CN1085928A - 在透明涂料中使用氨基甲酸酯官能聚合物的彩色加透明复合涂料 - Google Patents

在透明涂料中使用氨基甲酸酯官能聚合物的彩色加透明复合涂料 Download PDF

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CN1085928A
CN1085928A CN93118765A CN93118765A CN1085928A CN 1085928 A CN1085928 A CN 1085928A CN 93118765 A CN93118765 A CN 93118765A CN 93118765 A CN93118765 A CN 93118765A CN 1085928 A CN1085928 A CN 1085928A
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J·W·雷福斯
D·L·St·奥宾
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Abstract

叙述了一种制造具有彩色边透明复合涂层的制 品的方法。该方法的步骤包括向基底上涂敷彩色涂 料组合物和在彩色涂料组合物之上涂敷透明涂料组 合物，其中透明涂料组合物是一种可固化的涂料组合 物，它含有：
(a)一种第一组分，其中含有一个聚合物骨架，骨 架上附加有至少一个氨基甲酸酯官能基，
(b)一种第二组分，其中含有一种化合物，该化 合物中有许多对氨基甲酸酯基有反应活性的官能 基。

Description

本发明涉及彩色加透明复合涂料及方法，尤其是用于该涂料的透明涂料中的组合物。
彩色加透明复合涂料广泛地用于涂料工艺中。在要求有优越的光泽、色彩浓度、图象清晰度或特殊的金属色效果时，它们特别理想。汽车工业已经在汽车车身面板上广泛使用彩色加透明复合涂料。但是，这些涂料要求透明涂层的透明度极高，以达到所希望的视觉效果。就这方面而言，彩色加透明复合涂料的透明涂层对于称为环境侵蚀的一种现象特别敏感。环境侵蚀本身显示为在涂层的透明面涂层之上或之中的斑点或印迹，它们常常无法擦掉。
透明涂层对环境侵蚀的抗阻程度常常很难预测。很多知名的用于外部时具有耐久性和耐气候性的涂料组合物，例如高固体含量磁漆，在作为彩色加透明复合涂料的透明涂层使用时达不到所要求的抗阻环境侵蚀的水平。
曾经提出许多种组合物作为彩色加透明复合涂料的透明涂料，例如聚氨酯、酸-环氧树脂体系等。但是，很多先有工艺体系在诸如可涂性，与着色底涂层的相容性、溶解度等方面存在缺点。另外，很少有一组分的涂料组合物能具有令人满意的抗环境侵蚀性，尤其是在汽车涂料的苛求的环境中。因此，对于可固化的涂料组合物存在着持久的需要，要求它们在作为彩色加透明复合涂料的透明涂料使用时具有令人满意的抗环境侵蚀性能。
现在发现，氨基甲酸酯官能的丙烯酸聚合物可以用在彩色加透明复合涂料的透明涂料组合物中。因此，根据本发明，提供了一种施用彩色加透明复合涂料的方法，该方法包括将着色的涂料组合物涂敷到基底上和在着色的涂料组合物上涂敷透明的涂料组合物等步骤，其中的透明涂料组合物是一种可固化的涂料组合物，含有：
（a）第一种组分，它具有聚合物骨架，骨架上有至少一个附加的氨基甲酸酯官能基，
（b）第二种组分，其中含有许多个对该氨基甲酸酯基有活性的官能基。
