CN101022948B - 挤出热塑性基材的涂布方法和由此形成的物体 - Google Patents

挤出热塑性基材的涂布方法和由此形成的物体 Download PDF

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CN101022948B
CN101022948B CN2005800313819A CN200580031381A CN101022948B CN 101022948 B CN101022948 B CN 101022948B CN 2005800313819 A CN2005800313819 A CN 2005800313819A CN 200580031381 A CN200580031381 A CN 200580031381A CN 101022948 B CN101022948 B CN 101022948B
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K·汉拉罕
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Abstract

本发明涉及一种通过将聚合物溶液在PVC挤出的过程中在线喷涂、辊涂、刷涂、凹版印刷、柔性版印刷、热转移涂布或喷墨施涂到挤出PVC上而形成具有耐候性涂层的PVC制品的方法。本发明还涉及通过该方法涂布的硬质PVC制品。可以将聚偏二氟乙烯涂料施涂到PVC上，形成具有改善的光泽、良好的耐候性、良好的颜色保持性和耐污染性的制品。

Description

挤出热塑性基材的涂布方法和由此形成的物体
本申请根据U.S.C.§119(e)要求于2004年9月24日提交的美国临时申请60/612678的优先权。 
发明领域
本发明涉及一种通过将聚合物溶液在线(in line)喷涂、辊涂、刷涂、凹版印刷、柔性版印刷、热转移涂布或喷墨施涂到挤出热塑性基材上而形成具有耐候性涂层的挤出制品的方法。用于该方法的优选基材是PVC和聚烯烃。本发明还涉及通过该方法涂布的PVC和聚烯烃制品。
发明背景
聚氯乙烯(PVC)和聚烯烃(PO)是能够挤出形成许多可用制品的经济型热塑性材料。不幸的是，PVC和聚烯烃制品如果长期暴露于日照中，会褪色，失去光泽，表面出现白斑，并且变脆。对于需要长期暴露于露天环境的制品(例如，房屋板壁、窗框、防雨系统、拱腹、装饰部分、管道、面板等)来说，这种褪色和变脆行为尤其有害。
已经使用了许多方法来提高PVC和PO制品的性能。已经在PVC树脂中使用稳定剂体系(诸如铅稳定剂、钙-锌稳定剂)，以及使用高含量的二氧化钛颜料。
另一种方法是将耐候性薄面料(capstock)作为叠层或通过共挤出施涂在PVC或PC基材上。面料可以是稳定的PVC或非PVC聚合物。丙烯酸类树脂由于它们在室外暴露中的颜色稳定性特别优选作为面料，但是它们的成本很高。还可以使用聚偏二氟乙烯的薄膜叠层。描述了耐候性叠层应用于硬质PVC基材组合物的专利文献包括EP 1061100、EP 0473379、US4,141,935、US 4,169,180、US 4,183,777、US 5,306,548和US 5,976,671。
面料和叠层方法的问题是它们需要第二件生产速率必须得到匹配以适应差温致冷的挤出或层压设备。另外，当生产线从一种颜色调换到另一种颜色时，会有明显的时间和材料损失。深色PVC或PO制品的生产/制造中还会出现其它困难，例如形成制品的热消散较慢，结果导致生产问题以及偶然的故障(脱层、变脆、丧失颜色、丧失光泽、出现白斑)。
US 5,972,514描述了一种通过空气喷涂或无空气喷涂或静电法使用聚合物涂料涂布PVC基材的方法。该涂料随后在红外辐射下交联。
例如在US 5,555,006中所描述，在非吸收性塑料基材上进行喷墨印刷在本领域中是已知的。
通过层叠预印刷、预涂布或透明的PVDF柔性膜在柔性PVC上形成KYNAR聚亚乙烯基类涂层。
需要更好的在线方法，用于在硬质PVC或PO基材上形成耐候性保护涂层。
令人惊奇的是，已经发现可以通过喷墨、刷涂、辊涂、凹版印刷、柔性版印刷、热转移印刷或喷涂聚合物溶液或悬浮液的方法进行在线施涂而在PVC或聚烯烃挤出基材上形成耐候性保护涂层。通过任何这些方法进行的在线涂料施涂方法的另一优点是容易在挤出PVC或聚烯烃上形成、定制或调节、或匹配颜色图案。
