CN110682621A - 高耐磨高耐蚀pvdf覆膜板 - Google Patents

高耐磨高耐蚀pvdf覆膜板 Download PDF

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CN110682621A
CN110682621A CN201910949803.4A CN201910949803A CN110682621A CN 110682621 A CN110682621 A CN 110682621A CN 201910949803 A CN201910949803 A CN 201910949803A CN 110682621 A CN110682621 A CN 110682621A
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film
pvdf
high wear
resistance
pvdf film
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段满益
许曲锋
周丹
张林元
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Suzhou Yangtze New Materials Co Ltd
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Abstract

本发明提供一种高耐磨高耐蚀PVDF覆膜板，所述覆膜板从上到下依次设有第一防腐膜层、第一胶黏层、铝箔层、第二胶黏层、第二防腐膜层，其中，所述第一防腐膜层和第二防腐膜层结构相同，均包括从上到下依次设置的陶瓷膜层、粘接膜层、改性PVDF膜层。本发明提供的PVDF覆膜板采用对称结构，防腐膜层与粘接膜层相互套接，显著的改善覆膜板结构的稳定性、耐磨性、耐腐蚀性等，从而促使本发明提供的PVDF覆膜板具有高耐磨性、耐蚀性以及使用寿命长等有益效果。

Description

高耐磨高耐蚀PVDF覆膜板
技术领域
本发明涉及覆膜板，更具体地说，本发明涉及一种高耐磨高耐蚀覆膜板。
背景技术
随着科学技术的发展，覆膜板在生产和生活中的应用越来越广泛，现有技术中，通常采用的是PVDF覆膜板，PVDF中文名称为聚偏二氟乙烯，PVDF的膜材料具有良好的耐腐蚀性、化学稳定性、耐紫外线辐射性、耐候性等特点，可以用于多种高档次的建筑材料，也可以用于强酸或者强碱的生产车间用厂房材料，但是由于PVDF自身的摩擦系数低，使其在加工时很难粘接，且韧性低，抗弯折能力差，使用寿命短，结构稳定性弱，这就限制了PVDF覆膜板在实际生产生活中的进一步应用，因此，研发一种具有高耐磨高耐蚀特性的PVDF覆膜板一直是该领域的研究热点。
发明内容
本发明的目的是针对上述技术中的不足，提供一种高耐磨高耐蚀PVDF覆膜板，其中，所述覆膜板从上到下依次设有第一防腐膜层、第一胶黏层、铝箔层、第二胶黏层、第二防腐膜层，其中，所述第一防腐膜层和第二防腐膜层结构相同，均包括从上到下依次设置的陶瓷膜层、粘接膜层、改性PVDF膜层。
优选的是，其中，改性PVDF膜以重量计份包括如下成分：
Figure BDA0002225412730000011
优选的是，其中，所述马来酸酐-聚偏氟二氯乙烯嵌段共聚物的数均分子量为12000-15000g/mol，聚偏氟二氯乙烯的含量为30％-40％。
优选的是，其中，改性PVDF膜还包括1-3份纳米氧化铝。
无机纳米Al2O3具有较好的强度，纳米Al2O3的加入增大了膜表面孔径和表面粗糙度，增加膜液的粘度，使得PVDF膜的机械性能有所提高。
优选的是，其中，改性PVDF膜还包括0.1-0.3份无机填料，所述无机填料包括滑石粉、碳酸钙、云母粉、硅藻土、硫酸钡中的至少一种。
优选的是，其中，石墨颗粒的粒径为36-100nm。
石墨颗粒在基体表面形成均匀分布、形状不规则并且无取向的凹坑，凹坑的形成促进PVDF膜层形成各向异性表面，这种各向异性促进粘接层的附着，提高防腐层与粘接层之间的粘接强度。
优选的是，其中，陶瓷膜层为无机陶瓷膜，所述无机陶瓷膜包括氧化钛、氧化硅、氧化铁、氧化钼、金属复合膜中的一种。
优选的是，其中，粘接层以重量计份包括如下成分：
Figure BDA0002225412730000021
优选的是，其中，环氧树脂为双酚环氧树脂、酚醛环氧树脂、液晶环氧树脂中的至少一种，所述无机晶须包括硼酸铝晶须、氢氧化镁晶须、碳化硅晶须中的至少一种。
双酚环氧树脂、酚醛环氧树脂、液晶环氧树脂分子高度有序、分子之间深度交联形成聚合物网络，形成力学性能优异的自增强结构，具有非常高的粘接强度。
优选的是，其中，改性剂为为金属粉与玻璃鳞片的混合物，所述金属粉包括锌粉、铝粉、铁粉中的至少一种。
改性剂的加入降低了固化物的热膨胀系数和固化收缩率，减少了内应力，当超负荷作用出现裂纹时，改性剂的添加阻止裂纹的扩展，从而提高材料的粘接强度。
