CN103402493A - 聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物及其制备方法 - Google Patents
聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物及其制备方法 Download PDFInfo
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- CN103402493A CN103402493A CN2011800649134A CN201180064913A CN103402493A CN 103402493 A CN103402493 A CN 103402493A CN 2011800649134 A CN2011800649134 A CN 2011800649134A CN 201180064913 A CN201180064913 A CN 201180064913A CN 103402493 A CN103402493 A CN 103402493A
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Abstract
本发明提供难以随时间推移或通过加热而着色的新型氨基官能化有机聚硅氧烷,并提供拥有制备难以时间推移或通过加热而着色的新型氨基官能化有机聚硅氧烷的方法,其中可以防止环状副产物的产生,并且上述氨基官能化有机聚硅氧烷可以在不使用复杂和/或麻烦操作的情况下容易地合成。通过使其中两个末端均被SiH基团封端的聚硅氧烷与一个分子中具有两个脂族不饱和键的胺或甲硅烷基胺经历加成反应,获得氧烷-亚烃基氨基亚烃基多嵌段共聚物。
Description
技术领域
本发明涉及一种聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物及其制备方法,以及所述共聚物的用途。
本发明要求2010年12月24日提交的日本专利申请No.2010-288649的优先权,该专利的内容以引用方式并入本文。
背景技术
迄今,已知用于制备氨基官能化有机聚硅氧烷的方法。例如,用于制备所需的氨基官能化有机聚硅氧烷的方法在以下专利中描述:JP-B-S36-8598,其中使用氨基烷基甲基聚硅氧烷与八甲基环四硅氧烷之间的平衡聚合;JP-B-S40-1185,其中使用氯烷基甲基聚硅氧烷与有机胺之间的脱氢氯化反应;以及JP-B-S46-28090,其中使用含末端硅醇基二有机聚硅氧烷与氨基烷基烷氧基硅烷之间的缩合反应。如上所述获得的氨基官能化有机聚硅氧烷已经广泛用于织物处理剂、化妆品添加剂、皮革处理剂、涂料添加剂等内。
发明公开
技术问题
使用平衡聚合的上述制备方法具有的问题在于当增加氨基含量时,大量的环状产物通过环-链平衡而附带产生,并且由于伯氨基通常与有机聚硅氧烷结合,因此随着时间的推移或通过加热易于着色。
另一方面,根据氯烷基甲基聚硅氧烷与有机胺之间的脱氢氯化反应,难以随时间推移或通过加热而着色的仲氨基改性聚硅氧烷可能通过与仲胺的反应合成。然而,存在的问题在于,由于氯化氢作为副产物因使用过量有机胺被捕获,因此附带产生大量的有机胺盐酸盐,并因而需要麻烦的分离和/或纯化操作。
在通过含末端硅醇基的二有机聚硅氧烷与氨基烷基烷氧基硅烷之间的缩合而产生氨基官能化有机聚硅氧烷的方法中,通过使用仲氨基烷基烷氧基硅烷,可以获得仲氨基改性的聚硅氧烷。然而,存在的问题在于,当合成具有增加的氨基含量的聚硅氧烷时,必须使用具有极低分子量的含末端硅醇基的二有机聚硅氧烷,并且由于这个原因,在缩合反应期间不可能避免环化反应,并附带产生氨基官能化环状聚硅氧烷。
本发明的目标是提供一种难以随时间推移或通过加热而着色的新型氨基官能化有机聚硅氧烷。
此外,本发明的另一个目标是提供一种用于产生难以随时间推移或通过加热而着色的新型氨基官能化有机聚硅氧烷的方法,其中可以防止环状副产物的产生,并且上述氨基官能化有机聚硅氧烷可以在不使用复杂和/或麻烦操作的情况下容易地合成。
技术方案
本发明的目标可以通过具有至少一个由以下通式表示的单元的聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物而实现:
其中
每个A独立地表示不具有脂族不饱和键的单价烃基;
每个B独立地表示二价烃基;并且
m表示1至1,000范围内并包括1和1,000的数值。
上述A优选地为甲基。上述B优选地为亚丙基。此外,上述单元的数目可以范围从2至1,000。
本发明的共聚物可以优选地在水性或乳状液组合物中混合。
本发明的共聚物可以尤其优选地在表面处理剂、油漆或化妆品中混合。
本发明的另一个目标可以通过用于产生聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物的方法而实现,包括使其中两个末端均被SiH基团封端的由以下通式表示的聚硅氧烷:
其中
每个A独立地表示不具有脂族不饱和键的单价烃基;并且
m表示1至1,000范围内并包括1和1,000的数值,
以及在一个分子中具有两个脂族不饱和键的由以下通式表示的胺或甲硅烷基胺:
其中
每个C独立地表示含有脂族不饱和键的单价烃基;并且
D表示氢原子或三有机甲硅烷基,
发生加成反应,并任选地进行脱硅反应(desilylation reaction)。
上述A优选地为甲基。上述B优选地为亚丙基。
上述聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物优选地具有至少一个由以下通式表示的单元:
其中
A和m与上述的那些相同;并且
每个B独立地表示二价烃基。
上述单元的数目优选地范围从2至1,000。
发明有益效果
本发明的聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物是一种新型氨基官能化有机聚硅氧烷,并且由于在分子的主链中存在仲氨基,因此随时间推移或通过加热而着色的趋势减低。因此,本发明的共聚物适合作为纤维、织造织物、非织造织物、皮革、粉末等的表面处理剂的组分,以及油漆或化妆品的组分。此外,本发明的共聚物表现出与水的优异相容性,并且可以形成稳定的水性组合物。此外,本发明的共聚物可以稳定具有水相和油相的乳状液的乳化状态。因此,本发明的共聚物优选地用作水性或乳状液组合物的组分。
由于在分子的主链中存在仲氨基,本发明的聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物还可以用作其他有机官能化有机硅多嵌段共聚物的前体。
在用于产生本发明的聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物的方法中,可以防止环状副产物(例如环状聚硅氧烷等)的产生,并且可以在不使用复杂和/或麻烦操作的情况下产生难以随时间推移或通过加热而着色的氨基官能化有机聚硅氧烷。
附图说明
图1是在实例1中产生的聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物的29Si-NMR图。
图2是在实例1中产生的聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物的13C-NMR图。
图3是在实例1中产生的聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物的IR图表。
实施本发明的最佳方式
本发明的聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物是在分子的主链中具有仲氨基的共聚物。
本发明的聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物具有至少一个由以下通式表示的单元:
其中
每个A独立地表示不具有脂族不饱和键的单价烃基;
每个B独立地表示二价烃基;并且
m表示1至1,000范围内并包括1和1,000的数值。
不具有脂族不饱和键的单价烃基的例子包括(例如)取代或未取代的和直链、环状或支链单价烃基。作为其例子,可以提及饱和脂族烃基,例如甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、癸基、十二烷基等;饱和脂环族烃基,例如环戊基、环己基等;芳族烃基,例如苯基、甲苯基、二甲苯基、萘基等;其取代的基团,其中与上述基团的碳原子结合的氢原子至少部分地被卤素原子(例如氟原子等)或有机基团(包括环氧基团、缩水甘油基、酰基、羧基、氨基、甲基丙烯酰基、巯基等)取代。
不具有脂族不饱和键的单价烃基的碳原子数目不受特别限制,并优选地范围从1至30,更优选地范围从1至20,并且还优选地范围从1至10。作为上述A,甲基、乙基或苯基是优选的,并且甲基是尤其优选的。
二价烃基的例子包括(例如)取代或未取代的和直链或支链的二价烃基。作为其例子,可以提及例如直链或支链的亚烷基,例如亚甲基、二亚甲基、三亚甲基、四亚甲基、五亚甲基、六亚甲基、七亚甲基、八亚甲基等;亚烯基,例如亚乙烯基、亚丙烯基、亚丁烯基、亚己烯基、亚辛烯基等;亚芳基,例如亚苯基、二亚苯基等;亚烷基亚芳基,例如二亚甲基亚苯基等;及其取代基团,其中与上述基团的碳原子结合的氢原子至少部分地被卤素原子(例如氟原子等)或有机基团(包括环氧基团、缩水甘油基、酰基、羧基、氨基、甲基丙烯酰基、巯基等)取代。
