CN110358548B - 液晶组合物及液晶显示元器件 - Google Patents
液晶组合物及液晶显示元器件 Download PDFInfo
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Abstract
Description
技术领域
本发明涉及液晶显示技术领域。更具体地,涉及一种液晶组合物及液晶显示元器件。
背景技术
目前,液晶化合物的应用范围拓展的越来越广,其可应用于多种类型的显示器、电光器件、传感器等中。用于上述显示领域的液晶化合物的种类繁多,其中向列相液晶应用最为广泛。向列相液晶已经应用在无源TN、STN矩阵显示器和具有TFT有源矩阵的系统中。
对于薄膜晶体管技术(TFT-LCD)应用领域,近年来市场虽然已经非常巨大,技术也逐渐成熟,但人们对显示技术的要求也在不断的提高,尤其是在实现快速响应,降低驱动电压以降低功耗等方面。液晶材料作为液晶显示器重要的光电子材料之一,对改善液晶显示器的性能发挥重要的作用。
作为液晶材料,需要具有良好的化学和热稳定性以及对电场和电磁辐射的稳定性。而作为薄膜晶体管技术(TFT-LCD)用液晶材料,不仅需要具有如上稳定性外,还应具有较宽的向列相温度范围、合适的双折射率各向异性、非常高的电阻率、良好的抗紫外线性能、高电荷保持率以及低蒸汽压等性能。
对于动态画面显示应用,消除显示画面残影和拖尾,要求液晶具有很快的响应速度,因此要求液晶具有较低的旋转粘度γ1;另外,对于便携式设备,为了降低设备能耗,希望液晶的驱动电压尽可能低;而对于电视等用途的显示器来说,对于液晶的驱动电压要求不是那么的低。
因此,本发明提供了一种液晶组合物及液晶显示元器件,至少解决上述之一的问题。
发明内容
本发明的一个目的在于提供一种液晶组合物。该液晶组合物响应时间短,具有更低的旋转粘度γ1,并具有较高的清亮点,较好的低温互溶性。
本发明的另一个目的在于提供一种包含该液晶组合物的液晶显示元器件。该液晶显示元器件具有较宽的向列相温度范围、合适的双折射率各向异性、非常高的电阻率、良好的抗紫外线性能、高电荷保持率,以及响应快速的特点。
为达到上述第一个目的,本发明采用下述技术方案:
一种液晶组合物,包含一种或多种结构式如式I-1所示的化合物和/或一种或多种结构式如式I-2所示的化合物、一种或多种结构式如式II所示的化合物和一种或多种结构式如式III所示的化合物:
其中,
R1、R2、R3、R5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,并且所述R1、R2、R3和R5所示基团中任意一个或多个不相连的CH2可各自独立地被环戊基、环丁基、环丙基或氧取代;
R4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,并且所述R4所示基团中任意一个或多个不相连的CH2可被环戊基、环丁基或环丙基取代;
Z1表示单键、-CH2CH2-、-CH2O-或-CF2O-;
X1表示F、氟代烷基、氟代烷氧基、氟代烯基或氟代烯氧基;
X2、X3、X4各自独立地表示H、F、氟代烷基、氟代烷氧基、氟代烯基、氟代烯氧基或甲基;
本发明中,上述液晶组合物包含一种或多种结构式如式I-1所示的化合物、一种或多种结构式如式II所示的化合物和一种或多种结构式如式III所示的化合物;或者包含一种或多种结构式如式I-2所示的化合物、一种或多种结构式如式II所示的化合物和一种或多种结构式如式III所示的化合物;或者包含一种或多种结构式如式I-1所示的化合物、一种或多种结构式如式I-2所示的化合物、一种或多种结构式如式II所示的化合物和一种或多种结构式如式III所示的化合物。
本发明中,式I-1所示的化合物、式I-2所示的化合物相比于与其具有相近的三联苯结构的液晶化合物具有更低的旋转粘度,能够提高液晶组合物的响应速度;式II所示的化合物在液晶组合物中的作为稀释剂,能够降低液晶组合物的旋转粘度,提高响应速度;、式III所示的化合物为正介电各向异性,通过调节式Ⅲ所示化合物的质量百分比含量,调节液晶组合物的驱动电压。
优选地,所述液晶组合物中,所述结构式如式I-1和/或式I-2所示的化合物的质量百分比含量为1~25%,优选为5~15%;所述结构式如式II所示的化合物的质量百分比含量为10~70%,优选为20~60%;所述结构式如式III所示的化合物的质量百分比含量为1~60%,优选为20~50%。
