WO2014043953A1 - 液晶介质混合物及使用其的液晶显示器 - Google Patents

液晶介质混合物及使用其的液晶显示器 Download PDF

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Publication number
WO2014043953A1
WO2014043953A1 PCT/CN2012/082994 CN2012082994W WO2014043953A1 WO 2014043953 A1 WO2014043953 A1 WO 2014043953A1 CN 2012082994 W CN2012082994 W CN 2012082994W WO 2014043953 A1 WO2014043953 A1 WO 2014043953A1
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liquid crystal
group
carbon atoms
polymerizable
straight
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French (fr)
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冯惺
顾毓波
杨流洋
钟新辉
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TCL China Star Optoelectronics Technology Co Ltd
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Shenzhen China Star Optoelectronics Technology Co Ltd
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Priority to US13/703,440 priority Critical patent/US9127198B2/en
Publication of WO2014043953A1 publication Critical patent/WO2014043953A1/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
    • C09K19/062—Non-steroidal liquid crystal compounds containing one non-condensed benzene ring
    • 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
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • 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
    • C09K19/3098—Unsaturated non-aromatic rings, e.g. cyclohexene rings
    • C—CHEMISTRY; METALLURGY
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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
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C09K19/322—Compounds containing a naphthalene ring or a completely or partially hydrogenated naphthalene ring
    • 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
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
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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
    • 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
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    • 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
    • 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
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C09K2019/3422—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a six-membered ring
    • 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
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/542—Macromolecular compounds
    • C09K2019/548—Macromolecular compounds stabilizing the alignment; Polymer stabilized alignment
    • 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
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133742—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers for homeotropic alignment

Definitions

  • the present invention relates to liquid crystal display technology, and more particularly to a liquid crystal medium mixture and a liquid crystal display using the same. Background technique
  • the liquid crystal used for the TN (Twisted nematic) or STN (Super Twisted Nematic) liquid crystal display is a positive liquid crystal, and the long axis of the liquid crystal molecules is parallel to the surface of the substrate when the power is not applied.
  • the alignment direction of the liquid crystal molecules on the surface of the substrate is determined by the rubbing direction of the alignment layer (Polyimide).
  • the alignment direction of the two substrates is perpendicular, so the molecules of the liquid crystal layer from one substrate surface to the other substrate surface. It is in a continuous twisting state. When a voltage is applied, the long axes of the liquid crystal molecules will tend to align in the direction of the electric field.
  • the disadvantage of the TN/STN type liquid crystal display is that the viewing angle is small, the luminance difference and the chromatic aberration are large at a large viewing angle, and it is required to be improved by the compensation film, thereby improving the manufacturing cost of the display.
  • MVA Multi-domain vertical alignment
  • TFT-LCD 4 solves the problem of viewing angle limitation of TN/STN display. It uses negative liquid crystal and vertical alignment film materials. When no voltage is applied, the long axis of the liquid crystal molecules is perpendicular to the surface of the substrate, and application of a voltage causes the liquid crystal molecules to pour, and the long axes of the liquid crystal molecules tend to be aligned in the direction of the vertical electric field.
  • one sub-pixel is divided into a plurality of regions, so that the liquid crystal molecules are tilted in different directions, so that the effects seen by the display from different directions tend to be uniform. There are various methods for directing liquid crystal molecules of different regions into different directions within one sub-pixel.
  • the first is to make a Bump (bulge) on the upper and lower substrates of the LCD by exposure and development, so that the liquid crystal molecules around the Bump generate a certain pretilt angle, and the liquid crystal molecules are directed to tilt in a fixed direction; the second is on the upper and lower substrates.
  • a Bump bulge
  • this technique is called PVA (Patterned Vertical Alignment) technology; the third is forming ITO slit (crack) on the TFT side of the LCD substrate, the other side For Full ITO, a polymerizable monomer is added to the liquid crystal medium, and the liquid crystal molecules are first poured by an electric field, and the panel is irradiated with ultraviolet light to polymerize the monomer to form a polymer particle having a liquid crystal molecule to be poured, and deposited on the surface of the substrate. As a function of alignment, this technique becomes a PSVA (Polymer stabilized vertical alignment) technology.
  • PSVA Polymer stabilized vertical alignment
  • the reaction rate of the polymerizable monomer, the size and distribution of the polymer, the uniformity of the surface of the substrate, and the strength of the alignment force have important influences on the optical taste and mass production stability of the panel. These factors are affected by the process conditions. In addition, the main reason for determining these factors is the molecular structure of the polymerizable monomer, because the molecular structure of the polymerizable monomer directly determines the speed of its photoreaction, the characteristics of the polymer formed, the alignment force to the liquid crystal, and the like. Since the existing liquid crystal medium generally contains an alkenyl compound, which is advantageous for obtaining a low rotational viscosity, the response of the liquid crystal medium can be improved.
  • the existing liquid crystal medium generally contains an alkenyl compound, it is advantageous to obtain a low rotational viscosity.
