WO2016149996A1 - 黑色矩阵与其制作方法及具有该黑色矩阵的液晶面板 - Google Patents

黑色矩阵与其制作方法及具有该黑色矩阵的液晶面板 Download PDF

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Publication number
WO2016149996A1
WO2016149996A1 PCT/CN2015/078867 CN2015078867W WO2016149996A1 WO 2016149996 A1 WO2016149996 A1 WO 2016149996A1 CN 2015078867 W CN2015078867 W CN 2015078867W WO 2016149996 A1 WO2016149996 A1 WO 2016149996A1
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Prior art keywords
black matrix
black
azo compound
light
substrate
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PCT/CN2015/078867
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English (en)
French (fr)
Inventor
于承忠
陈雅惠
陈孝贤
李泳锐
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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 US14/764,986 priority Critical patent/US20180246368A1/en
Publication of WO2016149996A1 publication Critical patent/WO2016149996A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133512—Light shielding layers, e.g. black matrix
    • 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
    • C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • C09J131/06—Homopolymers or copolymers of esters of polycarboxylic acids
    • C09J131/08—Homopolymers or copolymers of esters of polycarboxylic acids of phthalic acid
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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    • G02F1/133514—Colour filters
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    • 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
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G02F1/133516—Methods for their manufacture, e.g. printing, electro-deposition or photolithography
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    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
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    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/085—Photosensitive compositions characterised by adhesion-promoting non-macromolecular additives
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/03—Viewing layer characterised by chemical composition
    • C09K2323/031—Polarizer or dye
    • 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
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • G—PHYSICS
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    • 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
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    • G02F2203/07—Polarisation dependent

Definitions

  • the present invention relates to the field of display technologies, and in particular, to a black matrix, a method of fabricating the same, and a liquid crystal panel having the black matrix.
  • LCD Liquid crystal display
  • PDA personal digital assistant
  • digital camera computer screen or laptop screen.
  • a liquid crystal display device includes a housing, a liquid crystal display panel disposed in the housing, and a backlight module disposed in the housing.
  • the structure of the liquid crystal display panel is mainly composed of a Thin Film Transistor Array Substrate (TFT Array Substrate), a color filter substrate (Color Filter, CF), and a liquid crystal layer disposed between the two substrates ( Liquid Crystal Layer) is constructed by controlling the rotation of the liquid crystal molecules of the liquid crystal layer by applying a driving voltage on the two glass substrates, and refracting the light of the backlight module to produce a picture.
  • a black matrix (BM) is disposed on the CF substrate side to prevent light leakage at each pixel.
  • the black matrix was originally made of a metal film of a chromium-based material, but was gradually replaced by a black matrix of a resin-type material due to complicated processes, high cost, environmental pollution, and the like.
  • Resin type black matrix (RBM) means that a light-shielding material such as carbon black is dispersed in a resin, mixed with other resin, photoinitiator, monomer, and solvent, and applied to a CF substrate, and dried. And patterned by photolithography to obtain a black matrix.
  • the optical density (OD) value is a physical unit used to measure the shading performance. With the high performance of the color filter, the optical density value of the resin black matrix is continuously increased.
  • the existing methods for increasing the optical density value are mainly The following are:
  • Another object of the present invention is to provide a method for fabricating a black matrix, which can improve the optical density value of the black matrix, reduce the amount of the light shielding material, increase the impedance value of the black matrix, and improve the stability of the black matrix film forming process. .
  • a further object of the present invention is to provide a liquid crystal panel in which a black matrix on a CF substrate has both polarizing characteristics and light absorbing characteristics, has a strong light blocking effect, and has a high optical density value, and the amount of the light shielding material in the black matrix is small. With a large impedance value.
  • the present invention provides a black matrix which is obtained by applying a mixed resin composition onto a substrate, drying and patterning by photolithography, wherein the mixed resin composition includes adhesion.
  • the structure of the azo compound is wherein R1 is amino, hydroxy, alkoxy, ester, aminoacyl, amine aldehyde, phenyl or alkyl, and R2 is acyl, aldehyde, carboxyl, amido, sulfonate, nitrile, nitro, Halogenated or quaternary amino group.
  • the light shielding material is a black inorganic pigment or a black organic pigment
  • the binder resin is 2-(meth)acryloyloxyethylphthalic acid
  • the small molecule monomer is styrene, acrylate or methyl Acrylate
  • the photoinitiator is ethane ketone or 1-[9-ethyl-6(2-methylbenzoyl)-9hydro-indazole-3-substituent]-, 1-(oxygen- Acetylhydrazine)
  • the solvent is propylene glycol methyl ether acetate, cyclohexanone, 3-methoxybutyl acetate or diethylene glycol butyl ether acetate.
  • the black inorganic pigment is carbon black, chromium oxide, iron oxide, titanium oxide or graphite, and the black organic pigment is perylene black, cyanine black or aniline black.
  • the mass percentage of each component is: 5 to 10% of the binder resin, 0 to 1% of the photoinitiator, 0 to 1% of the small molecule, 70 to 80% of the solvent, and the light shielding material 5 -10%, azo compound 1-5%, additive 0-0.5%.
  • the invention also provides a method for manufacturing a black matrix, comprising the following steps:
  • Step 1 based on the total weight of the mixed resin composition to be prepared, the binder resin is weighed according to a ratio of 5 to 10% by weight, and the photoinitiator is weighed according to a ratio of 0 to 1 wt%, and is 0 to 1 wt%.
  • the monomer in a ratio
  • the ratio of the additive is weighed, and then the above accurately weighed components are uniformly mixed to obtain a mixed resin composition; wherein the azo compound has a polarizing property;
  • Step 2 The mixed resin composition is applied onto a substrate, and a black matrix having polarization characteristics is obtained by soft baking, exposure, development, and hard baking.
  • the structure of the azo compound is wherein R1 is amino, hydroxy, alkoxy, ester, aminoacyl, amine aldehyde, phenyl or alkyl, and R2 is acyl, aldehyde, carboxyl, amido, sulfonate, nitrile, nitro, Halogenated or quaternary amino group.
