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CN103740376B - Containing negative dielectric anisotropy liquid crystal composition and the application thereof of two fluorine bis cyclohexane compound - Google Patents

Containing negative dielectric anisotropy liquid crystal composition and the application thereof of two fluorine bis cyclohexane compound Download PDF

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CN103740376B
CN103740376B CN201310746451.5A CN201310746451A CN103740376B CN 103740376 B CN103740376 B CN 103740376B CN 201310746451 A CN201310746451 A CN 201310746451A CN 103740376 B CN103740376 B CN 103740376B
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陈海光
陈卯先
杭德余
姜天孟
田会强
储士红
贺树芳
孙丽丽
张琳
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Beijing Bayi Space LCD Technology Co Ltd
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Abstract

本发明涉及一种负介电各向异性液晶组合物,更确切地说,本发明涉及含有一种或几种双氟双环己烷结构化合物的负介电各向异性液晶组合物,以及它的应用;该组合物主要用于电光调节,尤其适用于FFS显示器、IPS显示器和MVA/PVA/PSVA构型的VA型显示器。本发明提供的液晶组合物,具有大的光学各向异性和优异的低温互溶性,以及良好的高温和UV稳定性,适用于多种显示模式的快响应显示装置中;克服了光学各向异性较小的缺点,有效的提升了组合物的光学各向异性,降低了液晶层的厚度,以此来加快液晶显示器的响应速度;其应用在液晶显示装置中,能明显改善装置响应慢的问题,具有巨大的应用前景和市场价值。The present invention relates to a liquid crystal composition with negative dielectric anisotropy, more precisely, the present invention relates to a liquid crystal composition with negative dielectric anisotropy containing one or several difluorobicyclohexane structure compounds, and its Application: The composition is mainly used for electro-optic adjustment, especially for FFS display, IPS display and VA display in MVA/PVA/PSVA configuration. The liquid crystal composition provided by the invention has large optical anisotropy and excellent low-temperature miscibility, and good high-temperature and UV stability, and is suitable for fast-response display devices of various display modes; overcomes optical anisotropy Smaller shortcomings, effectively improve the optical anisotropy of the composition, reduce the thickness of the liquid crystal layer, in order to speed up the response speed of the liquid crystal display; its application in the liquid crystal display device can significantly improve the problem of slow response of the device , has huge application prospects and market value.

Description

含双氟双环己烷化合物的负介电各向异性液晶组合物及其应用Negative dielectric anisotropic liquid crystal composition containing difluorobicyclohexane compound and its application

技术领域 technical field

本发明涉及液晶组合物领域,具体涉及一种负介电各向异性液晶组合物,更确切地说,本发明涉及含有一种或几种双氟双环己烷结构化合物的负介电各向异性液晶组合物,以及它的应用;该组合物主要用于电光调节,尤其适用于FFS显示器、IPS显示器和MVA/PVA/PSVA构型的VA型显示器。 The invention relates to the field of liquid crystal compositions, in particular to a liquid crystal composition with negative dielectric anisotropy, more precisely, the invention relates to a liquid crystal composition with negative dielectric anisotropy containing one or several difluorobicyclohexane structural compounds Liquid crystal composition and its application; the composition is mainly used for electro-optic adjustment, especially for FFS display, IPS display and VA display with MVA/PVA/PSVA configuration.

背景技术 Background technique

1888年奥地利植物学家FriedrichReinitzer发现了第一种液晶材料安息香酸胆固醇(cholesterylbenzoate),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。M.Born(1916年)和K.Lichtennecker(1926年)分别发现并研究了液晶的介电各向异性。1932年,W.Kast据此将向列相分为正、负性两大类。1927年,V.Freedericksz和V.Zolinao发现向列相液晶在电场(或磁场)作用下,发生形变并存在电压阈值(Freederichsz转变)。这一发现为液晶显示器的制作提供了依据。利用液晶的电光效应,英国科学家在上世纪制造了第一块液晶显示器即LCD显示器。与传统的CRT相比,LCD不但体积小,厚度薄、重量轻、耗能少、工作电压低,且无辐射、无闪烁并能直接与CMOS集成电路匹配。由于其优点众多,LCD从1998年开始进入台式机应用领域。近几十年,特别是近十几年来信息技术的飞速发展以及人们对信息显示方式的不断追求,使液晶显示得到了最迅猛的发展。今天,液晶显示正以多姿多彩的形态展示在人们面前,它的许多产品由于其优异的特性使其正成为时尚的追求,以及商场里炙手可得的商品。 In 1888, the Austrian botanist Friedrich Reinitzer discovered the first liquid crystal material, cholesterol benzoate (cholesterylbenzoate), which is a liquid crystal, which means that a substance has both the fluidity of a liquid and a certain arrangement characteristic similar to a crystal. M.Born (1916) and K.Lichtennecker (1926) respectively discovered and studied the dielectric anisotropy of liquid crystals. In 1932, W.Kast divided the nematic phase into two categories, positive and negative. In 1927, V.Freedericksz and V.Zolinao discovered that the nematic liquid crystal was deformed and had a voltage threshold (Freederichsz transition) under the action of an electric field (or magnetic field). This finding provides a basis for the production of liquid crystal displays. Utilizing the electro-optic effect of liquid crystals, British scientists manufactured the first liquid crystal display, or LCD display, in the last century. Compared with the traditional CRT, LCD is not only small in size, thin in thickness, light in weight, low in energy consumption, low in working voltage, but also has no radiation, no flicker and can directly match with CMOS integrated circuits. Due to its many advantages, LCD has entered the desktop application field since 1998. In recent decades, especially the rapid development of information technology and people's continuous pursuit of information display methods in the past ten years, liquid crystal display has achieved the most rapid development. Today, liquid crystal displays are being displayed in front of people in a variety of forms, and many of its products are becoming fashionable pursuits and popular commodities in shopping malls due to their excellent characteristics.

