CN112442240B - 一种自清洁膜及其制备方法 - Google Patents

一种自清洁膜及其制备方法 Download PDF

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CN112442240B
CN112442240B CN202011344235.4A CN202011344235A CN112442240B CN 112442240 B CN112442240 B CN 112442240B CN 202011344235 A CN202011344235 A CN 202011344235A CN 112442240 B CN112442240 B CN 112442240B
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王玉林
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Abstract

本发明属于PVC膜技术领域，具体涉及一种自清洁膜及其制备方法。该自清洁膜由如下重量组分的各原料制成：含硅氯乙烯共聚物100‑200份、聚甲基丙烯酸甲酯10‑30份，增韧剂8‑15份，无机纳米填充剂0.5‑3份，稳定剂1‑8份。本发明提供的汽车贴膜在PVC结构中成功引入有机硅烷结构，可以较好的对膜材料的微观结构表面进行改造，提高其疏水突起比例，实验结果表明，本发明的膜材料具有优异的疏水性能。同时该材料的引入也有效地提高了膜材料的透光性能及其力学性能。

Description

一种自清洁膜及其制备方法
技术领域
本发明属于PVC膜技术领域，具体涉及一种自清洁膜及其制备方法。
背景技术
汽车贴膜是通过高分子聚合材料贴附于汽车前后挡风玻璃、车窗玻璃内表面以及天窗上，可以改善汽车玻璃的光学性能，提高汽车的安全性。目前，市售的汽车玻璃贴膜的功能主要体现在以下几个方面：防晒、防爆、防划伤、隔紫外线。这些汽车贴膜虽然可以在一定程度上起到隔离太阳光、防窥视、防止玻璃爆破的作用，但仍存在两大问题，其中一个问题是易雾化、疏水差的问题，下雨天气，前挡风玻璃有雨刮的情况下还好，但后视镜玻璃上经常因为挂水影响司机视野；另一个问题是抗老化性能差，导致易起泡起层问题，不仅影响性能也影响其美观。
发明内容
为了解决现有技术的上述问题，本发明的目的在于提供一种高疏水、高透光且耐老化性能优异的汽车用自清洁膜。
为了实现上述发明目的，本发明提供如下技术方案：
一种自清洁膜，其由如下重量组分的各原料制成：含硅氯乙烯共聚物100-200份、聚甲基丙烯酸甲酯10-30份，增韧剂8-15份，无机纳米填充剂0.5-3份，稳定剂1-8份。
优选地，所述增韧剂为大分子聚酯醚类物质。
进一步优选地，所述增韧剂为EVA。
优选地，所述无机纳米填充剂为纳米二氧化钛、纳米二氧化硅和纳米二氧化二铝中的一种或多种。
优选地，所述稳定剂包括抗氧剂和抗紫外吸收剂，所述抗氧剂为双酚A和亚磷酸酯的组合；所述抗紫外吸收剂为UV-531。
本发明还提供了一种所述自清洁膜的制备方法，其包括如下步骤：
S1将硅氯乙烯共聚物、聚甲基丙烯酸甲酯与40-60％增韧剂、40-60％无机纳米填充剂和40-60％稳定剂搅拌混匀后经第一双螺杆挤出机熔融挤出、冷却、造粒得母粒1；
S2将母粒1和剩余的增韧剂、无机钠米填充剂和稳定剂混合后经第二双螺杆挤出机挤出后双向拉伸。
优选地，步骤S2熔融挤出段温度为220-280℃，螺杆温度60-80℃。
优选地，步骤S2混合时螺杆的转速为250-280r/min。
本发明与现有技术相比，存在如下有益效果：
本发明提供的汽车贴膜在PVC结构中成功引入有机硅烷结构，可以较好的对膜材料的微观结构表面进行改造，提高其疏水突起比例，实验结果表明，本发明的膜材料具有优异的疏水性能。同时该材料的引入也有效地提高了膜材料的透光性能及其力学性能。试验结果表明，实施例1-3提供的膜还表现出剥离性能及抗老化性能。
具体实施方式
下面结合实施例对本发明做进一步阐述。这些实施例仅是出于解释说明的目的，而不限制本发明的范围和实质。本发明所述的各原料或市场购入或利用本领域的常规方法或基于已公开方法根据需要进行调整后得到。
实施例1
一种汽车贴膜，其由如下重量组分的各原料制成：含硅氯乙烯共聚物120份，聚甲基丙烯酸甲酯10份，增韧剂EVA 9份，纳米二氧化钛1份，双酚A 0.4份和亚磷酸酯的组合0.2份,抗紫外吸收剂为UV-531 0.4份。
该汽车贴膜的制备方法包括如下步骤：
S1将硅氯乙烯共聚物、聚甲基丙烯酸甲酯与50％增韧剂、50％无机纳米填充剂和50％稳定剂搅拌混匀后经第一双螺杆挤出机熔融挤出、冷却、造粒得母粒1；
S3将母粒1和剩余的增韧剂、无机钠米填充剂和稳定剂混合后经第二双螺杆挤出机挤出后双向拉伸。其中，挤出温度为：一区220℃,二区230℃，三区240℃，四区250℃,五区260℃,机头280℃；螺杆温度80℃；螺杆转速260r/min。
其中，所述硅氯乙烯共聚物的制备参照专利CN108148160A公开的方法，其中有机硅单体为八甲基环四硅氧烷、三乙基硅烷和乙烯基七甲基环四硅氧烷，乳化剂为十二烷基苯磺酸钠，催化剂为十二烷基苯磺酸。
实施例2
一种汽车贴膜，其由如下重量组分的各原料制成：含硅氯乙烯共聚物120份，聚甲基丙烯酸甲酯30份，增韧剂EVA 15份，纳米二氧化钛1.5份，双酚A 0.4份和亚磷酸酯的组合0.2份,抗紫外吸收剂为UV-531 0.4份。
该汽车贴膜的制备方法同实施例1。
实施例3
一种汽车贴膜，其由如下重量组分的各原料制成：含硅氯乙烯共聚物200份，聚甲基丙烯酸甲酯10份，增韧剂EVA 9份，纳米二氧化钛1份，双酚A 0.4份和亚磷酸酯的组合0.2份,抗紫外吸收剂为UV-531 0.4份。
该汽车贴膜的制备方法同实施例1。
对比例1
一种汽车贴膜，其由如下重量组分的各原料制成：氯乙烯200份，聚甲基丙烯酸甲酯10份，增韧剂EVA 9份，纳米二氧化钛1份，双酚A 0.4份和亚磷酸酯的组合0.2份,抗紫外吸收剂为UV-531 0.4份。
该汽车贴膜的制备方法同实施例1。
对比例2
一种汽车贴膜，其由如下重量组分的各原料制成：含硅氯乙烯共聚物200份，增韧剂EVA 9份，纳米二氧化钛1份，双酚A 0.4份和亚磷酸酯的组合0.2份,抗紫外吸收剂为UV-531 0.4份。
该汽车贴膜的制备方法同实施例1。
对比例3
一种汽车贴膜，其由如下重量组分的各原料制成：含硅氯乙烯共聚物60份，聚甲基丙烯酸甲酯60份，增韧剂EVA 9份，纳米二氧化钛1份，双酚A 0.4份和亚磷酸酯的组合0.2份,抗紫外吸收剂为UV-531 0.4份。
该汽车贴膜的制备方法同实施例1。
性能测试
1、透明度测试采用雾度与透光率表示，参照GB/T2410-2008执行。
2、采用JC2000C1静滴接触角/界面张力测量仪测量去离子水在各实施例所制汽车贴膜表面的接触角θ1。
3、剥离强度的测定：从样品离布边50mm以上处沿经纬向等间距各取三块长150mm，宽100mm的试样，每块试样沿宽度的中心线平分为二，经高频(测试仪功率为2.5KW，热合时间为7.5S)或热风焊接后(焊缝宽度为50mm)，从一端将其剥开50mm，分别夹于拉伸试验机夹具上，以100mm/min的拉伸速度进行试验，记录试样的最大剥离强力，试验结果以三块试样的算术平均值表示，精确至1N。
表1
雾度％ 透过率％ θ<sub>1</sub> 剥离强度N/5cm
实施例1 1.5 99.2 110.5 148
实施例2 1.1 99.5 112.3 153
实施例3 1.7 99.0 110 150
对比例1 2.1 97.4 90.8 122
对比例2 2.3 95.2 87.5 125
对比例3 1.8 98.1 106.1 139
从检测结果可以看出，采用本发明实施例的方法制得的自清洁膜具有较好疏水性和透光性能，同时也具有更优异的剥离强度。另外采用本发明的自清洁膜进行抗老化测试，结果表明，2000h耐老化测试(GB/T 16422.2中A法)，各实施例提供的自清洁膜的纵向拉伸强度降低比例不超过3％(实施例2仅为0.2％)；而对比例的则基本维持在8-12％。
本行业的技术人员应该了解，本发明不受上述实施例的限制，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。

