WO2019184860A1 - 一种液晶组合物及液晶显示器件 - Google Patents

一种液晶组合物及液晶显示器件 Download PDF

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WO2019184860A1
WO2019184860A1 PCT/CN2019/079484 CN2019079484W WO2019184860A1 WO 2019184860 A1 WO2019184860 A1 WO 2019184860A1 CN 2019079484 W CN2019079484 W CN 2019079484W WO 2019184860 A1 WO2019184860 A1 WO 2019184860A1
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liquid crystal
crystal composition
carbon atoms
group
compound
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PCT/CN2019/079484
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French (fr)
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马文阳
徐海彬
韩文明
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江苏和成显示科技有限公司
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Priority to JP2020538106A priority Critical patent/JP7074862B2/ja
Publication of WO2019184860A1 publication Critical patent/WO2019184860A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/46—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing esters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate

Definitions

  • the present application belongs to the technical field of liquid crystal materials, and relates to a liquid crystal composition and a liquid crystal display device.
  • the liquid crystal display element is applied to various fields such as home appliances, computers, mobile phones, and electronic dictionaries by means of watches, electronic calculators, and display screens.
  • Typical examples of the liquid crystal display method include a TN (twisted nematic) type, an STN (super twisted nematic) type, a DS (dynamic light scattering) type, a GH (guest-host) type, and an IPS (in-plane switching) type.
  • OCB optical compensation birefringence
  • ECB voltage controlled birefringence
  • VA vertical alignment
  • CSH color super vertical
  • FLS strong dielectric liquid crystal
  • PSA polymer stable alignment
  • the driving method of components it is divided into PM (passive matrix) type and AM (active matrix) type.
  • PM is divided into static and multi-channel types.
  • the AM is classified into a TFT (Thin Film Transistor), a MIM (Metal-Insulator-Metal), and the like.
  • TFT Thin Film Transistor
  • MIM Metal-Insulator-Metal
  • the liquid crystal material used is required to have a low driving voltage, a high response speed, a wide operating temperature range, a large absolute value of dielectric anisotropy, a high phase transition temperature, and good mutual solubility.
  • liquid crystal composition which has a large absolute value of negative dielectric anisotropy, a low temperature stability, and a fast response.
  • a liquid crystal composition having a large absolute value of dielectric anisotropy has a high critical voltage, high power consumption, and a relatively slow response speed. Therefore, in order to meet the increasing demand for applications, there is a need in the art for liquid crystal compounds that continuously improve negative dielectric anisotropy.
  • the image residue is in the same picture.
  • the liquid crystal is polarized due to long-time driving, so that the liquid crystal deflection is not controlled by the signal voltage, so that the same picture is displayed on the screen for a while, and the phenomenon also changes with time. Weakened and finally disappeared.
  • the image residue is divided into line residue and surface residue. Among them, the line residue has a great relationship with the reliability of the liquid crystal material.
  • the performance parameter commonly used to characterize the reliability of the liquid crystal material is the voltage retention rate (VHR), and the higher the VHR,
  • VHR voltage retention rate
  • the liquid crystal material is less likely to be affected by interference factors such as liquid crystal impurities, high and low temperature, UV radiation, and the like.
  • An object of the present application is to provide a liquid crystal composition and a liquid crystal display device.
  • the liquid crystal composition of the present application has suitable optical anisotropy, dielectric anisotropy, and good low-temperature mutual solubility and voltage holding ratio.
  • the application provides a liquid crystal composition comprising at least one compound of Formula I, at least one compound of Formula II, and at least one compound of Formula III:
  • liquid crystal composition contains the compounds of the formulae I, II and III at the same time, the components are coordinated to each other such that the composition has higher optical anisotropy, dielectric anisotropy, and good low-temperature mutual solubility. And excellent voltage retention, which can better solve the problem of image sticking.
  • the compound of formula I comprises from 1 to 60%, such as 1%, 2%, 4%, 6%, 8%, 10%, 15%, 20%, 25%, of the total weight of the liquid crystal composition. 30%, 35%, 40%, 45%, 50%, 55%, 60%, optionally 5-50%, optionally 10-45%; the compound of the formula III accounts for the total weight of the liquid crystal composition 1-20%, such as 1%, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18% or 20%. If the content of the compound of the formula III is more than 20%, the mutual solubility of the liquid crystal composition is deteriorated.
  • the compound of the formula II accounts for more than 10% by weight of the total liquid crystal composition, such as 10%, 12%, 13%, 15%, 18%, 20%, 23%, 25%, 28% or 30%, optional 10-30%, optional 13-30%, optional 15-30%. If the content of the compound of the formula II is less than 10%, the phase transition temperature of the liquid crystal composition is lowered, so that the working scene of the liquid crystal composition is limited.
  • R 1 and R 2 are as defined above and will not be described herein.
  • the compound of the formula II is any one or a combination of at least two of the following structures:
  • R 3 and R 4 are as defined above and will not be described herein.
  • the compound of the formula III is any one or a combination of at least two of the following structures:
  • R 5 and R 6 are as defined above and will not be described herein.
  • the linear or branched alkyl or alkoxy group having 1 to 12 carbon atoms may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, A linear or branched alkyl or alkoxy group of 11 or 12 carbon atoms.
  • examples of the linear or branched alkyl group may be methyl, ethyl, propyl, isopropyl, butyl, pentyl, octyl, heptyl, ketone, dodecane Base.
  • Examples of the linear or branched alkoxy group may be a methoxy group, an ethoxy group, a propoxy group, a butoxy group or the like.
  • liquid crystal composition of the present application further comprises at least one compound of the formula IV:
  • R 7 and R 8 are each independently a linear or branched alkyl or alkoxy group having 1 to 12 carbon atoms, a linear or branched alkenyl group having 2 to 12 carbon atoms or an oxyalkylene group; a cycloalkyl group having 3 to 12 carbon atoms; or a linear or branched alkyl or alkoxy group having 1 to 12 carbon atoms or a linear or branched chain having 2 to 12 carbon atoms
  • the compound of the formula IV accounts for 5-80%, such as 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, of the total weight of the liquid crystal composition. 45%, 50%, 55%, 60%, 65%, 70%, 75% or 80%, optional 10-70%, optional 15-60%.
  • the compound of the formula IV is any one or a combination of at least two of the following structures:
  • R 7 and R 8 are as defined above, and are not described herein again.
  • liquid crystal composition of the present application further comprises at least one compound of the formula V:
  • X 1 and X 2 are independently a linear or branched alkyl group having 1 to 12 carbon atoms, and a linear or branched alkenyl group having 2 to 12 carbon atoms.
  • the compound of the formula V accounts for 1-30%, such as 1%, 3%, 5%, 8%, 10%, 13%, 15%, 18%, 20%, of the total weight of the liquid crystal composition. 23%, 25%, 28% or 30%, optional 1-20%, optional 1-15%.
  • liquid crystal composition of the present application further comprises at least one compound of the formula VI:
  • the compound of the formula VI accounts for 0-60%, such as 0%, 1%, 3%, 5%, 8%, 10%, 15%, 18%, 20%, of the total weight of the liquid crystal composition. 25%, 30%, 35%, 40%, 45%, 50%, 55% or 60%, optional 1-30%, optional 1-20%.
  • the compound of the formula VI is any one or a combination of at least two of the following structures:
  • R 9 and R 10 are as defined above, and are not described herein again.
  • the alkenyl or alkenyloxy group having 2 to 12 carbon atoms may be straight containing 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms.
  • the cycloalkyl group having 3 to 12 carbon atoms is a cycloalkyl group having 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms, and a specific example may be a cyclopropyl group. Cyclobutyl, cyclopentyl, cyclohexyl and the like.
  • the linear or branched alkyl or alkoxy group having 1 to 12 carbon atoms the linear or branched alkenyl group or alkenyloxy group having 2 to 12 carbon atoms,
