CN114957762B - Ito抗静电复合膜、制备方法及显示设备 - Google Patents

Ito抗静电复合膜、制备方法及显示设备 Download PDF

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CN114957762B
CN114957762B CN202210443586.3A CN202210443586A CN114957762B CN 114957762 B CN114957762 B CN 114957762B CN 202210443586 A CN202210443586 A CN 202210443586A CN 114957762 B CN114957762 B CN 114957762B
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严俊
于佩强
汪金铭
胡业新
刘世琴
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Jiangsu Rijiu Optoelectronics Joint Stock Co ltd
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Abstract

本发明公开了ITO抗静电复合膜、制备方法及显示设备，其中复合膜包括顺次设置的基材层、硬化层、打底层、ITO导电层以及抗静电涂层，抗静电涂层由抗静电涂布液形成，抗静电涂层满足：其表面的抗静电值达为106‑109Ω和折射率在1.60‑1.65，抗静电涂布液其组成包括，以重量份数计：丙烯酸类树脂15‑25份；非离子型抗静电剂1‑10份；光引发剂1‑5份；填料5‑10份；分散剂1‑5份；溶剂50‑70份。本发明方案的复合膜其通过优化ITO导电层与抗静电涂层，实现了良好的静电疏导性能，并且具有良好的匹配光学性能，实现消影的目的。

Description

ITO抗静电复合膜、制备方法及显示设备
技术领域
本发明是关于电子显示技术，特别是关于一种具有能够在ITO上实现消影的抗静电涂层的ITO抗静电复合膜、制备方法及显示设备。
背景技术
近年来，PET(聚对苯二甲酸乙二醇酯)基材上镀ITO(氧化铟锡)在制作液晶显示器、平板显示器、等离子显示器、触摸屏、电子纸、有机发光二极管、太阳能电池、EMI屏蔽的透明传导膜、各种光学膜等领域有广泛的应用。
ITO应用电子显示屏领域需要通过磺化或者激光进行蚀刻线路，但单层的ITO蚀刻前后的反射曲线变化很大，蚀刻痕严重，很影响用户的使用体验。因此我们在ITO的上层涂布一层折射率与底层硬化层接近的抗静电涂层，保证在不影响下层ITO方阻的前提下，经过蚀刻工艺，解决电子显示屏制程中出现的色差痕，实现消影的最终目的。
现有技术应用于提高塑料薄膜制品抗静电性能的方法主要是掺入导电物质和添加抗静电剂。金属粉末、导电炭黑、金属氧化物等导电物质的使用成本高，且对涂布设备的要求高，故抗静电剂成为提高薄膜材料抗静电性能的主要方式。目前，常用的抗静电剂主要包括阳离子型抗静电剂、阴离子型抗静电剂、两性抗静电剂和非离子型抗静电剂。其中常用的离子型抗静电剂通过吸收环境水分，降低材料表面电阻率达到抗静电目的，所以对环境湿度的依赖性较大。显然，环境湿度越高，抗静电剂分子的吸水性就越强，抗静电性能就越显著。与此同时，环境湿度小，涂层的抗静电性能减弱，这说明离子型抗静电剂分子受环境的影响比较大，抗静电性能不稳定。