  • the light shielding material is a black inorganic pigment or a black organic pigment
  • the binder resin is 2-(meth)acryloyloxyethylphthalic acid
  • the small molecule monomer is styrene , acrylate or methacrylate
  • the photoinitiator is ethane ketone or 1-[9-ethyl-6(2-methylbenzoyl)-9hydro-oxazol-3- substituent]- , 1-(oxy-acetyl oxime)
  • the solvent is propylene glycol methyl ether acetate, cyclohexanone, 3-methoxybutyl acetate or diethylene glycol butyl ether acetate.
  • the black inorganic pigment is carbon black, chromium oxide, iron oxide, titanium oxide or graphite, and the black organic pigment is perylene black, cyanine black or aniline black.
  • the present invention also provides a liquid crystal panel comprising a CF substrate, a TFT substrate disposed opposite to the CF substrate, and a liquid crystal layer filled between the CF substrate and the TFT substrate, wherein the CF substrate is provided with a black matrix and A color photoresist, the black matrix being a black matrix as described above.
  • the black matrix of the present invention contains an azo compound having polarization characteristics, has good light-shielding property, has a high optical density value, and has a small amount of light-shielding material in a black matrix, and has a large impedance value. .
  • the method for fabricating the black matrix of the present invention enhances the shading performance of the black matrix by adding an azo compound having a polarizing property to the black matrix, improves the optical density value of the black matrix, and makes black due to the addition of the azo compound.
  • the black matrix on the CF substrate contains The azo compound with polarizing characteristics has both polarizing characteristics and light absorbing properties.
  • the black matrix absorbs and blocks the polarized light after the lower polarizer and the liquid crystal are rotated by the light shielding material, and also has a polarization function, so that the light is transmitted to the black matrix.
  • the shading performance is further enhanced, the optical density value of the black matrix is improved, and the amount of the light-shielding material in the black matrix is reduced due to the addition of the azo compound, and the black matrix is added. Impedance value.
  • FIG. 1 is a schematic view showing the molecular orbital of an azo compound in a black matrix of the present invention
  • 2 is a graph showing the relationship between the impedance value of the conventional black matrix and the carbon black content
  • FIG. 3 is a flow chart of a method for fabricating a black matrix of the present invention.
  • FIG. 4 is a schematic cross-sectional view showing a liquid crystal panel of the present invention.
  • FIG. 5 is a schematic diagram of light entering a conventional liquid crystal panel
  • FIG. 6 is a schematic view showing light entering of a liquid crystal panel of the present invention.
  • Fig. 7 is a graph showing the relationship between the optical density value and the carbon black content of the black matrix of the present invention and the conventional black matrix.
  • the present invention firstly provides a black matrix which is obtained by applying a mixed resin composition onto a substrate, drying and patterning by photolithography, wherein the mixed resin composition includes a binder resin (Polymer).
  • a binder resin Polymer
  • the binder resin is capable of forming a film layer and capable of supporting a crosslinking reaction, the photoinitiator capable of rapidly forming a radical under illumination, the small molecule monomer capable of polymerizing a functional group capable of adjusting coating properties,
  • the light-shielding material can have a light-shielding effect, and the azo compound has a polarizing property and can be uniformly dispersed in the system.
  • the azo compound used in the present invention is an aromatic hydrocarbon azo compound, and the structure thereof is Wherein R1 is a push electron group such as an amino group, a hydroxyl group, an alkoxy group, an ester group, an aminoacyl group, an amine aldehyde group, a phenyl group or an alkyl group; and R2 is an electron withdrawing group such as an acyl group, an aldehyde group, a carboxyl group, An amide group, a sulfonic acid group, a nitrile group, a nitro group, a haloform group or a quaternary amine group.
  • R1 is a push electron group such as an amino group, a hydroxyl group, an alkoxy group, an ester group, an aminoacyl group, an amine aldehyde group, a phenyl group or an alkyl group
  • R2 is an electron withdrawing group such as an acyl group, an aldehyde group
  • FIG. 1 is a schematic diagram of the molecular orbital of an azo compound in a black matrix of the present invention.
  • the compound has polarizing properties.
  • the light shielding material may be an inorganic pigment such as carbon black, chromium oxide, iron oxide, titanium oxide or graphite, or may be a perylene blace or flower having better heat resistance, light resistance and solvent resistance.
  • Black organic pigments such as cyanine blace and aniline black.
  • the binder resin is an alkali-soluble resin such as 2-(meth)acryloyloxyethylphthalic acid or the like.
  • the small molecule monomer is styrene, acrylate or methacrylate having an unsaturated double bond structure.
  • the photoinitiator is ethane ketone or 1-[9-ethyl-6(2-methylbenzoyl)-9hydro-oxazol-3-substituted]-, 1-(oxy-acetyl oxime) [trade name: CGI-2424, Ciba Specialty Chemicals].
  • the solvent is propylene glycol methyl ether acetate (PGMEA), cyclohexanone, 3-Methoxy butyl acetate or diethylene glycol butyl ether acetate (2-( 2-butoxyethoxy)-Ethanol acetate).
  • PGMEA propylene glycol methyl ether acetate
  • cyclohexanone 3-Methoxy butyl acetate
  • diethylene glycol butyl ether acetate 2-( 2-butoxyethoxy)-Ethanol acetate
  • the mass percentage of each component is: 5 to 10% of the binder resin, 0 to 1% of the photoinitiator, 0 to 1% of the small molecule, 70 to 80% of the solvent,
  • the light-shielding material is 5-10%
  • the azo compound is 1-5%
  • the additive is 0-0.5%.
  • FIG. 2 is a relationship between the impedance value (Rs) and the carbon black content of the existing black matrix.
  • the optical density value of the black matrix in the liquid crystal panel depends on the content of carbon black. Under the same conditions, the content of carbon black in the black matrix is higher. More, the corresponding optical density value is larger. However, since the carbon black has a conductive property, the more the carbon black content in the black matrix, the smaller the impedance value of the black matrix. In the present invention, since the black matrix of the present invention has the same optical density value due to the addition of the azo compound, the amount of the light-shielding material such as carbon black can be relatively reduced, thereby increasing the impedance value of the black matrix.