二价烃基的碳原子数目不受特别限制,优选地范围从1至30,更优选地范围从1至20,并且还优选地范围从1至10。作为上述B,直链或支链亚烷基是优选的,并且亚丙基是尤其优选的。
m优选地范围从1至500,更优选地范围从1至300,并且还优选地范围从1至200。如果m超过1,000,则分子中仲氨基的含量降低,并且仲氨基的效果在一些情况下可能无法充分表现出来。
本发明的聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物可以具有2至1,000个由上述化学式表示的单元。上述单元的数目优选地范围从2至500,更优选地范围从2至300,并且还优选地范围从2至100。
本发明的聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物的分子量不受特别限制,并且聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物可以具有(例如)范围从100至100,000的数均分子量。上述数均分子量优选地范围从100至50,000,更优选地范围从100至10,000,并且还优选地范围从100至5,000。
本发明的聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物的分散度(重均分子量/数均分子量)不受特别限制,并且聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物可以具有范围从(例如)1至2.5的分散度。上述分散度优选地范围1至2.0,更优选地范围从1至1.9,并且还优选地范围从1至1.8。
本发明的聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物的氨基可以由酸中和。酸的类型不受特别限制。可以使用无机酸,例如盐酸、硫酸、磷酸等;或有机酸,例如羧酸,如甲酸、乙酸、丙酸等;或脂肪酸,例如月桂酸、硬脂酸等。
在本发明的聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物中,仲氨基存在于分子的主链中。为此,与其中仲氨基或伯氨基存在于分子的侧链中或位于分子链末端的情况相比,该聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物难以随时间推移而着色。
此外,通过用其他有机基团取代上述共聚物中的仲氨基的氢原子,本发明的聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物可以转化成多种有机官能化有机硅多嵌段共聚物。因此,本发明的共聚物适合作为其他有机官能化有机硅多嵌段共聚物的前体。
用于产生本发明的聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物的方法的特征在于:使其中两个末端均被SiH(键合硅原子的氢原子)基团封端的聚硅氧烷与一个分子中具有两个脂族不饱和键的胺或甲硅烷基胺经历加成反应。
在用于产生本发明的聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物的方法中,使其中两个末端均被SiH基团封端的由以下通式表示的聚硅氧烷:
其中
每个A独立地表示不具有脂族不饱和键的单价烃基;并且
m表示1至1,000范围内并包括1和1,000的数值,
以及在一个分子中具有两个脂族不饱和键的由以下通式表示的胺或甲硅烷基胺:
其中
每个C独立地表示含有脂族不饱和键的单价烃基;并且
D表示氢原子或三有机甲硅烷基,
经历加成反应,并任选地进行脱硅反应。
不具有脂族不饱和键的上述单价烃基与如上所述的那些相同。作为上述A,甲基是优选的。
上述含有脂族不饱和键的单价烃基的例子包括(例如)取代或未取代的和直链或支链的具有至少一个脂族不饱和键的单价烃基。作为其例子,可以提及具有2至10个碳原子的烯基,例如乙烯基、烯丙基、丁烯基、己烯基、辛烯基等;烯基芳基,例如乙烯基苯基等;等等。
上述含有脂族不饱和键的单价烃基的碳原子数目不受特别限制,并优选地范围从2至30,更优选地范围从2至20,并且还优选地范围从2至10。作为上述C,直链或支链烯基是优选的,并且烯丙基是尤其优选的。
作为上述三有机甲硅烷基,可以使用通常在有机反应中用作保护基团的甲硅烷基。作为其例子,可以提及三甲基甲硅烷基、三乙基甲硅烷基、苯基二甲基甲硅烷基、叔丁基二甲基甲硅烷基等。
上述加成反应可以在硅氢加成反应的通用条件下进行。为了加速加成反应,优选地使用氢化硅烷化催化剂。所用的催化剂不受特别限制。可以优选地使用VIII族过渡金属,例如镍、钌、铑、钯、铱、铂等或其化合物。作为其化合物的例子,可以提及VIII族过渡金属的氯络合物、烯烃络合物、醛络合物、酮络合物、膦络合物、硫化物络合物、腈络合物等。在这些之中,基于铂的催化剂例如铂黑、氯铂酸、铂烯烃络合物、铂醛络合物、铂酮络合物等是优选的,并且铂烯烃络合物是尤其优选的。
上述加成反应可以在无任何溶剂的情况下进行,也可以在存在溶剂的情况下进行。作为可以使用的溶剂的例子,可以提及芳族烃,例如苯、甲苯、二甲苯等;脂族烃,例如己烷、庚烷、环己烷等;醚,例如四氢呋喃、乙醚等;酮,例如丙酮、甲基乙基酮等;以及酯,例如乙酸乙酯、乙酸丁酯等。
当上述D为三有机甲硅烷基时,在完成加成反应后,应通过合适的方法例如水解、醇解等进行脱硅反应,并因此将甲硅烷基氨基转化成仲氨基。
脂族不饱和键与SiH基团之间的当量比率((脂族不饱和键)/(SiH基团))不受特别限制。在其中脂族不饱和键要保留在产物末端的情况下,(脂族不饱和键)/(SiH基团)的比率必须大于1。在另一方面,在其中SiH基团要保留在产物末端的情况下,(脂族不饱和键)/(SiH基团)的比率必须小于1。当上述比率接近1时,得到分子量升高的产物。当上述比率远离1时,得到分子量降低的产物。因此,通过控制上述比率,可以控制产物的分子量。
反应方法优选地为这样一种方法,在该方法中,将其中两个末端均被SiH基团封端的聚硅氧烷与氢化硅烷化催化剂的混合物加热,然后将一个分子中具有两个脂族不饱和键的胺或甲硅烷基胺逐渐地逐滴加入其中。另一方面,不优选其中首先将一个分子中具有两个脂族不饱和键的胺或甲硅烷基胺与氢化硅烷化催化剂混合并加热随后向其中逐滴添加其中两个末端均被SiH基团封端的聚硅氧烷的方法,因为氨基与铂配位,并因而铂可能失活。此外,在其中将两个末端均被SiH基团封端的聚硅氧烷与一个分子中具有两个脂族不饱和键的胺或甲硅烷基胺混合并加热然后向其中加入氢化硅烷化催化剂的情况下,反应立即发生。为此,要求密切注意失控反应。
在本发明中,如上所述进行基于硅氢加成反应的加成反应。反应进展可以通过红外吸收光谱、核磁共振分析等加以确认。在确认反应完成后,通过加热在减压下除去具有低沸点的物质,如溶剂等。从而,可以得到所需的聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物。
在其中两个末端均被SiH基团封端的聚硅氧烷的键合硅原子的氢原子与在一个分子中具有两个脂族不饱和键的胺或甲硅烷基胺的脂族不饱和键之间的加成反应中,产生α加合物和β加合物二者,具体取决于氢原子加成到不饱和键的加成模式。β加合物和α加合物的比率可以通过核磁共振分析测定。在使用二烯丙基胺作为一个分子中具有两个脂族不饱和键的胺的情况下,在寻常硅氢加成条件下,β加合物和α加合物的比率为约7:3。因此,在加成反应中产生的(亚丙基氨基亚丙基产物):(亚丙基氨基甲基亚乙基产物):(甲基亚乙基氨基甲基亚乙基产物)的比率可以为约49:42:9。
在本发明的制备方法中,可以获得上述聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物。在本发明的制备方法中,不产生环状产物作为副产物。因此,聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物可以在不产生环状副产物的情况下容易地获得。
本发明的共聚物表现出与水增强的混溶性。为此,通过在水中溶解或分散本发明的共聚物,可以形成稳定的水性组合物。上述水性组合物可以通过(例如)将本发明的共聚物借助普通搅拌器溶解或分散在水中而产生。
此外,本发明的共聚物可以稳定具有水相和油相的乳状液的乳化状态。具体地讲,与常规氨基改性的聚硅氧烷的盐相比,通过用酸中和本发明的共聚物得到的盐表现出优异的乳状液稳定性。上述乳状液可以通过诸如均质混匀机、匀化器、胶体磨、混炼机、在线式连续乳化机、真空乳化机、超声乳化机、连续混合装置等乳化机对水相组分、油相组分和本发明的共聚物以及任选另一种乳化剂(必要时)进行乳化和/或分散而制备。
因此,本发明的共聚物适合作为水性组合物或乳状液组合物的组分。
此外,本发明的共聚物难以随时间推移或通过加热而着色。为此,本发明的共聚物可用作纤维、织造织物、非织造织物、皮革、粉末等的表面处理剂的组分,或用作油漆或化妆品的组分。
