CN111123589B - 一种液晶显示层、液晶介质组合物及其制备方法 - Google Patents

一种液晶显示层、液晶介质组合物及其制备方法 Download PDF

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CN111123589B
CN111123589B CN201911295599.5A CN201911295599A CN111123589B CN 111123589 B CN111123589 B CN 111123589B CN 201911295599 A CN201911295599 A CN 201911295599A CN 111123589 B CN111123589 B CN 111123589B
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韦宏权
曾德仁
廖东
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TCL Huaxing Photoelectric Technology Co Ltd
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Abstract

本发明提供了一种液晶显示层,其上基板层、下基板层、分别设于上基板层和下基板层内侧的透明电极,所述透明电极上贴附配向膜,配向膜之间分布有液晶介质组合物,在所述液晶介质组合物中混合有至少两种可聚合单体,所述可聚合单体含有至少两个环结构或稠环结构,以及两个与环结构直接或间接相连的反应官能团。本发明还提供了液晶介质组合物的制备方法。

Description

一种液晶显示层、液晶介质组合物及其制备方法
技术领域
本发明涉及光电技术领域,特别是涉及一种液晶显示层、液晶介质组合物及其制备方法。
背景技术
薄膜晶体管液晶显示器(TFT-LCD),以其重量轻、功耗低、图像质量好等优点得到了广泛的应用。近几年来,人们已经开发出了各种各样的液晶显示器,它们具有宽视角、高对比度和高图像质量。液晶显示器已经成为人们生活中不可缺少的一部分。常见的显示模式有TN/IPS/VA型,其中,VA型又分有MVA/PVA/PSVA等,MVA存在对比度不足、透过率偏低的问题,PVA存在响应时间偏慢的问题,而PSVA(polymer-stabilized vertical alignment)具有快响应、高对比、高穿透的优良特性,因此,在大尺寸LCD技术之中,PSVA模式仍是首选。
PSVA技术中的液晶介质组合物通常是由负性液晶材料和在紫外光下发生聚合反应的可聚合单体(RM)组成,在PSVA制程过程中,可聚合单体从液晶介质中发生相分离,在紫外光照的条件下在PI表面发生可聚合反应,从而形成聚合物颗粒。但为了提升显示面板的生产产能,需要缩短紫外光光照时间。
缩短紫外光光照时间可以通过提升紫外光的光照强度,但这种方式带来的坏处:1)增加功耗,增加电力成本,增加灯管损耗,缩短灯管寿命;2)过快的反应,易使聚集形成的聚合物颗粒粒径过大,形成碎亮点造成漏光等问题。
发明内容
本发明提供了一种液晶显示层,其上基板层、下基板层、分别设于上基板层和下基板层内侧的透明电极,所述透明电极上贴附配向膜,配向膜之间分布有液晶介质组合物,其特征在于:在所述液晶介质组合物中混合有至少两种可聚合单体,所述可聚合单体含有至少两个环结构或稠环结构,以及两个与环结构直接或间接相连的反应官能团。
所述可聚合单体的结构通式可为如下通式中任选一种或多种:
Figure BDA0002320431430000021
优选地,所述P1、P2相同或不同,可选自甲基丙烯酸酯、丙烯酸酯、乙烯氧基或环氧基中任选一种;Z1、Z2、Z3、Z4、Z5相同或不同,可选自单键或碳原子数为1~5的亚烷基,其中任意的亚甲基可以被-O-、-S-、-CO-、-COO-、-OCO-、-OCOO-、-CH=CH-、-C=C-或-C≡C-取代;
Figure BDA0002320431430000022
