WO2014114013A1 - 一种聚合物稳定垂直配向液晶显示面板及液晶显示器 - Google Patents

一种聚合物稳定垂直配向液晶显示面板及液晶显示器 Download PDF

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Publication number
WO2014114013A1
WO2014114013A1 PCT/CN2013/071236 CN2013071236W WO2014114013A1 WO 2014114013 A1 WO2014114013 A1 WO 2014114013A1 CN 2013071236 W CN2013071236 W CN 2013071236W WO 2014114013 A1 WO2014114013 A1 WO 2014114013A1
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liquid crystal
epoxy resin
structural formula
crystal display
group
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PCT/CN2013/071236
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English (en)
French (fr)
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钟新辉
黄宏基
李冠政
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深圳市华星光电技术有限公司
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Priority to US13/824,404 priority Critical patent/US20150277190A1/en
Publication of WO2014114013A1 publication Critical patent/WO2014114013A1/zh

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • 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
    • C09K19/32—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
    • 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
    • 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
    • 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
    • G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
    • 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
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • 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
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K2019/523—Organic solid particles
    • 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
    • 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
    • G02F1/13775—Polymer-stabilized liquid crystal layers

Definitions

  • the invention relates to a polymer stable vertical alignment liquid crystal display panel and a liquid crystal display.
  • the application is filed on January 23, 2013, and the application number is 201310024692.9.
  • the priority of the Chinese Patent Application the entire contents of which are hereby incorporated by reference.
  • the present invention relates to liquid crystal display technology, and more particularly to a polymer stabilized vertical alignment liquid crystal display panel and a liquid crystal display.
  • 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 direction of the 4# column of the liquid crystal molecules on the surface of the substrate is determined by the rubbing direction of the alignment layer (Polyimide), and the alignment direction of the two substrates is perpendicular, so that the liquid crystal layer is from one substrate surface to the other substrate surface.
  • the molecules are in a state of continuous twisting. 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 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
  • ITO Indium Tin Oxide, Indium Tin Oxide
  • PVA Plasma Vertical Alignment
  • the third is to form an ITO slit on the TFT side of the LCD substrate, and the other side is Full ITO, adding a polymerizable monomer to the liquid crystal medium, first tilting the liquid crystal molecules by an electric field, and simultaneously using ultraviolet rays.
  • the light-illuminating panel causes the monomer to polymerize to form polymer particles having a liquid crystal molecule to be poured, and deposits on the surface of the substrate to align.
  • This technique becomes a PSVA (Polymer Stabilized Vertical Alignment) technique.
  • the formation process of polymer bump in PSVA technology is a phase separation process.
  • the monomer is small molecule before polymerization, and has good compatibility with liquid crystal medium.
  • the panel needs to be irradiated with ultraviolet light source.
  • the polymerization reaction occurs under irradiation, and when the polymer is formed, it is separated from the liquid crystal medium to form polymer particles insoluble in the liquid crystal medium, which is a polymer bump having an alignment function.
  • the frame glue currently used is mostly a composite curing method, which contains a thiol acrylate monomer requiring ultraviolet curing and an epoxy resin requiring heat curing, so it is necessary to first irradiate ultraviolet ray to make thiol acrylate.
  • the ester resin is polymerized, cross-linking curing reaction occurs, and then heated and cured at a high temperature to crosslink the other epoxy resin in the rubber material to improve the adhesion between the sealant and the glass substrate, so that two glass substrates are obtained.
  • the tight combination prevents the liquid crystal from overflowing while preventing moisture and oxygen in the air from entering the inside of the liquid crystal cell.
  • the mercaptoacrylate monomer in the frame glue has a structure very similar to that of the polymerizable monomer in the liquid crystal, a part of the mercaptoacrylate monomer in the frame rubber may be dissolved by the liquid crystal during the panel manufacturing process.
  • the polymerization reaction is carried out, and the bump near the frame rubber is likely to form a bump of a large particle, which produces a bright spot visible in the dark state, causing light leakage around the PSVA panel. It can be seen that the frame glue used in the PSVA technology needs to be further improved.
  • the technical problem to be solved by the present invention is to provide a liquid crystal display panel and a corresponding liquid crystal display, which can prevent thiol acrylate resin or propylene in the frame glue by reasonable matching of the liquid crystal material and the frame glue.
  • the acid ester resin is dissolved by the liquid crystal and participates in the polymerization reaction to prevent formation. Large bump particles, which reduce the light leakage of the frame glue attachment.
  • an embodiment of the present invention provides a polymer-stabilized vertical alignment liquid crystal display panel, which includes a first substrate, a second substrate, a liquid crystal layer sandwiched between the two substrates, and a liquid crystal sealed in the two substrates.
  • Border glue where:
  • the liquid crystal layer material comprises: a negative liquid crystal material, a stabilizer and a reactive monomer which can undergo polymerization under ultraviolet light irradiation; wherein the reactive monomer accounts for 0.1% to 1% by weight of the liquid crystal medium composition.
