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CN108603081A - 一种耐高温聚氯乙烯胶带的制作方法 - Google Patents

一种耐高温聚氯乙烯胶带的制作方法 Download PDF

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CN108603081A
CN108603081A CN201680080847.2A CN201680080847A CN108603081A CN 108603081 A CN108603081 A CN 108603081A CN 201680080847 A CN201680080847 A CN 201680080847A CN 108603081 A CN108603081 A CN 108603081A
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polyvinyl chloride
high temperature
resistant polyvinyl
temperature resistant
tape according
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王凤
齐淑琴
金春明
李爽
杨玉昆
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Shanghai Jujiao Enterprise Development Co.,Ltd.
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Hebei Huaxia Industrial Co ltd
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Abstract

本发明涉及一种耐高温聚氯乙烯胶带的制作方法，将可紫外光交联的热熔压敏粘合剂施用于耐高温的聚氯乙烯膜上制作成耐高温胶带的方法和生产工艺。耐高温的聚氯乙烯膜是含液体高分子型增塑剂、固体高分子增塑剂和热稳定剂的耐高温型材料。热熔压敏粘合剂可在130‑150℃下直接涂布于耐高温聚氯乙烯膜上，然后用紫外光进行交联固化，制成耐高温聚氯乙烯胶带。通过本发明提供的新型耐高温聚氯乙烯胶带的制作方法制作的耐高温聚氯乙烯胶带相对于传统的聚氯乙烯胶带具有无挥发性、耐高温和环保性高等优点。

Description

一种耐高温聚氯乙烯胶带的制作方法 技术领域
本发明涉及化学化工技术领域，具体而言，涉及一种耐高温聚氯乙烯胶带的制作方法，更具体地涉及一种通过将可紫外光交联的热熔压敏粘合剂施用于耐高温的聚氯乙烯膜上来制成胶带的方法和生产工艺。耐高温的聚氯乙烯膜是含液体高分子型增塑剂、固体高分子增塑剂和热稳定剂的耐高温型材料。热熔压敏粘合剂可在130-150℃下直接涂布于耐高温的聚氯乙烯膜上，然后用紫外光进行辐照交联制成聚氯乙烯胶带。
背景技术
以软聚氯乙烯(SPVC)薄膜为基材的电气压敏胶带因其具有优良的机械性能、阻燃性能、电绝缘性能、耐热变形性能和优越的加工应用性能等而广泛应用于汽车、机械制造、仪器仪表和家电等领域。但聚氯乙烯薄膜基材含有低分子增塑剂，如邻苯二甲酸二辛酯(DOP)、邻苯二甲酸二丁酯(DBP)和磷酸三正丁酯(TBP)等，具有较差的耐温性能。另外，这些低分子增塑剂会迁移到胶粘剂层中致使胶带的粘合力下降，从而无法达到工业上的应用要求。传统的高分子聚氯乙烯提高了耐高温性能，但无法在大于120℃的高温下涂布。