相同或不同,可选自:1,4-亚苯基、1,4-亚环己基、1,4-双环[2,2,2]亚辛基、嘧啶-2,5-二基、萘-2,6-二基、四氢萘-2,6-二基、十氢萘-2,6-二基、1,3-二噁烷-2,5-二基或茚满-2,5-二基;其环上的H可被烷基、卤代烷基、烷氧基、卤素所取代。
其中,所述可聚合单体组合物的质量百分比含量为0.01-1%。
所述可聚合单体组合物进一步包含有带有负性介电常数的液晶组合物组合而成。液晶混合物,含可聚合单体,中性单体或负性介电单体。其中,25℃时的液晶混合物介电常数各向异性(Δε)在-2.0至-8.0的范围。因为VA型显示模式的液晶是负性的,所以限定为负的。
本发明还提供了一种用于液晶显示层的液晶介质组合物的制备方法,其包括以下步骤:
步骤1)在上基板层和下基板层的内侧贴附透明电极,在透明电极上贴附配向膜,将液晶介质组合物填充于上基板层和下基板层的配向膜之间,其中,所述液晶介质组合物中混合有至少两种可聚合单体,所述可聚合单体含有至少两个环结构或稠环结构,以及两个与环结构直接或间接相连的反应官能团;
步骤2)对透明电极施加电压,液晶发生偏转,照射紫外光,使得液晶介质组合物的可聚合单体发生聚合反应,使液晶分子取向,形成预倾角,发生交联反应,会形成网络聚合物。
与现有技术相比,本发明提供了一种改进材料的液晶显示装置,即采用多种可聚合物单体,搭配现有的PSVA显示模式,可通过加速HVA制程中聚合过程,实现减少UV照射时间,提升HVA制程产能的目的。同时,在该制程中,可聚合单体形成的聚合物表面更均匀、突起物颗粒更小,减少了液晶面板碎亮点形成的风险。
在PSVA过程中,对上下基板的透明电极施加电压的情况下,液晶发生偏转,同时照射紫外光,该可聚合单体发生聚合反应。所使用的液晶组合物中,包含有两种或多种以上的可聚合单体,其可聚合单体含两个或多个环结构或稠环结构和两个与环结构直接或间接相连的反应官能团。
由于本发明使用的多个可聚合单体的体系,在PSVA光照反应过程中,利用其多环体系,紫外吸收更强,在相同的照度下,反应活性更强,可增加聚合反应速度,缩短UV照射时间;同时,由于其含有2个或2个以上的环结构,相比于1环和2环的,多环结构的可聚合单体分子刚性更强,对液晶分子具有更强的取向能力,因此,在达到相同预倾角时,多环结构的可聚合单体所需要的UV照射时间更短。同时,利用其中含有多种可聚合单体,通过调整第二种或第三种可聚合单体,控制其聚合分子量,反应位点的增多,所以,聚合物形成颗粒会更小;同时由于在聚合过程中更容易形成网络聚合物,此过程可以使聚合物膜层更加致密,分布更加均匀。
在本发明中,通过提供含2种或多种可聚合单体的液晶组分与PSVA显示模式相结合的方式,降低了制程UV光照时间,从而降低了节拍时间(tact time),实现提升产能的目的;另外,我们得到的聚合物表面形貌更加均匀,突起物颗粒尺寸更小,利于减轻液晶面板的碎亮点和漏光等显示不良,提升显示品味。
附图说明
图1为本发明液晶显示层的结构示意图。
具体实施方式
参照图1所示,本发明提供了一种改进的液晶显示层,其上基板层1、下基板层2、分别设于上基板层1和下基板层2内侧的透明电极3,所述透明电极3上贴附配向膜4,配向膜4之间分布有液晶介质组合物5,在所述液晶介质组合物5中混合有至少两种可聚合单体,所述可聚合单体含有至少两个环结构或稠环结构,以及两个与环结构直接或间接相连的反应官能团。在聚合物稳定的垂直排列液晶(PSVA,Polmer Stabilized Vertivally Aligned)的制备过程中,对上下基板的透明电极施加电压的情况下,液晶发生偏转,同时照射紫外光,该可聚合单体发生聚合反应。
其中,所述可聚合单体的结构通式可为如下通式中任选一种或多种:
Figure BDA0002320431430000041
优选地,所述P1、P2相同或不同,可选自甲基丙烯酸酯、丙烯酸酯、乙烯氧基或环氧基中任选一种;Z1、Z2、Z3、Z4、Z5相同或不同,可选自单键或碳原子数为1~5的亚烷基,其中,任意的亚甲基可以被-O-、-S-、-CO-、-COO-、-OCO-、-OCOO-、-CH=CH-、-C=C-或-C≡C-取代;