发明概述
本发明的目的是提供将耐候性涂料施涂到如PVC或聚烯烃之类的挤出基材上的在线方法。
本发明的另一个目的是提供一种在一步过程中在PVC或聚烯烃基材上印刷图案和保护涂料的方法。
本发明的另一个目的是提供在PVC或聚烯烃基材上施涂有色图案和耐候性涂料的方法。
依据本发明优选实施方式的原理，本发明的目的可通过用于形成耐候性PVC或PO制品的方法来实现，包括将聚合物溶液在线喷涂、辊涂、刷涂、凹版印刷、柔性版印刷、热转移印刷或喷墨施涂到挤出PVC上。
具体而言，本发明涉及一种形成耐候性聚氯乙烯(PVC)或聚烯烃(PO)制品的方法，该方法包括在一步过程中通过在线喷涂、辊涂、刷涂、凹版印刷、柔性版印刷或喷墨施涂将聚合物溶液在线施涂到挤出的硬质PVC或PO上，形成耐候性涂层，其中所述涂层包含氟化聚合物，并且基于干膜厚度，所述耐候性涂层的厚度为0.02-4.0密耳。在上述方法中，所述聚合物溶液是含着色剂的或透明的；所述聚合物溶液是溶剂基的溶液或分散体；所述聚合物溶液是水性溶液、分散体或乳液。所述氟化聚合物包括聚亚乙烯基的均聚物或共聚物。基于干膜厚度，所述耐候性聚合物涂层的厚度为0.02-1.2密耳。上述方法还包括以下步骤：在施涂耐候性涂料之前，用面料或涂料覆盖PVC或PO基材。
本发明还涉及一种挤出的PVC或PO制品，其由硬质PVC或PO基材组成，所述基材具有在一步过程中施涂到所述基材上的耐候性聚偏二氟乙烯均聚物或共聚物涂层，所述涂层通过喷墨、辊涂、刷涂、凹版印刷、柔性版印刷或喷涂方法进行施涂，其中所述涂层的厚度为0.02-1.2密耳。在上述制品中，所述耐候性聚合物涂层具有由两种或多种不同的有色喷墨像素形成的图案。
发明详述
本发明涉及一种通过聚合物溶液的喷涂、辊涂、刷涂、凹版印刷、柔性版印刷、热转移印刷或喷墨施涂而形成耐候性挤出制品的在线方法。优选的是PVC和聚烯烃制品。
PVC基材是硬质聚氯乙烯。PVC可以是氯乙烯聚合物或共聚物组合物，特别是一种或多种选自下组的加聚物：氯乙烯均聚物，其可以任选地被过度氯化；任选接枝的共聚物，由氯乙烯和一种或多种烯键式不饱和共聚单体发生共聚反应形成。
可用于形成PVC共聚物的共聚单体包括，但不限于：1，1-二卤乙烯，诸如1，1-二氯乙烯或1，1-二氟乙烯，羧酸乙烯酯，诸如乙酸乙烯酯、丙酸乙烯酯或丁酸乙烯酯，丙烯酸和甲基丙烯酸，腈，酰胺和源自这些物质的烷基酯，特别是丙烯腈、丙烯酰胺、甲基丙烯酰胺、甲基丙烯酸甲酯、丙烯酸甲酯、丙烯酸丁酯、丙烯酸乙酯。或者是丙烯酸2-乙基己基酯，芳族乙烯基衍生物，诸如苯乙烯或乙烯基萘，或烯烃，诸如二环[2.2.]庚-2-烯、乙烯、丙烯或1-丁烯。
一般优选的PVC聚合物是K值约为65的氯乙烯的均聚物和共聚物。
可用于本发明的聚烯烃基材包括聚乙烯、聚丙烯、聚丁烯、聚异戊二烯、它们的共聚物和它们的混合物。
用于喷涂、辊涂、刷涂、凹版印刷、柔性版印刷、热转移印刷或喷墨施涂到PVC或PO挤出基材上的聚合物溶液是有颜色或没有颜色、含染料或不含染料的溶剂或水性溶液、分散体、乳液或它们的组合，它们的固体含量为2-50重量％，优选为10-50重量％。
可用于在PVC上形成涂层的溶液、分散体或乳液的聚合物中含有重均分子量大于100000、玻璃化转变温度在-50℃至+50℃之间的聚合物体系。可用于本发明的聚合物溶液、分散体或乳液的聚合物包括，但不限于，溶液、分散体或乳液形式的丙烯酸类树脂、氟化聚合物、聚氨酯、硅树脂(silicones)、聚硅氧烷、聚酯、环氧树脂、稳定的PVC和它们的混合物。
在本发明的一个优选实施方式中，聚合物溶液含有一种或多种耐候性极佳的含氟聚合物。这些含氟聚合物可以是均聚物，诸如聚偏二氟乙烯；或共聚物和三元共聚物，诸如，但不限于，1，1-二氟乙烯/六氟丙烯共聚物、偏二氟乙烯/氯四氟乙烯共聚物、偏二氟乙烯/四氟乙烯共聚物、乙烯/四氟乙烯共聚物、氟化乙烯丙烯(FEP)和它们的混合物。本发明的含氟聚合物还包括部分氟化的聚合物，诸如ETFE和ECTFE，它们的分解产物与完全氟化的聚合物的分解产物类似。