  • Increasing the response of the liquid crystal medium, and the alkenyl compound contained in the liquid crystal medium easily affects the reaction polymerization of the polymerizable monomer, thereby affecting the alignment of the liquid crystal medium, so usually, usually, a single polymerizable monomer It is difficult to achieve these factors, and the situation is often due to the loss of uniformity of the polymer, but the formation of the polymer is not enough, or the alignment force is too strong, but the reaction speed is too slow and so on. Summary of the invention
  • the technical problem to be solved by the present invention is to provide a liquid crystal medium mixture, which can be reasonably matched by using two or more polymerizable monomers having different functionalities, the reaction speed of the polymerization reaction, the uniformity of polymer formation, and The strength of the alignment force can reach equilibrium at the same time, and both get higher levels.
  • liquid crystal display wherein the liquid crystal medium mixture is properly matched by two or more polymerizable monomers having different functionalities, the reaction speed of the polymerization of the monomer, the uniformity of forming the polymer, and the strength of the alignment force. It can achieve balance at the same time, and both get higher levels, which improves the optical taste and overall performance of the panel and achieves stable mass production.
  • a liquid crystal medium mixture including components: at least one anisotropic liquid crystal material and two or more polymerizable polymerizations that can be irradiated under ultraviolet light.
  • the liquid crystal material comprising an alkenyl compound which is stable to polymerization when the polymerizable monomer is polymerized, the polymerizable monomer being at least one part by weight of the total composition of the liquid crystal medium mixture,
  • the structural formulas of the two or more polymerizable monomers are the same, the number of groups is different:
  • P represents a polymerizable group selected from at least one of a methacrylate group, an acrylate group, an ethenyl group, a vinyloxy group, and an epoxy group; n is bonded to the same The number of polymerizable groups P on the aromatic ring, n is an integer of 1-3, and if n is greater than 1, the polymerizable groups may be the same or different, wherein the polymerizable groups in the formulae I to IV are different a mercapto acrylate group;
  • X represents a substituent group selected from at least one of -F, -CI, -Br, fluorenyl, -CN, and a linear or branched alkyl group of 2-8 carbon atoms, in the alkyl group
  • Non-adjacent one or more thiol groups can be Substituted by an oxygen or sulfur atom
  • m is the number of substituent groups X attached to the same aromatic ring, m is an integer of 1-3, and if m is greater than 1, the substituent groups may be the same or different
  • Z in Formula IV Is - 0-, -C -OCH 2 0-, -0(CH 2 ) 2 0-,
  • the hydrogen atom on any aromatic ring in the structural formula of the polymerizable monomer may be substituted with a group such as -F, -Cl, -Br, fluorenyl or -CN.
  • the hydrogen atom on any non-aromatic ring in the structural formula of the polymerizable monomer may be substituted with a group such as -F, -Cl, -Br or fluorenyl.
  • the molar ratio of the two polymerizable monomers in the liquid crystal medium mixture is 1:5.
  • R1 represents a straight or branched alkenyl group having 2 to 9 carbon atoms
  • R2 represents a straight or branched alkyl group having 1 to 12 carbon atoms
  • X independently represents 11, F, Cl, OCF 3 or CF 3 ;
  • n 1;
  • n and k represent 0 ⁇ 3 respectively.
  • a liquid crystal display includes: an upper substrate and a lower substrate disposed opposite to each other, and a liquid crystal medium mixture disposed between the upper substrate and the lower substrate, the liquid crystal medium mixture including a group Divided into: at least one anisotropic liquid crystal material and two or more polymerizable monomers which are polymerizable under ultraviolet light irradiation, the liquid crystal material comprising an alkene which is stable to polymerization during polymerization of the polymerizable monomer a base compound, the polymerizable monomer being from 0.1% to 1% by weight based on the total amount of the liquid crystal medium mixture;
  • the structural formula of the two or more polymerizable monomers is as follows At least one of the formulas, when the two or more polymerizable monomers have the same structural formula, the number of groups is different:
  • P represents a polymerizable group selected from at least one of a methacrylate group, an acrylate group, an ethenyl group, a vinyloxy group, and an epoxy group; n is bonded to the same The number of polymerizable groups P on the aromatic ring, n is an integer of 1-3, and if n is greater than 1, the polymerizable groups may be the same or different, wherein the polymerizable groups in the formulae I to IV are different a mercapto acrylate group;
  • X represents a substituent group selected from at least one of -F, -CI, -Br, fluorenyl, -CN, and a linear or branched alkyl group of 2-8 carbon atoms, in the alkyl group
  • Non-adjacent one or more mercapto groups may be substituted by oxygen or sulfur atoms
  • m is the number of substituent groups X attached to the same aromatic ring, m is an integer from 1 to 3, if m is greater than 1, substituted
  • the groups may be the same or different;
  • Z in formula IV is -0-, -C-OCH 2 0-, -0(CH 2 ) 2 0-,
  • the hydrogen atom on any aromatic ring in the structural formula of the polymerizable monomer may be substituted with a group such as -F, -Cl, -Br, fluorenyl or -CN.
  • the hydrogen atom on any non-aromatic ring in the structural formula of the polymerizable monomer may be substituted with a group such as -F, -Cl, -Br or fluorenyl.
