CN112622377A - 一种基于光固化聚合物分散液晶体系的光学扩散膜的制备方法 - Google Patents

一种基于光固化聚合物分散液晶体系的光学扩散膜的制备方法 Download PDF

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CN112622377A
CN112622377A CN202011464502.1A CN202011464502A CN112622377A CN 112622377 A CN112622377 A CN 112622377A CN 202011464502 A CN202011464502 A CN 202011464502A CN 112622377 A CN112622377 A CN 112622377A
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liquid crystal
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张兰英
周乐
张帅锋
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Abstract

本发明公开了一种基于光固化聚合物分散液晶体系的光学扩散膜的制备方法，将光可聚合单体、交联剂和向列相液晶均匀混合，其中光可聚合单体包括异氰酸酯单体和丙烯酸酯单体，以硫醇类化合物作为交联剂，光可聚合单体和交联剂的总质量与向列相液晶的质量比为3:7～7:3，并且加入光引发剂和玻璃微珠，搅拌均匀后将混合体系涂覆于高透过率薄膜中间，辊压形成厚度均匀的膜，紫外光照射一段时间，形成基于聚合物分散液晶体系的光学扩散膜。该方法避免了传统光学扩散膜中纳米粒子的分散问题，显著缩短光固化时间，降低了能耗。所制备的膜具有良好的光学指标和优异的力学性能，可广泛应用于投影、液晶显示、智能玻璃和相关领域的研究中。

Description

一种基于光固化聚合物分散液晶体系的光学扩散膜的制备 方法
技术领域
本发明属于液晶应用技术领域，涉及光学扩散膜的制备方法，特别涉及一种基于聚合物分散液晶(polymer dispersed liquid crystal,PDLC)体系的光学扩散膜的制备方法。
背景技术
聚合物分散液晶(polymer dispersed liquid crystal,PDLC)是一种向列相的液晶微滴均匀分散于连续的聚合物基体中形成的复合材料，能够通过施加电压实现透明态和散射态的转变，其中散射态的PDLC膜材料可应用在光学扩散膜上。在没有施加电场的情况下，液晶微滴的指向矢随机分布，由于光通过液晶微滴的有效折射率与通过聚合物基体的折射率不匹配，光线在液晶与聚合物的界面上发生多次反射和折射，PDLC膜强烈散射入射光且呈现乳白色的不透明态，可以应用于光学扩散膜。
PDLC液晶显示与传统的TN、STN器件相比，它不需要偏振片，降低了光的损失，透光率很高；不需要取向层和封盒工艺，因而制备工艺简单；PDLC膜材料具有薄型、量轻、高亮度、宽视角和易于大面积化等诸多优点，可以应用于电控智能玻璃、大面积柔性显示、液晶光栅和衍射光学等方面。
在液晶显示装置中，光学扩散膜是背光源模组中的关键部件，其作用是改变光线角度，使背光源所发出的光均匀化，为液晶面板提供一个均匀的面光源。光学扩散膜广泛应用于液晶显示、照明灯具等需要光源的装置中。对于液晶显示器来说，其光学模组中需要两片光学扩散膜，即上扩散膜和下扩散膜，上扩散膜具有高透光能力，可以改善视角、增加光源柔和性，兼具扩散即保护棱镜膜的作用；下扩散膜靠近导光板，主要功能是集光、遮蔽导光板印刷网点或线光源、灯管黑影。显示屏的均匀度与亮度主要取决于扩散膜的光学扩散性能。