这种复合涂料在固化时形成一种坚固而有柔性、耐久、吸引人的透明涂层面涂层，它对环境侵蚀有高度的抗阻力。这种透明涂层组合物可以作为一组分体系有效地施用，而不是象在二组分体系中那样必须刚好在施用前与活性物质混合。
本发明组合物中使用的聚合物组分（a）可以用多种方式制备。制备这类聚合物的一种方法是制备一种丙烯酸酯单体，在该单体的酯部分有氨基甲酸酯官能度。这些单体是工艺上熟知的，例如在美国专利3，479，328、3，674，838、4，126，747、4，279，833和4，340，497中有说明，其公开内容在本发明中引用作为参考。一种合成方法涉及羟基酯与尿素反应形成氨基甲酰氧基羧酸酯（即，氨基甲酸酯改性的丙烯酸酯）。另一种合成方法是α，β-不饱和酸的酯与羟基氨基甲酸酯反应，形成氨基甲酰氧基羧酸酯。还有另一种方法涉及伯胺、仲胺或二胺与环状碳酸酯（例如碳酸乙二酯）反应形成氨基甲酸羟烷酯。氨基甲酸羟基烷基酯上的羟基随后通过与丙烯酸或甲基丙烯酸反应酯化，形成单体。在工艺中还描叙了制备氨基甲酸酯改性的丙烯酸单体的其它方法，它们同样可以应用。随后如果需要，可以用工艺中熟知的方法将丙烯酸单体与其它的烯属不饱和单体一起聚合。
制备在本发明组合物使用的聚合物（a）的另一途径是将一种已形成的聚合物（例如丙烯酸聚合物）与另一组分反应，形成连接在聚合物骨架上的氨基甲酸酯官能基，如美国专利4，758，632所述，该专利的公开内容在本文引用作为参考。制备可用作组分（a）的聚合物的一种方法涉及在羟基官能的丙烯酸聚合物存在下将尿素热分解（放出氨基和HNCO），以形成氨基甲酸酯官能的丙烯酸聚合物。另一种方法涉及使氨基甲酸羟基烷基酯的羟基与异氰酸酯官能的丙烯酸单体或乙烯基单体的异氰酸酯基反应，形成氨基甲酸官能的丙烯酸聚合物。异氰酸酯官能的丙烯酸聚合物是工艺中已知的，在例如美国专利4，301，257中有说明，其公开内容在本发明中引用作为参考。异氰酸酯乙烯基单体是工艺中已知的，包括不饱和的间四甲基二甲苯异氰酸酯（American Cyanamid公司以TMIR名称销售）。另一种方法是环状碳酸酯官能的丙烯酸聚合物上的环状碳酸酯基团与氨反应，以便形成氨基甲酸酯官能的丙烯酸聚合物。环状碳酸酯官能的丙烯酸聚合物是工艺中已知的，在例如美国专利2，979，514中有叙述，该专利的公开内容在本发明中引用作为参考。一种较困难但是可以实现的制备聚合物的方法是用氨基甲酸羟基烷基酯使丙烯酸酯聚合物发生酯基转移作用。
聚合物（a）的分子量一般为2000-20，000，优选4000-6000。分子量可以用凝胶渗透色谱法测定，采用聚苯乙烯标准样。聚合物中的氨基甲酸酯含量，按每当量氨基甲酸酯官能度的分子量计，一般在200和1500之间，优选300至350。可以调节组分（a）和（b）的玻璃化转变温度Tg，以得到Tg适合实际应用的固化的涂料。未反应的组分（a）和（b）的平均Tg值应该在10℃和80℃之间，同时调节各自的Tg′以达到性能最佳。
聚合物组分（a）可以用符合下式的无规重复的单元表示
在上式中，R1代表H或CH3。R2代表H，烷基，优选1至6个碳原子的烷基，或环烷基，优选最多达6个环碳原子的环烷基。应该理解，烷基和环烷基一词包括取代的烷基和环烷基，例如卤素取代的烷基或环烷基。然而，应避免对固化物质的性能有不利影响的取代基。例如，醚键被认为易于水解，应当避免将醚键置于交联基质中的部位。X和Y的值代表重量百分数，X是10%到90%，优选40%到60%，Y是90%至10%，优选60%至40%。
