CN106519413B - 一种防静电复合膜 - Google Patents

一种防静电复合膜 Download PDF

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CN106519413B
CN106519413B CN201611002502.3A CN201611002502A CN106519413B CN 106519413 B CN106519413 B CN 106519413B CN 201611002502 A CN201611002502 A CN 201611002502A CN 106519413 B CN106519413 B CN 106519413B
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王震
尹强
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SHANDONG ZHONGSU TAIFU TECHNOLOGY Co Ltd
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Abstract

本发明公开了一种防静电复合膜，包括聚氨酯底层、设置在所述底层上的防静电层，所述防静电层是包含有改性导电聚苯胺纤维的线型低密度聚乙烯聚合物层；所述改性导电聚苯胺纤维在线型低密度聚乙烯聚合物层中的含量是5‑20wt%；本发明采用苯系化合物含量和烷烃类化合物含量均较低的低密度聚乙烯颗粒为原料，加入可以改进导电性和机械强度的改性导电聚苯胺纤维，按照本发明方法制得的防静电薄膜，在保证基本防静电性能的通式可以有效的减少抗静电膜中金属的用量，大大减轻对环境的污染和回收处理的难度，有利于保护环境。改性导电聚苯胺纤维的加入可以大大改进抗静电膜的抗撕裂性能，提高了抗静电膜的机械强度，有利于保护包装膜中的电子元器件收到机械损坏。

