WO2022198776A1 - Liquid crystal composition containing polymerizable compound and application thereof - Google Patents

Liquid crystal composition containing polymerizable compound and application thereof Download PDF

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WO2022198776A1
WO2022198776A1 PCT/CN2021/095040 CN2021095040W WO2022198776A1 WO 2022198776 A1 WO2022198776 A1 WO 2022198776A1 CN 2021095040 W CN2021095040 W CN 2021095040W WO 2022198776 A1 WO2022198776 A1 WO 2022198776A1
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liquid crystal
general formula
crystal composition
compound represented
group
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PCT/CN2021/095040
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French (fr)
Chinese (zh)
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李承贺
郭云鹏
叶宇行
王智成
陈卯先
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北京八亿时空液晶科技股份有限公司
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Publication of WO2022198776A1 publication Critical patent/WO2022198776A1/en

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    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
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    • 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
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
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    • 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
    • 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
    • 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
    • G02F1/137—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
    • C09K2019/122—Ph-Ph
    • 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
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/3004—Cy-Cy
    • 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
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/3009—Cy-Ph
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/301—Cy-Cy-Ph
    • 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
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/3016—Cy-Ph-Ph

Definitions

  • the present invention relates to the technical field of liquid crystal materials, in particular to a liquid crystal composition containing a polymerizable compound and its application.
  • a PSVA (Polymer Stabilized Vertically Aligned Liquid Crystal) type liquid crystal display element has a structure in which a polymer structure is formed in a liquid crystal cell to control the pretilt angle of liquid crystal molecules, and is used as a liquid crystal display element due to its high-speed response and high contrast.
  • a PSVA type display element is manufactured by injecting a polymerizable composition containing a liquid crystal compound and a polymerizable compound between substrates, irradiating with ultraviolet rays, and polymerizing the polymerizable compound in a state where the liquid crystal molecules are aligned.
  • the polymerizable compound as the main material is of great significance.
  • the present invention provides a liquid crystal composition containing a polymerizable compound and its application.
  • a reactive mesogen (RM) containing three polymerizable groups is introduced into the nematic liquid crystal composition, and the three polymerizable groups can speed up the reaction time and reduce the process time, so that the alignment of the liquid crystal composition can be achieved.
  • the effect is better, the polymerization is more complete, the residue is lower, and the low temperature mutual solubility of the liquid crystal composition can be effectively improved, and the angle-forming time can be reduced.
  • the response time of the measurable pre-tilt in the test box can be shortened without obvious damage to other parameters, which has important application value.
  • the present invention provides a liquid crystal composition containing a polymerizable compound, comprising one or more of the polymerizable compounds represented by the general formula I, and a nematic liquid crystal composition,
  • L 1 represents H, -F, -Cl, -CH 3 , -C 2 H 5 , -OCH 3 , -OC 2 H 5 , -CF 3 or OCF 3 ;
  • P 1 , P 2 , P 3 independently of one another represent an acrylate group, a methacrylate group, a fluoroacrylate group, a chloroacrylate group, a vinyloxy group, an oxetanyl group or an epoxy group;
  • L 1 represents H, -F, -CH 3 or -OCH 3 ;
  • P 1 , P 2 , P 3 independently of each other represent a methacrylate group, an acrylate group, a fluoroacrylate group or a chloroacrylate group, preferably P 1 , P 2 , P 3 are each other independently represents a methacrylate group or an acrylate group;
  • Z 1 , Z 2 , Z 3 independently of each other represent a single bond, -O-, -S-, -CO-O-, -O-CO-, C 1 -C 6 alkylene or C 2 - C6 alkenyl; or, at least one hydrogen atom in the C1 - C6 alkylene or C2 - C6 alkenyl is substituted by F; or, the C1 -C One -CH 2 - or at least two non-adjacent -CH 2 - in the alkylene group of 6 or the alkenyl group of C 2 -C 6 is substituted by -O- in a manner that is not directly connected to each other; preferably, Z 1 , Z 2 , Z 3 independently of each other represent a single bond, -O-, an alkylene group of C 1 -C 6 ;
  • the polymerizable compound represented by the general formula I is selected from one or more of the formulae I1-I4:
  • the nematic liquid crystal composition comprises one or more of the compounds represented by the general formula II, and one or more of the compounds represented by the general formula III,
  • R 1 and R 2 each independently represent a C 1 -C 12 straight-chain alkyl group, a straight-chain alkoxy group or a C 2 -C 12 straight-chain alkenyl group, and A 1 and A 2 each independently represent a trans 1,4-cyclohexyl or 1,4-phenylene, Z 4 is a single bond, -CH 2 CH 2- or -CH 2 O-; a is 0 or 1;
  • R 3 and R 4 each independently represent a C 1 -C 12 straight-chain alkyl group, a straight-chain alkoxy group or a C 2 -C 12 straight-chain alkenyl group, and A 3 and A 4 each independently represent a trans 1,4-cyclohexyl or 1,4-phenylene.
  • the compound represented by the general formula II is selected from one or more of the formulas IIA-1 to IIF-16:
  • the compound represented by the general formula II is selected from the group consisting of formulae IIA-9 ⁇ IIA-24, IIB-19 ⁇ IIB-38, IIC-9 ⁇ IIC-24, IID-9 ⁇ IID-24, IIE-1 ⁇ IIE -20.
  • the compound represented by general formula II is selected from formulae IIA-13 ⁇ IIA-24, IIB-23 ⁇ IIB-38, IIC-13 ⁇ IIC-24, IID-13 ⁇ IID-24, IIE-1, IIE -2, IIE-5, IIE-6, IIE-9, IIE-10, IIE-13, IIE-14, IIE-17, IIE-18, IIF-1, IIF-2, IIF-5, IIF-6 , one or more of IIF-9, IIF-10, IIF-13, IIF-14.
  • the compound represented by the general formula III is selected from one or more of the formulas IIIA1 to IIIC24:
  • the compound represented by general formula III is selected from one or more of formulae IIIA-1 to IIIA-22, IIIB-1 to IIIB-24, and IIIC-1 to IIIC-22;
  • the compound represented by general formula III is selected from one or more of formulae IIIA-1 to IIIA-12, IIIB-17 to IIIB-24, IIIC-1 to IIIC-4, and IIIC-15 to IIIC-18. kind.
  • the nematic liquid crystal composition also includes one or more of the compounds represented by the general formula IV:
  • R 5 and R 6 each independently represent a C 1 -C 12 straight-chain alkyl group, a straight-chain alkoxy group or a C 2 -C 12 straight-chain alkenyl group, and A 5 represents a trans-1,4-cyclohexyl group or 1,4-phenylene;
  • the compound represented by the general formula IV is selected from one or more of IVA ⁇ IVB:
  • R 5 and R 6 each independently represent a C 1 -C 7 straight-chain alkyl group, a straight-chain alkoxy group or a C 2 -C 7 straight-chain alkenyl group;
  • the compound represented by general formula IV is selected from one or more of IVA1 ⁇ IVB25:
  • the compound represented by the general formula IV is selected from one or more of IVA-11-IVA-15 and IVB-11-IVB-15.
  • nematic liquid crystal composition comprises the following components in mass percentage:
  • the nematic liquid crystal composition comprises the following components in mass percentage:
  • the nematic liquid crystal composition comprises the following components in mass percentage:
  • the nematic liquid crystal composition comprises the following components in mass percentage:
  • liquid crystal composition further includes an antioxidant, and the antioxidant includes one or more of the compounds represented by the general formula V:
  • R 7 represents C 1 -C 7 straight-chain alkyl, straight-chain alkoxy or C 2 -C 7 straight-chain alkenyl
  • a 6 represents trans 1,4-cyclohexyl or 1,4-idene phenyl
  • b is 0 or 1;
  • the compound represented by the general formula V is selected from one or both of V-1 to V-2:
  • the compound represented by the general formula V is 0.005-1%, preferably 0.005-0.1%, more preferably 0.005-0.05%.
  • the polymerizable compound represented by the general formula I is 0.01-5%, preferably 0.05-1%, more preferably 0.1-0.5%, more preferably 0.25-0.37% %.
  • the present invention also provides the application of the above-mentioned liquid crystal composition containing a polymerizable compound in a PSVA type liquid crystal display device.
  • the liquid crystal composition can shorten the pretilt correlation measurable in a test cell without obvious damage to other parameters.
  • the response time has important application value.
