CN112920811B - 液晶组合物、液晶显示元件、液晶显示器 - Google Patents

液晶组合物、液晶显示元件、液晶显示器 Download PDF

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CN112920811B
CN112920811B CN201911397807.2A CN201911397807A CN112920811B CN 112920811 B CN112920811 B CN 112920811B CN 201911397807 A CN201911397807 A CN 201911397807A CN 112920811 B CN112920811 B CN 112920811B
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liquid crystal
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crystal composition
carbon atoms
crystal display
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CN112920811A (zh
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张伟
康素敏
王小龙
乔云霞
崔青
温刚
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Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
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Priority to US17/251,041 priority patent/US11441072B2/en
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Abstract

本发明公开了一种介电负性的液晶组合物,包含该液晶组合物的液晶显示元件、液晶显示器,属于液晶显示领域。本公开的液晶组合物,包含式Ⅰ所示化合物、式Ⅱ所示化合物、两种以上的式Ⅲ所表示的化合物以及一种或多种式Ⅳ所表示的化合物,本发明的液晶组合物具有高的介电各向异性,高的弹性常数K,低旋转粘度,可以用于开发大介电、快速响应的液晶显示元件或液晶显示器。

Description

液晶组合物、液晶显示元件、液晶显示器
技术领域
本公开属于液晶显示领域,更具体地,涉及液晶组合物及包含该液晶组合物的液晶显示元件、液晶显示器。
背景技术
液晶显示元件根据显示方式分为下列模式:扭曲向列相(TN)模式、超扭曲向列相(STN)模式、共面模式(IPS)、垂直配向(VA)模式。无论何种显示模式均需要液晶组合物有以下特性:
(1)化学、物理性质稳定;(2)粘度低;(3)具有合适的介电△ε;(4)合适的折射率△n;(5)与其他液晶化合物的互溶性好。
早期商用的TFT-LCD产品基本采用了TN显示模式,其最大问题是视角窄。随着产品尺寸的增加,特别是在TV领域的应用,具有广视野角特点的IPS显示模式、VA显示模式依次被开发出来并加以应用。
另外,FFS模式、IPS模式、VA模式等的显示元件所用的液晶介质,本身并不完美,对于显示器件所用的液晶材料,要求具有①低的驱动电压:液晶材料具有适当的负介电各向异性和弹性系数K;②快速响应:液晶材料具有适当的旋转粘度γ1和弹性系数K;③高可靠性:高的电荷保持率,高的比电阻值,优良的耐高温稳定性及对UV光或常规的背光照明来照射的稳定性有严格要求等的特点。
含有介电各向异性的绝对值大的液晶组合物的液晶显示元件能够降低基础电压值、降低驱动电压,并能进一步降低消耗电功率。较低阈值电压的液晶组合物的液晶显示元件能够有效的降低显示的功耗,特别是在消耗品,类似手机,平板电脑等便携式电子产品有更长的续航时间。
同时随着LCD产品技术更新速度越来越快,对LCD产品的响应速度要求也越来越高,除了器件厂商通过降低盒厚d来提升响应速度外,实际应用中,我们的液晶材料的响应速度也需要得到更高的提升。现有技术液晶材料的响应速度受限于液晶的旋转粘度γ1/弹性常数K,因此,需要想尽方法去降低液晶介质的旋转粘度γ1同时提升弹性常数K来达到加快响应时间。而在实际研究中发现,旋转粘度和弹性常数是一对较为矛盾的参数,降低旋转粘度的同时会引起弹性常数的下降,达不到降低响应时间的目标。因此,开发更快的响应速度的液晶组合物就成了比较棘手的问题。
发明内容
为了解决上述存在的至少一个问题,本发明人等进行了深入研究后发现,本公开的液晶组合物具有高的介电各向异性,高的K值、低的旋转粘度,从而完成了本公开。
为达到上述目的,本公开采用下述技术方案:
本公开提供液晶组合物,其中包含式Ⅰ所示化合物、式Ⅱ所示化合物、两种以上的式Ⅲ所表示的化合物、一种或多种式Ⅳ所表示的化合物,
Figure BDA0002346773550000021
其中,R1、R2、R3、R4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的烷氧基或氟取代的碳原子数为1~5的烷氧基;
R1、R2、R3、R4所示基团中任意一个或多个不相连的-CH2-任选被亚环戊基、亚环丁基或亚环丙基取代;
m表示1或2。
本公开的液晶组合物在提升组合物的介电各向异性和K值的同时有效控制了组合物旋转粘度的增长,实现了组合物具有高介电各向异性,高K值及低旋转粘度的特性。
本公开还提供液晶显示元件,其包含本公开的液晶组合物,所述液晶显示元件为有源矩阵寻址显示元件或者无源矩阵寻址显示元件。
本公开还提供液晶显示器,其包含本公开的液晶组合物,所述液晶显示器为有源矩阵寻址显示器或者无源矩阵寻址显示器。
具体实施方式
[液晶组合物]
本公开的液晶组合物包含式Ⅰ所示化合物、式Ⅱ所示化合物、两种以上的式Ⅲ所表示的化合物、一种或多种式Ⅳ所表示的化合物:
Figure BDA0002346773550000031
其中,R1、R2、R3、R4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的烷氧基或氟取代的碳原子数为1~5的烷氧基;
R1、R2、R3、R4所示基团中任意一个或多个不相连的-CH2-任选被亚环戊基、亚环丁基或亚环丙基取代;
m表示1或2。
本公开的技术方案具有高介电各向异性、高K值、低旋转粘度,能够降低液晶组合物的阈值电压、响应时间。
作为前述碳原子数为1~5的烷基,可以列举出例如,甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基等。
作为前述碳原子数为1~5的烷氧基,可以列举出例如,甲氧基、乙氧基、丙氧基等。
前述的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的烷氧基中的“氟取代”可以是单氟取代,或者二氟取代、三氟取代等多氟取代,也可以是全氟取代,对氟的取代数没有特别的限定。例如,作为氟取代的碳原子数为1~5的烷基,可以列举出氟代甲基、二氟甲基、三氟甲基、1-氟代乙基、2-氟代乙基、1,2-二氟乙基、1,1-二氟乙基以及三氟甲氧基等但不限于此。
本公开的液晶组合物中,优选地,前述式Ⅲ所示的化合物选自下述式Ⅲ-1至Ⅲ-9所示的化合物组成的组:
Figure BDA0002346773550000041
Figure BDA0002346773550000051
前述的式Ⅲ所示化合物具有负介电各项异性,通过在本公开的液晶组合物中含有式Ⅲ所示化合物,可以调节液晶组合物的驱动电压。
本公开的液晶组合物中,优选地,前述式Ⅳ所示的化合物选自下述式Ⅳ-1至Ⅳ-6所示的化合物组成的组:
Figure BDA0002346773550000052
其中,R31、R41各自独立地表示碳原子数为1~5的烷基或碳原子数为1~5的烷氧基。
前述的式Ⅳ所示化合物具有负介电各项异性,通过在本公开的液晶组合物中含有式Ⅳ所示化合物,可以调节液晶组合物的驱动电压。
本公开的液晶组合物,优选地,前述液晶组合物还包含一种或多种式Ⅴ所示化合物:
Figure BDA0002346773550000061
其中,R5、R6各自独立地表示碳原子数为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;
Figure BDA0002346773550000062
表示
Figure BDA0002346773550000063
通过在本公开的液晶组合物中含有式Ⅴ所示化合物,能够增大液晶组合物的光学各向异性和提高液晶组合物的清亮点。
本公开的液晶组合物,优选地,前述液晶组合物还包含一种或多种式Ⅵ所示化合物:
Figure BDA0002346773550000064
其中,R7、R8各自独立地表示碳原子数为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;
X1、Y1各自独立地表示H或F。
通过在本公开的液晶组合物中含有式Ⅵ所示化合物,能够增大液晶组合物的光学各向异性和提高液晶组合物的清亮点。
本公开的液晶组合物,优选地,前述液晶组合物还包含一种或多种式Ⅶ所示化合物:
Figure BDA0002346773550000065
其中,R9、R10各自独立地表示碳原子数为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。
通过在本公开的液晶组合物中含有式Ⅶ所示化合物,能够增大液晶组合物的光学各向异性以搭配更低的盒厚,从而达到更快的响应速度。
本公开的液晶组合物中,优选地,前述式Ⅶ所示化合物选自下述式Ⅶ-1至Ⅶ-7所示的化合物组成的组:
Figure BDA0002346773550000071
