CN110540645B - 聚合物分散液晶的预聚体、聚合物分散液晶组合物及显示面板 - Google Patents

聚合物分散液晶的预聚体、聚合物分散液晶组合物及显示面板 Download PDF

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CN110540645B
CN110540645B CN201910867176.XA CN201910867176A CN110540645B CN 110540645 B CN110540645 B CN 110540645B CN 201910867176 A CN201910867176 A CN 201910867176A CN 110540645 B CN110540645 B CN 110540645B
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兰松
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Shenzhen China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Abstract

一种聚合物分散液晶的预聚体、聚合物分散液晶组合物及显示面板，所述聚合物分散液晶组合物包括聚合物单体和液晶分子，其中，所述聚合物的单体为具有化学键键合聚苯胺的含氟聚酰亚胺单体。在本发明中，将导电的聚苯胺以化学键方式引入含氟聚酰亚胺单体中，以提高聚酰亚胺单体的导电率，进而获得一种驱动电压低于30V且同时兼具优异的绝缘性能以及耐辐照性的聚合物分散液晶膜。

Description

聚合物分散液晶的预聚体、聚合物分散液晶组合物及显示 面板
技术领域
本发明涉及显示技术领域，特别涉及一种聚合物分散液晶的预聚体、聚合物分散液晶组合物及显示面板。
背景技术
聚合物分散液晶(Polymer Dispersed Liquid Crystal,PDLC)是将低分子液晶与预聚物混合，在一定条件下经聚合反应以形成微米级的液晶微滴均匀地分散于高分子网络的结构。由于液晶分子的介电各向异性，因此，所述聚合物分散液晶是一种具有电光响应特性的材料。
由所述聚合物分散液晶制成的聚合物分散液晶膜是一种将液晶和聚合物结合在一起的综合性能优异的膜材料。由于液晶分子赋予了聚合物分散液晶膜显著的电光特性，使其受到了广泛的关注，并有着广阔的应用前景。
相对于传统显示器件来说，聚合物分散型液晶显示器具有很多优点，例如不需偏振片和取向层，制备工艺简单，易于制成大面积柔性显示器等。目前，聚合物分散液晶膜已在光学调制器、热敏及压敏器件、电控玻璃、光阀、投影显示、电子书等方面获得广泛应用。
但是，由于目前使用的聚合物分散液晶膜的聚合物基体大多是聚丙烯酸酯、环氧树脂或硫醇类，存在不耐高低温、化学稳定性差、机械强度及抗辐照性能不佳等缺点，限制了聚合物分散液晶膜的应用。而目前已知的采用聚酰亚胺作为聚合物基体的聚合物分散液晶膜则存在驱动电压超出50V以上的问题。
因此，有必要提出一种新的材料，可以解决目前已知的聚合物分散液晶膜驱动电压高或综合性能差的问题，以克服上述缺陷。
发明内容
本发明的目的在于提供一种聚合物分散液晶的预聚体和聚合物分散液晶组合物，用于制成一聚合物分散液晶膜。所述聚合物分散液晶组合物中通过化合键引入导电聚苯胺，从而制得一种具有低驱动电压的聚合物分散液晶膜，扩大了聚合物分散液晶膜的应用。
为了达到上述目的，根据本发明的一方面，提供一种聚合物分散液晶的预聚体，可以用于制成一聚合物分散液晶膜。所述预聚体包括含氟二酐单体、含氟二胺单体和聚苯胺，其中，所述含氟二酐单体具有式(i-1)至(i-3)所示的任意一种结构：
Figure GDA0002655986060000021
并且，所述含氟二胺单体具有式(ii-1)至(ii-4)所示的任意一种结构：
Figure GDA0002655986060000022
在本发明一实施例中，所述聚苯胺具有式(iii)所示的结构：
Figure GDA0002655986060000031
其中，n为3～5。
在本发明一实施例中，所述预聚体还包括溶剂。优选地，以所述预聚体的总质量计算，所述溶剂的质量分数为90％。
在本发明一实施例中，所述溶剂为N-甲基吡咯烷酮(NMP)或N-乙基吡咯烷酮(NEP)。