Figure BDA0002320431430000042
相同或不同,可选自:1,4-亚苯基、1,4-亚环己基、1,4-双环[2,2,2]亚辛基、嘧啶-2,5-二基、萘-2,6-二基、四氢萘-2,6-二基、十氢萘-2,6-二基、1,3-二噁烷-2,5-二基或茚满-2,5-二基;其环上的H可被烷基、卤代烷基、烷氧基、卤素所取代。
所述液晶显示装置,当无外加电压时,液晶垂直于表面排列。聚合物聚合后,会析出沉积在配向膜表面。
其中,所述可聚合单体组合物的质量百分比含量为0.01-1%。
所述可聚合单体组合物进一步包含有带有负性介电常数的液晶组合物组合而成。液晶混合物,含可聚合单体,中性单体,负性介电单体。其中,25℃时的液晶混合物介电常数各向异性(Δε)在-2.0至-8.0的范围。因为VA型显示模式的液晶是负性的,所以限定为负的。
本发明还提供了一种用于液晶显示层的液晶介质组合物,一种液晶介质组合物的制备方法,其包括以下步骤:
步骤1)在上基板层和下基板层的内侧贴附透明电极,在透明电极上贴附配向膜,将液晶介质组合物填充于上基板层和下基板层的配向膜之间,其中,所述液晶介质组合物中混合有至少两种可聚合单体,所述可聚合单体含有至少两个环结构或稠环结构,以及两个与环结构直接或间接相连的反应官能团;
步骤2)对透明电极施加电压,液晶发生偏转,照射紫外光,使得液晶介质组合物的可聚合单体发生聚合反应,使液晶分子取向,形成预倾角,发生交联反应,会形成网络聚合物。
其中,在步骤2)中,照射紫外光,施加电压强度:1V~36V;紫外线波长范围:200~400nm,紫外照度:0.1~100mw/cm2
不同聚合物单体会同时反应的,本身是一个自由基聚合的过程。原理是:加电后,液晶倾倒,聚合物反应,形成聚合物网络,锚定住PI表面的液晶分子,从而形成液晶分子定向排列。一般形成预倾角,是第一次曝光,曝光时间:10s~300s,此时需要同步加电;然后进行第二次曝光,目的是消耗剩余的聚合物,提升产品信赖性。自由基反应中,无法控制第二/第三种单体,之前进行调配好后,进行制程。因为可聚合单体是多个官能团的,会发生交联反应,因此会形成网络聚合物。
本发明中的液晶介质组合物,混合有至少两种可聚合单体,所述可聚合单体含有至少两个环结构或稠环结构,以及两个与环结构直接或间接相连的反应官能团。
可聚合单体的结构通式可为如下通式中任选一种或多种:
Figure BDA0002320431430000051
所述P1、P2相同或不同,可选自甲基丙烯酸酯、丙烯酸酯、乙烯氧基或环氧基中任选一种;Z1、Z2、Z3、Z4、Z5相同或不同,可选自单键或碳原子数为1~5的亚烷基,其中
任意的亚甲基可以被-O-、-S-、-CO-、-COO-、-OCO-、-OCOO-、-CH=CH-、-C=C-或-C
≡C-取代;
Figure BDA0002320431430000052
相同或不同,可选自:1,4-亚苯基、1,4-
亚环己基、1,4-双环[2,2,2]亚辛基、嘧啶-2,5-二基、萘-2,6-二基、四氢萘-2,6-二基、十氢萘-2,6-二基、1,3-二噁烷-2,5-二基或茚满-2,5-二基;其环上的H可被烷基、卤代烷基、烷氧基、卤素所取代。
以下分别具体供通式1、通式2和通式3的组合,按两两聚合或三者一起聚合一起的聚合反应的反应式详列如下:
通式1和通式3:
Figure BDA0002320431430000061
通式1和通式2:
Figure BDA0002320431430000062
通式1、通式2、和通式3三者一起聚合反应:
Figure BDA0002320431430000063
在本发明中,所述通式1、通式2和通式3之间可发生两两聚合和三种结构的聚合反应,其聚合度为1000以上。三种不同的聚合方式中,若选择需要更短的聚合时间,优先三个混合物相互聚合反应,次之选择通式1和通式2之间的聚合反应;聚合后,液晶Host介质不会发生变化;液晶Host不参与反应。