优选地,所述结构式如式II所示的化合物的结构式具体选自下述式II-1至II-13中的一种或多种:
其中,
R3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,并且所述R3所示基团中任意一个或多个不相连的CH2可被环戊基、环丁基、环丙基或氧取代;
R4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,并且所述R4所示基团中任意一个或多个不相连的CH2可被环戊基、环丁基或环丙基取代。
优选地,所述结构式如式III所示的化合物的结构式具体选自下述式III-1至III-47中的一种或多种:
其中,R5、R6各自独立地表示碳原子数为1-5的烷基、氟取代的碳原子数为1-5的烷基、碳原子数为1-5的烷氧基、氟取代的碳原子数为1-5的烷氧基、碳原子数为2-5的链烯基、氟取代的碳原子数为2-5的链烯基、碳原子数为3-5的链烯氧基或氟取代的碳原子数为3-5的链烯氧基;
(F)表示F或H。
优选地,所述液晶组合物为正介电各向异性液晶组合物,其还包含一种或多种式IV所示化合物:
其中,R7、R8表示碳原子数为1-10的烷基、碳原子数为1-10的烷氧基、碳原子数为2-10的链烯基或碳原子数为3-8的链烯氧基;且所述R7和R8所示基团中任一个或多个CH2可各自独立地被环戊基、环丁基或环丙基取代;
P表示1或2。
本发明中,式IV所示的化合物具有低的粘度和高的清亮点,大的弹性常数,介电各项异性接近零,为中性化合物,应用于液晶组合物中可以提高液晶组合物的清亮点。
优选地,所述液晶组合物中,所述结构式如式IV所示的化合物的质量百分比含量为1~40%,优选为5~20%。
优选地,所述结构式如式IV所示的化合物的结构式具体选自下述式IV-1至IV-6中的一种:
R7、R8表示碳原子数为1-5的烷基、碳原子数为1-5的烷氧基、碳原子数为2-5的链烯基或碳原子数为3-8的链烯氧基,且所述R7和R8所示基团中任一个或多个CH2可各自独立地被环戊基、环丁基或环丙基取代。
优选地,所述液晶组合物为正介电各向异性液晶组合物,所述液晶组合物还包含一种或多种式Ⅴ所示的化合物:
其中,R9、R10各自独立地表示碳原子数为1-10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,且所述R9和R10中任一个或多个CH2可各自独立地被环戊基、环丁基或环丙基取代;
Z3、Z4各自独立地表示单键、-CH2CH2-或-CH2O-;
m表示1或2;n表示0、1或2。
本发明中,式V所示化合物具有大的垂直介电常数,能够提高液晶组合物的透过率。
优选地,所述液晶组合物中,所述结构式如式V所示的化合物的质量百分比含量为1~20%,优选为5~15%。
优选地,所述结构式如式V所示的化合物的结构式具体选自下述式V-1至V-11中的一种:
其中,R9、R10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,且所述R9和R10所示基团中任一个或多个CH2可各自独立地被环戊基、环丁基或环丙基取代。
优选地,所述液晶组合物为正介电各向异性液晶组合物,所述液晶组合物还包含一种或多种式VI所示的化合物
其中,R11、R12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,且所述R11和R12所示基团中任一个或多个CH2可各自独立地被环戊基、环丁基或环丙基取代;
Lx表示CH2、CH2CH2、O、S、CH2O、OCH2、CH2S、SCH2或CF2。
本发明中,式VI示化合物相对于式Ⅴ所示化合物具有更大的垂直介电常数,能够进一步提高液晶组合物的透过率,但其旋转粘度相对于式Ⅴ所示化合物也更大,会降低液晶组合物的响应速度。
优选地,所述液晶组合物中,所述结构式如式VI所示的化合物的质量百分比含量为1~15%,优选为2~10%。
液晶组合物各成分的不同比例,会表现出略有差异的性能,比如介电各向异性Δε、光学各向异性Δn、液晶的向列相转化为液体的转变温度点Cp、低温下稳定性都会有所差异,可以应用于不同类型的显示器件,但是相同的特点是其旋转粘度γ1较低。应用于液晶显示器件,可以实现快速响应。
优选地,本发明的液晶组合物中还可以加入各种功能的掺杂剂;所述液晶组合物中,以质量百分比计,所述掺杂剂含量优选在0.01-1%之间。