根据本发明的另一方面，提供一种聚合物分散液晶组合物，包括聚合物单体和液晶分子，其中，所述聚合物单体为具有化学键键合聚苯胺的含氟聚酰亚胺单体。
在本发明一实施例中，所述含氟聚酰亚胺单体包含含氟二酐单体与含氟二胺单体的缩聚单元；其中，
所述含氟二酐单体具有式(i-1)至(i-3)所示的任意一种结构：
Figure GDA0002655986060000032
并且，所述含氟二胺单体具有式(ii-1)至(ii-4)所示的任意一种结构：
Figure GDA0002655986060000041
在本发明一实施例中，所述聚合物单体具有式(I)所示的结构：
Figure GDA0002655986060000042
其中，Ar1选自
Figure GDA0002655986060000043
中的任意一种；Ar2选自
Figure GDA0002655986060000051
Figure GDA0002655986060000052
中的任意一种；并且，n为3～5。
在本发明一实施例中，所述聚合物单体与所述液晶分子的质量比为(70～90):(10～30)。
根据本发明的另一方面还提供一种聚合物分散液晶膜的制备方法，包括：
以含氟二胺单体、含氟二胺单体及聚苯胺室温反应获得聚酰亚胺酸的步骤；
以聚酰亚胺酸高温反应形成聚合物膜的步骤；以及，
以液晶材料与聚合物膜混合后熔融，冷却成膜以形成所述聚合物分散液晶膜的步骤。
在本发明一实施例中，在获得聚酰亚胺酸的步骤中，以上述任意一种预聚体室温反应完全而获得聚酰亚胺酸。
在本发明一实施例中，在形成聚合物膜的步骤中，使获得的聚酰亚胺酸首先以80℃～100℃反应1～3小时，然后再以200℃～230℃反应1～3小时，以获得聚合物膜。
在本发明一实施例中，在形成所述聚合物分散液晶膜的步骤中，将获得的聚合物膜与液晶材料按照质量比为(70～90):(10～30)的比例混合，高温熔融后，以5℃～10℃/分钟的降温速率降温冷却，以获得所述聚合物分散液晶膜的步骤。
根据本发明的另一方面，还提供一种显示面板，包括第一基板和与所述第一基板平行设置的一对置基板，以及，夹设于所述第一基板与所述对置基板之间的聚合物分散液晶膜；其中，所述聚合物分散液晶膜由上述任意一种预聚体与液晶分子混合而制成，或者由上述任意一种聚合物分散液晶组合物制成，或者由上述任意一种制备方法制成。
在本发明一实施例中，所述显示面板还包括第一电极和第二电极，所述第一电极设置于所述第一基板面朝所述对置基板的表面，所述第二电极设置于所述对置基板面朝所述第一基板的表面，并且，所述聚合物分散液晶膜接触所述第一电极和所述第二电极。
在本发明一实施例中，所述第一电极或所述第二电极中的至少一者为氧化铟锡(ITO)薄膜电极。
在本发明中，将导电的聚苯胺以化学键方式引入含氟聚酰亚胺单体中，以提高聚酰亚胺单体的导电率。经实验表明，本发明所述的聚合物分散液晶膜的驱动电压低于30V，且同时具有耐高低温、高强度与高模量、低热膨胀系数和介电常数、优异的绝缘性能以及耐辐照性等优异性能。
因此，本发明所述的聚合物分散液晶膜可应用于显示面板或显示装置中，有效解决现有聚合物分散液晶膜驱动电压高(高于50V)且综合性能不佳的问题。
附图说明
图1是根据本发明一实施例的聚合物膜的扫描电镜图像；
图2是根据本发明一实施例的显示面板的结构示意图；
图3A和图3B是图2所示显示面板的透光原理图。
具体实施方式
以下，结合具体实施方式，对本发明的技术进行详细描述。应当知道的是，以下具体实施方式仅用于帮助本领域技术人员理解本发明，而非对本发明的限制。
实施例1.聚合物分散液晶的预聚体
在本实施例中，提供一种聚合物分散液晶的预聚体，可以用于制成一聚合物分散液晶膜。所述预聚体包括含氟二酐单体、含氟二胺单体和聚苯胺，以及溶剂。以所述预聚体的总质量计算，所述溶剂的质量分数为90％，为N-甲基吡咯烷酮(NMP)或N-乙基吡咯烷酮(NEP)。
所述含氟二酐单体具有式(i-1)至(i-3)所示的任意一种结构：
Figure GDA0002655986060000061
所述含氟二胺单体具有式(ii-1)至(ii-4)所示的任意一种结构：
Figure GDA0002655986060000062
所述聚苯胺具有式(iii)所示的结构：
Figure GDA0002655986060000071
(iii)；其中，n为3～5。