本发明的表面处理剂包含本发明的聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物。上述共聚物的混合量不受特别限制,并且例如可以是表面处理剂总重量(质量)的0.1至99.9重量(质量)%并可优选地范围从1至90重量(质量)%。
在本发明的表面处理剂中,通常在表面处理剂中混合的添加剂可以在不损害本发明效果的范围内混合。例如,就纤维、织造织物、非织造织物或皮革的表面处理剂而言,可以按合适的量混合以下物质:诸如油、树脂、树胶、橡胶等各种形式的有机硅化合物,诸如二甲基聚硅氧烷、二甲基甲基苯基聚硅氧烷、氨基改性的二甲基聚硅氧烷、环氧基改性的二甲基聚硅氧烷、聚醚改性的二甲基聚硅氧烷、聚己内酯改性的二甲基聚硅氧烷、α-烯烃改性的二甲基聚硅氧烷、聚硅氧烷/聚氧化烯嵌段共聚物等;硅烷化合物、交联剂、防腐剂、盐、表面活性剂,例如烷基苯磺酸盐、聚氧化烯烷基硫酸酯、烷基硫酸酯、烷烃磺酸盐、烷基乙氧基羧酸盐、琥珀酸衍生物、烷基胺氧化物、咪唑啉类化合物、聚氧乙烯烷基或烯基醚、聚氧乙烯烷基苯基醚、高级脂肪酸烷醇酰胺或其烯化氧加合物等;等等。
作为可以向其施加本发明表面处理剂的纤维材料的例子,根据材料的性质,可以提及天然纤维,例如棉、亚麻、羊毛、丝绸、木浆、皮革等;再生纤维,例如人造丝、醋酸纤维、铜氨纤维、短纤维等;有机合成纤维,例如聚酯、聚酰胺、维尼纶、聚丙烯腈、聚乙烯、聚丙烯、聚酯醚、聚偏二氯乙烯、聚氯乙烯、斯潘德克斯弹性纤维等;无机合成纤维,例如玻璃纤维、碳纤维、碳化硅纤维等;等等。此外,作为其例子,根据形式,可以提及短纤维、长丝、藤条、线丝、织造织物、针织物、非织造织物、树脂加工纤维、纸张、合成皮革等。
将本发明的表面处理剂通过喷雾等粘附到上述纤维材料上,接着干燥以从纤维材料中除去多余水等,然后在必要时加热。从而,可以获得所需的处理效果。干燥步骤和加热步骤可以同时进行。加热步骤可以在80至225℃进行30秒至20分钟,优选地在100至180℃进行1分钟至10分钟。在上述范围的高温进行上述范围的长时间的加热步骤时,改善赋予柔韧性的效果以及效果的耐久性,并因此这是优选的。然而,存在因加热步骤所致的缺点,例如增加成本、使纤维材料着色等等。因此,可以根据处理装置、纤维用途等适当地选择加热条件。
就向粉末施加本发明表面处理剂而言,对其形式(球状、条状、针状、板状、非晶态、纺锤状等)、粒度(气溶胶、微粒、颜料级颗粒等)及其颗粒结构(多孔、无孔等)无限制。粉末的平均原生粒度优选地范围从1nm至100μm。
作为上述粉末的例子,可以提及例如无机粉末、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、金属粉末颜料等。此外,也可以使用上述颜料的杂合产物。
更具体地讲,作为无机粉末的例子,可以提及氧化钛、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、硅酸酸酐、硅酸铝、硅酸钠、硅酸镁钠、硅酸镁、硅酸铝镁、硅酸钙、硅酸钡、硅酸锶、钨酸金属盐、羟基磷灰石、蛭石、higilite(氢氧化铝)、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、氮化硼等。
作为有机粉末的例子,可以提及聚酰胺粉末、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、聚四氟乙烯粉末、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、聚甲基倍半硅氧烷球状粉末、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、脲树脂、酚树脂、氟树脂、有机硅树脂、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、淀粉粉末、月桂酰赖氨酸等。
作为表面活性剂金属盐粉末的例子,可以提及硬脂酸锌、硬脂酸铝、硬脂酸钙、硬脂酸镁、肉豆蔻酸锌、肉豆蔻酸镁、棕榈酸锌、月桂酸锌、鲸蜡基磷酸锌、鲸蜡基磷酸钙、鲸蜡基磷酸钠锌等。
作为有色颜料的例子,可以提及无机红色颜料,例如红色氧化铁、氧化铁、氢氧化铁、钛酸铁等;无机棕色颜料,例如γ氧化铁等;无机黄色颜料,例如黄色氧化铁、赭石等;无机黑色铁颜料,例如黑色氧化铁、炭黑等;无机紫色颜料,例如锰紫、钴紫等;无机绿色颜料,例如氢氧化铬、氧化铬、氧化钴、钛酸钴等;无机蓝色颜料,例如普鲁士蓝、群青蓝等;焦油色素的色淀颜料,例如红色3号、红色104号、红色106号、红色201号、红色202号、红色204号、红色205号、红色220号、红色226号、红色227号、红色228号、红色230号、红色401号、红色505号、黄色4号、黄色5号、黄色202号、黄色203号、黄色204号、黄色401号、蓝色1号、蓝色2号、蓝色201号、蓝色404号、绿色3号、绿色201号、绿色204号、绿色205号、橙色201号、橙色203号、橙色204号、橙色206号、橙色207号等,天然色素的色淀颜料,例如胭脂红酸、紫胶色酸、红花黄、巴西木素、藏红花素等。
作为珠光颜料的例子,可以提及氧化钛涂层云母、钛云母、氧化铁涂层钛云母、氧化钛涂层云母、氯氧化铋、氧化钛涂层氯氧化铋、氧化钛涂层滑石、鱼鳞粉、氧化钛涂层有色云母等。
作为金属粉末颜料的例子,可以提及诸如铝、金、银、铜、铂、不锈钢等金属的粉末。
此外,在上述粉末中,其一部分或所有部分可以尤其优选地经受表面处理,例如拒水处理、亲水处理等。此外,可以使用其中将上述粉末互相复合的复合产物。此外,还可以使用其中上述粉末经受了一般油剂、非本发明共聚物的有机硅化合物、氟化合物、表面活性剂、增稠剂等表面处理的表面处理产物。必要时,可使用其一种类型或其两种或更多种类型。
拒水处理不受特别限制。上述粉末可以用各种类型的拒水表面处理剂处理。作为其例子,可以提及有机硅氧烷处理,例如甲基氢聚硅氧烷处理、有机硅树脂处理、有机硅树胶处理、丙烯酰有机硅处理、氟化有机硅处理等;金属皂处理,例如硬脂酸锌处理等;硅烷处理,例如硅烷偶联剂处理、烷基硅烷处理等;氟化合物处理,例如全氟烷基硅烷处理、全氟烷基磷酸处理、全氟聚醚处理等;氨基酸处理,例如N-月桂酰-L-赖氨酸处理等;油剂处理,例如角鲨烷处理等;丙烯酰处理,例如丙烯酸烷基酯处理等。上述处理可以按其两种或更多种的组合使用。
作为上述粉末,还可以使用有机硅弹性体粉末。有机硅弹性体粉末为主要从二有机硅氧烷单元(D单元)形成的线型二有机聚硅氧烷的交联产物。有机硅弹性体粉末可以优选地在硅氢加成反应催化剂存在的情况下通过以下两者的交联反应产生:在侧链或末端具有键合硅的氢原子的有机氢聚硅氧烷,以及在侧链或末端具有不饱和烃基例如烯基等的二有机聚硅氧烷。与从T单元和Q单元形成的有机硅树脂粉末相比,有机硅弹性体粉末具有增强的柔韧性和弹性并表现出优异的吸油性。为此,有机硅弹性体粉末吸收皮肤上的皮脂并可以防止化妆品流失。此外,当使用上述本发明的共聚物进行表面处理时,可以赋予润湿的触感,而不降低有机硅弹性体粉末的似绒面触感。此外,在化妆品中将上述本发明的共聚物与有机硅弹性体粉末一起混合的情况下,可以改善整个化妆品中上述粉末的分散稳定性,并且可以得到随时间推移而稳定的化妆品。
有机硅弹性体粉末可以处于各种形式,例如球状形式、平坦形式、非晶态形式等。有机硅弹性体粉末可以为油分散剂的形式。在本发明的化妆品中,可以优选地混合颗粒形式的有机硅弹性体粉末,该粉末具有范围从0.1至50μm的通过电子显微镜观察到的原生粒度和/或通过激光衍射/散射方法测得的平均原生粒度,并且其中初级颗粒为球形形式。此外,当根据JIS K6253“Method for determining hardness of vulcanized rubber or thermoplasticrubber”(测定硫化橡胶或热塑性橡胶硬度的方法)通过A型硬度计测量时,构成有机硅弹性体粉末的有机硅弹性体可以具有优选地不超过80、并且更优选地不超过65的硬度。
有机硅弹性体粉末可以经受用有机硅树脂、二氧化硅等表面处理。作为上述表面处理的例子,可以提及例如在以下专利中所述的那些:日本未经审查专利申请,首次公开号H02-243612;日本未经审查专利申请,首次公开号H08-12545;日本未经审查专利申请,首次公开号H08-12546;日本未经审查专利申请,首次公开号H08-12524;日本未经审查专利申请,首次公开号H09-241511;日本未经审查专利申请,首次公开号H10-36219;日本未经审查专利申请,首次公开号H11-193331;日本未经审查专利申请,首次公开号2000-281523等。作为有机硅弹性体粉末,对应的是在“JapaneseCosmetic Ingredients Codex(JCIC)”(《日本化妆品成分法典》)中所列的交联有机硅粉末。作为市售产品,存在道康宁东丽株式会社(Dow CorningToray Co.,Ltd.)生产的Trefil E-506S、Trefil E-508、9701化妆品粉末和9702粉末等。作为表面处理剂的例子,可以提及甲基氢聚硅氧烷、有机硅树脂、金属皂、硅烷偶联剂、无机氧化物(例如二氧化硅、氧化钛等)和氟化合物(例如全氟烷基硅烷、全氟烷基磷酸酯盐等)。
