CN110499162A - 正介电各向异性液晶组合物及液晶显示器件 - Google Patents
正介电各向异性液晶组合物及液晶显示器件 Download PDFInfo
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Abstract
本发明涉及正介电各向异性液晶组合物、液晶显示器件,所述正介电各向异性液晶组合物包含一种或多种式Ⅰ化合物、一种或多种式Ⅱ化合物。本发明所公开的液晶组合物具有正介电、高电荷保持率,低旋转粘度、响应时间快,尤其是透过率高的特点,适用于制造高透过率、快速响应的TFT‑LCD。
Description
技术领域
本发明属于液晶材料技术领域,具体涉及液晶组合物,液晶显示器件。
背景技术
在19世纪末,奥地利植物学家发现了液晶,即液态的晶体,也就是说一种物质同时具备了液体的流动性和类似晶体的某种排列特性。在电场的作用下,液晶分子的排列会产生变化,从而影响它的光学性质。英国科学家利用这个性质在上世纪制造了第一块液晶显示器即LCD(Liquid Crystal Display)。液晶显示材料具有驱动电压低、功耗微小、可靠性高、显示信息量大、彩色显示等优点,液晶显示器得到了较快的发展,液晶单体更新换代速度加快。目前液晶单体已有1万多种,主要应用于TN、STN发展到现在彩色大屏幕的TN-TFT、VA-TFT、IPS-TFT、PDLC等显示模式。
目前在液晶显示器件行业,显示模式主要有,面内切换(in-plane switching,IPS),边缘场切换(fringe-field switching,FFS),和垂直排列(vertical alignment,VA)等显示模式。其中,面内切换(IPS)具有宽视角的特点,液晶分子指向矢和玻璃基板方向是平行的,平行排列方式的IPS,液晶的介电各向异性(△ε)既可以是正的,也可以是负的。边缘场切换(FFS)属于面内切换(IPS)模式中的一种。垂直取向模式(VA)具有良好的对比度,液晶分子在零场时和玻璃基板方向垂直,与垂直入射光线平行。当偏振片正交时,会显示良好的暗态,液晶的介电各向异性(△ε)必须是负的。
穿透率影响液晶面板的对比度,是一个很重要的因素。穿透率在面内切换,边缘场切换,和垂直排列等显示模式中只有大约5%左右的背光能够穿透显示器件,大部分光被消耗了,造成面板能耗较高。
发明内容
为了解决上述技术问题,本发明提供了一种正介电各向异性液晶组合物,其特征在于,所述液晶组合物包含一种或多种式Ⅰ所示的负性化合物以及一种或多种式Ⅱ所示的中性化合物,
式I中,R1表示环丙基、环丁基、环戊基;Z表示单键、-CH2-、-O-、-CH2CH2-或-CH2O-;R2表示氢原子、氟原子、碳原子数为1-7的烷基或碳原子数为1-7的烷氧基,X表示氧原子或硫原子;
式II中,R3、R4各自独立地表示碳原子数为1-10的烷基、氟取代的碳原子数为1-10的烷基、碳原子数为1-10的烷氧基、氟取代的碳原子数为1-10的烷氧基、碳原子数为2-10的链烯基、氟取代的碳原子数为2-10的链烯基、碳原子数为3-8的链烯氧基或氟取代的碳原子数为3-8的链烯氧基;
各自独立地表示