实施例2.聚合物分散液晶的预聚体A
在本实施例中，提供一种聚合物分散液晶的预聚体A，可以用于制成一聚合物分散液晶膜。所述预聚体A包括含氟二酐单体、含氟二胺单体和聚苯胺，以及溶剂。以所述预聚体的总质量计算，所述溶剂的质量分数为90％，为N-甲基吡咯烷酮(NMP)或N-乙基吡咯烷酮(NEP)。
所述含氟二酐单体具有式i-1所示的结构，所述含氟二胺单体式ii-4所示的结构，所述聚苯胺具有式iii所示的结构且n为4。
在本实施例所述的预聚体中，所述含氟二酐单体、所述含氟二胺单体于所述聚苯胺的摩尔比为10：9：1。
实施例3.聚合物分散液晶组合物
在本实施例中，提供一种聚合物分散液晶组合物，所述聚合物分散液晶组合物包含实施例1所述的预聚体和液晶分子。所述液晶分子为本领域常用的液晶分子，在此不再赘述。
在本实施例中，所述聚合物单体具有式(I-1)至式(I-12)所示的结构，n为3～5：
Figure GDA0002655986060000072
Figure GDA0002655986060000081
Figure GDA0002655986060000091
实施例4.聚合物膜A
在本实施例中，提供一种聚合物膜A，所述聚合物膜A由实施例2所述的预聚体A制成。在本实施例中，所述聚合物膜A的聚合物单体具有式(I-4)所示的结构，且n为4。
所述聚合物膜A的制备方法具体如下：
(1)将具有式(i-1)所示的含氟二酐单体、具有式(ii-4)所示的含氟二胺单体、具有式(iii)所示的导电聚苯胺按照摩尔比为10：9：1的比例溶解于作为溶剂的NEP或NMP，使得所述溶剂的质量分数为90％；
(2)室温反应24小时后，获得聚酰亚胺酸，具有以下结构：
Figure GDA0002655986060000101
(3)随后，使聚酰亚胺酸首先以80℃～100℃反应1～3小时，然后再以200℃～230℃反应1～3小时成膜，以获得聚合物膜A，为一种导电聚酰亚胺膜。所述聚合物膜A的扫描电镜图像请见图1。如图1所示，在本实施例的所述聚合物膜A形成了均匀的高分子网络中，适合于制备聚合物分散液晶膜。
实施例5.聚合物分散液晶膜A
在本实施例中，提供一种聚合物分散液晶膜A，具体制备方法为：将实施例4所述的聚合物A与液晶材料按照质量比为(70～90):(10～30)的比例混合后，在100℃至150℃下熔融，随后以5℃～10℃/分钟的降温速率降温冷却，获得所述聚合物分散液晶膜A。
本领域技术人员可以理解的是，本实施例中所述液晶材料为本领域已知常规液晶材料，在此不再赘述。此外，当所述聚合物分散液晶膜A应用于一显示面板时，将熔融的聚合物A与液晶材料注入液晶盒(cell)中，随后5℃～10℃/分钟的降温速率降温冷却，使得液晶盒内形成所述聚合物分散液晶膜A。
经实验表明，所述聚合物分散液晶膜A具有耐高低温、高强度与高模量、低热膨胀系数和介电常数、优异的绝缘性能以及耐辐照性等优异性能。
实施例6.显示面板
请参见图2，在本实施例中，提供一种显示面板100。如图2所示，所述显示面板100包括：一第一基板110，与所述第一基板110平行设置的一对置基板120，设置于所述第一基板110面朝所述对置基板120的表面的第一电极111，设置于所述对置基板120面朝所述第一基板110的表面的第二电极121，以及，夹设于所述第一基板110与对置基板120之间且于所述第一电极和所述第二电极接触的聚合物分散液晶膜200。
如图2所示，所述聚合物分散液晶膜200包括已经成膜的聚合物膜210，以及分散于所述聚合物膜210内的液晶分子220。所述聚合物分散液晶膜200可以是实施例5所述的聚合物分散液晶膜A。
如图3A所示，由于所述液晶分子220的介电各向异性，因此当不向所述第一电极111和第二电极121施加电压时，所述聚合物分散液晶膜200不透光，即所述显示面板无显示效果。而当向所述第一电极111和第二电极121施加电压时，如图3B所示，所述聚合物分散液晶膜200透光，即所述显示面板显示。并且经实验表明，所述显示面板100的驱动电压低于30V，相较于目前已知的同类显示面板的高于50V的驱动电压，本实施例所述显示面板100具有明显的有益效果。
本发明已由上述相关实施例加以描述，然而上述实施例仅为实施本发明的范例。必需指出的是，已公开的实施例并未限制本发明的范围。相反地，包含于权利要求书的精神及范围的修改及均等设置均包括于本发明的范围内。