  • the molar ratio of the two polymerizable monomers in the liquid crystal medium mixture is 1:
  • R1 represents a straight or branched alkenyl group having 2 to 9 carbon atoms
  • R2 represents a straight or branched alkyl group having 1 to 12 carbon atoms
  • X independently represents 11, F, Cl, OCF 3 or CF 3 ;
  • n 1;
  • n and k represent 0 ⁇ 3 respectively.
  • the liquid crystal medium mixture of the present invention adopts two or more kinds of polymerizable monomers which can be polymerized under ultraviolet light irradiation and a reasonable ratio thereof, and can be polymerized to obtain polymer protrusions with small size and uniformity.
  • the phenomenon that the liquid crystal alignment is poor and the dark state of the liquid crystal panel is avoided is avoided, so that the response speed of the liquid crystal panel is increased and high contrast is obtained.
  • Applying it to a liquid crystal display improves the optical taste and overall performance of the liquid crystal display panel, and achieves stable mass production. detailed description
  • the present invention provides a liquid crystal medium mixture for a liquid crystal display, the liquid crystal medium mixture comprising the following components: at least one anisotropic liquid crystal material and two or more kinds of polymerization which can be polymerized under ultraviolet light irradiation a polymerizable monomer; the liquid crystal material comprising an alkenyl compound which is stable to polymerization when the polymerizable monomer is polymerized, the polymerizable monomer being from 0.1% to 1% by weight based on the total amount of the liquid crystal medium mixture;
  • the structural formula of the polymerizable monomer is composed of a single benzene ring, two benzene rings or a single naphthalene ring, and the two benzene ring structures are directly connected by two benzene rings or indirectly connected by a group, the benzene ring and The naphthalene ring is directly bonded to at least one polymerizable group. At least one of the groups, when the two or more polymerizable monomers have
  • P represents a polymerizable group selected from at least one of a methacrylate group, an acrylate group, an ethenyl group, a vinyloxy group, and an epoxy group; ⁇ is bonded to the same The number of the polymerizable groups ⁇ on the aromatic ring, ⁇ is an integer of 1-3, and if ⁇ is greater than 1, the polymerizable groups may be the same or different, wherein the polymerizable groups in the formulae I to IV are different a mercapto acrylate group;
  • X represents a substituent group selected from at least one of -F, -CI, -Br, fluorenyl, -CN, and a linear or branched alkyl group of 2-8 carbon atoms, in the alkyl group
  • Non-adjacent one or more mercapto groups may be substituted by oxygen or sulfur atoms
  • m is the number of substituent groups X attached to the same aromatic ring, m is an integer from 1 to 3, if m is greater than 1, substituted
  • the groups may be the same or different;
  • Z in formula IV is -0-, -C-OCH 2 0-, -0(CH 2 ) 2 0-,
  • the hydrogen atom on any aromatic ring in the structural formula of the polymerizable monomer may be substituted by the following groups: -F, -Cl, -Br, fluorenyl or -CN.
  • the hydrogen atom on any non-aromatic ring in the structural formula of the polymerizable monomer may be substituted with a group: -F, -Cl, -Br or fluorenyl.
  • R1 represents a straight or branched alkenyl group having 2 to 9 carbon atoms
  • R2 represents a straight or branched alkyl group having 1 to 12 carbon atoms
  • X independently represents 11, F, Cl, OCF 3 or CF 3 ;
  • n 1;
  • n and k represent 0 ⁇ 3 respectively.
  • the molar ratio of the two polymerizable monomers in the liquid crystal medium mixture is 1:5.
  • the at least one anisotropic liquid crystal molecular material is specifically:
  • R is a linear or branched alkyl group of 1 to 9 carbon atoms, and non-adjacent one or more fluorenyl or fluorenylene groups in the alkyl group may be substituted by an oxygen or sulfur atom;
  • the amount of the heterogeneous liquid crystal material is 20% to 90% in the liquid crystal medium mixture.
  • the liquid crystal medium mixture is as follows:
  • RM-B1 The structural formula of RM-B1 is as follows:
  • the molar ratio of RM-A1 to RM-B1 is 1:5, and the total content of both accounts for 3000 ppm of the liquid crystal dielectric layer.
  • RM-A1 and RM-B1 are mixed, and the polymer generated by ultraviolet irradiation is small in size and uniform, and there is no dark state of light.
  • the liquid crystal medium mixture uses a negative liquid crystal material and two polymerizable monomers, as follows: 1.
  • the structural formula of RM-A1 is as follows:
  • RM-B1 The structural formula of RM-B1 is as follows:
  • the molar ratio of RM-A1 to RM-B1 is 1:5, and the total content of both accounts for 1000 ppm of the liquid crystal dielectric layer.
  • RM-A1 and RM-B1 are mixed, and the polymer generated by ultraviolet irradiation is small in size and uniform, and there is no dark state of light.
  • RM-B1 The structural formula of RM-B1 is as follows:
  • the molar ratio of RM-A1 to RM-B1 is 1:5, and the total content of both accounts for 10,000 ppm of the liquid crystal dielectric layer.
  • RM-A1 and RM-B1 are mixed, and the polymer generated by ultraviolet irradiation is small in size and uniform, and there is no dark state of light.
  • the liquid crystal medium mixture for liquid crystal display of the present invention passes through two or more kinds of polymerizable monomers which can be polymerized under ultraviolet light irradiation and suitable for the liquid crystal medium mixture.