  • the liquid crystal composition further comprises at least one polymerizable compound; alternatively, the polymerizable compound is selected from any one or a combination of at least two of the compounds having the structure represented by the formula RM:
  • P 1 and P 2 are each independently
  • the compound having the structure represented by the formula RM is selected from any one or a combination of at least two of the following compounds:
  • the compound having the structure represented by the formula RM is selected from the group consisting of RM-1, RM-2, RM-3, RM-4, RM-5, RM-6, RM-7, RM-8, RM. -11, RM-12, RM-13, RM-14, RM-29, RM-30, RM-31, RM-32, RM-33 or RM-34, or a combination of at least two.
  • the polymer particles formed are relatively uniform, and it is difficult to form large polymer particles, and a bright spot is not formed in the panel to affect the display effect.
  • the liquid crystal composition of the present application may contain, in addition to the above compounds, a usual nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, an antioxidant, an ultraviolet absorber, an infrared absorber, or a light stabilizer.
  • an additive such as an antioxidant or a light stabilizer used in the liquid crystal composition of the present application, the following may be selected:
  • the light stabilizer is selected from the group consisting of stabilizers as follows:
  • n is a positive integer from 1 to 12, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.
  • the light stabilizer may optionally be 0-5% of the total weight of the liquid crystal composition; for example, 0.05%, 0.08%, 0.1%, 0.5%, 0.8%, 1%, 1.3% , 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%, optionally, the light stabilizer accounts for 0-1% of the total weight of the liquid crystal composition; Alternatively, the light stabilizer accounts for 0-0.1% of the total weight of the liquid crystal composition.
  • the present application provides a liquid crystal display device comprising the liquid crystal composition as described above.
  • liquid crystal composition of the present application has suitable optical anisotropy, dielectric anisotropy, good low-temperature mutual solubility and voltage retention, and can better solve the problem of image sticking;
  • the formed polymer particles are relatively uniform, and it is difficult to form large polymer particles, and a bright spot is not formed in the panel to affect the display effect.
  • nCPPm the number of carbon atoms of the left-end alkyl group, for example, n is 3, which means that the alkyl group is -C 3 H 7 , and C in the code indicates Cyclohexane group, P represents a phenyl group, and m represents the number of carbon atoms of the right-end alkyl group.
  • m is 2, which means that the alkyl group is -C 2 H 5 .
  • Test project code meaning ⁇ n: Optical anisotropy (589 nm, 25 ° C) ⁇ : Dielectric anisotropy (1KHz, 25°C) Cp: Clearing point (nematic-isotropic phase transition temperature, °C) LTS Low temperature stability VHR: Voltage retention VHR (initial): Initial voltage holding ratio (%) VHR (UV): Voltage retention rate after UV light irradiation (%)
  • VHR initial
  • the test temperature was 65 ° C
  • the test voltage was 5 V
  • the test frequency was 6 Hz.
  • VHR (UV) was tested using a liquid crystal property evaluation system of TOY06254 type; after the liquid crystal was irradiated with light having a wavelength of 365 nm and an energy of 6000 mJ/cm 2 , the test temperature was 65 ° C, the test voltage was 5 V, and the test frequency was 6 Hz.
  • liquid crystal compositions of the following examples can be synthesized by a known method or can be obtained commercially, and the components of the obtained liquid crystal composition are tested to meet the standards of electronic compounds.
  • the liquid crystal composition in the following examples is according to each group distribution ratio (the parental formula of the components in the parentheses at the end of the components in the respective examples), and is mixed by a conventional preparation method such as heating, ultrasonic wave, suspension, or the like. A liquid crystal composition was obtained.
  • the liquid crystal composition includes the mass percentage components as shown in the following table, and the performance test results are listed in the following table:
  • the liquid crystal composition includes the mass percentage components as shown in the following table, and the performance test results are listed in the following table:
  • the liquid crystal composition includes the mass percentage components as shown in the following table, and the performance test results are listed in the following table:
  • 3CCV(IV-1) 43% ⁇ n 0.106 3PPO1(III-1) 3% ⁇ -3.2 3C1OWO2(I-1) 10% Cp(°C) 82 2CC1OWO2 (I-2) 7% LTS (°C) ⁇ -20 3CC1OWO2 (I-2) 13% VHR (65 ° C, initial) 96.26% 2CC1ONa(3F)O2 1% VHR (65 ° C, UV) 88.33% 3PWP1 5% 3PWP2 5% 2CPP2(II-1) 5% 3CPP2(II-1) 5% 2CPP3(II-1) 3%
  • the liquid crystal composition includes the mass percentage components as shown in the following table, and the performance test results are listed in the following table:
  • 3CPO2(IV-2) 3% ⁇ n 0.104 3CPP2(II-1) 11% ⁇ -2.7 3CPPC3 (II-6) 1% Cp(°C) 73.4 3CGPC3 (II-7) 1% LTS (°C) ⁇ -20 3C1OWO2(I-1) 8% VHR (65 ° C, initial) 96.36% 2CC1OWO2 (I-2) 4% VHR (65 ° C, UV) 92.21% 3CC1OWO2 (I-2) 16% 3CCWO2 (VI-7) 4% 3CC2(IV-1) 20% 4CC3(IV-1) 4% 2CPP2(II-1) 5% 5PP1(V) 12% 3PPO2(III-1) 4% 2C1OWO2(I-1) 5% 3CPWO4 (VI-10) 2%
  • the liquid crystal composition includes the mass percentage components as shown in the following table, and the performance test results are listed in the following table:
  • 3CPO2(IV-2) 2% ⁇ n 0.109 3CPP2(II-1) 15% ⁇ -3 3C1OWO2(I-1) 12% Cp(°C) 74.6 2CC1OWO2 (I-2) 4% LTS (°C) ⁇ -20 3CC1OWO2 (I-2) 12% VHR (65 ° C, initial) 95.36% 3CCWO2 (VI-7) 7% VHR (65 ° C, UV) 90.21% 3CC2(IV-1) 18% 4CC3(IV-1) 2%
  • the liquid crystal composition includes the mass percentage components as shown in the following table, and the performance test results are listed in the following table:
  • the liquid crystal composition includes the mass percentage components as shown in the following table, and the performance test results are listed in the following table:
  • 3CPP2(II-1) 13% ⁇ n 0.120 2CPP3(II-1) 5% ⁇ -3.6 3CPPC3 (II-6) 1% Cp(°C) 76.3 3C1OWO2(I-1) 11% LTS (°C) ⁇ -20 2CC1OWO2 (I-2) 14% VHR (65 ° C, initial) 95.67% 3CC1OWO2 (I-2) 12% VHR (65 ° C, UV) 91.87% 3CC2(IV-1) 14% 2CPP2(II-1) 4% 5PP1(V) 8% 3PPO2(III-1) 4% 5PPO2(III-1) 6% 3GPO2 (III-2) 2% 2C1OWO2(I-1) 6%
  • the liquid crystal composition includes the mass percentage components as shown in the following table, and the performance test results are listed in the following table:
  • 3CGPC3 (II-7) 1% LTS (°C) ⁇ -20 3C1OWO2(I-1) 8% VHR (65 ° C, initial) 96.36% 2CC1OWO2 (I-2) 4% VHR (65 ° C, UV) 92.21% 3CC1OWO2 (I-2) 16% 3CCWO2 (VI-7) 4% 3CCV(IV-1) 15% 3CCV1(IV-1) 9% 2CPP2(II-1) 5% 5PP1(V) 12% 3PPO2(III-1) 4% 2C1OWO2(I-1) 5% 3CPWO4 (VI-10) 2%
  • liquid crystal composition included the mass percentage components shown in the following table, and the performance test results are listed in the following table:
  • liquid crystal composition included the mass percentage components shown in the following table, and the performance test results are listed in the following table:
  • liquid crystal composition included the mass percentage components shown in the following table, and the performance test results are listed in the following table:
  • liquid crystal composition included the mass percentage components shown in the following table, and the performance test results are listed in the following table:
  • 3CPO2(IV-2) 2% ⁇ n 0.105 3CPP2(II-1) 15% ⁇ -3 3C1OWO2(I-1) 12% Cp(°C) 69.3 2CC1OWO2 (I-2) 4% LTS (°C) ⁇ -20 3CC1OWO2 (I-2) 12% VHR (65 ° C, initial) 93.16% 3CCWO2 (VI-7) 7% VHR (65 ° C, UV) 88.23% 3CC2(IV-1) 18% 4CC3(IV-1) 2% 5PP1(V) 14% 2C1OWO2(I-1) 4% 3OWWO4O1 (VI-6) 2% 2CPP2(II-1) 8%
  • liquid crystal composition of the present application has good low-temperature mutual solubility while maintaining a relatively high clearing point, dielectric anisotropy, and optical anisotropy. And the voltage retention rate, the problem of image sticking can be better solved; it can be seen from the comparison between Example 5 and Comparative Example 4 that the liquid crystal composition of the present application is improved in addition to low-temperature mutual solubility and voltage holding ratio. And optical anisotropy has also been significantly improved.
  • the composition of the present application when used in combination with a polymerizable material, the composition of the present application can make the polymerizable material polymerize uniformly, and the phenomenon of poor bright spots is less likely to occur, and the display panel of the liquid crystal display device is improved. The display effect.
  • the present application describes the liquid crystal composition and the liquid crystal display device of the present application by the above embodiments, but the present application is not limited to the above embodiments, that is, it does not mean that the present application must be implemented by relying on the above embodiments.

