CN111732866B - 一种透明pi基材用高附着力增韧底涂层 - Google Patents
一种透明pi基材用高附着力增韧底涂层 Download PDFInfo
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Abstract
本发明提供一种透明PI基材用高附着力增韧底涂层,底涂层的配方包括如下重量份:低Tg高附着力树脂10份、高Tg高硬度树脂5~25份、脂肪族环氧树脂1~8份、固化剂0.5~3份、光引发自由基引发剂0.1~0.5份、光引发阳离子引发剂0.1~0.5份、稀释剂150~250份。本发明提出的一种透明PI基材用高附着力增韧底涂层,不仅具有较高的附着力,而且可以分散层间应力。
Description
技术领域
本发明属于复合涂层技术领域,具体涉及一种透明PI基材用高附着力增韧底涂层。
背景技术
柔性显示技术作为5G时代的重要组成之一日益受到关注,目前柔性显示盖板主要是透明PI(聚酰亚胺)硬化膜和超薄玻璃两种方案,其中透明PI硬化膜因为弯折性能更佳逐渐成为目前的主流趋势。普通聚酰亚胺材料因为分子链中有大量的共轭结构,导致其制品都带有黄色,其薄膜产品通常透过率较低且YI值较高。透明PI的改性方法通常是在分子链中引入含氟基团、将芳环氟化、用脂肪环替换部分芳环等,因此透明PI的分子链中通常会含有较多的F元素。当F元素含量较多时,会导致透明PI材料表面张力降低,导致表面硬化处理时硬化涂层难附着,尤其在老化测试中,表面硬化涂层的分子链蠕变后,与PI基材的层间附着力进一步降低,对透明PI硬化膜的弯折性能和使用寿命是极大的威胁。目前改善透明PI表面附着力的主流方法,是通过强溶剂对透明PI表面物理腐蚀形成粗糙表面,从而提高附着力,但这种方案会导致透明PI本身的一些优异性能衰减,比如铅笔硬度、模量、光学性能等,还会因为制造工艺导致的各方向上的均匀程度导致附着力有波动。在其他涂布领域经常使用的提高基材表面附着力的方法比如电晕处理、等离子处理等,对透明PI基材的表面附着性能没有改善,反而会产生含氟分子碎片,导致表面硬化涂层因相容性差异出现大量缺陷点。
因此,关于透明PI硬化膜的开发方向,目前主要期望是朝向高硬度、高耐磨、可弯折、低翘曲等开发方向。但选择高硬度硬化涂层时,通常会出现翘曲高、韧性偏差的问题,通常在断裂伸长率1%时就可能出现裂纹。透明PI基材的韧性相对较好,通常断裂伸长率可以达到10%~30%。同时因为透明PI基材与硬化层的模量不同,所以硬化膜承受拉伸应力时,即使薄膜各层形变量相同,但实际的应力分布不同。因此通过底涂层将拉伸应力分散,也可以对硬化层的出现断裂的伸长率有改善,并且可以保持原有的硬度。
发明内容
本发明要解决的技术问题是提供一种透明PI基材用高附着力增韧底涂层,解决上述技术的问题。
为解决上述技术问题,本发明提供一种透明PI基材用高附着力增韧底涂层,底涂层的配方包括如下重量份:低Tg高附着力树脂10份、高Tg高硬度树脂5~25份、脂肪族环氧树脂1~8份、固化剂0.5~3份、光引发自由基引发剂0.1~0.5份、光引发阳离子引发剂0.1~0.5份、稀释剂150~250份。