根据液晶分子的排列方式,常把液晶显示器分为:窄视角的TN(TwistedNematic)、STN(SuperTwistedNematic)、DSTN(DoublelayerSuperTwistedNematic)等,这些窄视角的液晶显示器中所用的液晶组合物均为介电正性的。宽视角的有IPS(In-PlaneSwitching)、VA(VerticalAlignment)、FFS(FringeFiledSwitching)等,对于宽视角的液晶显示器,所使用的液晶介质多数为负介电各向异性的,其中IPS既可以使用负介电各向异性的液晶组合物,也可使用正介电各向异性的液晶组合物。从液晶面板的驱动方式来看,目前最常见的是TFT(ThinFilmTransistor)型驱动,相比之前的无源驱动可以实现更精细的显示效果。目前大多数液晶显示器、液晶电视及部分手机均采用TFT驱动。液晶显示器多用窄视角的TN模式,液晶电视多用宽视角的VA、IPS等模式,它们通称为TFT-LCD。 According to the arrangement of liquid crystal molecules, liquid crystal displays are often divided into: narrow viewing angle TN (Twisted Nematic), STN (Super Twisted Nematic), DSTN (Doublelayer Super Twisted Nematic), etc. The liquid crystal compositions used in these narrow viewing angle liquid crystal displays are dielectric positive sexual. Wide viewing angles include IPS (In-Plane Switching), VA (Vertical Alignment), FFS (Fringe Filed Switching), etc. For liquid crystal displays with wide viewing angles, most of the liquid crystal media used are negative dielectric anisotropy, and IPS can use negative dielectric anisotropy. As the liquid crystal composition with dielectric anisotropy, a liquid crystal composition with positive dielectric anisotropy can also be used. From the perspective of the driving method of the LCD panel, the most common one is the TFT (ThinFilmTransistor) type driver, which can achieve a finer display effect than the previous passive driver. At present, most LCD monitors, LCD TVs and some mobile phones are driven by TFT. LCD monitors mostly use TN mode with narrow viewing angles, and LCD TVs mostly use VA and IPS modes with wide viewing angles. They are commonly called TFT-LCD.

现有技术所提供的液晶显示器存在响应速度慢的缺点,液晶显示器的响应速度主要受限于液晶层厚度和液晶的旋转粘度,减小液晶层厚度可有效加快液晶显示器响应速度,这就需要提升液晶组合物的光学各向异性。 The liquid crystal display provided by the prior art has the disadvantage of slow response speed. The response speed of the liquid crystal display is mainly limited by the thickness of the liquid crystal layer and the rotational viscosity of the liquid crystal. Reducing the thickness of the liquid crystal layer can effectively speed up the response speed of the liquid crystal display, which needs to be improved. Optical anisotropy of liquid crystal compositions.

液晶显示器响应速度由以下公式决定: The LCD response speed is determined by the following formula:

ττ offoff == γdγd 22 ππ 22 KK 3333

△n*d=常数;γ为液晶的旋转粘度;d为液晶层厚度;K33为液晶的弯曲弹性常数;△n为液晶光学各向异性;△n*d为液晶层的光学延迟量。 Δn*d=constant; γ is the rotational viscosity of the liquid crystal; d is the thickness of the liquid crystal layer; K 33 is the bending elastic constant of the liquid crystal; Δn is the optical anisotropy of the liquid crystal; Δn*d is the optical retardation of the liquid crystal layer.

由以上公式可以看出,提高液晶显示器响应速度就需要降低液晶层厚度和减小液晶旋转粘度。若开发出应用于液晶显示器的液晶组合物,能够实现上述目的,势必将会有巨大的应用前景的经济价值。 It can be seen from the above formula that increasing the response speed of the liquid crystal display requires reducing the thickness of the liquid crystal layer and reducing the rotational viscosity of the liquid crystal. If a liquid crystal composition applied to a liquid crystal display is developed to achieve the above purpose, it will certainly have a huge application prospect and economic value.

发明内容 Contents of the invention

针对现有技术中存在的问题,本发明的目的是提供一种含双氟双环己烷化合物的负介电各向异性液晶组合物。该液晶组合物具有低粘度和较大的光学各向异性,并因而具备快响应速度以及优异的光稳定性和热稳定性,适用于快响应的液晶显示装置。 Aiming at the problems existing in the prior art, the object of the present invention is to provide a liquid crystal composition with negative dielectric anisotropy containing a difluorobicyclohexane compound. The liquid crystal composition has low viscosity and large optical anisotropy, and thus has fast response speed, excellent light stability and thermal stability, and is suitable for fast response liquid crystal display devices.

本发明的另一目的是提供所述含双氟双环己烷化合物的负介电各向异性液晶组合物在液晶显示装置中的应用。 Another object of the present invention is to provide the application of the negative dielectric anisotropy liquid crystal composition containing a difluorobicyclohexane compound in a liquid crystal display device.

