CN108659856B - 具有正介电各向异性的液晶组合物及其显示器件 - Google Patents
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Abstract
本发明公开了一种正介电各向异性的液晶组合物,其包含:一种或多种通式Ⅰ的化合物;一种或多种通式Ⅱ的化合物;以及一种或多种通式Ⅲ的化合物。本发明还公开了包括本发明的液晶组合物的液晶显示器件。本发明提供的液晶组合物具有低温互溶性好、响应快、LC漏光小对比度高等优点,在满足大介电、低盒厚、快响应的同时,能够兼顾对比度,特别适用于主动矩阵薄膜晶体管(AM‑TFT)驱动的液晶显示元件中。
Description
技术领域
本发明涉及液晶材料领域,具体涉及具有正介电各向异性的液晶组合物及其显示器件。
背景技术
液晶显示元件可以在以钟表、电子计算器为代表的家庭用各种电器、测定机器、汽车用面板、文字处理机、电脑、打印机、电视等中使用。根据显示模式的类型分为PC(phasechange,相变)、TN(twist nematic,扭曲向列)、STN(super twisted nematic,超扭曲向列)、ECB(electrically controlled birefringence,电控双折射)、OCB(opticallycompensated bend,光学补偿弯曲)、IPS(in-plane switching,共面转变)、VA(verticalalignment,垂直配向)等类型。根据元件的驱动方式分为PM(passive matrix,被动矩阵)型和AM(active matrix,主动矩阵)型。PM分为静态(static)和多路(multiplex)等类型。AM分为TFT(thin film transistor,薄膜晶体管)、MIM(metal insulator metal,金属-绝缘层-金属)等类型。TFT的类型有非晶硅(amorphous silicon)和多晶硅(polycrystalsilicon)。后者根据制造工艺分为高温型和低温型。液晶显示元件根据光源的类型分为利用自然光的反射型、利用背光的透过型、以及利用自然光和背光两种光源的半透过型。
在低信息量中,一般采用无源方式驱动,但是随着信息量的加大,显示尺寸和显示路数的增多,串扰和对比度降低现象变得严重,因此一般采用有源矩阵(AM)方式驱动,目前较多的采用薄膜晶体管(TFT)来进行驱动。在AM-TFT元件中,TFT开关器件在二维网格中寻址,在处于导通的有限时间内对像素电极进行充值,之后又变成截止状态,直至下一周期中再被寻址。因此,在两个寻址周期之间,不希望像素点上的电压发生改变,否则像素点的透光率会发生改变,导致显示的不稳定。像素点的放电速度取决于电极容量和电极间介电材料的电阻率。因此要求液晶材料有较高的电阻率,同时要求材料有合适的光学各向异性Δn(Δn值一般在0.08-0.10左右),以及较低的阈值电压,以达到降低的驱动电压,降低功耗的目的;还要求具有较低的粘度,以满足快速响应的需要。这类液晶组合物已经有很多文献报道,例如WO9202597、WO9116398、WO9302153、WO9116399、CN1157005A等。
研究表明,影响液晶显示元件的对比度的最主要因素为液晶材料的漏光(LCScattering),而LC Scattering与弹性常数平均值(Kave)的关系式如下:
LC Scattering与Kave成反比例,在提升Kave的情况下,可以降低液晶材料的漏光。
此外,对比度(CR)与亮度(L)的关系式如下:
CR=L255/L0×100%,
其中,L255为开态亮度,L0为关态亮度。可以看出,影响CR明显的应该是L0的变化。关态下,L0与液晶分子的介电无关,与液晶材料本身的LC Scattering相关,LC Scattering小,L0也愈小,这样CR就会显著提高。
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。