本公开的液晶组合物,优选地,前述液晶组合物还包含一种或多种式Ⅷ所示化合物:
Figure BDA0002346773550000072
其中,R11表示碳原子数为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,其中任意一个或多个不相连的-CH2-任选被亚环戊基、亚环丁基或亚环丙基取代;
R12表示碳原子数为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;
W表示O或S。
通过在本公开的液晶组合物中含有式Ⅷ所示化合物,能够增大液晶组合物的介电各向异性和提升液晶组合物的响应速度。
本公开的液晶组合物中,优选地,前述式Ⅷ所示化合物选自下述式Ⅷ-1至Ⅷ-9所示的化合物组成的组:
Figure BDA0002346773550000081
W表示O或S。
本公开的液晶组合物,优选地,前述液晶组合物还包含一种或多种式Ⅸ所示化合物:
Figure BDA0002346773550000091
其中,R13、R14各自独立地表示碳原子数为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;
Figure BDA0002346773550000092
表示
Figure BDA0002346773550000093
X2表示H或F。
通过在本公开的液晶组合物中含有式Ⅸ所示化合物,能够增大液晶组合物的介电各向异性,提升液晶组合物的清亮点。
本公开的液晶组合物中,优选地,前述式Ⅸ所示化合物选自下述式Ⅸ-1至Ⅸ-3所示的化合物组成的组:
Figure BDA0002346773550000094
其中,R13、R14各自独立地表示碳原子数为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。
本公开的液晶组合物,优选地,前述液晶组合物还包含一种或多种除所述式Ⅰ、式Ⅱ所示化合物之外的式Ⅹ所示化合物:
Figure BDA0002346773550000095
其中,R15、R16各自独立地表示碳原子数为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;
Figure BDA0002346773550000101
各自独立地表示
Figure BDA0002346773550000102
通过在本公开的液晶组合物中含有式Ⅹ所示化合物,能够提升液晶组合物的响应速度。
本公开的液晶组合物中,优选地,前述除式Ⅰ、式Ⅱ所示化合物之外的式Ⅹ所示化合物选自下述式Ⅹ-1至Ⅹ-8所示的化合物组成的组:
Figure BDA0002346773550000103
本公开的液晶组合物中,式Ⅰ所示化合物在液晶组合物中的添加量(质量比)为1-50%,优选为20-45%;式Ⅱ所示化合物在液晶组合物中的添加量(质量比)为1-20%,优选为1-15%;式Ⅲ所示化合物在液晶组合物中的添加量(质量比)为1-30%,优选为5-18%;式Ⅳ所示化合物在液晶组合物中的添加量(质量比)为1-45%,优选为5-30%;式Ⅴ所示化合物在液晶组合物中的添加量(质量比)为0-25%,优选为3-15%;式Ⅵ所示化合物在液晶组合物中的添加量(质量比)为0-10%,优选为1-15%;式Ⅶ所示化合物在液晶组合物中的添加量(质量比)为0-30%,优选为5-20%;式Ⅷ所示化合物在液晶组合物中的添加量(质量比)为0-30%,优选为5-20%;式Ⅸ所示化合物在液晶组合物中的添加量(质量比)为0-15%,优选为3-10%;式Ⅹ所示化合物在液晶组合物中的添加量(质量比)为0-45%,优选为0-20%;。
本公开的液晶组合物中,可选的,还可以加入各种功能的掺杂剂,在含有掺杂剂的情况下,掺杂剂的含量优选在液晶组合物中所占的质量百分比为0.01~1.5%,这些掺杂剂可以列举出例如抗氧化剂、紫外线吸收剂、手性剂。
抗氧化剂可以列举出,
Figure BDA0002346773550000111
t表示1~10的整数;
手性剂可以列举出,
Figure BDA0002346773550000112
R表示碳原子数为1-10的烷基;
光稳定剂可以列举出,
Figure BDA0002346773550000113
Z1表示碳数为1~20的亚烷基,所述亚烷基中任意的一个或多个氢任选被卤素取代,任意的一个或多个-CH2-任选被-O-取代;
紫外线吸收剂可以列举出,
Figure BDA0002346773550000121
R表示碳原子数为1-10的烷基。
[液晶显示元件或液晶显示器]
本公开还涉及包含上述任意一种液晶组合物的液晶显示元件或液晶显示器;所述显示元件或显示器为有源矩阵显示元件或显示器或无源矩阵显示元件或显示器。
可选的,所述液晶显示元件或液晶显示器优选有源矩阵液晶显示元件或液晶显示器。
可选的,所述有源矩阵显示元件或显示器为IPS-TFT、FFS-TFT、VA-TFT液晶显示元件或显示器。