为了实现上述目的,本发明提供的含双氟双环己烷化合物的负介电各向异性液晶组合物,包括以下重量百分比的组分: In order to achieve the above object, the negative dielectric anisotropy liquid crystal composition containing difluorobicyclohexane compound provided by the present invention comprises the following components in weight percent:

(1)5%~50%通式IA或/和IB所代表的化合物; (1) 5% to 50% of compounds represented by general formula IA or/and IB;

(2)10%~80%通式Ⅱ所代表的化合物; (2) 10% to 80% of the compound represented by general formula II;

(3)0%~60%通式III所代表的化合物; (3) 0% to 60% of the compound represented by general formula III;

(4)1%~20%通式IV所代表的化合物; (4) 1% to 20% of the compound represented by general formula IV;

其中,所述通式IA、IB、II、III、IV所代表的化合物的结构式如下所示: Wherein, the structural formula of the compound represented by the general formula IA, IB, II, III, IV is as follows:

其中,R1、R2、R3、R5、R7和R8各自独立地代表烷基; Wherein, R 1 , R 2 , R 3 , R 5 , R 7 and R 8 each independently represent an alkyl group;

R4和R6各自独立地代表烷基或烷氧基;n=0或1。 R 4 and R 6 each independently represent an alkyl or alkoxy group; n=0 or 1.

进一步地,R1、R2、R3、R5、R7和R8各自独立地代表C1~C12的烷基;R4和R6各自独立地代表C1~C12的烷基或C1~C12的烷氧基。 Further, R 1 , R 2 , R 3 , R 5 , R 7 and R 8 each independently represent a C 1 -C 12 alkyl group; R 4 and R 6 each independently represent a C 1 -C 12 alkyl group or a C 1 -C 12 alkoxy group.

更进一步地,R1、R2、R3、R5、R7和R8各自独立地代表C2~C5的烷基;R4代表C1~C5的烷基或C2~C5的烷氧基;R6代表C2~C5的烷基或C1~C5的烷氧基。 Further, R 1 , R 2 , R 3 , R 5 , R 7 and R 8 each independently represent a C 2 -C 5 alkyl group; R 4 represents a C 1 -C 5 alkyl group or a C 2 -C 5 alkoxy; R 6 represents C 2 -C 5 alkyl or C 1 -C 5 alkoxy.

本发明中所用的烷基和烷氧基,均优选直链的。 The alkyl and alkoxy groups used in the present invention are preferably linear.

进一步地,R1和R2可以相同或不同,R3和R4可以相同或不同,R5和R6可以相同或不同,R7和R8可以相同或不同。 Further, R 1 and R 2 may be the same or different, R 3 and R 4 may be the same or different, R 5 and R 6 may be the same or different, R 7 and R 8 may be the same or different.

其中,所述通式III所代表的化合物的重量百分比优选10%~60%。 Wherein, the weight percentage of the compound represented by the general formula III is preferably 10%-60%.

优选地,本发明提供的含双氟双环己烷化合物的负介电各向异性液晶组合物,包括下述重量百分比的组分: Preferably, the negative dielectric anisotropy liquid crystal composition containing difluorobicyclohexane compound provided by the present invention includes the following components in weight percentage:

(1)10%~50%通式IA或/和IB所代表的化合物; (1) 10% to 50% of compounds represented by general formula IA or/and IB;

(2)10%~70%通式Ⅱ所代表的化合物; (2) 10% to 70% of the compound represented by general formula II;

(3)10%~60%通式III所代表的化合物; (3) 10% to 60% of the compound represented by general formula III;

(4)1%~20%通式IV所代表的化合物。 (4) 1% to 20% of the compound represented by the general formula IV.

更优选地,本发明提供的含双氟双环己烷化合物的负介电各向异性液晶组合物,包括下述重量百分比的组分: More preferably, the negative dielectric anisotropy liquid crystal composition containing difluorobicyclohexane compound provided by the present invention includes the following components in weight percentage:

(1)10%~40%通式IA或/和IB所代表的化合物; (1) 10% to 40% of compounds represented by general formula IA or/and IB;

(2)10%~70%通式Ⅱ所代表的化合物; (2) 10% to 70% of the compound represented by general formula II;

(3)10%~60%通式III所代表的化合物; (3) 10% to 60% of the compound represented by general formula III;

(4)5%~20%通式IV所代表的化合物。 (4) 5% to 20% of the compound represented by general formula IV.

其中,优选地,所述通式IA所代表的化合物为式IA-1~式IA-16所代表化合物中的一种或几种: Among them, preferably, the compound represented by the general formula IA is one or more of the compounds represented by the formula IA-1 to formula IA-16:

其中,优选地,所述通式IB所代表的化合物为式IB-1~式IB-16所代表化合物中的一种或几种: Among them, preferably, the compound represented by the general formula IB is one or more of the compounds represented by the formula IB-1 to formula IB-16:

其中,优选地,所述通式II所代表的化合物为式IIA、式IIB或式IIC所代表化合物中的一种或几种: Wherein, preferably, the compound represented by the general formula II is one or more of the compounds represented by the formula IIA, formula IIB or formula IIC:

其中,R3为C2~C5的烷基,R4为C2~C5的烷氧基(式IIA中),R4’为C2~C5的烷氧基(式IIB中),R4’’为C1~C5的烷基(式IIC中)。 Among them, R 3 is C 2 -C 5 alkyl, R 4 is C 2 -C 5 alkoxy (in formula IIA), R4' is C 2 -C 5 alkoxy (in formula IIB), R 4 '' is a C 1 -C 5 alkyl group (in formula IIC).

其中,更优选地,所述通式II所代表的化合物为式IIA-1~式IIA-12、式IIB-1~式IIIB-12或式IIC-1~式IIIC-20所代表化合物中的一种或几种: Among them, more preferably, the compound represented by the general formula II is one of the compounds represented by formula IIA-1 to formula IIA-12, formula IIB-1 to formula IIIB-12 or formula IIC-1 to formula IIIC-20 One or more:

其中,优选地,所述通式III所代表的化合物为式IIIA或式IIIB所代表化合物中的一种或几种: Wherein, preferably, the compound represented by the general formula III is one or more of the compounds represented by the formula IIIA or the formula IIIB:

其中,R5为C2~C5的烷基,R6’为C2~C5的烷基(式IIIA中),R6’’为C1~C5的烷氧基(式IIIB中)。 Among them, R 5 is C 2 -C 5 alkyl, R 6 ' is C 2 -C 5 alkyl (in formula IIIA), R 6 '' is C 1 -C 5 alkoxy (in formula IIIB ).