Description

一种防静电复合膜
技术领域
本发明涉及一种防静电复合膜，尤其是一种适用于包裹电子元器件的防静电复合膜。
背景技术
静电是一种常见却又复杂的物理现象，它无影无踪、无处不在。随着科学技术的迅猛发展，生产的高效率和自动化程度的提高，电子设备的广泛采用，使静电和电磁环境越来越恶化，这就给对静电及电磁辐射敏感的产品如集成电路、电磁控制系统、化学药剂等造成了威胁。由于外界电磁辐射引起集成电路、电磁控制系统失效、误动作，化工产品燃烧、爆炸的事故时有发生。化工产品、电子器件在生产、储存、运输及使用过程中由于摩擦、撞击、接触、分离产生静电积累并放电，造成的后果是破坏性甚至是灾难性的。
在电子元器件的生产运输中，需要采用防静电材料如防静电膜包装，防止被静电损坏。上世纪90年代已经市场化的单质防静电聚乙烯薄膜，因其为极性材料，且双表面电阻值低，无法进行电晕处理，因而不能与其它基材复合成层状包装材料。单质的薄膜因其机械物理性能低，无法给内包装产品提供可靠的防护，因而限制了它的广泛应用。
聚酯膜与金属箔复合膜也是一种已经完全工业化生产应用的防静电膜，这种复合膜也可以在聚乙烯膜表层涂布静电层制成。如采用在聚酯膜的表层用铝、镍、钛、铜、铬、锌等金属物质蒸镀或者喷涂方式，在聚酯膜的表层蒸镀或喷涂上金属膜层，从而得到具有防静电功能的聚酯膜材料，并用该材料制成防静电用包装袋；或者利用表面活性剂、炭黑通过涂布方式在聚乙烯薄膜表面涂布成防静电涂层，从而得到具有防静电功能的聚乙烯膜材料，然后将其制作成防静电用包装袋。
塑料材料要获得一定的导电性能，需将导电性物质如导电炭黑以一定比例与热塑性树脂混合，并添加偶联剂、增塑剂、滑爽剂、稳定剂、抗氧剂等多种添加剂。
CN103481616 A公开了一种防静电多层共挤膜及其制备方法。所述防静电多层共挤膜分为五层，从外层到内存依次是第一PE层，第二PE层，第三PA层，第四PE层和第五PE层，所述五层共挤薄膜的厚度依次是1.5-2:1.25-1.75:1-2:1.25-1.75-1.5-2。其制备方法是将各层原料分别加入各层挤出机进行熔融塑化、挤出，然后在吹胀比为1:2-5，温度为70-90℃的条件下进行吹膜，冷却后得到所述多层共挤膜。该共挤膜工艺较为复杂，且防静电能力不突出。
CN102371743 A公开了一种抗静电聚酯薄膜及其制备方法，所述抗静电聚酯薄膜包括聚酯薄膜本体和至少一个含有有机防静电剂和无机纳米防静电剂的聚酯层，所述聚酯层中的有机防静电剂和无机纳米防静电剂的重量比为20∶1～100∶1，所述抗静电聚酯薄膜经双向拉伸得到。本发明的抗静电聚酯薄膜既具有稳定、持久的抗静电性能，又具有优异耐湿热老化性能；同时保持了优异的光学性能以及力学性能，它适用于电子产品组装，尤其适用于生产增量膜，扩散膜，防划伤膜等平板显示器背光模组的膜片。
发明内容
现有的防静电膜基本都需要在膜材料中混入大量的导电金属，这就造成防静电膜在回收处理时难以处理。一方面如果对这些高分子塑料材料进行焚烧处理，则会产生大量的含金属粉尘，容易污染大气；另一方面，如果对这些含大量金属的高分子塑胶材料进行热解处理，其中含有的大量金属组分会使热解催化剂很快失活。因此目前的防静电膜材料存在难以处理的弊端。本发明人意外的发现，在防静电膜材料中加入改性聚苯胺导电纤维，在保证基本的防静电性能的同时可以大幅降低材料中金属的总含量，而且可以提高膜材料整体的加工性能和抗撕裂性。本发明将含有改性聚苯胺导电纤维的低密度聚乙烯聚合物材料与聚氨酯材料结合，克服了单层抗静电层机械性能不理想的缺憾，并且能够与所述抗静电层很好的结合，具有不容易分层的特点。
一种防静电复合膜，包括聚氨酯底层、设置在所述底层上的防静电层，所述防静电层是包含有改性导电聚苯胺纤维的线型低密度聚乙烯聚合物层；所述改性导电聚苯胺纤维在线型低密度聚乙烯聚合物层中的含量是5-20wt%；所述防静电层厚度是聚氨酯底层厚度的50-200%。
所述改性导电聚苯胺纤维的制备方法包括以下步骤：先把原纤维浸泡在5-10wt%苯胺的盐酸-重铬酸钾溶液中1-3h，使原纤维表面吸附苯胺单体，然后加入氧化剂和掺杂剂，苯胺发生氧化聚合反应并掺杂；所述氧化剂和掺杂剂的添加量分别是苯胺的盐酸-重铬酸钾溶液的1-10wt%和0.2-5wt%，优选是2-4wt%和0.5-1wt%；所得聚苯胺导电纤维具有皮芯结构。
所述原纤维是涤纶纤维、聚丙烯纤维、乙烯丙烯共聚物纤维中的一种或多种。
所述改性导电聚苯胺纤维的长度是10-1000微米，直径是0.1-1微米；优选长度是100-1000微米，直径为0.5-1微米。
所述氧化剂是过硫酸铵、碘酸钠、过硫酸铵中的一种或多种。
所述掺杂剂是硝酸镍、硝酸铜中的一种。
一种防静电复合膜的制备方法，包括以下步骤：将改性导电聚苯胺纤维、线型低密度聚乙烯、硅烷偶联剂、溶剂油、抗氧剂混合得到混合料；混合料和聚氨酯分别加入多层共挤吹膜机中挤出，冷却即得所述复合防静电膜；所述硅烷偶联剂为混合料质量的5-10%、溶剂油为混合料质量的5-10%、抗氧剂的加入量是为混合料质量的0.5-2%。
所述制备过程中的挤出温度设置为底层挤出温度为160℃～200℃，防静电层挤出温度为180℃～220℃；优选底层挤出温度为180℃～190℃，防静电层挤出温度为200℃～210℃。
本发明的技术效果主要体现在：
①本发明采用苯系化合物含量和烷烃类化合物含量均较低的低密度聚乙烯颗粒为原料，加入可以改进导电性和机械强度的改性导电聚苯胺纤维，按照本发明方法制得的防静电薄膜，可以有效的减少抗静电膜中金属的用量，大大减轻对环境的污染和回收处理的难度，有利于保护环境。
②改性导电聚苯胺纤维的加入可以大大改进抗静电膜的抗撕裂性能，提高了抗静电膜的机械强度，有利于保护包装膜中的电子元器件收到机械损坏。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
实施例１：
改性导电聚苯胺纤维的制备：先把涤纶浸泡在10wt%苯胺的盐酸-重铬酸钾溶液中1h，使原纤维表面吸附苯胺单体，然后加入苯胺的盐酸-重铬酸钾溶液2wt%的过硫酸铵和苯胺的盐酸-重铬酸钾溶液1wt%硝酸镍，即得所述改性聚苯胺导电纤维。
防静电复合膜的制备方法，包括以下步骤：将改性导电聚苯胺纤维、线型低密度聚乙烯、硅烷偶联剂、溶剂油、抗氧剂混合得到混合料；混合料和聚氨酯分别加入多层共挤吹膜机中挤出，冷却即得所述复合防静电膜；所述改性导电聚苯胺纤维为混合料质量的10%，所述硅烷偶联剂为混合料质量的5%、溶剂油为混合料质量的5%、抗氧剂的加入量是为混合料质量的0.5%。制备过程中的挤出温度设置为底层挤出温度为180℃，防静电层挤出温度为200℃，即得所述复合防静电膜。
实施例２：
改性导电聚苯胺纤维的制备：先把涤纶浸泡在5wt%苯胺的盐酸-重铬酸钾溶液中3h，使原纤维表面吸附苯胺单体，然后加入苯胺的盐酸-重铬酸钾溶液4wt%的碘酸钠和苯胺的盐酸-重铬酸钾溶液1wt%硝酸铜，即得所述改性聚苯胺导电纤维。
防静电复合膜的制备方法，包括以下步骤：将改性导电聚苯胺纤维、线型低密度聚乙烯、硅烷偶联剂、溶剂油、抗氧剂混合得到混合料；混合料和聚氨酯分别加入多层共挤吹膜机中挤出，冷却即得所述复合防静电膜；所述改性导电聚苯胺纤维为混合料质量的10%、所述硅烷偶联剂为混合料质量的5%、溶剂油为混合料质量的5%、抗氧剂的加入量是为混合料质量的0.5%。制备过程中的挤出温度设置为底层挤出温度为180℃，防静电层挤出温度为200℃，即得所述复合防静电膜。
对比例1（不加入改性导电聚苯胺纤维的空白膜）：
防静电复合空白膜的制备方法，包括以下步骤：将线型低密度聚乙烯、硅烷偶联剂、溶剂油、抗氧剂混合得到混合料；混合料和聚氨酯分别加入多层共挤吹膜机中挤出，冷却即得所述复合防静电膜；所述硅烷偶联剂为混合料质量的5%、溶剂油为混合料质量的5%、抗氧剂的加入量是为混合料质量的0.5%。制备过程中的挤出温度设置为底层挤出温度为180℃，防静电层挤出温度为200℃，即得所述复合防静电空白膜。
对比例2（茂金属类抗静电膜）：
防静电复合膜的制备方法，包括以下步骤：将茂金属抗静电剂、线型低密度聚乙烯、硅烷偶联剂、溶剂油、抗氧剂混合得到混合料；混合料和聚氨酯分别加入多层共挤吹膜机中挤出，冷却即得所述复合防静电膜；所述改性茂金属抗静电剂为混合料质量的10%、所述硅烷偶联剂为混合料质量的5%、溶剂油为混合料质量的5%、抗氧剂的加入量是为混合料质量的0.5%。制备过程中的挤出温度设置为底层挤出温度为180℃，防静电层挤出温度为200℃，即得所述复合防静电膜。
针对实施例制得的防静电复合膜进行性能检测，具体数据如下：
电阻率（Ω·m） 拉伸率（%） 撕裂强度（MPa） 拉断力（N/15mm） 金属含量（ppm）
实施例1 6.9×10<sup>6</sup> 85 12 91 16
实施例2 3.7×10<sup>5</sup> 79 13 95 35
对比例1 2.1×10<sup>9</sup> 61 8 66 6
对比例2 5.7×10<sup>7</sup> 60 8 63 204
从对比试验结果可以看出，本发明的复合抗静电膜具有较为均衡的机械性能，显著的降低了膜材料中的金属含量，有利于环保；且具有较为优异的导电性能，可以很好的保护电子元件不受静电伤害。

