二乙醚、二丁醚、四氢呋喃、二噁烷等等;酮,诸如丙酮、甲基乙基酮、甲基异丁基酮、二异丁基酮等等;酯,诸如乙酸甲酯、乙酸乙酯、乙酸丁酯、乙酸异丁酯等等;醇,诸如甲醇、乙醇、异丙醇、丁醇等等;以及有机硅氧烷低聚物,诸如八甲基环四硅氧烷、十甲基环五硅氧烷、六甲基二硅氧烷、八甲基三硅氧烷等等。一般用于自由基聚合方法的任何常规已知的化合物可用作自由基引发剂。自由基引发剂的具体例子包括偶氮二类化合物,诸如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)、二甲基-2,2'-偶氮二(2-甲基丙酸酯)等等;以及有机过氧化物,诸如过氧化苯甲酰、过氧化月桂酰、过氧化苯甲酸叔丁酯、过氧化-2-乙基己酸叔丁酯等等。自由基引发剂可单独使用或以其两种或更多种类型的组合使用。自由基引发剂的用量优选地相对于100重量份的组分(A)至(C)总量在0.1至5重量份的范围内。此外,可在聚合期间加入链转移剂。链转移剂的具体例子包括巯基化合物,诸如2-巯基乙醇、丁硫醇、正十二烷硫醇、3-巯基丙基三甲氧基硅烷、具有巯基丙基基团的聚二甲基硅氧烷等等;以及卤化化合物,诸如二氯甲烷、氯仿、四氯化碳、溴丁烷、3-氯丙基三甲氧基硅烷等等。
在聚合后,可通过如下方法进行纯化:通过减压加热来移除剩余未反应的基于乙烯基的单体的方法,或者在存在氢化催化剂的情况下进行因无溶剂或有溶剂的氢化反应而发生的除臭处理并且通过与氮气接触进行减压蒸馏来移除轻组分的方法。具体地讲,在用作其中需要减少气味并与其他化妆品组分可混和的外用制剂的情况下,优选地使用纯化的产物。在氢化反应和汽提过程中,用于纯化常规有机聚硅氧烷共聚物的溶剂、反应条件、减压条件等等可在无任何限制的情况下使用或选择。
为了极大地改善本发明的共聚物相对于皮肤或毛发的附着性质,或为了在使用后提供适当的清洁性质,可通过使用含氨基基团的基于乙烯基的单体诸如丙烯酸二甲氨基乙酯、甲基丙烯酸二甲氨基乙酯、丙烯酸二乙氨基乙酯、甲基丙烯酸二乙氨基乙酯等等作为原材料单体的一部分,将氨基基团引入基于乙烯基的聚合物的侧链中,然后使用卤化脂肪酸的碱金属盐、铵盐或胺盐诸如一氯乙酸的钾盐、一氯乙酸的铵盐、一氯乙酸的氨基甲基丙醇盐、一溴乙酸的三乙醇胺盐、一氯丙酸的钠盐等等进行改性。或者,可通过使用含羧酸的基于乙烯基的单体诸如丙烯酸、甲基丙烯酸、衣康酸、巴豆酸、富马酸、马来酸等等作为原材料单体的一部分,将羧酸基团引入基于乙烯基的聚合物的侧链中,然后使用胺诸如三乙胺、二乙胺、三乙醇胺等等中和。
从共混于化妆品中的容易度角度看,共聚物的重均分子量优选地在3,000至2,000,000的范围内,并且更优选地在5,000至800,000的范围内。共聚物的形态被示例为液体、胶、糊剂、固体和粉末。在共混于化妆品中时,优选溶液或分散体的形式,其中共聚物用溶剂或粉末稀释。
具体地讲,本发明的共聚物优选地分散于(D)一种或多种类型的油剂中,并且本发明的共聚物优选地以包含至少一种类型的油剂的液体组合物的形式使用。油剂的例子包括一般用于化妆品的动物油、植物油、合成油等等。只要油剂为疏水的,则油剂可衍生自任何来源,可为固体、半固体或液体的形式,并且可为不挥发的、半挥发的或挥发的。当本发明的共聚物以液体组合物的形式使用时,组分(D)优选地完全为液体并且具有挥发性。具体地讲,油剂优选地为选自有机硅油、烃油和脂肪酸酯油的一种类型的油剂或者两种或更多种类型的油剂的混合物。当油剂作为两种或更多种类型的液体和半固体(胶状)共混时,从足够形成液体组合物的能力角度看,整体为液体形式的油剂混合物是本发明的有用形式。
本发明的共聚物具有特别优异的与油剂的可混和性,并且可获得在较长时间间隔内都是均匀的共聚物组合物。该组合物可在不改性的情况下自身用作表面处理剂。或者,从处理能力和贮存稳定性角度看,该组合物尤其可用作用于化妆品的原材料。更具体地讲,可优选地使用由100质量份的本发明的共聚物以及5至1,000质量份的油剂、优选50至500质量份的油剂并且更优选100至400质量份的油剂形成的共聚物组合物。在通过用油剂稀释本发明的共聚物来获得共聚物组合物的情况下,可通过机械力将在聚合反应后移除了溶剂和未反应单体的共聚物均匀地分散于油剂中。或者,可将聚合反应中使用的挥发性溶剂替换为油剂。
有机硅油优选地作为油剂。只要有机硅油为油剂,则其是疏水的,并且其分子结构可为环状、直链或支链结构。有机硅油在25℃下的粘度通常在0.65至100,000mm2/s的范围内,并且优选地在0.65至10,000mm2/s的范围内。具体地讲,当本发明的共聚物用作化妆品原材料时,通过添加至少一种类型的此类有机硅油,可以改善所得化妆品的随时间的稳定性,并且可以实现有机硅油的特有清新感。
有机硅油的具体例子包括环状有机聚硅氧烷、直链有机聚硅氧烷和支链有机聚硅氧烷。在这些示例性有机硅油中,挥发性的直链有机聚硅氧烷、支链有机聚硅氧烷和环状有机聚硅氧烷是优选的。由环状有机聚硅氧烷构成的挥发性有机硅油是最适当的。
由下列通式(3)、(4)和(5)表示的有机聚硅氧烷可用作有机硅油。
[式18]
在该式中,
R9为氢原子、羟基基团、或选自具有1至30个碳原子的单价未取代的或者氟或氨基取代的烷基基团、芳基基团或烷氧基基团的基团、以及由(CH3)3SiO{(CH3)2SiO}lSi(CH3)2CH2CH2-表示的基团(其中I为0至1,000范围内的整数);
a'为0至3的整数;
b为0至1,000的整数;且
c'为0至1,000的整数,其中1≤b+c≤2,000。
[式19]