本发明的发明人等经过深入研究发现,通过在液晶组合物中组合使用式I所示的具有氧芴、硫芴类液晶组合物与式II所示的液晶化合物,获得了具有高的折射率从而穿透率显著提高的液晶组合物。虽然折射率提高的详细原理并不十分清楚,发明人推测,由于氧芴、硫芴类液晶化合物侧向具有二个氟原子,并且分子内存在刚性结构,从而限制了二个苯环之间的偏转,使得这类化合物的介电各向异性的绝对值很大,从而具有很高的折射率,能够明显的提升液晶组合物的穿透率。通过在液晶组合物中添加式Ⅰ所示的氧芴、硫芴类液晶化合物,能够提高液晶组合物的透过率、响应时间,可明显地提升液晶显示器件的穿透率,降低液晶显示器件的能耗。本发明的液晶组合物可应用于IPS-TFT、FFS-TFT和OCB等模式的显示器件。
本发明的正介电各向异性液晶组合物中,一种或多种式Ⅰ所示的负性化合物的总质量含量优选为1-30%,一种或多种式Ⅱ所示的中性化合物的总质量含量优选为20-80%;
本发明的正介电各向异性液晶组合物中,优选的是,一种或多种式Ⅰ所示的负性化合物选自下列式I1至式I24所示的化合物组成的组:
优选的是,一种或多种式Ⅱ所示的中性化合物选自下述的式Ⅱ1至Ⅱ3所示的化合物组成的组:
其中,D1、D2各自独立地表示碳原子数为1-10的烷基、氟取代的碳原子数为1-10的烷基、碳原子数为1-10的烷氧基、氟取代的碳原子数为1-10的烷氧基、碳原子数为2-10的链烯基、氟取代的碳原子数为2-10的链烯基、碳原子数为3-8的链烯氧基或氟取代的碳原子数为3-8的链烯氧基。
本发明的正介电各向异性液晶组合物中,优选的是,一种或多种式III所示的化合物选自下述的式III-a-III-q所示化合物组成的组:
其中,R7表示碳原子数为1~10的直链烷基、碳原子数为1~10的烷氧基或碳原子数为2~10的链烯基;Y1表示表示F、未取代或者被F单取代或多取代的碳原子数1-6的烷基、未取代或者被F单取代或多取代的碳原子数1-6的烷氧基、未取代或者被F单取代或多取代的碳原子数2-6的链烯基;(F)表示氢或氟。
本发明的正介电各向异性液晶组合物中,优选的是,还包含一种或多种式VI所示的化合物:
式VI中,R11、R12各自独立地表示碳原子数为1~10的直链烷基、 碳原子数为1~10的烷氧基或碳原子数为2~10的链烯基;
选自③或④所示的基团组成的组,
③表示反式1,4-亚环己基、1,4-环己烯基,其中一个或多个不相邻的-CH2-基团被-O-或-S-取代或未取代;
④表示1,4-亚苯基基团,其中一个或两个-CH-被O取代或未取代,一个或两个H被F取代或未取代;
Z5表示氢或者酯基;c、d各自独立地表示1或者2。
本发明的正介电各向异性液晶组合物中,优选的是,一种或多种式VI所示的化合物选自下述的式VI-a至式VI-e所示的化合物组成的组:
其中,R11、R12各自独立地表示碳原子数为1~10的直链烷基、 碳原子数为1~10的烷氧基或碳原子数为2~10的链烯基。
本发明的正介电各向异性液晶组合物中,优选的是,还包含一种或多种式VII所示的化合物:
式VII中,R13各自独立地表示碳原子数为1~10的直链烷基、 碳原子数为1~10的烷氧基或碳原子数为2~10的链烯基;
R14表示碳原子数为1~5的直链烷基、或者、氧原子与苯环相连的烷基醚;
选自⑤或⑥所示的基团组成的组:
⑤表示反式1,4-亚环己基、1,4-环己烯基,其中一个或多个不相邻的-CH2-基团被-O-或-S-取代或未取代;
⑥表示1,4-亚苯基基团,其中一个或两个-CH-被N取代或未取代,一个或两个H被F取代或未取代;
Z3表示单键、-CH2-、-CH2-CH2-、-(CH2)3-、-(CH2)4-、-CH=CH-、-C≡C-、-COO-、-OOC-、-CF2O-、-OCH2-、-CH2O-、-OCF2-、-CF2CH2-、-CH2CF2-、-C2F4-或-CF=CF-;