  • the black matrix of the present invention contains an azo compound having polarizing characteristics, it has good light-shielding properties, has a high optical density value, and has a small amount of light-shielding material in the black matrix, thereby having a large impedance value.
  • the present invention further provides a method for fabricating a black matrix, including the following steps:
  • Step 1 based on the total weight of the mixed resin composition to be prepared, the binder resin is weighed according to a ratio of 5 to 10% by weight, and the photoinitiator is weighed according to a ratio of 0 to 1 wt%, and is 0 to 1 wt%.
  • the monomer in a ratio
  • the ratio is weighed, and then the above accurately weighed components are uniformly mixed to obtain a mixed resin composition; wherein the azo compound has a polarizing property.
  • the light-shielding material may be an inorganic pigment such as carbon black, chromium oxide, iron oxide, titanium oxide or graphite, or may be a perylene blace or flower having better heat resistance, light resistance and solvent resistance.
  • Black organic pigments such as cyanine blace and aniline black.
  • the binder resin is an alkali-soluble resin such as 2-(meth)acryloyloxyethylphthalic acid or the like.
  • the small molecule monomer is styrene, acrylate or methacrylate having an unsaturated double bond structure.
  • the photoinitiator is ethane ketone or 1-[9-ethyl-6(2-methylbenzoyl)-9hydro-oxazol-3-substituted]-, 1-(oxy-acetyl oxime) [trade name: CGI-2424, Ciba Specialty Chemicals].
  • the solvent is propylene glycol methyl ether acetate (PGMEA), cyclohexanone, 3-Methoxy butyl acetate or diethylene glycol butyl ether acetate (2-( 2-butoxyethoxy)-Ethanol acetate).
  • PGMEA propylene glycol methyl ether acetate
  • cyclohexanone 3-Methoxy butyl acetate
  • diethylene glycol butyl ether acetate 2-( 2-butoxyethoxy)-Ethanol acetate
  • R1 is a push electron group such as an amino group, a hydroxyl group, an alkoxy group, an ester group, an aminoacyl group, an amine aldehyde group, a phenyl group or an alkyl group
  • R2 is an electron withdrawing group such as an acyl group, an aldehyde group, a carboxyl group, An amide group, a sulfonic acid group, a nitrile group, a nitro group, a haloform group or a quaternary amine group.
  • Step 2 The mixed resin composition is applied onto a substrate, and a black matrix having polarization characteristics is obtained by soft baking, exposure, development, and hard baking.
  • the black matrix is not directionally stretched in the hard baking process, so that the black matrix obtained is relatively random to the choice of polarized light.
  • the method for fabricating the above black matrix enhances the shading performance of the black matrix by adding an azo compound having a polarizing property to the black matrix, improves the optical density value of the black matrix, and causes the black matrix to be added due to the addition of the azo compound.
  • the amount of shading material is reduced, the impedance of the black matrix is increased, and the ultraviolet light is more easily irradiated to the bottom of the film during the exposure process of the black matrix yellow light process, thereby reducing many engineering problems and increasing the process. Stability.
  • the present invention further provides a liquid crystal panel including a CF substrate 1, a TFT substrate 2 disposed opposite to the CF substrate 1, and a liquid crystal layer 3 filled between the CF substrate 1 and the TFT substrate 2.
  • a black matrix 11 and a color resist are provided on the substrate 1, and the black matrix 11 is obtained by applying a mixed resin composition onto a substrate, drying and patterning by photolithography, and the mixed resin composition is obtained.
  • a binder resin, a photoinitiator, a small molecule monomer, a solvent, a light shielding material, an azo compound, and an additive are included, and the azo compound has a polarizing property.
  • the light shielding material may be an inorganic pigment such as carbon black, chromium oxide, iron oxide, titanium oxide or graphite, or may be a perylene blace or flower having better heat resistance, light resistance and solvent resistance.
  • Black organic pigments such as cyanine blace and aniline black.
  • the binder resin is an alkali-soluble resin such as 2-(meth)acryloyloxyethylphthalic acid or the like.
  • the small molecule monomer is styrene, acrylate or methacrylate having an unsaturated double bond structure.
  • the photoinitiator is ethane ketone or 1-[9-ethyl-6(2-methylbenzoyl)-9hydro-oxazol-3-substituted]-, 1-(oxy-acetyl oxime) [trade name: CGI-2424, Ciba Specialty Chemicals].
  • the solvent is propylene glycol methyl ether acetate (PGMEA), cyclohexanone, 3-Methoxy butyl acetate or diethylene glycol butyl ether acetate (2-( 2-butoxyethoxy)-Ethanol acetate).
  • PGMEA propylene glycol methyl ether acetate
  • cyclohexanone 3-Methoxy butyl acetate
  • diethylene glycol butyl ether acetate 2-( 2-butoxyethoxy)-Ethanol acetate
  • R1 is a push electron group such as an amino group, a hydroxyl group, an alkoxy group, an ester group, an aminoacyl group, an amine aldehyde group, a phenyl group or an alkyl group
  • R2 is an electron withdrawing group such as an acyl group, an aldehyde group, a carboxyl group, An amide group, a sulfonic acid group, a nitrile group, a nitro group, a haloform group or a quaternary amine group.
  • the mass percentage of each component is: 5 to 10% of the binder resin, 0 to 1% of the photoinitiator, 0 to 1% of the small molecule, 70 to 80% of the solvent,
  • the light-shielding material is 5-10%
  • the azo compound is 1-5%
  • the additive is 0-0.5%.
  • FIG. 5 is a schematic diagram of light entrance of a conventional liquid crystal panel.
  • the black matrix 110 of the conventional liquid crystal panel includes a binder resin, a photoinitiator, a small molecule, a solvent, carbon black, and an additive, and does not contain The azo compound, and thus the black matrix 110 has only a light-shielding effect.
  • the black matrix 110 absorbs and blocks the polarized light that has passed through the lower polarizer 500 and the liquid crystal after being rotated by the carbon black component.