光学扩散膜的制作方法一般采用散射粒子型的湿法涂布方法，将散射粒子和粘合树脂涂覆于透明光学级PET膜上，涂层经高温烘干去除溶剂，经紫外固化形成的具有一定透光率和雾度的光扩散膜。但溶剂涂布及紫外光固化均对工作环境不利，且光学扩散膜的均匀性受PET膜质量、扩散粒子涂布液和涂布工艺所限制，难以对产品质量进行有效控制。光固化的PDLC膜不需要分散散射粒子，并且可以通过对光可聚合单体和液晶的选择来控制网络大小，从而控制光散射效果。同时光固化的PDLC膜具备高透光率和高雾度，是光学扩散膜的优选。目前的PDLC膜主要是通过紫外聚合方式制备，但选用的光可聚合单体一般为丙烯酸酯单体，膜与基底的粘结力不够。而热聚合没有得到应用的主要原因是聚合温度高、聚合时间长。
发明内容
本发明的目的是提供一种基于光固化聚合物分散液晶体系的光扩散膜的制备方法，一方面通过改变聚合体系的成分使光固化制备PDLC膜的能耗降低，生产周期缩短；另一方面通过高分子网络的优化，包括聚合单体的选择和聚合条件的控制，改善PDLC膜的光扩散性能。
为实现上述技术目的，本发明利用异氰酸酯和硫醇类化合物的光聚合诱导相分离，形成均匀的交联网络，并且加入丙烯酸酯单体加速体系的反应速率，从而缩短反应时间，降低制备PDLC膜的能耗，实现PDLC膜的大面积制备。具体的，本发明的技术方案如下：
一种光学扩散膜的制备方法，将光可聚合单体、交联剂和向列相液晶均匀混合，其中所述光可聚合单体包括异氰酸酯单体和丙烯酸酯单体，以硫醇类化合物可以作为光可聚合单体的交联剂，光可聚合单体和交联剂的总质量与向列相液晶的质量的比例为3:7～7:3，并且加入占光可聚合单体总质量的0.1wt％～5.0wt％的光引发剂，同时加入玻璃微珠，玻璃微珠的含量为混合体系总质量的0.2～1.0wt％，搅拌均匀后将混合体系涂覆于高透过率的薄膜(例如50μm厚的PET膜)中间，用辊压形成厚度均匀的膜，紫外光照射一段时间，形成基于聚合物分散液晶体系的光学扩散膜(参见图1)。
上述制备方法中，所述异氰酸酯单体的活性官能团数量一般为2(即二异氰酸酯)，优选为下面所示结构的异氰酸酯单体中的一种或多种：六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、二环己基甲烷二异氰酸酯(HMDI)、二苯基甲烷二异氰酸酯(MDI)。
Figure BDA0002833501710000021
上述制备方法中，所述丙烯酸酯单体优选为下列结构的丙烯酸酯单体中的一种或多种：聚二季戊四醇五丙烯酸酯(DPEPA)、季戊四醇四丙烯酸酯(PET4A)、季戊四醇三丙烯酸酯(PETA)、三羟甲基丙烷三丙烯酸酯(TMPTA)、乙氧基化三羟甲基丙烷三丙烯酸酯(ETPTA)。
Figure BDA0002833501710000031
上述制备方法中，所用光交联剂为硫醇类化合物，优选下列所示结构的光交联剂中的一种或多种：3,6-二氧杂-1,8-辛二硫醇(DODT)、双巯基乙酸乙二醇酯(GDMA)、三羟甲基丙烷三(3-巯基丙酸酯)(TTMP)、四(2-巯基乙酸)季戊四醇酯(PTMP)、肌醇六(巯基丙酸酯)(DHMP)。
Figure BDA0002833501710000032
上述制备方法中，所述异氰酸酯单体、丙烯酸酯单体和交联剂的摩尔比优选为8:12:25～15:5:25。
上述制备方法中，所述液晶优选为与所选的光可聚合单体的折射率相匹配的向列相液晶，如向列相液晶SLC1717、SLC7011-100、E7和E8的一种或者多种。
上述制备方法中，所述向列相液晶与光可聚合单体和交联剂的总质量的比例为3:7～7:3。
上述制备方法中，所述光引发剂优选为安息香双甲醚、2,4,6(三甲基苯甲酰基)二苯基氧化膦、1-羟基-环己基-苯基甲酮、2-羟基-2-甲基-1-苯基-1-丙酮中的一种或多种。
上述制备方法中，所述玻璃微珠的粒径优选为5μm～50μm。