其中,更优选地,所述通式III所代表的化合物为式IIIA-1~式IIIA-16或式IIIB-1~式IIIB-20所代表化合物中的一种或几种: Among them, more preferably, the compound represented by the general formula III is one or more of the compounds represented by formula IIIA-1 to formula IIIA-16 or formula IIIB-1 to formula IIIB-20:

其中,优选地,所述通式IV所代表的化合物为式IVA-1~式IVA-16所代表化合物中的一种或几种: Among them, preferably, the compound represented by the general formula IV is one or more of the compounds represented by formula IVA-1 to formula IVA-16:

本发明还提供上述任意一项含双氟双环己烷化合物的负介电各向异性液晶组合物在液晶显示装置中的应用。 The present invention also provides the application of any one of the above-mentioned negative dielectric anisotropy liquid crystal compositions containing difluorobicyclohexane compounds in liquid crystal display devices.

其中,本发明提供的上述任意一项含双氟双环己烷化合物的负介电各向异性液晶组合物在液晶显示装置中的应用,尤其是在FFS显示器、IPS显示器或MVA/PVA/PSVA构型的VA型显示器中的应用。 Among them, the application of any one of the above-mentioned negative dielectric anisotropy liquid crystal compositions containing difluorobicyclohexane compound provided by the present invention in liquid crystal display devices, especially in FFS displays, IPS displays or MVA/PVA/PSVA structures type of VA display applications.

本发明所述含双氟双环己烷化合物的负介电各向异性液晶组合物的组分中: Among the components of the negative dielectric anisotropy liquid crystal composition containing difluorobicyclohexane compound of the present invention:

通式I所代表的双氟双环己烷类化合物具有一定的负介电各向异性,粘度低,最早见于JP4669085专利中,但存在光学各向异性小的问题; The difluorobicyclohexane compounds represented by the general formula I have certain negative dielectric anisotropy and low viscosity, which were first seen in the JP4669085 patent, but there is a problem of small optical anisotropy;

通式II所代表的2,3-二氟类结构的化合物具有较强的负介电各向异性,粘度低,两环类结构清亮点低,三环类有较高的清亮点; The 2,3-difluoro compound represented by the general formula II has strong negative dielectric anisotropy, low viscosity, low clearing point of the bicyclic structure, and high clearing point of the tricyclic structure;

通式III所代表的双环结构粘度低,在混晶中拥有降低体系粘度的作用; The bicyclic structure represented by the general formula III has a low viscosity and has the effect of reducing the viscosity of the system in the mixed crystal;

通式IV所代表的四环三联苯结构化合物为非极性化合物,具有大的光学各向异性和高的清亮点,可以有效提升体系的清亮点和光学各向异性。 The tetracyclic terphenyl compound represented by the general formula IV is a non-polar compound with large optical anisotropy and high clearing point, which can effectively improve the clearing point and optical anisotropy of the system.

本发明主要是加入通式I所代表的化合物,可以增加体系介电各向异性,同时降低体系的粘度,以提高液晶的响应速度。 The present invention mainly adds the compound represented by the general formula I, which can increase the dielectric anisotropy of the system and reduce the viscosity of the system at the same time, so as to improve the response speed of the liquid crystal.

本发明所述含双氟双环己烷化合物的负介电各向异性液晶组合物的制备方法无特殊限制,可采用常规方法将两种或多种化合物混合进行生产,如通过在高温下混合不同组分并彼此溶解的方法制备,其中,将液晶组合物溶解在用于该化合物的溶剂中并混合,然后在减压下蒸馏出该溶剂;或者本发明所述含双氟双环己烷化合物的负介电各向异性液晶组合物可按照常规的方法制备,如将其中含量较小的组分在较高的温度下溶解在含量较大的主要组分中,或将各所属组分在有机溶剂中溶解,如丙酮、氯仿或甲醇等,然后将溶液混合去除溶剂后得到。 The preparation method of the negative dielectric anisotropy liquid crystal composition containing difluorobicyclohexane compound of the present invention is not particularly limited, and two or more compounds can be mixed by conventional methods for production, such as by mixing different Components are prepared by dissolving each other, wherein the liquid crystal composition is dissolved in a solvent for the compound and mixed, and then the solvent is distilled off under reduced pressure; or the difluorobicyclohexane-containing compound of the present invention The negative dielectric anisotropy liquid crystal composition can be prepared according to conventional methods, such as dissolving the components with a smaller content in the main component with a larger content at a higher temperature, or dissolving each component in an organic Dissolve in a solvent, such as acetone, chloroform or methanol, etc., and then mix the solutions to remove the solvent.

本发明提供的含双氟双环己烷化合物的负介电各向异性液晶组合物,具有大的光学各向异性和优异的低温互溶性,以及良好的高温和UV稳定性,适用于多种显示模式的快响应显示装置中;克服了光学各向异性较小的缺点,有效的提升了组合物的光学各向异性,降低了液晶层的厚度,以此来加快液晶显示器的响应速度;其应用在液晶 The negative dielectric anisotropy liquid crystal composition containing difluorobicyclohexane compound provided by the present invention has large optical anisotropy, excellent low-temperature mutual solubility, and good high-temperature and UV stability, and is suitable for various displays In the fast response display device of mode; overcome the shortcoming of small optical anisotropy, effectively improve the optical anisotropy of the composition, reduce the thickness of the liquid crystal layer, so as to speed up the response speed of the liquid crystal display; its application in LCD

显示装置中,能明显改善装置响应慢的问题,具有巨大的应用前景和市场价值。 In the display device, the problem of slow response of the device can be obviously improved, and has great application prospect and market value.