  • the reactive monomer comprises at least one or more polymerizable monomers as described in Structural Formula 1 to Structural Formula 4:
  • Structural formula 4 Wherein P in the structural formula 1-4 represents a polymerizable group, and may be one of the following structures: a mercapto acrylate group, an acrylate group, a vinyl group, a vinyloxy group, an epoxy group; At least one of the polymerizable groups P contained in one or more of the polymerizable group monomers described in Structural Formula 1 to Structural Formula 4 is an acrylate group, and each of the polymerizable group monomers has a molecular formula smaller than 500;
  • the frame glue contains:
  • a mercapto acrylate resin or an acrylate resin for ultraviolet curing the mercapto acrylate resin or acrylate resin having a molecular weight of 500 or more;
  • At least one material from the following:
  • the epoxy resin material comprises an aromatic ring-containing epoxy resin and/or an aromatic epoxy resin.
  • the epoxy resin material comprises at least one of the following materials:
  • the curing agent is one or more of a polyamine curing agent and an acid anhydride curing agent.
  • the filler is selected from the group consisting of silica, alumina, zinc oxide, titanium oxide, magnesium oxide, calcium sulfate, aluminum nitride, silicon nitride.
  • a polymer stabilized vertical alignment liquid crystal display panel includes a first substrate, a second substrate, a liquid crystal layer sandwiched between the two substrates, and a liquid crystal sealed on the two a frame glue inside the substrate, wherein:
  • the liquid crystal layer material comprises: a negative liquid crystal material, a stabilizer and a reactive monomer capable of undergoing a polymerization reaction under ultraviolet light irradiation; wherein the reactive monomer accounts for a liquid crystal medium composition by weight
  • the reactive monomer comprises at least one or more polymerizable monomers as described in Structural Formula 1 to Structural Formula 4:
  • Structural formula 4 Wherein P in the structural formula 1-4 represents a polymerizable group, and may be one of the following structures: a mercapto acrylate group, an acrylate group, a vinyl group, a vinyloxy group, an epoxy group; At least one of the polymerizable groups P contained in one or more of the polymerizable group monomers described in Structural Formula 1 to Structural Formula 4 is an acrylate group, and each of the polymerizable group monomers has a molecular formula smaller than 500;
  • the frame glue contains:
  • a mercapto acrylate resin or an acrylate resin for ultraviolet curing the mercapto acrylate resin or acrylate resin having a molecular weight of 500 or more;
  • the epoxy resin material comprises an aromatic ring-containing epoxy resin and/or an aromatic epoxy resin.
  • the epoxy resin material comprises at least one of the following materials:
  • Bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolac type epoxy resin, biphenyl type epoxy resin, epoxy resin containing cyclohexene oxide structure or containing oxidation An epoxy resin having a cyclopentene structure.
  • the curing agent is one or more of a polyamine curing agent and an acid anhydride curing agent.
  • the filler is selected from the group consisting of silica, alumina, zinc oxide, titanium oxide, magnesium oxide, calcium sulfate, aluminum nitride, silicon nitride.
  • the silane coupling agent is selected from at least one of the following materials:
  • a polymer stabilized vertical alignment liquid crystal display includes a liquid crystal display panel, and the liquid crystal display panel includes a first substrate, a second substrate, and a liquid crystal sandwiched between the two substrates. a layer, and a frame glue for sealing the liquid crystal in the two substrates, wherein: the liquid crystal layer material comprises: a negative liquid crystal material, a stabilizer and a reactive monomer which can be polymerized under ultraviolet light irradiation; wherein the reaction The monomer is in parts by weight of the liquid crystal medium composition
  • the reactive monomer comprises at least one or more polymerizable monomers as described in Structural Formula 1 to Structural Formula 4:
  • Structural formula 4 Wherein P in the structural formula 1-4 represents a polymerizable group, and may be one of the following structures: a mercapto acrylate group, an acrylate group, a vinyl group, a vinyloxy group, an epoxy group; At least one of the polymerizable groups P contained in one or more of the polymerizable group monomers described in Structural Formula 1 to Structural Formula 4 is an acrylate group, and each of the polymerizable group monomers has a molecular formula smaller than 500;
  • the frame glue contains:
  • a mercapto acrylate resin or an acrylate resin for ultraviolet curing the mercapto acrylate resin or the acrylate resin having a molecular weight of 500 or more;
  • the epoxy resin material comprises an aromatic ring-containing epoxy resin and/or an aromatic epoxy resin.
  • the epoxy resin material comprises at least one of the following materials:
  • Bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolac type epoxy resin, biphenyl type epoxy resin, epoxy resin containing cyclohexene oxide structure or containing oxidation An epoxy resin having a cyclopentene structure.
  • the curing agent is one or more of a polyamine curing agent and an acid anhydride curing agent.
  • the filler is selected from the group consisting of silica, alumina, zinc oxide, titanium oxide, magnesium oxide, calcium sulfate, aluminum nitride, silicon nitride.