d表示0、1或2;当d=2时,可以相同或不同。
本发明的正介电各向异性液晶组合物中,优选的是,一种或多种式VII所示的化合物选自下述的式VII-a-式VII-i所示的化合物组成的组:
其中,R13各自独立地表示碳原子数为1~10的直链烷基 碳原子数为1~10的烷氧基或碳原子数为2~10的链烯基;R14表示碳原子数为1~5的直链烷基、或者、氧原子与苯环相连的烷基醚。
本发明的液晶组合物中,可以包含一种或多种选自UV稳定剂、掺杂剂和/或抗氧化剂作为添加剂。
抗氧化剂、紫外线吸收剂、光稳定剂可以列举下述的物质:
S为选自1-10的整数。
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:
本发明的液晶组合物可采用将液晶化合物混合的方法进行生产,如在高温下混合不同组分并彼此溶解的方法制备,本发明的液晶组合物也可按照其他常规的制备方法,如采取加热,超声波,悬浮等方式制备。
本说明书中的百分比为质量百分比,温度为摄氏度(℃),其他符号的具体意义及测试条件如下:
Cp表示液晶清亮点(℃),DSC定量法测试;
S-N表示液晶的晶态到向列相的熔点(℃);
Δn表示光学各向异性,no为寻常光的折射率,ne为非寻常光的折射率,测试条件为25±2℃,589nm,阿贝折射仪测试;
Δε表示介电各向异性,Δε=ε∥-ε⊥,其中,ε∥为平行于分子轴的介电常数,ε⊥为垂直于分子轴的介电常数,测试条件为25±0.5℃,20微米平行盒,INSTEC:ALCT-IR1测试;
γ1表示旋转粘度(mPa·s),测试条件为25±0.5℃,20微米平行盒,INSTEC:ALCT-IR1测试;
ρ表示电阻率(Ω·cm),测试条件为25±2℃,测试仪器为TOYO SR6517高阻仪和LE-21液体电极。
VHR表示电压保持率(%),测试条件为20±2℃、电压为±5V、脉冲宽度为10ms、电压保持时间16.7ms。测试设备为TOYO Model6254液晶性能综合测试仪。
τ表示响应时间(ms),测试仪器为DMS-501,测试条件为25±0.5℃,测试盒为3.3微米IPS测试盒,电极间距和电极宽度均为10微米,摩擦方向与电极夹角为10°。
T(%)表示透过率,T(%)=100%*亮态(Vop)亮度/光源亮度,测试设备DMS501,测试条件为25±0.5℃,测试盒为3.3微米IPS测试盒,电极间距和电极宽度均为10微米,摩擦方向与电极夹角为10°。
对比例1
实施例1
由实施例1和对比例1的比较可以看出,组合使用有式Ⅰ所示的负性化合物和式II所示的中性化合物的实施例1在维持清亮点、折射率、响应时间等性能的水平与对比例1相当的基础上其透过率显著增大,从而,获得了响应快速、透过率高的性能优异的液晶组合物。
实施例2
实施例2和对比例1的比较可以看出,透过率增大,响应快,适用于低盒厚的大尺寸IPS-TV等显示应用,有利于实现宽视角,高对比度,优质的动态画面播放等性能。
实施例3
实施例3和对比例1的比较,折射率基本不变,垂直介电增大,透过率再次增大,同时具有很好的高低温稳定性,结合IPS显示模式的宽视角优势,适用于TV、中小尺寸液晶显示等领域。
实施例4
实施例4的液晶组合物具有合适的折射率和清亮点,高透过率,快速响应,结合IPS显示模式的宽视角优势,适用于中小尺寸的手持终端显示应用。
实施例5
实施例5的液晶组合物具有合适的折射率和清亮点,高透过率,快速响应,结合IPS显示模式的宽视角优势,适用于手持终端显示应用。