在该式中,
R9与上述相同;
d为0至8的整数;且
e为0至8的整数,其中3≤d+e≤8。
[式20]
R9 (4-f)Si(OSiCH3)g (5)
在该式中,
R9与上述相同;
f为1至4的整数;且
g为0至500的整数。
具有1至30个碳原子的单价未取代的或者氟或氨基取代的烷基基团、芳基基团和烷氧基基团被示例为具有1至30个碳原子的直链或支链的烷基基团,诸如甲基基团、乙基基团、丙基基团、丁基基团、戊基基团、己基基团、庚基基团、辛基基团、癸基基团、十二烷基基团等等;具有3至30个碳原子的环烷基基团,诸如环戊基基团、环己基基团等等;具有6至30个碳原子的芳基基团,诸如苯基基团、甲苯基基团、二甲苯基基团、萘基基团等等;具有1至30个碳原子的烷氧基基团,诸如甲氧基基团、乙氧基基团、丙氧基基团等等;以及其取代的基团,其中键合至上述基团的碳原子的氢原子至少部分地被氟原子或氨基基团取代。未取代的烷基基团或芳基基团是优选的,并且具有1至6个碳原子的未取代的烷基基团或芳基基团是进一步优选的。甲基基团、乙基基团或苯基基团是特别优选的。
具体而言,具有上述结构的有机硅油的例子包括环状有机聚硅氧烷,诸如六甲基环三硅氧烷(D3)、八甲基环四硅氧烷(D4)、十甲基环五硅氧烷(D5)、十二甲基-环六硅氧烷(D6)、1,1-二乙基六甲基环四硅氧烷、苯基七甲基环四硅氧烷、1,1-二苯基六甲基环四硅氧烷、1,3,5,7-四乙烯基四甲基环四硅氧烷、1,3,5,7-四甲基环四硅氧烷、1,3,5,7-四环己基四甲基环四硅氧烷、三(3,3,3-三氟丙基)三甲基环三硅氧烷、1,3,5,7-四(3-甲基丙烯酰氧基丙基)四甲基环四硅氧烷、1,3,5,7-四(3-丙烯酰氧基丙基)四甲基环四硅氧烷、1,3,5,7-四(3-羧丙基)四甲基环四硅氧烷、1,3,5,7-四(3-乙烯氧基丙基)四甲基环四硅氧烷、1,3,5,7-四(对乙烯基苯基)四甲基环四硅氧烷、1,3,5,7-四[3-(对乙烯基苯基)丙基]四甲基环四硅氧烷、1,3,5,7-四(N-丙烯酰基-N-甲基-3-氨丙基)四甲基环四硅氧烷、1,3,5,7-四(N,N-双(月桂酰)-3-氨丙基)四甲基环四硅氧烷等等。
直链有机聚硅氧烷的例子包括二甲基聚硅氧烷,其中两个分子末端用三甲基甲硅烷氧基基团封端(具有低粘度诸如2cst或6cst的二甲基有机硅至具有高粘度诸如1,000,000cst的二甲基有机硅);有机氢聚硅氧烷;甲基苯基聚硅氧烷,其中两个分子末端用三甲基甲硅烷氧基基团封端;甲基苯基硅氧烷与二甲基硅氧烷的共聚物,其中两个分子末端用三甲基甲硅烷氧基基团封端;二苯基聚硅氧烷,其中两个分子末端用三甲基甲硅烷氧基基团封端;二苯基硅氧烷与二甲基硅氧烷的共聚物,其中两个分子末端用三甲基甲硅烷氧基基团封端;三甲基五苯基三硅氧烷;苯基(三甲基甲硅烷氧基)硅氧烷;甲基烷基聚硅氧烷,其中两个分子末端用三甲基甲硅烷氧基基团封端;甲基烷基硅氧烷与二甲基聚硅氧烷的共聚物,其中两个分子末端用三甲基甲硅烷氧基基团封端;甲基(3,3,3-三氟丙基)硅氧烷与二甲基硅氧烷的共聚物,其中两个分子末端用三甲基甲硅烷氧基基团封端;α,ω-二羟基聚二甲基硅氧烷;α,ω-二乙氧基聚二甲基硅氧烷;1,1,1,3,5,5,5-七甲基-3-辛基三硅氧烷;1,1,1,3,5,5,5-七甲基-3-十二烷基三硅氧烷;1,1,1,3,5,5,5-七甲基-3-十六烷基三硅氧烷;三(三甲基甲硅烷氧基)甲基硅烷;三(三甲基甲硅烷氧基)烷基硅烷;四(三甲基甲硅烷氧基)硅烷;四甲基-1,3-二羟基二硅氧烷;八甲基-1,7-二羟基四硅氧烷;六甲基-1,5-二乙氧基三硅氧烷;六甲基二硅氧烷;八甲基三硅氧烷;高级烷氧基改性有机硅;高级脂肪酸改性有机硅等等。
支链有机聚硅氧烷的例子包括甲基三(三甲基甲硅烷氧基)硅烷、乙基三(三甲基甲硅烷氧基)硅烷、丙基三(三甲基甲硅烷氧基)硅烷、四(三甲基甲硅烷氧基)硅烷、苯基三(三甲基甲硅烷氧基)硅烷等等。
优选地,除有机硅油之外的油剂在5至100℃下为液体。优选地,除有机硅油之外的油剂为烃油和/或脂肪族酯油。此类油剂可单独使用或可与有机硅油一起使用。
当本发明的共聚物用作化妆品原材料时,通过烃油和/或脂肪酸酯油与有机硅油的组合使用,除了有机硅油的特有清新感觉之外,还可以保持皮肤上的水分并赋予光滑感觉或保湿感觉(也称为“湿润感觉”)就好像皮肤或毛发被化妆品润湿一样。然而,即使当本发明的共聚物用作表面处理剂时,本发明的共聚物也是有利的,因为不会失去化妆品的随时间的稳定性。此外,当化妆品组合物包含烃油和/或脂肪酸酯油和有机硅油时,这些保湿组分可更稳定和均匀地施用于皮肤或毛发上,保湿组分对皮肤的保湿效果得以改善,并且与仅包含除有机硅油之外的油剂(烃油和/或脂肪族酯油)的化妆品组合物相比,赋予了更光滑、更丰腴的触感。
烃油的例子包括液体石蜡、轻质液体异链烷烃、重质液体异链烷烃、凡士林、正链烷烃、异链烷烃、异十二烷、异十六烷、聚异丁烯、氢化聚异丁烯、聚丁烯、地蜡、纯地蜡、微晶蜡、石蜡、聚乙烯蜡、聚乙烯/聚丙烯蜡、角鲨烷、角鲨烯、姥鲛烷、聚异戊二烯等等。