具体实施方式 Detailed ways

以下实施例用于说明本发明,但不用来限制本发明的保护范围。 The following examples are used to illustrate the present invention, but are not intended to limit the protection scope of the present invention.

本发明实施例中液晶组合物的制备均采用如下方法:均匀液晶的制备采用业内普遍使用的热溶解方法,首先用天平按重量百分比称量液晶化合物,其中称量加入顺序无特定要求,通常以液晶化合物熔点由高到低的顺序依次称量混合,在60~100℃下加热搅拌使得各组分熔解均匀,再经过滤、旋蒸,最后封装即得目标样品。 The preparation of the liquid crystal composition in the examples of the present invention adopts the following method: the preparation of the uniform liquid crystal adopts the thermal dissolution method commonly used in the industry, and first weighs the liquid crystal compound by weight percentage with a balance, wherein there is no specific requirement for the order of weighing and adding, usually Liquid crystal compounds are weighed and mixed in order of melting point from high to low, heated and stirred at 60-100°C to make each component melt evenly, then filtered, rotary evaporated, and finally packaged to obtain the target sample.

除非另有说明,上下文中百分比为重量百分比,所有的温度以摄氏度给出。使用下述缩写: Unless otherwise stated, percentages in this context are by weight and all temperatures are given in degrees Celsius. Use the following abbreviations:

△n为光学各向异性(20℃,589nm);Δε为介电各向异性(25℃,1000Hz);V10为阈值电压,是在相对透过率改变10%时的特征电压(V,25℃);η为体积粘度(mm2/s,20℃);Cp为液晶组合物的清亮点(℃);τoff为关态响应时间,表征液晶在撤除电压后,相对透过率改变90%的时间(ms,25℃);△n*d为液晶层的光学延迟量(μm);γ1为液晶的旋转粘度(mPa.s,25℃)。 △n is the optical anisotropy (20°C, 589nm); Δε is the dielectric anisotropy (25°C, 1000Hz); V 10 is the threshold voltage, which is the characteristic voltage when the relative transmittance changes by 10% (V, 25°C); η is the bulk viscosity (mm 2 /s, 20°C); Cp is the clearing point of the liquid crystal composition (°C); τ off is the off-state response time, which represents the relative transmittance change of the liquid crystal after the voltage is removed 90% time (ms, 25°C); △n*d is the optical retardation of the liquid crystal layer (μm); γ1 is the rotational viscosity of the liquid crystal (mPa.s, 25°C).

本发明中,通式II、III和IV所代表的化合物可由北京八亿时空液晶科技股份有限公司提供。 In the present invention, the compounds represented by general formulas II, III and IV can be provided by Beijing Bayi Space-Time Liquid Crystal Technology Co., Ltd.

为了便于表示,以下实施例中,液晶化合物中基团结构用表0所示代码表示: For ease of expression, in the following examples, the group structure in the liquid crystal compound is represented by the code shown in Table 0:

表0:液晶化合物的基团结构代码 Table 0: Group Structure Codes of Liquid Crystal Compounds

以如下结构为例: Take the following structure as an example:

该结构用表1所列代码表示,则表示为3HH(2F)3; The structure is represented by the code listed in Table 1, which is then expressed as 3HH(2F)3;

再如以下结构: Another example is the following structure:

该结构用表1所列代码表示,则表示为3HHFF3; The structure is represented by the code listed in Table 1, and it is represented as 3HHFF3;

再如以下结构: Another example is the following structure:

该结构用表1所列代码表示,则表示为2HBGB3。 The structure is represented by the code listed in Table 1, and it is expressed as 2HBGB3.

实施例1 Example 1

取以下重量百分比的液晶化合物,并以上述制备方法配制得到液晶组合物,具体配比及所得的液晶组合物(非各个组分)的性能参数见表1。 The liquid crystal compound in the following weight percentages was taken, and the liquid crystal composition was prepared by the above-mentioned preparation method. The specific proportion and the performance parameters of the obtained liquid crystal composition (not the individual components) are shown in Table 1.

表1:实施例1的液晶组合物中各组分的重量百分比及整体组合物的性能参数 Table 1: The weight percent of each component in the liquid crystal composition of Example 1 and the performance parameters of the overall composition

组分的结构式编号 The structural formula number of the component 代码 the code 重量百分比(%) Weight percentage (%) 性能参数 Performance parameters 参数值 parameter value IA-5 IA-5 2HHFF3 2HHFF3 17 17 △n Δn 0.095 0.095 IIA-2 IIA-2 3HWO2 3HWO2 10 10 △ε △ε -2.8 -2.8 IIA-4 IIA-4 5HWO2 5HWO2 8 8 V10 V 10 2.50 2.50 IIB-1 IIB-1 2HHWO2 2HHWO2 4 4 η n 19 19 IIB-2 IIB-2 3HHWO2 3HHWO2 10 10 Cp Cp 76 76 IIB-4 IIB-4 5HHWO2 5HHWO2 6 6 τoff τ off 4.0 4.0 IIC-1 IIC-1 2HHW1 2HHW1 9 9 △n*d △n*d 0.32 0.32 IIC-2 IIC-2 3HHW1 3HHW1 8 8 γ1 gamma 1 75 75 IIIA-4 IIIA-4 5HB2 5HB2 6 6

IIIB-2 IIIB-2 3HBO1 3HBO1 6 6 IIIB-6 IIIB-6 3HBO2 3HBO2 6 6 IVA-13 IVA-13 5HBGB2 5HBGB2 5 5 IVA-10 IVA-10 4HBGB3 4HBGB3 5 5

实施例2 Example 2

取以下重量百分比的液晶化合物,并以上述制备方法配制得到液晶组合物,具体配比及所得的液晶组合物(非各个组分)的性能参数见表2。 The liquid crystal compound in the following weight percentages was taken, and the liquid crystal composition was prepared by the above-mentioned preparation method. The specific proportion and the performance parameters of the obtained liquid crystal composition (not the individual components) are shown in Table 2.