  • the final light is emitted by the upper polarizer 400. Since the intensity of the light transmitted through the color filter substrate depends only on the carbon black content, the light shielding performance is poor and the light transmittance is relatively high.
  • FIG. 6 is a schematic diagram of the light incident of the liquid crystal panel of the present invention.
  • the black matrix 11 of the liquid crystal panel of the present invention incorporates an azo compound having polarization characteristics.
  • the black matrix 11 absorbs and blocks the polarized light that has passed through the lower polarizer 5 and the liquid crystal by using a light-shielding material such as carbon black, and also has a polarization function, so that the light is transmitted to the black.
  • the lower polarizer 5 and the black matrix 11 form a polarizing system, and the final light is emitted from the upper polarizer 4.
  • the black matrix 11 has both polarizing characteristics and light absorbing characteristics, further enhancing the light shielding performance, reducing the light transmittance (which can reduce the light transmittance to within 3.5% at most), thereby increasing the optical density value of the black matrix 11 while Due to the addition of the azo compound, the amount of the light-shielding material in the black matrix 11 is reduced, and the impedance value of the black matrix 11 is increased.
  • FIG. 7 is a relationship between the optical density value and the carbon black content of the black matrix of the present invention and the existing black matrix, wherein the black matrix of the present invention contains an azo compound, and the existing black matrix does not. Contains azo compounds.
  • the black matrix of the present invention has a higher optical density value than the existing black matrix, and has stronger light blocking performance.
  • the black matrix of the present invention has a lower content of carbon black, and thus the black matrix of the present invention has a higher impedance value than the conventional black matrix.
  • the black matrix on the CF substrate contains an azo compound having polarization characteristics, and has both polarization characteristics and light absorption characteristics, and the black matrix absorbs polarized light after being rotated by the lower polarizer and the liquid crystal by using a light shielding material.
  • it also has a polarization function, so that when the light is transmitted to the black matrix, the lower polarizer and the black matrix form a polarizing system, which further enhances the shading performance, improves the optical density value of the black matrix, and at the same time, due to the addition of the azo compound, The amount of shading material in the black matrix is reduced, and the impedance value of the black matrix is increased.