  • the polymerization reaction can be controlled to form the size and uniformity of the polymer protrusions, and the poor alignment of the liquid crystal and the dark spot phenomenon of the liquid crystal panel are avoided, so that the liquid crystal panel obtains good optical performance, such as high contrast and high response speed. .
  • the liquid crystal medium mixture of the present invention is applicable to a display, and the liquid crystal display using the liquid crystal medium mixture of the present invention comprises: an upper substrate and a lower substrate disposed opposite to each other, and a liquid crystal medium disposed between the upper substrate and the lower substrate
  • the mixture, the liquid crystal medium mixture is the above-mentioned liquid crystal medium mixture of the present invention, which will not be described herein.
  • the liquid crystal medium mixture can simultaneously achieve a balance between the reaction rate of the polymerizable reaction, the uniformity of formation of the polymer, and the strength of the alignment force, and a higher level is obtained, that is, When the polymerization rate is fast, the uniformity of the polymer formation and the strength of the alignment force are also high, so that the optical taste and overall performance of the liquid crystal display panel can be improved, and stable mass production can be achieved.

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Description

液晶介质混合物及使用其的液晶显示器 本申请要求于 2012 年 9 月 21 日提交中国专利局、 申请号为 201210360734.1、 发明名称为 "液晶介质混合物及使用其的液晶显示器" 的 中国专利申请的优先权， 上述专利的全部内容通过引用结合在本申请中。 技术领域
本发明涉及液晶显示技术， 尤其涉及一种液晶介质混合物及使用其的液 晶显示器。 背景技术
TN ( Twisted nematic, 扭曲向列型）或 STN ( Super twisted nematic, 超 扭曲向列型 )液晶显示器所用的液晶为正型液晶， 未加电时液晶分子长轴平 行于基板表面。 基板表面液晶分子的排列方向由配向层 ( Alignment layer, 材质通常为 Polyimide ) 的摩擦方向 （Rubbing direction ) 决定， 两基板表面 配向方向垂直， 所以从一个基板表面到另一个基板表面， 液晶层的分子呈连 续扭转排列状态。 当施加电压之后， 液晶分子的长轴将倾向于沿电场的方向 排列。 TN/STN型液晶显示器的缺点是可视角小， 在大视角下的亮度差异和 色差严重， 需要通过补偿膜对此进行改善， 从而提高了显示器的制造成本。