就向粉末施加本发明的表面处理剂而言,可以将上述表面处理剂直接与粉末混合,或者作为另外一种选择,可以将上述表面处理剂事先溶于有机溶剂中,然后可以将这种溶液与粉末混合,接着干燥并移除有机溶剂。作为有机溶剂的例子,可以提及脂族烃,例如己烷、辛烷、癸烷、环己烷等;芳族烃,例如苯、甲苯、二甲苯等;醚,例如乙醚、二丁基醚、四氢呋喃、二噁烷等;酮,例如丙酮、甲基乙基酮、甲基异丁基酮、二异丁基酮等;酯,例如乙酸甲酯、乙酸乙酯、乙酸丁酯、乙酸异丁酯等;以及醇,例如甲醇、乙醇、异丙醇、丁醇等。干燥温度优选地范围从室温至180℃。
通过本发明的表面处理剂对粉末的处理比率优选地为其中表面处理剂的量相对于100重量(质量)份的粉末范围从0.1至30重量(质量)的比率,并且更优选地为其中表面处理剂的量相对于100重量(质量)份的粉末范围从0.1至15重量(质量)份的比率。
本发明的油漆包含本发明的聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物。上述共聚物的混合量不受特别限制,可以相对于油漆的总量范围从0.1至30重量(质量)并可优选地范围从1至20重量(质量)%。
在本发明的油漆中,通常可以在不损害本发明效果的范围内混合普通油漆中所混合的添加剂。作为其例子,可以提及例如溶剂,例如水;醇,例如甲醇、乙醇、异丙醇、叔丁醇、乙二醇、1-甲氧基-2-乙醇等;酮,例如丙酮、甲基乙基酮、甲基异丁基酮、环己酮等;醚,例如乙醚、二丁基醚、四氢呋喃、二噁烷等;酯,例如乙酸乙酯、乙酸异丁酯等;芳族化合物,例如甲苯、二甲苯等;烃,例如正己烷、环己烷等;氮化合物,例如N,N-二甲基甲酰胺、乙腈等;硫化合物,例如二甲基亚砜等;氟化烃,例如三氯氟甲烷、二氯二氟甲烷、二氯四氟乙烷等;氯化和氟化烃等。除此之外,还有液化气体,例如低级烃(LPG),如丙烷、正丁烷、异丁烯等、二氧化碳等;处于例如油、树脂、树胶、橡胶、粉末等各种形式的有机硅化合物,例如二甲基聚硅氧烷、二甲基甲基苯基聚硅氧烷、二甲基二苯基聚硅氧烷、氨基改性的二甲基聚硅氧烷、环氧基改性的二甲基聚硅氧烷、聚醚改性的二甲基聚硅氧烷、聚己内酯改性的二甲基聚硅氧烷、α-烯烃改性的二甲基聚硅氧烷、羧基改性的二甲基聚硅氧烷等;表面活性剂,例如烷基苯磺酸盐、聚氧化烯烷基磺酸酯、烷基硫酸酯、烷烃磺酸盐、烷基乙氧基羧酸盐、琥珀酸衍生物、烷基胺氧化物、咪唑啉型化合物、聚氧乙烯烷基或烯基醚、聚氧乙烯烷基苯基醚、高级脂肪酸烷醇酰胺或烯化氧加合物等;其他聚合物化合物,例如羟乙基纤维素、羟丙基纤维素、羟丙基甲基纤维素、甲基纤维素、阳离子化纤维素、阳离子化聚合物、聚(2-丙烯酰胺-2-甲基丙烷磺酸)钠、日本未经审查专利申请首次公开号H05-310538中所公开的阳离子树脂和丙烯酸树脂、聚酰胺、聚酯、聚酰亚胺、聚苯乙烯、酚树脂、醇酸树脂等;抗氧化剂;紫外吸收剂;染料;颜料;着色剂;防腐剂;固定剂;等等。将本发明的油漆通过内涂或不通过内涂而施加到各种基材的表面上,并因而可以形成(固化的)涂层膜,该涂层膜表现出优异的脱模性、耐久性、不转移性、抗污染性等。施加方法不受限制,可以使用普通方法。例如,可以通过刷子、条码机或喷雾进行涂布。此外,本发明的油漆表现出优异的贮存稳定性。具体地讲,就向印刷电路板底板(manuscript)的表面保护膜的表面施加油漆而言,可以获得适于防止光致抗蚀剂或焊接掩膜粘附的脱模层。在这种情况下,就操作效率而言,通过喷雾施加是优选的。
本发明的化妆品包含本发明的聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物。上述共聚物的混合量不受特别限制,可以相对于化妆品的总量范围例如从1至99重量(质量)%并可以优选地范围从10至90重量(质量)%。
作为在本发明化妆品中混合的其他组分的例子,可以提及例如油剂、亲水介质、湿润剂、有机硅、紫外线掩蔽剂、水溶性聚合物、水溶胀性粘土矿物、防腐剂、抗微生物剂、生理活性组分、pH调节剂、有机溶剂、抗氧化剂、螯合剂、香料、颜料等。
油剂可以是来自任何来源的固体、半固体或液体形式中的任何一种,只要它们是疏水性的。油剂可以是非挥发性的、半挥发性的或挥发性的。作为其例子,可以提及硅油、烃油和蜡、动物或植物油、高级醇、酯油等。具体地讲,硅油是优选的,因为它们可以在使用期间赋予清爽感。油剂可以作为单一类型或其两种或更多种类型的组合使用。油剂在化妆品中的混合量优选地相对于化妆品的总重量(质量)范围从1至50重量(质量)%。
硅油的分子结构可以为环状结构、直链结构和支化结构中的任一种。其25℃的粘度可以范围从0.65至100,000mm2/s,并优选地范围从0.65至10,000mm2/s。
具体地讲,作为环状硅油的例子,可以提及六甲基环三硅氧烷(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-氨基丙基)四甲基环四硅氧烷、1,3,5,7-四(N-(2-氨基乙基)3-氨基丙基)四甲基环四硅氧烷、1,3,5,7-四(3-巯丙基)四甲基环四硅氧烷、1,3,5,7-四(3-缩水甘油氧基丙基)四甲基环四硅氧烷、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-乙烯基氧丙基)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[3-(对异丙烯基苯甲酰基氨基)丙基]四甲基环四硅氧烷、1,3,5,7-四(N-甲基丙烯酰-N-甲基-3-氨基丙基)四甲基环四硅氧烷、1,3,5,7-四(N-月桂酰-N-甲基-3-氨基丙基)四甲基环四硅氧烷、1,3,5,7-四(N-丙烯酰-N-甲基-3-氨基丙基)四甲基环四硅氧烷、1,3,5,7-四(N,N-双(甲基丙烯酰)-3-氨基丙基)四甲基环四硅氧烷、1,3,5,7-四(N,N-双(月桂酰)-3-氨基丙基)四甲基环四硅氧烷等。
作为直链硅油的例子,可以提及其中两个分子末端均被三甲基硅氧基封端的二甲基聚硅氧烷、其中两个分子末端均被三甲基硅氧基封端的甲基苯基聚硅氧烷、其中两个分子末端均被三甲基硅氧基封端的甲基苯基硅氧烷与二甲基聚硅氧烷的共聚物、其中两个分子末端均被三甲基硅氧基封端的甲基(3,3,3-三氟丙基)硅氧烷与二甲基硅氧烷的共聚物、α,ω-二羟基聚二甲基硅氧烷、α,ω-二甲氧基聚二甲基硅氧烷、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、八甲基三硅氧烷等。
作为支化硅油的例子,可以提及甲基三(三甲基)硅氧基硅烷、乙基三(三甲基)硅氧基硅烷、丙基三(三甲基)硅氧基硅烷、四(三甲基)硅氧基硅烷、苯基三(三甲基)硅氧基硅烷等。
在这些之中,挥发性的硅油是优选的。上述硅油可以按其两种或更多种类型的组合使用。
作为烃油和蜡的例子,可以提及地蜡、角鲨烷、角鲨烯、纯地蜡、链烷烃、石蜡、液体异链烷烃、姥鲛烷、聚异丁烯、聚丁烯、微晶蜡、凡士林等。它们可以按其两种或更多种类型的组合使用。
作为动物或植物油的例子,可以提及鳄梨油、亚麻籽油、杏仁油、水蜡树蜡(ibota wax)、紫苏油、橄榄油、可可脂、木棉蜡、榧子油、巴西棕榈蜡、肝油、小烛树蜡、牛油、氢化牛油、牛骨油、固化牛油、杏仁油、鲸蜡、氢化油、小麦胚芽油、芝麻油、米胚芽油、米糠油、甘蔗蜡、山茶花油、红花油、乳木果油(shear butter)、中国桐油、肉桂油、霍霍巴蜡、紫胶蜡、海龟油、大豆油、荼籽油、山荼油、月见草油、玉米油、猪油、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、向日葵油、葡萄油、杨梅蜡、霍霍巴油、澳洲胡桃油、蜂蜡、貂油、棉籽油、棉蜡、日本蜡、日本蜡核油、蒙旦蜡、椰子油、氢化椰子油、三-椰子油脂肪酸甘油酯、羊油、花生油、羊毛脂、液态羊毛脂、还原的羊毛脂、羊毛脂醇、硬质羊毛脂、乙酸羊毛脂、羊毛脂脂肪酸异丙酯、月桂酸己酯、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,前提条件是POE是指聚氧乙烯。它们可以按其两种或更多种类型的组合使用。
作为高级醇的例子,可以提及月桂醇、肉豆蔻醇、棕榈醇、硬脂醇、二十二醇、十六醇、油醇、异硬脂醇、己基十二烷醇、辛基十二烷醇、十八十六醇、2-癸基十四烷醇、胆固醇、植物甾醇、POE胆固醇醚、单硬脂基甘油醚(鲨肝醇)、单油基甘油基醚(鲨油醇)等。它们可以按其两种或更多种类型的组合使用。
作为酯油的例子,可以提及己二酸二异丁酯、2-己基癸醇己二酸酯、二-2-庚基十一烷醇己二酸酯、N-烷基二醇单异硬脂酸酯、异鲸蜡醇异硬脂酸酯、三羟甲基丙烷三异硬脂酸酯、乙二醇二-2-乙基己酸酯、鲸蜡醇2-乙基己酸酯、三羟甲基丙烷三-2-乙基己酸酯、季戊四醇四-2-乙基己酸酯、鲸蜡醇辛酸酯、辛基十二醇树胶酯、油酸油醇酯、辛基十二醇油酸酯、油酸癸酯、异壬酸异壬酯、新戊二醇二癸酸酯、柠檬酸三乙酯、2-乙基己醇琥珀酸酯、醋酸戊酯、乙酸乙酯、乙酸丁酯、异鲸蜡醇硬脂酸酯、硬脂酸丁酯、癸二酸二异丙酯、二-2-乙基己醇癸二酸酯、鲸蜡醇乳酸酯、乳酸肉豆蔻酯、棕榈酸异丙酯、2-乙基己醇棕榈酸酯、2-己基癸醇棕榈酸酯、2-庚基十一烷醇棕榈酸酯、胆甾醇基12-羟基硬脂酸酯、二季戊四醇脂肪酸酯、肉豆蔻酸异丙酯、2-乙基己醇肉豆蔻酸酯、辛基十二醇肉豆蔻酸酯、2-庚基十一烷醇肉豆蔻酸酯、肉豆蔻醇肉豆蔻酸酯、己基癸基二甲基辛酸酯、月桂酸乙酯、月桂酸己酯、2-辛基十二烷基N-月桂酰-L-谷氨酸酯、二异硬脂醇苹果酸酯等。作为甘油酯油的例子,可以提及乙酰甘油基、甘油基三异辛酸酯、甘油基三异硬脂酸酯、甘油基三异棕榈酸酯、甘油基三(辛酸酯/癸酸酯)、甘油基单硬脂酸酯、甘油基二-2-庚基十一酸酯、甘油基三肉豆蔻酸酯、二甘油基肉豆蔻酸酯异硬脂酸酯等。它们可以按其两种或更多种类型的组合使用。