  • the black matrix of the present invention contains an azo compound having polarizing characteristics, has good light-shielding properties, has a high optical density value, and has a small amount of light-shielding material in the black matrix and has a large impedance value.
  • the method for fabricating the black matrix of the present invention enhances the shading performance of the black matrix by adding an azo compound having a polarizing property to the black matrix, improves the optical density value of the black matrix, and makes black due to the addition of the azo compound.
  • the black matrix on the CF substrate contains an azo compound having polarization characteristics, and has both polarization characteristics and light absorption characteristics, and the black matrix absorbs polarized light after being rotated by the lower polarizer and the liquid crystal by the light shielding material.
  • the lower polarizer and the black matrix form a polarizing system, which further enhances the shading performance, improves the optical density value of the black matrix, and is also added by the azo compound. This reduces the amount of shading material in the black matrix and increases the impedance of the black matrix.

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Abstract

一种黑色矩阵(11)与其制作方法及具有黑色矩阵(11)的液晶面板，黑色矩阵(11)通过将混合树脂组合物涂布于基板上，干燥后通过光刻法进行图案化而制得，混合树脂组合物包括粘合树脂、光引发剂、小分子单体、溶剂、遮光材料、偶氮化合物、及添加剂，黑色矩阵(11)中通过加入具有偏光特性的偶氮化合物，提升了遮光性能，提高了黑色矩阵(11)的光学密度值，并可减少黑色矩阵(11)中遮光材料的用量，增大黑色矩阵(11)的阻抗值。

Description

黑色矩阵与其制作方法及具有该黑色矩阵的液晶面板 技术领域
本发明涉及显示技术领域，尤其涉及一种黑色矩阵与其制作方法及具有该黑色矩阵的液晶面板。
背景技术
液晶显示装置(LCD，Liquid Crystal Display)具有机身薄、省电、无辐射等众多优点，得到了广泛的应用。如：液晶电视、移动电话、个人数字助理(PDA)、数字相机、计算机屏幕或笔记本电脑屏幕等。
通常液晶显示装置包括壳体、设于壳体内的液晶显示面板及设于壳体内的背光模组(Backlight module)。其中，液晶显示面板的结构主要是由一薄膜晶体管阵列基板(Thin Film Transistor Array Substrate，TFT Array Substrate)、一彩色滤光片基板(Color Filter，CF)、以及配置于两基板间的液晶层(Liquid Crystal Layer)所构成，其工作原理是通过在两片玻璃基板上施加驱动电压来控制液晶层的液晶分子的旋转，将背光模组的光线折射出来产生画面。
当前主流的液晶面板，在CF基板侧设置有黑色矩阵(Black Matrix，BM)，以阻止每个像素处漏光的发生。黑色矩阵起初采用的是铬系材料的金属薄膜，但是由于工序复杂、成本高、环境污染等原因而逐渐被树脂型材料的黑矩阵取代。树脂型黑矩阵(RBM)是指将碳黑(Carbon)等遮光材料分散到树脂中，并与其他的树脂、光引发剂、单体、溶剂混和，将其涂布在CF基板上，干燥后并通过光刻法进行图案化而得到黑色矩阵。光学密度(OD)值是用来衡量遮光性能的物理单位，随着彩色滤光片的高性能化，对树脂黑矩阵的光学密度值的要求不断提高，现有提高光学密度值的方法主要有以下几种：
一、提高黑色矩阵光阻的膜厚。该种方法会导致涂在黑色矩阵上的彩色像素(R、G、B)所产生的表面阶差变大，因而会导致滤色器的平坦性降低，液晶的取向紊乱等问题。
二、在膜厚不变的前提下增加碳黑等遮光材料的含量。该种方法会使得树脂型黑矩阵的树脂比率减小，从而降低与基板的附着力；另外在曝光制程中碳黑易吸收紫外光，从而使底层的光阻因曝光不足不能固化而产生剥离。
三、降低碳黑的粒径来提高遮光性。该种方法易团聚而产生凝胶等问题。此外，由于碳黑为导电粒子，如果光阻体系中的碳黑较多时，会导致黑色矩阵的阻抗值(Rs)降低。
发明内容
本发明的目的在于提供一种黑色矩阵，具有较高的光学密度值，且遮光材料用量较少，具有较大的阻抗值。
本发明的另一目的在于提供一种黑色矩阵的制作方法，可提高黑色矩阵的光学密度值，并可减少遮光材料的用量，增大黑色矩阵的阻抗值，提高黑色矩阵成膜制程的稳定性。
本发明的再一目的在于提供一种液晶面板，其CF基板上的黑色矩阵兼具偏光特性与吸光特性，遮光效果强，具有较高的光学密度值，同时黑色矩阵中遮光材料的用量较少，具有较大的阻抗值。