  • the preparation method of the liquid crystal composition of the present invention is not particularly limited, and can be produced by mixing two or more compounds by conventional methods, such as by mixing different components at high temperature and dissolving each other.
  • the percentages in the present invention are percentages by weight; the unit of temperature is degrees Celsius; ⁇ n represents optical anisotropy (25°C); ⁇ and ⁇ represent parallel and perpendicular dielectric constants (25°C, 1000Hz), respectively; ⁇ represents the dielectric anisotropy (25°C, 1000Hz); ⁇ 1 represents the rotational viscosity (mPa.s, 25°C); Cp represents the clearing point (°C) of the liquid crystal composition; K 11 , K 22 , and K 33 represent the Splay, twist and bend elastic constants (pN, 25°C). ⁇ represents resistivity ( ⁇ cm), and the test condition is 25 ⁇ 2°C.
  • the preparation of the liquid crystal composition adopts the thermal dissolution method, which includes the following steps: weighing the liquid crystal compound by weight percentage with a balance, wherein there is no specific requirement for the order of weighing and adding, usually the melting point of the liquid crystal compound is from high to low. Weighing and mixing in sequence, heating and stirring at 60-100°C to make each component melt evenly, then filtering, rotary steaming, and finally encapsulating to obtain the target sample.
  • Table 2 Weight percentage and performance parameters of each component in the liquid crystal composition
  • Nematic liquid crystal composition LC2 Nematic liquid crystal composition LC2:
  • Table 3 The weight percentage and performance parameters of each component in the liquid crystal composition
  • Table 4 The weight percentage and performance parameters of each component in the liquid crystal composition
  • Table 5 Weight percentage and performance parameters of each component in the liquid crystal composition
  • Table 6 Weight percentage and performance parameters of each component in the liquid crystal composition
  • Table 7 The weight percentage and performance parameters of each component in the liquid crystal composition
  • Table 8 Weight percentage and performance parameters of each component in the liquid crystal composition
  • Table 9 Weight percentage and performance parameters of each component in the liquid crystal composition
  • Table 10 Weight percentage and performance parameters of each component in the liquid crystal composition
  • Table 11 The weight percentage and performance parameters of each component in the liquid crystal composition
  • the weight % of RM monomer I and antioxidant are based on the weight of the nematic liquid crystal composition, and are added separately in addition to the mass percentage of the nematic liquid crystal composition.
  • the liquid crystal composition containing the polymerizable compound was injected into a PSVA test cell with a cell gap of 3.2 ⁇ m by a vacuum injection method. Then, the liquid crystal cell was irradiated with ultraviolet rays using a fluorescent lamp through a color filter for filtering out ultraviolet rays of 310 nm or less. At this time, the illuminance measured on the condition of the center wavelength of 365 nm was adjusted to be 100 mW/cm 2 , and ultraviolet rays with a cumulative light amount of 30 J/cm 2 were irradiated (irradiation condition 1).
  • UV1 is the ultraviolet irradiation process through irradiation condition 1
  • UV2 is the process through irradiation condition 1 and irradiation condition 2.
  • the liquid crystal composition containing the polymerizable compound was injected into a PSVA test cell with a cell gap of 3.2 ⁇ m by a vacuum injection method. Then, the liquid crystal cell was irradiated with ultraviolet rays using a fluorescent lamp through a color filter for filtering out ultraviolet rays of 310 nm or less. At this time, the illuminance measured on the condition of the center wavelength of 365 nm was adjusted to be 100 mW/cm 2 , and ultraviolet rays with a cumulative light amount of 30 J/cm 2 were irradiated (irradiation condition 1).
  • UV1 is the ultraviolet irradiation process through irradiation condition 1
  • UV2 is the process through irradiation condition 1 and irradiation condition 2.
  • a polymerizable compound is added to the composition, which is consumed by polymerization to form a polymer.
  • the conversion of this reaction is preferably a large conversion.
  • the residual amount of the polymer compound (the amount of the unreacted polymerizable compound) is preferably small from the viewpoint of afterimage of the image.
  • the present invention can speed up the reaction time, reduce the process time, improve the response speed, and reduce the response time by adding RM monomers containing three polymerizable groups.
  • Comparative Example 1 The response time is 5.7ms, the highest response time of the embodiment is 5.5ms, and the lowest is 5.1ms. Compared with Comparative Example 1, the response time is improved by 4%-10% after adding the RM monomer containing three polymerizable groups. time has improved significantly.
  • the present invention provides a liquid crystal composition containing a polymerizable compound and an application thereof, comprising one or more of the polymerizable compounds represented by the general formula I, and a nematic liquid crystal composition.
  • a reactive mesogen (RM) containing three polymerizable groups is introduced into the nematic liquid crystal composition, and the three polymerizable groups can speed up the reaction time and reduce the process time, so that the alignment of the liquid crystal composition can be achieved.
  • the effect is better, the polymerization is more complete, the residue is lower, and the low temperature mutual solubility of the liquid crystal composition can be effectively improved, and the angle-forming time can be reduced.
  • the measurable pre-tilt-related response time in the test box can be shortened, which has good economic value and application prospect.

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Abstract

The present invention provides a liquid crystal composition containing a polymerizable compound and an application thereof, the liquid crystal composition comprising one or more of polymerizable compounds represented by general formula (I), and a nematic liquid crystal composition. According to the present invention, a reactive mesogen (RM) containing three polymerizable groups is introduced into the nematic liquid crystal composition, and the three polymerizable groups can accelerate the reaction and shorten the process time, such that the liquid crystal composition is better in alignment effect, more complete in polymerization, and lower in residue, the low-temperature intersolubility of the liquid crystal composition can be effectively improved, and the angulation time is reduced. Especially for existing PSVA liquid crystals, under the condition that other parameters are not obviously damaged, the response time related to measurable pre-tilt in a test box can be shortened, and the liquid crystal composition has important application value.

Description

一种含可聚合化合物的液晶组合物及其应用A kind of liquid crystal composition containing polymerizable compound and its application
交叉引用cross reference
本申请要求2021年3月24日提交的专利名称为“一种含可聚合化合物的液晶组合物及其应用”的第202110315782.8号中国专利申请的优先权，其全部公开内容通过引用整体并入本文。This application claims the priority of Chinese Patent Application No. 202110315782.8 filed on March 24, 2021 and entitled "A liquid crystal composition containing a polymerizable compound and its application", the entire disclosure of which is incorporated herein by reference in its entirety .
技术领域technical field
本发明涉及液晶材料技术领域，尤其涉及一种含可聚合化合物的液晶组合物及其应用。The present invention relates to the technical field of liquid crystal materials, in particular to a liquid crystal composition containing a polymerizable compound and its application.
背景技术Background technique
PSVA(聚合物稳定的垂直排列液晶)型液晶显示元件在液晶单元中形成聚合物结构以控制液晶分子的预倾角的结构，并且由于其高速响应和高对比度而被用作液晶显示元件。通过在基板之间注入包含液晶化合物和可聚合化合物的可聚合组合物，通过紫外照射并在液晶分子取向的状态下聚合该可聚合化合物来制造PSVA型显示元件。其中作为主要材料的可聚合化合物具有重要意义，通过搭配合适液晶组合物，提升对比度，解决显示残像问题等。A PSVA (Polymer Stabilized Vertically Aligned Liquid Crystal) type liquid crystal display element has a structure in which a polymer structure is formed in a liquid crystal cell to control the pretilt angle of liquid crystal molecules, and is used as a liquid crystal display element due to its high-speed response and high contrast. A PSVA type display element is manufactured by injecting a polymerizable composition containing a liquid crystal compound and a polymerizable compound between substrates, irradiating with ultraviolet rays, and polymerizing the polymerizable compound in a state where the liquid crystal molecules are aligned. Among them, the polymerizable compound as the main material is of great significance. By matching with a suitable liquid crystal composition, the contrast ratio can be improved and the problem of display afterimage can be solved.
特别是对于监视器以及尤其是TV应用，缩短制程时间，以及响应时间的优化一直以来被作为研发领域的重要课题。有鉴于此，特提出本发明。Especially for monitors and especially for TV applications, shortening the process time and optimizing the response time has been an important topic in the research and development field. In view of this, the present invention is proposed.