包含前述的化合物或液晶组合物的液晶显示元件或液晶显示器,具有较低的阈值电压、较快的响应速度。
实施例
为了更清楚地说明本公开,下面结合优选实施例对本公开做进一步的说明。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,不应以此限制本公开的保护范围。
本说明书中,如无特殊说明,百分比均是指质量百分比,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,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;
K11为扭曲弹性常数,K33为展曲弹性常数,测试条件为:25℃、INSTEC:ALCT-IR1、20微米平行盒;
液晶组合物的制备方法如下:将各液晶单体按照一定配比称量后放入不锈钢烧杯中,将装有各液晶单体的不锈钢烧杯置于磁力搅拌仪器上加热融化,待不锈钢烧杯中的液晶单体大部份融化后,往不锈钢烧杯中加入磁力转子,将混合物搅拌均匀,冷却到室温后即得液晶组合物。
本公开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
Figure BDA0002346773550000131
表2 端基与链接基团的对应代码
Figure BDA0002346773550000132
Figure BDA0002346773550000141
举例:
Figure BDA0002346773550000142
其代码为CC-Cp-V1;
Figure BDA0002346773550000143
其代码为CPY-2-O2;
Figure BDA0002346773550000144
其代码为CCY-3-O2;
Figure BDA0002346773550000151
其代码为COY-3-O2;
Figure BDA0002346773550000152
其代码为CCOY-3-O2;
Figure BDA0002346773550000153
其代码为Sb-CpO-O4;
Figure BDA0002346773550000154
其代码为Sc-CpO-O4。
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
Figure BDA0002346773550000155
Figure BDA0002346773550000161
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
Figure BDA0002346773550000162
Figure BDA0002346773550000171
对比例1
液晶组合物的配方及相应的性能如下表5所示。
表5 对比例1液晶组合物的配方及相应的性能
Figure BDA0002346773550000172
Figure BDA0002346773550000181
将实施例2中的CC-3-V1替换为CC-3-2,作为对比例1,并将对比例1清亮点调至与实施例2相同。与对比例1相比,本发明实施例2的液晶组合物具有适当的清亮点(Cp)、光学各向异性(Δn),同时具有大的介电各向异性(Δε)、旋转粘度(γ1)更低、弹性常数(K)更高,可以用于开发低阈值电压、快速响应的液晶显示器。
实施例3
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3液晶组合物的配方及相应的性能
Figure BDA0002346773550000182
Figure BDA0002346773550000191
对比例2
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2液晶组合物的配方及相应的性能
Figure BDA0002346773550000192
Figure BDA0002346773550000201
将实施例3中的CLY-3-O2等CLY类单体替换为CCY-3-O2等CCY类单体,作为对比例2,并将对比例2清亮点调至与实施例3相同。与对比例2相比,本发明实施例3的液晶组合物具有适当的清亮点(Cp),且介电各向异性(Δε)更大、旋转粘度更低、弹性常数K更高、光学各向异性(Δn)更高,可以用于开发低阈值电压、快速响应液晶显示器。
实施例4
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4液晶组合物的配方及相应的性能
Figure BDA0002346773550000202
Figure BDA0002346773550000211
对比例3
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3液晶组合物的配方及相应的性能
Figure BDA0002346773550000212
Figure BDA0002346773550000221