在上式中，A代表从一个或多个烯属不饱和单体衍生出的重复单元。这些用来与丙烯酸单体共聚的单体是工艺中已知的。它们包括丙烯酸或甲基丙烯酸的烷基酯，例如丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己基酯、甲基丙烯酸丁酯、甲基丙烯酸异癸酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯等;以及乙烯基单体，例如不饱和的间四甲基二甲苯异氰酸酯（American Cyanamid公司销售，商品名称TMIR）、苯乙烯、乙烯基甲苯等。
L代表二价的连接基，优选1至8个碳原子的脂族基，环脂基或6到10个碳原子的芳族连接基。L的实例包括
Figure 931187656_IMG3
等。在一项优选的实施方案中，-L-表示-COO-L′-，其中L′是一个二价的连接基。因此，在本发明的一项优选的实施方案中，聚合物组分（a）由化学式如下的无规重复的单元表示：
Figure 931187656_IMG4
在此化学式中，R1、R2、A、X和Y的定义如上。L′可以是一个二价的脂族连接基团，优选1至8个碳原子，例如-（CH2）-、-（CH2）2-、-（CH2）4-等，或是二价的环脂族连接基团，优选8个碳原子以下的环脂族连接基，如环己基，以及类似基团。但是也可以根据用来制备聚合物的方法使用其它的二价连接基。例如，如果氨基甲酸羟烷基酯被加成到异氰酸酯官能的丙烯酸聚合物上，连接基L′将包含一个-NHCOO-尿烷连接基作为异氰酸酯基的残基。
本发明的组合物通过氰基甲酸酯官能的聚合物组分（a）与组分（b）反应实现固化，组分（b）是一种有许多能与组分（a）上的氨基甲酸酯基团反应的官能基团的化合物。这种活性基团包括在氨基塑料交联剂或其它化合物（例如酚/醛加成物）上的活性羟甲基或甲基烷氧基、异氰酸酯基、硅氧烷基、环碳酸酯基和酸酐基团。（b）化合物的实例包括蜜胺甲醛树脂（包括单体的或聚合的蜜胺树脂和部分或全部烷基化的蜜胺树脂）、尿素树脂（例如羟甲基尿素如脲甲醛树脂，烷氧基尿素如丁基化脲甲醛树脂）、聚酐（例如聚丁二酸酐）和聚硅氧烷（例如三甲氧基硅氧烷）。氨基塑料树脂（例如蜜胺甲醛树脂或脲甲醛树脂）特别优选。更为优选的是氨基塑料树脂中的一个或多个氨基氮被氨基甲酸酯基取代以便用于固化温度低于150℃的工艺中，这在John.W.Rehfuss和Donald.L.st.Aubin的同时申请的题为“用于固化聚合物组合物的去氨基甲酸酯官能的氨基塑料”的美国专利申请。
在实施本发明时使用的透明涂料组合物中必要时可以使用溶剂。虽然本发明的组合物可以在例如基本上是固体粉末或分散体的形式使用，但是常常希望组合物基本上处于液态，这可以通过使用溶剂来实现。这种溶剂应该对于氨基甲酸酯官能的聚合物（a）和组分（b）都起溶剂作用。一般来说，根据组分（a）和（b）的溶解度特性，该溶剂可以是任何有机溶剂和/或水。在一项优选的实施方案中，溶剂是极性有机溶剂。溶剂是极性脂族溶剂或极性芳族溶剂较好。更优选的溶剂是酮、酯、乙酸酯、质子惰性的酰胺、质子惰性的亚砜或质子惰性的胺。可用的溶剂的实例包括甲乙酮、甲基异丁基酮、乙酸间戊基酯、乙二醇丁醚-乙酸酯、丙二醇单甲醚乙酸酯、二甲苯、N-甲基吡咯烷酮或是芳烃的掺混物。在另一项优选的实施方案中，溶剂是水或水与少量含水共溶剂的混合物。