Claims (8)

1.一种液晶显示层,其包括上基板层、下基板层、分别设于上基板层和下基板层内侧的透明电极,所述透明电极上贴附配向膜,配向膜之间分布有液晶介质组合物,其特征在于:在所述液晶介质组合物中混合有至少两种可聚合单体,所述可聚合单体的结构通式至少包含如下通式:
通式1
Figure FDA0003066550890000011
通式2
Figure FDA0003066550890000012
其中所述P1、P2相同或不同,可选自甲基丙烯酸酯、丙烯酸酯、乙烯氧基或环氧基中任选一种;
Z1、Z2、Z4、Z5相同或不同,可选自单键或碳原子数为1~5的亚烷基,其中任意的亚甲基可以被-O-、-S-、-CO-、-COO-、-OCO-、-OCOO-、-CH=CH-、-C=C-或-C≡C-取代;
Figure FDA0003066550890000013
相同或不同,可选自:1,4-亚苯基、1,4-亚环己基、1,4-双环[2,2,2]亚辛基、嘧啶-2,5-二基、萘-2,6-二基、四氢萘-2,6-二基、十氢萘-2,6-二基、1,3-二噁烷-2,5-二基或茚满-2,5-二基;其环上的H可被烷基、卤代烷基、烷氧基或卤素所取代。
2.根据权利要求1所述液晶显示层,其特征在于:所述可聚合单体的结构通式进一步包含如下通式:
通式3
Figure FDA0003066550890000014
其中所述P1、P2相同或不同,可选自甲基丙烯酸酯、丙烯酸酯、乙烯氧基或环氧基中任选一种;
Z1、Z4、Z5相同或不同,可选自单键或碳原子数为1~5的亚烷基,其中任意的亚甲基可以被-O-、-S-、-CO-、-COO-、-OCO-、-OCOO-、-CH=CH-、-C=C-或-C≡C-取代;
Figure FDA0003066550890000021
相同或不同,可选自:1,4-亚苯基、1,4-亚环己基、1,4-双环[2,2,2]亚辛基、嘧啶-2,5-二基、萘-2,6-二基、四氢萘-2,6-二基、十氢萘-2,6-二基、1,3-二噁烷-2,5-二基或茚满-2,5-二基;其环上的H可被烷基、卤代烷基、烷氧基或卤素所取代。
3.根据权利要求1所述液晶显示层,其特征在于:所述可聚合单体占所述组合物的质量百分比为0.01-1%。
4.根据权利要求1所述液晶显示层,其特征在于:所述组合物进一步包含有带有负性介电常数的液晶组合物。
5.一种用于液晶显示层的液晶介质组合物,其特征在于:所述液晶介质组合物中混合有至少两种可聚合单体,所述可聚合单体的结构通式至少包含如下通式:
通式1
Figure FDA0003066550890000022
通式2
Figure FDA0003066550890000023
其中所述P1、P2相同或不同,可选自甲基丙烯酸酯、丙烯酸酯、乙烯氧基或环氧基中任选一种;
Z1、Z2、Z4、Z5相同或不同,可选自单键或碳原子数为1~5的亚烷基,其中任意的亚甲基可以被-O-、-S-、-CO-、-COO-、-OCO-、-OCOO-、-CH=CH-、-C=C-或-C≡C-取代;
Figure FDA0003066550890000024
相同或不同,可选自:1,4-亚苯基、1,4-亚环己基、1,4-双环[2,2,2]亚辛基、嘧啶-2,5-二基、萘-2,6-二基、四氢萘-2,6-二基、十氢萘-2,6-二基、1,3-二噁烷-2,5-二基或茚满-2,5-二基;其环上的H可被烷基、卤代烷基、烷氧基或卤素所取代。
6.根据权利要求5所述的液晶介质组合物,其特征在于:可聚合单体的结构通式进一步包含如下通式:
通式3
Figure FDA0003066550890000031
其中所述P1、P2相同或不同,可选自甲基丙烯酸酯、丙烯酸酯、乙烯氧基或环氧基中任选一种;
Z1、Z4、Z5相同或不同,可选自单键或碳原子数为1~5的亚烷基,其中任意的亚甲基可以被-O-、-S-、-CO-、-COO-、-OCO-、-OCOO-、-CH=CH-、-C=C-或-C≡C-取代;
Figure FDA0003066550890000032
相同或不同,可选自:1,4-亚苯基、1,4-亚环己基、1,4-双环[2,2,2]亚辛基、嘧啶-2,5-二基、萘-2,6-二基、四氢萘-2,6-二基、十氢萘-2,6-二基、1,3-二噁烷-2,5-二基或茚满-2,5-二基;其环上的H可被烷基、卤代烷基、烷氧基或卤素所取代。
7.一种液晶介质组合物的制备方法,其特征在于包括以下步骤:
步骤1)在上基板层和下基板层的内侧贴附透明电极,在透明电极上贴附配向膜,将液晶介质组合物填充于上基板层和下基板层的配向膜之间,其中,所述液晶介质组合物中混合有至少两种可聚合单体,
所述可聚合单体的结构通式至少包含如下通式:
通式1
Figure FDA0003066550890000033
通式2
Figure FDA0003066550890000034
其中所述P1、P2相同或不同,可选自甲基丙烯酸酯、丙烯酸酯、乙烯氧基或环氧基中任选一种;
Z1、Z2、Z4、Z5相同或不同,可选自单键或碳原子数为1~5的亚烷基,其中任意的亚甲基可以被-O-、-S-、-CO-、-COO-、-OCO-、-OCOO-、-CH=CH-、-C=C-或-C≡C-取代;
Figure FDA0003066550890000041
相同或不同,可选自:1,4-亚苯基、1,4-亚环己基、1,4-双环[2,2,2]亚辛基、嘧啶-2,5-二基、萘-2,6-二基、四氢萘-2,6-二基、十氢萘-2,6-二基、1,3-二噁烷-2,5-二基或茚满-2,5-二基;其环上的H可被烷基、卤代烷基、烷氧基或卤素所取代;
步骤2)对透明电极施加电压,液晶发生偏转,照射紫外光,使得液晶介质组合物的可聚合单体发生聚合反应,使液晶分子取向,形成预倾角,发生交联反应,会形成网络聚合物。
8.根据权利要求7所述的液晶介质组合物的制备方法,其特征在于:在步骤2)照射紫外光,施加电压强度:1V~36V;紫外线波长范围:200~400nm,紫外照度:0.1~100mw/cm2
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