脂肪酸酯油的例子包括辛酸己基癸酯、辛酸鲸蜡醇酯、肉豆蔻酸异丙酯、棕榈酸异丙酯、硬脂酸丁酯、月桂酸己酯、肉豆蔻酸肉豆蔻酯、油酸油醇酯、油酸癸酯、肉豆蔻酸辛基十二烷醇酯、二甲基辛酸己基癸酯、乳酸鲸蜡醇酯、乳酸肉豆蔻酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯、乙酸羊毛脂酯、乙二醇单硬脂酸酯、丙二醇单硬脂酸酯、丙二醇二油酸酯、单硬脂酸甘油酯、单油酸甘油酯、三-2-乙基己酸甘油酯、三羟甲基丙烷三-2-乙基己酸酯、三羟甲基丙烷三乙基己酸酯、三羟甲基丙烷异硬脂酸酯/癸二酸酯、三羟甲基丙烷三辛酸酯、三羟甲基丙烷三异硬脂酸酯、己二酸二异丙酯、己二酸二异丁酯、己二酸2-己基癸酯、己二酸二-2-庚基十一烷醇酯、二异硬脂醇苹果酸酯、氢化蓖麻油单硬脂酸酯、N-烷基二醇单异硬脂酸酯、异硬脂酸辛基十二烷醇酯、异硬脂酸异丙酯、异硬脂酸异鲸蜡醇酯、乙二醇二-2-乙基己酸酯、2-乙基己酸鲸蜡醇酯、季戊四醇四-2-乙基己酸酯、辛基十二烷基胶酯、油酸乙酯、油酸辛基十二烷酯、新戊二醇二癸酸酯、柠檬酸三乙酯、琥珀酸2-乙基己酯、琥珀酸二辛酯、硬脂酸异鲸蜡醇酯、癸二酸二异丙酯、癸二酸二-2-乙基己酯、癸二酸二乙酯、癸二酸二辛酯、癸二酸二丁基辛酯、棕榈酸鲸蜡醇酯、棕榈酸辛基十二烷酯、棕榈酸辛酯、棕榈酸2-乙基己酯、棕榈酸2-己基癸酯、棕榈酸2-庚基十一烷酯、胆甾醇12-羟基硬脂酸酯、二季戊四醇脂肪酸酯、肉豆蔻酸2-己基癸酯、月桂酸乙酯、N-月桂酰基-L-谷氨酸2-辛基十二烷酯、二(胆甾醇/山嵛醇/辛基十二烷醇)N-月桂酰基-L-谷氨酸酯、二(胆甾醇/辛基十二烷醇)N-月桂酰基-L-谷氨酸酯、二(植物甾醇/山嵛醇/辛基十二烷醇)N-月桂酰基-L-谷氨酸酯、二(植物甾醇/辛基十二烷醇)N-月桂酰基-L-谷氨酸酯、N-月桂酰基肌氨酸异丙酯、二异硬脂醇苹果酸酯、新戊二醇二辛酸酯、新戊酸异癸酯、新戊酸异十三烷酯、异硬脂醇新戊酸酯、异壬酸异壬酯、异壬酸异十三烷基酯、异壬酸辛酯、异壬酸十三烷基酯、二乙基戊二醇二新戊酸酯、甲基戊二醇二新戊酸酯、新癸酸辛基十二烷酯、2-丁基-2-乙基-1,3-丙二醇二辛酸酯、季戊四醇四辛酸酯、季戊四醇氢化松香、季戊四醇三乙基己酸酯、二季戊四醇(羟基硬脂酸酯/硬脂酸酯/松脂酸酯)、聚甘油四异硬脂酸酯、聚甘油-10九异硬脂酸酯、聚甘油-8十(芥酸酯/异硬脂酸酯/蓖麻醇酸酯)、(己基十二烷酸/癸二酸)二甘油基低聚酯、乙二醇二硬脂酸酯(glycoldistearate)(乙二醇二硬脂酸酯(ethylene glycol distearate))、二聚亚油酸二异丙酯、二异硬脂醇二聚亚油酸酯、二(异硬脂醇/植物甾醇)二聚亚油酸酯、(植物甾醇/山嵛醇)二聚亚油酸酯、(植物甾醇/异硬脂醇/鲸蜡醇/硬脂醇/山嵛醇)二聚亚油酸酯、二聚亚油醇二聚亚油酸酯、二聚亚油醇二异硬脂酸酯、二聚亚油醇氢化松香浓缩物、二聚二亚油酸硬化蓖麻油、羟基烷基二聚亚油醇醚、三异辛酸甘油酯、三异硬脂酸甘油酯、三肉豆蔻酸甘油酯、三异棕榈酸甘油酯、三辛酸甘油酯、三油酸甘油酯、二异硬脂酸甘油酯、甘油三(辛酸酯/癸酸酯)、甘油三(辛酸酯/癸酸酯/豆蔻酸酯/硬脂酸酯)、氢化松香甘油三酯(氢化酯胶)、松香甘油三酯(酯胶)、甘油山嵛酸酯二十烷二酸酯(glyceryl behenate eicosane dioate)、二-2-庚基十一烷酸甘油酯、二甘油豆蔻酸酯异硬脂酸酯、胆甾醇乙酸酯、胆甾醇壬酸酯、胆甾醇硬脂酸酯、胆甾醇异硬脂酸酯、胆甾醇油酸酯、胆甾醇12-羟基硬脂酸酯、澳洲坚果油脂肪酸的胆甾醇酯、澳洲坚果油脂肪酸的植物甾醇酯、植物甾醇异硬脂酸酯、软羊毛脂脂肪酸的胆甾醇酯、硬羊毛脂脂肪酸的胆甾醇酯、长链支链脂肪酸的胆甾醇酯、长链α-羟基脂肪酸的胆甾醇酯、蓖麻醇酸辛基十二烷酯、羊毛脂脂肪酸的辛基十二烷酯、芥酸辛基十二烷酯、异硬脂酸硬化蓖麻油、鳄梨脂肪酸的乙酯、羊毛脂脂肪酸的异丙酯等。
除了上述以外,脂肪和油、高级醇、高级脂肪酸、基于氟的油等等可以其两种或更多种类型的组合使用。例如,下述油剂也可以两种或更多种类型的组合使用。在下文中,将详细描述可用于本发明的除有机硅油、烃油和脂肪酸酯油之外的油剂。
此类脂肪和油的例子包括天然动物或植物脂肪和油以及半合成脂肪和油,诸如鳄梨油、亚麻籽油、扁桃仁油、水蜡树蜡、紫苏子油、橄榄油、可可脂、爪哇木棉蜡、榧子油、巴西棕榈蜡、肝油、小烛树蜡、牛脂、牛脚油、牛骨脂、氢化牛脂、杏仁油、鲸蜡、氢化油、麦胚芽油、芝麻油、米胚芽油、米糠油、甘蔗蜡、山茶花油、红花油、乳木果脂、中国桐油、肉桂油、霍霍巴蜡、橄榄油、角鲨烷、紫胶蜡、海龟油、大豆油、茶籽油、山茶油、月见草油、玉米油、猪油、菜籽油、日本桐油、米糠蜡、胚芽油、马脂、桃仁油、棕榈油、棕榈仁油、蓖麻油、氢化蓖麻油、蓖麻油脂肪酸甲酯、葵花油、葡萄油、杨梅蜡、霍霍巴油、氢化霍霍巴酯、澳洲坚果油、蜂蜡、貂油、棉籽油、棉蜡、日本蜡、日本蜡核油、褐煤蜡、椰子油、氢化椰子油、三椰子油脂肪酸甘油酯、羊脂、花生油、羊毛脂、液体羊毛脂、还原的羊毛脂、羊毛脂醇、硬羊毛脂、羊毛脂乙酸酯、羊毛脂脂肪酸异丙酯、POE羊毛脂醇醚、POE羊毛脂醇乙酸酯、羊毛脂脂肪酸聚乙二醇、POE氢化羊毛脂醇醚、蛋黄油等等。本文中,“POE”意指“聚氧乙烯”。
高级醇的例子包括月桂醇、肉豆蔻醇、棕榈醇、硬脂醇、山嵛醇、十六烷醇、油醇、异硬脂醇、己基十二烷醇、辛基十二烷醇、鲸蜡硬脂醇、2-癸基十四烷醇、胆甾醇、谷甾醇、植物甾醇、羊毛甾醇、POE胆甾醇醚、单硬脂基甘油醚(鲨肝醇)、单油基甘油醚(鲨油醇)等等。
高级脂肪酸的例子包括月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、山萮酸、十一碳烯酸、油酸、亚油酸、亚麻酸、花生四烯酸、二十碳五烯酸(EPA)、二十二碳六烯酸(DHA)、异硬脂酸、12-羟基硬脂酸等等。
基于氟的油的例子包括全氟聚醚、全氟萘烷、全氟辛烷等。