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Abstract

本申请提供了一种液晶组合物和液晶显示器件，所述液晶组合物包含至少一种通式I的化合物、至少一种通式II的化合物以及至少一种通式III的化合物，通过这三种化合物的配合，可以使得该组合物具有更好的更高的光学各向异性，介电各向异性，良好的低温互溶性，以及优异的电阻率和紫外线照射后电压保持率。

Description

一种液晶组合物及液晶显示器件 技术领域
本申请属于液晶材料技术领域，涉及一种液晶组合物及液晶显示器件。
背景技术
液晶显示元件以钟表、电子计算器、显示屏幕为代表被应用至家电、电脑、手机、电子词典等各领域中。作为液晶显示方式，其代表性的方式为TN(扭转向列)型、STN(超扭转向列)型、DS(动态光散射)型、GH(宾主)型、IPS(面内切换)型、OCB(光学补偿双折射)型、ECB(电压控制双折射)型、VA(垂直取向)型、CSH(彩色超垂直)型、FLS(强介电性液晶)型或者PSA(聚合物稳定配向)型等。根据元件的驱动方式分为PM(被动矩阵)型和AM(主动矩阵)型。PM分为静态和多路等类型。AM分为TFT(薄膜晶体管)、MIM(金属-绝缘层-金属)等类型。无论何种显示模式均要求所使用的液晶材料具有低的驱动电压、高的响应速度、宽的操作温度范围、介电各向异性的绝对值较大、相转移温度高以及良好的互溶性。
然而，相关技术中，很难得到一种同时具备大的负介电各向异性的绝对值、低温稳定性好且响应迅速的液晶组合物。介电各向异性的绝对值大的液晶组合物，临界电压高，消耗的电力也高，响应速度也会相对较慢。因此，为了适应越来越高的应用需求，本领域内存在着持续改进负介电各向异性的液晶化合物的需求。
另外，随着液晶显示领域的发展，液晶面板的厚度越来越薄，对于液晶显示元件的显示效果也提出了更高的要求，而且由于液晶显示器在制造和使用过程中会经历可见光UV辐射、高温以及长时间的寻址驱动，很多液晶介质并不能很好地解决显示品质存在的问题，导致液晶显示元件的成品率恶化，其中，影像残留是液晶显示元件品质问题的代表之一。
影像残留是在同一个画面下，液晶由于受到长时间的驱动被极化，造成液晶偏转不受信号电压控制，使屏幕上一段时间内显示同一画面，而该现象也随着时间的推移有所减弱，最后达到消失。而影像残留又分为线残留和面残留，其中，线残留与液晶材料本身的可靠性有很大关系，常用来表征液晶材料可靠性的性能参数为电压保持率(VHR)，VHR越高，液晶材料受干扰因素(如液晶杂质、高低温、UV辐射等)影响的可能性越低。
然而目前的液晶介质并不能同时满足如上所述的要求，例如日本特开平9-124529和日本特开2006-169472公开的液晶组合物虽然其中加入了对热稳定的抗氧剂，然而其对光、热的稳定性仍然较差，不能满足要求。
因此，如何开发一种既能够保证具有合适的光学各向异性、介电各向异性的同时，还具有相对较高的电压保持率VHR，从而提高液晶显示器件的显示品质的液晶组合物是本领域的研究重点。
发明内容
本申请的目的在于提供一种液晶组合物及液晶显示器件，本申请的液晶组合物具有合适的光学各向异性、介电各向异性，还具有良好的低温互溶性和电压保持率。
为达此目的，本申请采用以下技术方案：
一方面，本申请提供一种液晶组合物，所述液晶组合物包含至少一种通式I的化合物、至少一种通式II的化合物以及至少一种通式III的化合物：
Figure PCTCN2019079484-appb-000001
其中R 1、R 2、R 3、R 4和R 5各自独立地为含有1-12个碳原子的直链或支链的烷基或烷氧基、含有2-12个碳原子的直链或支链的烯基或烯氧基、含3-12个碳原子的环烷基中的任意一种；或者所述含有1-12个碳原子的直链或支链的烷基或烷氧基、含有2-12个碳原子的直链或支链的烯基或烯氧基、含3-12个碳原子的环烷基中的一个或两个不相邻的-CH 2-基团以氧原子不直接相邻的方式被-O-、-CH＝CH-、-CO-、-OCO-或-COO-基团替代后的基团；R 6为含有1-12个碳原子的直链或支链的烷基；环
Figure PCTCN2019079484-appb-000002
各自独立地为
Figure PCTCN2019079484-appb-000003
Figure PCTCN2019079484-appb-000004
n 1为1或2；n 2为0或1；m 1和m 2独立地为0或1。
在本申请中，由于液晶组合物中同时包含通式I、II和III的化合物，组分相互配合使得该组合物具有更高的光学各向异性，介电各向异性，良好的低温互溶性，以及优异的电压保持率，可以更好地解决图像残留的问题。
可选地，所述通式I的化合物占液晶组合物总重量的1-60％，例如1％、2％、4％、6％、8％、10％、15％、20％、25％、30％、35％、40％、45％、50％、55％、60％，可选5-50％，可选10-45％；所述通式III的化合物占液晶组合物总重量的1-20％，例如1％、2％、4％、6％、8％、10％、12％、14％、16％、18％或20％。如果通式III的化合物含量高于20％，则液晶组合物的互溶性就会变差。
可选地，所述通式II的化合物占液晶组合物总重量的10％以上，例如10％、12％、13％、15％、18％、20％、23％、25％、28％或30％，可选10-30％，可选13-30％，可选15-30％。如果通式II的化合物含量低于10％，则液晶组合物的相转变温度就会降低，使得液晶组合物的工作场景产生限制。
可选地，所述通式I的化合物为：
Figure PCTCN2019079484-appb-000005
Figure PCTCN2019079484-appb-000006
其中R 1和R 2的限定如上文所述，在此不再赘述。
所述通式II的化合物为具有如下结构的化合物中的任意一种或至少两种的组合：
Figure PCTCN2019079484-appb-000007
Figure PCTCN2019079484-appb-000008
其中R 3和R 4的限定如上文所述，在此不再赘述。
所述通式III的化合物为具有如下结构的化合物中的任意一种或至少两种的组合：
Figure PCTCN2019079484-appb-000009
其中R 5和R 6的限定如上文所述，在此不再赘述。
在本申请中，所述含有1-12个碳原子的直链或支链的烷基或烷氧基可以为含有1、2、3、4、5、6、7、8、9、10、11或12个碳原子的直链或支链的烷基或烷氧基。在本申请中，所述直链或支链的烷基的实例可以为甲基、乙基、丙基、异丙基、丁基、戊基、辛基、庚基、葵基、十二烷基等。所述直链或支链的烷氧基的实例可以为甲氧基、乙氧基、丙氧基、丁氧基等。
可选地，本申请所述液晶组合物还包含至少一种通式IV的化合物：
Figure PCTCN2019079484-appb-000010
其中R 7和R 8各自独立地为含有1-12个碳原子的直链或支链的烷基或烷氧基、含有2-12个碳原子的直链或支链的烯基或烯氧基、含3-12个碳原子的环烷基；或者所述含有1-12个碳原子的直链或支链的烷基或烷氧基、2-12个碳原子的直链或支链的烯基或烯氧基、含3-12个碳原子的环烷基中一个或两个不相邻的-CH 2-基团以氧原子不直接相邻的方式被-O-、-CH＝CH-、-CO-、-OCO-或-COO-替代后的基团，环
Figure PCTCN2019079484-appb-000011
为
Figure PCTCN2019079484-appb-000012
Figure PCTCN2019079484-appb-000013