实施例6
实施例6的混晶化合物具有合适的折射率和清亮点,高透过率,快速响应,结合IPS显示模式的宽视角优势,适用于智能手机等小尺寸显示应用。
实施例7
实施例7的液晶组合物具有较高的折射率,适用于低盒厚的显示器,和较高清亮点,有较宽的使用温度,高透过率,快速响应,结合IPS显示模式的宽视角优势,适用于户外显示应用。
实施例8
实施例8的液晶组合物具有合适的折射率和清亮点,高透过率,快速响应,结合IPS显示模式的宽视角优势,适用于智能手机等小尺寸显示应用。
本发明虽然仅仅列举了上述8个实施例的具体物质和配比质量百分比,并对组成的液晶组合物的性能进行了测试,但是本发明的液晶组合物可以在上述实施例的基础上,利用本发明所涉及的通式Ⅰ、Ⅱ、III、Ⅵ、Ⅶ所代表的化合物、以及通式Ⅰ、Ⅱ、III、Ⅵ、Ⅶ的优选的化合物进行进一步拓展和修改,均能达到本发明的目的。
Claims (10)
1.一种正介电各向异性液晶组合物,其特征在于,所述液晶组合物包含一种或多种式Ⅰ所示的负性化合物以及一种或多种式Ⅱ所示的中性化合物,
式I中,R1表示环丙基、环丁基或环戊基;Z表示单键、-CH2-、-O-、-CH2CH2-或-CH2O-;R2表示氢原子、氟原子、碳原子数为1-7的烷基或碳原子数为1-7的烷氧基,X表示氧原子或硫原子;
式II中,R3、R4各自独立地表示碳原子数为1-10的烷基、氟取代的碳原子数为1-10的烷基、碳原子数为1-10的烷氧基、氟取代的碳原子数为1-10的烷氧基、碳原子数为2-10的链烯基、氟取代的碳原子数为2-10的链烯基、碳原子数为3-8的链烯氧基或氟取代的碳原子数为3-8的链烯氧基;
各自独立地表示
2.根据权利要求1所述的正介电各向异性液晶组合物,其特征在于,所述液晶组合物中所述一种或多种式Ⅰ所示的负性化合物的总质量含量为1-30%,所述一种或多种式Ⅱ所示的中性化合物的总质量含量为20-80%。
3.根据权利要求1或2所述的正介电各向异性液晶组合物,其特征在于,所述式Ⅰ所示的负性化合物选自式I1至式I24所示化合物组成的组:
所述式Ⅱ所示的中性化合物选自下述的式II1-式II3所示的化合物组成的组:
其中,D1、D2各自独立地表示碳原子数为1-10的烷基、氟取代的碳原子数为1-10的烷基、碳原子数为1-10的烷氧基、氟取代的碳原子数为1-10的烷氧基、碳原子数为2-10的链烯基、氟取代的碳原子数为2-10的链烯基、碳原子数为3-8的链烯氧基或氟取代的碳原子数为3-8的链烯氧基。
4.根据权利要求1~3的任一项所述的正介电各向异性液晶组合物,其特征在于,所述正介电各向异性液晶组合物还包含一种或多种式III所示的化合物:
式III中,R7表示碳原子数为1~10的直链烷基、碳原子数为1~10的烷氧基或碳原子数为2~10的链烯基;
X3、X4各自独立地表示H或者F,X5表示H或者甲基;
Y1表示F、未取代或者被F单取代或多取代的碳原子数1-6的烷基、未取代或者被F单取代或多取代的碳原子数1-6的烷氧基、未取代或者被F单取代或多取代的碳原子数2-6的链烯基;
选自①或②所示基团组成的组,
①表示反式1,4-亚环己基、1,4-环己烯基,其中一个或多个不相邻的-CH2-基团任选被-O-或-S-取代或未取代;
②表示1,4-亚苯基,其中一个或两个-CH-任选被O取代或未取代,一个或两个H任选被F、CH3取代或未取代;