发明内容SUMMARY OF THE INVENTION
为此，本发明提供一种含可聚合化合物的液晶组合物及其应用。本发明通过在向列相液晶组合物中引入含有三个可聚合基团的反应性介晶(RM)，三个可聚合基团可以加快反应速度时间，降低制程时间，使得液晶组合物的配向效果更好，聚合更完全，残留更低，并且能有效改善液晶组合物的低温互溶性，降低成角时间。特别是对于现有PSVA液晶来说，在对其他参数没有明显损害的情况下，能缩短在测试盒中可测量的预倾斜相关的响应时间，具有重要的应用价值。To this end, the present invention provides a liquid crystal composition containing a polymerizable compound and its application. In the present invention, a reactive mesogen (RM) containing three polymerizable groups is introduced into the nematic liquid crystal composition, and the three polymerizable groups can speed up the reaction time and reduce the process time, so that the alignment of the liquid crystal composition can be achieved. The effect is better, the polymerization is more complete, the residue is lower, and the low temperature mutual solubility of the liquid crystal composition can be effectively improved, and the angle-forming time can be reduced. Especially for the existing PSVA liquid crystal, the response time of the measurable pre-tilt in the test box can be shortened without obvious damage to other parameters, which has important application value.
具体而言，本发明提供一种含可聚合化合物的液晶组合物，包含通式I所代表的可聚合化合物中的一种或多种，及向列相液晶组合物，Specifically, the present invention provides a liquid crystal composition containing a polymerizable compound, comprising one or more of the polymerizable compounds represented by the general formula I, and a nematic liquid crystal composition,
Figure PCTCN2021095040-appb-000001
Figure PCTCN2021095040-appb-000001
其中，L 1表示H、-F、-Cl、-CH 3、-C 2H 5、-OCH 3、-OC 2H 5、-CF 3或OCF 3； Wherein, L 1 represents H, -F, -Cl, -CH 3 , -C 2 H 5 , -OCH 3 , -OC 2 H 5 , -CF 3 or OCF 3 ;
P 1、P 2、P 3彼此独立地表示丙烯酸酯基、甲基丙烯酸酯基、氟代丙烯酸酯基、氯代丙烯酸酯基、乙烯氧基、氧杂环丁烷基或环氧基； P 1 , P 2 , P 3 independently of one another represent an acrylate group, a methacrylate group, a fluoroacrylate group, a chloroacrylate group, a vinyloxy group, an oxetanyl group or an epoxy group;
Z 1、Z 2、Z 3彼此独立地表示单键、-O-、-S-、-CO-、-CO-O-、-O-CO-、-O-CO-O-、-CH＝N-、-N＝CH-、-N＝N-、C 1-C 12的亚烷基或C 2-C 12的链烯基；或，所述C 1-C 12的亚烷基或C 2-C 12的链烯基中的至少一个氢原子彼此独立地被F、Cl或CN取代；或，所述C 1-C 12的亚烷基或C 2-C 12的链烯基中一个-CH 2-或至少两个不相邻的-CH 2-彼此独立地被-O-、-S-、-NH-、-CO-、-CO-O-、-OCO-、-OCOO-、-SCO-、-COS-或-C＝C-以不相互直接相连的方式取代。 Z 1 , Z 2 , and Z 3 independently represent a single bond, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH= N-, -N=CH-, -N=N-, C 1 -C 12 alkylene or C 2 -C 12 alkenyl; or, the C 1 -C 12 alkylene or C At least one hydrogen atom in the 2 -C 12 alkenyl group is independently substituted by F, Cl or CN; or, one of the C 1 -C 12 alkylene groups or the C 2 -C 12 alkenyl group -CH 2 - or at least two non-adjacent -CH 2 - independently of each other by -O-, -S-, -NH-, -CO-, -CO-O-, -OCO-, -OCOO-, -SCO-, -COS- or -C=C- are substituted without being directly connected to each other.
进一步地，通式I中，L 1表示H、-F、-CH 3或-OCH 3； Further, in the general formula I, L 1 represents H, -F, -CH 3 or -OCH 3 ;
和/或，P 1、P 2、P 3彼此独立地表示甲基丙烯酸酯基、丙烯酸酯基、氟代丙烯酸酯基或氯代丙烯酸酯基，优选地，P 1、P 2、P 3彼此独立地表示甲基丙烯酸酯基或丙烯酸酯基； and/or, P 1 , P 2 , P 3 independently of each other represent a methacrylate group, an acrylate group, a fluoroacrylate group or a chloroacrylate group, preferably P 1 , P 2 , P 3 are each other independently represents a methacrylate group or an acrylate group;
和/或，Z 1、Z 2、Z 3彼此独立地表示单键、-O-、-S-、-CO-O-、-O-CO-、C 1-C 6的亚烷基或C 2-C 6的链烯基；或，所述C 1-C 6的亚烷基或C 2-C 6的链烯基中的至少一个氢原子被F取代；或，所述C 1-C 6的亚烷基或C 2-C 6的链烯基中一个-CH 2-或至少两个不相邻的-CH 2-被-O-以不相互直接相连的方式取代；优选地，Z 1、Z 2、Z 3彼此独立地表示单键、-O-、C 1-C 6的亚烷基； And/or, Z 1 , Z 2 , Z 3 independently of each other represent a single bond, -O-, -S-, -CO-O-, -O-CO-, C 1 -C 6 alkylene or C 2 - C6 alkenyl; or, at least one hydrogen atom in the C1 - C6 alkylene or C2 - C6 alkenyl is substituted by F; or, the C1 -C One -CH 2 - or at least two non-adjacent -CH 2 - in the alkylene group of 6 or the alkenyl group of C 2 -C 6 is substituted by -O- in a manner that is not directly connected to each other; preferably, Z 1 , Z 2 , Z 3 independently of each other represent a single bond, -O-, an alkylene group of C 1 -C 6 ;
更优选地，通式I所代表的可聚合化合物选自式I1～I4中的一种或多种：More preferably, the polymerizable compound represented by the general formula I is selected from one or more of the formulae I1-I4:
Figure PCTCN2021095040-appb-000002
Figure PCTCN2021095040-appb-000002
Figure PCTCN2021095040-appb-000003
Figure PCTCN2021095040-appb-000003
进一步地，所述向列相液晶组合物包含通式II所代表化合物中的一种或多种，以及通式III所代表的化合物中的一种或多种，Further, the nematic liquid crystal composition comprises one or more of the compounds represented by the general formula II, and one or more of the compounds represented by the general formula III,
Figure PCTCN2021095040-appb-000004
Figure PCTCN2021095040-appb-000004
其中，R 1、R 2各自独立地代表C 1-C 12的直链烷基、直链烷氧基或C 2-C 12的直链烯基，A 1、A 2各自独立地代表反式1，4-环己基或1，4-亚苯基，Z 4为单键、-CH 2CH 2-或-CH 2O-；a为0或1； Wherein, R 1 and R 2 each independently represent a C 1 -C 12 straight-chain alkyl group, a straight-chain alkoxy group or a C 2 -C 12 straight-chain alkenyl group, and A 1 and A 2 each independently represent a trans 1,4-cyclohexyl or 1,4-phenylene, Z 4 is a single bond, -CH 2 CH 2- or -CH 2 O-; a is 0 or 1;
Figure PCTCN2021095040-appb-000005
Figure PCTCN2021095040-appb-000005
其中，R 3、R 4各自独立地代表C 1-C 12的直链烷基、直链烷氧基或C 2-C 12的直链烯基，A 3、A 4各自独立地代表反式1，4-环己基或1，4-亚苯基。 Wherein, R 3 and R 4 each independently represent a C 1 -C 12 straight-chain alkyl group, a straight-chain alkoxy group or a C 2 -C 12 straight-chain alkenyl group, and A 3 and A 4 each independently represent a trans 1,4-cyclohexyl or 1,4-phenylene.
