CN1078823C - 不导电表面的静电涂漆方法 - Google Patents

不导电表面的静电涂漆方法 Download PDF

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CN1078823C
CN1078823C CN96122454A CN96122454A CN1078823C CN 1078823 C CN1078823 C CN 1078823C CN 96122454 A CN96122454 A CN 96122454A CN 96122454 A CN96122454 A CN 96122454A CN 1078823 C CN1078823 C CN 1078823C
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ethylenedioxy thiophene
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F·琼纳斯
U·冈特曼
K·勒希
A·邦克
H·巴斯滕
P·汤梅策克
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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Abstract

本发明涉及不导电表面的静电涂漆方法。为了这个目的，在该表面上涂覆由聚吡咯类、聚苯胺类或聚噻吩类制成的有机导电聚合物的导电层然后静电喷涂。

Description

不导电表面的静电涂漆方法
在过去几十年里，由于环境的原因，静电低溶剂和/或无溶剂涂漆方法已经逐渐地引起人们的重视。粉末涂漆就是无溶剂涂漆的一个例子。在这种情况下把热塑性或交联聚合物粉末涂覆到要涂漆的表面上然后一起加热烧结和/或熔融形成涂漆膜。
就导电材料如金属来说，优选地是用静电涂漆方法来涂覆聚合物粉末和/或漆。粉末漆粒子与高压电极直接接触，就会使静电涂漆所需要的粉末漆粒子带电。还有一种可能性是通过利用摩擦带电的性质来摩擦生电。
对于静电涂漆来说，涂漆的物体表面必须是导电的。因为塑料通常是绝缘体，在静电涂漆之前，必须使它们导电。为了这一目的，可以将导电填料如碳黑或金属氧化物加入到塑料中。这种方法的缺点是就加入碳黑来说成型部件是黑的和/或就加入金属氧化物来说需要大量的填料，这会使机械性能差。
使塑料表面变为导电的另一种行方式是用导电漆涂覆。如果使用碳黑填料导电漆，表面又会变黑，以致于很难产生透明的和/或薄涂层。
现在人们已经发现有机的导电聚合物是非常适合作为进行静电涂漆的塑料的导电涂层。因此本发明提出了一种不导电表面的静电涂漆的方法，其特征在于在涂漆之前用导电有机聚合物涂覆不导电表面。
合适的有机聚合物的例子有聚苯胺、聚苯乙烯和聚噻吩和/或它们的衍生物。使用不同的方法在不导电表面产生导电涂层。合适的方法例子如下：
1.在不导电表面上就地生成导电聚合物，如EP-A339340中所述使用3，4-亚乙二氧基噻吩的聚合。
2.用包含细分散的和/或胶体的或溶解形式的导电聚合物的漆涂覆不导电表面。适合的涂层溶液的例子是在溶剂如甲苯、二甲苯或甲基异丁基(甲)酮(例如Incoblend-Lack和/或Versicon)中的聚苯胺的分散体或充满聚吡咯的胶乳，如在EP-A589529中所述。优选的是在EP-A440957和DE-OS4211459中描述的聚噻吩衍生物。
特别优选的是在这些专利申请中所述的和从作为单体的3，4-亚乙二氧基噻吩衍生出的以及还包含从聚合羧酸或磺酸衍生的聚阴离子的含水聚噻吩分散体和/或溶液。利用这些溶液能够产生无色、透明的导电涂层，该涂层没有黑色、填充碳黑的涂层的缺点。
按照本发明能够涂漆的塑料的例子是酰胺类、聚砜类、聚碳酸酯类、聚酰亚胺类、聚酯类、ABS、聚苯乙烯、聚氯乙烯以及它们的混合和共聚物类，以及例如由酚醛树脂、环氧树脂、环氧二异氰酸酯树脂制成的那些硬质体。
塑料也包含传统的填料如无机矿物，例如高岭土或玻璃纤维。按照本发明的方法，也可以在由木头制成的不导电表面如压板面板、玻璃、 由氧化铝、氮化硅做的陶瓷例如瓷器的不导电表面上涂漆。
导电聚合物分散体和/或溶液可以单独使用或与粘结剂一起使用。合适的粘结剂的例子是聚亚胺酯、聚乙酸乙烯酯、聚丙烯酸酯类、不饱和聚酯树脂和/或它们的混合物。
粘结剂优选地作为液体分散体或乳剂或溶液使用。
使用导电涂层应以产生表面电阻＜1010Ω/□并且允许好的静电涂漆的量为准。
通常所说的层厚为0.05-50μm，优选0.1-5μm是需要的。