  • the silane coupling agent is selected from at least one of the following materials:
  • the mercapto acrylate resin or the acrylate resin used in the bezel material provided by the embodiment of the present invention has a molecular weight of more than 500, and the selected liquid crystal material comprises at least one negative liquid crystal molecular material and one or more a polymerizable monomer capable of reacting under ultraviolet light irradiation, the molecular weight of the polymerizable monomer being less than 500; since the molecular weight of the mercapto acrylate resin or the acrylate resin in the frame rubber is much larger than that of the liquid crystal medium
  • the molecular weight of the polymerizable monomer used in the liquid crystal medium so that it has a significant difference from the polymerizable monomer in the liquid crystal medium, since the thiol acrylate or the acrylate resin in the frame material can be prevented. It is dissolved by the liquid crystal medium, thereby avoiding the formation of excessive bum particles in the vicinity of the frame, thereby reducing light leakage near the frame.
  • FIG. 1 is a schematic view of a polymer stabilized vertical alignment liquid crystal display panel of the present invention. detailed description
  • FIG. 1 a schematic diagram of a polymer stabilized vertical alignment liquid crystal display panel of the present invention is shown.
  • the liquid crystal display panel includes: a first substrate 1 and a second substrate 2 sandwiched between the two substrates The liquid crystal layer 3 and the frame glue 4 which seals the liquid crystal in the two substrates.
  • the ITO electrode 5 is further provided on the opposite side of the first substrate 1 and the second substrate 2.
  • the liquid crystal layer contains at least liquid crystal molecules 30 and a polymerizable monomer.
  • the polymerizable monomer forms a Bump (protrusion) 31 on the first substrate 1 and the second substrate 2, wherein
  • the polymerizable monomer in the liquid crystal layer has a molecular weight of less than 500, wherein the polymerizable monomer is selected from at least one structural formula:
  • Structural formula 4 Wherein P in the structural formula 1-4 represents a polymerizable group, and may be one of the following structures: a mercapto acrylate group, an acrylate group, a vinyl group, a vinyloxy group, an epoxy group; At least one of the polymerizable groups P contained in one or more of the polymerizable group monomers described in Structural Formula 1 to Structural Formula 4 is an acrylate group.
  • the first substrate is made of glass or a transparent plastic plate, and comprises a TFT active driving matrix, a peripheral circuit, an alignment layer material, and the like; and the second substrate is made of glass or a transparent plastic plate. It includes a color filter, a black matrix, a photo spacer, and an alignment layer material.
  • the frame glue 4 includes at least the following components: Epoxy resin, 20% ⁇ 60% by weight;
  • Hardener 5% ⁇ 50% by weight
  • a mercapto acrylate resin or acrylate resin for ultraviolet curing 20% to 60% by weight
  • the epoxy resin accounts for 20%-60% of the total weight of the frame rubber
  • the epoxy resin material can be composed of a combination of one or more different structural epoxy resins, and the selected structure can be represented by the following structural formula:
  • the materials are selected but not limited to the following materials:
  • the aromatic ring-containing epoxy resin includes bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and phenolic epoxy resin (such as phenol). Phenolic epoxy resin, nonylphenol novolac epoxy resin, biphenyl type epoxy resin, and the like.
  • the aromatic ring-containing epoxy resin contains one or more epoxy groups in its molecular structure, and the epoxy equivalent of the resin can be suitably selected.
  • the aromatic ring-free epoxy resin is an epoxy resin having no aromatic ring structure in its molecular structure, and usually contains a ring-shaped epoxy group such as an epoxy resin containing a cyclohexene oxide structure or an oxycyclopentene structure.
  • the curing agent that is, the epoxy resin hardener, 5%-50% of the total weight of the frame rubber, may be composed of one or more compositions, and may be a preferred one of a polyamine hardener and an acid anhydride hardener. Or a combination of multiple.
  • An organic resin material containing a mercapto acrylate group or an acrylate group structure which may be composed of one or more different resin compositions having an average molecular weight of more than 500, It accounts for 20%-60% of the total weight of the frame rubber.
  • the photoinitiator which has a specific gravity of 0.1% ⁇ 1%, is a type of ultraviolet (UV) sensitive substance capable of absorbing ultraviolet light having a wavelength of less than 380 nm and capable of initiating polymerization, such as Ciba's IRGACURE 1173, 651, etc.
  • a photoinitiator which may be composed of one or more.
  • the filler which accounts for 5%-35% of the specific gravity of the frame rubber, is selected from, but not limited to, the following inorganic fillers: such as silica, alumina, zinc oxide, titanium oxide, magnesium oxide, calcium sulfate, aluminum nitride, nitriding Silicon and so on.
  • the silane coupling agent which accounts for 0.05%-5% of the specific gravity of the frame rubber, is selected from, but not limited to, the following materials:
  • embodiments of the present invention provide a polymer stabilized vertical alignment liquid crystal display comprising the liquid crystal display panel described in FIG. 1 above.
  • Embodiments of the present invention employ a larger molecular weight mercapto acrylate resin or acrylate resin as a frame.
  • the ultraviolet curable resin in the rubber material, and the selected liquid crystal material comprises at least one negative liquid crystal molecular material and one or more polymerizable monomers capable of reacting under ultraviolet light, the molecular weight of the polymerizable monomer Less than 500; since the molecular weight of the mercapto acrylate resin or the acrylate resin in the frame rubber is much larger than the molecular weight of the polymerizable monomer used in the liquid crystal medium, it is polymerizable with the polymerizable monomer in the liquid crystal medium.