公开于该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不应当被视为承认或以任何形式暗示该信息构成已为本领域一般技术人员所公知的现有技术。
发明内容
本发明的目的在于提供一种ITO抗静电复合膜、制备方法及显示设备，其通过优化ITO导电层与抗静电涂层，有效改善了抗静电涂层的稳定性，实现了良好的静电疏导性能，并且具有良好的匹配光学性能，实现消影的目的。并且通过高精度的镀制技术实现了ITO导电层的精密调节，从而极大改善了电子稳定性和结构稳定性。
为实现上述目的，本发明的实施例提供了ITO抗静电复合膜，包括顺次设置的基材层、硬化层、打底层、ITO导电层以及抗静电涂层，抗静电涂层由抗静电涂布液形成，抗静电涂层满足：其表面的抗静电值达为106-109Ω和折射率在1.60-1.65，抗静电涂布液其组成包括，以重量份数计：丙烯酸类树脂15-25份；非离子型抗静电剂1-10份；光引发剂1-5份；填料5-10份；分散剂1-5份；溶剂50-70份。
在本发明的一个或多个实施方式中，非离子型抗静电剂选自：乙氧基化硼酸脂、乙氧基化烷基胺、乙氧基月桂酷胺、甘油-硬脂酸酯。
在本发明的一个或多个实施方式中，光引发剂选自2-羟基-2-甲基-1-苯基-1-丙酮、4-二甲胺基-苯甲酸乙酯、1-羟基-环己基-苯基甲酮、2,4,6-三甲基甲酰基-二苯基氧化膦中的至少一种。
在本发明的一个或多个实施方式中，填料选自二氧化硅、氧化铝、二氧化钛、氧化锆。
在本发明的一个或多个实施方式中，分散剂选自乙烯基双硬脂酰胺、硬脂酸单甘油酯、三硬脂酸甘油酯。
在本发明的一个或多个实施方式中，溶剂选自甲基乙基酮、丙二醇甲醚、甲基异丁基酮、异丙醇、乙酸乙酯、甲苯。
在本发明的一个或多个实施方式中，丙烯酸树脂的平均分子量为3000-10000,粘度为1500-6000CP。
在本发明的一个或多个实施方式中，ITO导电层的方阻为15Ω-150Ω。
在本发明的一个或多个实施方式中，ITO抗静电复合膜的制备方法，包括如下步骤：在基材层的高折面上，涂布形成树脂材质的硬化层；在硬化层上通过磁控溅射形成SiO2打底层；在打底层上镀制形成ITO导电层；在ITO导电层上以抗静电涂布液精密涂布形成抗静电涂层。
在本发明的一个或多个实施方式中，通过精密涂布在采用了微凹版涂布(Micro-grave)、逗号刮刀(Comma)等涂布方式后,精密涂布厚度可以控制在微纳米级别，精度达5％，具体的操作可以参照现有技术的方案进行。
在本发明的一个或多个实施方式中，显示设备，包括框架以及配合地设置到框架的如前述的ITO抗静电复合膜。
抗静电涂层指的是在涂布液中加入非离子型抗静电剂,可以很好的分散在可印刷的涂布液中起到乳化、分散、偶联和一定的润滑功能。抗静电剂的作用原理是，在与高分子基体混合加工时亲油部分与基体均匀分散并结合，便于材料的加工成型，提高复合材料的基本物理性能；亲水部分在制品的表面形成吸水导电层，在浅表层呈微细的层状或筋状分布，构成导电性表层，在内部则形成“芯壳结构”并以此通路泄漏静电荷，既能表面吸水构成导电性表层达到抗静电效果，又能降低材料电阻率达到长期抗静电效果。
与现有技术相比，根据本发明实施方式的ITO抗静电复合膜、制备方法及显示设备，所采用的ITO的厚度可以精确到纳米级别，可以根据需求，调整ITO的方阻从15Ω到150Ω。抗静电涂层与ITO直接的层间附着力好，可以保持ITO的方阻稳定均一可测。膜层抗静电值可以适应市场需求进行调控，可以控制抗静电值的范围在106-109Ω。折射率在1.60-165的抗静电涂层可以很好的匹配光学性能，实现消影的目的。