作为亲水介质的例子,可以提及一元低级醇,例如乙醇、正丙醇、异丙醇、正丁醇等;二元醇,例如1,3-丁二醇、乙二醇、丙二醇等;聚亚烷基二醇,例如聚乙二醇、双丙二醇、聚丙二醇等;多元醇,例如甘油、双甘油、三羟甲基丙烷、季戊四醇、山梨醇等。它们可以按其两种或更多种类型的组合使用。上述亲水介质在化妆品中的混合量优选地相对于化妆品的总量范围从1至80重量(质量)%。
作为湿润剂的例子,可以提及葡萄糖、木糖醇、麦芽糖醇、透明质酸、硫酸软骨素、吡咯烷酮羧酸盐、聚氧乙烯甲基葡萄糖苷、聚氧丙烯甲基葡萄糖苷等。它们可以按其两种或更多种类型的组合使用。也作为亲水介质的诸如1,3-丁二醇、乙二醇、聚乙二醇、丙二醇、双丙二醇、聚丙二醇、甘油、双甘油、三羟甲基丙烷、季戊四醇、山梨醇等上述亲水介质也可以在一些情况下有助于改善化妆品的保湿感。湿润剂在化妆品中的混合量优选地相对于化妆品的总重量(质量)范围从0.1至30重量(质量)%。
作为有机硅的例子,可以提及例如有机硅树胶、有机硅树脂和有机硅弹性体粉末。它们可以按其两种或更多种类型的组合使用。
有机硅树胶为具有超高聚合度的线型二有机聚硅氧烷,其也称为有机硅生橡胶或有机聚硅氧烷树胶。作为代表性例子,一种有机硅树胶由(CH3)3SiO{(CH3)2SiO}f{(CH3)R7SiO}gSi(CH3)3表示,其中R7选自乙烯基、苯基、具有6至20个碳原子的烷基、具有3至15个碳原子的氨基烷基、具有3至15个碳原子的全氟烷基,以及具有3至15个碳原子的包含季铵碱的烷基;f=3000至6000;并且g=0至1000,f+g=3,000至6,000。它们可以按其两种或更多种类型的组合使用。
有机硅树脂为具有高度支化结构、网状结构或笼状结构的有机聚硅氧烷,它在室温为液体或固体形式。作为固体有机硅树脂的例子,可以提及例如,包含三有机硅氧基单元(M单元)(其中有机基团为单独的甲基,或与乙烯基或苯基组合的甲基)、二有机硅氧基单元(D单元)(其中有机基团为单独的甲基,或与乙烯基或苯基组合的甲基)、一有机硅氧基单元(T单元)(其中有机基团为甲基、乙烯基或苯基)和硅氧基单元(Q单元)的任何组合的MQ树脂、MDQ树脂、MTQ树脂、MDTQ树脂、TD树脂、TQ树脂或TDQ树脂。另外,作为它们的其他例子,可以提及三甲基硅氧基硅酸、聚烷基硅氧基硅酸、包含二甲基硅氧基单元的三甲基硅氧基硅酸以及烷基(全氟烷基)硅氧基硅酸。上述有机硅树脂优选地为油溶的,并且,具体地讲,优选地可溶解于八甲基四硅氧烷(D4)或十甲基环五硅氧烷(D5)。它们可以按其两种或更多种类型的组合使用。
有机硅树胶和有机硅树脂可以单独混合在化妆品中,也可以溶解于挥发性或非挥发性硅油、或挥发性或非挥发性烃油中,然后混合在化妆品中。有机硅树胶和有机硅树脂的混合量优选地范围从化妆品总量的0.1至20重量(质量)%,更优选地范围从1至10重量(质量)%。为了获得展现出与皮肤的粘附性增加的化妆品,相对于100重量(质量)份的化妆品,可以优选地混合范围从50至500重量(质量)份的有机硅树胶或有机硅树脂。
有机硅弹性体粉末是作为主要组分的线型二有机基聚硅氧烷的交联产物,并且可以处于各种形式,例如球形形式、平坦形式、非晶态形式等。可优选地混合颗粒形式的有机硅弹性体粉末,该粉末具有范围从0.1至50μm的通过电子显微镜观察时的原生粒度和/或通过激光衍射/散射方法测得的平均原生粒度,并且其中初级颗粒处于球形形式。此外,当根据JIS K 6253“Method for determining hardness of vulcanized rubber or thermoplasticrubber”(测定硫化橡胶或热塑性橡胶硬度的方法)通过A型硬度计测量时,构成有机硅弹性体粉末的有机硅弹性体可以具有优选地不超过80、并且更优选地不超过65的硬度。有机硅弹性体粉末可以按其两种或更多种类型的组合使用。
有机硅弹性体粉末可以通过,例如,固化处于乳化状态或喷雾状态的组合物产生,其中所述组合物包含含有两个或更多个烯基的二有机聚硅氧烷、具有两个或更多个键合硅原子的氢原子的烷基氢聚硅氧烷、以及氯铂酸。作为包含两个或更多个烯基的二有机聚硅氧烷的例子,可以提及例如其中两个末端均被二甲基乙烯基硅氧基封端的二甲基聚硅氧烷。可以使用分子中具有两个或更多个乙烯基或烯丙基的有机化合物,例如α,ω-烯基双烯、甘油三烯丙基醚、聚氧炔基化的甘油三烯丙基醚、三羟甲基丙烷三烯丙基醚、聚氧炔基化的三羟甲基丙烷三烯丙基醚等。
作为有机硅弹性体粉末的例子,可以提及例如在以下专利中所述的那些:日本未经审查专利申请,首次公开号No.H02-243612;日本未经审查专利申请,首次公开号H08-12545;日本未经审查专利申请,首次公开号H08-12546;日本未经审查专利申请,首次公开号H08-12524;日本未经审查专利申请,首次公开号H09-241511;日本未经审查专利申请,首次公开号H10-36219;日本未经审查专利申请,首次公开号H11-193331;日本未经审查专利申请,首次公开号2000-281523等。作为市售产品,存在道康宁东丽株式会社(Dow Coming Toray Co.,Ltd.)生产的Trefil E系列的Trefil E-505、E-506、E-507或E-508,等等。作为有机硅弹性体粉末,对应的是在“Japanese Cosmetic Ingredients Codex(JCIC)”(《日本化妆品成分法典》)中所列的交联有机硅粉末。上述有机硅弹性体粉末可以经受表面处理。作为表面处理剂的例子,可以提及甲基氢聚硅氧烷、有机硅树脂、金属皂、硅烷偶联剂、无机氧化物(例如二氧化硅、氧化钛等)和氟化合物(例如全氟烷基硅烷、全氟烷基磷酸酯盐等)。
优选地在化妆品中混合糊剂形式的有机硅弹性体粉末,它是具有油组分或水性分散体的捏合产物。更具体地讲,作为它们的例子,可以提及糊膏或分散体形式的产物,其中所述糊膏通过捏合有机硅弹性体粉末和在室温为液体并且选自酯油、烃油、高级醇和动物或植物油的油剂获得;分散体通过将有机硅弹性体粉末分散在包含乳化剂的水中获得。
许多有机硅弹性体粉末具有超过10μm的粒度,并且难以将它们稳定地混合在水性组合物中。有机硅弹性体粉末可以通过与本发明的氨基改性的有机聚硅氧烷乳状液一起使用来稳定地混合。化妆品中的有机聚硅氧烷弹性体粉末的混合量优选地范围从化妆品总重量(质量)的0.1至30重量(质量)%。
作为有机硅,可以混合有机硅改性的有机聚合物。作为有机硅改性的有机聚合物的例子,可以提及例如日本未经审查专利申请首次公开号2000-063225中公开的基于丙烯酰基的聚二甲基硅氧烷接枝共聚物、基于丙烯酰基的羧基硅氧烷树枝状体接枝共聚物,日本未经审查专利申请首次公开号2003-226611中公开的基于丙烯酰基的具有氟化有机基团和羧基硅氧烷树枝状体结构的共聚物。它们可以按其两种或更多种类型的组合使用。
紫外线掩蔽剂可以是无机紫外线掩蔽剂或有机紫外线掩蔽剂中的任何一种。无机紫外线掩蔽剂通常为无机粉末。作为它们的例子,可以提及例如金属氧化物,例如氧化钛、氧化锌、氧化铈、低价氧化钛、铁掺杂的氧化钛等;金属氢氧化物,例如氢氧化铁等;金属薄片,例如板状氧化铁、铝薄片等;以及陶瓷,例如碳化硅等。在这些之中,选自平均粒度范围从1至100nm的细粒状金属氧化物和细粒状金属氢氧化物的至少一种类型的材料是特别优选的。它们可以按其两种或更多种类型的组合使用。上述粉末优选地经历常规表面处理,例如氟化合物处理,其中全氟烷基磷酸处理、全氟烷基硅烷处理、全氟聚醚处理、氟硅氧烷处理、氟化有机硅树脂处理是优选的;有机硅处理,其中甲基氢聚硅氧烷处理、二甲基聚硅氧烷处理和气相四甲基四氢环四硅氧烷处理是优选的;有机硅树脂处理,其中三甲基硅氧基硅酸处理是优选的;侧基处理,它们是在气相有机硅处理后添加烷基链的方法;硅烷偶联剂处理;钛偶联剂处理;硅烷处理,其中烷基硅烷处理和烷基硅氮烷处理是优选的;油剂处理;N-酰化赖氨酸处理;聚丙烯酸处理;金属皂处理,其中优选地使用硬脂酸盐或肉豆蔻酸盐;丙烯酸树脂处理;金属氧化物处理等。优选地进行上文所述的多种处理。例如,可以在细粒状氧化钛的表面涂覆金属氧化物,如氧化硅、氧化铝等,然后可以用烷基硅烷进行表面处理。按粉末的量计,表面处理所用材料的总量可以优选地范围从0.1至50重量(质量)%。