进一步地，通式II所代表化合物选自IIA～IIF中的一种或多种：Further, the compound represented by general formula II is selected from one or more of IIA～IIF:
Figure PCTCN2021095040-appb-000006
Figure PCTCN2021095040-appb-000006
Figure PCTCN2021095040-appb-000007
Figure PCTCN2021095040-appb-000007
优选地，通式II所代表化合物选自式IIA-1～IIF-16中的一种或多种：Preferably, the compound represented by the general formula II is selected from one or more of the formulas IIA-1 to IIF-16:
Figure PCTCN2021095040-appb-000008
Figure PCTCN2021095040-appb-000008
Figure PCTCN2021095040-appb-000009
Figure PCTCN2021095040-appb-000009
Figure PCTCN2021095040-appb-000010
Figure PCTCN2021095040-appb-000010
Figure PCTCN2021095040-appb-000011
Figure PCTCN2021095040-appb-000011
Figure PCTCN2021095040-appb-000012
Figure PCTCN2021095040-appb-000012
更优选地，通式II所代表化合物选自式IIA-9～IIA-24、IIB-19～IIB-38、IIC-9～IIC-24、IID-9～IID-24、IIE-1～IIE-20、IIF-1～IIF-16中的一种或多种；More preferably, the compound represented by the general formula II is selected from the group consisting of formulae IIA-9～IIA-24, IIB-19～IIB-38, IIC-9～IIC-24, IID-9～IID-24, IIE-1～IIE -20. One or more of IIF-1～IIF-16;
最优选地，通式II所代表化合物选自式IIA-13～IIA-24、IIB-23～IIB-38、IIC-13～IIC-24、IID-13～IID-24、IIE-1、IIE-2、IIE-5、IIE-6、IIE-9、IIE-10、IIE-13、IIE-14、IIE-17、IIE-18、IIF-1、IIF-2、IIF-5、IIF-6、IIF-9、IIF-10、IIF-13、IIF-14中的一种或多种。Most preferably, the compound represented by general formula II is selected from formulae IIA-13～IIA-24, IIB-23～IIB-38, IIC-13～IIC-24, IID-13～IID-24, IIE-1, IIE -2, IIE-5, IIE-6, IIE-9, IIE-10, IIE-13, IIE-14, IIE-17, IIE-18, IIF-1, IIF-2, IIF-5, IIF-6 , one or more of IIF-9, IIF-10, IIF-13, IIF-14.
进一步地，通式III所代表化合物选自式IIIA～IIIC中的一种或多种：Further, the compound represented by general formula III is selected from one or more of formulae IIIA～IIIC:
Figure PCTCN2021095040-appb-000013
Figure PCTCN2021095040-appb-000013
优选地，通式III所代表化合物选自式IIIA1～IIIC24中的一种或多种：Preferably, the compound represented by the general formula III is selected from one or more of the formulas IIIA1 to IIIC24:
Figure PCTCN2021095040-appb-000014
Figure PCTCN2021095040-appb-000014
Figure PCTCN2021095040-appb-000015
Figure PCTCN2021095040-appb-000015
Figure PCTCN2021095040-appb-000016
Figure PCTCN2021095040-appb-000016
更优选地，通式III所代表化合物选自式IIIA-1～IIIA-22、IIIB-1～IIIB-24、IIIC-1～IIIC-22中的一种或多种；More preferably, the compound represented by general formula III is selected from one or more of formulae IIIA-1 to IIIA-22, IIIB-1 to IIIB-24, and IIIC-1 to IIIC-22;
最优选地，通式III所代表化合物选自式IIIA-1～IIIA-12、IIIB-17～IIIB-24、IIIC-1～IIIC-4、IIIC-15～IIIC-18中的一种或多种。Most preferably, the compound represented by general formula III is selected from one or more of formulae IIIA-1 to IIIA-12, IIIB-17 to IIIB-24, IIIC-1 to IIIC-4, and IIIC-15 to IIIC-18. kind.
进一步地，所述向列相液晶组合物还包含通式IV所代表化合物中的一种或多种：Further, the nematic liquid crystal composition also includes one or more of the compounds represented by the general formula IV:
Figure PCTCN2021095040-appb-000017
Figure PCTCN2021095040-appb-000017
其中，R 5、R 6各自独立地代表C 1-C 12的直链烷基、直链烷氧基或C 2-C 12的直链烯基，A 5代表反式1，4-环己基或1，4-亚苯基； Wherein, R 5 and R 6 each independently represent a C 1 -C 12 straight-chain alkyl group, a straight-chain alkoxy group or a C 2 -C 12 straight-chain alkenyl group, and A 5 represents a trans-1,4-cyclohexyl group or 1,4-phenylene;
优选地，通式IV所代表化合物选自IVA～IVB中的一种或多种：Preferably, the compound represented by the general formula IV is selected from one or more of IVA～IVB:
Figure PCTCN2021095040-appb-000018
Figure PCTCN2021095040-appb-000018
其中，R 5、R 6各自独立地代表C 1-C 7的直链烷基、直链烷氧基或C 2-C 7的直链烯基； Wherein, R 5 and R 6 each independently represent a C 1 -C 7 straight-chain alkyl group, a straight-chain alkoxy group or a C 2 -C 7 straight-chain alkenyl group;
更优选地，通式IV所代表化合物选自IVA1～IVB25中的一种或多种：More preferably, the compound represented by general formula IV is selected from one or more of IVA1～IVB25:
Figure PCTCN2021095040-appb-000019
Figure PCTCN2021095040-appb-000019
Figure PCTCN2021095040-appb-000020
Figure PCTCN2021095040-appb-000020
Figure PCTCN2021095040-appb-000021
Figure PCTCN2021095040-appb-000021
最优选地，通式IV所代表化合物选自IVA-11～IVA-15、IVB-11～IVB-15中的一种或多种。Most preferably, the compound represented by the general formula IV is selected from one or more of IVA-11-IVA-15 and IVB-11-IVB-15.
进一步地，所述向列相液晶组合物包含以下质量百分比的组分：Further, the nematic liquid crystal composition comprises the following components in mass percentage:
(1)、1～80％的通式II所代表的化合物；(1), 1-80% of the compound represented by the general formula II;
(2)、1～70％的通式III所代表的化合物；(2), 1-70% of the compound represented by the general formula III;
(3)、0～40％的通式IV所代表的化合物；(3), 0～40% of the compound represented by general formula IV;
优选地，所述向列相液晶组合物包含以下质量百分比的组分：Preferably, the nematic liquid crystal composition comprises the following components in mass percentage:
(1)、5～70％的通式II所代表的化合物；(1), 5-70% of the compound represented by the general formula II;
(2)、20～60％的通式III所代表的化合物；(2), 20-60% of the compound represented by the general formula III;
(3)、0～35％的通式IV所代表的化合物；(3), 0～35% of the compound represented by general formula IV;
更优选地，所述向列相液晶组合物包含以下质量百分比的组分：More preferably, the nematic liquid crystal composition comprises the following components in mass percentage:
(1)、10～70％的通式II所代表的化合物；(1), 10-70% of the compound represented by the general formula II;
(2)、25～60％的通式III所代表的化合物；(2), 25-60% of the compound represented by the general formula III;
(3)、0～30％的通式IV所代表的化合物；(3), 0～30% of the compound represented by general formula IV;
进一步优选地，所述向列相液晶组合物包含以下质量百分比的组分：Further preferably, the nematic liquid crystal composition comprises the following components in mass percentage:
(1)、20～70％的通式II所代表的化合物；(1), 20-70% of the compound represented by the general formula II;
(2)、25～50％的通式III所代表的化合物；(2), 25-50% of the compound represented by the general formula III;
(3)、0～20％的通式IV所代表的化合物。(3), 0-20% of the compound represented by the general formula IV.
进一步地，所述液晶组合物还包括抗氧化剂，所述抗氧化剂包括通式V所代表化合物中的一种或多种：Further, the liquid crystal composition further includes an antioxidant, and the antioxidant includes one or more of the compounds represented by the general formula V:
Figure PCTCN2021095040-appb-000022
Figure PCTCN2021095040-appb-000022
其中，R 7代表C 1-C 7的直链烷基、直链烷氧基或C 2-C 7的直链烯基，A 6代表反式1，4-环己基或1，4-亚苯基；b为0或1； Wherein, R 7 represents C 1 -C 7 straight-chain alkyl, straight-chain alkoxy or C 2 -C 7 straight-chain alkenyl, A 6 represents trans 1,4-cyclohexyl or 1,4-idene phenyl; b is 0 or 1;
优选地，通式V所代表化合物选自V-1～V-2中的一种或两种：Preferably, the compound represented by the general formula V is selected from one or both of V-1 to V-2:
Figure PCTCN2021095040-appb-000023
Figure PCTCN2021095040-appb-000023
和/或，以所述向列相液晶组合物的重量为基准，通式V所代表化合物为0.005～1％，优选0.005～0.1％，进一步优选0.005～0.05％。And/or, based on the weight of the nematic liquid crystal composition, the compound represented by the general formula V is 0.005-1%, preferably 0.005-0.1%, more preferably 0.005-0.05%.
