CN110484279B - 液晶组合物及液晶显示元件、液晶显示器 - Google Patents
液晶组合物及液晶显示元件、液晶显示器 Download PDFInfo
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- CN110484279B CN110484279B CN201810457277.5A CN201810457277A CN110484279B CN 110484279 B CN110484279 B CN 110484279B CN 201810457277 A CN201810457277 A CN 201810457277A CN 110484279 B CN110484279 B CN 110484279B
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 82
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 150000001875 compounds Chemical class 0.000 claims abstract description 78
- 125000004432 carbon atom Chemical group C* 0.000 claims description 105
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 21
- 125000003342 alkenyl group Chemical group 0.000 claims description 18
- 125000003545 alkoxy group Chemical group 0.000 claims description 13
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 11
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 11
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 4
- 230000005611 electricity Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 210000002858 crystal cell Anatomy 0.000 description 3
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了液晶组合物及液晶显示元件、液晶显示器，所述液晶组合物包含有一种或多种式Ⅰ所示化合物、一种或多种式II所示化合物、一种或多种式III所示化合物以及一种或多种式Ⅳ所示化合物，
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及其含有该液晶组合物的液晶显示元件、液晶显示器。
背景技术
目前，液晶显示技术已经成熟应用于各类显示器件中，成为当今信息显示领域的主流产品，在仪器仪表、电脑、电视、手机等各种显示器中得到了广泛的应用。根据液晶显示方式的不同，液晶显示器件可以分为扭曲向列相(TN)模式、超扭曲向列相(STN)模式、共面(IPS)模式、垂直配向(VA)模式等多种模式。
薄膜晶体管显示器(TFT-LCD)也迅速成长为主流显示器，这与它具有的优点是分不开的。
其优点有：
1)低粘度，满足快速响应需求；
2)高电压保持率(VHR)，这就需要液晶材料的电阻率高，一般会达到1013Ω·cm；
3)较低的阈值电压，可以满足低电压驱动，实现低功耗环保性能；
4)与TFT-LCD相匹配的光学各项异性(Δn)，消除彩虹效应，获得较好的对比度与视角性能。
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低的要求要缓和一些。
液晶化合物的粘度，尤其是旋转粘度γ1直接影响液晶加电后的响应时间，不管是上升时间(ton)还是下降时间(toff)，都与液晶的旋转粘度γ1成正比关系，上升时间(ton)由于还与液晶盒和驱动电压有关，可以通过加大驱动电压的方法与降低液晶盒盒厚来调节；而下降时间(toff)与驱动电压无关，主要是与液晶的弹性常数和液晶盒盒厚有关，盒厚的趋薄会降低下降时间(toff)，而不同显示模式下，液晶分子的运动方式不一样，TN、IPS、VA三种模式分别与平均弹性常数K、扭曲弹性常数、弯曲弹性常数成反比关系。