方阻可控的ITO可以满足电子显示屏、EMI屏蔽的透明传导膜、各种光学膜等市场，同时，具备折射率匹配的抗静电涂层可以很好的疏导静电荷，使得涂层表面的抗静电值达到106-109Ω，从而实现下层的ITO方阻稳定均一可测，两者结合适用信息设备、智能家电等电子产品制程中出现的色差痕，实现消影的最终目的。
通过精密涂布工艺，在基材PET的高折面先涂布一层折射率在1.60-1.65的树脂硬化层，再通过磁控溅射一层打底层SiO2，然后镀上ITO导电层，最后在ITO导电层上涂布一层折射率在1.60-1.65的抗静电值达到106-109Ω的抗静电涂层，实现薄膜在电子产品制程中消影效果好的目的。
附图说明
图1是根据本发明一实施方式的ITO抗静电复合膜的结构示意图；
图2是根据本发明一实施方式的ITO蚀刻前后反射曲线图。
具体实施方式
下面结合本发明的具体实施方式，对本发明技术方案进行示例性的详细描述，但应当理解本发明的保护范围并不受具体实施方式的限制。
除非另有其它明确表示，否则在整个说明书和权利要求书中，术语“包括”或其变换如“包含”或“包括有”等等将被理解为包括所陈述的元件或组成部分，而并未排除其它元件或其它组成部分。
如图1所示，根据本发明优选实施方式的ITO抗静电复合膜，包括顺次设置的基材层1、硬化层2、打底层3、ITO导电层4以及抗静电涂层5，抗静电涂层5由抗静电涂布液形成，抗静电涂层满足：其表面的抗静电值达为106-109Ω和折射率在1.60-1.65。
基材1可以选择PET基材，其厚度可以为50μm-188μm，在具体实施过程中可以选择50μm、100μm、125μm、188μm以及50μm-188μm范围内的其他任一值。
基材1的高折面涂布形成硬化层2，其厚度可以为700nm-1000nm，在具体实施过程中可以选择700nm、800nm、900nm、1000nm以及700nm-1000nm范围内的其他任一值。
硬化层2上形成打底层3，其厚度可以为5-15nm，在具体实施过程中可以选择5nm、10nm、15nm、188nm以及5nm-15nm范围内的其他任一值，打底层3可以为SiO2层等。
打底层3上镀制形成ITO导电层4，其厚度可以为15nm-150nm，在具体实施过程中可以选择15nm、30nm、60nm、90nm、120nm、150nm以及15nm-150nm范围内的其他任一值。
ITO导电层4上涂布形成抗静电涂层5，其厚度可以为60nm-120nm，在具体实施过程中可以选择60nm、80nm、100nm、120nm以及60nm-120nm范围内的其他任一值。
实施例1：在相同底涂硬化层(相同底涂指硬化层是指在PET基材上硬化层2的配方和厚度保持不变，下同)上，通过磁控溅射一层厚度为10nm的打底层SiO2，然后镀上一层厚度为20nm的导电ITO层，再通过精密涂布工艺涂一层抗静电涂层。抗静电涂层涂布配方：丙烯酸类树脂20份，乙氧基化硼酸脂类抗静电剂6份，2-羟基-2-甲基-1-苯基-1-丙酮2份，乙烯基双硬脂酰胺2份，氧化锆20份，甲基乙基酮20份，丙二醇甲醚30份。抗静电涂层涂层厚度为100nm。
实施例2：在相同底涂硬化层上，通过磁控溅射一层厚度为10nm的打底层SiO2，然后镀上一层厚度为20nm的导电ITO层，再通过精密涂布工艺涂一层抗静电涂层。抗静电涂层涂布配方：丙烯酸类树脂24份，乙氧基月桂酷胺类抗静电剂6份，4-二甲胺基-苯甲酸乙酯3份，硬脂酸单甘油酯2份，氧化锆15份，甲基乙基酮20份，丙二醇甲醚30份。抗静电涂层涂层厚度为110nm。