共聚物具备成膜能力。共聚物能够在粉末的表面上形成膜并且将粉末的表面性质改变为斥水粉末的表面性质。因此,本发明的共聚物或者包含本发明的共聚物的液体组合物特别可用作表面处理剂并且可有利地用于使粉末具有斥水性。此外,由于不会产生氢气,共聚物是安全的。
本发明的共聚物作为表面处理剂的用途将在下文详细阐述。
本发明的表面处理剂有利地用于对(E)一种或多种类型的粉末或染色剂进行表面处理,特别是用于对化妆品中所用的任何粉末(包括用作染色剂的粉末颜料)进行表面处理。本发明的表面处理剂可提供具有优异的使用感觉、抗水性、抗皮脂性等等的处理过的粉末。任何形态(球形、针形、片状等等)、粒径(气溶胶状、微粒、颜料级尺寸等等)或粒子结构(多孔、无孔等等)均是容许的且可用作粉末和染色剂,只要粉末和染色剂通常用于化妆品即可。粉末或染色剂被示例为无机粉末、有机粉末、表面活性剂金属盐粉末、有色颜料、珠光颜料、金属粉末颜料、焦油颜料、天然颜料等等。该粉末等等优选地为选自具有1nm至20μm范围内的平均粒径的无机颜料粉末、有机颜料粉末和树脂粉末的至少一种类型。
此外,粉末等等优选部分地或全部地进行表面处理,诸如斥水处理、亲水化处理等等。应注意,可配混这些粉末。具体而言,可使用已用氟化合物、表面活性剂、增稠剂等等进行表面处理的粉末等等。根据需要,可使用其一种或两种或更多种类型。具体而言,粉末等等优选地经受斥水处理。
斥水处理不受到特别限制,并且其例子包括各种处理,其中粉末等等用斥水剂进行表面处理。其具体例子包括有机硅处理,诸如甲基氢聚硅氧烷处理、有机硅树脂处理、有机硅胶处理、丙烯酰基有机硅处理、氟化有机硅处理等等;金属皂处理,如硬脂酸锌处理等;硅烷处理,诸如硅烷偶联剂处理、烷基硅烷处理等等;氟化合物处理,诸如全氟烷基硅烷处理、全氟烷基磷酸酯处理、全氟聚醚处理等等;氨基酸处理,如N-月桂酰基-L-赖氨酸处理等;油剂处理,如角鲨烷处理等;以及丙烯酰处理,诸如丙烯酸烷基酯处理等等。可使用上述处理中两种或更多种的组合。
最优选地,用于本发明的粉末等等使用氟化化合物诸如全氟烷基硅烷、全氟烷基磷酸酯、全氟聚醚等等进行处理,或者通过甲基氢聚硅氧烷处理、有机硅树脂处理、有机硅胶处理、丙烯酰基有机硅处理、氟化有机硅处理等等进行有机硅处理,以产生(E1)斥水性处理过的粉末或染色剂。
粉末或染色剂的具体例子包括无机粉末、有机粉末、表面活性剂金属盐粉末(金属皂)、有色颜料、珠光颜料、金属粉末颜料、有机硅弹性体粉末等等。另外,也可使用这些颜料的复合产品。此外,该粉末或染色剂包括充当紫外线阻断组分的粉末和染色剂。
更具体地讲,无机粉末的例子包括氧化钛、氧化锆、氧化锌、氧化铈、氧化镁、硫酸钡、硫酸钙、硫酸镁、碳酸钙、碳酸镁、滑石、云母、高岭土、绢云母、白云母、合成云母、金云母、红云母、黑云母、锂云母、硅酸、硅酸酐、硅酸铝、硅酸镁、硅酸铝镁、硅酸钙、硅酸钡、硅酸锶、钨酸的金属盐、羟基磷灰石、蛭石、氢氧化铝(higilite)、膨润土、蒙脱石、锂蒙脱石、沸石、陶瓷粉末、磷酸二钙、氧化铝、氢氧化铝(aluminum hydroxide)、氮化硼、二氧化硅等等。有机粉末的例子包括聚酰胺粉末、聚酯粉末、聚乙烯粉末、聚丙烯粉末、聚苯乙烯粉末、聚氨酯粉末、苯并胍胺粉末、聚甲基苯并胍胺粉末、四氟乙烯粉末、聚(甲基丙烯酸甲酯)粉末、纤维素、丝粉、尼龙粉末、尼龙12、尼龙6、有机硅粉末、苯乙烯和丙烯酸的共聚物、二乙烯基苯和苯乙烯的共聚物、乙烯基树脂、尿素树脂、酚树脂、氟树脂、硅树脂、丙烯酸树脂、三聚氰胺树脂、环氧树脂、聚碳酸酯树脂、微晶纤维粉末、淀粉、月桂酰赖氨酸等等。表面活性剂金属盐粉末(金属皂)的例子包括硬脂酸锌、硬脂酸铝、硬脂酸钙、硬脂酸镁、肉豆蔻酸锌、肉豆蔻酸镁、鲸蜡基磷酸锌、鲸蜡基磷酸钙、鲸蜡基磷酸锌钠等等。有色颜料的例子包括无机红色颜料,诸如氧化铁、氢氧化铁、钛铁矿等等;无机棕色颜料,诸如γ-氧化铁等等;无机黄色颜料,诸如氧化铁黄、黄赭石等等;无机黑铁颜料,诸如氧化铁黑、碳黑等等;无机紫色颜料,诸如锰紫、钴紫等等;无机绿色颜料,如氢氧化铬、氧化铬、氧化钴、钛酸钴等;无机蓝色颜料,如普鲁士蓝(Prussian blue)、群青蓝等;作为此类粉末的复合物制备的色淀处理过的焦油颜料、色淀处理过的天然颜料和合成树脂粉末等等;珠光颜料,诸如氧化钛涂布的云母、氯氧化铋、氧化钛涂布的氯氧化铋、氧化钛涂布的滑石、鱼鳞箔、氧化钛涂布的有色云母等等;以及金属粉末颜料,诸如铝粉、铜粉、不锈钢粉等等。焦油颜料的例子包括红No.3、红No.104、红No.106、红No.201、红No.202、红No.204、红No.205、红No.220、红No.226、红No.227、红No.228、红No.230、红No.401、红No.505、黄No.4、黄No.5、黄No.202、黄No.203、黄No.204、黄No.401、蓝No.1、蓝No.2、蓝No.201、蓝No.404、绿No.3、绿No.201、绿No.204、绿No.205、橙No.201、橙No.203、橙No.204、橙No.206、橙No.207等等。天然颜料的例子包括胭脂红酸、紫胶酸、红花素、巴西木素、藏红花素等等。
有机硅弹性体粉末是主要由二有机硅氧基单元(D单元)形成的直链二有机聚硅氧烷的交联产物,并可优选通过以下方式获得:使在侧链或分子末端上具有硅键合的氢原子的有机氢聚硅氧烷与在侧链或分子末端上具有诸如烯基等之类的不饱和烃基的二有机聚硅氧烷在存在硅氢加成反应催化剂的情况下交联。与由T单元和Q单元形成的有机硅树脂粉末相比,所述有机硅弹性体粉末柔软、具有弹性并具有优异的吸油性。因此,可吸收皮肤上的油脂,并可防止化妆品变花。