  • the mercapto acrylate resin or the acrylate resin in the frame material can be prevented from being dissolved by the liquid crystal medium, thereby avoiding the formation of excessive bump particles in the vicinity of the frame, thereby reducing the vicinity of the frame.
  • the light leakage phenomenon improves the yield of the liquid crystal panel.

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Abstract

一种聚合物稳定垂直配向液晶显示面板，其包含第一基板、第二基板、夹于两基板之间的液晶层，以及将液晶封于两基板内的边框胶材，所述液晶层材料包含：负型液晶材料，稳定剂及在紫外光照射下可发生聚合反应的反应性单体；所述边框胶材包括：环氧树脂、硬化剂、甲基丙稀酸酯树脂或丙稀酸酯树脂、光引发剂、填料以及硅烷偶联剂。相应提供一种液晶显示器。所述液晶显示面板、液晶显示器可以防止边框胶材中的甲基丙稀酸酯树脂或丙稀酸酯树脂被液晶介质所溶出，从而可以避免在边框附近形成过大的隆起物颗粒，从而减少边框附近的漏光现象，提高了产品良率。

Description

一种聚合物稳定垂直配向液晶显示面板及液晶显示器 本申请要求于 2013 年 1 月 23 日提交中国专利局、 申请号为 201310024692.9、 发明名称为 "一种聚合物稳定垂直配向液晶显示面板及液 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， 尤其涉及一种聚合物稳定垂直配向液晶显示 面板及液晶显示器。
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 4#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 很好的解决了 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。
PSVA技术中聚合物 bump的形成过程为一相分离过程， monomer未聚 合之前为小分子， 与液晶介质具有较好的相容性， 制程过程中需要采用紫外 光源对面板进行照射， monomer在紫外光照射下发生聚合反应， 形成高分子 时便从液晶介质中分离出来， 形成不溶于液晶介质的聚合物颗粒， 此即为具 有配向作用的聚合物 bump。
然而， 目前所采用的边框胶多为复合型的固化方式， 含有需要紫外光固 化的曱基丙烯酸酯类单体与需要热固化的环氧树脂， 所以需要先进行紫外光 照射使其中曱基丙烯酸酯类树脂发生聚合反应， 发生交联固化反应， 再进行 加热高温固化， 使胶材中的另外一部分环氧树脂发生交联反应， 提高框胶与 玻璃基板的粘接力， 使两片玻璃基板紧密结合， 阻止液晶外溢， 同时阻止空 气中的水汽和氧气进入液晶盒内部。
由于边框胶中的曱基丙烯酸酯类单体与液晶中可聚合单体 monomer具 有十分相似的结构， 所以在面板制造过程中边框胶中的部分曱基丙烯酸酯类 单体有可能被液晶溶出， 在紫外光照射下参与聚合反应， 在面板四周靠近边 框胶材的附近位置往往易形成较大颗粒的 bump,产生在暗态下可见的亮点， 使 PSVA面板四周出现漏光的现象。 由此可见 PSVA技术中所用的边框胶材 还有待进一步改进。
发明内容
本发明所要解决的技术问题在于，提供一种液晶显示面板以及相应的液 晶显示器， 通过对液晶材料与边框胶材的合理搭配， 可以防止边框胶材中的 曱基丙稀酸酯树脂或丙稀酸酯树脂被液晶溶出， 参与聚合反应， 防止形成过 大的 bump颗粒， 从而减少边框胶附件的漏光现象。
为解决上述技术问题， 本发明实施例提供一种聚合物稳定垂直配向液晶 显示面板， 其包含第一基板、 第二基板、 夹于两基板之间的液晶层， 以及将 液晶封于两基板内的边框胶材， 其中：
该液晶层材料包含： 负型液晶材料， 稳定剂及在紫外光照射下可发生聚 合反应的反应性单体； 其中， 该反应性单体按重量份占液晶介质组合物的 0.1%- 1%, 该反应性单体至少包含一种或多种如结构通式 1至结构通式 4所 描述的可聚合基单体：
结构通式 1 :
结构通式 2:
结构通式 3 :
结构通式 4:
Figure imgf000005_0001
其中， 结构通式 1-4中的 P表示聚合基团， 可以为以下结构之一： 曱基 丙烯酸酯基、 丙烯酸酯基、 乙烯基、 乙烯氧基、 环氧基； 液晶介质组合物中 所含的一种或多种如结构通式 1至结构通式 4所描述的可聚合基单体中至少 有一个聚合基团 P为丙烯酸酯基，且每个该可聚合基单体的分子式小于 500; 该的边框胶材包含：
环氧树脂；
硬化剂；
用于进行紫外线固化的曱基丙稀酸酯树脂或丙稀酸酯树脂， 该曱基丙稀 酸酯树脂或丙稀酸酯树脂的分子量大于等于 500; 光引发剂；
填料； 以及
硅烷偶联剂
自于如下的至少一种材料:
及
Figure imgf000006_0001
其中， 该环氧树脂材料包含有含芳环环氧树脂或 /及不含芳环氧树脂。 其中， 该环氧树脂材料包含有下述至少一种材料：
双酚 A型环氧树脂、 双酚 F型环氧树脂、 双酚 S型环氧树脂、 酚醛型 环氧树脂、 联苯型环氧树脂、 含有氧化环己烯结构的环氧树脂或含有氧化环 戊烯结构的环氧树脂。 其中， 该硬化剂为多胺类硬化剂以及酸酐类硬化剂中一种或多种。
其中， 该填料选自于如下无机填料： 二氧化硅、 氧化铝、 氧化锌、 氧化 钛、 氧化镁、 硫酸钙、 氮化铝、 氮化硅。
相应地， 本发明实施例的另一方面， 提供一种聚合物稳定垂直配向液晶 显示面板， 其包含第一基板、 第二基板、 夹于两基板之间的液晶层， 以及将 液晶封于两基板内的边框胶材， 其中：
该液晶层材料包含： 负型液晶材料， 稳定剂及在紫外光照射下可发生聚 合反应的反应性单体； 其中， 该反应性单体按重量份占液晶介质组合物的
0.1%- 1%, 该反应性单体至少包含一种或多种如结构通式 1至结构通式 4所 描述的可聚合基单体：
结构通式 1 :
结构通式 2:
结构通式 3 :
结构通式 4:
Figure imgf000007_0001
其中， 结构通式 1-4中的 P表示聚合基团， 可以为以下结构之一： 曱基 丙烯酸酯基、 丙烯酸酯基、 乙烯基、 乙烯氧基、 环氧基； 液晶介质组合物中 所含的一种或多种如结构通式 1至结构通式 4所描述的可聚合基单体中至少 有一个聚合基团 P为丙烯酸酯基，且每个该可聚合基单体的分子式小于 500; 该的边框胶材包含：
环氧树脂；
硬化剂； 用于进行紫外线固化的曱基丙稀酸酯树脂或丙稀酸酯树脂， 该曱基丙稀 酸酯树脂或丙稀酸酯树脂的分子量大于等于 500;
光引发剂；
填料； 以及
硅烷偶联剂。
其中， 该环氧树脂材料包含有含芳环环氧树脂或 /及不含芳环氧树脂。 其中， 该环氧树脂材料包含有下述至少一种材料：
双酚 A型环氧树脂、 双酚 F型环氧树脂、 双酚 S型环氧树脂、 酚醛型 环氧树脂、 联苯型环氧树脂、 含有氧化环己烯结构的环氧树脂或含有氧化环 戊烯结构的环氧树脂。
其中， 该硬化剂为多胺类硬化剂以及酸酐类硬化剂中一种或多种。 其中， 该填料选自于如下无机填料： 二氧化硅、 氧化铝、 氧化锌、 氧化 钛、 氧化镁、 硫酸钙、 氮化铝、 氮化硅。
其中， 该硅烷偶联剂选自于如下的至少一种材料：
Figure imgf000008_0001
、 及
Figure imgf000009_0001
相应地， 本发明实施例的再一方面， 提供一种聚合物稳定垂直配向液晶 显示器， 包含有液晶显示面板， 该液晶显示面板包含第一基板、 第二基板、 夹于两基板之间的液晶层， 以及将液晶封于两基板内的边框胶材， 其中： 该液晶层材料包含： 负型液晶材料， 稳定剂及在紫外光照射下可发生聚 合反应的反应性单体； 其中， 该反应性单体按重量份占液晶介质组合物的
0.1%- 1%, 该反应性单体至少包含一种或多种如结构通式 1至结构通式 4所 描述的可聚合基单体：
结构通式 1 :
结构通式 2:
结构通式 3 :
结构通式 4:
Figure imgf000009_0002
其中， 结构通式 1-4中的 P表示聚合基团， 可以为以下结构之一： 曱基 丙烯酸酯基、 丙烯酸酯基、 乙烯基、 乙烯氧基、 环氧基； 液晶介质组合物中 所含的一种或多种如结构通式 1至结构通式 4所描述的可聚合基单体中至少 有一个聚合基团 P为丙烯酸酯基，且每个该可聚合基单体的分子式小于 500; 该的边框胶材包含：
环氧树脂；
硬化剂；
用于进行紫外线固化的曱基丙稀酸酯树脂或丙稀酸酯树脂， 该曱基丙稀 酸酯树脂或丙稀酸酯树脂的分子量大于等于 500;
光引发剂；
填料； 以及
硅烷偶联剂。
其中， 该环氧树脂材料包含有含芳环环氧树脂或 /及不含芳环氧树脂。 其中， 该环氧树脂材料包含有下述至少一种材料：