作为有机紫外线掩蔽剂的例子,可以提及例如基于水杨酸的紫外线掩蔽剂,例如水杨酸高孟酯、水杨酸辛酯、水杨酸三乙醇胺等;基于苯甲酸的紫外线掩蔽剂,例如对氨基苯甲酸、乙基二羟基丙基对氨基苯甲酸、甘油基对氨基苯甲酸、辛基二甲基对氨基苯甲酸、戊基对氨基苯甲酸酯、2-乙基己基对二甲基氨基苯甲酸酯等;基于二苯甲酮的紫外线掩蔽剂,例如4-(2-β-吡喃葡萄糖基氧代)丙氧基-2-羟基二苯甲酮、二羟基二甲氧基二苯甲酮、二羟基二甲氧基二苯甲酮二磺酸钠、2-羟基-4-甲氧基二苯酮、羟基甲氧基二苯酮磺酸和它的三水合物盐、羟基甲氧基二苯酮磺酸钠、2-羟基-4-甲氧基二苯酮5-磺酸盐、2,2’-二羟基-4-甲氧基二苯酮、2,4-二羟基二苯甲酮、2,2’,4,4’-四羟基二苯甲酮、2,2’-二羟基-4,4’-二甲氧基二苯甲酮、2-羟基-4-正-辛氧基二苯甲酮等;基于肉桂酸的紫外线掩蔽剂,例如2-乙基己基对甲氧基肉桂酸酯(或者称为:辛基对甲氧基肉桂酸酯)、甘油基一-2-乙基己酰基-二对甲氧基肉桂酸酯、甲基2,5-二异丙基肉桂酸酯、2,4,6-三[4-(2-乙基己氧基羰基)苯氨基]-1,3,5-三嗪、甲基双(三甲基硅氧基)甲硅烷基]异戊基三甲氧基肉桂酸酯、异丙基对甲氧基肉桂酸酯与二异丙基对甲氧基肉桂酸酯的肉桂酯混合物、对甲氧基氢化肉桂酸二乙醇胺盐等;基于苯甲酰甲烷的紫外线掩蔽剂,例如2-苯基-苯并咪唑5-硫酸、4-异丙基二苯甲酰基甲烷、4-叔丁基-4’-甲氧基-苯甲酰甲烷等;2-乙基己基2-氰基-3,3-二苯基丙-2-烯酸酯(INCI:氰双苯丙烯酸辛酯)、2-乙基己基二甲氧基亚苄基二氧代咪唑烷丙酸酯、1-(3,4-二甲氧基苯基)-4,4-二甲基-1,3-戊二酮、西诺沙酯、甲基-邻-氨基苯甲酸酯、2-乙基己基-2-氰基-3,3-二苯基丙烯酸酯、3-(4-甲基亚苄基)樟脑、辛基三嗪酮、2-乙基己基4-(3,4-二甲氧基苯基亚甲基)-2,5-二氧代-1-咪唑烷丙酸酯、它们的聚合物衍生物和它们的硅烷衍生物。它们可以按其两种或更多种类型的组合使用。
可以使用其中有机紫外线掩蔽剂分散于聚合物粉末内的产物。聚合物粉末可以是空心或实心的,可以具有范围从0.1至50μm的平均原生粒度,并可以具有较宽或较窄的粒度分布。作为聚合物的例子,可以提及丙烯酸树脂、甲基丙烯酸树脂、苯乙烯树脂、聚氨酯树脂、聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯、有机硅树脂、尼龙、丙烯酰胺树脂等。以相对于粉末的量范围从0.1至30重量(质量)%的量含有有机紫外线掩蔽剂的聚合物粉末是优选的。特别优选的是包含紫外A吸收剂4-叔丁基-4’-甲氧基二苯甲酰基甲烷的聚合物粉末。
作为紫外线掩蔽剂,通常使用选自细粒状氧化钛、细粒状氧化锌、2-乙基己基对甲氧基肉桂酸酯、4-叔丁基-4’-甲氧基二苯甲酰基甲烷和基于二苯甲酮的紫外线吸收剂的至少一种类型,因为它们容易商购获得并表现出增强的紫外线控制效果。因此,可以优选地使用它们。具体地讲,无机紫外线掩蔽剂和有机紫外线掩蔽剂优选地一起使用。另外,紫外A的紫外线掩蔽剂和紫外B的紫外线掩蔽剂更优选地一起使用。相对于化妆品的总量,化妆品中全部无机和/或有机紫外线掩蔽剂的总紫外线掩蔽剂混合量优选地范围从0.1至60重量(质量)%,更优选地范围从3至40重量%。另外,无机紫外线掩蔽剂的混合量优选地范围从化妆品量的0.1至30重量%,并且有机紫外线掩蔽剂的混合量优选地范围从化妆品量的0.1至20重量%。
作为水溶性聚合物的例子,可以提及两性、阳离子、阴离子或非离子的水溶性聚合物。它们可以按其两种或更多种类型的组合使用。
作为两性水溶性聚合物的例子,可以提及例如两性化淀粉;二甲基二烯丙基氯化铵衍生物,例如丙烯酰胺、丙烯酸和二甲基二烯丙基氯化铵的共聚物,以及丙烯酸和二甲基二烯丙基氯化铵的共聚物;以及甲基丙烯酸衍生物,例如聚甲基丙烯酰乙基二甲基甜菜碱,以及N-甲基丙烯酰氧基乙基N,N-二甲基铵α-甲基羧基甜菜碱和甲基丙烯酸烷基酯的共聚物。
作为阳离子水溶性聚合物的例子,可以提及季氮改性的多糖类,例如阳离子改性的纤维素、阳离子改性的羟乙基纤维素、阳离子改性的瓜耳胶、阳离子改性的刺槐豆胶、阳离子改性的淀粉等;二甲基二烯丙基氯化铵衍生物,例如二甲基二烯丙基氯化铵与丙烯酰胺的共聚物、聚(二甲基亚甲基氯化哌啶)等;乙烯基吡咯烷酮衍生物,例如以下共聚物的盐:乙烯基吡咯烷酮和二甲基氨乙基甲基丙烯酸的共聚物,乙烯基吡咯烷酮和甲基丙烯酰胺丙基三甲基氯化铵的共聚物,乙烯基吡咯烷酮和甲基乙烯基氯化咪唑的共聚物等;以及甲基丙烯酸衍生物,例如甲基丙烯酰乙基二甲基甜菜碱、甲基丙烯酰乙基三甲基氯化铵和甲基丙烯酸2-羟乙酯的共聚物,甲基丙烯酰乙基二甲基甜菜碱、甲基丙烯酰乙基三甲基氯化铵和甲氧基聚乙二醇甲基丙烯酸酯的共聚物等。
作为阴离子水溶性聚合物的例子,可以提及例如聚丙烯酸或其碱金属盐、聚甲基丙烯酸或其碱金属盐、透明质酸或其碱金属盐、乙酰化透明质酸或其碱金属盐、脂族羧酸或其金属盐的水溶性聚合物,例如甲基乙烯基醚和马来酸酐等的共聚物的水解产物,羧基甲基纤维素或其碱金属盐、甲基乙烯基醚-马来酸半酯共聚物、丙烯酸树脂链烷醇胺液体、羧乙烯基聚合物等。它们可以按其两种或更多种类型的组合使用。
作为非离子水溶性聚合物的例子,可以提及例如聚乙烯基吡咯烷酮、高度聚合的聚乙二醇、乙烯基吡咯烷酮/乙酸乙烯酯共聚物、乙烯基吡咯烷酮/甲基丙烯酸二甲氨基乙酯共聚物、乙烯基己内酰胺/乙烯基吡咯烷酮/甲基丙烯酸二甲氨基乙酯共聚物、纤维素或其衍生物(例如甲基纤维素、乙基纤维素、羟乙基纤维素、羟丙基纤维素和羧甲基纤维素)、天然聚合物(例如角蛋白和胶原或它们的衍生物、海藻酸钙、普鲁兰多糖、琼脂、明胶、罗望子种子多糖类、黄原胶、角叉菜胶、高甲氧基果胶、低甲氧基果胶、瓜耳胶、果胶、阿拉伯树胶、结晶纤维素、阿拉伯半乳聚糖、刺梧桐树胶、黄蓍胶、藻酸、白蛋白、酪蛋白、凝胶多糖、结冷胶、葡聚糖、温柏树籽胶、甲壳质脱乙酰壳多糖衍生物、淀粉(大米、玉米、马铃薯或小麦)等。它们可以按其两种或更多种类型的组合使用。
将水溶性聚合物溶解或分散在水中以形成均匀水溶液或分散体之后,优选地将水溶性聚合物与化妆品的其他原材料混合。化妆品中的水溶性聚合物的混合量优选地范围从化妆品量的0.001至5重量(质量)%,更优选地范围从0.01至3重量(质量)%。就小于0.001重量(质量)%的水溶性聚合物混合量而言,不可以获得足够的增稠效果。另一方面,就超过5重量(质量)%的水溶性聚合物混合量而言,化妆品的粘度太高,并且可能破坏使用期间的感觉。
水溶胀性粘土矿物是一种具有三层结构的含胶体的硅酸铝,并且它的例子包括,例如由下式表示的那些:(X,Y)2-3(Si,Al)4O10(OH)221/3.nH2O,其中X为Al、Fe(III)、Mn(III)或Cr(III);Y为Mg、Fe(II)、Ni、Zn或Li;并且Z为K、Na或Ca。作为上述水溶胀性粘土矿物的例子,可以提及膨润土、蒙脱石、贝得石、囊脱石、滑石粉、锂蒙脱石和硅酸铝镁盐。它们可以是天然材料和合成材料中的任何一种。它们可以按其两种或更多种类型的组合使用。
将水溶胀性粘土矿物溶解或分散在水中以形成均匀的水溶液或分散体之后,优选地将水溶胀性粘土矿物与化妆品的其他原材料混合。化妆品中的水溶胀性粘土矿物的混合量优选地范围从化妆品量的0.001至5重量(质量)%,更优选地范围从0.01至3重量(质量)%。就小于0.001重量(质量)%的溶胀性粘土矿物混合量而言,不可以获得足够的增稠效果。另一方面,就超过5重量(质量)%的溶胀性粘土矿物混合量而言,化妆品的粘度太高,并且可能破坏使用期间的感觉。
作为防腐剂的例子,可以提及烷基对羟基苯甲酸酯、苯甲酸、苯甲酸钠、山梨酸、山梨酸钾、苯氧基乙醇等。它们可以按其两种或更多种类型的组合使用。防腐剂的混合量优选范围从化妆品总重量(质量)的0.1至5重量(质量)%。
作为抗微生物剂的例子,可以提及苯甲酸、水杨酸、石炭酸、山梨酸、烷基对羟基苯甲酸酯、对氯间甲酚、六氯酚、苯扎氯铵、盐酸氯己定、三氯碳酰苯胺、三氯生、光敏剂、苯氧基乙醇、甲基异噻唑啉酮等。它们可以按其两种或更多种类型的组合使用。抗微生物剂的混合量优选地范围从化妆品总重量(质量)的0.1至5重量(质量)%。
作为生理活性组分的例子,可以提及例如抗炎剂、抗衰老剂、收敛剂、生发剂、生发油、血液循环促进剂、干燥剂、凉感剂、发暖剂、维生素、氨基酸、伤口愈合促进剂、刺激缓解剂、镇痛剂、细胞活化剂和酶组分。在这些之中,由天然植物提取组分、海藻提取组分或中草药组分组成的那些是优选的。优选地将一种类型的或两种或更多种类型的上述生理活性组分混合在化妆品中。化妆品中的生理活性组分的混合量优选地范围从化妆品总重量(质量)的0.1至10重量(质量)%。