目前工业上的软聚氯乙烯胶带产品都是用溶剂型橡胶压敏粘合剂直接涂布于软聚氯乙烯薄膜上制成的。溶剂型橡胶压敏粘合剂中含有大量的有机溶剂，一般为甲苯。在涂布过程中，有机溶剂会部分挥发到大气中造成 环境污染。所得的聚氯乙烯胶带也含有溶剂残留，残留的溶剂会在使用过程中缓慢释放出来而污染到使用环境，如汽车的室内环境，完全不能满足欧盟委员会颁布的《关于在电子电气中限制使用某些有物质指令》(RoHS指令)要求。而且溶剂型橡胶压敏粘合剂的涂布工艺所用能耗较高，涂布设备的占地面积较大，因而生产成本较高。
紫外光交联的热熔压敏粘合剂具有很好的环保性，而且所需设备小巧，能耗较低，因而生产成本较低。更重要的是，这种类型的压敏粘合剂具有较好的抗增塑剂性能，高分子增塑剂的迁移不会导致胶带的性能下降很大。因此，这类热熔压敏粘合剂能广泛满足工业上的需求。但用低分子增塑剂和传统高分子增塑剂增塑的聚氯乙烯膜，其耐温性能都不够高。涂布时为了防止聚氯乙烯膜受到热破坏，只能降低涂布时的温度，并使用能量较低的紫外灯。降低涂布温度，粘合剂的粘度变高，流动性能变差，这导致了涂层的不均匀。这样就会限制涂布的速度，降低了生产效率。申请人在中国发明专利CN101372607B中描述了乳液压敏粘合剂在聚氯乙烯膜上的应用，但其在耐高温性能方面还有待进一步地提高。
发明内容
为了解决现有技术中的上述问题，本发明提供了一种新型耐高温聚氯乙烯胶带的制作方法，在耐高温性能上，紫外光交联型热熔粘合剂的性能具有更大的优势。这种制作方法是：将可紫外光交联的热熔压敏粘合剂在130-150℃的温度下直接热熔涂布在耐高温聚氯乙烯薄膜基材上，再经紫外光辐照交联制成这种新型耐高温聚氯乙烯胶带。
根据本发明提供的一种耐高温聚氯乙烯胶带的制作方法，所述方法包括：
将可紫外光交联的热熔压敏粘合剂在130-150℃的温度下热熔涂布在耐高温聚氯乙烯膜上，再经一组紫外灯的紫外光辐照交联制成，所述耐高温聚乙烯膜包含液体高分子增塑剂、固体高分子增塑剂和热稳定剂。
进一步地，在涂布过程中，对所述耐高温聚氯乙烯膜进行冷却保护，以防止耐高温聚氯乙烯膜在涂布和紫外光照射时受到破坏，。
可选地，所述可紫外光交联的热熔压敏粘合剂含有一种或多种可聚合光敏引发剂与丙烯酸酯单体的共聚物，或者含有一种或多种可聚合光敏引发剂的低聚体和丙烯酸酯聚合物的混合物，丙烯酸酯是指所有的丙烯酸酯类，例如，丙烯酸正丁酯(BA)、甲基丙烯酸甲酯(MMA)等。
进一步地，所述可紫外光交联的热熔压敏粘合剂还含有热稳定剂、光稳定剂、增粘树脂和增塑剂。
可选地，所述液体高分子增塑剂选自由液体聚己二酸乙二醇酯和液体聚己二酸丙二醇酯组成的组中的至少一种。
可选地，所述固体高分子增塑剂选自由乙烯-醋酸乙烯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸丁酯共聚物、丁腈橡胶粉和氯化聚乙烯组成的组中的至少一种。
可选地，所述热稳定剂选自由非铅类的液体或固体钡锌稳定剂、镉钡锌稳定剂、钙锌稳定剂、有机锡类稳定剂组成的组中的至少一种。
优选地，所述可聚合光敏引发剂是含甲基丙烯酰氧基或丙烯酰氧基的苯乙酮或二苯甲酮衍生物。
可选地，热熔涂布中可紫外光交联的热熔压敏粘合剂的涂布量是10-35克/平方米。
可选地，所述紫外灯是高压汞灯、中低压汞灯或LED灯，其紫外光辐照能量至少为10mJ/cm2。
进一步地，采用夹缝式挤压、刮棒式或淋膜式的涂布方式进行涂布。