TFT-LCD面板的透过率是指背光源透过TFT-LCD面板前后的光强之比。TFT-LCD是透过率只有3％～10％的低效率器件，当背光源的亮度为100时，从背光源入射的光通过面板的各层后，大部分被吸收，最终透过面板后的光亮度只有5，也就是说透过率只有5％，只有一少部分光可以有效的利用、被人眼捕获。
如果可以对液晶的穿透率进行提高，那么就可以有效增加TFT-LCD面板的透过率，可以使得更多的光有效被利用；另一方面，也可以降低背光强度，从而实现节省能耗的目的，延长设备的使用时间。
发明内容
本发明需要解决的技术问题是，提供一种液晶组合物，其光和热的稳定性好，具有较低的粘度，较快的响应速度，可以得到较为宽泛的折射率、较高的清亮点(很宽的使用温度范围)，尤其是具有较高光穿透率的液晶组合物、具有较高的亮度或是具有节能省电的效果的液晶显示元件或显示器。
为了解决以上技术问题，本发明提供了一种液晶组合物，包含有一种或多种式Ⅰ所示化合物、一种或多种式II所示化合物、一种或多种式III所示化合物以及一种或多种式Ⅳ所示化合物，
其中，
R1、R2、R3、R5、R6、R7各自独立地表示碳原子数为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R1、R3所示基团中任意一个或多个不相连的CH2任选被环戊基、环丁基、环丙基、-O-替代；
R8表示F、CF3、OCF3、OCHF2或OCH2F；
R4表示F、CF3、OCF3、OCHF2或OCH2F；
m、p、w各自独立地表示1、2或3；
n、q各自独立地表示0或1；
e表示0、1、2或3。
本发明的液晶组合物中，优选的是，所述一种或多种式Ⅰ所示化合物为式Ⅰ1-Ⅰ14所示化合物中的一种或多种化合物；所述一种或多种式Ⅱ所示化合物为式Ⅱ1至Ⅱ14所示化合物中的一种或多种化合物；所述一种或多种式III所示化合物为式III1至III5所示化合物中的一种或多种化合物；所述一种或多种式Ⅳ所示化合物为式Ⅳ1至Ⅳ24所示化合物中的一种或多种化合物，
其中，R11、R31各自独立地表示碳原子数为1-6的烷基；
R21表示碳原子数为1-5的烷基；
R51、R61各自独立地表示碳原子数为1-6的烷基、碳原子数为1-6的烷氧基、碳原子数为2-6的链烯基或碳原子数为3-6的链烯氧基；
R71表示碳原子数为1-6的烷基、或碳原子数为2-6的烯基。
式Ⅰ所示化合物同时具有较大的液晶分子长轴平行方向、垂直方向的介电常数而长轴平行方向、垂直方向的介电各向异性(Δε)较小。式Ⅱ所示化合物同时具有较大的液晶分子长轴平行方向、垂直方向的介电各向异性，长轴平行方向、垂直方向的介电各向异性(Δε)较大。式IⅤ所示液晶化合物的分子长轴平行方向、垂直方向的介电常数较大，同时长轴平行方向、垂直方向的介电各向异性(Δε)较大。式Ⅰ、式Ⅱ和式IⅤ所示化合物的搭配组合使用，可以显著提升混合组合物的垂直方向的介电常数，同时液晶组合物的Δε不会变小，从而能够大幅提升液晶组合物的穿透率。式III所示化合物具有低的旋转粘度，还具有较高的清亮点(Cp)，与式Ⅰ、式Ⅱ和式Ⅴ所示化合物一起组合使用，液晶组合物的旋转粘度很低，响应速度快。
本发明的液晶组合物中，优选的是，所述一种或多种式Ⅰ所示化合物的总质量百分比含量为1-40％，所述一种或多种式Ⅱ所示化合物的总质量百分比含量为1-40％，所述一种或多种式III所示化合物的总质量百分比含量为1-80％，所述一种或多种式Ⅳ所示化合物的总质量百分比含量为0.5-30％。
本发明的液晶组合物中，优选还可以包含一种或多种式Ⅴ所示化合物，
其中，R9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所示基团中任意一个或多个CH2任选被环戊基、环丁基或环丙基替代；
r表示0、1、2或3；
Z1、Z2各自独立地表示单键、-CF2O-、-CH2CH2-或-CH2O-；
Y2表示F、氟取代的碳原子数为1-5的烷基、氟取代的碳原子数为1-5的烷氧基、氟取代的碳原子数为2-5的链烯基或氟取代的碳原子数为3-8的链烯氧基。