表2:实施例2的液晶组合物中各组分的重量百分比及整体组合物的性能参数 Table 2: The weight percent of each component in the liquid crystal composition of Example 2 and the performance parameters of the overall composition

组分的结构式编号 The structural formula number of the component 代码 the code 重量百分比(%) Weight percentage (%) 性能参数 Performance parameters 参数值 parameter value IB-5 IB-5 2HH(2F)3 2HH(2F)3 20 20 △n Δn 0.095 0.095 IA-6 IA-6 3HHFF3 3HHFF3 20 20 △ε △ε -2.0 -2.0 IIB-1 IIB-1 2HHWO2 2HHWO2 10 10 V10 V 10 3.05 3.05 IIIA-4 IIIA-4 5HB2 5HB2 6 6 η n 15 15 IIIB-2 IIIB-2 3HBO1 3HBO1 6 6 Cp Cp 80 80 IIIB-6 IIIB-6 3HBO2 3HBO2 6 6 τoff τ off 3.0 3.0 IIIB-7 IIIB-7 4HBO2 4HBO2 6 6 △n*d △n*d 0.32 0.32 IIIB-8 IIIB-8 5HBO2 5HBO2 6 6 γ1 gamma 1 55 55 IVA-10 IVA-10 4HBGB3 4HBGB3 7 7 IVA-13 IVA-13 5HBGB2 5HBGB2 7 7 IVA-14 IVA-14 5HBGB3 5HBGB3 6 6

实施例3 Example 3

取以下重量百分比的液晶化合物,并以上述制备方法配制得到液晶组合物,具体配比及所得的液晶组合物(非各个组分)的性能参数见表3。 The following liquid crystal compounds were taken in the following weight percentages, and the liquid crystal composition was prepared by the above-mentioned preparation method. The specific proportion and the performance parameters of the obtained liquid crystal composition (not the individual components) are shown in Table 3.

表3:实施例3的液晶组合物中各组分的重量百分比及整体组合物的性能参数 Table 3: The weight percent of each component in the liquid crystal composition of Example 3 and the performance parameters of the overall composition

组分的结构式编号 The structural formula number of the component 代码 the code 重量百分比(%) Weight percentage (%) 性能参数 Performance parameters 参数值 parameter value IA-5 IA-5 3HHFF3 3HHFF3 10 10 △n Δn 0.090 0.090

[0105][0105] IIB-1 IIB-1 2HHWO2 2HHWO2 10 10 △ε △ε -1.5 -1.5 IIB-2 IIB-2 3HHWO2 3HHWO2 10 10 V10 V 10 3.21 3.21 IIB-4 IIB-4 5HHWO2 5HHWO2 5 5 η n 15 15 IIIA-4 IIIA-4 5HB2 5HB2 6 6 Cp Cp 70 70 IIIB-2 IIIB-2 3HBO1 3HBO1 8 8 τoff τ off 3.5 3.5 IIIB-3 IIIB-3 4HBO1 4HBO1 8 8 △n*d △n*d 0.32 0.32 IIIB-4 IIIB-4 5HBO1 5HBO1 6 6 γ1 gamma 1 45 45 IIIB-6 IIIB-6 3HBO2 3HBO2 8 8 IIIB-7 IIIB-7 4HBO2 4HBO2 8 8 IIIB-8 IIIB-8 5HBO2 5HBO2 8 8 IIIB-14 IIIB-14 3HBO4 3HBO4 8 8 IVA-13 IVA-13 5HBGB2 5HBGB2 5 5

实施例4 Example 4

取以下重量百分比的液晶化合物,并以上述制备方法配制得到液晶组合物,具体配比及所得的液晶组合物(非各个组分)的性能参数见表4。 Take the following liquid crystal compound in the weight percentage, and prepare the liquid crystal composition by the above-mentioned preparation method. The specific proportion and the performance parameters of the obtained liquid crystal composition (not the individual components) are shown in Table 4.

表4:实施例4的液晶组合物中各组分的重量百分比及整体组合物的性能参数 Table 4: The weight percent of each component in the liquid crystal composition of Example 4 and the performance parameters of the overall composition

组分的结构式编号 The structural formula number of the component 代码 the code 重量百分比(%) Weight percentage (%) 性能参数 Performance parameters 参数值 parameter value IA-5 IA-5 3HHFF3 3HHFF3 10 10 △n Δn 0.105 0.105 IIA-2 IIA-2 3HWO2 3HWO2 10 10 △ε △ε -4.0 -4.0 IIA-4 IIA-4 5HWO2 5HWO2 10 10 V10 V 10 2.25 2.25 IIA-10 IIA-10 3HWO4 3HWO4 10 10 η n 25 25 IIB-2 IIB-2 3HHWO2 3HHWO2 10 10 Cp Cp 100 100 IIB-4 IIB-4 5HHWO2 5HHWO2 5 5 τoff τ off 5.0 5.0 IIB-6 IIB-6 3HHWO3 3HHWO3 8 8 △n*d △n*d 0.32 0.32 IIC-1 IIC-1 2HHW1 2HHW1 9 9 γ1 gamma 1 101 101 IIC-2 IIC-2 3HHW1 3HHW1 8 8 IIIB-2 IIIB-2 3HBO1 3HBO1 5 5 IIIB-6 IIIB-6 3HBO2 3HBO2 5 5