将实施例4中的COY-3-O2替换为CY-3-O2,其余与实施例4相同,作为对比例3。与对比例3相比,本发明实施例4的液晶组合物具有适当的光学各向异性(Δn)、清亮点(Cp),且介电各向异性(Δε)更高、旋转粘度更低(γ1)、弹性常数(K)值更大,可以用于开发低阈值电压、快速响应的液晶显示器。
实施例5
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5液晶组合物的配方及相应的性能
Figure BDA0002346773550000222
Figure BDA0002346773550000231
对比例4
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4液晶组合物的配方及相应的性能
Figure BDA0002346773550000232
Figure BDA0002346773550000241
将实施例5中的CLY-3-O2、CLY-4-O2替换为CLY-1V-O2、CLY-V2-O2,其余与实施例5相同,作为对比例4。与对比例4相比,本发明实施例5的液晶组合物具有适当的光学各向异性(Δn)、清亮点(Cp),且介电各向异性(Δε)更高、旋转粘度更低(γ1)、弹性常数(K)更大,可以用于开发低阈值电压、快速响应的液晶显示器。
实施例6
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6液晶组合物的配方及相应的性能
Figure BDA0002346773550000242
Figure BDA0002346773550000251
显然,本公开的上述实施例仅仅是为清楚地说明本公开所作的举例,而并非是对本公开的实施方式的限定,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,凡是属于本公开的技术方案所引伸出的显而易见的变化或变动仍处于本公开的保护范围之列。

Claims (5)

1.一种介电负性的液晶组合物,其特征在于,所述液晶组合物包含式Ⅰ所示的化合物、式Ⅱ所示的化合物、式Ⅲ-1、式Ⅲ-2和式Ⅲ-3所示的化合物以及式Ⅳ-1所示的化合物,还包括式V所示的化合物、式VIII-5所示的化合物和式X-7所示的化合物:
Figure FDA0003975398880000011
其中,
R31表示碳原子数为3的烷基,R41表示碳原子数为2的烷氧基;
R5、R6表示碳原子数为1的链烯基,R6表示碳原子数为2的烷基;
Figure FDA0003975398880000021
表示
Figure FDA0003975398880000022
式Ⅰ所示化合物在液晶组合物中的添加量质量比为36%;式Ⅱ所示化合物在液晶组合物中的添加量质量比为2%;式Ⅲ-1、式Ⅲ-2和式Ⅲ-3所示化合物在液晶组合物中的添加量质量比为22%;式Ⅳ-1所示化合物在液晶组合物中的添加量质量比为12.5%;式V所示化合物在液晶组合物中的添加量质量比为10%;式VIII-5所示化合物在液晶组合物中的添加量质量比为15%;式X-7所示化合物在液晶组合物中的添加量质量比为2.5%。
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所示化合物:
Figure FDA0003975398880000023
其中,R7、R8各自独立地表示碳原子数为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;
X1、Y1各自独立地表示H或F。
3.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Ⅶ所示化合物:
Figure FDA0003975398880000024
其中,R9、R10各自独立地表示碳原子数为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。
4.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Ⅸ所示化合物:
Figure FDA0003975398880000025
其中,R13、R14各自独立地表示碳原子数为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;
Figure FDA0003975398880000031
表示
Figure FDA0003975398880000032
X2表示H或F。
5.一种液晶显示元件或液晶显示器,其特征在于,包含权利要求1~4的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寻址显示元件或显示器,或者无源矩阵寻址显示元件或显示器。
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