本发明具有以下有益效果：(1)本发明制备的PVDF覆膜板具有稳定优异的粘接强度、耐腐蚀性、耐磨性以及使用寿命长的有益效果；(2)PVDF覆膜板采用对称结构，防腐膜层与粘接膜层相互套接，提高覆膜板结构的稳定性；(3)防腐层采用复合膜结构，改性PVDF膜层具有优良的耐腐蚀性，而陶瓷膜采用无机陶瓷膜，提高复合膜的耐磨性能，粘接膜层则通过改良配方的方法，提高其粘接强度，从而促使PVDF覆膜板在兼具优良的耐磨性和耐蚀性之外，还同时具有化学稳定性和较强的粘接强度。
本发明的其它优点、目标和特征将部分通过下面的说明体现，部分还将通过对本发明的研究和实践而为本领域的技术人员所理解。
附图说明
图1为高耐磨高耐蚀PVDF覆膜板的结构示意图。
附图标记说明：
1—第一防腐膜层；2—第一胶黏层；3—铝箔层；4—第二胶黏层；5—第二防腐膜层；
具体实施方式
下面结合附图对本发明做进一步的详细说明，以令本领域技术人员参照说明书文字能够据以实施。
应当理解，本文所使用的诸如“具有”、“包含”以及“包括”术语并不配出一个或多个其它元件或其组合的存在或添加。
实施例1
一种高耐磨高耐蚀PVDF覆膜板，覆膜板从上到下依次设有第一防腐膜层、第一胶黏层、铝箔层、第二胶黏层、第二防腐膜层，其中，第一防腐膜层和第二防腐膜层结构相同，均包括从上到下依次设置的陶瓷膜层、粘接膜层、改性PVDF膜。
其中，改性PVDF膜以重量计份包括如下成分：
Figure BDA0002225412730000041
其中，马来酸酐-聚偏氟二氯乙烯嵌段共聚物的数均分子量为12000g/mol，聚偏氟二氯乙烯的含量为32％。
其中，粘接膜层以重量计份包括如下成分：
Figure BDA0002225412730000042
其中，环氧树脂为双酚环氧树脂，无机晶须为硼酸铝晶须，改性剂为锌粉与玻璃鳞片的混合物。
实施例2
本实施例与实施例1的原料和工艺基本相同，唯一不同之处在于改性PVDF膜层还包括1-3份纳米氧化铝。
实施例3
本实施例与实施例1的原料和工艺基本相同，唯一不同之处在于，改性PVDF膜层还包括0.1-0.3份滑石粉。
实施例4
本实施例与实施例一的原料和工艺基本相同，唯一不同之处在于，改性PVDF膜层还包括1-3份纳米氧化铝和0.1-0.3份硫酸钡。
实施例5
本实施例与实施例1的原料和工艺基本相同，唯一不同之处在于，陶瓷膜为氧化钼膜。
实施例6
本实施例与实施例1的原料和工艺基本相同，唯一不同之处在于，粘接膜层的环氧树脂为酚醛环氧树脂。
以上实施例1-6及对比例1-3的产品性能如下表所示，以下为性能测试结果：
Figure BDA0002225412730000051
Figure BDA0002225412730000061
Figure DA00022254127363609
耐酸性测试：按照GB/T31034-2014第6.15节。
耐碱性测试：按照GB/T31034-2014第6.16节。
耐溶剂性测试：按照GB/T31034-2014第6.17节。
耐磨性测试：按照GB/T10006-1988检测标准。
硬度测试：按照GB/T 6739-2006检测标准。
实施例1与对比例1相比，PVDF覆膜板均无起泡、开裂及其他可见变化，硬度289A下降至210A,表明石墨颗粒的添加能够提高覆模板的硬度、耐酸碱性以及耐溶剂性，这是由于石墨颗粒能够避免薄膜中微小尺寸的缺陷，使得改性PVDF薄膜中的分子有序排列，提高薄膜的致密度，从而提高薄膜的耐腐蚀性能。
实施例3与对比例2与相比，PVDF覆膜板无起泡、开裂及其他可见变化，而对比例2则出现起泡、开裂等现象，说明丙烯酸改性醇酸树脂的添加能够提高覆膜板耐酸碱性和耐候性，当覆膜板与酸碱等溶剂接触时，醇酸树脂极性主链和非极性侧链使其与化合物较好地混溶，丙烯酸改性的醇酸树脂则通过醇酸树脂中双键、羧基、羟基等反应性基团，引入丙烯酸单体，丙烯酸类单体与醇酸树脂上的非共轭不饱和双键发生共聚反应，从而使得丙烯酸改性醇酸树脂能够显著提高薄膜高温返粘性、薄膜硬度、抗冲击性以及耐酸耐碱性等综合性能。
实施例4与对比例3相比，PVDF覆膜板在20℃、80℃、-50℃的粘接强度分别从6.23MPa、6.01MPa、5.93MPa下降至4.74MPa、3.01MPa、2.73MPa，这表明改性剂的添加能够改善薄膜的粘接强度，提高薄膜的稳定，由于改性剂降低了固化物的热膨胀系数和固化收缩率，减少了内应力，当超负荷作用出现裂纹时，改性剂的添加阻止裂纹的扩展，从而提高材料的粘接强度。
可见，本发明提供的PVDF覆膜板具有高耐蚀性、耐磨性以及使用寿命长的有益效果。
尽管本发明的实施方案已公开如上，但其并不仅仅限于说明书和实施方式中所列运用，它完全可以被适用于各种适合本发明的领域，对于熟悉本领域的人员而言，可容易地实现另外的修改，因此在不背离权利要求及等同范围所限定的一般概念下，本发明并不限于特定的细节。