优选地,所述掺杂剂选自抗氧化剂、紫外线吸收剂和手性剂中的一种或多种。
优选地,所述抗氧化剂选自下述结构式所示化合物中的一种或多种:
其中,S表示1-10的整数。
优选地,所述紫外线吸收剂选自下述结构式所示化合物中的一种或多种:
其中,S表示1-10的整数。
优选地,所述手性剂为左旋手性剂或右旋手性剂;进一步地,所述手性剂的结构式选自下述结构式所示化合物中的一种或多种:
为达到上述第二个目的,本发明采用下述技术方案:
一种包含上述液晶组合物的液晶显示元器件。可以理解,所述液晶显示元器件包括液晶显示元件和液晶显示器件。液晶显示元件可为有源矩阵寻址液晶显示元件或无源矩阵显示元件;液晶显示器件可为有源矩阵寻址液晶显示器或无源矩阵显示器。
优选地,所述有源矩阵寻址液晶显示元件为VA-TFT或IPS-TFT液晶显示元件。
优选地,所述有源矩阵寻址液晶显示器件为VA-TFT或IPS-TFT液晶显示器件。
本发明的有益效果如下:
本发明所提供的液晶组合物具有较低的粘度,可以实现快速响应,同时具有适中的介电各向异性Δε、适中的光学各向异性Δn、高的对热和光的稳定性。包含本发明所提供的液晶组合物的液晶显示元器件具有较宽的向列相温度范围、合适的双折射率各向异性、非常高的电阻率、良好的抗紫外线性能、高电荷保持率,以及响应快速的特点。
具体实施方式
为了更清楚地说明本发明,下面结合优选实施例对本发明做进一步的说明。本领域技术人员应当理解,下面所具体描述的内容是说明性的而非限制性的,不应以此限制本发明的保护范围。
本发明中,制备方法如无特殊说明则均为常规方法。所用的原料如无特别说明均可从公开的商业途径获得或根据现有技术制得,所述百分比如无特殊说明均为质量百分比,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,Δn=ne-no,其中,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),的测试仪器为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°。
本发明中,液晶组合物的制备所用的设备和仪器为:
(1)电子精密天平(精确度0.1mg);
(2)不锈钢烧杯:用于称量液晶单体;
(3)勺子:用于加入液晶单体;
(4)磁力转子:用于搅拌;
(5)控温电磁搅拌器。
液晶组合物的制备方法包括以下步骤:
(1)将所用液晶单体按顺序摆放整齐;
(2)把不锈钢烧杯放置在天平上,用小勺将液晶单体盛入不锈钢烧杯中;
(3)依次按所需重量添加液晶单体;
(4)把加好料的不锈钢烧杯放置在磁力搅拌仪器上加热融化;
(5)待不锈钢烧杯中混合物大部份融化后,往不锈钢烧杯中加入一颗磁力转子,将液晶混合物搅拌均匀,冷却到室温后即得液晶组合物。
本发明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1、表2。
表1环结构的对应代码
表2端基与链接基团的对应代码
举例:
以下采用以下具体实施例来对本发明进行说明:
实施例1
液晶组合物的配方及相应的性能如下表3所示。
表3实施例1液晶组合物的配方及相应的性能
结论:实施例1液晶组合物具有较低的粘度,可以实现快速响应,同时具有适中的介电各向异性Δε、适中的光学各向异性Δn、高的对热和光的稳定性。
实施例2
液晶组合物的配方及相应的性能如下表4所示。
表4实施例2液晶组合物的配方及相应的性能
结论:实施例2液晶组合物具有较低的粘度,可以实现快速响应,同时具有适中的介电各向异性Δε、适中的光学各向异性Δn、高的对热和光的稳定性。
实施例3
液晶组合物的配方及相应的性能如下表5所示。
表5实施例3液晶组合物的配方及相应的性能
结论:实施例3液晶组合物具有较低的粘度,可以实现快速响应,同时具有适中的介电各向异性Δε、适中的光学各向异性Δn、高的对热和光的稳定性。
实施例4
液晶组合物的配方及相应的性能如下表6所示。
表6实施例4液晶组合物的配方及相应的性能
对比例1
液晶组合物的配方及相应的性能如下表7所示。
表7对比例1液晶组合物的配方及相应的性能
结论:与实施例4相比,对比例1将结构式为式I-1和式I-2的化合物替换为结构式为PGP-3-5和PGP-2-3的式IV类化合物。实施例4具有更低的旋转粘度γ1,更高的清亮点Cp,和更高的介电各向异性Δε,说明虽然结构式为PGP-3-5和PGP-2-3的化合物与式I-1和式I-2的化合物具有相似的结构,但是式I-1和式I-2的化合物具有更低的旋转粘度、更高的清亮点和更高的介电各向异性,使得包含式I-1和式I-2化合物的实施例4具有更低的驱动电压、更宽的使用温度范围和更快的响应速度。