上述制备方法中，在常温下进行紫外光照射聚合，光照强度优选为1～50mW/cm2，光照时间一般为200～2000s。
在本发明的一些实施例中，对于光可聚合单体，其中异氰酸酯单体选择异佛尔酮二异氰酸酯，丙烯酸酯单体选择聚二季戊四醇五丙烯酸酯或季戊四醇四丙烯酸酯，硫醇类光交联剂选择四(2-巯基乙酸)季戊四醇酯，异氰酸酯单体、丙烯酸酯单体及交联剂的摩尔比为12:8:25，液晶与光可聚合单体和交联剂的总质量的比例为5:5，加入占光可聚合单体总质量的1.0wt％的光引发剂，并加入粒径为20μm的玻璃微珠，玻璃微珠的含量为混合体系总质量的0.5wt％。搅拌均匀后将混合体系涂覆于两片50μm厚的商用PET膜中间，用辊压匀形成厚度均匀的膜，在光照强度为5.0mW/cm2的365nm的紫外光下照射800s，光固化形成PDLC膜材料。
将本发明方法制备的光固化PDLC膜材料应用在光学扩散膜上，其透光率和雾度均能达到现有光学扩散膜的性能，并且避免了传统光学扩散膜中纳米粒子的分散问题。通过在光固化体系中加入丙烯酸酯单体，能够显著缩短光固化时间，使得制备光学扩散膜的能耗降低，达到节能高效制备光学扩散膜的目的，并且该光学扩散膜具有优异的力学性能。所制备的膜具有良好的光学指标，还可以广泛应用于投影、液晶显示、智能玻璃和相关领域的研究中。
附图说明
图1为本发明制备的光学扩散膜的结构示意图，其中，1-聚合物/液晶复合膜，2-高透过率薄膜。
图2是实施例1制备的光固化聚合物分散液晶膜材料的聚合物网络的扫描电镜图片。
图3是实施例2制备的光固化聚合物分散液晶膜材料的聚合物网络的扫描电镜图片。
图4是实施例1制备的光固化聚合物分散液晶膜材料的透光率和雾度随波长的变化图。
图5是实施例1制备的光固化聚合物分散液晶膜材料的光强-角度分布图。
图6是实施例2制备的光固化聚合物分散液晶膜材料的透光率和雾度随波长的变化图。
图7是实施例2制备的光固化聚合物分散液晶膜材料的光强-角度分布图。
图8是实施例1制备的光固化聚合物分散液晶膜材料的力学性能图。
具体实施方式
下面结合附图，通过实施例进一步详细描述本发明的技术方案，但不以任何方式限制本发明的范围。
实施例1：
将光可聚合单体、交联剂和向列相液晶均匀混合，其中光可聚合单体为异佛尔酮二异氰酸酯和聚二季戊四醇五丙烯酸酯，硫醇类交联剂选用四(2-巯基乙酸)季戊四醇酯，异氰酸酯单体、丙烯酸酯单体和硫醇类交联剂的摩尔比为12:8:25，加入占可聚合单体总质量的1.0wt％的光引发剂安息香甲醚，所选液晶为向列相液晶SLC1717(TNI＝365.2K，no＝1.519，ne＝1.720)，向列相液晶与光可聚合单体和硫醇类交联剂的总质量的比例为1:1，加入粒径为20μm的玻璃微珠，玻璃微珠的含量为混合体系总质量的0.5wt％。搅拌均匀后将混合体系涂覆于两片50μm厚的商用PET膜中间，用辊压匀形成厚度均匀的膜，在365nm的紫外光下(聚合光强为5.0mW/cm2)室温照射800s，固化形成PDLC膜材料，即得到实施例1的光学扩散膜。
从图2、图4和图5中可以看出，所得光学扩散膜的聚合物形貌为聚合物框架，这种微结构的存在使得薄膜可以同时具有高透过率、高雾度(当光波波长为560nm时，透过率为89.99％，雾度为80.66％)和优异的光扩散能力。
实施例2：
将光可聚合单体、交联剂和向列相液晶均匀混合，其中光可聚合单体为异佛尔酮二异氰酸酯和季戊四醇四丙烯酸酯，硫醇类交联剂选用四(2-巯基乙酸)季戊四醇酯，异氰酸酯单体、丙烯酸酯单体和硫醇类交联剂的摩尔比为12:8:25，加入占可聚合单体总质量的1.0wt％的安息香双甲醚，所选液晶为向列相液晶SLC1717(TNI＝365.2K，no＝1.519，ne＝1.720)，向列相液晶与光可聚合单体和硫醇类交联剂的总质量的比例为1:1，加入粒径为20μm的玻璃微珠，玻璃微珠的含量为混合体系总质量的0.5wt％。搅拌均匀后将混合体系涂覆于两片50μm厚的商用PET膜中间，用辊压匀形成厚度均匀的膜，在365nm的紫外光下(聚合光强为5.0mW/cm2)室温照射800s，固化形成PDLC膜材料，即得到实施例2的光学扩散膜。