Claims (7)

1.一种聚合物分散液晶的预聚体，包括含氟二酐单体、含氟二胺单体和聚苯胺，其中，所述含氟二酐单体具有式(i-1)至(i-3)所示的任意一种结构：
Figure FDA0002655986050000011
所述含氟二胺单体具有式(ii-1)至(ii-4)所示的任意一种结构：
Figure FDA0002655986050000012
Figure FDA0002655986050000021
并且，所述聚苯胺具有式(iii)所示的结构：
Figure FDA0002655986050000022
其中，n为3～5。
2.如权利要求1所述的预聚体，其特征在于，所述预聚体还包括溶剂。
3.如权利要求2所述的预聚体，其特征在于，所述溶剂为N-甲基吡咯烷酮或N-乙基吡咯烷酮。
4.一种聚合物分散液晶组合物，包括聚合物单体和液晶分子，其特征在于，所述聚合物单体为具有以化学键键合聚苯胺的含氟聚酰亚胺单体，并且，所述聚合物单体具有式(I)所示的结构：
Figure FDA0002655986050000023
其中，Ar1选自
Figure FDA0002655986050000024
中的任意一种；
Ar2选自
Figure FDA0002655986050000025
Figure FDA0002655986050000031
中的任意一种；并且，n为3～5。
5.如权利要求4所述的聚合物分散液晶组合物，其特征在于，所述聚合物单体与所述液晶分子的质量比为(70～90):(10～30)。
6.一种显示面板，其特征在于，所述显示面板包括第一基板和与所述第一基板平行设置的一对置基板，以及，夹设于所述第一基板与所述对置基板之间的聚合物分散液晶膜；其中，所述聚合物分散液晶膜由权利要求4所述的聚合物分散液晶组合物制成，或由权利要求1所述的预聚体与液晶分子混合而制成。
7.如权利要求6所述的显示面板，其特征在于，所述显示面板还包括第一电极和第二电极，所述第一电极设置于所述第一基板面朝所述对置基板的表面，所述第二电极设置于所述对置基板面朝所述第一基板的表面，并且，所述聚合物分散液晶膜接触所述第一电极和所述第二电极。
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