Z 1为-CH 2CH 2-、-CH 2O-、-OCH 2-、-CO-O-、-O-CO-或单键，n 3为0、1或2，a为0或1，当a为0时，n 3为1且环
Figure PCTCN2019079484-appb-000014
不为
Figure PCTCN2019079484-appb-000015
可选地，所述通式IV的化合物占液晶组合物总重量的5-80％，例如5％、8％、10％、15％、20％、25％、30％、35％、40％、45％、50％、55％、60％、65％、70％、75％或80％，可选10-70％，可选15-60％。
可选地，所述通式IV的化合物为具有如下结构的化合物中的任意一种或至少两种的组合：
Figure PCTCN2019079484-appb-000016
Figure PCTCN2019079484-appb-000017
其中R 7和R 8的限定如上文所述，在此不再赘述。
可选地，本申请所述液晶组合物还包含至少一种通式V的化合物：
Figure PCTCN2019079484-appb-000018
其中，X 1和X 2独立地为含有1-12个碳原子的直链或支链的烷基，含有2-12个碳原子的直链或支链的烯基。
可选地，所述通式V的化合物占液晶组合物总重量的1-30％，例如1％、3％、5％、8％、10％、13％、15％、18％、20％、23％、25％、28％或30％，可选1-20％，可选1-15％。
可选地，本申请所述液晶组合物还包含至少一种通式VI的化合物：
Figure PCTCN2019079484-appb-000019
其中，R 9和R 10各自独立地为含有1-12个碳原子的直链或支链的烷基或烷氧基、含有2-12个碳原子的直链或支链的烯基或烯氧基、含3-12个碳原子的环烷基中的任意一种，或者所述含有1-12个碳原子的直链或支链的烷基或烷氧基、含有2-12个碳原子的直链或支链的烯基或烯氧基、含3-12个碳原子的环烷基中一个或两个不相邻的-CH 2-基团以氧原子不直接相邻的方式被-O-、-CH＝CH-、-CO-、-OCO-或-COO-替代后的基团；环
Figure PCTCN2019079484-appb-000020
为
Figure PCTCN2019079484-appb-000021
Figure PCTCN2019079484-appb-000022
n 4为1、2或3；Z 2为-CH 2CH 2-、-CO-O-、-O-CO-、-C≡C-或单键。
可选地，所述通式VI的化合物占液晶组合物总重量的0-60％，例如0％、1％、3％、5％、8％、10％、15％、18％、20％、25％、30％、35％、40％、45％、50％、55％或60％，可选1-30％，可选1-20％。
可选地，所述通式VI的化合物为具有如下结构的化合物中的任意一种或至少两种的组合：
Figure PCTCN2019079484-appb-000023
Figure PCTCN2019079484-appb-000024
Figure PCTCN2019079484-appb-000025
其中R 9和R 10的限定如上文所述，在此不再赘述。
在本申请中，所述含有2-12个碳原子的烯基或烯氧基可以为含有2、3、4、5、6、7、8、9、10、11或12个碳原子的直链或支链的烯基或烯氧基。在本申请中，所述直链或支链的烯基的实例可以为H 2C＝CH-、H 3C-HC＝CH-、H 2C＝CH-HC＝CH-、H 3C-HC＝CH-HC＝CH-等，所述直链或支链的烯氧基的实例可以为H 2C＝CH-O-、H 3C-HC＝CH-O-、CH 2＝CH-HC＝CH-O-等。
可选地，所述含3-12个碳原子的环烷基为碳原子数为3、4、5、6、7、8、9或10的环烷基，具体实例可以为环丙基、环丁基、环戊基、环己基等。
在本申请中，所述含有1-12个碳原子的直链或支链的烷基或烷氧基、含有2-12个碳原子的直链或支链的烯基或烯氧基、含3-12个碳原子的环烷基中的一个或两个不相邻的-CH 2-基团以氧原子不直接相邻的方式被-O-、-CH＝CH-、-CO-、-OCO-或-COO-基团替代是指在含有1-12个碳原子的直链或支链的烷基或烷氧基、含有2-12个碳原子的直链或支链的烯基或烯氧基、含3-12个碳原子的环烷基中-CH 2-基团可以被-O-、-CH＝CH-、-CO-、-OCO-或-COO-基团所取代，但是不能是相邻的两个-CH 2-基团同时被取代，并且不能以氧原子直接相连的方式进行取代，例如将-OCH 2CH 2CH 3中一个-CH 2-替换成-O-即为-CH 2OCH 3，将-OCH 2CH 2CH 3中一个-CH 2-替换成-O-即为-OCH 2OCH 3，而不能是-OOCH 2CH 3。
可选地，所述液晶组合物还包含至少一种可聚合化合物；可选地，所述可聚合化合物选自具有通式RM所示结构的化合物中的任意一种或至少两种的组合：
Figure PCTCN2019079484-appb-000026
其中，P 1和P 2各自独立地为
Figure PCTCN2019079484-appb-000027
Figure PCTCN2019079484-appb-000028
Figure PCTCN2019079484-appb-000029
或-SH；r 1为1-3的整数(例如1、2或3)；r 2和r 3各自独立地为0-6的整数(例如0、1、2、3、4、5或6)；r 4和r 5各自独立地为0-4的整数(例如0、1、2、3或4)；Z为单键、-CH 2CH 2-、-COO-、-OCO-、-CH 2O-、-OCH 2-或-CH＝CH-COO-；Z p1和Z p2相同或不同，各自 独立地选自单键、-O-、-S-、-NH-、-NHCOO-、-OCONH-、-CF 2O-、-OCF 2-、-CF 2S-、-SCF 2-、-CH 2CH 2-、-CF 2CH 2-、-CH 2CF 2-、-CF 2CF 2-、-CF＝CH-、-CH＝CF-、-CF＝CF-、-CO-、-COO-、-OCO-、-OCOO-、-CH 2-、-OCH 2-、-SCH 2-、-CH 2S-、-CH＝CH-、-C≡C-、-CH＝CH-COO-或-OCO-CH＝CH-；Y 1和Y 2各自独立地为H、卤素、C原子数为1-3(例如1、2或3)的烷基或烷氧基；
可选地，P 1和P 2各自独立地为
Figure PCTCN2019079484-appb-000030
可选地，所述具有通式RM所示结构的化合物选自如下化合物中的任意一种或至少两种的组合：
Figure PCTCN2019079484-appb-000031
Figure PCTCN2019079484-appb-000032
Figure PCTCN2019079484-appb-000033
Figure PCTCN2019079484-appb-000034
Figure PCTCN2019079484-appb-000035
可选地，所述具有通式RM所示结构的化合物选自RM-1、RM-2、RM-3、RM-4、RM-5、RM-6、RM-7、RM-8、RM-11、RM-12、RM-13、RM-14、RM-29、RM-30、RM-31、RM-32、RM-33或RM-34中的任意一种或至少两种的组合。
将本申请的液晶组合物与可聚合化合物在聚合时，形成的聚合颗粒比较均匀，不易形成较大的聚合颗粒，进而在面板内不会形成亮点而影响显示效果。
本申请的液晶组合物除上述化合物以外，也可含有通常的向列型液晶、近晶型液晶、胆固醇型液晶、抗氧化剂、紫外线吸收剂、红外线吸收剂或光稳定剂等。
作为本申请的液晶组合物所使用的抗氧化剂、光稳定剂等添加剂可选以下物质：
Figure PCTCN2019079484-appb-000036