涂覆应用已知的技术，例如涂漆、浸渍、刷涂、印刷。
涂覆之后干燥涂层。在室温或高达250℃、优选200℃的温度下进行干燥。
可以把辅助溶剂如低级醇例如甲醇、乙醇、异丙醇，或酮例如丙酮，或开链或环酰胺例如N-甲基吡咯烷酮加到导电聚合物和任选的粘结剂的水分散体中。还有的添加剂的例子是表面活性剂如长链脂族的或芳基脂族的磺酸盐。
可以加入粘结促进剂如有机硅烷，例如3-缩水甘油丙氧基三甲氧基硅烷以改进粘合性。
然后按照已知的方法静电涂漆到涂覆的表面上。
优选地对塑料进行粉末涂漆。合适的粉末涂漆体系的例子是环氧树脂粉末漆、聚丙烯酸酯漆、与羧酸酐类、羧酸或聚异氰酸酯交联的羟基官能团聚酯、与聚官能团环氧化物如三缩水甘油异氰酸酯交联的羧基官能团聚酯。
在涂覆粉末漆涂层后，将其在高温下一起烧结和/或熔融。温度为50℃-300℃，优选100℃-250℃。
本发明的方法的最大优点是在一个步骤中用静电涂漆方法可以将金属和塑料的结合体共同地涂漆，而在过去首先按照其它方法对不导电体塑料部分单独涂漆然后与静电涂漆的金属部分结合。
实施例
实施例1
由填充玻璃纤维的聚酰胺6.6(30％重量的玻璃)制成的圆形塑料盘(直径6cm，厚3mm)在500转/分的涂漆离心机上用下面的溶液涂覆：
10.0g的3，4-聚亚乙二氧基噻吩/聚苯乙烯磺酸酯溶液，含水1.3％(AI4071，Bayer AG)
0.6g的N-甲基吡咯烷酮
0.2g的3-缩水甘油丙氧基三甲氧基硅烷
12.5g的异丙醇
2.5g的水
涂覆后用50℃的热空气进行干燥。干燥后，得到大约1.0μm厚的涂层。
按照这种方法涂覆的盘子的表面电阻为3kΩ/□。用粉末漆静电喷涂该盘子，该漆是基于三缩水甘油异氰酸酯(AralditTT 810，Ciba-Geigy AG)和包含羧基的聚酯(Uralac4200，DSM N.V.)，包含相对于粘结剂为50％的氧化钛。按照木发明漆粉末均匀地和完全地覆盖涂层。然后在180℃下用空气循环炉对粉末漆烘烤10分钟。
冷却后，获得了与塑料粘合很好的高光泽的漆涂层(栅极消减0)。
在填充玻璃纤维的聚酰胺6(30％重量的玻璃)制成的塑料、聚砜(UDEL1700，Amoco公司制造)、玻璃和氧化铝陶瓷上涂覆得到相同的结果。对比试验
按照本发明用粉末漆静电喷涂没有涂层的玻璃盘子和聚碳酸酯盘子。漆粉只能涂覆盘子的一小部分。
实施例2
在涂漆离心机上按照实施例1用下面配方涂覆塑料和玻璃盘子：配方a
4.20g的3，4-聚亚乙二氧基噻吩/聚苯乙烯磺酸酯溶液，含水1.3％(AI4071，Bayer AG)
0.5g的N-甲基吡咯烷酮
1.8g的聚丙烯酸酯分散体(MowlithDM771，Hoechst AG)，固体含量50％
4.0g的异丙醇
2.0g的水
干燥后，获得的0.8μm厚的涂层表面电阻为2.5×106Ω/□。配方b
8.3g的3，4-聚亚乙二氧基噻吩/聚苯乙烯磺酸酯溶液，含水1.3％(AI4071，Bayer AG)
0.5g的N-甲基吡咯烷酮
1.6g的聚乙酸乙烯酯分散体(MowlithDC，，Hoechst AG)，固体含量56％
2.0g的异丙醇
干燥后，获得的0.2μm厚的涂层表面电阻为4×107Ω/□。配方c
6.0g的3，4-聚亚乙二氧基噻吩/聚苯乙烯磺酸酯溶液，含水1.3％(AI4071，Bayer AG)
0.2g的N-甲基吡咯烷酮
1.8g的聚亚胺酯分散体(BayhydrolLS 2953，Bayer AG)，固体含量40％
0.2g的3-缩水甘油丙氧基三甲氧基硅烷
0.6g的异丙醇
干燥后，获得的0.8μm厚的涂层表面电阻为2×107Ω/□。
涂层干燥后，按照实施例1用粉末漆喷涂盘子然后烘烤漆。在各种情况下均获得均匀的、粘合性好的、高光泽漆涂层。

Claims (4)

1.不导电表面的静电涂漆方法，其特征在于在该表面上涂覆由聚吡咯、聚苯胺或聚噻吩和/或它们的衍生物制成的有机导电聚合物的导电层然后按照已知的方法静电涂漆。
2.按照权利要求1的方法，其特征在于采用了3，4-聚亚乙二氧基噻吩作为导电聚合物。
3.按照权利要求2的方法，其特征在于采用于了3，4-聚亚乙二氧基噻吩作为水分散体或溶液。
4.按照权利要求3的方法，其特征在于3，4-聚亚乙二氧基噻吩制剂也包含有机或无机粘结剂。
CN96122454A 1995-10-02 1996-10-02 不导电表面的静电涂漆方法 Expired - Fee Related CN1078823C (zh)

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