本发明提供的新型耐高温聚氯乙烯胶带的制作方法，采用了耐高温型聚氯乙烯薄膜作为基材。这种耐高温聚氯乙烯薄膜除主体聚氯乙烯树脂外，还采用了液体高分子增塑剂、固体高分子增塑剂和热稳定剂。本发明所采用的液体高分子增塑剂是液体己二酸乙二醇聚酯增塑剂和液体己二酸丙二醇聚酯增塑剂等；所用的固体高分子增塑剂是乙烯-醋酸乙烯共聚物(EVA)、乙烯-丙烯酸甲酯共聚物(EMA)、乙烯-丙烯酸乙酯共聚物(EEA)、乙烯-丙烯酸丁酯共聚物(EBA)、丁腈橡胶粉(NBR)和氯化聚乙烯(CPE)等；所用的热稳定剂是非铅类的液体或固体钡锌稳定剂、镉钡锌稳定剂、钙锌稳定剂、有机锡类稳定剂等。此外，根据需要还采用一些色料和填料。
这种耐高温聚氯乙烯薄膜基材的采用可以将胶带的热熔涂布温度提高到150℃，从而加快了涂布速度，提高了生产效率。另外，这种聚氯乙烯膜中加入高分子增塑剂，降低了膜中的增塑剂向胶层的迁移。也就是说，胶带在储存和使用过程中或经60-80℃的高温烘烤后，虽然可能发生了基材的少量增塑剂向胶层的迁移，但胶带的性能仍能保持满足工业上的应用需求。因此，使用本发明的制作方法制作的聚氯乙烯胶带具有环保、耐高温、低VOC等优良性能。
众所周知，紫外光交联的热熔压敏粘合剂不含溶剂，所以在涂布加工过程中不需要溶剂回收体系，具有环保和节能等优点。常用的热熔压敏粘合剂的涂布方式为夹缝式挤压、刮棒式和淋膜式涂布。相对于传统的水性和溶剂型压敏粘合剂的涂布设备，热熔压敏粘合剂的涂布设备占地面积小，操作需要的人工少，可以大大提高生产效率。热熔压敏粘合剂的熔融粘度是非常重要的一个参数，熔融粘度的大小直接影响到涂布速度的快慢。目前工业上采用的橡胶型热熔压敏粘合剂的熔融粘度一般都比较大，用以涂布软聚氯乙烯(SPVC)薄膜来制造SPVC胶带时，只能采用复杂的转移涂布方法(即先将其涂布在防粘纸上干燥后再将胶层转移到SPVC薄膜上的方法)，无法采用简单的直接涂布方法。因为直接涂布时，为了提高涂布速度必须将橡胶型热熔压敏粘合剂的温度升高到150℃以上以降低其粘度，才能进行正常涂布(是最常用的一种方法)。但涂布时粘合剂温度的提高却会带来很多负面的影响，比如能破坏不耐高温的基材(尤其是SPVC基材)使其产生热变形甚至热降解，也能增加粘合剂的不稳定性。本发明采用的可紫外光交联的热熔压敏粘合剂的熔融粘度比橡胶型热熔压敏粘合剂低，可以在较低温度(130-150℃)下在SPVC基材上进行直接涂布，不会破坏软聚氯乙烯薄膜基材。本发明在涂布生产过程中还对SPVC基材进行冷却，以达到进一步的保护作用。
已知的可紫外光交联热熔压敏粘合剂的主要成份是丙烯酸酯类单体及其共聚合物的混合物。在丙烯酸酯类单体中，除了采用常用的丙烯酸正丁酯、丙烯酸异辛酯、丙烯酸、甲基丙烯酸、丙烯酸羟乙酯、丙烯酸羟丙酯外，还采用了甲基丙烯酰胺、N-羟甲基丙烯酰胺、N-丁氧基丙烯酰胺、β-CEA 等特殊单体。其他特殊软单体，如丙烯酸正辛酯、顺丁烯二酸二丁酯、顺丁烯二酸二辛酯和丙烯酸降冰片酯或其混合物，有时也被采用。为了增加粘合力，可以使用松香树脂、萜烯树脂、石油树脂及其相应的氢化、酯化改性树脂等增粘树脂。为了防止粘合剂的老化，通常还加入适量的防老剂。紫外光交联的热熔压敏粘合剂还必须包含一种或多种光敏引发剂，最常用的光敏引发剂是苯乙酮和二苯甲酮的衍生物。光敏引发剂在紫外光的照射下，更具体说是在UVC的辐射下，产生自由基团，从而使粘合剂中的丙烯酸酯类单体进一步聚合并使丙烯酸酯聚合物产生交联而固化。