Figure PCTCN2019079484-appb-000037
Figure PCTCN2019079484-appb-000038
Figure PCTCN2019079484-appb-000039
可选地，所述光稳定剂选自如下所示的稳定剂：
Figure PCTCN2019079484-appb-000040
其中n为1-12的正整数，例如1、2、3、4、5、6、7、8、9、10、11或12。
在本申请的实施方案中，可选所述光稳定剂占所述液晶组合物总重量的0-5％；例如0.05％、0.08％、0.1％、0.5％、0.8％、1％、1.3％、1.5％、2％、2.5％、3％、3.5％、4％、4.5％或5％，可选地，所述光稳定剂占所述液晶组合物总重量的0-1％；作为可选方案，所述光稳定剂占所述液晶组合物总重量的0-0.1％。
另一方面，本申请提供一种液晶显示器件，所述液晶显示器件包含如上所述的液晶组合物。
相对于相关技术，本申请具有以下有益效果：
(1)本申请的液晶组合物具有合适的光学各向异性、介电各向异性，还具有良好的低温互溶性和电压保持率，可以更好地解决图像残留的问题；
(2)将本申请的液晶组合物与可聚合化合物聚合时，形成的聚合颗粒比较均匀，不易形成较大的聚合颗粒，进而在面板内不会形成亮点而影响显示效果。
具体实施方式
下面通过具体实施方式来进一步说明本申请的技术方案。本领域技术人员应该明了，所 述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。
为了便于表达，在以下实施例中，液晶组合物的基团结构以表1中所列的代码来表示：
表1液晶组合物中化合物基团结构代码
Figure PCTCN2019079484-appb-000041
Figure PCTCN2019079484-appb-000042
以如下结构式的化合物为例对其结构代码进行说明：
Figure PCTCN2019079484-appb-000043
该结构式如果用表1所示代码表示，则可以表达为nCPPm，代码中n表示左端烷基的碳原子数，例如n为3，即表示该烷基为-C 3H 7，代码中C表示环己烷基，P表示苯基，m表示右端烷基的碳原子数，例如m为2，即表示该烷基为-C 2H 5。
在以下实施例中，性能测试项目的简写代号如表2所示。
表2性能测试项目简写代号
测试项目代号 含义
Δn： 光学各向异性(589nm，25℃)
Δε： 介电各向异性(1KHz，25℃)
Cp： 清亮点(向列-各向同性相转变温度，℃)
LTS 低温稳定性
VHR： 电压保持率
VHR(初始)： 初始电压保持率(％)
VHR(UV)： UV光照射后的电压保持率(％)
其中，VHR(初始)是使用TOY06254型液晶物性评价系统测试得；测试温度为65℃，测试电压为5V，测试频率为6Hz。
VHR(UV)是使用TOY06254型液晶物性评价系统测试得；使用波长为365nm、能量为6000mJ/cm 2的光照射液晶后测试，测试温度65℃，测试电压为5V，测试频率为6Hz。
在本以下实施例的液晶组合物中所采用的各成分，均可以通过公知的方法进行合成或者可以通过商业途径获得，所得液晶组合物的各成分经测试符合电子类化合物标准。
以下实施例中的液晶组合物按照各组分配比(各实施例中组分末尾的括号中为所述组分的归属通式)，并通过常规制备方法如采用加热、超声波、悬浮等方式混合得到液晶组合物。
实施例1
在本实施例中，液晶组合物包括如下表所示质量百分含量的组分，并且在下表中列出了其性能测试结果：
5CCEWCO2 3％ △n 0.104
5CPEWC3 3％ △ε -2.7
5CCQWP3 3％ Cp(℃) 82.7
3CCV(IV-1) 12％ LTS(℃) ＜-20
3CCV1(IV-1) 5％ VHR(65℃，初始) 95.23％
VCWO2(VI-1) 3％ VHR(65℃，UV) 86.26％
1VCWO2(VI-1) 5％    
3C2WO2(VI-2) 21％    
3CC2WO2(VI-8) 3％    
2PWP4 2％    
2C1OWO2(I-1) 5％    
VC1OWO2(I-1) 5％    
VPP1(V) 4％    
3CCEPC3(IV-9) 5％    
3CPPC3(II-6) 3％    
3CGPC3(II-7) 3％    
3CGPC2(II-7) 3％    
3PPO4(III-1) 6％    
3CPP2(II-1) 6％    
实施例2
在本实施例中，液晶组合物包括如下表所示质量百分含量的组分，并且在下表中列出了其性能测试结果：
5CC1OWC3 2％ △n 0.084
5CC1OWCO2 2％ △ε -3
3CCV(IV-1) 28％ Cp(℃) 85.1
3CCV1(IV-1) 7％ LTS(℃) ＜-20
VCWO3(VI-1) 4％ VHR(65℃，初始) 95.73％
3C2WO2(VI-2) 8％ VHR(65℃，UV) 87.67％
5CC2WO2(VI-8) 2％    
3CC1OWO2(I-2) 5％    
VC1OWO2(I-1) 6％    
3AICWO2(VI) 5％    
3ACWO2(VI) 5％    
3CC1OW(1)O2 3％    
5CP(F，Cl)O2 3％    
VPPO1(III-1) 3％    
3CCEC5(IV-5) 1％    
1O1CPPC4(II-6) 3％    
3CPPC3(II-6) 2％    
3CPP2(II-1) 11％    
实施例3
在本实施例中，液晶组合物包括如下表所示质量百分含量的组分，并且在下表中列出了其性能测试结果：
3CCV(IV-1) 43％ △n 0.106
3PPO1(III-1) 3％ △ε -3.2
3C1OWO2(I-1) 10％ Cp(℃) 82
2CC1OWO2(I-2) 7％ LTS(℃) ＜-20
3CC1OWO2(I-2) 13％ VHR(65℃，初始) 96.26％
2CC1ONa(3F)O2 1％ VHR(65℃，UV) 88.33％
3PWP1 5％    
3PWP2 5％    
2CPP2(II-1) 5％    
3CPP2(II-1) 5％    
2CPP3(II-1) 3％    
实施例4
在本实施例中，液晶组合物包括如下表所示质量百分含量的组分，并且在下表中列出了其性能测试结果：
3CPO2(IV-2) 3％ △n 0.104
3CPP2(II-1) 11％ △ε -2.7
3CPPC3(II-6) 1％ Cp(℃) 73.4
3CGPC3(II-7) 1％ LTS(℃) ＜-20
3C1OWO2(I-1) 8％ VHR(65℃，初始) 96.36％
2CC1OWO2(I-2) 4％ VHR(65℃，UV) 92.21％
3CC1OWO2(I-2) 16％    
3CCWO2(VI-7) 4％    
3CC2(IV-1) 20％    
4CC3(IV-1) 4％    
2CPP2(II-1) 5％    
5PP1(V) 12％    
3PPO2(III-1) 4％    
2C1OWO2(I-1) 5％    
3CPWO4(VI-10) 2％    
实施例5
在本实施例中，液晶组合物包括如下表所示质量百分含量的组分，并且在下表中列出了其性能测试结果：
3CPO2(IV-2) 2％ △n 0.109
3CPP2(II-1) 15％ △ε -3
3C1OWO2(I-1) 12％ Cp(℃) 74.6
2CC1OWO2(I-2) 4％ LTS(℃) ＜-20