为实现上述目的，本发明提供一种黑色矩阵，其通过将混合树脂组合物涂布于基板上，干燥后通过光刻法进行图案化而制得，其中，所述混合树脂组合物包括粘合树脂、光引发剂、小分子单体、溶剂、遮光材料、偶氮化合物、及添加剂，所述偶氮化合物具有偏光特性。
所述偶氮化合物的结构为
Figure PCTCN2015078867-appb-000001
其中，R1为氨基、羟基、烷氧基、酯基、氨酰基、胺醛基、苯基或烷基，R2为酰基、醛基、羧基、酰氨基、磺酸基、腈基、硝基、卤仿基或季胺基。
所述遮光材料为黑色无机颜料或黑色有机颜料；所述粘合树脂为2-(甲基)丙烯酰氧乙基邻苯二甲酸；所述小分子单体为苯乙烯、丙烯酸脂或甲基丙烯酸脂；所述光引发剂为乙烷酮或1-[9-乙基-6(2-甲基苯甲酰基)-9氢-咔唑-3-取代基]-,1-(氧-乙酰肟)；所述溶剂为丙二醇甲醚醋酸酯、环己酮、3-甲氧基丁基乙酸酯或二乙二醇丁醚醋酸酯。
所述黑色无机颜料为碳黑、氧化铬、氧化铁、氧化钛或石墨，所述黑色有机颜料为二萘嵌苯黑、花青黑或苯胺黑。
所述混合树脂组合物中，各组分的质量百分比为：粘合树脂5～10％、光引发剂0～1％、小分子单体0～1％、溶剂70～80％、遮光材料5-10％、偶氮化合物1-5％、添加剂0-0.5％。
本发明还提供一种黑色矩阵的制作方法，包括如下步骤：
步骤1、以所需制备的混合树脂组合物的总重量为基准，按照5～10wt％的比例称取粘合树脂、按照0～1wt％的比例称取光引发剂、按照0～1wt％的比例称取小分子单体、按照70～80wt％的比例称取溶剂、按照5-10wt％的比例称取遮光材料、按照1-5wt％的比例称取偶氮化合物、按照0-0.5wt％的比例称取添加剂，然后将上述准确称量的各组分混合均匀，制得混合树脂组合物；其中，所述偶氮化合物具有偏光特性；
步骤2、将上述混合树脂组合物涂布于基板上，通过软烤、曝光、显影、及硬烤制程制得具有偏光特性的黑色矩阵。
所述步骤1中，所述偶氮化合物的结构为
Figure PCTCN2015078867-appb-000002
其中，R1为氨基、羟基、烷氧基、酯基、氨酰基、胺醛基、苯基或烷基，R2为酰基、醛基、羧基、酰氨基、磺酸基、腈基、硝基、卤仿基或季胺基。
所述步骤1中，所述遮光材料为黑色无机颜料或黑色有机颜料；所述粘合树脂为2-(甲基)丙烯酰氧乙基邻苯二甲酸；所述小分子单体为苯乙烯、丙烯酸脂或甲基丙烯酸脂；所述光引发剂为乙烷酮或1-[9-乙基-6(2-甲基苯甲酰基)-9氢-咔唑-3-取代基]-,1-(氧-乙酰肟)；所述溶剂为丙二醇甲醚醋酸酯、环己酮、3-甲氧基丁基乙酸酯或二乙二醇丁醚醋酸酯。
所述黑色无机颜料为碳黑、氧化铬、氧化铁、氧化钛或石墨，所述黑色有机颜料为二萘嵌苯黑、花青黑或苯胺黑。
本发明还提供一种液晶面板，包括CF基板、与所述CF基板相对设置的TFT基板、及填充于所述CF基板与TFT基板之间的液晶层，所述CF基板上设有黑色矩阵与彩色光阻，所述黑色矩阵为如上任一所述的黑色矩阵。
本发明的有益效果：本发明的黑色矩阵，含有具有偏光特性的偶氮化合物，遮光性能好，具有较高的光学密度值，并且黑色矩阵中遮光材料的用量较少，具有较大的阻抗值。本发明的黑色矩阵的制作方法，通过在黑色矩阵中加入具有偏光特性的偶氮化合物，增强了黑色矩阵的遮光性能，提高了黑色矩阵的光学密度值，并且由于偶氮化合物的加入，使得黑色矩阵中遮光材料的用量减少，增加了黑色矩阵的阻抗值，同时使得在曝光过程中，紫外光更容易照射到膜的底部，从而减少了许多工程上的问题，增加了制程的稳定性。本发明的液晶面板，CF基板上的黑色矩阵中含有具有 偏光特性的偶氮化合物，兼具偏光特性与吸光特性，黑色矩阵除了利用遮光材料对经过下偏光片、液晶旋转后的偏振光进行吸收与遮挡外，还具有偏振功能，使得光传到黑色矩阵时，下偏光片、黑色矩阵形成了偏光系统，进一步增强了遮光性能，提高了黑色矩阵的光学密度值，同时由于偶氮化合物的加入，使得黑色矩阵中遮光材料的用量减少，增加了黑色矩阵的阻抗值。
为了能更进一步了解本发明的特征以及技术内容，请参阅以下有关本发明的详细说明与附图，然而附图仅提供参考与说明用，并非用来对本发明加以限制。
附图说明
下面结合附图，通过对本发明的具体实施方式详细描述，将使本发明的技术方案及其他有益效果显而易见。
附图中，
图1为本发明的黑色矩阵中偶氮化合物分子轨道示意图；
图2为现有的黑色矩阵的阻抗值与碳黑含量的关系图；
图3为本发明的黑色矩阵的制作方法的流程图；
图4为本发明的液晶面板的剖面示意图；
图5为一种现有液晶面板的入光示意图；
图6为本发明的液晶面板的入光示意图；
图7为本发明的黑色矩阵与现有的黑色矩阵的光学密度值与碳黑含量的关系图。
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。
本发明首先提供一种黑色矩阵，其通过将混合树脂组合物涂布于基板上，干燥后通过光刻法进行图案化而制得，其中，所述混合树脂组合物包括粘合树脂(Polymer)、光引发剂(Photo Initiator)、小分子单体(Monomer)、溶剂(Solvent)、遮光材料、偶氮化合物、及添加剂，所述偶氮化合物具有偏光特性。所述粘合树脂能够形成膜层并支持交联反应，所述光引发剂能够在光照下快速形成自由基，所述小分子单体能够聚合官能团，所述溶剂能够调节涂布性能，所述遮光材料能够起到遮光作用，所述偶氮化合物具有偏光特性且能够均匀分散于体系中。
具体的，本发明采用的偶氮化合物为芳香烃偶氮化合物，其结构为
Figure PCTCN2015078867-appb-000003
其中，R1为推电子基团，如氨基、羟基、烷氧基、酯基、氨酰基、胺醛基、苯基或烷基等，R2为吸电子基团，如酰基、醛基、羧基、酰氨基、磺酸基、腈基、硝基、卤仿基或季胺基等。
请参阅图1，为本发明的黑色矩阵中偶氮化合物的分子轨道示意图。所述偶氮化合物分子结构在两个芳环之间以N＝N双键连接，形成共轭结构，分子链刚性很强，使得分子共面而呈线形排列，该种结构使得所述偶氮化合物具有偏光特性。
具体的，所述遮光材料可以为碳黑、氧化铬、氧化铁、氧化钛或石墨等无机颜料，也可以为耐热耐光与耐溶剂性较佳的二萘嵌苯黑(Perylene blace)、花青黑(cyanine blace)、苯胺黑(aniline black)等黑色有机颜料。
所述粘合树脂为碱溶性树脂，如2-(甲基)丙烯酰氧乙基邻苯二甲酸等。
所述小分子单体为具有不饱和双键结构的苯乙烯、丙烯酸脂或甲基丙烯酸脂等。
