CN113913197B - 液晶组合物及包含该液晶组合物的液晶显示元件或液晶显示器 - Google Patents

液晶组合物及包含该液晶组合物的液晶显示元件或液晶显示器 Download PDF

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CN113913197B
CN113913197B CN202111206923.9A CN202111206923A CN113913197B CN 113913197 B CN113913197 B CN 113913197B CN 202111206923 A CN202111206923 A CN 202111206923A CN 113913197 B CN113913197 B CN 113913197B
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员国良
康素敏
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Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
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Abstract

本发明提供了一种液晶组合物，该液晶组合物中含有两种或多种通式Ⅰ化合物和一种或多种通式Ⅱ化合物，本发明所提供的液晶组合物能在非常高和非常低的温度下工作、具有非常短的响应时间、具有较好的对光和热的可靠性，特别是展示出长时间运行后无图像残留或显著降低的图像残留。

Description

液晶组合物及包含该液晶组合物的液晶显示元件或液晶显 示器
本申请是名称为“液晶组合物及包含该液晶组合物的液晶显示元件或液晶显示器”，申请号201710053538.2的发明专利申请的分案申请。
技术领域
本发明属于液晶显示领域，具体涉及一种液晶组合物及包含该液晶组合物的液晶显示元件或液晶显示器。
背景技术
显示是把电信号(数据信息)转变为可视光(视觉信息)的过程，完成显示的设备即人机界面(Man-Machine Interface，MMI)，平板显示器(Flat Panel Display，FPD)是目前最为流行的一类显示设备。液晶显示器(Liquid Crystal Display，LCD)是FPD中最早被开发出来，并被商品化的产品。目前，薄膜晶体管液晶显示器(Thin Film Transistor LiquidCrystal，TFT-LCD)已经成为LCD应用中的主流产品。
TFT-LCD的发展经历了漫长的基础研究阶段，在实现大生产，商业化之后，TFT-LCD产品以其轻薄、环保、高性能等优点，其尺寸越做越大，应用越来越广。无论是小尺寸的手机屏、还是大尺寸的笔记本电脑(Notebook PC)或监视器(Monitor)，以及大型化的液晶电视(LCDTV)，到处可见TFT-LCD的应用。TFT-LCD可分为三大类，分别是扭曲向列/超扭曲向列(TN/STN)型、平面转换(IPS)型、及垂直配向(VA)型。早期商用的TFT-LCD产品基本采用了扭曲向列(Twisted Nematic，TN)型显示模式，其最大问题是视角不够大。随着TFT-LCD产品尺寸的增加，特别是TFT-LCD在TV领域的应用，具有广视野角特点的面内切换(In-PlaneSwiching，IPS)显示模式被开发出来并加以运用。IPS显示模式最早由美国人R.Soref(索里夫)在1974年论文上发表，并由德国人G.Baur(鲍尔)提出把IPS作为广视角技术应用于TFT-LCD中。1995年，日本的日立公司开发出了世界首款13.3寸IPS模式的广视野角TFT-LCD产品。
VA性液晶显示器相对其他种类的液晶显示器具有极高的对比度，是因为在不加电的暗态时，液晶分子垂直于基板表面排列，不产生任何相位差，漏光极低，暗态亮度很小，暗态亮度越低，则对比度越高，在大尺寸显示，如电视等方面具有非常广的应用。然而，为了追求更高的性能规格，加快响应速度、降低阈值电压、提高电压保持率、降低离子密度、提高显示良品率已经成为各家器件厂商追求的目标。
发明内容
本发明需要解决的技术问题是提供一种负介电各向异性液晶组合物，所述特定液晶组合物不具有以上所述缺点。特别地，他们能在非常高和非常低的温度下工作、具有非常短的响应时间、，具有较好的对光和热的可靠性，特别是展示出长时间运行后无图像残留或显著降低的图像残留。
令人惊讶的是，两种或多种式I所示液晶化合物和一种或多种式II所示液晶化合物用于液晶混合物中，特别是用于具有负介电各向异性、优选用于VA、IPS和FFS显示器的LC混合物，则可改善旋转粘度值和相应的响应时间。
为了实现以上技术效果，本发明提供了一种液晶组合物，所述液晶组合物含有两种或多种式I所示化合物以及一种或多种式Ⅱ所示化合物,
其中，R1、R2、R3、R4各自独立地表示碳原子数为1-5的直链烷基、碳原子数为1-5的直链烷氧基、碳原子数为2-5的烯基、F、Cl、CF3、OCF3、任意一个亚甲基可以被替代；；
表示/>
n表示0或1。
本发明技术方案的进一步改进在于：所述两种或多种式Ⅰ所示化合物总质量含量为1-20％，所述一种或多种式Ⅱ所示化合物总质量含量为1-25％。
所述两种或多种式Ⅰ所示化合物优选式Ⅰ1-Ⅰ27所示化合物中的一种或多种，