双酚 A型环氧树脂、 双酚 F型环氧树脂、 双酚 S型环氧树脂、 酚醛型 环氧树脂、 联苯型环氧树脂、 含有氧化环己烯结构的环氧树脂或含有氧化环 戊烯结构的环氧树脂。
其中， 该硬化剂为多胺类硬化剂以及酸酐类硬化剂中一种或多种。 其中， 该填料选自于如下无机填料： 二氧化硅、 氧化铝、 氧化锌、 氧化 钛、 氧化镁、 硫酸钙、 氮化铝、 氮化硅。
其中， 该硅烷偶联剂选自于如下的至少一种材料：
Figure imgf000010_0001
Figure imgf000011_0001
实施本发明实施例， 具有如下的有益效果：
本发明实施例提供的边框材料中所采用的曱基丙稀酸酯树脂或丙稀酸 酯树脂其分子量大于 500, 而所选的液晶材料包含至少一种负型液晶分子材 料和一种或多种以上可在紫外光照射下反应的可聚合单体，该可聚合单体的 分子量小于 500; 由于边框胶材中的曱基丙稀酸酯树脂或丙稀酸酯树脂的分 子量远大于液晶介质中所采用的可聚合单体的分子量，故其与液晶介质中的 可聚合单体具有明显的差异性， 由于可以防止边框材料中的曱基丙稀酸酯树 月旨或丙稀酸酯树脂被液晶介质所溶出，从而可以避免在边框附近形成过大的 bum 颗粒， 从而减少边框附近的漏光现象。 附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案， 下面将对实 施例或现有技术描述中所需要使用的附图作简单地介绍， 显而易见地， 下面 描述中的附图仅仅是本发明的一些实施例， 对于本领域普通技术人员来讲， 在不付出创造性劳动的前提下， 还可以根据这些附图获得其他的附图。
图 1为本发明的一种聚合物稳定垂直配向液晶显示面板的示意图。 具体实施方式
如图 1所示， 示出了本发明的一种聚合物稳定垂直配向液晶显示面板的 示意图， 该液晶显示面板包括： 第一基板 1、 第二基板 2、 夹于两基板之间 的液晶层 3 , 以及将液晶封于两基板内的边框胶材 4。 其中， 在第一基板 1 与第二基板 2相向侧进一步设置有 ITO电极 5。 液晶层中至少包含有液晶分 子 30, 以及可聚合单体， 在 ITO电极 5连通的情形下， 该可聚合单体在第 一基板 1及第二基板 2上形成 Bump (隆起物） 31 , 其中， 该液晶层中的可 聚合单体的分子量小于 500, 其中所述可聚合单体选自如下至少一种结构通 式：
结构通式 1 :
结构通式 2:
结构通式 3 :
结构通式 4:
Figure imgf000012_0001
其中， 结构通式 1-4中的 P表示聚合基团， 可以为以下结构之一： 曱基 丙烯酸酯基、 丙烯酸酯基、 乙烯基、 乙烯氧基、 环氧基； 液晶介质组合物中 所含的一种或多种如结构通式 1至结构通式 4所描述的可聚合基单体中至少 有一个聚合基团 P为丙烯酸酯基。
进一步地， 所述第一基板由玻璃或透明塑料板为基材， 其上包含 TFT 有源驱动矩阵， 周边电路， 配向层材料等； 所述第二基板由玻璃或透明塑料 板为基材， 其上包含滤色镜片 ( Color filter ), 黑色矩阵片 ( Black matrix )、 柱状隔垫物（ Photo spacer ) 以及配向层材料等。
其中， 边框胶材 4至少包含如下的组份： 环氧树脂， 20%〜60%重量份；
硬化剂， 5%〜50%重量份；
用于进行紫外线固化的曱基丙稀酸酯树脂或丙稀酸酯树脂， 20%〜60%重 量份；
光引发剂， 0.1%〜1%重量份；
填料， 5%〜35%重量份； 以及
硅烷偶联剂。
其中， 环氧树脂， 占框胶材总重量比重为 20%-60%, 环氧树脂材料可由 一种或多种不同结构环氧树脂的组合组成， 其选用结构可有以下结构通式进 行表示，但材料选于但不限于以下材料： 含芳环环氧树脂包括双酚 A型环氧 树脂、 双酚 F型环氧树脂、 双酚 S型环氧树脂、 酚醛型环氧树脂（如苯酚酚 醛型环氧树脂、 曱酚酚醛环氧树脂）、 联苯型环氧树脂等。 含芳环环氧树脂 在其分子结构中含有一个或一个以上的环氧基团，树脂的环氧当量可进行适 当优选。 不含芳环环氧树脂是分子结构中不含芳香环结构的环氧树脂， 它们 通常含有环变形的环氧基团，如含有氧化环己烯结构或氧化环戊烯结构的环 氧树脂。
固化剂， 即环氧树脂硬化剂， 占框胶材总重量比重的 5%-50%, 可由一 种或多种组合物构成，可以为多胺类硬化剂以及酸酐类硬化剂中优选一种或 多种进行组合。
曱基丙婦 S史树脂或丙烯酸树脂， 为一类含有曱基丙烯酸酯基团或丙烯酸 酯基团结构的有机树脂材料， 可由一种或多种不同树脂组合物构成， 其平均 分子量大于 500, 其占框胶材总重量比重的 20%-60%。