进一步地，以所述向列相液晶组合物的重量为基准，通式I所代表的可聚合化合物为0.01～5％，优选0.05～1％，进一步优选0.1～0.5％，更优选0.25～0.37％。Further, based on the weight of the nematic liquid crystal composition, the polymerizable compound represented by the general formula I is 0.01-5%, preferably 0.05-1%, more preferably 0.1-0.5%, more preferably 0.25-0.37% %.
本发明同时提供上述含可聚合化合物的液晶组合物在PSVA型液晶显示装置中的应用，该液晶组合物在对其他参数没有明显损害的情况下，能缩短在测试盒中可测量的预倾斜相关的响应时间，具有重要的应用价值。The present invention also provides the application of the above-mentioned liquid crystal composition containing a polymerizable compound in a PSVA type liquid crystal display device. The liquid crystal composition can shorten the pretilt correlation measurable in a test cell without obvious damage to other parameters. The response time has important application value.
本发明所述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。The preparation method of the liquid crystal composition of the present invention is not particularly limited, and can be produced by mixing two or more compounds by conventional methods, such as by mixing different components at high temperature and dissolving each other.
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范围。The following examples are intended to illustrate the present invention, but not to limit the scope of the present invention.
除非另有说明，本发明中百分比为重量百分比；温度单位为摄氏度；△n代表光学各向异性(25℃)；ε ∥和ε ⊥分别代表平行和垂直介电常数(25℃，1000Hz)；△ε代表介电各向异性(25℃，1000Hz)；γ1代表旋转粘度(mPa.s，25℃)；Cp代表液晶组合物的清亮点(℃)；K 11、K 22、K 33分别代表展曲、扭曲和弯曲弹性常数(pN，25℃)。ρ表示电阻率(Ω·cm)，测试条件为25± 2℃。 Unless otherwise specified, the percentages in the present invention are percentages by weight; the unit of temperature is degrees Celsius; Δn represents optical anisotropy (25°C); ε∥ and ε⊥ represent parallel and perpendicular dielectric constants (25°C, 1000Hz), respectively; Δε represents the dielectric anisotropy (25°C, 1000Hz); γ1 represents the rotational viscosity (mPa.s, 25°C); Cp represents the clearing point (°C) of the liquid crystal composition; K 11 , K 22 , and K 33 represent the Splay, twist and bend elastic constants (pN, 25°C). ρ represents resistivity (Ω·cm), and the test condition is 25±2°C.
以下各实施例中，液晶化合物中基团结构用表1所示代码表示。In the following examples, the group structure in the liquid crystal compound is represented by the codes shown in Table 1.
表1：液晶化合物的基团结构代码Table 1: Group Structure Codes of Liquid Crystal Compounds
Figure PCTCN2021095040-appb-000024
Figure PCTCN2021095040-appb-000024
以如下化合物结构为例：Take the following compound structure as an example:
Figure PCTCN2021095040-appb-000025
Figure PCTCN2021095040-appb-000025
表示为：3PWO2Represented as: 3PWO2
Figure PCTCN2021095040-appb-000026
Figure PCTCN2021095040-appb-000026
表示为：3CCWO2Represented as: 3CCWO2
以下各实施例中，液晶组合物的制备均采用热溶解方法，包括以下步骤：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。In the following examples, the preparation of the liquid crystal composition adopts the thermal dissolution method, which includes the following steps: weighing the liquid crystal compound by weight percentage with a balance, wherein there is no specific requirement for the order of weighing and adding, usually the melting point of the liquid crystal compound is from high to low. Weighing and mixing in sequence, heating and stirring at 60-100°C to make each component melt evenly, then filtering, rotary steaming, and finally encapsulating to obtain the target sample.
向列相液晶组合物中各组分的重量百分比及液晶组合物的性能参数见下述表格。The weight percentage of each component in the nematic liquid crystal composition and the performance parameters of the liquid crystal composition are shown in the following table.
向列相液晶组合物LC1Nematic liquid crystal composition LC1
表2：液晶组合物中各组分的重量百分比及性能参数Table 2: Weight percentage and performance parameters of each component in the liquid crystal composition
Figure PCTCN2021095040-appb-000027
Figure PCTCN2021095040-appb-000027
向列相液晶组合物LC2：Nematic liquid crystal composition LC2:
表3：液晶组合物中各组分的重量百分比及性能参数Table 3: The weight percentage and performance parameters of each component in the liquid crystal composition
Figure PCTCN2021095040-appb-000028
Figure PCTCN2021095040-appb-000028
向列相液晶组合物LC3Nematic liquid crystal composition LC3
表4：液晶组合物中各组分的重量百分比及性能参数Table 4: The weight percentage and performance parameters of each component in the liquid crystal composition
Figure PCTCN2021095040-appb-000029
Figure PCTCN2021095040-appb-000029
向列相液晶组合物LC4Nematic liquid crystal composition LC4
表5：液晶组合物中各组分的重量百分比及性能参数Table 5: Weight percentage and performance parameters of each component in the liquid crystal composition
Figure PCTCN2021095040-appb-000030
Figure PCTCN2021095040-appb-000030
向列相液晶组合物LC5Nematic liquid crystal composition LC5
表6：液晶组合物中各组分的重量百分比及性能参数Table 6: Weight percentage and performance parameters of each component in the liquid crystal composition
Figure PCTCN2021095040-appb-000031
Figure PCTCN2021095040-appb-000031
Figure PCTCN2021095040-appb-000032
Figure PCTCN2021095040-appb-000032
向列相液晶组合物LC6Nematic liquid crystal composition LC6
表7：液晶组合物中各组分的重量百分比及性能参数Table 7: The weight percentage and performance parameters of each component in the liquid crystal composition
Figure PCTCN2021095040-appb-000033
Figure PCTCN2021095040-appb-000033
向列相液晶组合物LC7Nematic liquid crystal composition LC7
表8：液晶组合物中各组分的重量百分比及性能参数Table 8: Weight percentage and performance parameters of each component in the liquid crystal composition
Figure PCTCN2021095040-appb-000034
Figure PCTCN2021095040-appb-000034
Figure PCTCN2021095040-appb-000035
Figure PCTCN2021095040-appb-000035
向列相液晶组合物LC8Nematic liquid crystal composition LC8
表9：液晶组合物中各组分的重量百分比及性能参数Table 9: Weight percentage and performance parameters of each component in the liquid crystal composition
Figure PCTCN2021095040-appb-000036
Figure PCTCN2021095040-appb-000036
向列相液晶组合物LC9Nematic liquid crystal composition LC9
表10：液晶组合物中各组分的重量百分比及性能参数Table 10: Weight percentage and performance parameters of each component in the liquid crystal composition
Figure PCTCN2021095040-appb-000037
Figure PCTCN2021095040-appb-000037
Figure PCTCN2021095040-appb-000038
Figure PCTCN2021095040-appb-000038
向列相液晶组合物LC10Nematic liquid crystal composition LC10
表11：液晶组合物中各组分的重量百分比及性能参数Table 11: The weight percentage and performance parameters of each component in the liquid crystal composition
Figure PCTCN2021095040-appb-000039
Figure PCTCN2021095040-appb-000039
以下实施例中，RM单体I、及抗氧化剂的重量％都是以向列相液晶组合物的重量为基准，在所述向列相液晶组合物质量百分比外单独添加。In the following examples, the weight % of RM monomer I and antioxidant are based on the weight of the nematic liquid crystal composition, and are added separately in addition to the mass percentage of the nematic liquid crystal composition.
实施例见表12。Examples are shown in Table 12.
表12Table 12
Figure PCTCN2021095040-appb-000040
Figure PCTCN2021095040-appb-000040
Figure PCTCN2021095040-appb-000041
Figure PCTCN2021095040-appb-000041
将含有可聚合化合物的液晶组合物以真空注入法注入单元间隙3.2μm的PSVA测试盒。然后，隔着滤除310nm以下的紫外线的滤色器，使用荧光 灯对液晶单元照射紫外线。此时，调整成以中心波长365nm的条件测得的照度为100mW/cm 2，照射累积光量30J/cm 2的紫外线(照射条件1)。接着，使用荧光UV灯，调整成以中心波长313nm的条件测得的照度为3mW/cm 2，照射累积光量10J/cm 2的(紫外线照射条件2)。UV1为经过照射条件1紫外照射过程，UV2为经过照射条件1和照射条件2过程。 The liquid crystal composition containing the polymerizable compound was injected into a PSVA test cell with a cell gap of 3.2 μm by a vacuum injection method. Then, the liquid crystal cell was irradiated with ultraviolet rays using a fluorescent lamp through a color filter for filtering out ultraviolet rays of 310 nm or less. At this time, the illuminance measured on the condition of the center wavelength of 365 nm was adjusted to be 100 mW/cm 2 , and ultraviolet rays with a cumulative light amount of 30 J/cm 2 were irradiated (irradiation condition 1). Next, using a fluorescent UV lamp, the illuminance measured under the condition of the center wavelength of 313 nm was adjusted to be 3 mW/cm 2 , and the accumulated light amount was 10 J/cm 2 (ultraviolet irradiation condition 2). UV1 is the ultraviolet irradiation process through irradiation condition 1, and UV2 is the process through irradiation condition 1 and irradiation condition 2.