在实施本发明中使用的透明涂料组合物可以包括一种提高固化反应速度的催化剂。例如，当使用氨基塑料化合物，尤其是单体的蜜胺作为组分（b）时，可以使用一种强酸催化剂来加快固化反应。这类催化剂是工艺上熟知的，包括例如对甲苯磺酸、二壬基萘二磺酸、十二烷基苯磺酸、酸式磷酸苯酯、马来酸单丁酯、磷酸丁酯和羟基磷酸酯。可以用在本发明组合物中的其它催化剂包括路易斯酸、锌盐和锡盐。
在本发明的一项优选实施方案中，透明涂料组合物中的溶剂数量约为0.01%至99%重量，优选从约10%至约60%重量，更优选从约30%至约50%重量。
可以用工艺上熟知的许多方法中的任何一种将涂料组合物涂布在制品上。这些方法包括例如喷涂、浸涂、辊涂、淋涂等。对于汽车车身面板，优选喷涂。
供这些复合涂料用的着色底涂层组合物是工艺上熟知的，这里无须详细解释。工艺上已知的可用于底涂层组合物中的聚合物包括丙烯酸聚合物、乙烯基聚合物、聚氨酯、聚碳酸酯、聚酯、醇酸树酯和聚硅氧烷。优选的聚合物包括丙烯酸聚合物和聚氨酯。在本发明的一项优选的实施方案中，底涂层组合物中还使用一种氨基甲酸酯官能的丙烯酸聚合物、底涂层聚合物最好是可交联的，因此含有一种或多种可交联的官能基。这些基团包括例如羟基、异氰酸酯基、胺基、环氧基、丙烯酸酯基、乙烯基、硅烷基和乙酰乙酸酯基。这些基团可以用某种方式掩蔽或封闭，以便使它们在所要求的固化条件下（一般是在较高的温度）脱去封闭，供交联反应之用。适用的可交联的官能基包括羟基、环氧基、酸、酐、硅烷和乙酰乙酸基。优选的可交联的官能基包括羟基官能基和氨基官能基。
底涂层聚合物可以是可自交联的，或者需要一种分离的交联剂，该交联剂对于聚合物的官能基有反应活性。例如，当聚合物含有羟基官能基时，交联剂可以是氨基塑料树脂，、异氰酸酯和封闭的异氰酸酯（包括异氰脲酸酯），以及酸或酸酐官能的交联剂。
在制品涂敷了上述各层之后，使组合物经受涂层固化的条件。可以使用各种固化方法，但以加热固化为优。一般来说，热固化是通过将涂敷过的制品置于主要由辐射热源提供的高温下进行的。固化温度将随在交联剂中使用的具体的封闭剂而变，但是它们通常是在93℃到177℃之间，优选在121℃至141℃之间。固化时间随所用的具体组分和诸如层厚等物理参数而变，但是，典型的固化时间是从15到60分钟。
下列实施例进一步说明了本发明
制备例1-氨基甲酸酯官能的丙烯酸聚合物
5升的三口圆底烧瓶的中间孔中装有搅拌器，一个侧孔中装有热电偶以便监测反应温度。氮吹洗管也经由此孔送入。第二个侧孔中装有克莱森接收器和水冷凝管。
向烧瓶中加入198克尿烷级混合芳族溶剂（SolvessoR100）和225克尿烷级甲苯。在氮气吹洗下将混合物搅拌并加热回流。当混合物达到回流温度（127℃）时，停止氮气吹洗。
将923克TMIR（不饱和的间四甲基二甲苯异氰酸酯，Ameri-can  Cyanamid公司）、692克丙烯酸乙基己基酯和269克过乙酸叔丁酯在无臭溶剂油中的50%溶液装入另一容器中。在3.5小时内将此混合物泵入到回流的溶剂中。在这第一次加料结束时，在30分钟内完成第二次加料，加入27克过乙酸叔丁酯溶液和27克尿烷级混合芳族化合物。在第二次引发剂加料后，经过泵使8.2克尿烷级混合芳族化合物流放入反应混合物中。然后使反应混合物保持回流（135℃）1小时。