从图3、图6和图7中可以看出，所得光学扩散膜的聚合物形貌为聚合物微球聚集体，这种微结构的存在使得薄膜可以同时具有高透过率、高雾度(当光波波长为560nm时，透过率为84.18％，雾度为89.49％)和优异的光扩散能力。图8体现了丙烯酸酯单体对光学扩散膜的力学性能的影响，当不添加丙烯酸酯单体时，应力为336MPa，当添加丙烯酸酯单体后，应力为382MPa，说明添加丙烯酸酯单体后，聚合物框架结构的生成导致了力学性能的增大。
从上述两个例子的数据对比来看，实施例1由于聚合物框架结构的存在，透过率相对较高，适合液晶显示器的上扩散膜，实施例2由于聚合物微球聚集体的存在，雾度相对较高，适合液晶显示器的下扩散膜。基于光固化的聚合物分散液晶体系，控制聚合单体种类及固化条件可以制备出多种不同聚合物形貌的薄膜，这样光学扩散膜的透过率、雾度以及光扩散能力容易得到调控，为光学扩散膜的制备提供了新的方法。
最后所应说明的是，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该理解，对本发明的技术方案进行修改或者等同替换，都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 (10)

1.一种光学扩散膜的制备方法，将光可聚合单体、交联剂和向列相液晶进行均匀混合，其中所述光可聚合单体包括异氰酸酯单体和丙烯酸酯单体，以硫醇类化合物作为交联剂，光可聚合单体和交联剂的总质量与向列相液晶的质量比为3:7～7:3，并且加入占光可聚合单体总质量的0.1～5.0wt％的光引发剂，同时加入玻璃微珠，玻璃微珠的含量为混合体系总质量的0.2～1.0wt％，搅拌均匀后将混合体系涂覆于高透过率的薄膜中间，用辊压形成厚度均匀的膜，紫外光照射一段时间，形成基于聚合物分散液晶体系的光学扩散膜。
2.如权利要求1所述制备方法，其特征在于，所述异氰酸酯单体为活性官能团数量为2的二异氰酸酯。
3.如权利要求2所述制备方法，其特征在于，所述异氰酸酯单体选自下列异氰酸酯单体中的一种或多种：六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、二苯基甲烷二异氰酸酯(MDI)、二环己基甲烷二异氰酸酯(HMDI)。
4.如权利要求1所述制备方法，其特征在于，所述丙烯酸酯单体选自下列丙烯酸酯单体中的一种或多种：聚二季戊四醇五丙烯酸酯(DPEPA)、季戊四醇四丙烯酸酯(PET4A)、季戊四醇三丙烯酸酯(PETA)、三羟甲基丙烷三丙烯酸酯(TMPTA)、乙氧基化三羟甲基丙烷三丙烯酸酯(ETPTA)。
5.如权利要求1所述制备方法，其特征在于，所述异氰酸酯单体、丙烯酸酯单体和硫醇类交联剂的摩尔比为8:12:25～15:5:25。
6.如权利要求1所述制备方法，其特征在于，所述向列相液晶为与所述光可聚合单体的折射率相匹配的向列相液晶，选自向列相液晶SLC1717、SLC7011-100、E7和E8的一种或者多种。
7.如权利要求1所述制备方法，其特征在于，所述光引发剂选自安息香双甲醚、2,4,6(三甲基苯甲酰基)二苯基氧化膦、1-羟基-环己基-苯基甲酮、2-羟基-2-甲基-1-苯基-1-丙酮中的一种或多种。
8.如权利要求1所述制备方法，其特征在于，所述玻璃微珠的粒径为5μm～50μm。
9.如权利要求1所述制备方法，其特征在于，在常温下进行紫外光照射聚合，光照强度为1～50mW/cm2，光照时间为200～2000s。
10.权利要求1～9中任一所述制备方法得到的光学扩散膜。
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