有机硅弹性体粉末可以为各种形式,如球形、扁平、无定形等。有机硅弹性体粉末可以为油分散体的形式。对于本发明的化妆品组合物,可优选配混具有颗粒形状,具有使用电子显微镜观测到的0.1至50μm范围内的原生粒度和/或通过激光衍射/散射法测得的0.1至50μm范围内的平均原生粒度,以及具有球形原生粒子的有机硅弹性体粉末。构成有机硅弹性体粉末的有机硅弹性体优选为具有80或更低的硬度,更优选65或更低的硬度的弹性体,所述硬度如使用在JIS K 6253中指定的“Rubber,Vulcanized orThermoplastic-Determination of Hardness”(硫化或热塑性橡胶硬度测定)中的A型硬度计测得。
有机硅弹性体粉末可任选地使用有机硅树脂、二氧化硅等等进行表面处理。表面处理的例子包括日本未经审查的专利申请公布No.H02-243612、H08-12545、H08-12546、H08-12524、H09-241511、H10-36219、H11-193331和2000-281523中所述的那些。应注意,如“Standards ofCosmetic Components by Category”(按类别的化妆品组分的标准)中列举的交联有机硅粉末对应于有机硅弹性体粉末。可作为有机硅弹性体粉末市售的产品被示例为由道康宁东丽株式会社(Dow Corning Toray Co.,Ltd.)制造的Trefil E-506S、Trefil E-508、9701化妆品粉末和9702粉末等等。
如果本发明的表面处理剂用于粉末等等的表面处理时,表面处理可例如通过干法或湿法进行,干法是使用本发明的表面处理剂与要进行处理的粉末的干混合,在湿法中,本发明的表面处理剂分散于溶剂中,将溶剂混合物与要进行处理的粉末进一步湿混合,然后干燥处理过的粉末。然而,表面处理方法不限于这些方法。此外,表面处理可通过如下方式进行:将本发明的表面处理剂稀释于化妆品中所用的油剂中以制备液体组合物形式的本发明的表面处理剂,然后将液体组合物与粉末混合以形成浆液状分散体。
对于使用本发明的表面处理剂对粉末等等进行表面处理而言,湿法是优选的。任何温度均可用于湿法中的混合,但混合温度优选地为60至80℃。此外,虽然混合时间将根据处理过的粉末的量、粉末的类型等等而变化,但混合时间通常为1至3小时。
虽然本发明的表面处理剂的用量将根据用于粉末等等的表面处理的粉末的类型而变化,但一般来讲,该用量优选地为未处理过的粉末的1至10重量%,并且进一步优选地为1至5重量%。当表面处理剂的用量小于1重量%时,在共混于化妆品中时感觉等等的改善效果可能不足。如果表面处理剂的用量超过10重量%,并且如果将处理过的粉末共混于化妆品中,则存在的问题是使用感觉会变得更糟,因为化妆品涂层会变厚等等。
本发明的共聚物用作具有亲水性基团且具有多元接枝到主链的非直链的(即高度支化的)树枝状有机硅的共聚物。因此可以使用本发明的共聚物对广泛的化妆品粉末等等进行表面处理,并且可获得包含本发明的共聚物和(E)一种或多种类型的粉末或染色剂的粉末组合物。本发明的粉末组合物具有优异的粉末等等的分散稳定性、在用于制备浆液时的流动性、处理能力、以及化妆品等等中的配混稳定性。此外,当施用于皮肤时,本发明的共聚物被表征为能够在油剂挥发后几乎完全抑制粉末等等的分散失效,即使当粉末等等通过斥水处理而制备(诸如氟处理过的粉末或染色剂)时也是如此。
由于本发明的共聚物、以及包含该共聚物的液体组合物、表面处理剂和粉末组合物具有上述特性,本发明的共聚物、包含该共聚物的液体组合物、表面处理剂和粉末组合物可用作化妆品原材料。通过与其他化妆品原材料诸如各种类型的粉末、油剂等等一起共混于化妆品中,可以提供从抗水性、抗皮脂性、光泽、感觉、对毛发的附着性、对皮肤的附着性等等的角度看优异的表面保持、外观和使用感觉。
当本发明的共聚物、或者包含该共聚物的液体组合物、表面处理剂或粉末组合物作为化妆品原材料共混于各种类型的化妆品中时,化妆品原材料的其他类型和共混的化妆品的类型例如与日本未经审查的专利申请公布No.2011-148784中公开的化妆品原材料等等相同,而不受到特别限制。
具体而言,也可将选自阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂和两性表面活性剂的至少一种类型表面活性剂与本发明的化妆品原材料一起共混于化妆品中。表面活性剂的具体例子与日本未经审查的专利申请公布No.2011-148784的第0079至0084段等等中公开的那些相同,而不受到特别限制。
此外,除了(D)一种或多种类型的油剂和(E)一种或多种类型的粉末或染色剂之外,本发明的化妆品原材料还可包含多种成分诸如水溶性聚合物、油溶性胶凝剂、有机改性粘土矿物、有机硅胶、有机硅树脂、有机硅弹性体、有机改性有机硅、紫外线阻断组分等等。此类成分的具体例子与日本未经审查的专利申请公布No.2011-148784的第0087至0101段等等中公开的那些相同,而不受到特别限制。
优选地将选自微粒氧化钛、微粒氧化锌、对甲氧基肉桂酸2-乙基己酯、4-叔丁基-4'-甲氧基二苯甲酰基甲烷、以及基于二苯甲酮的紫外线吸收剂的至少一种类型的紫外线阻断组分与本发明的化妆品原材料一起共混于化妆品中。优选地将氟处理过的微粒氧化钛和氟处理过的微粒氧化锌与本发明的化妆品原材料一起共混于化妆品中。通常使用这些紫外线阻断组分,它们易于获取,并具有高紫外线阻断效果,并因此可有益地加以使用。具体地讲,同时使用无机和有机紫外线阻断组分是优选的,并且与UV-B阻断组分结合使用UV-A阻断组分是更优选的。