其中，alkyl、alkyl*各自独立地表示碳原子数为1-5的直链烷基；
alkoxy、alkoxy*各自独立地表示碳原子数为1-5的直链烷氧基；
alkenyl、alkenyl*各自独立地表示碳原子数为2-5的烯基；
所述一种或多种式Ⅱ所示化合物优选为式Ⅱ1-Ⅱ4所示化合物中的一种或多种，
R3、R4各自独立地表示碳原子数为1-5的直链烷基、碳原子数为1-5的直链烷氧基或碳原子数为2-5的烯基或F、Cl、CF3、OCF3、
所述液晶组合物还可以包含一种或多种通式Ⅲ所示的化合物，
其中，R5、R6各自独立地表示碳原子数为1-5的直链烷基或碳原子数为1-5的直链烷氧基；
Z1表示单键、-CH2O-、-OCH2-；
m表示1或2。
所述液晶组合物还可以包含一种或多种通式Ⅳ所示的化合物，
其中，R7、R8各自独立地表示碳原子数为1-5的直链烷基或碳原子数为1-5的直链烷氧基；
X1表示H或F。
所述液晶组合物还可以包含一种或多种通式Ⅴ所示的化合物，
其中，R9、R10各自独立地表示碳原子数为1-5的直链烷基或碳原子数为1-5的直链烷氧基；
X2、X3、X4、X5、X6、X7各自独立的表示H或F，并且至少两个表示F原子。
所述液晶组合物中，所述两种或多种式I所示化合物的总质量百分含量优选为1～10％，所述一种或多种式Ⅲ所示化合物的总质量百分含量优选为1～50％，所述一种多种式Ⅳ所示化合物的总质量百分含量优选为1～15％，所述一种或多种式Ⅴ所示化合物的总质量百分含量优选为1～20％。
所述液晶组合物还可以包含一种或多种可聚合性化合物。
可聚合性化合物优选为通式RM-1所示之化合物：
其中，X8表示H或F。
本申请还请求保护包含以上任一所述液晶组合物的液晶显示元件或液晶显示器，所述液晶显示元件或液晶显示器为有源矩阵显示元件或显示器、无源矩阵显示元件。
本发明技术方案的进一步改进在于：将少量的可聚合化合物加入液晶介质中，并在填装入液晶盒之后在于电极之间施加或不施加电压的情况下使其通常通过UV光聚合而原位聚合或交联。导致液晶分子在盒中的预倾斜，该预倾斜对响应时间有积极的作用。此外，本发明中的液晶组合物+通式RM-1的可聚合组分组成的材料体系具有低的旋转粘度和较佳的电性能，特别是：“电压保持比”(VHR或HR)。由于UV曝光是显示器生产过程中的一个必要部分，因此这点至关重要。
具体实施方式
下面结合具体实施例对本发明做进一步详细说明，但本发明并不限于以下实施例。所述方法如无特别说明均为常规方法。所述原料如无特别说明均能从公开商业途径而得。所述百分比如无特别说明，均为质量百分比。
下述实施例中，
CP表示清亮点，直接使用WRX-1S显微热分析仪测定，设定升温速率为3℃/min。
Δn表示光学各向异性(589nm，20℃)，
Δε表示介电各向异性(25℃，1KHz，HP4284A，5.2微米TN左旋盒)，
γ1表示20℃时旋转粘度(mpas)，VHR(％)代表电荷保持率(5V,60Hz,20℃)，ρ(×1013Ω·cm)代表电阻率(20℃)，
ID：70℃时的离子密度(pC/cm2)
τ表示响应时间：ton+toff
ton直至达到最大对比度90％时接通时的时间
toff直至达到最大对比度10％时切断时的时间
电压保持率VHR(％)的测试仪与电阻率ρ(×1013Ω·cm)均为TOYO06254和TOYO6517型液晶物性评价系统(测试温度20℃，时间16ms，测试盒为7.0微米)。
烧屏：
液晶显示元件的烧屏评价，是在显示区域内使规定的固定图案显示1000小时后，通过目测对进行全画面均匀显示时的固有图案的残影水平进行以下的4阶段评价。
◎无残影
○有极少量的残影，为可以容许的水平
△有残影，为不能允许的水平
×有残影，相当差
此外，本发明申请实施例液晶单体结构用代码表示，液晶环结构、端基、连接基团的代码表示方法见下表(一)、表(二)。
表(一)：环结构的对应代码
表(二)：端基与链接基团的对应代码
举例：
表示为CC-3-V1，
表示为DFDB(S)F-1-O2以下列表为对比液晶和液晶组成物配方及基本光学参数：对比液晶组合物：
液晶组合物4
液晶组合物5
液晶组合物7
液晶组合物9
在彩色滤光片玻璃基板和阵列基板各自的相对侧形成水平取向性取向膜后进行弱摩擦处理，制成IPS(平面转换技术)单元，在两基板之间夹持以下所示的对比液晶组合物以及液晶组合物1-9，其特点是液晶分子在两基板间呈现水平转换分子排列，对获得的液晶显示元件的VHR、ID以及响应时间进行测定。此外，进行获得的液晶显示元件的烧屏评价。
下表为IPS液晶显示器与液晶的性能评价测量数据：
另外，在彩色滤光片玻璃基板和阵列基板内表面特定区域涂布垂直配向剂或在液晶中加入一类辅助配向剂的物质，制成VA(垂直配向技术)单元，使对比液晶组合物以及液晶组合物中的液晶分子在液晶显示装置的基板表面垂直排列，对获得的液晶显示元件的VHR、ID以及响应时间进行测定。此外，进行获得的液晶显示元件的烧屏评价。
下表为VA液晶显示器与液晶的性能评价测量数据：
由以上测试结果可以明显看出：本发明公开的负介电各向异性液晶组合物与对比例相比具有较低的旋转粘度值，并且使用本发明公开的负介电各向异性液晶组合物制成的IPS(平面转换技术)显示器和VA(垂直配向技术)显示器VHR更高、可靠性更好、ID更小、τ更短，在烧屏评价中性能更优异，特别是长期运行后无图像残留。