作为本发明所述的一种透明PI基材用高附着力增韧底涂层的一种优选方案,,所述底涂层的制备方法为:按所述底涂层的配方配制得到底涂液,由湿涂量为3~50g/m2的微凹辊涂布,在温度为60~150℃的条件下加热1~10min,使得所述低Tg高附着力树脂热固化形成高弹性高附着力的柔性网络结构,然后在照度为100~1000mW/cm2、光量为100~1000mJ/cm2的条件下UV光固化,使得所述高Tg高硬度树脂形成高硬度网络结构,最终获得底涂层。
作为本发明所述的一种透明PI基材用高附着力增韧底涂层的一种优选方案,所述底涂层的厚度范围为100nm-5μm。
作为本发明所述的一种透明PI基材用高附着力增韧底涂层的一种优选方案,所述低Tg高附着力树脂的Tg温度为-50℃~10℃。
作为本发明所述的一种透明PI基材用高附着力增韧底涂层的一种优选方案,所述高Tg高硬度树脂的Tg温度为60℃~120℃。
作为本发明所述的一种透明PI基材用高附着力增韧底涂层的一种优选方案,所述低Tg高附着力树脂为聚氨酯、聚丙烯酸酯、聚酰胺、环氧树脂或聚酯树脂中的任意一种或多种,并且含有羟基、羧基、氨基或环氧基中的任意一种或多种可热固化官能团。
作为本发明所述的一种透明PI基材用高附着力增韧底涂层的一种优选方案,所述高Tg高硬度树脂为多官聚酯丙烯酸酯、多官聚醚丙烯酸酯、多官聚氨酯丙烯酸酯中的任意一种或多种。
作为本发明所述的一种透明PI基材用高附着力增韧底涂层的一种优选方案,所述脂肪族环氧树脂包括端基为三元环环氧、四元环环氧或环己基环氧中的任意一种或多种,官能度为2~6,主链链段为聚酯、聚醚或聚酰胺中的任意一种或多种。
作为本发明所述的一种透明PI基材用高附着力增韧底涂层的一种优选方案,所述固化剂为异氰酸酯类、氨基树脂类、环氧类固化剂或酸酐类固化剂中的任意一种或多种,所述光引发自由基引发剂为α-羟基酮类或苯乙酮类引发剂中的任意一种或两种,所述光引发阳离子引发剂为二苯基碘鎓盐、三苯基硫鎓盐、二烷基苯甲酰甲基硫鎓盐或η6-异丙苯茂铁(II)六氟磷酸盐中的任意一种或多种,所述稀释剂为PGM、IPA、BAC、MEK或MIBK中的一种或多种。
本发明提出的一种透明PI基材用高附着力增韧底涂层,不仅具有较高的附着力,而且可以分散层间应力。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂,下面结合具体实施方式对本发明作进一步详细的说明。
此处所称的“一个实施例”或“实施例”是指可包含于本发明至少一个实现方式中的特定特征、结构或特性。在本说明书中不同地方出现的“在一个实施例中”并非均指同一个实施例,也不是单独的或选择性的与其他实施例互相排斥的实施例。
一种透明PI基材用高附着力增韧底涂层,该底涂层是由如下成分和重量比例的物质组成:
各成分的优选重量比例如下:
上述配方中,对各成份要求如下:
1、低Tg(玻璃化转变温度)高附着力树脂,Tg温度在-50℃~10℃范围内,并优选Tg温度在-30℃~0℃范围内。低Tg高附着力树脂是聚氨酯、聚丙烯酸酯、聚酰胺、环氧树脂、聚酯树脂中的任意一种或多种,含有可热固化官能团羟基、羧基、氨基、环氧基中的任意一种或多种。优选使用带有羟基、羧基的聚丙烯酸酯树脂或聚氨酯树脂。低Tg高附着力树脂为定制合成产品,通过丙烯酸正丁酯、丙烯酸异辛酯、丙烯酸-2-羟乙酯、甲基丙烯酸甲酯、丙烯酸等单体和引发剂BPO通过自由基聚合获得。