可在不削弱本发明效果的范围内将通常用于化妆品的其他成分与本发明的化妆品原材料一起共混于化妆品中。此类其他成分被示例为醇、有机树脂、保湿剂、防腐剂、抗微生物剂、香料、盐、抗氧化剂、pH调节剂、螯合剂、清新剂、抗炎剂、美肤组分(诸如亮肤剂、细胞活化剂、皮肤粗糙改善剂、循环促进剂、收敛剂、抗皮脂溢剂等等)、维生素、氨基酸、核酸、激素、包合物化合物等等。此类成分的具体例子与日本未经审查的专利申请公布No.2011-148784的第0103至0116段等等中公开的那些相同,而不受到特别限制。
可根据其目的将本发明的化妆品原材料与一种类型或者两种或更多种类型的天然植物提取物组分、海藻提取物组分、草本植物提取物等等共混于化妆品中。此类天然组分的具体例子与日本未经审查的专利申请公布No.2011-148784的第0119段等等中公开的那些相同,而不受到特别限制
根据其目的,在化妆品中,除水诸如纯化水、矿质水等等之外,本发明的化妆品原材料还可与溶剂诸如轻质异链烷烃、醚、LPG、N-甲基吡咯烷酮、或者含氯氟烃等等共混。
除本发明的共聚物之外,本发明的化妆品原材料可包含选自其他丙烯酰基有机硅树枝状共聚物(包括日本未经审查的专利申请公布No.2011-148784等等中公开的那些)、聚酰胺改性有机硅、烷基改性有机硅蜡、以及烷基改性有机硅树脂蜡的至少一种类型的组分。此类组分的具体例子与日本未经审查的专利申请公布No.2011-148784的第0122至0125段等等中公开的那些相同,而不受到特别限制。
本发明的化妆品原材料可共混成任何形式诸如液体、乳状洗剂、乳霜、固体、糊剂、凝胶、粉末、多层、摩丝、喷剂等等的化妆品的成分。
不受到特别限制,本发明化妆品原材料可共混于其中的产品的具体例子包括皮肤护理产品,诸如皮肤清洁剂产品、皮肤护理产品、化妆产品、防汗产品、紫外线阻断产品等等;毛发化妆品,诸如毛发洗涤产品、毛发定型产品、毛发染料产品、脱发治疗产品、护发产品、毛发调理产品、毛发处理产品等等;沐浴化妆产品;毛发再生剂、毛发生长促进剂、止痛剂、杀菌剂、抗炎剂、清新剂以及皮肤抗老化剂。
皮肤用化妆产品可用于全身的任何部位,包括头皮、面部(包括嘴唇、眉毛和脸颊)、手指和指甲。其具体例子包括清洁凝胶、清洁膏、清洁泡沫、洁面霜、眼部卸妆液、洁面泡沫、液体皂(沐浴皂)、洗手皂、凝胶状肥皂、剃须膏、洗甲水、祛痘化妆品组合物以及类似的皮肤清洁剂产品;护肤霜、头皮护理剂、皮肤乳液、乳状洗剂、乳液、面膜、香体粉、精华液、剃须乳液、按摩乳液以及类似的护肤产品;粉底、液体粉底、油性粉底、隔离霜、粉饼、扑面粉、颊彩、护唇膏、唇膏、唇彩、护眼霜、睫毛膏、眉笔、睫毛化妆产品以及类似的彩妆产品;除臭剂和类似的止汗剂;以及防晒剂、美黑用药物(美黑剂),以及类似的紫外线遮蔽产品。
头皮用化妆产品的例子包括洗发剂、冲洗型洗发水以及类似的头发用清洁剂;发蜡、卷发保持剂、定型剂、发乳、发胶、发液和类似的美发产品;染发物质、染发喷雾、染发水、染发棒以及类似的头发用染色产品;生发油、头发护理精华液、发膜和类似的生发产品;以及护发油、护发膏、护理膏、护发素、头发护理剂以及类似的护发液或护发产品。此外,沐浴用化妆产品的例子包括沐浴液。
可将本发明的共聚物共混于用于其他应用的非化妆产品中,诸如各种类型的外用制剂、涂料、涂层剂、消泡剂、除臭剂等等。
实例
下文将参照实践例和比较例详细描述本发明,但是应当理解本发明不限于这些实践例。在25℃下测量粘度(动力粘度)值。此外,分子量值指示使用凝胶渗透色谱法(GPC)基于聚苯乙烯测定的重均分子量,或表示为重均分子量除以数均分子量的比率(Mw/Mn)。
实践例1
将100g的异丙醇(IPA)置于配备有搅拌器、温度计和回流冷凝器的500mL四颈烧瓶中。使用氮气鼓泡并进行充分的脱气,然后将烧瓶加热至80℃。将25g的甲基丙烯酸甲酯、10g的丙烯酸2-乙基己酯、20g的甲基丙烯酸羟乙酯、45g的由下式(A)表示的碳硅氧烷树枝状单体、
式21
30g的异丙醇和1.0g的2,2'-偶氮二-2-甲基丁腈(由大冢化学株式会社(Otsuka Chemical Co.,Ltd.)制造)加入滴液漏斗中,并使混合物溶解。当单体混合物在氮气氛下保持于80℃时,使用滴液漏斗在2小时内逐滴添加。在完成逐滴添加后,将混合物在氮气氛下搅拌并加热6小时。在完成搅拌后,通过气相色谱法分析反应产物的聚合加成率。结果,发现聚合的加成率为97%,并且确定获得了基于乙烯基的聚合物。将250g的十甲基五环硅氧烷加入基于乙烯基的聚合物的异丙醇溶液中。然后通过在120℃下蒸馏来移除IPA。通过减压蒸馏来移除过量的十甲基五环硅氧烷和未反应的单体以将固体含量调节至30重量%。该聚合物的重均分子量为21,700,并且Mw/Mn为1.66。
实践例2
使用与实践例1相同的工序,不同的是向滴液漏斗加入18g的甲基丙烯酸甲酯、7g的丙烯酸2-乙基己酯、30g的甲基丙烯酸羟乙酯、45g的由式(A)表示的碳硅氧烷树枝状单体、以及1.0g的2,2'-偶氮二-2-甲基丁腈(由大冢化学株式会社制造)。获得了乙烯基聚合物的十甲基五硅氧烷溶液。该聚合物的重均分子量为12,800,并且Mw/Mn为2.24。
实践例3
使用与实践例1相同的工序,不同的是向滴液漏斗加入32g的甲基丙烯酸2-乙基己酯、5g的丙烯酸2-乙基己酯、18g的甲基丙烯酸甘油酯、45g的由式(A)表示的碳硅氧烷树枝状单体、以及1.0g的2,2'-偶氮二-2-甲基丁腈(由大冢化学株式会社制造)。获得了乙烯基聚合物的十甲基五硅氧烷溶液。