3CC1OWO2(I-2) 12％ VHR(65℃，初始) 95.36％
3CCWO2(VI-7) 7％ VHR(65℃，UV) 90.21％
3CC2(IV-1) 18％    
4CC3(IV-1) 2％    
5PP1(V) 7％    
3PPO2(III-1) 7％    
2C1OWO2(I-1) 4％    
3OWWO4O1(VI-6) 2％    
2CPP2(II-1) 8％    
实施例6
在本实施例中，液晶组合物包括如下表所示质量百分含量的组分，并且在下表中列出了其性能测试结果：
3CPP2(II-1) 13％ △n 0.109
2CPP3(II-1) 5％ △ε -3.1
3CPPC3(II-6) 1％ Cp(℃) 75
3C1OWO2(I-1) 11％ LTS(℃) ＜-20
2CC1OWO2(I-2) 6％ VHR(65℃，初始) 95.87％
3CC1OWO2(I-2) 10％ VHR(65℃，UV) 93.34％
3CCWO2(VI-7) 6％    
3CC2(IV-1) 19％    
2CPP2(II-1) 4.5％    
5PP1(V) 12％    
3PPO2(III-1) 3.5％    
2C1OWO2(I-1) 4％    
4C1OWO2(I-1) 3％    
3CPWO4O1(VI-10) 2％    
实施例7
在本实施例中，液晶组合物包括如下表所示质量百分含量的组分，并且在下表中列出了其性能测试结果：
3CPP2(II-1) 13％ △n 0.120
2CPP3(II-1) 5％ △ε -3.6
3CPPC3(II-6) 1％ Cp(℃) 76.3
3C1OWO2(I-1) 11％ LTS(℃) ＜-20
2CC1OWO2(I-2) 14％ VHR(65℃，初始) 95.67％
3CC1OWO2(I-2) 12％ VHR(65℃，UV) 91.87％
3CC2(IV-1) 14％    
2CPP2(II-1) 4％    
5PP1(V) 8％    
3PPO2(III-1) 4％    
5PPO2(III-1) 6％    
3GPO2(III-2) 2％    
2C1OWO2(I-1) 6％    
实施例8
在本实施例中，液晶组合物包括如下表所示质量百分含量的组分，并且在下表中列出了其性能测试结果：
3CPO2(IV-2) 3％ △n 0.107
3CPP2(II-1) 11％ △ε -2.7
3CPPC3(II-6) 1％ Cp(℃) 80.2
3CGPC3(II-7) 1％ LTS(℃) ＜-20
3C1OWO2(I-1) 8％ VHR(65℃，初始) 96.36％
2CC1OWO2(I-2) 4％ VHR(65℃，UV) 92.21％
3CC1OWO2(I-2) 16％    
3CCWO2(VI-7) 4％    
3CCV(IV-1) 15％    
3CCV1(IV-1) 9％    
2CPP2(II-1) 5％    
5PP1(V) 12％    
3PPO2(III-1) 4％    
2C1OWO2(I-1) 5％    
3CPWO4(VI-10) 2％    
对比例1
在该对比例中，液晶组合物包括如下表所示质量百分含量的组分，并且在下表中列出了其性能测试结果：
5CCEWCO2(IV) 6％ △n 0.106
5CPEWC3 3％ △ε -3
5CCQWP3 3％ Cp(℃) 84.3
3CCV(IV-1) 12％ LTS(℃) ＜-20
3CCV1(IV-1) 5％ VHR(65℃，初始) 93.26％
VCWO2(VI-1) 3％ VHR(65℃，UV) 84.23％
1VCWO2(VI-1) 5％    
3C2WO2(VI-2) 15％    
3CC2WO2(VI-8) 3％    
2PWP4 5％    
2C1OWO2(I-1) 11％    
VC1OWO2(I-1) 5％    
VPP1(V) 10％    
3CCEPC3(IV-9) 5％    
3CPPC3(II-6) 3％    
3CGPC3(II-7) 3％    
3CGPC2(II-7) 3％    
对比例2
在该对比例中，液晶组合物包括如下表所示质量百分含量的组分，并且在下表中列出了其性能测试结果：
5CC1OWC3 5％ △n 0.081
5CC1OWCO2 5％ △ε -3
3CCV(IV-1) 28％ Cp(℃) 83.3
3CCV1(IV-1) 7％ LTS(℃) ＜-20
VCWO3(VI-1) 4％ VHR(65℃，初始) 94.71％
3C2WO2(VI-2) 8％ VHR(65℃，UV) 85.17％
5CC2WO2(VI-8) 12％    
VC1OWO2(I-1) 6％    
3AICWO2(VI) 5％    
3ACWO2(VI) 5％    
3CC1OW(1)O2 3％    
5CP(F，Cl)O2 3％    
VPPO2(III-1) 3％    
3CCEC5(IV-5) 3％    
1O1CPPC4(II-6) 3％    
对比例3
在该对比例中，液晶组合物包括如下表所示质量百分含量的组分，并且在下表中列出了其性能测试结果：
3CCV(IV-1) 43％ △n 0.107
3PPO1(III-1) 3％ △ε -3.3
3C1OWO2(I-1) 7％ Cp(℃) 80
2CC1OWO2(I-2) 13％ LTS(℃) ＜-10
3CC1OWO2(I-2) 13％ VHR(65℃，初始) 95.26％
2CC1ONa(3F)O2 3％ VHR(65℃，UV) 78.33％
3PWP1 9％    
3PWP2 9％    
对比例4
在该对比例中，液晶组合物包括如下表所示质量百分含量的组分，并且在下表中列出了其性能测试结果：
3CPO2(IV-2) 2％ △n 0.105
3CPP2(II-1) 15％ △ε -3
3C1OWO2(I-1) 12％ Cp(℃) 69.3
2CC1OWO2(I-2) 4％ LTS(℃) ＜-20
3CC1OWO2(I-2) 12％ VHR(65℃，初始) 93.16％
3CCWO2(VI-7) 7％ VHR(65℃，UV) 88.23％
3CC2(IV-1) 18％    
4CC3(IV-1) 2％    
5PP1(V) 14％    
2C1OWO2(I-1) 4％    
3OWWO4O1(VI-6) 2％    
2CPP2(II-1) 8％    
由实施例1-3与对比例1-3对比可以看到，本申请的液晶组合物在维持相对高的清亮点、介电各向异性、光学各向异性的同时，具有良好的低温互溶性和电压保持率，可以更好地解决图像残留的问题；由实施例5与对比例4对比可以看到，本申请的液晶组合物除了在低温互溶性及电压保持率方面得到改善外，清亮点和光学各向异性也得到明显改善。
实施例9
在本实施例中，将实施例1-8以及对比例1-4的液晶组合物中分别加入0.3％对的可聚合化合物RM-13，完全溶解后分别灌入4μm的负性液晶垂面排列(VA)盒中，施加16V的电压并经UV照射180s，使用光学显微镜观察孔内的聚合亮点情况，结果如表4所示。
表4
Figure PCTCN2019079484-appb-000044
Figure PCTCN2019079484-appb-000045
由表4数据可以看出，当本申请的液晶组合物与可聚合材料组合使用时，本申请组合物可以使得可聚合材料聚合均匀，更不容易出现亮点不良的现象，提高液晶显示器件显示面板的显示效果。
本申请通过上述实施例来说明本申请的液晶组合物以及液晶显示器件，但本申请并不局限于上述实施例，即不意味着本申请必须依赖上述实施例才能实施。