MVA ( Multi-domain vertical alignment, 多象限垂直配向型） TFT-LCD 4艮好的解决了 TN/STN显示器视角限制的问题， 它采用负型液晶与垂直配向 膜材料。 未施加电压时， 液晶分子长轴均垂直于基板表面， 施加电压会使液 晶分子倾倒，液晶分子长轴倾向于沿垂直电场方向排列。为了解决视角问题， 一个亚像素被分成多个区域， 使液晶分子朝不同的方向倾倒， 让显示器从不 同的方向看到的效果趋于一致。在一个亚像素内使不同区域的液晶分子导向 不同的方向有多种方法。 第一种是通过曝光显影的办法在 LCD的上下基板 制作出 Bump (隆起物 ), 使 Bump周围的液晶分子产生一定的预倾角， 引导 液晶分子朝固定方向倾倒； 第二种是在上下基板上形成具有一定图案的 ITO ( Indium Tin Oxide, 氧化铟锡 )像素电极， 由此产生的电场具有一定的倾斜 角度， 从而控制不同区域的液晶分子的导向， 此技术被称为 PVA ( Patterned vertical alignment, 垂直取向构型 )技术； 第三种是在 LCD基板的 TFT侧形 成 ITO slit(裂缝），另一侧为 Full ITO,在液晶介质中添加可聚合的 monomer (单体）， 先通过电场使液晶分子倾倒， 同时用紫外光照射面板使 monomer 聚合形成具有引导液晶分子倾倒的聚合物颗粒，沉积在基板表面起到配向的 作用， 这种技术成为 PSVA ( Polymer stabilized vertical alignment, 聚合物稳、 定垂直对齐）技术。
可聚合单体的反应速度、 聚合物的大小及分布、 在基板表面均匀性、 配 向力的强弱等因素对面板的光学品味、 量产稳定性有重要影响， 这些因素除 了受制程条件的影响之外， 决定这些因素的主要原因是可聚合单体的分子结 构， 因为可聚合单体的分子结构直接决定了其光反应的快慢、 形成聚合物的 特性、对液晶的配向力强弱等。由于现有的液晶介质中一般含有烯基化合物， 有利于获得低的旋转粘度， 因而可提高液晶介质的响应， 由于现有的液晶介 质中一般含有烯基化合物， 有利于获得低的旋转粘度以提高液晶介质的响 应， 而在液晶介质中含有的烯基化合物容易影响可聚合单体的反应聚合， 从 而影响到液晶介质的配向， 故通常情况， 故通常情况， 单一一种可聚合单体 ί艮难达到让这几个因素都处于有利的情况， 出现的情况往往是顾此失彼， 比 如形成聚合物的均匀性好但是配向力不够，或配向力强但是反应速度太慢等 诸如此类问题。 发明内容
本发明的所要解决的技术问题在于， 提供一种液晶介质混合物， 采用两 种或两种以上功能性不同的可聚合单体进行合理搭配， 其聚合反应的反应速 度、 形成聚合物的均匀性及配向力的强度能同时达到平衡， 且均得到较高的 水平。
以及提供一种液晶显示器，其液晶介质混合物采用两种或两种以上功能 性不同的可聚合单体进行合理搭配， 单体的聚合反应的反应速度、 形成聚合 物的均匀性及配向力的强度能同时达到平衡， 且均得到较高的水平， 提高了 面板的光学品味和总体表现， 实现稳定的量产性。 为解决上述技术问题， 本发明实施例提供一种液晶介质混合物， 其包括 组分： 至少一种各相异性的液晶材料和两种或两种以上可在紫外光照射下发 生聚合反应的可聚合单体，该液晶材料包括在可聚合单体聚合时对聚合反应 稳定的烯基化合物，所述可聚合单体按重量份计算占所述液晶介质混合物总 构通式中的至少一种， 当该两种或两种以上的可聚合单体的结构通式相同 时， 团个数不同：
Figure imgf000004_0001
式 I至 IV中， P代表可聚合基团，其选自曱基丙烯酸酯基、丙烯酸酯基、 乙婦基、 乙烯氧基、 及环氧基中的至少一种； n为连接于同一个芳香环上的 可聚合基团 P的个数， n为 1-3的整数， 如果 n大于 1 , 可聚合基团可以相 同或不同， 其中， 式 I至式 IV中的可聚合基团不同时为曱基丙烯酸酯基；
X代表取代基团， 其选自 -F, -CI, -Br、 曱基、 -CN、 及 2-8个碳原子构 成的直链或支链烷基中的至少一种， 该烷基中非相邻的一个或多个曱基可被 氧或硫原子取代； m为连接于同一个芳香环上的取代基团 X的个数， m为 1-3的整数， 如果 m大于 1 , 取代基团可以相同或不同； 式 IV中的 Z为- 0-、 -C -OCH20-、 -0(CH2)20-、
-COCH2-、 亚曱基、 -C≡C -、
Figure imgf000005_0001
其中， 所述可聚合单体的结构通式中的任意芳香环上的氢原子可以被如 下基团取代： -F、 -Cl、 -Br、 曱基或 -CN。
其中， 所述可聚合单体的结构通式中任意非芳香环上的氢原子可以被如 下基团取代： -F、 -Cl、 -Br或曱基。
Figure imgf000005_0002
所述两种可聚合单体在液晶介质混合物中的含量摩尔比例为 1 :5。
结构通式：
Figure imgf000005_0003
其中,
Figure imgf000006_0001
Rl表示具有 2-9个碳原子的直链或支链烯基；
R2表示具有 1-12个碳原子的直链或支链烷基;
X分别独立的表示11、 F、 Cl、 OCF3或 CF3;
m表示 1-4;
n、 k分别表示 0~3。
本发明实施例的另一方面， 提供一种液晶显示器， 其包括： 相对平行设 置的上基板与下基板、 及设于该上基板与下基板之间的液晶介质混合物， 该 液晶介质混合物包括组分： 至少一种各相异性的液晶材料和两种或两种以上 可在紫外光照射下发生聚合反应的可聚合单体， 该液晶材料包括在可聚合单 体聚合时对聚合反应稳定的烯基化合物， 所述可聚合单体按重量份计算占所 述液晶介质混合物总量的 0.1%-1%； 所述两种或两种以上的可聚合单体的结 构通式为如下所示结构通式中的至少一种， 当该两种或两种以上的可聚合单 体的结构通式相同时， 其基团个数不同：
I
Figure imgf000006_0002
式 II
Figure imgf000006_0003
Figure imgf000007_0001
Figure imgf000007_0002