实践例4
使用与实践例1相同的工序,不同的是向滴液漏斗加入20g的甲基丙烯酸三氟乙酯、5g的丙烯酸2-乙基己酯、30g的甲基丙烯酸羟乙酯、45g的由式(A)表示的碳硅氧烷树枝状单体、以及1.0g的2,2'-偶氮二-2-甲基丁腈(由大冢化学株式会社制造)。获得了乙烯基聚合物的十甲基五硅氧烷溶液。该聚合物的重均分子量为9,300,并且Mw/Mn为4.65。
实践例5
使用与实践例1相同的工序,不同的是向滴液漏斗加入16g的甲基丙烯酸三氟乙酯、4g的丙烯酸2-乙基己酯、35g的甲基丙烯酸羟乙酯、45g的由式(A)表示的碳硅氧烷树枝状单体、以及1.0g的2,2'-偶氮二-2-甲基丁腈(由大冢化学株式会社制造)。获得了乙烯基聚合物的十甲基五硅氧烷溶液。
实践例6
使用与实践例1相同的工序,不同的是向滴液漏斗加入42g的甲基丙烯酸甲酯、10g的丙烯酸2-乙基己酯、3g的甲基丙烯酸羟乙酯、45g的由式(A)表示的碳硅氧烷树枝状单体、以及1.0g的2,2'-偶氮二-2-甲基丁腈(由大冢化学株式会社制造)。获得了乙烯基聚合物的十甲基五硅氧烷溶液。该聚合物的重均分子量为73,300,并且Mw/Mn为3.35。
实践例7
使用与实践例1相同的工序,不同的是向滴液漏斗加入35g的甲基丙烯酸甲酯、10g的丙烯酸2-乙基己酯、10g的甲基丙烯酸羟乙酯、45g的由式(A)表示的碳硅氧烷树枝状单体、以及1.0g的2,2'-偶氮二-2-甲基丁腈(由大冢化学株式会社制造)。获得了乙烯基聚合物的十甲基五硅氧烷溶液。该聚合物的重均分子量为71,400,并且Mw/Mn为3.13。
实践例8
使用与实践例1相同的工序,不同的是向滴液漏斗加入32g的甲基丙烯酸三氟乙酯、5g的丙烯酸2-乙基己酯、18g的甲基丙烯酸甘油酯、45g的由式(A)表示的碳硅氧烷树枝状单体、以及1.0g的2,2'-偶氮二-2-甲基丁腈(由大冢化学株式会社制造)。获得了乙烯基聚合物的十甲基五硅氧烷溶液。该聚合物的重均分子量为6,080,并且Mw/Mn为3.38。
比较例1
使用与实践例1相同的工序,不同的是向滴液漏斗加入36g的甲基丙烯酸甲酯、14g的丙烯酸2-乙基己酯、5g的乙烯基乙酰胺、45g的由式(A)表示的碳硅氧烷树枝状单体、以及1.0g的2,2'-偶氮二-2-甲基丁腈(由大冢化学株式会社制造)。获得了乙烯基聚合物的十甲基五硅氧烷溶液。该聚合物的重均分子量为79,000,并且Mw/Mn为3.35。
比较例2
使用与实践例1相同的工序,不同的是向滴液漏斗加入25g的甲基丙烯酸甲酯、25g的丙烯酸2-乙基己酯、5g的乙烯基乙酰胺、45g的由式(A)表示的碳硅氧烷树枝状单体、以及1.0g的2,2'-偶氮二-2-甲基丁腈(由大冢化学株式会社制造)。获得了乙烯基聚合物的十甲基五硅氧烷溶液。该聚合物的重均分子量为91,100,并且Mw/Mn为4.07。
评价实例1
使用分散器混合12g的有机硅处理过的颜料等级氧化钛(由大东化成工业株式会社(Daito Kasei Kogyo Co.,Ltd.)制造)、1g的实践例中所述的分散剂、以及7g的十甲基五硅氧烷。使用E型旋转粘度计测量粘度,并评价分散性。结果示于表1中。评价标准如下所示。此外,作为比较例3,示出了使用FA 4001CM有机硅丙烯酸酯(由道康宁东丽株式会社生产,表中缩写为“FA 4001CM”)作为分散剂获得的评价结果。
评价标准
●:粘度小于或等于350cP。
○:粘度为350至600cP。
Δ:粘度大于或等于600cP。
[评价实例2]
使用分散器混合12g的有机硅处理过的微粒氧化钛(由帝国化工公司(Tayca Corp.)生产)、3g的实践例中所述的分散剂、以及15g的十甲基五硅氧烷。加入氧化锆小珠(0.8mm),并且使用油漆摇动器分散混合物。分散后,通过过滤移除氧化锆小珠,使用E型旋转粘度计测量粘度,并评价分散性。评价标准如下所示。此外,作为比较例3,示出了使用FA 4001CM有机硅丙烯酸酯(由道康宁东丽株式会社生产,表中缩写为“FA 4001CM”)作为分散剂获得的评价结果。
评价标准
●:粘度小于或等于1,500cP。
○:粘度为1,501至5,000cP。
×:出现胶凝。
[表1]
工业实用性
根据本申请的本发明的共聚物具有优异的稳定性且不产生氢气。高度支化(非直链)树枝状有机硅被多元接枝到共聚物的主链,并且所用共聚物具有亲水性基团。因此,与各种类型的其他有机化合物和粉末原材料的相容性良好,并且可以在化妆品领域之外的工业应用中使用。不受到特别限制,此类应用被示例为具有优异耐热性、耐候性和电特性的清漆和油漆添加剂;各种类型聚氨酯和泡沫材料的改性剂;脱模剂和分离剂;消泡剂;油脂和油化合物;用作绝缘的油、抛光剂、防水剂、加热介质、冷却介质、润滑剂等等;用于橡胶和树脂的改性剂、表面处理剂和添加剂;用于硅烷偶联剂的共混材料、改性剂和前体;用于建筑和衬层应用的涂层材料和密封材料;用于光纤和电线的保护剂、润滑剂和缓冲剂;等等。
Claims (12)
1.一种共聚物,包含:
(A)具有由下式(1)表示的碳硅氧烷树枝状结构的不饱和单体:
其中,
Z为二价有机基团;
p为0或1;
R1和R2各自独立地表示选自烷基基团、芳基基团和芳烷基基团的基团,其具有1至10个碳原子;且
L1为甲硅烷基烷基基团,在i=1的情况下,由下式(2)表示:
其中,
Z和p与上文定义相同;
R1和R2与上文定义相同;