IVA-13 IVA-13 5HBGB2 5HBGB2 5 5 IVA-10 IVA-10 4HBGB3 4HBGB3 5 5

实施例5 Example 5

取以下重量百分比的液晶化合物,并以上述制备方法配制得到液晶组合物,具体配比及所得的液晶组合物(非各个组分)的性能参数见表5。 The following liquid crystal compounds were taken in the following weight percentages, and the liquid crystal composition was prepared by the above-mentioned preparation method. The specific proportion and the performance parameters of the obtained liquid crystal composition (not the individual components) are shown in Table 5.

表5:实施例5的液晶组合物中各组分的重量百分比及整体组合物的性能参数 Table 5: The weight percent of each component in the liquid crystal composition of Example 5 and the performance parameters of the overall composition

组分的结构式编号 The structural formula number of the component 代码 the code 重量百分比(%) Weight percentage (%) 性能参数 Performance parameters 参数值 parameter value IA-5 IA-5 2HHFF3 2HHFF3 20 20 △n Δn 0.096 0.096 IA-6 IA-6 3HHFF3 3HHFF3 20 20 △ε △ε -3.5 -3.5 IA-10 IA-10 3HHFF4 3HHFF4 10 10 V10 V 10 2.32 2.32 IIA-2 IIA-2 3HWO2 3HWO2 10 10 η n 20 20 IIA-4 IIA-4 5HWO2 5HWO2 10 10 Cp Cp 75 75 IIB-6 IIB-6 3HHWO3 3HHWO3 10 10 τoff τ off 4.5 4.5 IVA-13 IVA-13 5HBGB2 5HBGB2 7 7 △n*d △n*d 0.32 0.32 IVA-14 IVA-14 5HBGB3 5HBGB3 7 7 γ1 gamma 1 90 90 IVA-10 IVA-10 4HBGB3 4HBGB3 6 6

实施例6 Example 6

取以下重量百分比的液晶化合物,并以上述制备方法配制得到液晶组合物,具体配比及所得的液晶组合物(非各个组分)的性能参数见表6。 Take the following liquid crystal compound in the weight percentage, and prepare the liquid crystal composition by the above-mentioned preparation method. The specific proportion and the performance parameters of the obtained liquid crystal composition (not the individual components) are shown in Table 6.

表6:实施例6的液晶组合物中各组分的重量百分比及整体组合物的性能参数 Table 6: The weight percent of each component in the liquid crystal composition of Example 6 and the performance parameters of the overall composition

组分的结构式编号 The structural formula number of the component 代码 the code 重量百分比(%) Weight percentage (%) 性能参数 Performance parameters 参数值 parameter value IA-5 IA-5 2HHFF3 2HHFF3 20 20 △n Δn 0.100 0.100 IB-6 IB-6 3HH(2F)3 3HH(2F)3 20 20 △ε △ε -3.7 -3.7 IIA-10 IIA-10 3HWO4 3HWO4 10 10 V10 V 10 2.32 2.32 IIA-2 IIA-2 3HWO2 3HWO2 10 10 η n 20 20 IIA-4 IIA-4 5HWO2 5HWO2 10 10 Cp Cp 75 75

IIB-6 IIB-6 3HHWO3 3HHWO3 10 10 τoff τ off 4.3 4.3 IVA-13 IVA-13 5HBGB2 5HBGB2 7 7 △n*d △n*d 0.32 0.32 IVA-14 IVA-14 5HBGB3 5HBGB3 7 7 γ1 gamma 1 98 98 IVA-10 IVA-10 4HBGB3 4HBGB3 6 6

对比例1 Comparative example 1

取以下重量百分比的液晶化合物,并以上述制备方法配制得到液晶组合物,具体配比及所得的液晶组合物(非各个组分)的性能参数见表7。 Take the following liquid crystal compound in the weight percentage, and prepare the liquid crystal composition by the above preparation method. The specific proportion and the performance parameters of the obtained liquid crystal composition (not the individual components) are shown in Table 7.

表7:对比例1的液晶组合物中各组分的重量百分比及整体组合物的性能参数 Table 7: The weight percent of each component in the liquid crystal composition of Comparative Example 1 and the performance parameters of the overall composition

组分 components 重量百分比(%) Weight percentage (%) 性能参数 Performance parameters 参数值 parameter value 3HH2 3HH2 8 8 △n Δn 0.080 0.080 3HH5 3HH5 9 9 △ε △ε -3.0 -3.0 2HHW1 2HHW1 9 9 V10 V 10 2.45 2.45 3HHW1 3HHW1 8 8 η n 20 20 3HHWO2 3HHWO2 12 12 Cp Cp 68 68 5HHWO2 5HHWO2 11 11 τoff τ off 5.0 5.0 3HWO2 3HWO2 16 16 △n*d △n*d 0.32 0.32 5HWO2 5HWO2 14 14 γ1 gamma 1 82 82 3HBO1 3HBO1 6 6 5HB2 5HB2 7 7

本发明所述负介电各向异性液晶组合物中,以实施例1~4中各组分配比制备的液晶组合物具有大的光学各向异性以及优异的光稳定性和热稳定性,同时因具有低粘度而适用于快响应的液晶显示装置中。 Among the negative dielectric anisotropy liquid crystal compositions of the present invention, the liquid crystal compositions prepared with the ratios of the components in Examples 1 to 4 have large optical anisotropy and excellent light stability and thermal stability, and at the same time Due to its low viscosity, it is suitable for liquid crystal display devices with fast response.