作为它们的例子,可以提及例如明日叶(Angelica keiskei)提取物、鳄梨提取物、粗齿绣球(Hydrangea serrata)提取物、药蜀葵(Althaea officinalis)提取物、山金车(Arnica montana)提取物、芦荟提取物、杏提取物、杏仁提取物、银杏(Gingko biloba)提取物、小茴香提取物、姜黄根提取物、乌龙荼提取物、野蔷薇(Rosa multiflora)提取物、狭叶松果菊(Echinacea angustifolia)叶提取物、黄芩(Scutellaria baicalensis)根提取物、黄柏(Phellodendronamurense)树皮提取物、黄连根茎(Coptis rhizome)提取物、大麦(Hordeumvulgare)种子提取物、贯叶连翘(Hypericum perforatum)提取物、短柄野芝麻(Lamium album)提取物、豆瓣菜(Nasturtium officinale)提取物、橙提取物、干燥海水溶液、海藻提取物、水解弹性蛋白、水解小麦粉、水解蚕丝、洋甘菊(Chamomilla recutita)提取物、胡萝卜提取物、茵陈蒿(Artemisia capillaris)花提取物、光果甘草(Glycyrrhiza glabra)提取物、玫瑰茄(Hibiscus sabdariffa)提取物、火棘(Pyracantha fortuneana)提取物、猕猴桃提取物、红金鸡纳树(Cinchona succirubra)提取物、黄瓜提取物、鸟苷、栀子仁(Gardenia florida)提取物、维氏熊竹(Sasa veitchii)提取物、苦参沙枣(Sophora angustifolia)提取物、胡桃木提取物、柚子提取物、葡萄叶铁线莲(Clematis vitalba)叶提取物、小球藻提取物、桑(Morus alba)提取物、黄龙胆(Genuana lutea)提取物、红茶提取物、酵母提取物、牛蒡提取物、发酵米糠提取物、米胚芽油、聚合草(Symphytum officinale)叶提取物、胶原、越桔(Vaccinum vitis idaea)提取物、细辛(Asiasarum sieboldi)提取物、柴胡(Bupleurum falcatum)提取物、脐带提取物、石榴(Punica granatum)提取物、丹参(Salvia)提取物、藏红花(Crocus sativus)提取物、赤竹(sasa)竹草提取物、野山楂(Crataegus cuneata)果实提取物、川椒(Zanthoxylum piperitum)提取物、蕈(Corthellus shiitake)提取物、地黄(Rehmannia chinensis)根提取物、紫草(Lithospermumerythrorhizone)根提取物、紫苏(Perilla ocymoides)提取物、欧洲椴(Tiliacordata)提取物、榆绣线菊(Spiraea ulmaria)提取物、芍药(Paeonia albiflora)提取物、菖蒲(Acorns calamus)根提取物、白桦(Betula alba)提取物、问荆草(Equisetum arvense)提取物、常春藤(Hedera helix)提取物、锐刺山楂(Crataegus oxyacantha)提取物、欧洲接骨木(Sambucus nigra)提取物、欧蓍草(Achillea millefolium)提取物、辣薄荷(Mentha piperita)叶提取物、鼠尾草提取物、欧锦葵(Malva sylvestris)提取物、川芎(Cnidium officinale)根提取物、日本獐牙菜(Swertia japonica)提取物、大豆种子提取物、枣(Zizyphus jujuba)果实提取物、百里香提取物、茶树(Camellia sinensis)叶提取物、丁香(Eugeniacaryophyllus)花提取物、白茅(Imperata cylindrica)提取物、温州蜜柑(Citrusunshiu)皮提取物、东当归(Angelica acutiloba)根提取物、金盏草(Calendulaofficinalis)提取物、油桃(Prunus persica)仁提取物、枳实(Citrus aurantium)皮提取物、鱼腥草(Houttuynia cordata)提取物、番茄提取物、纳豆提取物、胡萝卜提取物、大蒜提取物、犬蔷薇(Rosa canina)果实提取物、芙蓉提取物、麦冬(Ophiopogon japonicus)根提取物、荷花(Nelumbo nucifera)提取物、欧芹提取物、蜂蜜、金缕梅(Hamamelis virginiana)提取物、药用墙草(Parietariaofficinalis)提取物、毛果香荼菜(Isodon trichocarpus)提取物、红没药醇、枇杷(Eriobotrya japonica)提取物、款冬(Tussilago farfara)花提取物、蜂斗菜(Petasites laponicus)提取物、茯苓(Poria cocos)提取物、假叶树(Ruscusaculeatus)根提取物、葡萄提取物、蜂胶、丝瓜(Luffa cylindrica)果实提取物、红花提取物、胡椒薄荷提取物、南京椴(Tilliamiquellana)提取物、牡丹(Paeonia suffruticosa)根提取物、啤酒花(Humulus lupulus)提取物、樟子松(Pinus sylvestris)球果提取物、马栗树提取物、观音莲(Lysichitoncamtschatcense)提取物、无患子(Sapindus mukurossi)皮提取物、香蜂草(Melissa officinalis)叶提取物、桃提取物、矢车菊(Centaurea cyanus)花提取物、蓝桉(Eucalyptus globulus)叶提取物、草莓虎耳草(Saxifraga sarementosa)提取物、香橙(Citrus junos)提取物、薏苡(Coix lacryma-jobi)种子提取物、魁蒿(Artemisia princeps)提取物、薰衣草提取物、苹果提取物、莴苣提取物、柠檬提取物、紫云英(Astragalus sinicus)提取物、玫瑰提取物、迷迭香提取物、罗马洋甘菊(Roman chamomile)提取物、蜂王浆提取物等。
另外,作为它们的例子,可以提及生物聚合物,例如脱氧核糖核酸、粘多糖、透明质酸钠、硫酸软骨素钠、胶原、弹性蛋白、甲壳质、脱乙酰壳多糖、水解蛋壳膜等;氨基酸,例如甘氨酸、缬氨酸、亮氨酸、异亮氨酸、丝氨酸、苏氨酸、苯基丙氨酸、精氨酸、赖氨酸、天冬氨酸、谷氨酸、胱氨酸、半胱氨酸、甲硫氨酸、色氨酸等;激素,例如雌二醇、乙烯基雌二醇等;油基组分,例如鞘脂、神经酰胺、胆固醇、胆固醇衍生物、磷脂等;抗炎剂,例如ε-氨基己酸、甘草酸、β-甘草次酸、溶菌酶氯化物、愈创木薁、氢化可的松、尿囊素、氨甲环酸、薁等;维生素,例如维生素A、B2、B6、C、D和E、泛酸钙、生物素、烟酰胺、维生素C酯等;活性组分,例如尿囊素、二氯醋酸二异丙胺、4-氨基甲基环己烷羧酸等;细胞活化剂,例如α-羟基酸、β-羟基酸等;血液循环促进剂,例如γ-谷维素、维生素E衍生物等;伤口愈合剂,例如视黄醇、视黄醇衍生物等;清凉剂,如千金藤素、甘草提取物、辣椒酊剂、扁柏酚、碘化大蒜提取物、盐酸吡哆醇、dl-α-生育酚、dl-α-生育酚醋酸酯、烟酸、烟酸衍生物、泛酸钙、D-泛醇、乙酰基泛酰乙醚、生物素、尿囊素、异丙基甲基苯酚、雌二醇、乙炔基雌二醇、卡普氯铵(capronium chloride)、苯扎氯铵、氯化苯海拉明、takanal、樟脑、水杨酸、壬酸香兰基酰胺、壬酸香兰基酰胺、羟甲辛吡酮乙醇胺、甘油十五烷酸酯、1-薄荷醇、樟脑等;生发剂,例如一硝基愈创木酚、间苯二酚、γ-氨基丁酸、苄索氯铵、盐酸美西律、植物生长素、雌性激素、斑蝥酊剂、环孢霉素、吡硫鎓锌、氢化可的松、米诺地尔、聚氧乙烯一硬脂酸脱水山梨醇酯、薄荷油、笠锦米(大米变种)提取物等;等等。
作为pH调节剂的例子,可以提及例如乳酸、柠檬酸、乙醇酸、琥珀酸、酒石酸、dl-苹果酸、碳酸钾、碳酸氢钠、碳酸氢铵等。它们可以按其两种或更多种类型的组合使用。化妆品中的pH调节剂的混合量优选地相对于化妆品的总重量(质量)范围从0.1至5重量(质量)%。
作为有机溶剂的例子,可以提及例如醚,并且作为推进剂的例子,可以提及LPG、N-甲基吡咯烷酮和下一代氯氟烃。它们可以按其两种或更多种类型的组合使用。有机溶剂在化妆品中的混合量优选地相对于化妆品的总重量(质量)范围从0.1至5重量(质量)%。
作为氧化抑制剂(抗氧化剂)的例子,可以提及例如生育酚、丁基羟基茴香醚、二丁基羟基甲苯、植酸、类胡萝卜素、类黄酮、单宁酸、木脂素、皂草苷等。它们可以按其两种或更多种类型的组合使用。抗氧化剂在化妆品中的混合量优选地相对于化妆品的总重量(质量)范围从0.1至5重量(质量)%。
作为螯合剂的例子,可以提及例如乙二胺四乙酸、丙氨酸、依地酸钠、聚磷酸钠、偏磷酸钠、磷酸等。它们可以按其两种或更多种类型的组合使用。螯合剂在化妆品中的混合量优选地是化妆品总量(质量)的0.1至5重量(质量)%。
作为香料的例子,可以提及例如,从多种植物的花、种子、叶和根中提取的香料;从海藻中提取的香料;从动物的多个部分或分泌腺提取的香料,例如麝香和鲸油;或人工合成的香料,例如薄荷醇、麝香、醋酸酯和香草,包括作为生理活性组分列出的多种提取物;它们可以按其两种或更多种类型的组合使用。香料在化妆品中的混合量优选地相对于化妆品的总重量(质量)范围从0.1至5重量(质量)%。
作为颜料,存在例如染料、着色剂、荧光增白剂。作为染料,有水溶性染料、油溶性染料、天然染料、合成染料等。作为着色剂,有填充剂、无机着色剂、有机着色剂等。它们可以按其两种或更多种类型的组合使用。颜料在化妆品中的混合量优选地相对于化妆品的总重量(质量)范围从0.1至5重量(质量)%。
本发明的化妆品的形式和性质不受特别限制。优选的是水包油乳状液形式的化妆品,特别是连续水相中的分散相具有10.Oμm或更小、0.5μm(500nm)或更小,以及特别地0.2μm(200nm)或更小的平均粒度的水包油乳状液化妆品,其中平均粒度借助激光衍射/散射方法测得。平均粒度为0.5μm或更小的水包油乳状液化妆品具有半透明到混浊的外观,并具有随时间推移特别显示超强稳定性的优点。