式 I至 IV中， P代表可聚合基团，其选自曱基丙烯酸酯基、丙烯酸酯基、 乙婦基、 乙烯氧基、 及环氧基中的至少一种； n为连接于同一个芳香环上的 可聚合基团 P的个数， n为 1-3的整数， 如果 n大于 1 , 可聚合基团可以相 同或不同， 其中， 式 I至式 IV中的可聚合基团不同时为曱基丙烯酸酯基；
X代表取代基团， 其选自 -F, -CI, -Br、 曱基、 -CN、 及 2-8个碳原子构 成的直链或支链烷基中的至少一种， 该烷基中非相邻的一个或多个曱基可被 氧或硫原子取代； m为连接于同一个芳香环上的取代基团 X的个数， m为 1-3的整数， 如果 m大于 1 , 取代基团可以相同或不同； 式 IV中的 Z为- 0-、 -C -OCH20-、 -0(CH2)20-、
-COCH2-、 亚曱基、 -C≡C -、
Figure imgf000007_0003
其中， 所述可聚合单体的结构通式中的任意芳香环上的氢原子可以被如 下基团取代： -F、 -Cl、 -Br、 曱基或 -CN。
其中， 所述可聚合单体的结构通式中任意非芳香环上的氢原子可以被如 下基团取代： -F、 -Cl、 -Br或曱基。
其中， 所述两种可聚合单体分别为：
Figure imgf000008_0001
所述两种可聚合单体在液晶介质混合物中的含量摩尔比例为 1:
其具有如下结构通式：
Figure imgf000008_0002
其中，
Figure imgf000008_0003
或 〉
R1表示具有 2-9个碳原子的直链或支链烯基；
R2表示具有 1-12个碳原子的直链或支链烷基；
X分别独立的表示11、 F、 Cl、 OCF3或 CF3;
m表示 1-4;
n、 k分别表示 0~3。
实施本发明的实施例， 本发明具有如下有益效果: 本发明的液晶介质混合物，采用两种或两种以上可在紫外光照射下发生 聚合反应的可聚合单体及其合理配比， 可以聚合反应得到尺寸较小、 均匀性 好的聚合物突起物， 避免了液晶配向不良、 液晶面板暗态亮点现象的发生， 从而使液晶面板响应速度变快并获得高对比度。。将其应用于液晶显示器中， 提高了液晶显示器面板的光学品味和总体表现， 实现稳定的量产性。 具体实施方式
为更进一步阐述本发明所采取的技术手段及其效果， 以下结合本发明的 优选实施例及其附图进行详细描述。
本发明提供一种用于液晶显示器的液晶介质混合物， 所述液晶介质混合 物包括如下组分： 至少一种各相异性的液晶材料及两种或两种以上可在紫外 光照射下发生聚合反应的可聚合单体； 该液晶材料包括在可聚合单体聚合时 对聚合反应稳定的烯基化合物，所述可聚合单体按重量份计算占液晶介质混 合物总量的 0.1%-1%； 所述可聚合单体的结构通式由单个苯环、 两个苯环或 单个萘环构成， 该两个苯环结构由两个苯环直接连接或通过一个基团间接连 接构成， 所述苯环和萘环上直接连接至少有一个可聚合基团。 的至少一种， 当该两种或两种以上的可聚合单体的结构通式相同时， 其基团 个数不 ：
Figure imgf000009_0001
式 III
Figure imgf000010_0001
Figure imgf000010_0002
式 I至 IV中， P代表可聚合基团，其选自曱基丙烯酸酯基、丙烯酸酯基、 乙婦基、 乙烯氧基、 及环氧基中的至少一种； η为连接于同一个芳香环上的 可聚合基团 Ρ的个数， η为 1-3的整数， 如果 η大于 1 , 可聚合基团可以相 同或不同， 其中， 式 I至式 IV中的可聚合基团不同时为曱基丙烯酸酯基；
X代表取代基团， 其选自 -F, -CI, -Br、 曱基、 -CN、 及 2-8个碳原子构 成的直链或支链烷基中的至少一种， 该烷基中非相邻的一个或多个曱基可被 氧或硫原子取代； m为连接于同一个芳香环上的取代基团 X的个数， m为 1-3的整数， 如果 m大于 1 , 取代基团可以相同或不同； 式 IV中的 Z为- 0-、 -C -OCH20-、 -0(CH2)20-、
-COCH2-、 亚曱基、 -C≡C -、
Figure imgf000010_0003
所述可聚合单体的结构通式中的任意芳香环上的氢原子可以被如下基 团取代： -F、 -Cl、 -Br、 曱基或 -CN。
所述可聚合单体的结构通式中的任意非芳香环上的氢原子可以被如下 基团取代： -F、 -Cl、 -Br或曱基。
如下结构通式：
Figure imgf000010_0004
其中，
Figure imgf000011_0001
R1表示具有 2-9个碳原子的直链或支链烯基；
R2表示具有 1-12个碳原子的直链或支链烷基;
X分别独立的表示11、 F、 Cl、 OCF3或 CF3;
m表示 1-4;
n、 k分别表示 0~3。
Figure imgf000011_0002
所述两种可聚合单体在液晶介质混合物中的含量摩尔比例为 1 :5。 所述至少一种各相异性的液晶分子材料具体为：
Figure imgf000011_0003
上述结构式中， R为 1-9个碳原子的直链或支链烷基， 烷基中非相邻的 个或多个曱基或亚曱基可被氧或硫原子取代； 所述各相异性的液晶材料的 量含量在液晶介质混合物中所占比例为 20%至 90%。
下面通过具体实施例， 说明本发明实施方式。
实施例 1 :
所述液晶介质混合物采用 具体如下：
负型液晶材料的结构式为
Figure imgf000012_0001
B1 , RM-A1的结构式如下所示:
Figure imgf000012_0002
RM-B1的结构式如下所示:
Figure imgf000012_0003
RM-A1 与 RM-B1 的摩尔比是 1:5 , 两者的总含量占液晶介质层的 3000ppm。 液晶介质混合物中， 混合使用 RM-A1和 RM-B1 , 通过紫外线照 射生成的聚合物 bump的尺寸小、 均匀， 不存在暗态亮光现象。
实施例 2:
所述液晶介质混合物采用负型液晶材料及两种可聚合单体， 具体如下：
Figure imgf000012_0004
1 ,RM-A1的结构式如下所示:
Figure imgf000013_0001
RM-B1的结构式如下所示:
Figure imgf000013_0002
RM-A1 与 RM-B1 的摩尔比是 1:5, 两者的总含量占液晶介质层的 1000ppm。 液晶介质混合物中， 混合使用 RM-A1和 RM-B1, 通过紫外线照 射生成的聚合物 bump的尺寸小、 均匀， 不存在暗态亮光现象。
实施例 3:
具体如下：
Figure imgf000013_0003
B1 ,RM-A1的结构式如下所示:
Figure imgf000013_0004
RM-B1的结构式如下所示:
Figure imgf000014_0001
RM-A1 与 RM-B1 的摩尔比是 1:5 , 两者的总含量占液晶介质层的 10000ppm。 液晶介质混合物中， 混合使用 RM-A1和 RM-B1 , 通过紫外线照 射生成的聚合物 bump的尺寸小、 均匀， 不存在暗态亮光现象。
综上所述， 本发明所述的用于液晶显示器的液晶介质混合物， 通过该液 晶介质混合物中含有的两种或两种以上可在紫外光照射下发生聚合反应的 可聚合单体以及合适配比， 可以控制聚合反应形成聚合物突起物的大小和均 匀性， 避免了液晶配向不良、 液晶面板暗态亮点现象的发生， 以此使得液晶 面板获得好的光学表现， 如高对比度和高响应速度。
本发明的液晶介质混合物可应用于显示器， 本发明的使用上述液晶介质 混合物的液晶显示器， 其包括： 相对平行设置的上基板与下基板、 及设于该 上基板与下基板之间的液晶介质混合物， 该液晶介质混合物即为本发明上述 的液晶介质混合物， 在此不累赘述之。 液晶介质混合物通过使用功能性不同 的可聚合单体， 使得可聚合单体在聚合反应的反应速度、 形成聚合物的均匀 性及配向力的强度能同时达到平衡， 且获得较高的水平， 即， 聚合反应速度 快的同时， 形成聚合物均匀性及配向力强度也高， 从而可提高液晶显示器面 板的光学品味和总体表现， 实现稳定的量产性。
以上所述， 对于本领域的普通技术人员来说， 可以根据本发明的技术方 案和技术构思作出其他各种相应的改变和变形， 而所有这些改变和变形都应 属于本发明权利要求的保护范围。

Claims

权 利 要 求
1、 一种液晶介质混合物， 其特征在于， 其包括组分： 至少一种各相异 性的液晶材料和两种或两种以上可在紫外光照射下发生聚合反应的可聚合 单体， 该液晶材料包括在可聚合单体聚合时对聚合反应稳定的烯基化合物， 所述可聚合单体按重量份计算占所述液晶介质混合物总量的 0.1%-1%； 所述 种，当 以上的可聚合单体的结构通式相同时，其基团个数不同：
Figure imgf000015_0001
Figure imgf000015_0002
式 I至 IV中， P代表可聚合基团，其选自曱基丙烯酸酯基、丙烯酸酯基、 乙婦基、 乙烯氧基、 及环氧基中的至少一种； n为连接于同一个芳香环上的 可聚合基团 P的个数， n为 1-3的整数， 如果 n大于 1 , 可聚合基团可以相 同或不同， 其中， 式 I至式 IV中的可聚合基团不同时全为曱基丙烯酸酯基;
X代表取代基团， 其选自 -F, -CI, -Br、 曱基、 -CN、 及 2-8个碳原子构 成的直链或支链烷基中的至少一种， 该烷基中非相邻的一个或多个曱基可被 氧或硫原子取代； m为连接于同一个芳香环上的取代基团 X的个数， m为 1-3的整数， 如果 m大于 1 , 取代基团可以相同或不同； 式 IV中的 Z为- 0-、 -C -OCH20-、 -0(CH2)20-、
-COCH2-、 亚曱基、 -C≡C -、
Figure imgf000016_0001
2、 如权利要求 1所述的液晶介质混合物， 其特征在于， 所述可聚合单 体的结构通式中的任意芳香环上的氢原子可以被如下基团取代： -F、 -Cl、 -Br、 曱基或 -CN。
3、 如权利要求 1所述的液晶介质混合物， 其特征在于， 所述可聚合单 体的结构通式中任意非芳香环上的氢原子可以被如下基团取代： -F、 -Cl、 -Br 或曱基。
4、 如权利要求 1所述的液晶介质混合物， 其特征在于， 所述两种可聚 合单
Figure imgf000016_0002
所述两种可聚合单体在液晶介质混合物中的含量摩尔比例为 1 :5。
5、 如权利要求 1所述的液晶介质混合物， 其特征在于， 所述婦基化合 物，
Figure imgf000016_0003
或 /及
Figure imgf000017_0001
Figure imgf000017_0002
Rl表示具有 2-9个碳原子的直链或支链烯基；
R2表示具有 1-12个碳原子的直链或支链烷基；
X分别独立的表示11、 F、 Cl、 OCF3或 CF3;
m表示 1-4;
n、 k分别表示 0~3。
6、 如权利要求 2所述的液晶介质混合物， 其特征在于， 所述婦基化合