在这段时间之后，将该批料冷却到70℃。将1.1克二月桂酸二丁锡加入该批料中混合5分钟。此时，在30分钟内将565克氨基甲酸羟丙酯加到反应混合物中。然后将该批料缓慢加热到100℃并保持在此温度下，直到用红外光谱仪或滴定法测得异氰酸酯官能度已经消失。在异氰酸酯消失后，将852克乙二醇单丁醚加到容器中并令其均化。关掉反应的热源，从容器中取出氨基甲酸酯官能的丙烯酸聚合物。
制备例2-氨基甲酸酯改性的蜜胺
5升的三口圆底烧瓶在中间的孔中装有真空密封的搅拌器，一个侧孔中装有热电偶以监测反应温度。第二个侧孔暂时装上水冷凝器，通过经由反应瓶的这一侧孔的收集器和过冷冷凝器施加真空。
将1708克六甲氧基化的单体蜜胺和1044克氨基甲酸丁酯装入烧瓶中。在缓慢地加热到60℃的同时，用搅拌器将混合物均化。当混合物达到60℃时，向容器中加入1.2克十二烷基苄基磺酸。取下冷凝管，将烧瓶连接到真空装置上。将混合物以1℃/分的速度加热到100℃。当混合物达到70℃时，施加15-20″的真空。收集在过冷冷凝器中冷凝的甲醇。在25″真空和100℃下在2.5小时内除掉计量数量的甲醇（279克）。在除掉了此数量之后，停止加热和抽真空。向容器中加入433克二甲苯，均化，从混合物中分离出氨基甲酸酯改性的蜜胺。
实施例1
将以下物质混合，制成透明涂料组合物：
665克氨基甲酸酯化的丙烯酸聚合物（制备例1）
167克氨基甲酸酯化的蜜胺（制备例2）
345克乙酸丁酯
44克ExxateR800（辛酸甲酯异构体）
19克TinuvinR384B
6克TinuvinR123
12克25%活性的恶唑烷封闭的十二烷基苄基磺酸
将涂料组合物喷涂在事先已喷涂丙烯酸基着色底涂层并且闪干的钢板上。用乙酸丁酯将粘度调节到30秒。将钢板在82℃下烤10分钟，132℃下烤20分钟。
膜的构造：底涂层15微米
透明涂层51微米
Tukon硬度13.5
MEK（甲乙酮）摩擦200次，轻微划伤
实施例1的钢板在Jacksonville，FL的恶劣的气候条件下经历16周，与涂有透明涂层的对照钢板相比，显示出环境侵蚀显著减少，该对照涂层是用蜜胺交联的羟基官能的丙烯酸聚合物。
实施例2
将以下物质组合，制备透明涂料组合物：
184克氨基甲酸酯化的丙烯酸聚合物（制备例1）
60克六甲氧基化的单体蜜胺
130克乙酸丁酯
14克丁基乙酸溶纤素
6克TinuvinR384B
1.9克TinuvinR123
3.8克25%活性的恶唑烷封闭的十二烷基苄基磺酸
将涂料组合物喷涂到事先已喷涂了丙烯酸基着色底涂层并闪干了的钠板上。用乙酸丁酯将粘度调节到20秒。将钢板在82℃下烤10分钟，132℃下烤20分钟。
膜的构造：底涂层15微米
透明涂层58微米
将实施例2的钢板在Jacksonville，FL的恶劣气候条件下暴露16周，与涂有透明涂层的对照钢板相比，环境侵蚀大大减少，对照透明涂层是用蜜胺交联的羟基官能的丙烯酸聚合物。
制备例3-氨基甲酸酯官能的丙烯酸聚合物
5升的圆底三口烧瓶的中间孔中装有搅拌器，在一个侧孔中装有热电偶以监测反应温度。氮气吹洗/喷射管也由此口进入。第二个侧孔中装有克莱森接收器和水冷凝器。
向烧瓶中加入235克二甲苯和356克乙酸戊酯。在氮气吹洗下搅拌混合物并加热回流。当混合物开始回流时（143℃），停止吹入氮气。将301克苯乙烯、196克丙烯酸乙基己基酯、337克甲基丙烯酸乙基己基酯、445克甲基丙烯酸羟乙酯、226克甲基丙烯酸环己酯、123克过乙酸叔丁酯在无臭溶剂油中的50%溶液和116克二甲苯装入另一容器中。将此混合物在4小时内泵送到回流的溶剂中。在加料结束时，用泵将35克二甲苯加入到反应混合物中。将反应混合物保持回流（140℃）1小时。