水包油乳状液形式的化妆品可以通过以下方式获得:用常规设备,如桨式搅拌器、螺旋桨搅拌器、亨舍尔搅拌器、TK高度搅拌器(由特殊机化工业株式会社(Tokushu Kika Kogyo Co.,Ltd.)制造)、TK高速分散器(由特殊机化工业株式会社(Tokushu Kika Kogyo Co.,Ltd.)制造)等将本发明的聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物和如上所述常用的化妆品原材料与指定量的水混合。当它们混合时,高压乳化设备,或具有高剪切力的乳化机(如上述的胶体磨或胶体搅拌器)的使用不是特别必要的,但是优选的,因为可以获得具有小粒度至微粒尺度的稳定水包油乳状液。
为了制备水包油乳状液形式的化妆品,例如,首先均匀混合构成分散相的组分,以制备预混合物。随后,以范围从约500至5,000rpm的旋转速率搅拌构成水相的水和组分时,以任何顺序逐渐加入上述预混合物和本发明的共聚物,然后进一步搅拌混合物。水相对于预混合物的重量(质量)比不受限制,并且根据获得的水包油乳状液化妆品随时间推移的稳定性,有利地范围从0.05/0.95至0.50/0.50。就制备的少量化妆品而言,例如,当通过人用桨等搅拌任何容器中构成水相的水和组分时,可以逐渐加入上述预混合物和本发明的聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物。
本发明的水包油乳状液形式的化妆品随时间推移表现出超强的稳定性和在使用期间的优异感觉。
上述化妆品的用途不受特别限制,并且所述化妆品可以用于皮肤用化妆品,例如皮肤清洁制剂、皮肤护理化妆品、美容化妆品、止汗剂、控制紫外线的制剂等;毛发用化妆品,例如毛发清洁制剂、毛发定型组合物、毛发着色组合物、生发油、护发液等;沐浴用化妆品组合物;香料、古龙水等。包含本发明的聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物的化妆品特别优选地为皮肤用化妆品或毛发用化妆品。
可以在头皮、面部(包括嘴唇、眉毛和面颊)、指甲和整个身体的任何部分使用上述皮肤用化妆品。更具体地讲,作为它们的例子,可以提及皮肤清洁制剂,例如清洁凝胶、清洁霜膏、清洁泡沫、清洁乳、清洁洗液、洁面霜膏、眼部卸妆液、洁面泡沫、用于整个身体的液体肥皂、洗手皂、凝胶皂、固体皂、面部洗液、身体洗液、剃须膏、牙釉质去除剂、针对粉刺的化妆品等;皮肤护理化妆品,例如皮肤霜膏、头皮处理剂、皮肤乳状液、乳状洗液、乳状液、化妆洗剂、湿润剂、血清、面膜、爽身粉、精华液、剃须液等;美容化妆品,例如粉底、妆前底霜、定妆粉、化妆底粉、唇膏、唇霜、唇膏、唇彩、眼影、眼线、眼霜、眼线笔、眉笔、睫毛膏、腮红,面颊化妆品,例如颊彩或腮红、修甲油、修脚油、指甲彩、指甲涂剂、牙釉质去除剂、指甲油等;止汗剂制剂,例如除臭剂等;以及用于控制紫外线的制剂,例如防止晒黑的遮光制剂(防晒制剂)等。
作为上述毛发用化妆品的例子,可以提及毛发清洁制剂,例如洗发剂、洗护二合一洗发水等;毛发定型组合物,例如发油、卷发保持制剂、定形制剂、发膏、发胶、发液、发蜡等;染发组合物,例如毛发染料组合物、染发喷雾、染发水、染发棒等;生发剂组合物,例如生发油、毛发处理剂、护发膜等;护发液,如调理剂、油状护发素、膏状护发素、治疗护发素等;睫毛用化妆品,例如睫毛膏等。
另外,作为上述沐浴用化妆品的例子,可以提及浴油、浴盐和泡沫浴液。
用于容纳上述化妆品的容器不受特别限制。作为它们的例子,可以提及广口瓶、泵、管、瓶、加压释放容器、耐压气溶胶容器、遮光容器、紧凑容器、金属盘、棒状容器、叠层(bringing up)容器、喷雾容器、具有配备混合物释放口的隔板的容器等。就水包油乳状液型化妆品而言,容器的例子可以包括广口瓶、泵、瓶、喷雾容器等。用根据本发明的氨基酸改性的有机聚硅氧烷乳状液制备的水包油乳状液化妆品随时间推移表现出超强的稳定性。为此,即使化妆品装在透明容器中,化妆品也可以稳定地保存,并可以作为具有出色外观的产品进行柜台销售。
实例
下文结合实例对本发明进行详细描述。应当理解,本发明并不受所述实例的限制。
实例1
将铂与1,3-二乙烯基四甲基二硅氧烷之间的络合催化剂添加到80g(130.1mmol)两个末端均被SiH基团封端并具有6.5聚合度的聚二甲基硅氧烷中,从而铂金属的量为反应混合物总量的10ppm,并在氮气气氛下将混合物加热至90℃。随后,向其缓慢逐滴添加13.9g(143.1mmol,Vi(乙烯基)/SiH(键合硅原子的氢原子)比率=1.1)时,将混合物在90℃至140℃加热3小时。用反应混合物的IR分析确认SiH基团的特征吸收消失。随后,通过在减压下加热移除具有低沸点的产物。从而获得90.1g(产率=96%)淡黄色透明液体。图1中所示的29SiNMR的分析结果显示,聚硅氧烷-亚丙基氨基丙烯多嵌段共聚物具有由以下结构表示的重复单元:
其中得到α加成与β加成的比率为约30:70。另外,几乎所有末端烯丙基氨基均转移至乙基亚氨基。图2和图3分别示出了实例1中获得的聚硅氧烷-亚丙基氨基丙烯多嵌段共聚物的29SiNMR和IR吸收分析的结果。
另外,产物中的氨基用焦碳酸二乙酯进行酰胺化。随后,用GPC(凝胶渗透色谱法)测量它们的分子量。结果是,Mn(数均分子量)为6.3×103,分散度(Mw(重均分子量)/Mn)为1.57。氨基含有率为2.28%。
实例2至实例6
用与实例1所述相同的方式获得聚硅氧烷-亚丙基氨基丙烯多嵌段共聚物,不同的是使用其中两个末端均被SiH基团封端并具有不同的聚合度和变动性Vi/SiH的聚硅氧烷。用与实例1所述相同的方式分析获得的聚硅氧烷亚丙基氨基丙烯多嵌段共聚物。结果示于表1中。
表1
(*)NH2转化率
评价1
用高速分散机以3,000rpm的速率将实例4中获得的有机硅部分的重复聚合度为43的0.04g聚硅氧烷-亚丙基氨基丙烯多嵌段共聚物、0.04g乙酸、20g十甲基环五硅氧烷和20g水搅拌10分钟。7小时后获得的乳状液的分离率为1%
另一方面,从以下梳型氨基官能化聚硅氧烷
获得的乳状液的分离率为4%。从以下两端氨基官能化聚硅氧烷
获得的乳状液的分离率为11%。
评价2
将2g实例3的聚硅氧烷-亚丙基氨基丙烯多嵌段共聚物、实例5的聚硅氧烷-亚丙基氨基丙烯多嵌段共聚物或以下结构的梳型氨基改性的聚硅氧烷:
与上述共聚物的氨基等摩尔量的乙酸和18g其中两个末端均被三甲基硅基封端并具有6cs粘度的二甲基聚硅氧烷混合。每次添加,向其加入5g由氯化钠:甘油:水=1:5:74(重量(质量)比率)组成的水相混合物,每次添加后重复用牙科搅拌器将混合物混合36秒。直到水相从乳状液中分离时,获得水相的量。结果示于表2中。
表2
*参见上述化学式
实例的共聚物包含的水相量可以大于梳型氨基改性的聚硅氧烷包含的水相量。
评价3
用甲苯稀释实例6的有机硅部分的聚合度为107的聚硅氧烷-亚丙基氨基丙烯多嵌段共聚物(氨基含量=0.24%)和以下结构的梳型氨基官能化聚硅氧烷(氨基含量=0.26%):
以制备具有1重量(质量)%浓度的处理液。将尺寸为24cm×33cm的白色针织棉布浸入其中30秒。随后,用拧绞率调至100%的轧液辊拧绞上述布,并且随后在室温干燥。另外,用循环热空气干燥器在130℃将干燥的布加热处理5分钟,并且随后让其在室温下冷却。作为空白,只用甲苯进行如上所述的相同处理。根据JIS Z8722使用COLOR GUIDE便携式色度计(由毕克-加特纳公司(BYK-Gardner Inc.)制造)确定获得的布的YI值,并确定样品布与空白之间的色差△YI。从而评价泛黄程度。另外,用手的触感评价布的质地,与空白比较。作为总评价,如果显示具有改进的质地并且没有出现泛黄,则评价为O;如果只显示具有改进的质地,则评价为△;并且如果显示没有改进的质地,则评价为X。结果示于表3中。
表3
*参见上述化学式
用实例的共聚物处理过的纤维显示出良好质地,并且通过热处理减少泛黄现象。因此,上述聚合物适合用作纤维处理剂。
Claims (13)
1.一种聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物,其具有至少一个由以下通式表示的单元:
其中
每个A独立地表示不具有脂族不饱和键的单价烃基;
每个B独立地表示二价烃基;并且
m表示1至1,000范围内并包括1和1,000的数值。
2.根据权利要求1所述的共聚物,其中所述A为甲基。
3.根据权利要求1或2所述的共聚物,其中所述B为亚丙基。
4.根据权利要求1至3中任一项所述的共聚物,其中所述单元的数目范围从2至1,000。
5.水性或乳状液组合物,其包含根据权利要求1至4中任一项所述的共聚物。
6.表面处理剂,其包含根据权利要求1至4中任一项所述的共聚物。
7.油漆,其包含根据权利要求1至4中任一项所述的共聚物。
8.化妆品,其包含根据权利要求1至4中任一项所述的共聚物。
10.根据权利要求9所述的方法,其中所述A为甲基。
11.根据权利要求9或10所述的方法,其中所述C为烯丙基。
12.根据权利要求9至11中任一项所述的方法,其中所述聚硅氧烷-亚烃基氨基亚烃基多嵌段共聚物具有至少一个由以下通式表示的单元:
其中
A和m同以上定义;并且
每个B独立地表示二价烃基。
13.根据权利要求12所述的方法,其中所述单元的数目范围从2至1,000。
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