对比例1中为现有技术中所使用的负介电各向异性液晶组合物各组分配比,以此配比制备的液晶组合物主要存在着光学各向异性较小,导致所需液晶层厚度较大,所以响应时间较慢的问题。实施例1相对于对比例1,实施例1具有更低的粘度和更大的光学各向异性,所以显示器液晶层厚度较小,所以响应时间快于对比例1。 In Comparative Example 1, the ratio of each component of the negative dielectric anisotropy liquid crystal composition used in the prior art, the liquid crystal composition prepared with this ratio mainly has a small optical anisotropy, resulting in the desired liquid crystal layer The thickness is larger, so the problem of slower response time. Compared with Comparative Example 1, Example 1 has lower viscosity and greater optical anisotropy, so the thickness of the liquid crystal layer of the display is smaller, so the response time is faster than Comparative Example 1.

本发明所提供的负介电各向异性液晶组合物具有低粘度、高电阻率、较大的光学各向异性以及优异的光稳定性和热稳定性,可解决液晶显示器响应速度慢的问题,适用于快响应的液晶显示装置。 The negative dielectric anisotropic liquid crystal composition provided by the present invention has low viscosity, high resistivity, large optical anisotropy, and excellent light stability and thermal stability, and can solve the problem of slow response speed of liquid crystal displays. Suitable for liquid crystal display devices with fast response.

虽然,上文中已经用一般性说明、具体实施方式及试验,对本发明作了详尽的描述,但在本发明基础上,可以对之作一些修改或改进,这对本领域技术人员而言是显而易见的。因此,在不偏离本发明精神的基础上所做的这些修改或改进,均属于本发明要求保护的范围。 Although, the present invention has been described in detail with general description, specific implementation and test above, but on the basis of the present invention, some modifications or improvements can be made to it, which will be obvious to those skilled in the art . Therefore, the modifications or improvements made on the basis of not departing from the spirit of the present invention all belong to the protection scope of the present invention.

Claims (11)

1., containing a negative dielectric anisotropy liquid crystal composition for two fluorine bis cyclohexane compound, be made up of the component of following weight percent:
(1) 10% ~ 50% general formula I A is or/and compound representated by IB;
Compound representated by (2) 10% ~ 70% general formulas II;
Compound representated by (3) 10% ~ 60% general formula III;
Compound representated by (4) 1% ~ 20% general formula I V;
Wherein, the structural formula of the compound representated by described general formula I A, IB, II, III, IV is as follows:
Wherein, described R 1, R 2, R 3, R 5, R 7and R 8represent C independently of one another 2~ C 5alkyl; R 4represent C 1~ C 5alkyl or C 2~ C 5alkoxyl group; R 6represent C 2~ C 5alkyl or C 1~ C 5alkoxyl group, n=0 or 1.
2. liquid-crystal composition according to claim 1, is characterized in that, described R 1and R 2identical or different, R 3and R 4identical or different, R 5and R 6identical or different, R 7and R 8identical or different.
3. liquid-crystal composition according to claim 2, is characterized in that, this liquid-crystal composition is made up of the component of following weight per-cent:
(1) 10% ~ 40% general formula I A is or/and compound representated by IB;
Compound representated by (2) 10% ~ 70% general formulas II;
Compound representated by (3) 10% ~ 60% general formula III;
Compound representated by (4) 5% ~ 20% general formula I V.
4. the liquid-crystal composition according to claims 1 to 3 any one, is characterized in that, one or more in the compound representated by formula IA-1 ~ formula IA-16 of the compound representated by described general formula I A:
One or more in compound representated by described general formula I B compound representated by formula IB-1 ~ formula IB-16:
5. the liquid-crystal composition according to claims 1 to 3 any one, is characterized in that, the compound representated by described general formula I I is formula IIA, one or more in compound representated by formula IIB or formula IIC:
Wherein, R 3for C 2~ C 5alkyl, R 4for C 2~ C 5alkoxyl group, R4 ' is C 2~ C 5alkoxyl group, R 4" be C 1~ C 5alkyl.
6. the liquid-crystal composition according to claims 1 to 3 any one, is characterized in that, one or more in the compound representated by formula III A or formula III B of the compound representated by described general formula III:
Wherein, R 5for C 2~ C 5alkyl, R 6' be C 2~ C 5alkyl, R 6" be C 1~ C 5alkoxyl group.
7. the liquid-crystal composition according to claims 1 to 3 any one, is characterized in that, one or more in the compound representated by formula IVA-1 ~ formula IVA-16 of the compound representated by described general formula I V:
8. liquid-crystal composition according to claim 5, is characterized in that, one or more in the compound representated by formula IIA-1 ~ formula IIA-12, formula IIB-1 ~ formula IIB-12 or formula IIC-1 ~ formula IIC-20 of the compound representated by described general formula I I:
9. liquid-crystal composition according to claim 6, is characterized in that, one or more in the compound representated by formula III A-1 ~ formula III A-16 or formula III B-1 ~ formula III B-20 of the compound representated by described general formula III:
10. the application of negative dielectric anisotropy liquid crystal composition in liquid crystal indicator containing two fluorine bis cyclohexane compound described in claim 1 ~ 9 any one.
11. application according to claim 10, is characterized in that, described liquid crystal indicator is the VA escope of FFS indicating meter, IPS indicating meter or MVA/PVA/PSVA configuration.
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