Figure imgf000017_0003
Figure imgf000018_0001
Rl表示具有 2-9个碳原子的直链或支链烯基；
R2表示具有 1-12个碳原子的直链或支链烷基；
X分别独立的表示11、 F、 Cl、 OCF3或 CF3;
m表示 1-4;
n、 k分别表示 0~3。
7、 如权利要求 3所述的液晶介质混合物， 其特征在于， 所述婦基化合
Figure imgf000018_0002
Figure imgf000018_0003
Figure imgf000019_0001
Rl表示具有 2-9个碳原子的直链或支链烯基；
R2表示具有 1-12个碳原子的直链或支链烷基；
X分别独立的表示11、 F、 Cl、 OCF3或 CF3;
m表示 1-4;
n、 k分别表示 0~3。
8、 如权利要求 4所述的液晶介质混合物， 其特征在于， 所述婦基化合 物，
Figure imgf000019_0002
其中，
Figure imgf000019_0003
或 〉
R1表示具有 2-9个碳原子的直链或支链烯基；
R2表示具有 1-12个碳原子的直链或支链烷基;
X分别独立的表示11、 F、 Cl、 OCF3或 CF3;
m表示 1-4;
n、 k分别表示 0~3。
9、 一种液晶显示器， 其特征在于， 其包括： 相对平行设置的上基板与 下基板、 及设于该上基板与下基板之间的液晶介质混合物， 该液晶介质混合 物包括组分： 至少一种各相异性的液晶材料以及两种或两种以上可在紫外光 照射下发生聚合反应的可聚合单体，该液晶材料包括在可聚合单体聚合时对 聚合反应稳定的烯基化合物， 所述可聚合单体按重量份计算占所述液晶介质 下所示结构通式中的至少一种， 当该两种或两种以上的可聚合单体的结构通 式相 不同：
Figure imgf000020_0001
Figure imgf000020_0002
式 I至 IV中， P代表可聚合基团，其选自曱基丙烯酸酯基、丙烯酸酯基、 乙婦基、 乙烯氧基、 及环氧基中的至少一种； n为连接于同一个芳香环上的 可聚合基团 P的个数， n为 1-3的整数， 如果 n大于 1 , 可聚合基团可以相 同或不同， 其中， 式 I至式 IV中的可聚合基团不同时为曱基丙烯酸酯基；
X代表取代基团， 其选自 -F, -CI, -Br、 曱基、 -CN、 及 2-8个碳原子构 成的直链或支链烷基中的至少一种， 该烷基中非相邻的一个或多个曱基可被 氧或硫原子取代； m为连接于同一个芳香环上的取代基团 X的个数， m为 1-3的整数， 如果 m大于 1 , 取代基团可以相同或不同； 式 IV中的 Z为- 0-、 -C -OCH20-、 -0(CH2)20-、
-COCH2-、 亚曱基、 -C≡C -、
Figure imgf000021_0001
10、 如权利要求 9所述的液晶显示器， 其特征在于， 所述可聚合单体的 结构通式中的任意芳香环上的氢原子可以被如下基团取代： -F、 -Cl、 -Br、 曱基或 -CN。
11、 如权利要求 9所述的液晶显示器， 其特征在于， 所述可聚合单体的 结构通式中任意非芳香环上的氢原子可以被如下基团取代： -F、 -Cl、 -Br或 曱基。
12、 如权利要求 9所述的液晶显示器， 其特征在于， 所述两种可聚合单 体分
Figure imgf000021_0002
所述两种可聚合单体在液晶介质混合物中的含量摩尔比例为 1:5。
13、 如权利要求 9所述的液晶显示器， 其特征在于， 所述婦基化合物, 其
Figure imgf000021_0003
或 /及
Figure imgf000022_0001
Figure imgf000022_0002
Rl表示具有 2-9个碳原子的直链或支链烯基；
R2表示具有 1-12个碳原子的直链或支链烷基；
X分别独立的表示11、 F、 Cl、 OCF3或 CF3;
m表示 1-4;
n、 k分别表示 0~3。
14、 如权利要求 10所述的液晶显示器， 其特征在于， 所述婦基化合物 其
Figure imgf000022_0003
Figure imgf000023_0001
Rl表示具有 2-9个碳原子的直链或支链烯基；
R2表示具有 1-12个碳原子的直链或支链烷基；
X分别独立的表示11、 F、 Cl、 OCF3或 CF3;
m表示 1-4;
n、 k分别表示 0~3。
15、 如权利要求 11所述的液晶显示器， 其特征在于， 所述烯基化合物: 其
Figure imgf000023_0003
Figure imgf000024_0001
Rl表示具有 2-9个碳原子的直链或支链烯基；
R2表示具有 1-12个碳原子的直链或支链烷基；
X分别独立的表示11、 F、 Cl、 OCF3或 CF3;
m表示 1-4;
n、 k分别表示 0~3。
16、 如权利要求 12所述的液晶显示器， 其特征在于， 所述婦基化合物: 其
Figure imgf000024_0002
其中，
Figure imgf000024_0003
或 〉
R1表示具有 2-9个碳原子的直链或支链烯基；
R2表示具有 1-12个碳原子的直链或支链烷基;
X分别独立的表示11、 F、 Cl、 OCF3或 CF3;
m表示 1-4;
n、 k分别表示 0~3。
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