实施例3：在相同底涂硬化层上，通过磁控溅射一层厚度为10nm的打底层SiO2，然后镀上一层厚度为20nm的导电ITO层，再通过精密涂布工艺涂一层抗静电涂层。抗静电涂层涂布配方：丙烯酸类树脂21份，甘油-硬脂酸脂类抗静电剂6份，1-羟基-环己基-苯基甲酮1份，三硬脂酸甘油酯3份，氧化锆22份，甲基乙基酮17份，丙二醇甲醚30份。抗静电涂层涂层厚度为90nm。
实施例4：在相同底涂硬化层上，通过磁控溅射一层厚度为5nm的打底层SiO2，然后镀上一层厚度为140nm的导电ITO层，再通过精密涂布工艺涂一层抗静电涂层。抗静电涂层涂布配方：丙烯酸类树脂20份，乙氧基化硼酸脂类抗静电剂6份，质量比1:1:1的2-羟基-2-甲基-1-苯基-1-丙酮、4-二甲胺基-苯甲酸乙酯、1-羟基-环己基-苯基甲酮混合物2份，质量比1:3的乙烯基双硬脂酰胺、硬脂酸单甘油酯混合物2份，氧化锆20份，甲基乙基酮20份，丙二醇甲醚30份。抗静电涂层涂层厚度为100nm。
实施例5：在相同底涂硬化层上，通过磁控溅射一层厚度为5nm的打底层SiO2，然后镀上一层厚度为140nm的导电ITO层，再通过精密涂布工艺涂一层抗静电涂层。抗静电涂层涂布配方：丙烯酸类树脂24份，乙氧基月桂酷胺类抗静电剂6份，2,4,6-三甲基甲酰基-二苯基氧化膦3份，质量比1:2:4的乙烯基双硬脂酰胺、硬脂酸单甘油酯、三硬脂酸甘油酯混合物2份，氧化锆15份，甲基乙基酮20份，丙二醇甲醚30份。抗静电涂层涂层厚度为110nm。
实施例6：在相同底涂硬化层上，通过磁控溅射一层厚度为5nm的打底层SiO2，然后镀上一层厚度为140nm的导电ITO层，再通过精密涂布工艺涂一层抗静电涂层。抗静电涂层涂布配方：丙烯酸类树脂21份，甘油-硬脂酸脂类抗静电剂6份，质量比1:5的4-二甲胺基-苯甲酸乙酯、1-羟基-环己基-苯基甲酮的混合物1份，质量比1:1的乙烯基双硬脂酰胺、三硬脂酸甘油酯混合物3份，氧化锆22份，甲基乙基酮17份，丙二醇甲醚30份。抗静电涂层涂层厚度为90nm。
对比例1：在相同底涂硬化层上，通过磁控溅射一层厚度为10nm的打底层SiO2，然后镀上一层厚度为20nm的导电ITO层，再通过精密涂布工艺涂一层抗静电涂层。抗静电涂层涂布配方：丙烯酸类树脂20份，市场上常用的阳离子型类抗静电剂如Cyastat SN 6份，2-羟基-2-甲基-1-苯基-1-丙酮5份，乙烯基双硬脂酰胺5份，氧化锆15份，甲基乙基酮20份，丙二醇甲醚30份。抗静电涂层涂层厚度为100nm。
对比例2：在相同底涂硬化层上，通过磁控溅射一层厚度为20nm的打底层SiO2，然后镀上一层厚度为140nm的导电ITO层，再通过精密涂布工艺涂一层抗静电涂层。抗静电涂层涂布配方：丙烯酸类树脂20份，市场上常用的阴离子型类抗静电剂如单烷基磷酸酯盐6份，质量比1:1:1的2-羟基-2-甲基-1-苯基-1-丙酮、4-二甲胺基-苯甲酸乙酯、1-羟基-环己基-苯基甲酮混合物5份，质量比1:3的乙烯基双硬脂酰胺、硬脂酸单甘油酯混合物5份，氧化锆15份，甲基乙基酮20份，丙二醇甲醚30份。抗静电涂层涂层厚度为100nm。
表一：有无抗静电涂层的ITO变化
由表一可知，实施例中使用乙氧基化硼酸脂、乙氧基月桂酷胺、甘油-硬脂酸脂这类非离子型抗静电剂，经过涂布工艺得到的抗静电涂层基本不会影响下层ITO方阻的数值，而对比例中的离子型抗静电剂会使得下层ITO方阻出现较大的波动。
由图2可知，未加抗静电涂层的ITO蚀刻前后反射曲线变化大。而在ITO导电层上涂一层折射率与底涂硬化层接近的抗静电涂层，同时控制抗静电涂层厚度，可以降低蚀刻前后反射曲线波动，从而解决电子显示屏制程中出现的色差痕，实现消影的最终目的。