实施例5
液晶组合物的配方及相应的性能如下表8所示。
表8实施例5液晶组合物的配方及相应的性能
对比例2
液晶组合物的配方及相应的性能如下表9所示。
表9对比例2液晶组合物的配方及相应的性能
结论:与实施例5相比,对比例2将结构式为式I和式I-2的化合物替换为结构式为PGP-4-F和PGP-5-F的式III类化合物。实施例5具有更低的旋转粘度γ1,更高的介电各向异性Δε,而且对比例2在0℃环境下储存100小时后出现晶析,实施例5在相同条件下未出现晶析。说明虽然结构式为PGP-4-F和PGP-5-F的化合物与式I-1和式I-2的化合物具有相似的结构,但是式I-1和式I-2的化合物具有更低的旋转粘度、更高的介电各向异性,并且经过环戊基取代的式I-1化合物具有更好的互溶性。因此,包含式I-1和式I-2化合物的实施例5具有更低的驱动电压、更快的响应速度和更好的低温互溶性。
实施例6
液晶组合物的配方及相应的性能如下表10所示。
表10实施例6液晶组合物的配方及相应的性能
对比例3
液晶组合物的配方及相应的性能如下表11所示。
表11对比例3液晶组合物的配方及相应的性能
结论:与实施例6相比,对比例3将结构式为式I-1的化合物替换为结构式为PGU-V2-F和PGU-4-F的式III类化合物。实施例6与对比例3的介电各向异性相当,却具有更高的光学各向异性Δn,更高的清亮点Cp,更低的旋转粘度γ1。由于液晶显示器件的响应速度与盒厚有关,盒厚越小,响应速度越快。因此,降低液晶显示器件的盒厚是提高响应速度的方法之一。在相同延迟量设计的基础上,降低液晶显示器件的盒厚,必然需要提高液晶组合物的光学各向异性,所以具有更高的光学各向异性Δn的实施例6更适合目前快速响应液晶显示器件低盒厚的要求。
实施例7
液晶组合物的配方及相应的性能如下表12所示。
表12实施例7液晶组合物的配方及相应的性能
结论:实施例7中添加剂的含量是以实施例7的液晶组合物中式I、式Ⅱ、式Ⅲ式V所示的化合物的总含量为100%作为基准来计算得到的。由于式V所示化合物具有相对于式Ⅲ更大的垂直介电常数,通过在液晶组合物中添加式V所示化合物,能够提高液晶组合物的垂直介电常数,从而提高液晶组合物的透过率。并且,通过抗氧化添加剂,提高液晶组合物的稳定性。
实施例8
液晶组合物的配方及相应的性能如下表13所示。
表13实施例8液晶组合物的配方及相应的性能
结论:式Ⅵ所示化合物相对于式Ⅴ所示化合物具有更大的垂直介电常数,能够进一步提高液晶组合物的透过率,但其旋转粘度相对于式Ⅴ所示化合物也更大,使用过多会降低液晶组合物的响应速度。
实施例9
液晶组合物的配方及相应的性能如下表14所示。
表14实施例9液晶组合物的配方及相应的性能
实施例10
液晶组合物的配方及相应的性能如下表15所示。
表15实施例10液晶组合物的配方及相应的性能
实施例11
液晶组合物的配方及相应的性能如下表16所示。
表16实施例11液晶组合物的配方及相应的性能
实施例12
液晶组合物的配方及相应的性能如下表17所示。
表17实施例12液晶组合物的配方及相应的性能
结论:由以上实施例可以看出:本发明实施例提供的液晶组合物具有较低的旋转粘度γ1,用于液晶显示,可以实现快速响应,同时具有适中的介电各向异性Δε、适中的光学各向异性Δn、高的对热的稳定性。尤其适合于TN、IPS、VA模式用液晶材料。
显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定,对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动,这里无法对所有的实施方式予以穷举,凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。
Claims (2)
1.一种液晶组合物,其特征在于,所述液晶组合物的配方如下所示:
或者,
再或者是,
其中,环结构的对应代码为
端基与链接基团的对应代码为:
2.一种液晶显示元器件,其特征在于,所述液晶显示元器件包含如权利要求1所述的液晶组合物。
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