对比例1Comparative Example 1
对100质量份的向列相液晶组合物LC1添加0.3质量份由式RM-1表示的化合物和0.01质量份由式V-2表示的化合物得到含有可聚合化合物的液晶组合物，作为对比例1。To 100 parts by mass of the nematic liquid crystal composition LC1, 0.3 parts by mass of the compound represented by the formula RM-1 and 0.01 part by mass of the compound represented by the formula V-2 were added to obtain a liquid crystal composition containing a polymerizable compound, as Comparative Example 1 .
Figure PCTCN2021095040-appb-000042
Figure PCTCN2021095040-appb-000042
将含有可聚合化合物的液晶组合物以真空注入法注入单元间隙3.2μm的PSVA测试盒。然后，隔着滤除310nm以下的紫外线的滤色器，使用荧光灯对液晶单元照射紫外线。此时，调整成以中心波长365nm的条件测得的照度为100mW/cm 2，照射累积光量30J/cm 2的紫外线(照射条件1)。接着，使用荧光UV灯，调整成以中心波长313nm的条件测得的照度为3mW/cm 2，照射累积光量10J/cm 2的(紫外线照射条件2)。UV1为经过照射条件1紫外照射过程，UV2为经过照射条件1和照射条件2过程。 The liquid crystal composition containing the polymerizable compound was injected into a PSVA test cell with a cell gap of 3.2 μm by a vacuum injection method. Then, the liquid crystal cell was irradiated with ultraviolet rays using a fluorescent lamp through a color filter for filtering out ultraviolet rays of 310 nm or less. At this time, the illuminance measured on the condition of the center wavelength of 365 nm was adjusted to be 100 mW/cm 2 , and ultraviolet rays with a cumulative light amount of 30 J/cm 2 were irradiated (irradiation condition 1). Next, using a fluorescent UV lamp, the illuminance measured under the condition of a center wavelength of 313 nm was adjusted to be 3 mW/cm 2 , and irradiated with a cumulative light amount of 10 J/cm 2 (ultraviolet irradiation condition 2). UV1 is the ultraviolet irradiation process through irradiation condition 1, and UV2 is the process through irradiation condition 1 and irradiation condition 2.
效果测试effect test
1、可聚合化合物的转化率1. Conversion rate of polymerizable compounds
将可聚合化合物添加于组合物中，所述可聚合化合物因聚合而被消耗来形成聚合物。这一反应的转化率优选为大转化率。A polymerizable compound is added to the composition, which is consumed by polymerization to form a polymer. The conversion of this reaction is preferably a large conversion.
这是因为：就图像的残像观点而言，聚合物化合物的残留量(未反应的聚合性化合物的量)优选为少。This is because the residual amount of the polymer compound (the amount of the unreacted polymerizable compound) is preferably small from the viewpoint of afterimage of the image.
2、响应时间2. Response time
响应时间Toff测试，三官能团RM单体的添加，与在测试盒中可测量的预倾斜相关的响应时间的缩短能在对于其他参数没有明显损害的情况下 实现，从而提升响应速度，降低响应时间。Response time Toff test, addition of trifunctional RM monomers, the reduction in response time associated with measurable pretilt in the test cell can be achieved without significant damage to other parameters, resulting in increased response speed and reduced response time .
测试结果见表13-18。The test results are shown in Tables 13-18.
表13Table 13
Figure PCTCN2021095040-appb-000043
Figure PCTCN2021095040-appb-000043
表14Table 14
Figure PCTCN2021095040-appb-000044
Figure PCTCN2021095040-appb-000044
表15Table 15
Figure PCTCN2021095040-appb-000045
Figure PCTCN2021095040-appb-000045
Figure PCTCN2021095040-appb-000046
Figure PCTCN2021095040-appb-000046
表16Table 16
Figure PCTCN2021095040-appb-000047
Figure PCTCN2021095040-appb-000047
表17Table 17
Figure PCTCN2021095040-appb-000048
Figure PCTCN2021095040-appb-000048
表18Table 18
Figure PCTCN2021095040-appb-000049
Figure PCTCN2021095040-appb-000049
Figure PCTCN2021095040-appb-000050
Figure PCTCN2021095040-appb-000050
通过与对比例1比较，本发明通过添加含有三个可聚合基团的RM单体，三个可聚合基团可以加快反应速度时间，降低制程时间，提升响应速度，降低响应时间，对比例1响应时间为5.7ms，实施例响应时间最高为5.5ms，最低为5.1ms，相比于对比例1，添加含有三个可聚合基团的RM单体后响应时间提升4％-10％，响应时间有明显提升。Compared with Comparative Example 1, the present invention can speed up the reaction time, reduce the process time, improve the response speed, and reduce the response time by adding RM monomers containing three polymerizable groups. Comparative Example 1 The response time is 5.7ms, the highest response time of the embodiment is 5.5ms, and the lowest is 5.1ms. Compared with Comparative Example 1, the response time is improved by 4%-10% after adding the RM monomer containing three polymerizable groups. time has improved significantly.
最后应说明的是：以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that it can still be The technical solutions described in the foregoing embodiments are modified, or some technical features thereof are equivalently replaced; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.
工业实用性Industrial Applicability
本发明提供一种含可聚合化合物的液晶组合物及其应用，包含通式I所代表的可聚合化合物中的一种或多种，及向列相液晶组合物。本发明通过在向列相液晶组合物中引入含有三个可聚合基团的反应性介晶(RM)，三个可聚合基团可以加快反应速度时间，降低制程时间，使得液晶组合物的配向效果更好，聚合更完全，残留更低，并且能有效改善液晶组合物的低温互溶性，降低成角时间。特别是对于现有PSVA液晶来说，在对其他参数没有明显损害的情况下，能缩短在测试盒中可测量的预倾斜相关的响应时间，具有较好的经济价值和应用前景。The present invention provides a liquid crystal composition containing a polymerizable compound and an application thereof, comprising one or more of the polymerizable compounds represented by the general formula I, and a nematic liquid crystal composition. In the present invention, a reactive mesogen (RM) containing three polymerizable groups is introduced into the nematic liquid crystal composition, and the three polymerizable groups can speed up the reaction time and reduce the process time, so that the alignment of the liquid crystal composition can be achieved. The effect is better, the polymerization is more complete, the residue is lower, and the low temperature mutual solubility of the liquid crystal composition can be effectively improved, and the angle-forming time can be reduced. Especially for the existing PSVA liquid crystal, in the case of no obvious damage to other parameters, the measurable pre-tilt-related response time in the test box can be shortened, which has good economic value and application prospect.