表二：各实施例和对比例的抗静电值对比
样品 抗静电值/Ω 抗静电涂层附着力
实施例1 2.3x107 百格附着力OK
实施例2 4.9x107 百格附着力OK
实施例3 3.7x107 百格附着力OK
实施例4 2.5x107 百格附着力OK
实施例5 4.7x107 百格附着力OK
实施例6 3.2x107 百格附着力OK
对比例1 7.9x1012 百格附着力4B
对比例2 8.7x1012 百格附着力4B
由表二可知，实施例中使用乙氧基化硼酸脂、乙氧基月桂酷胺、甘油-硬脂酸脂这类非离子型抗静电剂，经过涂布工艺得到的抗静电值可以达到107Ω，而对比例中的离子型抗静电剂只能将抗静电值做到1012量级，抗静电性能较差。抗静电剂的结构也会影响抗静电涂层与ITO的层间附着力。
包括而不限于上述实施例中，抗静电涂布液中的各组成未尽穷举的部分，同样在本发明所要求的范围内。
前述对本发明的具体示例性实施方案的描述是为了说明和例证的目的。这些描述并非想将本发明限定为所公开的精确形式，并且很显然，根据上述教导，可以进行很多改变和变化。对示例性实施例进行选择和描述的目的在于解释本发明的特定原理及其实际应用，从而使得本领域的技术人员能够实现并利用本发明的各种不同的示例性实施方案以及各种不同的选择和改变。本发明的范围意在由权利要求书及其等同形式所限定。

Claims (9)

1.一种ITO抗静电复合膜，包括顺次设置的基材层、硬化层、打底层、ITO导电层以及抗静电涂层，其特征在于，所述抗静电涂层由抗静电涂布液形成，所述抗静电涂层满足：其表面的抗静电值达为106-109Ω和折射率在1.60-1.65，所述抗静电涂布液其组成包括，以重量份数计：
丙烯酸类树脂15-25份；
非离子型抗静电剂1-10份，所述非离子型抗静电剂选自：乙氧基化硼酸脂、乙氧基化烷基胺、乙氧基月桂酷胺、甘油-硬脂酸酯；
光引发剂1-5份；
填料5-10份；
分散剂1-5份；
溶剂50-70份。
2.如权利要求1所述的ITO抗静电复合膜，其特征在于，所述光引发剂选自2-羟基-2-甲基-1-苯基-1-丙酮、4-二甲胺基-苯甲酸乙酯、1-羟基-环己基-苯基甲酮、2,4,6-三甲基甲酰基-二苯基氧化膦中的至少一种。
3.如权利要求1所述的ITO抗静电复合膜，其特征在于，所述填料选自二氧化硅、氧化铝、二氧化钛、氧化锆。
4.如权利要求1所述的ITO抗静电复合膜，其特征在于，所述分散剂选自乙烯基双硬脂酰胺、硬脂酸单甘油酯、三硬脂酸甘油酯。
5.如权利要求1所述的ITO抗静电复合膜，其特征在于，所述溶剂选自甲基乙基酮、丙二醇甲醚、甲基异丁基酮、异丙醇、乙酸乙酯、甲苯。
6.如权利要求1所述的ITO抗静电复合膜，其特征在于，所述丙烯酸类树脂的平均分子量为3000-10000,粘度为1500-6000cP。
7.如权利要求1所述的ITO抗静电复合膜，其特征在于，所述ITO导电层的方阻为15Ω-150Ω。
8.如权利要求1-7任一所述的ITO抗静电复合膜的制备方法，包括如下步骤：
在基材层的高折面上，涂布形成树脂材质的硬化层；
在硬化层上通过磁控溅射形成SiO2打底层；
在打底层上镀制形成ITO导电层；
在ITO导电层上以抗静电涂布液精密涂布形成抗静电涂层。
9.显示设备，包括框架以及配合地设置到所述框架的如权利要求1-7任一所述的ITO抗静电复合膜。
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