Claims (10)

1.一种高耐磨高耐蚀PVDF覆膜板，其特征在于，所述覆膜板从上到下依次设有第一防腐膜层、第一胶黏层、铝箔层、第二胶黏层、第二防腐膜层，其中，所述第一防腐膜层和第二防腐膜层结构相同，均包括从上到下依次设置的陶瓷膜层、粘接膜层、改性PVDF膜。
2.根据权利要求1所述高耐磨高耐蚀PVDF覆膜板，其特征在于，所述改性PVDF膜以重量计份包括如下成分：
Figure FDA0002225412720000011
3.根据权利要求2所述的高耐磨耐蚀PVDF覆膜板，其特征在于，所述马来酸酐-聚偏氟二氯乙烯嵌段共聚物的数均分子量为12000-15000g/mol，聚偏氟二氯乙烯的含量为30％-40％。
4.根据权利要求2所述的高耐磨耐蚀PVDF覆膜板，其特征在于，所述改性PVDF膜还包括1-3份纳米氧化铝。
5.根据权利要求2所述的高耐磨耐蚀PVDF覆膜板，其特征在于，所述改性PVDF膜还包括0.1-0.3份无机填料，所述无机填料包括滑石粉、碳酸钙、云母粉、硅藻土、硫酸钡中的至少一种。
6.根据权利要求2所述的高耐磨耐蚀PVDF覆膜板，其特征在于，所述石墨颗粒的粒径为36-100nm。
7.根据权利要求1所述的高耐磨耐蚀PVDF覆膜板，其特征在于，所述陶瓷膜层为无机陶瓷膜，所述无机陶瓷膜包括氧化钛、氧化硅、氧化铁、氧化钼、金属复合膜中的一种。
8.根据权利要求1所述的高耐磨耐蚀PVDF覆膜板，其特征在于，所述粘接膜层以重量计份包括如下成分：
9.根据权利要求8所述的高耐磨耐蚀PVDF覆膜板，其特征在于，所述环氧树脂为双酚环氧树脂、酚醛环氧树脂、液晶环氧树脂中的至少一种，所述无机晶须包括硼酸铝晶须、氢氧化镁晶须、碳化硅晶须中的至少一种。
10.根据权利要求8所述的高耐磨耐蚀PVDF覆膜板，其特征在于，所述改性剂为金属粉与玻璃鳞片的混合物，所述金属粉包括锌粉、铝粉、铁粉中的至少一种。
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CN101582459A (zh) * 2009-06-26 2009-11-18 上海海优威电子技术有限公司 以改性聚偏氟乙烯合金层为耐候保护层的太阳能电池背板
CN106760333A (zh) * 2015-11-21 2017-05-31 江阴华东装饰材料有限公司 一种室外专用防晒墙体pvdf装饰膜
CN109263204A (zh) * 2018-07-13 2019-01-25 浙江歌瑞新材料有限公司 一种高耐腐蚀的覆膜金属板及其制造工艺

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CN101582459A (zh) * 2009-06-26 2009-11-18 上海海优威电子技术有限公司 以改性聚偏氟乙烯合金层为耐候保护层的太阳能电池背板
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