Figure PCTCN2021095040-appb-000051
Figure PCTCN2021095040-appb-000051

Claims (10)

  1. 一种含可聚合化合物的液晶组合物，其特征在于，包含通式I所代表的可聚合化合物中的一种或多种，及向列相液晶组合物，A liquid crystal composition containing a polymerizable compound, characterized in that it comprises one or more of the polymerizable compounds represented by the general formula I, and a nematic liquid crystal composition,
    Figure PCTCN2021095040-appb-100001
    Figure PCTCN2021095040-appb-100001
    其中，L 1表示H、-F、-Cl、-CH 3、-C 2H 5、-OCH 3、-OC 2H 5、-CF 3或OCF 3； Wherein, L 1 represents H, -F, -Cl, -CH 3 , -C 2 H 5 , -OCH 3 , -OC 2 H 5 , -CF 3 or OCF 3 ;
    P 1、P 2、P 3彼此独立地表示丙烯酸酯基、甲基丙烯酸酯基、氟代丙烯酸酯基、氯代丙烯酸酯基、乙烯氧基、氧杂环丁烷基或环氧基； P 1 , P 2 , P 3 independently of one another represent an acrylate group, a methacrylate group, a fluoroacrylate group, a chloroacrylate group, a vinyloxy group, an oxetanyl group or an epoxy group;
    Z 1、Z 2、Z 3彼此独立地表示单键、-O-、-S-、-CO-、-CO-O-、-O-CO-、-O-CO-O-、-CH＝N-、-N＝CH-、-N＝N-、C 1-C 12的亚烷基或C 2-C 12的链烯基；或，所述C 1-C 12的亚烷基或C 2-C 12的链烯基中的至少一个氢原子彼此独立地被F、Cl或CN取代；或，所述C 1-C 12的亚烷基或C 2-C 12的链烯基中一个-CH 2-或至少两个不相邻的-CH 2-彼此独立地被-O-、-S-、-NH-、-CO-、-CO-O-、-OCO-、-OCOO-、-SCO-、-COS-或-C＝C-以不相互直接相连的方式取代。 Z 1 , Z 2 , and Z 3 independently represent a single bond, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH= N-, -N=CH-, -N=N-, C 1 -C 12 alkylene or C 2 -C 12 alkenyl; or, the C 1 -C 12 alkylene or C At least one hydrogen atom in the 2 -C 12 alkenyl group is independently substituted by F, Cl or CN; or, one of the C 1 -C 12 alkylene groups or the C 2 -C 12 alkenyl group -CH 2 - or at least two non-adjacent -CH 2 - independently of each other by -O-, -S-, -NH-, -CO-, -CO-O-, -OCO-, -OCOO-, -SCO-, -COS- or -C=C- are substituted without being directly connected to each other.
  2. 根据权利要求1所述的含可聚合化合物的液晶组合物，其特征在于，通式I中，L 1表示H、-F、-CH 3或-OCH 3； The liquid crystal composition containing a polymerizable compound according to claim 1, wherein, in the general formula I, L 1 represents H, -F, -CH 3 or -OCH 3 ;
    和/或，P 1、P 2、P 3彼此独立地表示甲基丙烯酸酯基、丙烯酸酯基、氟代丙烯酸酯基或氯代丙烯酸酯基，优选地，P 1、P 2、P 3彼此独立地表示甲基丙烯酸酯基或丙烯酸酯基； and/or, P 1 , P 2 , P 3 independently of each other represent a methacrylate group, an acrylate group, a fluoroacrylate group or a chloroacrylate group, preferably P 1 , P 2 , P 3 are each other independently represents a methacrylate group or an acrylate group;
    和/或，Z 1、Z 2、Z 3彼此独立地表示单键、-O-、-S-、-CO-O-、-O-CO-、C 1-C 6的亚烷基或C 2-C 6的链烯基；或，所述C 1-C 6的亚烷基或C 2-C 6的链烯基中的至少一个氢原子被F取代；或，所述C 1-C 6的亚烷基或C 2-C 6的链烯基中一个-CH 2-或至少两个不相邻的-CH 2-被-O-以不相互直接相连的方式取代；优选地，Z 1、Z 2、Z 3彼此独立地表示单键、-O-、C 1-C 6的亚烷基； And/or, Z 1 , Z 2 , Z 3 independently of each other represent a single bond, -O-, -S-, -CO-O-, -O-CO-, C 1 -C 6 alkylene or C 2 - C6 alkenyl; or, at least one hydrogen atom in the C1 - C6 alkylene or C2 - C6 alkenyl is substituted by F; or, the C1 -C One -CH 2 - or at least two non-adjacent -CH 2 - in the alkylene group of 6 or the alkenyl group of C 2 -C 6 is substituted by -O- in a manner that is not directly connected to each other; preferably, Z 1 , Z 2 , Z 3 independently of each other represent a single bond, -O-, an alkylene group of C 1 -C 6 ;
    更优选地，通式I所代表的可聚合化合物选自式I1～I4中的一种或多种：More preferably, the polymerizable compound represented by the general formula I is selected from one or more of the formulae I1-I4:
    Figure PCTCN2021095040-appb-100002
    Figure PCTCN2021095040-appb-100002
  3. 根据权利要求1或2所述的含可聚合化合物的液晶组合物，其特征在于，所述向列相液晶组合物包含通式II所代表化合物中的一种或多种，以及通式III所代表的化合物中的一种或多种，The liquid crystal composition containing a polymerizable compound according to claim 1 or 2, wherein the nematic liquid crystal composition comprises one or more of the compounds represented by the general formula II and the compounds represented by the general formula III. one or more of the compounds represented,
    Figure PCTCN2021095040-appb-100003
    Figure PCTCN2021095040-appb-100003
    其中，R 1、R 2各自独立地代表C 1-C 12的直链烷基、直链烷氧基或C 2-C 12的直链烯基，A 1、A 2各自独立地代表反式1，4-环己基或1，4-亚苯基，Z 4为单键、-CH 2CH 2-或-CH 2O-；a为0或1； Wherein, R 1 and R 2 each independently represent a C 1 -C 12 straight-chain alkyl group, a straight-chain alkoxy group or a C 2 -C 12 straight-chain alkenyl group, and A 1 and A 2 each independently represent a trans 1,4-cyclohexyl or 1,4-phenylene, Z 4 is a single bond, -CH 2 CH 2- or -CH 2 O-; a is 0 or 1;
    Figure PCTCN2021095040-appb-100004
    Figure PCTCN2021095040-appb-100004
    其中，R 3、R 4各自独立地代表C 1-C 12的直链烷基、直链烷氧基或C 2-C 12 的直链烯基，A 3、A 4各自独立地代表反式1，4-环己基或1，4-亚苯基。 Wherein, R 3 and R 4 each independently represent a C 1 -C 12 straight-chain alkyl group, a straight-chain alkoxy group or a C 2 -C 12 straight-chain alkenyl group, and A 3 and A 4 each independently represent a trans 1,4-cyclohexyl or 1,4-phenylene.
  4. 根据权利要求3所述的含可聚合化合物的液晶组合物，其特征在于，通式II所代表化合物选自IIA～IIF中的一种或多种：The liquid crystal composition containing a polymerizable compound according to claim 3, wherein the compound represented by the general formula II is selected from one or more of IIA to IIF:
    Figure PCTCN2021095040-appb-100005
    Figure PCTCN2021095040-appb-100005
    优选地，通式II所代表化合物选自式IIA-1～IIF-16中的一种或多种：Preferably, the compound represented by the general formula II is selected from one or more of the formulas IIA-1 to IIF-16:
    Figure PCTCN2021095040-appb-100006
    Figure PCTCN2021095040-appb-100006
    Figure PCTCN2021095040-appb-100007
    Figure PCTCN2021095040-appb-100007
    Figure PCTCN2021095040-appb-100008
    Figure PCTCN2021095040-appb-100008
    Figure PCTCN2021095040-appb-100009
    Figure PCTCN2021095040-appb-100009
    Figure PCTCN2021095040-appb-100010
    Figure PCTCN2021095040-appb-100010
    更优选地，通式II所代表化合物选自式IIA-9～IIA-24、IIB-19～IIB-38、IIC-9～IIC-24、IID-9～IID-24、IIE-1～IIE-20、IIF-1～IIF-16中的一种或多种；More preferably, the compound represented by the general formula II is selected from the group consisting of formulae IIA-9～IIA-24, IIB-19～IIB-38, IIC-9～IIC-24, IID-9～IID-24, IIE-1～IIE -20. One or more of IIF-1～IIF-16;
    最优选地，通式II所代表化合物选自式IIA-13～IIA-24、IIB-23～IIB-38、IIC-13～IIC-24、IID-13～IID-24、IIE-1、IIE-2、IIE-5、IIE-6、IIE-9、IIE-10、IIE-13、IIE-14、IIE-17、IIE-18、IIF-1、IIF-2、IIF-5、IIF-6、IIF-9、IIF-10、IIF-13、IIF-14中的一种或多种。Most preferably, the compound represented by general formula II is selected from formulae IIA-13～IIA-24, IIB-23～IIB-38, IIC-13～IIC-24, IID-13～IID-24, IIE-1, IIE -2, IIE-5, IIE-6, IIE-9, IIE-10, IIE-13, IIE-14, IIE-17, IIE-18, IIF-1, IIF-2, IIF-5, IIF-6 , one or more of IIF-9, IIF-10, IIF-13, IIF-14.