i为1至10范围内的整数,指示所述甲硅烷基烷基基团的总代数;
Li+1为选自氢原子,具有1至10个碳原子的烷基基团、芳基基团和芳烷基基团,以及所述甲硅烷基烷基基团的基团;然而,
在i=c(c为1至10范围内的整数,指示所述甲硅烷基烷基基团的代数)的情况下,Li+1为选自氢原子,具有1至10个碳原子的烷基基团、芳基基团和芳烷基基团的基团;并且在i<c的情况下,Li+1为所述甲硅烷基烷基基团;且
ai为0至3范围内的整数;和
(B)在所述分子中具有至少一个亲水性基团的不饱和单体;
具有所述碳硅氧烷树枝状结构的所述不饱和单体的含量为总单体的35至50质量%。
2.根据权利要求1所述的共聚物;
其中所述(B)在所述分子中具有至少一个亲水性基团的不饱和单体为(B1)具有一元或多元醇式羟基基团的不饱和单体。
3.根据权利要求1或2所述的共聚物;
其中所述共聚物还包含(C)在所述分子中具有至少一个含氟的有机基团的不饱和单体。
4.根据权利要求1至3中任一项所述的共聚物;
其中所述共聚物通过共聚如下物质而获得:所述(A)具有所述碳硅氧烷树枝状结构的不饱和单体、
所述(B)在所述分子中具有至少一个亲水性基团的不饱和单体、以及
所述(C)在所述分子中具有至少一个含氟的有机基团的不饱和单体,它们以一定质量比率范围共聚使得{组分(A)重量含量/总单体重量含量}:{组分(B)重量含量/总单体重量含量}:{组分(C)重量含量/总单体重量含量}分别在[0.35至0.50:0.01至0.40:0.00至0.60]的范围内;
并且满足下列条件:{组分(A)重量含量/总单体重量含量}≥{组分(B)重量含量/总单体重量含量}。
5.根据权利要求1至4中任一项所述的共聚物;
其中所述共聚物通过共聚如下物质而获得:所述(A)具有所述碳硅氧烷树枝状结构的不饱和单体、
所述(B1)在所述分子中具有至少一个一元或多元醇式羟基基团的不饱和单体、以及
(C1)由如下通式表示的不饱和单体:
CH2=CR15COORf
其中,R15为氢原子或甲基基团;Rf为氟代烷基基团或氟代烷氧基氟代亚烷基基团,
它们以一定质量比率范围共聚使得{组分(A)质量含量/总单体质量含量}:{组分(B1)质量含量/总单体质量含量}:{组分(C1)质量含量/总单体质量含量}分别在[0.35至0.50:0.10至0.40:0.10至0.50]的范围内;
并且满足下列条件:{组分(A)质量含量/总单体质量含量}≥{组分(B)质量含量/总单体质量含量}。
6.一种液体组合物,包含:
根据权利要求1至5中任一项所述的共聚物;和
(D)至少一种类型的油剂。
7.一种表面处理组合物,包含根据权利要求1至5中任一项所述的共聚物。
8.一种粉末组合物,包含:
根据权利要求1至5中任一项所述的共聚物;和
(E)至少一种类型的粉末或染色剂。
9.根据权利要求8所述的粉末组合物;
其中所述粉末为(E1)斥水性处理过的粉末或染色剂。
10.一种化妆品原材料,包含根据权利要求1至5中任一项所述的共聚物。
11.一种化妆品原材料,包含根据权利要求6所述的液体组合物。
12.一种化妆品原材料,包含根据权利要求8或9所述的粉末组合物。
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WO2011078407A1 (en) * | 2009-12-24 | 2011-06-30 | Dow Corning Toray Co., Ltd. | Copolymer having carbosiloxane dendrimer structure, and composition and cosmetic containing the same |
WO2012091161A2 (en) * | 2010-12-28 | 2012-07-05 | Dow Corning Toray Co., Ltd. | Curable composition and article having a cured layer from the composition |
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CN108135827A (zh) * | 2015-10-09 | 2018-06-08 | 道康宁东丽株式会社 | 成膜剂以及使用该成膜剂的化妆料组合物及化妆料 |
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US20150232601A1 (en) | 2015-08-20 |
JP6092545B2 (ja) | 2017-03-08 |
US9670301B2 (en) | 2017-06-06 |
EP2887920B1 (en) | 2017-02-22 |
WO2014030770A2 (en) | 2014-02-27 |
EP2887920A2 (en) | 2015-07-01 |
WO2014030770A3 (en) | 2014-04-24 |
KR20150046137A (ko) | 2015-04-29 |
KR102121175B1 (ko) | 2020-06-10 |
CN104684541B (zh) | 2020-03-03 |
JP2014040511A (ja) | 2014-03-06 |
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