Claims (10)

1.一种防静电复合膜，包括聚氨酯底层、设置在所述底层上的防静电层，所述防静电层是包含有改性导电聚苯胺纤维的线型低密度聚乙烯聚合物层；所述改性导电聚苯胺纤维在线型低密度聚乙烯聚合物层中的含量是5-20wt%；所述防静电层厚度是聚氨酯底层厚度的50-200%；所述改性导电聚苯胺纤维的制备方法包括以下步骤：先把原纤维浸泡在5-10wt%苯胺的盐酸-重铬酸钾溶液中1-3h，使原纤维表面吸附苯胺单体，然后加入氧化剂和掺杂剂，苯胺发生氧化聚合反应并掺杂；所述氧化剂和掺杂剂的添加量分别是苯胺的盐酸-重铬酸钾溶液的1-10wt%和0.2-5wt%；所得聚苯胺导电纤维具有皮芯结构。
2.如权利要求1所述的防静电复合膜，其特征在于所述原纤维是涤纶纤维、聚丙烯纤维、乙烯丙烯共聚物纤维中的一种或多种。
3.如权利要求1所述的防静电复合膜，其特征在于所述改性导电聚苯胺纤维的长度是10-1000微米，直径是0.1-1微米。
4.如权利要求1所述的防静电复合膜，其特征在于所述氧化剂是过硫酸铵、碘酸钠中的一种或多种。
5.如权利要求1所述的防静电复合膜，其特征在于所述掺杂剂是硝酸镍、硝酸铜中的一种。
6.如权利要求1所述的防静电复合膜，其特征在于所述氧化剂和掺杂剂的添加量分别是苯胺的盐酸-重铬酸钾溶液的2-4wt%和0.5-1wt%。
7.如权利要求3所述的防静电复合膜，其特征在于所述改性导电聚苯胺纤维的长度是100-1000微米，直径为0.5-1微米。
8.如权利要求1-7任一项所述防静电复合膜的制备方法，包括以下步骤：将改性导电聚苯胺纤维、线型低密度聚乙烯、硅烷偶联剂、溶剂油、抗氧剂混合得到混合料；混合料和聚氨酯分别加入多层共挤吹膜机中挤出，冷却即得所述复合防静电膜；所述硅烷偶联剂为混合料质量的5-10%、溶剂油为混合料质量的5-10%、抗氧剂的加入量是为混合料质量的0.5-2%。
9.如权利要求8所述的方法，其特征在于所述制备过程中的挤出温度设置为底层挤出温度为160℃～200℃，防静电层挤出温度为180℃～220℃。
10.如权利要求8所述的方法，其特征在于所述制备过程中的挤出温度设置为底层挤出温度为180℃～190℃，防静电层挤出温度为200℃～210℃。
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