Z2表示单键、-CH2-、-CH2-CH2-、-(CH2)3-、-(CH2)4-、-CH=CH-、-C≡C-、-COO-、-OOC-、-CF2O-、-OCH2-、-CH2O-、-OCF2-、-CF2CH2-、-CH2CF2-、-C2F4-或-CF=CF-;
b表示0、1或2;当b=2时,可以相同或者不同。
5.根据权利要求4所述的液晶组合物,其特征在于,所述一种或多种式III所示的化合物选自下述的式III-a-III-q所示化合物组成的组:
其中,R7表示碳原子数为1~10的直链烷基、碳原子数为1~10的烷氧基或碳原子数为2~10的链烯基;Y1表示表示F、未取代或者被F单取代或多取代的碳原子数1-6的烷基、未取代或者被F单取代或多取代的碳原子数1-6的烷氧基、未取代或者被F单取代或多取代的碳原子数2-6的链烯基;
(F)表示氢或氟。
6.根据权利要求1-5的任一项所述的正介电各向异性液晶组合物,其特征在于,所述正介电各向异性液晶组合物还包含一种或多种式VI所示的化合物:
式VI中,R11、R12各自独立地表示碳原子数为1~10的直链烷基、 碳原子数为1~10的烷氧基或碳原子数为2~10的链烯基;
选自③或④所示的基团组成的组,
③表示反式1,4-亚环己基、1,4-环己烯基基团,其中一个或多个不相邻的-CH2-基团被-O-或-S-取代或未取代;
④表示1,4-亚苯基基团,其中一个或两个-CH-被O取代或未取代,一个或两个H被F取代或未取代。
Z5表示氢或者酯基,c、d各自独立地表示1或者2。
7.根据权利要求6的液晶组合物,其特征在于,所述一种或多种式VI所示的化合物选自下述的式VI-a至式VI-e所示的化合物组成的组:
R11、R12各自独立地表示碳原子数为1~10的直链烷基、 碳原子数为1~10的烷氧基或碳原子数为2~10的链烯基。
8.根据权利要求1-7的任一项所述的正介电各向异性液晶组合物,其特征在于,所述正介电各向异性液晶组合物还包含一种或多种式VII所示的化合物:
式VII中,R13各自独立地表示碳原子数为1~10的直链烷基、 碳原子数为1~10的烷氧基、或碳原子数为2~10的链烯基;
R14表示碳原子数为1~5的直链烷基、或者、氧原子与苯环相连的烷基醚;
表示⑤或⑥所示基团中的任意一种或多种:
⑤表示反式1,4-亚环己基、1,4-环己烯基,其中一个或多个不相邻的-CH2-基团被-O-或-S-取代或未取代;
⑥表示1,4-亚苯基基团,其中一个或两个-CH-被N取代或未取代,一个或两个H被F取代或未取代;
Z3表示单键、-CH2-、-CH2-CH2-、-(CH2)3-、-(CH2)4-、-CH=CH-、-C≡C-、-COO-、-OOC-、-CF2O-、-OCH2-、-CH2O-、-OCF2-、-CF2CH2-、-CH2CF2-、-C2F4-或-CF=CF-中的一种;
d表示0、1或2;当d=2时,可以相同或不同。
9.根据权利要求8所述的正介电各向异性液晶组合物,其特征在于,所述一种或多种式VII所示的化合物选自下述的式VII-a-式VII-i所示的化合物组成的组:
其中,R13各自独立地表示碳原子数为1~10的直链烷基 碳原子数为1~10的烷氧基或碳原子数为2~10的链烯基;R14表示碳原子数为1~5的直链烷基、或者、氧原子与苯环相连的烷基醚。
10.一种液晶显示器件,其特征在于,所述液晶显示器件包括权利要求1-9任一项所述的正介电各向异性液晶组合物,所述液晶显示器件为有源矩阵显示器件或无源矩阵显示器件。
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