含有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。然而具有较低的阈值电压(一般含有大介电极性基团)的液晶组合物其分子的有序度低,而反应液晶分子有序度的Kave值也会降低,从而影响到液晶材料的漏光和对比度,两者通常难以兼顾。
粘度小的液晶组合物,可提高液晶显示元件响应速度。当液晶显示元件的响应速度快时,可适用于动画显示。另外,向液晶显示元件的液晶盒内注入液晶组合物时,可缩短注入时间,能够提高作业性。
现有技术公开了较低功耗,较快响应的液晶组合物,如专利文献CN102858918A,但现有技术的液晶组合物存在环保问题(如含氯化合物的使用)、使用寿命短(如UV或热稳定性差)、对比度低(如日光下显示屏幕泛白),以及无法兼顾在液晶电视、平板电脑等要求适当的光学各向异性、适当的介电各项异性、高电压保持率、抗UV稳定及高温稳定的性能均衡问题,不能同时满足各方面指标。
从液晶材料的制备角度出发,液晶材料的各项性能是互相牵制影响的,某项性能指标的提升可能会使其他性能发生变化。因此,制备各方面性能都合适的液晶材料往往需要创造性劳动。
液晶材料是液晶显示器的重要组成部分,而目前全球液晶显示器具有很大的市场需求,多用于电子电器产品中,但其生命周期较短。较短的生命周期自然存在废弃污染等问题,在如今绿色环保问题日益受到社会各界的重视的情况下,如若能从源头控制,即在液晶材料的调制过程中选择环保绿色的材质,就能极大降低处理废弃液晶显示器时所付出的环境代价。因此,制备各方面性能都合适,又经济、绿色环保的液晶材料往往更需要创造性劳动。
发明内容
发明目的:针对现有技术的缺陷,本发明的目的在于提供具有正介电各向异性液晶组合物,其具有较低的驱动电压(介电各向异性绝对值较大)、低温互溶性好、低盒厚、响应快、LC漏光小、对比度高等优点,在满足大介电、低盒厚、快响应的同时,能够兼顾对比度,此外,还提供包含所述液晶组合物的液晶显示器件。
本发明的技术方案:
一种正介电各向异性的液晶组合物,所述液晶组合物包含:
一种或多种通式Ⅰ的化合物
一种或多种通式Ⅱ的化合物
一种或多种通式Ⅲ的化合物
其中,
R1和R2各自独立的表示H、含有1-10个碳原子的直链烷基或烷氧基、含有2-10个碳原子的烯基或烯氧基、环丁基、环戊基;
R3表示H、F、含有1-10个碳原子的直链烷基或烷氧基、含有2-10个碳原子的烯基或烯氧基,其中所述含有1-10个碳原子的直链烷基或烷氧基和所述含有2-10个碳原子的烯基或烯氧基中的任意H能够被F取代;
R4和R5各自独立的表示H、含有1-10个碳原子的直链烷基或烷氧基、含有2-10个碳原子的烯基或烯氧基;
X表示H或F;
Y表示H、F或甲基;
其中,所述通式Ⅱ的化合物在所述液晶组合物中的含量>11wt%;
所述通式Ⅲ的化合物在所述液晶组合物中的含量≥23wt%。
进一步地,所述通式Ⅰ的化合物选自由如下化合物组成的组:
更进一步地,所述通式Ⅰ-1的化合物选自由如下化合物组成的组:
所述通式Ⅰ-2的化合物选自由如下化合物组成的组:
所述通式Ⅰ-3的化合物选自由如下化合物组成的组:
所述通式Ⅰ-4的化合物选自由如下化合物组成的组:
在本发明的实施方案中,优选所述通式Ⅰ的化合物占所述液晶组合物总重量的1-20%;更优地,所述通式Ⅰ的化合物占所述液晶组合物总重量的1-15%。
进一步地,所述通式Ⅱ的化合物选自由如下化合物组成的组:
优选地,所述通式Ⅱ的化合物选自由如下化合物组成的组:
在本发明的实施方案中,所述通式Ⅱ的化合物在本发明的液晶组合物中的含量≥11wt%。
进一步地,所述通式Ⅲ的化合物选自由如下化合物组成的组:
在本发明的实施方案中,所述通式Ⅲ的化合物在本发明的液晶组合物中的含量≥23wt%。
进一步地,所述液晶组合物还包含一种或多种通式Ⅳ的化合物:
其中,
R6表示H、含有1-10碳原子的直链烷基或烷氧基、含有2-10个碳原子的烯基或烯氧基;