优选含氟聚合物是聚偏二氟乙烯聚合物。“PVDF”或PVDF树脂或PVDF聚合物不仅指PVDF的均聚物，还包括由至少约75重量％的1，1-二氟乙烯(VDF)单体制备的共聚物。共聚单体可包括其它氟化单体，诸如：氟乙烯、六氟丙烯(HFP)、氯四氟乙烯(CTFE)、四氟乙烯(TFE)和氟乙烯。优选的是由VDF和HEP制成的均聚物和共聚物，向其中可以加入少量(最多约5重量％，优选约0.01-0.05重量％)PTFE。PVDF涂布的PVC制品具有改善的光泽和颜色保持性，以及耐污染性。
可用于施涂在PVC或聚烯烃上的聚合物溶液、分散体或乳液通过将所述聚合物溶解或分散在溶剂或水性介质中形成。可用的溶剂包括，但不限于，丙酮、四氢呋喃、己烷、庚烷、N-甲基吡咯烷酮、甲乙酮、乙酸甲酯、乙酸乙酯、环己酮、异佛尔酮、水、水与水混溶性溶剂、和它们的混合物。涂料以在室温下测量的为0.1-5000cps、优选为1-500cps的粘度施涂。这些粘度比通常在50℃-125℃的实际施涂温度时的粘度略低。
还可以向聚合物涂料溶液或悬浮液中加入本领域中已知的其它添加剂，包括但不限于：染料、着色剂、抗冲改性剂、抗氧化剂、阻燃剂、紫外稳定剂、流动助剂、用于电磁辐射屏蔽的金属添加剂、消泡剂和抗静电剂。
聚合物溶液可以在在线方法的任何点、在50℃-125℃的温度施涂到挤出PVC上。
在本发明的一个实施方式中，将喷墨、辊涂、刷涂、凹版印刷、柔性版印刷、热转移涂布或喷涂设备设置在基材挤出工艺之后、压纹处理之前。在本发明的另一个实施方式中，将喷墨、辊涂、刷涂、凹版印刷、柔性版印刷、热转移涂布或喷涂设备在线设置在压纹操作之后。在压纹步骤后，通常对涂布的PVC或聚烯烃基材进行切割、压花，形成最终的制品。硬质PVC或聚烯烃尤其可用于房屋壁板、窗框、防雨系统、拱腹、装饰部分、管道和面板。以0.02密耳至4.0密耳、优选0.02密耳至1.2密耳的干膜厚度施涂涂料。虽然通常只将耐候性聚合物涂料施涂到PVC或聚烯烃基材的一个面上，但是将耐候性聚合物涂料施涂到基材的两个面也属于本发明的范围。双面涂布的基材可以具有两个用相同或不同聚合物溶液在相同涂布循环的相同或不同的涂布阶段涂布的面。
本发明通过在便宜的硬质PVC或聚烯烃基材上提供非常薄的、较贵的、耐候性聚合物的膜而节省了成本。本发明还使生产变得灵活，因为在线施涂可以在生产过程的任何位置发生。因为只需要一个挤出机，可以提高生产量，而不需要使2个挤出机的不同冷却速率互相匹配(一个是基材，另一个是面料)。
本发明的另一方面是能够提供各种颜色的耐候性涂料，从透明涂料到黑色涂料，也就是着色剂的比色能力所限定的可见光谱内的所有颜色。容易得到较深的颜色，因为本发明的薄膜与现有技术相比更薄，热量可以迅速消散。另外，可以简单改变聚合物涂料溶液或在线混合的有色涂料的比例，迅速地完成颜色之间的完全转变。这样减少了现有方法中涉及的耗时和不合格产品。使用四色方法印刷、涂布可以进行现场颜色调配和数字化调节。容易得到指定的颜色。
喷墨法还可以用于在PVC或聚烯烃基材上印刷复合颜色图案，诸如人造砖、人造灰泥和其它图案。采用数字计算机控制，可以将人们能想像的任何可能图案施涂到硬质基板的外部。
在一些实施方式中，首先将白色涂料施涂到硬质基材上，然后进行喷墨涂布。喷墨图案的效果在位于白色背景上时更加明显。优选的是环氧化物或PVDF的白色涂料。
在本发明的另一个实施方式中，PVC或PO挤出基材与面料共挤出，然后对其施涂耐候性涂料。
实施例
实施例1
通过以下步骤形成PVDF涂料混合物：首先制备15％的PVDF的甲乙酮(溶剂)溶液，任选地加入着色剂和/或添加剂。然后将PVDF涂料放入到喷墨印刷机的一个或多个储槽中。校准喷墨印刷机，随着PVC或聚烯烃的挤出，在PVC或聚烯烃上印刷精确的图案和聚合物密度。然后使涂布的挤出PVC或聚烯烃形成最终的制品，诸如乙烯基壁板片、窗框、栅栏柱或其它制品。
实施例2：
通过以下步骤形成PVDF涂料混合物：首先制备PVDF的溶液，固体含量为10％，溶剂为丙酮和N-甲基吡咯烷酮。任选地，还可以加入颜料、染料、添加剂或共树脂(co-resin)。然后将该涂料在压纹步骤之前或之后喷涂到挤出PVC或聚烯烃上。然后将涂布的挤出物切割成板，由这些板制成乙烯基盖板。
实施例3：
将白色环氧底涂料在线施涂到挤出PVC或聚烯烃上。然后通过喷墨印刷法外涂人造砖设计图案。然后对涂布的PVC挤出物进行切割，成型为乙烯基壁板。