所述光引发剂为乙烷酮或1-[9-乙基-6(2-甲基苯甲酰基)-9氢-咔唑-3-取代基]-,1-(氧-乙酰肟)【商品名：CGI-2424,Ciba Specialty Chemicals】。
所述溶剂为丙二醇甲醚醋酸酯(PGMEA)、环己酮(Cyclohexanone)、3-甲氧基丁基乙酸酯(3-Methoxy butyl acetate)或二乙二醇丁醚醋酸酯(2-(2-butoxyethoxy)-Ethanol acetate)等。
具体地，所述混合树脂组合物中，各组分的质量百分比为：粘合树脂5～10％、光引发剂0～1％、小分子单体0～1％、溶剂70～80％、遮光材料5-10％、偶氮化合物1-5％、添加剂0-0.5％。
请参阅图2，为现有的黑色矩阵的阻抗值(Rs)与碳黑含量的关系图。
请参阅表1，为现有的黑色矩阵的光学密度(OD)值/阻抗(Rs)值与碳黑含量的关系数据表。
表1.黑色矩阵的光学密度值/阻抗值与碳黑含量的关系数据表
Figure PCTCN2015078867-appb-000004
Figure PCTCN2015078867-appb-000005
由图2和表1可知，在添加碳黑作为黑色矩阵的遮光材料时，所述液晶面板中黑色矩阵的光学密度值取决于碳黑的含量，相同条件下，黑色矩阵中碳黑的含量越多，相应的光学密度值就越大。然而由于碳黑具有导电特性，因此黑色矩阵中碳黑的含量越多，黑色矩阵的阻抗值就越小。而本发明中，由于偶氮化合物的加入，使得本发明的黑色矩阵在具有相同光学密度值的情况下，碳黑等遮光材料的用量可以相对减少，从而增加了黑色矩阵的阻抗值。
本发明的黑色矩阵，由于含有具有偏光特性的偶氮化合物，因此遮光性能好，具有较高的光学密度值，并且黑色矩阵中遮光材料的用量较少，从而具有较大的阻抗值。
请参阅图3，本发明还提供一种黑色矩阵的制作方法，包括如下步骤：
步骤1、以所需制备的混合树脂组合物的总重量为基准，按照5～10wt％的比例称取粘合树脂、按照0～1wt％的比例称取光引发剂、按照0～1wt％的比例称取小分子单体、按照70～80wt％的比例称取溶剂、按照5-10wt％的比例称取遮光材料、按照1-5wt％的比例称取偶氮化合物、按照0-0.5wt％的比例称取添加剂，然后将上述准确称量的各组分混合均匀，制得混合树脂组合物；其中，所述偶氮化合物具有偏光特性。
具体地，所述遮光材料可以为碳黑、氧化铬、氧化铁、氧化钛或石墨等无机颜料，也可以为耐热耐光与耐溶剂性较佳的二萘嵌苯黑(Perylene blace)、花青黑(cyanine blace)、苯胺黑(aniline black)等黑色有机颜料。
所述粘合树脂为碱溶性树脂，如2-(甲基)丙烯酰氧乙基邻苯二甲酸等。
所述小分子单体为具有不饱和双键结构的苯乙烯、丙烯酸脂或甲基丙烯酸脂等。
所述光引发剂为乙烷酮或1-[9-乙基-6(2-甲基苯甲酰基)-9氢-咔唑-3-取代基]-,1-(氧-乙酰肟)【商品名：CGI-2424,Ciba Specialty Chemicals】。
所述溶剂为丙二醇甲醚醋酸酯(PGMEA)、环己酮(Cyclohexanone)、3-甲氧基丁基乙酸酯(3-Methoxy butyl acetate)或二乙二醇丁醚醋酸酯(2-(2-butoxyethoxy)-Ethanol acetate)等。
所述偶氮化合物的结构为
Figure PCTCN2015078867-appb-000006
其中，R1为推电子基团，如氨基、羟基、烷氧基、酯基、氨酰基、胺醛基、苯基或烷基等，R2为吸电子基团，如酰基、醛基、羧基、酰氨基、磺酸基、腈基、硝基、卤仿基或季胺基等。
步骤2、将上述混合树脂组合物涂布于基板上，通过软烤、曝光、显影、及硬烤制程制得具有偏光特性的黑色矩阵。
值得说明的是，所述硬烤制程中没有对黑色矩阵进行定向拉伸，从而使制得的黑色矩阵对偏振光的选择相对随机。
上述黑色矩阵的制作方法，通过在黑色矩阵中加入具有偏光特性的偶氮化合物，增强了黑色矩阵的遮光性能，提高了黑色矩阵的光学密度值，并且由于偶氮化合物的加入，使得黑色矩阵中遮光材料的用量减少，增加了黑色矩阵的阻抗值，同时使得在黑色矩阵的黄光制程的曝光过程中，紫外光更容易照射到膜的底部，从而减少了许多工程上的问题，增加了制程的稳定性。
请参阅图4，本发明还提供一种液晶面板，包括CF基板1、与所述CF基板1相对设置的TFT基板2、填充于所述CF基板1与TFT基板2之间的液晶层3、设于所述CF基板1上表面的上偏光片4、设于所述TFT基板2下表面的下偏光片5、及粘结所述CF基板1与TFT基板2的框胶6，所述CF基板1上设有黑色矩阵11与彩色光阻，所述黑色矩阵11为通过将混合树脂组合物涂布于基板上，干燥后通过光刻法进行图案化而制得，所述混合树脂组合物包括粘合树脂、光引发剂、小分子单体、溶剂、遮光材料、偶氮化合物、及添加剂，所述偶氮化合物具有偏光特性。
具体的，所述遮光材料可以为碳黑、氧化铬、氧化铁、氧化钛或石墨等无机颜料，也可以为耐热耐光与耐溶剂性较佳的二萘嵌苯黑(Perylene blace)、花青黑(cyanine blace)、苯胺黑(aniline black)等黑色有机颜料。
所述粘合树脂为碱溶性树脂，如2-(甲基)丙烯酰氧乙基邻苯二甲酸等。
所述小分子单体为具有不饱和双键结构的苯乙烯、丙烯酸脂或甲基丙烯酸脂等。
所述光引发剂为乙烷酮或1-[9-乙基-6(2-甲基苯甲酰基)-9氢-咔唑-3-取代基]-,1-(氧-乙酰肟)【商品名：CGI-2424,Ciba Specialty Chemicals】。
所述溶剂为丙二醇甲醚醋酸酯(PGMEA)、环己酮(Cyclohexanone)、3-甲氧基丁基乙酸酯(3-Methoxy butyl acetate)或二乙二醇丁醚醋酸酯(2-(2-butoxyethoxy)-Ethanol acetate)等。
所述偶氮化合物的结构为
Figure PCTCN2015078867-appb-000007
其中，R1为推电子基团，如氨基、羟基、烷氧基、酯基、氨酰基、胺醛基、苯基或烷基等，R2为吸电子基团，如酰基、醛基、羧基、酰氨基、磺酸基、腈基、硝基、卤仿基或季胺基等。
具体地，所述混合树脂组合物中，各组分的质量百分比为：粘合树脂5～10％、光引发剂0～1％、小分子单体0～1％、溶剂70～80％、遮光材料5-10％、偶氮化合物1-5％、添加剂0-0.5％。
请参阅图5，为一种现有液晶面板的入光示意图，该现有液晶面板的黑色矩阵110包括粘合树脂、光引发剂、小分子单体、溶剂、碳黑、及添加剂，不含有偶氮化合物，因而黑色矩阵110只具有遮光效果，当背光由下偏光片500射入后，所述黑色矩阵110利用碳黑成分对经过下偏光片500、液晶旋转后的偏振光进行吸收与遮挡，最终光线由上偏光片400射出，由于光透过彩色滤光基板的强度只取决于碳黑含量的多少，因此遮光性能较差，透光率相对较高。