光引发剂， 含量占框胶比重为 0.1%〜1% , 为一类能够吸收波长小于 380nm紫外光并能引发聚合反应的紫外光（UV )敏感物质， 例如 Ciba公司 的 IRGACURE 1173、 651等型号的光引发剂， 其可由一种或多种组成。
填料， 其占框胶材比重的 5%-35%, 选于但不限于以下无机填料： 如二 氧化硅、 氧化铝、 氧化锌、 氧化钛、 氧化镁、 硫酸钙、 氮化铝、 氮化硅等。
硅烷偶联剂， 占框胶材比重的 0.05%-5%, 选于但不限于以下几种材料：
Figure imgf000014_0001
相应地， 本发明实施例的提供一种聚合物稳定垂直配向液晶显示器， 包 括前述图 1所描述的液晶显示面板。
通常来说， 同一类物质在另外介质中的溶解性会随其分子量的增大而下 降， 本发明的实施例通过采用较大分子量的曱基丙稀酸酯树脂或丙稀酸酯树 脂作为边框胶材中的紫外线固化树脂， 而所选的液晶材料包含至少一种负型 液晶分子材料和一种或多种以上可在紫外光照射下反应的可聚合单体， 该可 聚合单体的分子量小于 500; 由于边框胶材中的曱基丙稀酸酯树脂或丙稀酸 酯树脂的分子量远大于液晶介质中所采用的可聚合单体的分子量，故其与液 晶介质中的可聚合单体具有明显的差异性， 由于可以防止边框材料中的曱基 丙稀酸酯树脂或丙稀酸酯树脂被液晶介质所溶出，从而可以避免在边框附近 形成过大的 bump颗粒， 从而减少边框附近的漏光现象， 提高了液晶面板的 良品率。
以上所揭露的仅为本发明较佳实施例而已， 当然不能以此来限定本发明 之权利范围， 因此等同变化， 仍属本发明所涵盖的范围。

Claims

权 利 要 求
1、 一种聚合物稳定垂直配向液晶显示面板， 其包含第一基板、 第二基 板、夹于两基板之间的液晶层， 以及将液晶封于两基板内的边框胶材，其中： 所述液晶层材料包含： 负型液晶材料， 稳定剂及在紫外光照射下可发生 聚合反应的反应性单体； 其中， 所述反应性单体按重量份占液晶介质组合物 的 0.1%-1%, 所述反应性单体至少包含一种或多种如结构通式 1至结构通式 4所描述的可聚合基单体：
结构通式 1 :
结构通式 2:
结构通式 3 :
结构通式 4:
Figure imgf000015_0001
其中， 结构通式 1-4中的 P表示聚合基团， 可以为以下结构之一： 曱基 丙烯酸酯基、 丙烯酸酯基、 乙烯基、 乙烯氧基、 环氧基； 液晶介质组合物中 所含的一种或多种如结构通式 1至结构通式 4所描述的可聚合基单体中至少 有一个聚合基团 P 为丙烯酸酯基， 且每个所述可聚合基单体的分子式小于
500;
所述的边框胶材包含:
环氧树脂； 硬化剂；
用于进行紫外线固化的曱基丙稀酸酯树脂或丙稀酸酯树脂， 所述曱基丙 稀酸酯树脂或丙稀酸酯树脂的分子量大于等于 500;
光引发剂；
填料； 以及
硅烷偶联剂
其中， 所述硅烷偶联剂选自于如下的至少一种材料：
及
Figure imgf000016_0001
2、 如权利要求 1 所述的聚合物稳定垂直配向液晶显示面板， 其中， 所 述环氧树脂材料包含有含芳环环氧树脂或 /及不含芳环氧树脂。
3、 如权利要求 2所述的聚合物稳定垂直配向液晶显示面板， 其中， 所 述环氧树脂材料包含有下述至少一种材料：
双酚 A型环氧树脂、 双酚 F型环氧树脂、 双酚 S型环氧树脂、 酚醛型 环氧树脂、 联苯型环氧树脂、 含有氧化环己烯结构的环氧树脂或含有氧化环 戊烯结构的环氧树脂。
4、 如权利要求 3所述的聚合物稳定垂直配向液晶显示面板， 其中， 所 述硬化剂为多胺类硬化剂以及酸酐类硬化剂中一种或多种。
5、 如权利要求 4所述的聚合物稳定垂直配向液晶显示面板， 其中， 所 述填料选自于如下无机填料： 二氧化硅、 氧化铝、 氧化锌、 氧化钛、 氧化镁、 石克酸钙、 氮化铝、 氮化硅。
6、 一种聚合物稳定垂直配向液晶显示面板， 其包含第一基板、 第二基 板、夹于两基板之间的液晶层， 以及将液晶封于两基板内的边框胶材，其中： 所述液晶层材料包含： 负型液晶材料， 稳定剂及在紫外光照射下可发生 聚合反应的反应性单体； 其中， 所述反应性单体按重量份占液晶介质组合物 的 0.1%-1%, 所述反应性单体至少包含一种或多种如结构通式 1至结构通式 4所描述的可聚合基单体：
结构通式 1 :
Figure imgf000017_0001
结构通式 2:
结构通式 3 :
结构通式 4:
Figure imgf000018_0001
其中， 结构通式 1-4中的 P表示聚合基团， 可以为以下结构之一： 曱基 丙烯酸酯基、 丙烯酸酯基、 乙烯基、 乙烯氧基、 环氧基； 液晶介质组合物中 所含的一种或多种如结构通式 1至结构通式 4所描述的可聚合基单体中至少 有一个聚合基团 P 为丙烯酸酯基， 且每个所述可聚合基单体的分子式小于 500;