Z1和Z2各自独立的表示单键、-CH2CH2-、-CH2O-、-CF2O-、-CH=CH-或-C≡C-;
L1和L2各自独立的表示H或F;
L3表示F、-CF3或-OCF3;
n表示0、1或2;
b)L1和L2同时为H;
更进一步地,所述通式Ⅳ的化合物选自由如下化合物组成的组:
其中,
R61表示H、1-6个碳原子的烷基或烷氧基、2-6个碳原子的烯基或烯氧基。
进一步地,所述液晶组合物还包含一种或多种选自通式Ⅴ的化合物:
其中,
R7和R8各自独立的表示H、1-10个碳原子的烷基或烷氧基、2-10个碳原子的烯基或烯氧基;
更进一步地,所述通式Ⅴ的化合物选自由如下化合物组成的组:
其中,
R71和R81相同或不同,各自独立的表示H、1-6个碳原子的烷基或烷氧基、2-6个碳原子的烯基或烯氧基。
再进一步地,所述通式Ⅴ-1的化合物选自由如下化合物组成的组:
所述通式Ⅴ-2的化合物选自由如下化合物组成的组:
所述通式Ⅴ-3的化合物选自由如下化合物组成的组:
所述通式Ⅴ-4的化合物选自由如下化合物组成的组:
进一步地,所述液晶组合物还包含本领域技术人员已知和文献中描述的一种或多种添加剂。
如下提及例如可以加入到根据本发明的混合物中的稳定剂。
优选地,所述稳定剂选自如下所示的稳定剂。
在本发明的实施方案中,优选所述稳定剂占所述液晶组合物总重量的0-5%;更优地,所述稳定剂占所述液晶组合物总重量的0-1%;作为特别优选方案,所述稳定剂占所述液晶组合物总重量的0.01-0.1%。
本发明另一方面还提供一种液晶显示器,其包含本发明所提供的液晶组合物。
有益效果:
本发明提供的液晶组合物具有较低的驱动电压(介电各向异性绝对值较大)、低温互溶性好、低盒厚、响应快、LC漏光小对比度高等优点,在满足大介电、低盒厚、快响应的同时,能够兼顾对比度,特别适用于主动矩阵薄膜晶体管(AM-TFT)驱动的液晶显示元件中。
具体实施方式
以下将结合具体实施方案来说明本发明。需要说明的是,下面的实施例为本发明的示例,仅用来说明本发明,而不用来限制本发明。在不偏离本发明主旨或范围的情况下,可进行本发明构思内的其他组合和各种改良。
在本发明中如无特殊说明,所述的比例均为重量比,所有温度均为摄氏度温度。
为便于表达,以下各实施例中,液晶组合物的基团结构用表1所列的代码表示:
表1液晶化合物的基团结构代码
以如下结构式的化合物为例:
该结构式如用表1所列代码表示,则可表达为:nCCGF,代码中的n表示左端烷基的C原子数,例如n为“3”,即表示该烷基为-C3H7;代码中的C代表环己烷基,G代表2-氟-1,4-亚苯基,F代表氟。
以下实施例中测试项目的简写代号如下:
Cp(℃) 清亮点(向列-各向同性相转变温度)
Δn 光学各向异性(589nm,25℃)
Δε 介电各向异性(1KHz,25℃)
γ1 旋转粘度(mPa*s,在25℃下)
t-40℃ 低温储存时间(天,在-40℃下)
K11 展曲弹性常数
K22 扭曲弹性常数
K33 弯曲弹性常数
Kave 弹性常数平均值
Cell gap 盒厚(μm)
其中,
光学各向异性使用阿贝折光仪在钠光灯(589nm)光源下、25℃测试得。
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:25℃、1KHz、测试盒为TN90型,盒厚7μm。
γ1使用TOYO6254型液晶物性评价***测试得到;测试温度为25℃,测试电压为90V。
在以下的实施例中所采用的各成分,均可以通过公知的方法进行合成,或者通过商业途径获得。这些合成技术是常规的,所得到各液晶化合物经测试符合电子类化合物标准。
按照以下实施例规定的各液晶组合物的配比,制备液晶组合物。所述液晶组合物的制备是按照本领域的常规方法进行的,如采取加热、超声波、悬浮等方式按照规定比例混合制得。
制备并研究下列实施例中给出的液晶组合物。下面显示了各液晶组合物的组成和其性能参数测试结果。
对比例1
按表2中所列的各化合物及重量百分数配制成对比例1的液晶组合物,其填充于液晶显示器两基板之间进行性能测试,测试数据如下表所示:
表2液晶组合物配方及其测试性能
对比例2
按表3中所列的各化合物及重量百分数配制成对比例2的液晶组合物,其填充于液晶显示器两基板之间进行性能测试,测试数据如下表所示:
表3液晶组合物配方及其测试性能
实施例1
按表4中所列的各化合物及重量百分数配制成实施例1的液晶组合物,其填充于液晶显示器两基板之间进行性能测试,测试数据如下表所示:
表4液晶组合物配方及其测试性能
实施例2
按表5中所列的各化合物及重量百分数配制成实施例2的液晶组合物,其填充于液晶显示器两基板之间进行性能测试,测试数据如下表所示:
表5液晶组合物配方及其测试性能
实施例3
按表6中所列的各化合物及重量百分数配制成实施例3的液晶组合物,其填充于液晶显示器两基板之间进行性能测试,测试数据如下表所示:
表6液晶组合物配方及其测试性能
实施例4
按表7中所列的各化合物及重量百分数配制成实施例4的液晶组合物,其填充于液晶显示器两基板之间进行性能测试,测试数据如下表所示:
表7液晶组合物配方及其测试性能
实施例5
按表8中所列的各化合物及重量百分数配制成实施例5的液晶组合物,其填充于液晶显示器两基板之间进行性能测试,测试数据如下表所示:
表8液晶组合物配方及其测试性能
实施例6
按表9中所列的各化合物及重量百分数配制成实施例6的液晶组合物,其填充于液晶显示器两基板之间进行性能测试,测试数据如下表所示:
表9液晶组合物配方及其测试性能
实施例7
按表10中所列的各化合物及重量百分数配制成实施例7的液晶组合物,其填充于液晶显示器两基板之间进行性能测试,测试数据如下表所示:
表10液晶组合物配方及其测试性能
为了突出本发明的液晶组合物的有益效果,发明人选取和本发明实施例体系相近的对照例。通过以上对比例1、对比例2、实施例1、实施例2、实施例3、实施例4、实施例5、实施例6和实施例7可以看出,本发明提供的液晶组合物介电各向异性大,具有较低的驱动电压、较好的低温互溶性,具有较大的Kave值,液晶材料的漏光小,对比度高,响应时间短,应用到显示元件中时,能够兼顾对比度、低驱动电压和低盒厚,特别适用于主动矩阵薄膜晶体管(AM-TFT)驱动的液晶显示元件中。
以上实施方式只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人了解本发明内容并加以实施,并不能以此限制本发明的保护范围,凡根据本发明精神实质所做的等效变化或修饰,都应涵盖在本发明的保护范围内。
Claims (8)
1.一种正介电各向异性的液晶组合物,其特征在于,所述液晶组合物包含:
一种或多种通式Ⅰ的化合物
一种或多种通式Ⅱ的化合物
其中,
R1和R2各自独立的表示H、含有1-10个碳原子的直链烷基或烷氧基、含有2-10个碳原子的烯基或烯氧基、环丁基、环戊基;
R3表示H、F、含有1-10个碳原子的直链烷基或烷氧基、含有2-10个碳原子的烯基或烯氧基,其中所述含有1-10个碳原子的直链烷基或烷氧基和所述含有2-10个碳原子的烯基或烯氧基中的任意H能够被F取代;
R4和R5各自独立的表示H、含有1-10个碳原子的直链烷基或烷氧基、含有2-10个碳原子的烯基或烯氧基;
X表示F;
Y表示H、F或甲基;
其中,所述通式Ⅰ的化合物在所述液晶组合物中的含量6-16wt%;
所述通式Ⅱ的化合物在所述液晶组合物中的含量12-21wt%;
所述通式Ⅲ的化合物在所述液晶组合物中的含量23-35wt%;
所述通式Ⅰ的化合物选自由如下化合物组成的组:
所述通式Ⅰ-3的化合物选自由如下化合物组成的组:
所述通式Ⅰ-4的化合物选自由如下化合物组成的组:
7.根据权利要求1-6任一项所述的正介电各向异性的液晶组合物,其特征在于,还包含一种或多种添加剂。
8.一种液晶显示器,其特征在于,包括权利要求1至7中任一项所述的正介电各向异性的液晶组合物。
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