请参阅图6，为本发明的液晶面板的入光示意图，本发明的液晶面板的黑色矩阵11中加入了具有偏光特性的偶氮化合物。当背光由下偏光片5射入后，黑色矩阵11除了利用碳黑等遮光材料对经过下偏光片5、液晶旋转后的偏振光进行吸收与遮挡外，还具有偏振功能，使得光传到黑色矩阵11时，下偏光片5与黑色矩阵11形成了偏光系统，最终光线由上偏光片4射出。所述黑色矩阵11兼具偏光特性与吸光特性，进一步增强了遮光性能，降低了透光率(最多可使透光率降到3.5％以内)，从而提高了黑色矩阵11的光学密度值，同时由于偶氮化合物的加入，使得黑色矩阵11中遮光材料的用量减少，增加了黑色矩阵11的阻抗值。
请参阅图7，为本发明的黑色矩阵与现有的黑色矩阵的光学密度值与碳黑含量的关系图，其中，本发明的黑色矩阵中含有偶氮化合物，而现有的黑色矩阵中不含有偶氮化合物。由图7可以看出，在黑色矩阵具有相同的碳黑含量的情况下，本发明的黑色矩阵比现有的黑色矩阵的光学密度值更高，具有更强的遮光性能。同样的，在具有相同的光学密度值的情况下， 本发明的黑色矩阵中碳黑的含量更低，因此与现有的黑色矩阵相比，本发明的黑色矩阵具有更高的阻抗值。
上述液晶面板，其CF基板上的黑色矩阵中含有具有偏光特性的偶氮化合物，兼具偏光特性与吸光特性，黑色矩阵除了利用遮光材料对经过下偏光片、液晶旋转后的偏振光进行吸收与遮挡外，还具有偏振功能，使得光传到黑色矩阵时，下偏光片、黑色矩阵形成了偏光系统，进一步增强了遮光性能，提高了黑色矩阵的光学密度值，同时由于偶氮化合物的加入，使得黑色矩阵中遮光材料的用量减少，增加了黑色矩阵的阻抗值。
综上所述，本发明的黑色矩阵，含有具有偏光特性的偶氮化合物，遮光性能好，具有较高的光学密度值，并且黑色矩阵中遮光材料的用量较少，具有较大的阻抗值。本发明的黑色矩阵的制作方法，通过在黑色矩阵中加入具有偏光特性的偶氮化合物，增强了黑色矩阵的遮光性能，提高了黑色矩阵的光学密度值，并且由于偶氮化合物的加入，使得黑色矩阵中遮光材料的用量减少，增加了黑色矩阵的阻抗值，同时使得在曝光过程中，紫外光更容易照射到膜的底部，从而减少了许多工程上的问题，增加了制程的稳定性。本发明的液晶面板，CF基板上的黑色矩阵中含有具有偏光特性的偶氮化合物，兼具偏光特性与吸光特性，黑色矩阵除了利用遮光材料对经过下偏光片、液晶旋转后的偏振光进行吸收与遮挡外，还具有偏振功能，使得光传到黑色矩阵时，下偏光片、黑色矩阵形成了偏光系统，进一步增强了遮光性能，提高了黑色矩阵的光学密度值，同时由于偶氮化合物的加入，使得黑色矩阵中遮光材料的用量减少，增加了黑色矩阵的阻抗值。
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后附的权利要求的保护范围。

Claims (10)

  1. 一种黑色矩阵，其通过将混合树脂组合物涂布于基板上，干燥后通过光刻法进行图案化而制得，所述混合树脂组合物包括粘合树脂、光引发剂、小分子单体、溶剂、遮光材料、偶氮化合物、及添加剂，所述偶氮化合物具有偏光特性。
  2. 如权利要求1所述的黑色矩阵，其中，所述偶氮化合物的结构为
    Figure PCTCN2015078867-appb-100001
    其中，R1为氨基、羟基、烷氧基、酯基、氨酰基、胺醛基、苯基或烷基，R2为酰基、醛基、羧基、酰氨基、磺酸基、腈基、硝基、卤仿基或季胺基。
  3. 如权利要求1所述的黑色矩阵，其中，所述遮光材料为黑色无机颜料或黑色有机颜料；所述粘合树脂为2-(甲基)丙烯酰氧乙基邻苯二甲酸；所述小分子单体为苯乙烯、丙烯酸脂或甲基丙烯酸脂；所述光引发剂为乙烷酮或1-[9-乙基-6(2-甲基苯甲酰基)-9氢-咔唑-3-取代基]-,1-(氧-乙酰肟)；所述溶剂为丙二醇甲醚醋酸酯、环己酮、3-甲氧基丁基乙酸酯或二乙二醇丁醚醋酸酯。
  4. 如权利要求3所述的黑色矩阵，其中，所述黑色无机颜料为碳黑、氧化铬、氧化铁、氧化钛或石墨，所述黑色有机颜料为二萘嵌苯黑、花青黑或苯胺黑。
  5. 如权利要求1所述的黑色矩阵，其中，所述混合树脂组合物中，各组分的质量百分比为：粘合树脂5～10％、光引发剂0～1％、小分子单体0～1％、溶剂70～80％、遮光材料5-10％、偶氮化合物1-5％、添加剂0-0.5％。
  6. 一种黑色矩阵的制作方法，包括如下步骤：
    步骤1、以所需制备的混合树脂组合物的总重量为基准，按照5～10wt％的比例称取粘合树脂、按照0～1wt％的比例称取光引发剂、按照0～1wt％的比例称取小分子单体、按照70～80wt％的比例称取溶剂、按照5-10wt％的比例称取遮光材料、按照1-5wt％的比例称取偶氮化合物、按照0-0.5wt％的比例称取添加剂，然后将上述准确称量的各组分混合均匀，制得混合树脂组合物；其中，所述偶氮化合物具有偏光特性；
    步骤2、将上述混合树脂组合物涂布于基板上，通过软烤、曝光、显影、 及硬烤制程制得具有偏光特性的黑色矩阵。
  7. 如权利要求6所述的黑色矩阵的制作方法，其中，所述步骤1中，所述偶氮化合物的结构为
    Figure PCTCN2015078867-appb-100002
    其中，R1为氨基、羟基、烷氧基、酯基、氨酰基、胺醛基、苯基或烷基，R2为酰基、醛基、羧基、酰氨基、磺酸基、腈基、硝基、卤仿基或季胺基。
  8. 如权利要求6所述的黑色矩阵的制作方法，其中，所述步骤1中，所述遮光材料为黑色无机颜料或黑色有机颜料；所述粘合树脂为2-(甲基)丙烯酰氧乙基邻苯二甲酸；所述小分子单体为苯乙烯、丙烯酸脂或甲基丙烯酸脂；所述光引发剂为乙烷酮或1-[9-乙基-6(2-甲基苯甲酰基)-9氢-咔唑-3-取代基]-,1-(氧-乙酰肟)；所述溶剂为丙二醇甲醚醋酸酯、环己酮、3-甲氧基丁基乙酸酯或二乙二醇丁醚醋酸酯。
  9. 如权利要求8所述的黑色矩阵的制作方法，其中，所述黑色无机颜料为碳黑、氧化铬、氧化铁、氧化钛或石墨，所述黑色有机颜料为二萘嵌苯黑、花青黑或苯胺黑。
  10. 一种液晶面板，包括CF基板、与所述CF基板相对设置的TFT基板、及填充于所述CF基板与TFT基板之间的液晶层，所述CF基板上设有黑色矩阵与彩色光阻，所述黑色矩阵为权利要求1-5任意一项所述的黑色矩阵。
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