所述的边框胶材包含： 环氧树脂；
硬化剂；
用于进行紫外线固化的曱基丙稀酸酯树脂或丙稀酸酯树脂， 所述曱基丙 稀酸酯树脂或丙稀酸酯树脂的分子量大于等于 500; 光引发剂；
填料； 以及
硅烷偶联剂。
7、 如权利要求 6所述的聚合物稳定垂直配向液晶显示面板， 其中， 所 述环氧树脂材料包含有含芳环环氧树脂或 /及不含芳环氧树脂。
8、 如权利要求 6所述的聚合物稳定垂直配向液晶显示面板， 其中， 所 述环氧树脂材料包含有下述至少一种材料：
双酚 A型环氧树脂、 双酚 F型环氧树脂、 双酚 S型环氧树脂、 酚醛型 环氧树脂、 联苯型环氧树脂、 含有氧化环己烯结构的环氧树脂或含有氧化环 戊烯结构的环氧树脂。
9、 如权利要求 8所述的聚合物稳定垂直配向液晶显示面板， 其中， 所 述硬化剂为多胺类硬化剂以及酸酐类硬化剂中一种或多种。
10、 如权利要求 9所述的聚合物稳定垂直配向液晶显示面板， 其中， 所 述填料选自于如下无机填料： 二氧化硅、 氧化铝、 氧化锌、 氧化钛、 氧化镁、 石克酸钙、 氮化铝、 氮化硅。
11、 如权利要求 10所述的聚合物稳定垂直配向液晶显示面板， 其中， 所述硅烷偶联剂选自于如下的至少一种材料：
Figure imgf000019_0001
、 及
Figure imgf000020_0001
12、 一种聚合物稳定垂直配向液晶显示器， 包含有液晶显示面板， 所述 液晶显示面板包含第一基板、 第二基板、 夹于两基板之间的液晶层， 以及将 液晶封于两基板内的边框胶材， 其中：
所述液晶层材料包含： 负型液晶材料， 稳定剂及在紫外光照射下可发生 聚合反应的反应性单体； 其中， 所述反应性单体按重量份占液晶介质组合物 的 0.1%-1%, 所述反应性单体至少包含一种或多种如结构通式 1至结构通式 4所描述的可聚合基单体：
结构通式 1 :
结构通式 2:
结构通式 3 :
结构通式 4:
Figure imgf000020_0002
其中， 结构通式 1-4中的 P表示聚合基团， 可以为以下结构之一： 曱基 丙烯酸酯基、 丙烯酸酯基、 乙烯基、 乙烯氧基、 环氧基； 液晶介质组合物中 所含的一种或多种如结构通式 1至结构通式 4所描述的可聚合基单体中至少 有一个聚合基团 P 为丙烯酸酯基， 且每个所述可聚合基单体的分子式小于 500;
所述的边框胶材包含： 环氧树脂； 硬化剂； 用于进行紫外线固化的曱基丙稀酸酯树脂或丙稀酸酯树脂， 所述曱基丙 稀酸酯树脂或丙稀酸酯树脂的分子量大于等于 500; 光引发剂；
填料； 以及 硅烷偶联剂。
13、 如权利要求 12所述的聚合物稳定垂直配向液晶显示器， 其中， 所 述环氧树脂材料包含有含芳环环氧树脂或 /及不含芳环氧树脂。
14、 如权利要求 12所述的聚合物稳定垂直配向液晶显示器， 其中， 所 述环氧树脂材料包含有下述至少一种材料：
双酚 A型环氧树脂、 双酚 F型环氧树脂、 双酚 S型环氧树脂、 酚醛型 环氧树脂、 联苯型环氧树脂、 含有氧化环己烯结构的环氧树脂或含有氧化环 戊烯结构的环氧树脂。
15、 如权利要求 14所述的聚合物稳定垂直配向液晶显示器， 其中， 所 述硬化剂为多胺类硬化剂以及酸酐类硬化剂中一种或多种。
16、 如权利要求 15所述的聚合物稳定垂直配向液晶显示器， 其中， 所 述填料选自于如下无机填料： 二氧化硅、 氧化铝、 氧化锌、 氧化钛、 氧化镁、 硫酸钙、 氮化铝、 氮化硅。
17、 如权利要求 16所述的聚合物稳定垂直配向液晶显示器， 其中， 所 述硅烷偶联剂选自于如下的至少一种材料：
Figure imgf000022_0001
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US11175536B2 (en) 2014-09-22 2021-11-16 Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd. LC-based optical display system
EP3198334B1 (en) * 2014-09-22 2023-05-31 Yissum Research Development Company of The Hebrew University of Jerusalem Ltd. Lc-based optical display system

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