Claims (10)

  1. 一种液晶组合物，其中，所述液晶组合物包含至少一种通式I的化合物、至少一种通式II的化合物以及至少一种通式III的化合物：
    Figure PCTCN2019079484-appb-100001
    R 1、R 2、R 3、R 4和R 5各自独立地为含有1-12个碳原子的直链或支链的烷基或烷氧基、含有2-12个碳原子的直链或支链的烯基或烯氧基、含3-12个碳原子的环烷基中的任意一种，或者所述含有1-12个碳原子的直链或支链的烷基或烷氧基、含有2-12个碳原子的直链或支链的烯基或烯氧基或含3-12个碳原子的环烷基中的一个或两个不相邻的-CH 2-基团以氧原子不直接相邻的方式被-O-、-CH＝CH-、-CO-、-OCO-或-COO-基团替代后的基团；
    R 6为含有1-12个碳原子的直链或支链的烷基；环
    Figure PCTCN2019079484-appb-100002
    各自独立地为
    Figure PCTCN2019079484-appb-100003
    n 1为1或2；n 2为0或1；m 1和m 2独立地为0或1。
  2. 根据权利要求1所述的液晶组合物，其中，所述通式I的化合物占液晶组合物总重量的1-60％，可选5-50％，可选10-45％；所述通式III的化合物占液晶组合物总重量的1-20％。
  3. 根据权利要求1或2所述的液晶组合物，其中，所述通式II的化合物占液晶组合物总重量的10％以上，可选10-30％，可选13-30％，可选15-30％。
  4. 根据权利要求1-3中任一项所述的液晶组合物，其中，所述通式I的化合物为：
    Figure PCTCN2019079484-appb-100004
    所述通式II的化合物为具有如下结构的化合物中的任意一种或至少两种的组合：
    Figure PCTCN2019079484-appb-100005
    Figure PCTCN2019079484-appb-100006
    所述通式III的化合物为具有如下结构的化合物中的任意一种或至少两种的组合：
    Figure PCTCN2019079484-appb-100007
  5. 根据权利要求1-4中任一项所述的液晶组合物，其中，所述液晶组合物还包含至少一种通式IV的化合物：
    Figure PCTCN2019079484-appb-100008
    其中R 7和R 8各自独立地为含有1-12个碳原子的直链或支链的烷基或烷氧基、含有2-12个碳原子的直链或支链的烯基或烯氧基、含3-12个碳原子的环烷基中的任意一种；或者所述含有1-12个碳原子的直链或支链的烷基或烷氧基、2-12个碳原子的直链或支链的烯基或烯氧基、含3-12个碳原子的环烷基中一个或两个不相邻的-CH 2-基团以氧原子不直接相邻的方式 被-O-、-CH＝CH-、-CO-、-OCO-或-COO-替代后的基团，环
    Figure PCTCN2019079484-appb-100009
    为
    Figure PCTCN2019079484-appb-100010
    Figure PCTCN2019079484-appb-100011
    Z 1为-CH 2CH 2-、-CH 2O-、-OCH 2-、-CO-O-、-O-CO-或单键，n 3为0、1或2，a为0或1，当a为0时，n 3为1且环
    Figure PCTCN2019079484-appb-100012
    不为
    Figure PCTCN2019079484-appb-100013
    可选地，所述通式IV的化合物占液晶组合物总重量的5-80％，可选10-70％，可选15-60％；
    可选地，所述通式IV的化合物为具有如下结构的化合物中的任意一种或至少两种的组合：
    Figure PCTCN2019079484-appb-100014
  6. 根据权利要求1-5中任一项所述的液晶组合物，其中，所述液晶组合物还包含至少一种通式V的化合物：
    Figure PCTCN2019079484-appb-100015
    其中，X 1和X 2独立地为含有1-12个碳原子的直链或支链的烷基，含有2-12个碳原子的直链或支链的烯基；
    可选地，所述通式V的化合物占液晶组合物总重量的1-30％，可选1-20％，可选1-15％。
  7. 根据权利要求1-6中任一项所述的液晶组合物，其中，所述液晶组合物还包含至少一 种通式VI的化合物：
    Figure PCTCN2019079484-appb-100016
    其中，R 9和R 10各自独立地为含有1-12个碳原子的直链或支链的烷基或烷氧基、含有2-12个碳原子的直链或支链的烯基或烯氧基、含3-12个碳原子的环烷基中的任意一种，或者所述含有1-12个碳原子的直链或支链的烷基或烷氧基、含有2-12个碳原子的直链或支链的烯基或烯氧基、含3-12个碳原子的环烷基中一个或两个不相邻的-CH 2-基团以氧原子不直接相邻的方式被-O-、-CH＝CH-、-CO-、-OCO-或-COO-替代后的基团；环
    Figure PCTCN2019079484-appb-100017
    为
    Figure PCTCN2019079484-appb-100018
    Figure PCTCN2019079484-appb-100019
    n 4为1、2或3；Z 2为-CH 2CH 2-、-CO-O-、-O-CO-、-C≡C-或单键；
    可选地，所述通式VI的化合物占液晶组合物总重量的0-60％，可选1-30％，可选1-20％；
    可选地，所述通式VI的化合物为具有如下结构的化合物中的任意一种或至少两种的组合：
    Figure PCTCN2019079484-appb-100020
    Figure PCTCN2019079484-appb-100021
  8. 根据权利要求1-7中任一项所述的液晶组合物，其中，所述液晶组合物还包含至少一种可聚合化合物。
  9. 一种液晶显示器件，其中，所述液晶显示器件包含如权利要求1-8中任一项所述的液晶组合物。
  10. 根据权利要求9所述的液晶显示器件，其中，所述液晶显示器件的显示方式为垂直取向型、面内切换型或聚合物稳定配向型，所述液晶显示器件的驱动方式为主动矩阵型。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020097678A (ja) * 2018-12-18 2020-06-25 Dic株式会社 液晶組成物及び液晶表示素子
JP7380059B2 (ja) 2019-10-15 2023-11-15 Dic株式会社 液晶組成物及び液晶表示素子、並びに化合物