2、高Tg(玻璃化转变温度)高硬度树脂,Tg温度在60℃~120℃范围内,并优选Tg温度在80℃~100℃范围内。高Tg高硬度树脂是多官聚酯丙烯酸酯、多官聚醚丙烯酸酯、多官聚氨酯丙烯酸酯中的任意一种或多种。优选使用官能度3-15的多官聚氨酯丙烯酸酯,更优选官能度4-10的多官聚氨酯丙烯酸酯。可选用Photomer 6628(IGM)、Photomer 4335(IGM)Photomer 4306(IGM)等
3、脂肪族环氧树脂改善翘性能,脂肪族环氧树脂选择端基为三元环环氧、四元环环氧、环己基环氧中的任意一种或多种,官能度为2~6,主链链段为聚酯、聚醚、聚酰胺中的任意一种或多种。可选用TTA21(江苏泰特尔)、SYNASIA S-21(南通新纳希)、SYNASIA S-28(南通新纳希)等,选用环己基环氧的目的是环己基环氧相对反应速度快,且体积膨胀率相对较大。
4、固化剂为异氰酸酯类、氨基树脂类、环氧类固化剂、酸酐类固化剂中的任意一种或多种。
5、光引发自由基引发剂是α-羟基酮类、苯乙酮类引发剂中的任意一种或几种。
6、光引发阳离子引发剂是二苯基碘鎓盐、三苯基硫鎓盐、二烷基苯甲酰甲基硫鎓盐、η6-异丙苯茂铁(II)六氟磷酸盐中的任意一种或几种。光引发阳离子引发剂的作用是交联固化。
7、稀释剂PGM、IPA、BAC、MEK、MIBK中的任意一种或几种。
通过由上述成分及其添加比例,特别是低Tg高附着力树脂和高Tg高硬度树脂的相对比例,可以获得稳定的互穿网络结构。
其工艺方法为按上述成分及比例配制得到的底涂液,经过微凹辊涂布湿涂量3~50g/m2,经过60~150℃加热1~10min干燥和热固化,使低Tg高附着力树脂热固化形成高弹性高附着力的柔性网络结构,然后UV光固化,照度100~1000mW/cm2、光量100~1000mJ/cm2范围固化,使高Tg高硬度树脂光固化形成高硬度网络结构,最终获得厚度为100nm-5μm的底涂层。优选湿涂量5~25g/m2,60~80℃干燥1~3min,80~100℃加热1~3min,100~150℃加热1-10min,并在200~500mW/cm2照度、200~500mJ/cm2光量范围固化。
下面介绍具体实施例和对比例:
实施例1-3及对比例1-3
1)实施例及对比例底涂层各组分比例表:
注:定制低Tg丙烯酸树脂A的Tg为-27℃,Photomer 6628(IGM)的Tg为80℃。
2)定制低Tg丙烯酸树脂A的制备方法:
将丙烯酸正丁酯25kg、丙烯酸异辛酯8kg、丙烯酸-2-羟乙酯3kg、甲基丙烯酸甲酯8kg、丙烯酸6kg、引发剂BPO称取0.3kg、甲基异丁基酮10kg、醋酸乙酯20kg、醋酸丁酯10kg充分混合备用,向釜底加入上述混合液体的1/3,升温加热80℃,反应1小时后,将剩余的2/3缓慢滴加3小时,保温反应1小时,补加引发剂0.5kg和醋酸丁酯10公斤,保温反应2小时,降温至50℃,100目滤芯过滤出料,获得定制低Tg丙烯酸树脂A。其玻璃化转变温度为-27℃。
3)底涂层制备方法:
底涂层制备过程在无尘室黄光灯环境下进行,无尘等级10000级,将底涂的各组分依次缓慢加入并搅拌混合30分钟,并使用15μm防凝胶滤芯过滤,获得底涂。
4)透明PI硬化膜样品制备方法:
将底涂层使用微凹辊在透明PI基材上湿涂量15g/m2,60℃干燥2分钟,80℃加热2分钟,100℃加热1分钟,120℃加热1分钟,并在300mW/cm2照度、300mJ/cm2光量的UV条件下固化。