在本发明所采用的可紫外光交联的热熔压敏粘合剂的组成中，除上述各种成分外，还含有一种或多种可聚合光敏引发剂与丙烯酸酯单体的共聚物,或者含一种或多种可聚合光敏引发剂的低聚体和丙烯酸酯聚合物的混合物。这种可聚合光敏引发剂是含甲基丙烯酰氧基或丙烯酰氧基的苯乙酮或二苯甲酮衍生物，例如2-羟基-4-(甲基丙烯酰氧基)二苯甲酮。因此，含可聚合光敏引发剂的低聚体能降低热熔粘合剂的粘度，从而降低涂布温度，更好地保护聚氯乙烯基材。在可紫外光交联的热熔压敏粘合剂的组成中采用高分子量光敏引发剂，可以进一步降低胶层的挥发性，使胶带更好地满足环保的要求。
本发明提供的一种新型耐高温聚氯乙烯胶带的制作方法是在热熔涂布机上采用夹缝式挤压、刮棒式或淋膜式涂布工艺完成的。将耐高温聚氯乙烯膜基材安装到放卷轴上，并引出至收卷轴。设定熔胶箱温度为130-140℃，涂布头温度为130-150℃，根据上胶的重量调整胶泵的转速和主机速度的比值。设定收卷张力和放卷张力，并打开冷却装置。调整主机 速度，将涂布头慢慢靠至聚氯乙烯膜面，打开胶泵开关进行涂布，调整涂布头和基材之间的间隙距离，调整涂布机速度进行涂布，本发明所采用的热熔胶粘剂的涂布量是10-35克/平方米。胶层经一组紫外灯的紫外光辐照进行交联固化。本发明所用的紫外灯是高压汞灯、中低压汞灯或者LED灯，其紫外光的最小辐照能量需达到10mJ/cm2。交联固化后的胶带再经收卷分切后即制得所述的耐高温聚氯乙烯胶带制品。在涂布过程中为了防止聚氯乙烯膜基材在紫外光照射时受到破坏，应对聚氯乙烯膜进行冷却保护。本发明所采用的冷却方式可以是水冷凝或风冷却方式，也可以同时采用水冷凝和风冷却。
性能测试：将所制得的可紫外光交联热熔压敏粘合剂用上述方法热熔涂布于0.15毫米厚的聚氯乙烯薄膜基材上，制得胶层厚度为20微米的电气压敏粘合剂粘带小卷。经过在60℃，8小时老化以后，按照以下标准对胶粘性能进行测试：1)中国国家标准GB/T2792-1998测试180°剥离强度；2)中国国家标准GB/4852-1984测试胶带初粘性能；3)按照VW60360(LV312)评估耐高温等级；4)按照中国国家标准GB/T4581-1988测试胶带的持粘性能。
具体实施方式
下面详细介绍本发明的示例性实施例和比较例，提供这些示例性实施例的目的是为了使得本领域普通技术人员能够清楚地理解本发明，并且根据这里的描述能够实现本发明。具体实施例不旨在对本发明进行限定，本发明的范围由所附权利要求限定。
本发明的实施例和比较例分别采用以下聚氯乙烯膜：
1.耐高温型聚氯乙烯膜，其组份和按重量百分数用量如下：
将原材料进行混合，之后经高速搅拌机混合、高温开炼机、挤出机、三辊或者四辊压延机进行高温压延制备成聚氯乙烯膜。
2.目前市场上普遍使用的含DOP增塑剂的聚氯乙烯膜。
实施例1
将丙烯酸正丁酯、丙烯酸异辛酯、丙烯酸甲酯、丙烯酸和可共聚的光敏引发剂的丙烯酸酯共聚物按照上面描述的方式施加到上述耐高温聚氯乙烯膜上，制成聚氯乙烯胶带，应用的涂布温度为140℃。
实施例2
将丙烯酸正丁酯、丙烯酸和可共聚的光敏引发剂的丙烯酸酯共聚物按照上面描述的方式施加到上述耐高温聚氯乙烯膜上，制成聚氯乙烯胶带，应用的涂布温度为140℃。
实施例3
将20％的丙烯酸正丁酯、丙烯酸和可共聚的光敏引发剂的低聚体和80％的丙烯酸酯聚合物的混合物按照上面描写的方式施用到上述耐高温聚氯乙烯膜上，制成聚氯乙烯胶带，应用的涂布温度为130℃。
比较例1
将丙烯酸正丁酯、丙烯酸异辛酯、丙烯酸甲酯、丙烯酸和可共聚的光敏引发剂的丙烯酸酯共聚物因为直接涂布在含DOP增塑剂的聚氯乙烯膜会使膜受到破坏，所以在本比较例中只能采用转移涂布方式，即先涂布在离型纸上，然后转移到含DOP增塑剂的聚氯乙烯膜上，应用的涂布温度为140℃。