Claims (9)

1.一种形成耐候性聚氯乙烯(PVC)或聚烯烃(PO)制品的方法，该方法包括在一步过程中通过在线喷涂、辊涂、刷涂、凹版印刷、柔性版印刷或喷墨施涂将聚合物溶液在线施涂到挤出的硬质PVC或PO上，形成耐候性涂层，其中所述涂层包含氟化聚合物，并且基于干膜厚度，所述耐候性涂层的厚度为0.02-4.0密耳。
2.如权利要求1所述的方法，其特征在于，所述聚合物溶液是含着色剂的或透明的。
3.如权利要求1所述的方法，其特征在于，所述聚合物溶液是溶剂基的溶液或分散体。
4.如权利要求1所述的方法，其特征在于，所述聚合物溶液是水性溶液、分散体或乳液。
5.如权利要求1所述的方法，其特征在于，所述氟化聚合物包括聚亚乙烯基的均聚物或共聚物。
6.如权利要求1所述的方法，其特征在于，基于干膜厚度，所述耐候性聚合物涂层的厚度为0.02-1.2密耳。
7.如权利要求1所述的方法，其特征在于，还包括以下步骤：在施涂耐候性涂料之前，用面料或涂料覆盖PVC或PO基材。
8.一种挤出的PVC或PO制品，其由硬质PVC或PO基材组成，所述基材具有在一步过程中施涂到所述基材上的耐候性聚偏二氟乙烯均聚物或共聚物涂层，所述涂层通过喷墨、辊涂、刷涂、凹版印刷、柔性版印刷或喷涂方法进行施涂，其中所述涂层的厚度为0.02-1.2密耳。
9.如权利要求8所述的挤出的PVC或PO制品，其特征在于，所述耐候性聚合物涂层具有由两种或多种不同的有色喷墨像素形成的图案。
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