将混合物冷却到120℃，加入205克尿素。当尿素溶解时温度下降。将反应混合物慢慢加热到150℃，在合成过程的其余时间里保持这一温度。
然后向容器中加入2克King Industry公司的催化剂NacureRXP-348（金属的酚盐）。此时用氮气吹洗反应物以促进由尿素热分解形成的氨的蒸发。
一小时一次地渐增加入催化剂（0.5克），监测反应，用滴定法检验羟基的消失。当用滴定法检验不出羟基时，停止氮气吹入和加热，向混合物中加入560克甲基异丁基酮。将混合物均化，随后分离出聚合物。
实施例3
将50克制备例3的氨基甲酸酯官能的丙烯酸聚合物、7.7克六甲氧基化的单体蜜胺和0.6克恶唑烷封闭的十二烷基苄基磺酸相掺混，形成涂料组合物。将此组合物涂布在玻璃板上，接着真空拉延，形成200微米厚的薄层。将固化的涂层在132℃下烤30分钟。该涂层通过200次MEK摩擦试验。
本发明已参照优选实施例详细说明。但是应该清楚，在本发明的精神和范围之内可以进行变动和修改。

Claims (13)

1、一种制造具有彩色加透明复合涂层的制品的方法，其中的步骤包括向基底上涂敷彩色涂料组合物，在此彩色涂料组合物之上涂敷透明的涂料组合物，该方法的特点在于，所述的透明涂料组合物是一种可固化的涂料组合物，其中包括：
(a)第一组分，其中含有一个聚合物骨架，骨架上有至少一个氨基甲酸官能基，和
(b)第二组分，其中含有一种化合物有大量的对氨基甲酸酯基有反应活性的官能基。
2、根据权利要求1的一种方法，其特征在于，该聚合物骨架由一种或多种烯属不饱和单体衍生得到。
3、根据权利要求2的一种方法，其特征在于，该烯属不饱和单体含有一个氨基甲酸酯基。
4、根据权利要求2或3的一种方法，其特征在于，该烯属不饱和单体含有一种或几种丙烯酸单体。
5、根据权利要求2或3的一种方法，其特征在于烯属不饱和单体的10%-90%是丙烯酸单体。
6、根据权利要求1、2或3的方法，其特征在于，组分（b）选自氨基塑料树脂、聚硅氧烷、聚酐和具有许多活性羟甲基官能基的化合物。
7、根据权利要求6的一种方法，其特征在于，组分（b）是一种属于氨基塑料树脂的蜜胺甲醛树脂。
8、根据权利要求7的一种可固化的组合物，其特征在于，该蜜胺甲醛树脂是完全或部分烷基化的。
9、根据权利要求1、2或3的一种方法，其特征在于，第一组分由符合下式的无规重复的单元表示：
Figure 931187656_IMG1
其中R1代表H或CH3，R2代表H、烷基或环烷基，L代表一个二价连接基团，A代表由一个或多个烯属不饱和单体衍生的重复单元，X代表10%-90%重量，Y代表90%-10%重量。
10、根据权利要求9的一种方法，其特征在于R1代表CH3。
11、根据权利要求9的一种方法，其特征在于，X代表40%至60%重量，Y代表60%至40%重量。
12、根据权利要求9的一种方法，其特征在于，-L-用式-COO-L′表示，其中L′-是一个二价连接基。
13、一种制品，其中包括一个基底，基底上有根据权利要求1、2或3的方法制备的彩色加透明复合涂层。
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