式Ⅴ所示化合物具有较大的介电各向异性(Δε)，在本发明的液晶组合物中添加式V所示化合物有利于提升液晶组合物的介电各向异性(Δε)，降低液晶的驱动电压。添加有式V所示化合物的液晶组合物可以适用于正性TN、IPS、FFS模式使用，也可以适用PSA-正性TN、IPS、FFS模式。
本发明的液晶组合物中，在添加式V所示的化合物的情况下，优选的是，式V所示化合物的总添加量为5-40％的范围。本发明的液晶组合物中，在含有前述的一种或多种式Ⅴ所示化合物的情况下，所述一种或多种式Ⅴ所示化合物优选选自Ⅴ0-Ⅴ25所示的化合物组成的组。
其中，R9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所示基团中任意一个或多个CH2任选被环戊基、环丁基或环丙基替代；
(F)表示H或F；
式V23中，X1、X2各自独立地表示H或F，Y2表示F、氟取代的碳原子数为1-5的烷基、氟取代的碳原子数为1-5的烷氧基、氟取代的碳原子数为2-5的链烯基或氟取代的碳原子数为3-8的链烯氧基。
本发明的液晶组合物中，还可以包含一种或多种式Ⅵ所示的化合物，
其中，R10、R12各自独立地表示碳原子数为1-10的烷基、氟、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R10、R12所示基团中任意一个或多个CH2任选被环戊基、环丁基或环丙基替代；
Z3、Z4各自独立地表示单键、-CH2CH2-或CH2O-；
a表示1、2或3；
b表示0或1。
本发明的液晶组合物中，在包含一种或多种式ⅤI所示的化合物的情况下，所述一种或多种式Ⅵ所示的化合物优选选自Ⅵ1-Ⅵ12化合物。
其中，R10、R12各自独立地表示碳原子数为1-10的烷基、氟、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R10、R12所示基团中任意一个或多个CH2任选被环戊基、环丁基或环丙基替代。
本发明的液晶组合物中，含有式Ⅵ所示化合物的总添加量优选在0-60％的范围，进一步优选为5-30％。
本发明的液晶组合物中，还可以包含一种或多种式Ⅶ所示的化合物。
其中，R13、R14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R13、R14所示基团中任意一个或多个CH2任选被环戊基、环丁基或环丙基替代；
W表示-O-、-S-或-CH2O-。
本发明的液晶组合物中，还可以包含一种或多种式Ⅷ所示化合物。
其中，R15表示碳原子数为1-5的烷基、碳原子数为2-5的链烯基；
R16表示F原子、碳原子数为1-5的烷基、碳原子数为1-5的烷氧基或碳原子数为2-5的链烯基，且R15、R16所示基团中任意一个或多个CH2任选被环戊基、环丁基或环丙基替代；
n表示0或1；
(F)表示H或F。
本发明还涉及包含前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，或者无源矩阵显示元件或显示器。
显示元件或显示器可以是TN、ECB、VA、IPS、FFS、PS-TN、PS-VA、PS-IPS、PS-FFS、PA-VA、PA-IPS、PA-FFS、PI-less VA、PI-less IPS、PI-less-FFS LCD模式等中的任意一种模式。
具体实施方式
下面结合具体实施例对本发明作进一步阐述，但本发明并不限于以下实施例。液晶组合物中的化合物的合成方法如无特别说明均为常规方法。合成液晶组合物的原材料如无特别说明均能从公开商业途径得到。
反应过程一般通过TLC监控反应的进程，反应结束的后处理一般是水洗、提取、合并有机相后干燥、减压下蒸除溶剂，以及重结晶、柱层析，本领域的技术人员都能够按照下面的描述来实现本发明。
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；
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；
Tr(％)表示透过率，Tr(％)＝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°，因ε⊥与Tr存在正相关性，所以考察透过率时，可用ε⊥作为考察指标来指证。
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：
实施例1：
实施例2：
将液晶组合物灌入测试盒进行测试得到：实施例1的透过率为6.5％，实施例2的透过率为7.3％，较实施例1提高了12％。