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113293009B (zh) * 2021-06-07 2023-09-26 浙江汽车仪表有限公司 一种显示材料

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102057016A (zh) * 2008-06-16 2011-05-11 智索株式会社 液晶组成物以及液晶显示元件
CN102186946A (zh) * 2008-10-15 2011-09-14 Jnc株式会社 液晶组成物以及液晶显示元件
CN102292412A (zh) * 2009-01-22 2011-12-21 Jnc株式会社 液晶组成物以及液晶显示元件
CN106978194A (zh) * 2015-10-02 2017-07-25 东进世美肯株式会社 液晶组合物

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101886175B1 (ko) * 2011-12-21 2018-08-08 디아이씨 가부시끼가이샤 네마틱 액정 조성물 및 이것을 사용한 액정 표시 소자
JP6337335B2 (ja) * 2014-02-25 2018-06-06 Jnc株式会社 液晶組成物および液晶表示素子
CN105441085A (zh) * 2014-08-26 2016-03-30 江苏和成显示科技股份有限公司 液晶组合物及其液晶显示元件
TW201632609A (zh) * 2014-12-12 2016-09-16 Dainippon Ink & Chemicals 液晶顯示元件及其製造方法
KR20180022634A (ko) * 2015-06-24 2018-03-06 디아이씨 가부시끼가이샤 네마틱 액정 조성물 및 이것을 사용한 액정 표시 소자
WO2017026479A1 (ja) * 2015-08-11 2017-02-16 Dic株式会社 液晶表示素子
JPWO2017065078A1 (ja) * 2015-10-16 2018-03-08 Dic株式会社 ネマチック液晶組成物及びこれを用いた液晶表示素子
JP6745814B2 (ja) * 2015-11-10 2020-08-26 Dic株式会社 ネマチック液晶組成物及びこれを用いた液晶表示素子
TW201723153A (zh) * 2015-11-11 2017-07-01 Dainippon Ink & Chemicals 組成物及使用其之液晶顯示元件
JP2017095630A (ja) * 2015-11-26 2017-06-01 Dic株式会社 組成物及びそれを使用した液晶表示素子
TWI726081B (zh) * 2016-04-12 2021-05-01 日商迪愛生股份有限公司 液晶顯示元件及其製造方法
WO2017188002A1 (ja) * 2016-04-27 2017-11-02 Dic株式会社 液晶組成物及び液晶表示素子
JP2018004811A (ja) * 2016-06-29 2018-01-11 Dic株式会社 液晶配向用材料及びそれを用いた液晶表示素子
CN107663458A (zh) * 2016-07-27 2018-02-06 江苏和成显示科技股份有限公司 液晶组合物及其显示器件
JP6972525B2 (ja) * 2016-09-20 2021-11-24 Dic株式会社 液晶組成物用自発配向助剤
CN109207166A (zh) * 2017-06-30 2019-01-15 江苏和成显示科技有限公司 聚合性液晶组合物及其液晶显示器件
CN109575953B (zh) * 2017-09-28 2022-06-17 江苏和成显示科技有限公司 液晶组合物及其液晶显示器件

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102057016A (zh) * 2008-06-16 2011-05-11 智索株式会社 液晶组成物以及液晶显示元件
CN102186946A (zh) * 2008-10-15 2011-09-14 Jnc株式会社 液晶组成物以及液晶显示元件
CN102292412A (zh) * 2009-01-22 2011-12-21 Jnc株式会社 液晶组成物以及液晶显示元件
CN106978194A (zh) * 2015-10-02 2017-07-25 东进世美肯株式会社 液晶组合物

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020097678A (ja) * 2018-12-18 2020-06-25 Dic株式会社 液晶組成物及び液晶表示素子
JP7318204B2 (ja) 2018-12-18 2023-08-01 Dic株式会社 液晶組成物及び液晶表示素子
JP7380059B2 (ja) 2019-10-15 2023-11-15 Dic株式会社 液晶組成物及び液晶表示素子、並びに化合物

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