  5. 根据权利要求3或4所述的含可聚合化合物的液晶组合物，其特征在于，通式III所代表化合物选自式IIIA～IIIC中的一种或多种：The liquid crystal composition containing a polymerizable compound according to claim 3 or 4, wherein the compound represented by the general formula III is selected from one or more of the formulas IIIA to IIIC:
    Figure PCTCN2021095040-appb-100011
    Figure PCTCN2021095040-appb-100011
    Figure PCTCN2021095040-appb-100012
    Figure PCTCN2021095040-appb-100012
    优选地，通式III所代表化合物选自式IIIA1～IIIC24中的一种或多种：Preferably, the compound represented by the general formula III is selected from one or more of the formulas IIIA1 to IIIC24:
    Figure PCTCN2021095040-appb-100013
    Figure PCTCN2021095040-appb-100013
    Figure PCTCN2021095040-appb-100014
    Figure PCTCN2021095040-appb-100014
    Figure PCTCN2021095040-appb-100015
    Figure PCTCN2021095040-appb-100015
    更优选地，通式III所代表化合物选自式IIIA-1～IIIA-22、IIIB-1～IIIB-24、IIIC-1～IIIC-22中的一种或多种；More preferably, the compound represented by general formula III is selected from one or more of formulae IIIA-1 to IIIA-22, IIIB-1 to IIIB-24, and IIIC-1 to IIIC-22;
    最优选地，通式III所代表化合物选自式IIIA-1～IIIA-12、IIIB-17～IIIB-24、IIIC-1～IIIC-4、IIIC-15～IIIC-18中的一种或多种。Most preferably, the compound represented by general formula III is selected from one or more of formulae IIIA-1 to IIIA-12, IIIB-17 to IIIB-24, IIIC-1 to IIIC-4, and IIIC-15 to IIIC-18. kind.
  6. 根据权利要求1-5任一项所述的含可聚合化合物的液晶组合物，其特征在于，所述向列相液晶组合物还包含通式IV所代表化合物中的一种或多种：The liquid crystal composition containing a polymerizable compound according to any one of claims 1-5, wherein the nematic liquid crystal composition further comprises one or more of the compounds represented by the general formula IV:
    Figure PCTCN2021095040-appb-100016
    Figure PCTCN2021095040-appb-100016
    其中，R 5、R 6各自独立地代表C 1-C 12的直链烷基、直链烷氧基或C 2-C 12的直链烯基，A 5代表反式1，4-环己基或1，4-亚苯基； Wherein, R 5 and R 6 each independently represent a C 1 -C 12 straight-chain alkyl group, a straight-chain alkoxy group or a C 2 -C 12 straight-chain alkenyl group, and A 5 represents a trans-1,4-cyclohexyl group or 1,4-phenylene;
    优选地，通式IV所代表化合物选自IVA～IVB中的一种或多种：Preferably, the compound represented by the general formula IV is selected from one or more of IVA～IVB:
    Figure PCTCN2021095040-appb-100017
    Figure PCTCN2021095040-appb-100017
    其中，R 5、R 6各自独立地代表C 1-C 7的直链烷基、直链烷氧基或C 2-C 7的直链烯基； Wherein, R 5 and R 6 each independently represent a C 1 -C 7 straight-chain alkyl group, a straight-chain alkoxy group or a C 2 -C 7 straight-chain alkenyl group;
    更优选地，通式IV所代表化合物选自IVA1～IVB25中的一种或多种：More preferably, the compound represented by general formula IV is selected from one or more of IVA1～IVB25:
    Figure PCTCN2021095040-appb-100018
    Figure PCTCN2021095040-appb-100018
    Figure PCTCN2021095040-appb-100019
    Figure PCTCN2021095040-appb-100019
    Figure PCTCN2021095040-appb-100020
    Figure PCTCN2021095040-appb-100020
    最优选地，通式IV所代表化合物选自IVA-11～IVA-15、IVB-11～IVB-15中的一种或多种。Most preferably, the compound represented by the general formula IV is selected from one or more of IVA-11-IVA-15 and IVB-11-IVB-15.
  7. 根据权利要求3-6任一项所述的含可聚合化合物的液晶组合物，其特征在于，所述向列相液晶组合物包含以下质量百分比的组分：The liquid crystal composition containing a polymerizable compound according to any one of claims 3-6, wherein the nematic liquid crystal composition comprises the following components by mass percentage:
    (1)、1～80％的通式II所代表的化合物；(1), 1-80% of the compound represented by the general formula II;
    (2)、1～70％的通式III所代表的化合物；(2), 1-70% of the compound represented by the general formula III;
    (3)、0～40％的通式IV所代表的化合物；(3), 0～40% of the compound represented by general formula IV;
    优选地，所述向列相液晶组合物包含以下质量百分比的组分：Preferably, the nematic liquid crystal composition comprises the following components in mass percentage:
    (1)、5～70％的通式II所代表的化合物；(1), 5-70% of the compound represented by the general formula II;
    (2)、20～60％的通式III所代表的化合物；(2), 20-60% of the compound represented by the general formula III;
    (3)、0～35％的通式IV所代表的化合物；(3), 0～35% of the compound represented by general formula IV;
    更优选地，所述向列相液晶组合物包含以下质量百分比的组分：More preferably, the nematic liquid crystal composition comprises the following components in mass percentage:
    (1)、10～70％的通式II所代表的化合物；(1), 10-70% of the compound represented by the general formula II;
    (2)、25～60％的通式III所代表的化合物；(2), 25-60% of the compound represented by the general formula III;
    (3)、0～30％的通式IV所代表的化合物；(3), 0～30% of the compound represented by general formula IV;
    进一步优选地，所述向列相液晶组合物包含以下质量百分比的组分：Further preferably, the nematic liquid crystal composition comprises the following components in mass percentage:
    (1)、20～70％的通式II所代表的化合物；(1), 20-70% of the compound represented by the general formula II;
    (2)、25～50％的通式III所代表的化合物；(2), 25-50% of the compound represented by the general formula III;
    (3)、0～20％的通式IV所代表的化合物。(3), 0-20% of the compound represented by the general formula IV.
  8. 根据权利要求1-7任一项所述的含可聚合化合物的液晶组合物，其特征在于，所述液晶组合物还包括抗氧化剂，所述抗氧化剂包括通式V所代表化合物中的一种或多种：The liquid crystal composition containing a polymerizable compound according to any one of claims 1 to 7, wherein the liquid crystal composition further comprises an antioxidant, and the antioxidant comprises one of the compounds represented by the general formula V or more:
    Figure PCTCN2021095040-appb-100021
    Figure PCTCN2021095040-appb-100021
    其中，R 7代表C 1-C 7的直链烷基、直链烷氧基或C 2-C 7的直链烯基，A 6代表反式1，4-环己基或1，4-亚苯基；b为0或1； Wherein, R 7 represents C 1 -C 7 straight-chain alkyl, straight-chain alkoxy or C 2 -C 7 straight-chain alkenyl, A 6 represents trans 1,4-cyclohexyl or 1,4-idene phenyl; b is 0 or 1;
    优选地，通式V所代表化合物选自V-1～V-2中的一种或两种：Preferably, the compound represented by the general formula V is selected from one or both of V-1 to V-2:
    Figure PCTCN2021095040-appb-100022
    Figure PCTCN2021095040-appb-100022
    和/或，以所述向列相液晶组合物的重量为基准，通式V所代表化合物为0.005～1％，优选0.005～0.1％，进一步优选0.005～0.05％。And/or, based on the weight of the nematic liquid crystal composition, the compound represented by the general formula V is 0.005-1%, preferably 0.005-0.1%, more preferably 0.005-0.05%.
  9. 根据权利要求1-8任一项所述的含可聚合化合物的液晶组合物，其特征在于，以所述向列相液晶组合物的重量为基准，通式I所代表的可聚合化合物为0.01～5％，优选0.05～1％，进一步优选0.1～0.5％，更优选0.25～0.37％。The liquid crystal composition containing a polymerizable compound according to any one of claims 1-8, characterized in that, based on the weight of the nematic liquid crystal composition, the polymerizable compound represented by the general formula I is 0.01 ~5%, preferably 0.05 to 1%, more preferably 0.1 to 0.5%, more preferably 0.25 to 0.37%.
  10. 权利要求1-9任一项所述的含可聚合化合物的液晶组合物在PSVA型液晶显示装置中的应用。Application of the liquid crystal composition containing a polymerizable compound according to any one of claims 1 to 9 in a PSVA type liquid crystal display device.
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