实施例3：
实施例4：
实施例5：
实施例6：
实施例7：
实施例8：
实施例9：
实施例10：
实施例11：
实施例12：
本发明实施例通过使用式Ⅰ、式Ⅱ和式IⅤ所示化合物的搭配组合使用，可以显著提升液晶组合物的垂直方向的介电各向异性，同时液晶组合物的Δε不会变小，从而能够大幅提升液晶组合物的穿透率。式III所示化合物具有低的旋转粘度，还具有较高的清亮点(Cp)，与式Ⅰ、式Ⅱ和式Ⅴ所示化合物搭配组合使用，液晶组合物的旋转粘度降低，响应速度加快。本发明液晶组合物光和热的稳定性好，具有较低的粘度，较快的响应速度，可以得到较为宽泛的折射率、较高的清亮点(很宽的使用温度范围)，尤其是液晶组合物具有较高的光的穿透率，因而显示器件具有较高的亮度或是具有节能省电的效果。
Claims (6)
1.一种液晶组合物，其特征在于：所述液晶组合物包含有一种式Ⅰ1-a所示化合物、一种式Ⅰ5-a所示化合物、一种式Ⅰ11-a所示化合物、一种或多种式II5所示化合物、一种或多种式II8所示化合物、一种或多种式Ⅲ1所示化合物、一种或多种式Ⅲ3所示化合物、一种或多种式Ⅲ4所示化合物、一种式Ⅲ-a所示化合物、一种式Ⅲ-b所示化合物以及一种或多种式Ⅳ5所示化合物，还包含一种式V15所示化合物，
其中，
R11表示碳原子数为3的烷基；
R31表示碳原子数为3-5的烷基；
R51表示碳原子数为3的烷基或碳原子数为2-6的链烯基；
R61表示碳原子数为1-6的烷基、碳原子数为1-6的烷氧基、碳原子数为2-6的链烯基或碳原子数为3-6的链烯氧基；
R71表示碳原子数为1-6的烷基或碳原子数为2-6的烯基；R9表示碳原子数为3的烷基；
所述液晶组合物中，所述一种式Ⅰ1-a所示化合物、一种式Ⅰ5-a所示化合物和一种式Ⅰ11-a所示化合物的总质量百分比含量为9％，所述一种或多种式II5所示化合物和一种或多种式II8所示化合物的总质量百分比含量为5％，所述一种或多种式Ⅲ1所示化合物、一种或多种式Ⅲ3所示化合物、一种或多种式Ⅲ4所示化合物一种式Ⅲ-a所示化合物和一种式Ⅲ-b所示化合物的总质量百分比含量为80％，所述一种或多种式Ⅳ5所示化合物的总质量百分比含量为1％。
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式Ⅵ所示的化合物
其中，R10、R12各自独立地表示碳原子数为1-10的烷基、氟、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R10、R12所示基团中任意一个或多个CH2任选被环戊基、环丁基或环丙基替代；
Z3、Z4各自独立地表示单键、-CH2CH2-或CH2O-；
a表示1、2或3；
b表示0或1。
3.根据权利要求2所述的液晶组合物，其特征在于，所述一种或多种式Ⅵ所示的化合物选自Ⅵ1-Ⅵ8和Ⅵ10-Ⅵ12所示化合物组成的组，
其中，R10、R12各自独立地表示碳原子数为1-10的烷基、氟、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R10、R12所示基团中任意一个或多个CH2任选被环戊基、环丁基或环丙基替代。
4.根据权利要求1～3的任一项所述的液晶组合物，其特征在于，所述液晶组合物还包含一种或多种式Ⅶ所示的化合物，
其中，R13、R14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R13、R14所示基团中任意一个或多个CH2任选被环戊基、环丁基或环丙基替代；
W表示-O-、-S-或-CH2O-。
5.根据权利要求1～3的任一项所述的液晶组合物，其特征在于，还包含一种或多种式Ⅷ所示化合物，
其中，R15表示碳原子数为1-5的烷基或碳原子数为2-5的链烯基；
R16表示F原子、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，且R15、R16所示基团中任意一个或多个CH2任选被环戊基、环丁基或环丙基替代；
s表示0或1；
(F)表示H或F。
6.一种液晶显示元件或液晶显示器，其包含权利要求1-5任一项所述的液晶组合物，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，或者无源矩阵显示元件或显示器。
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