比较例2
目前工业上普遍使用的汽车线束用聚氯乙烯胶带为华夏胶带FC110(耐高温汽车线束用PVC胶粘带，河北华夏实业有限公司生产)，所用的胶水是溶剂型橡胶体系，所用的聚氯乙烯膜属于耐高温型聚氯乙烯膜。
比较例3
目前工业上普遍使用的汽车线束用聚氯乙烯胶带为华夏胶带UD110(汽车线束用PVC胶粘带，河北华夏实业有限公司生产)，所用的胶水是溶剂型橡胶体系，所用的聚氯乙烯膜属于含DOP增塑剂的聚氯乙烯膜。
表1制作的胶带的性能数据
从表1的实施例1-3的性能数据可以看出可紫外光交联的热熔压敏胶能显著提高聚氯乙烯胶带的耐高温性能，达到125℃的耐温等级。用溶剂型橡胶制成的胶带耐高温等级为105℃(比较例2)。从比较例1和比较例3的测试结果可以得知，可紫外光交联的热熔压敏胶抗低分子增塑剂性能不如溶剂型橡胶。总的来说，可紫外光交联的热熔压敏胶适合于施用于含高分子增塑剂的耐高温聚氯乙烯膜，而所制得的胶带符合工业应用指标。此外，胶带有优良的耐高温性能，适用于电缆束的包复和捆扎，尤其适用于汽车车体中的电缆束的包复和捆扎。

Claims (11)

  1. 一种耐高温聚氯乙烯胶带的制作方法，所述方法包括：
    将可紫外光交联的热熔压敏粘合剂在130-150℃的温度下热熔涂布在耐高温聚氯乙烯膜上，再经一组紫外灯的紫外光辐照交联制成，其中，所述耐高温聚乙烯膜包含液体高分子增塑剂、固体高分子增塑剂和热稳定剂。
  2. 根据权利要求1所述的耐高温聚氯乙烯胶带的制作方法，其中，在涂布过程中，对所述耐高温聚氯乙烯膜进行冷却保护。
  3. 根据权利要求1所述的耐高温聚氯乙烯胶带的制作方法，其中，所述可紫外光交联的热熔压敏粘合剂含有一种或多种可聚合光敏引发剂与丙烯酸酯单体的共聚物，或者含有一种或多种可聚合光敏引发剂的低聚体和丙烯酸酯聚合物的混合物。
  4. 根据权利要求3所述的耐高温聚氯乙烯胶带的制作方法，其中，所述可紫外光交联的热熔压敏粘合剂还含有热稳定剂、光稳定剂、增粘树脂和增塑剂。
  5. 根据权利要求1所述的耐高温聚氯乙烯胶带的制作方法，其中，所述液体高分子增塑剂选自由液体聚己二酸乙二醇酯和液体聚己二酸丙二醇酯组成的组中的至少一种。
  6. 根据权利要求1所述的耐高温聚氯乙烯胶带的制作方法，其中，所述固体高分子增塑剂选自由乙烯-醋酸乙烯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸丁酯共聚物、丁腈橡胶粉和氯化聚乙烯组成的组中的至少一种。
  7. 根据权利要求1所述的耐高温聚氯乙烯胶带的制作方法，其中，所述热稳定剂选自由非铅类的液体或固体钡锌稳定剂、镉钡锌稳定剂、钙锌稳定剂、有机锡类稳定剂组成的组中的至少一种。
  8. 根据权利要求3所述的耐高温聚氯乙烯胶带的制作方法，其中，所述可聚合光敏引发剂是含甲基丙烯酰氧基或丙烯酰氧基的苯乙酮或二苯甲酮衍生物。
  9. 根据权利要求1所述的耐高温聚氯乙烯胶带的制作方法，其中，热熔涂布中可紫外光交联的热熔压敏粘合剂的涂布量是10-35克/平方米。
  10. 根据权利要求1所述的耐高温聚氯乙烯胶带的制作方法，其中，所述紫外灯是高压汞灯、中低压汞灯或LED灯，其紫外光辐照能量至少为10mJ/cm2。
  11. 根据权利要求1所述的耐高温聚氯乙烯胶带的制作方法，其中，采用夹缝式挤压、刮棒式或淋膜式的涂布方式进行涂布。
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