UV硬化涂料选用DSM AgiSynTM 2423:引发剂2959:MIBK按比例3:0.1:7配制获得,使用微凹辊在底涂完的薄膜上,涂布湿涂量25g/m2,80℃加热1分钟,100℃加热2分钟,120℃加热2分钟,并在600mW/cm2照度、800mJ/cm2光量的UV条件下固化。
5)实施例及对比例测试数据表:
以上数据表明:当选用符合本发明要求范围的材料,并且添加比例在要求范围内时,可以获得稳定优异的性能;但当添加比例不在范围内时,会出现比如附着力、硬度、弯折等性能下降的情况。
6)评价项目测试方法:
翘曲测试方法:裁取样片10×10cm,涂布面朝上,平放在玻璃上,用直尺测量四角的最大翘曲高度或最大拱形高度,拱形翘曲记为“-”。
透过率测试方法:ASTM D1003@550nm
雾度测试方法:ASTM D1003@550nm
百格附着力测试方法:ASTM D3359
老化后百格附着力测试方法:340nm紫外老化72小时,然后测试百格附着力
铅笔硬度测试方法:JIS K5600,荷重750g
外弯折测试:涂布面朝外基材面向内对折,弯折半径为3mm,弯折20万次。
实施例4-6及对比例4-6
1)实施例及对比例底涂层各组分比例表:
注:定制低Tg丙烯酸树脂B的Tg为-8℃,定制低Tg丙烯酸树脂
C的Tg为-55℃,Photomer 4335(IGM)的Tg为100℃,Photomer 5429(IGM)Tg为45℃。
2)定制低Tg丙烯酸树脂B的制备方法:
将丙烯酸正丁酯13kg、丙烯酸异辛酯12kg、丙烯酸-2-羟乙酯3kg、甲基丙烯酸甲酯16kg、丙烯酸6kg、引发剂BPO称取0.3kg、甲基异丁基酮10kg、醋酸乙酯20kg、醋酸丁酯10kg充分混合备用,向釜底加入上述混合液体的1/3,升温加热80℃,反应1小时后,将剩余的2/3缓慢滴加3小时,保温反应1小时,补加引发剂0.5kg和醋酸丁酯10公斤,保温反应2小时,降温至50℃,100目滤芯过滤出料,获得定制低Tg丙烯酸树脂B。其玻璃化转变温度为-8℃。
3)定制低Tg丙烯酸树脂C的制备方法:
将丙烯酸正丁酯6kg、丙烯酸异辛酯36kg、丙烯酸-2-羟乙酯3kg、丙烯酸5kg、引发剂BPO称取0.3kg、甲基异丁基酮10kg、醋酸乙酯20kg、醋酸丁酯10kg充分混合备用,向釜底加入上述混合液体的1/3,升温加热80℃,反应1小时后,将剩余的2/3缓慢滴加3小时,保温反应1小时,补加引发剂0.5kg和醋酸丁酯10公斤,保温反应2小时,降温至50℃,100目滤芯过滤出料,获得定制低Tg丙烯酸树脂C。其玻璃化转变温度为-55℃。
4)底涂制备方法:
底涂制备过程在无尘室黄光灯环境下进行,无尘等级10000级,将底涂的各组分依次缓慢加入并搅拌混合30分钟,并使用15μm防凝胶滤芯过滤,获得底涂。
5)透明PI硬化膜样品制备方法:
将底涂使用微凹辊在透明PI基材上湿涂量15g/m2,75℃干燥2分钟,90℃加热1分钟,100℃加热1分钟,120℃加热2分钟,135℃加热5分钟并在300mW/cm2照度、300mJ/cm2光量的UV条件下固化。
光固化涂料选用DSM AgiSynTM 2423:引发剂2959:MIBK按比例3:0.1:7配制获得,使用微凹辊在底涂完的薄膜上,涂布湿涂量25g/m2,80℃加热1分钟,100℃加热2分钟,120℃加热2分钟,并在600mW/cm2照度、800mJ/cm2光量的UV条件下固化。