Claims (3)

1.一种自清洁膜，其特征在于，由如下重量组分的各原料制成：含硅氯乙烯共聚物100-200份、聚甲基丙烯酸甲酯10-30份，增韧剂8-15份，无机纳米填充剂0.5-3份，稳定剂1-8份；
所述增韧剂为EVA；
所述无机纳米填充剂为纳米二氧化钛；
所述稳定剂包括抗氧剂和抗紫外吸收剂；
所述抗氧剂为双酚A和亚磷酸酯的组合；所述抗紫外吸收剂为UV-531；
所述自清洁膜的制备方法，其包括如下步骤：
S1将硅氯乙烯共聚物、聚甲基丙烯酸甲酯与40-60％增韧剂、40-60％无机纳米填充剂和40-60％稳定剂搅拌混匀后经第一双螺杆挤出机熔融挤出、冷却、造粒得母粒1；
S2将母粒1和剩余的增韧剂、无机钠米填充剂和稳定剂混合后经第二双螺杆挤出机挤出后双向拉伸。
2.根据权利要求1所述的自清洁膜，其特征在于，步骤S2挤出温度为220-280℃，螺杆温度60-80℃。
3.根据权利要求1所述的自清洁膜，其特征在于，步骤S2混合时螺杆的转速为250-280r/min。
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