Claims (3)

1.一种液晶组合物，其特征在于：所述液晶组合物含有式I19、I20、I21所示化合物的组合，以及式Ⅱ1与式II2所示化合物,还包含两种不同的式Ⅲ所示化合物，一种式Ⅳ所示的化合物，一种式Ⅴ所示的化合物，和通式CC-3-V与通式CC-3-2所示的化合物，
R3表示碳原子数为3的直链烷基；R4表示碳原子数为2的直链烷基；
R5表示碳原子数为3的直链烷基；R6表示碳原子数为2的直链烷氧基；
Z1表示-CH2O-；
m表示1或2，且所述两种不同的式Ⅲ所示化合物中的m不相同；
R7表示碳原子数为2的直链烷基；R8表示碳原子数为3的直链烷基；
X1表示F；
R9表示碳原子数为2的直链烷基；R10各自独立地表示碳原子数为3的直链烷基；
X2、X3、X4各自独立的表示H，X5、X6、X7各自独立的表示F；
通式CC-3-V与通式CC-3-2中，C代表-3代表碳原子数为3的直链烷基，-2代表碳原子数为2的直链烷基，-V代表碳原子数为2的烯基；
所述式I19所示化合物质量含量为4％，所述式I20所示化合物质量含量为4％，所述式I21所示化合物质量含量为4％；所述式Ⅱ1所示化合物质量含量为8％；所述式Ⅱ2所示化合物质量含量为7％；所述两种不同的式Ⅲ所示化合物的质量含量分别为15％；所述一种式Ⅳ所示的化合物质量含量为8％；所述一种式Ⅴ所示的化合物质量含量为7％；所述通式CC-3-V质量含量为10％；所述通式CC-3-2所示的化合物质量含量为18％。
2.根据权利要求1所述的液晶组合物，其特征在于：所述液晶组合物还包含一种或多种可聚合性化合物。
3.根据权利要求2所述的液晶组合物，其特征在于：所述可聚合性化合物为通式RM-1所示化合物，
其中，X8表示H或F。
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