6)实施例及对比例测试数据表:
以上数据表明:当选用不符合本专利要求的Tg温度范围的材料时,会出现附着力、硬度、弯折等性能下降的问题。
7)评价项目测试方法:
翘曲测试方法:裁取样片10×10cm,涂布面朝上,平放在玻璃上,用直尺测量四角的最大翘曲高度或最大拱形高度,拱形翘曲记为“-”。
透过率测试方法:ASTM D1003@550nm
雾度测试方法:ASTM D1003@550nm
百格附着力测试方法:ASTM D3359
老化后百格附着力测试方法:340nm紫外老化72小时,然后测试百格附着力
铅笔硬度测试方法:JIS K5600,荷重750g
外弯折测试:涂布面朝外基材面向内对折,弯折半径为3mm,弯折20万次。
应说明的是,以上实施例仅用以说明本发明的技术方案而非限制,尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的精神和范围,其均应涵盖在本发明的权利要求范围当中。
Claims (5)
1.一种透明PI基材用高附着力增韧底涂层,其特征在于,底涂层的配方包括如下重量份:低Tg高附着力树脂10份、高Tg高硬度树脂5~25份、脂肪族环氧树脂1~8份、固化剂0.5~3份、光引发自由基引发剂0.1~0.5份、光引发阳离子引发剂0.1~0.5份、稀释剂150~250份,其中,所述低Tg高附着力树脂的Tg温度为-50℃~10℃,所述低Tg高附着力树脂为聚氨酯、聚丙烯酸酯、聚酰胺、环氧树脂或聚酯树脂中的任意一种或多种,并且含有羟基、羧基、氨基或环氧基中的任意一种或多种可热固化官能团,所述高Tg高硬度树脂的Tg温度为60℃~120℃,所述高Tg高硬度树脂为多官聚酯丙烯酸酯、多官聚醚丙烯酸酯、多官聚氨酯丙烯酸酯中的任意一种或多种。
2.如权利要求1所述的一种透明PI基材用高附着力增韧底涂层,其特征在于,所述底涂层的制备方法为:按所述底涂层的配方配制得到底涂液,由湿涂量为3~50g/m2的微凹辊涂布,在温度为60~150℃的条件下加热1~10min,使得所述低Tg高附着力树脂热固化形成高弹性高附着力的柔性网络结构,然后在照度为100~1000mW/cm2、光量为100~1000mJ/cm2的条件下UV光固化,使得所述高Tg高硬度树脂形成高硬度网络结构,最终获得底涂层。
3.如权利要求2所述的一种透明PI基材用高附着力增韧底涂层,其特征在于:所述底涂层的厚度范围为100nm-5μm。
4.如权利要求1所述的一种透明PI基材用高附着力增韧底涂层,其特征在于:所述脂肪族环氧树脂包括端基为三元环环氧、四元环环氧或环己基环氧中的任意一种或多种,官能度为2~6,主链链段为聚酯、聚醚或聚酰胺中的任意一种或多种。
5.如权利要求1所述的一种透明PI基材用高附着力增韧底涂层,其特征在于:所述固化剂为异氰酸酯类、氨基树脂类、环氧类固化剂或酸酐类固化剂中的任意一种或多种,所述光引发自由基引发剂为α-羟基酮类或苯乙酮类引发剂中的任意一种或两种,所述光引发阳离子引发剂为二苯基碘鎓盐、三苯基硫鎓盐、二烷基苯甲酰甲基硫鎓盐或η6-异丙苯茂铁(II)六氟磷酸盐中的任意一种或多种,所述稀释剂为PGM、IPA、BAC、MEK或MIBK中的一种或多种。
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