WO2020228176A1 - Matrice noire, procédé de préparation associé, et panneau d'affichage - Google Patents

Matrice noire, procédé de préparation associé, et panneau d'affichage Download PDF

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Publication number
WO2020228176A1
WO2020228176A1 PCT/CN2019/102517 CN2019102517W WO2020228176A1 WO 2020228176 A1 WO2020228176 A1 WO 2020228176A1 CN 2019102517 W CN2019102517 W CN 2019102517W WO 2020228176 A1 WO2020228176 A1 WO 2020228176A1
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WIPO (PCT)
Prior art keywords
black matrix
resin composition
spiropyran
value
auxiliary agent
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Application number
PCT/CN2019/102517
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English (en)
Chinese (zh)
Inventor
张霞
邵源
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深圳市华星光电技术有限公司
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Publication of WO2020228176A1 publication Critical patent/WO2020228176A1/fr

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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
    • 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
    • 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

Definitions

  • the invention relates to the field of display technology, in particular to a black matrix, a preparation method thereof, and a display panel.
  • a BM Black Matrix
  • CF Color Filter
  • the decrease of the BM line width and the increase of the carbon content in the BM will cause the adhesion between the BM in the thin film transistor liquid crystal display panel and the substrate and the sealant to decrease, which will cause bubbles to enter the panel and cause poor panel quality.
  • the object of the present invention is to provide a black matrix, a preparation method thereof, and a display panel.
  • a spiropyran derivative By adding a spiropyran derivative to the resin composition for preparing the black matrix, the spiropyran derivative can drive the polymer after structural isomerization.
  • the rearrangement of chains and doped molecules to eliminate the gap between the black matrix and the substrate, and solve the problem of low adhesion between the black matrix and the substrate.
  • the embodiment of the present invention provides a black matrix, the black matrix is made of a resin composition, the resin composition includes a spiropyran derivative, and the molecular structure of the spiropyran derivative is:
  • the R is: -CnH2n+1, -CmH2mOH, -Ar or -Ar-CHO, the value of n is 1-20, and the value of m is 1-3.
  • the resin composition further includes: a binding resin, the mass percentage of the binding resin in the resin composition is 5-15%; a photoinitiator, the photoinitiator is in the 0.01-2% by mass in the resin composition; polymerizable monomer, 0.01-1% by mass of the polymerizable monomer in the resin composition; shading material, the shading material in the resin composition
  • the mass percentage in the resin composition is 5-12%; auxiliary agent, the mass percentage of the auxiliary agent in the resin composition is 0-0.5%; the solvent, the mass percentage of the solvent in the resin composition is 70-85 %; wherein the mass percentage of the spiropyran derivative in the resin composition is 1-5%.
  • the adhesive resin includes a multifunctional acrylic resin, and the functional group includes at least one of an unsaturated double bond, an epoxy group, a hydroxyl group, and a carboxyl group.
  • the photoinitiator includes at least one of acetophenone compounds, imidazole compounds, benzophenone compounds, benzoin compounds, and acyl phosphine oxide derivatives.
  • the polymerizable monomer includes styrene, acrylate, or methacrylate with an unsaturated double bond structure.
  • the auxiliary agent includes an adhesion auxiliary agent and a leveling auxiliary agent
  • the adhesion auxiliary agent includes a silane coupling agent
  • the solvent includes tetrahydrofuran, cyclohexanone, propylene glycol methyl ether acetate, ethyl acetate, butyl acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate , Propylene glycol monomethyl ethyl acetate, acetone, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl ether acetate, ethylene glycol monomethyl ether , Propylene glycol monomethyl ether, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, propanol, n-butanol, toluene, xylene, ethylbenzene, dimethyl sulfoxide , At least one of dimethylacetamide.
  • the light-shielding material includes at least one of carbon black, organic black pigment, and inorganic black pigment.
  • the constituent material of the black matrix includes structural isomers of spiropyran derivatives, and the molecular structure of the structural isomers of spiropyran derivatives is:
  • the R is: -CnH2n+1, -CmH2mOH, -Ar or -Ar-CHO, the value of n is 1-20, and the value of m is 1-3.
  • the embodiment of the present invention also provides a method for preparing a black matrix, including:
  • the film is etched to form a black matrix
  • the constituent material of the black matrix includes structural isomers of spiropyran derivatives, and the molecular structure of the structural isomers of spiropyran derivatives is:
  • the R is: -CnH2n+1, -CmH2mOH, -Ar or -Ar-CHO, the value of n is 1-20, and the value of m is 1-3.
  • An embodiment of the present invention further provides a display panel, which includes a first substrate, a second substrate disposed opposite to the first substrate, and a black substrate disposed on the second substrate close to the first substrate. matrix;
  • the constituent material of the black matrix includes the structural isomer of the spiropyran derivative, and the molecular structure of the structural isomer of the spiropyran derivative is:
  • the R is: -CnH2n+1, -CmH2mOH, -Ar or -Ar-CHO, the value of n is 1-20, and the value of m is 1-3.
  • the present invention provides a black matrix, a preparation method thereof, and a display panel.
  • the resin composition includes the molecular structure
  • the structural isomer of the spiropyran derivative generated after structural isomerization of the spiropyran derivative can drive the rearrangement of polymer chains and doped molecules, and eliminate the gap between the black matrix and the substrate, Improve the yield rate of the display panel.
  • FIG. 1 is a flowchart of a method for preparing a black matrix according to an embodiment of the present invention.
  • FIG. 2 is a flowchart of another method for preparing a black matrix provided by an embodiment of the present invention.
  • FIG. 3 is a flowchart of yet another method for preparing a black matrix according to an embodiment of the present invention.
  • FIG. 4 is a flowchart of yet another method for preparing a black matrix provided by an embodiment of the present invention.
  • FIG. 5 is a schematic diagram of a cross-sectional structure of a display panel provided by an embodiment of the present invention.
  • the present invention provides a black matrix which includes a resin composition.
  • the present invention provides the resin composition, which includes a spiropyran derivative, a binding resin, a photoinitiator, a polymerizable monomer, a light-shielding material, an auxiliary agent and a solvent.
  • the mass percentage of the binder resin in the resin composition is 5-15%
  • the mass percentage of the photoinitiator in the resin composition is 0.01-2%
  • the polymerizable monomer The mass percentage in the resin composition is 0.01-1%
  • the mass percentage of the light-shielding material in the resin composition is 5-12%
  • the spiropyran derivative is in the resin composition.
  • the mass percentage of the additive is 1-5%
  • the mass percentage of the auxiliary agent in the resin composition is 0-0.5%
  • the mass percentage of the solvent in the resin composition is 70-85%.
  • the R is: -CnH2n+1, -CmH2mOH, -Ar or -Ar-CHO, n is 1-20, m is 1-3; the spiropyran derivative is under light conditions Structural isomerism can occur under the following conditions.
  • the molecular structure of the structural isomer of the spiropyran derivative is: Wherein, the R is: -CnH2n+1, -CmH2mOH, -Ar or -Ar-CHO, the value of n is 1-20, and the value of m is 1-3.
  • the adhesive resin includes a multifunctional acrylic resin, and the functional group includes at least one of an unsaturated double bond, an epoxy group, a hydroxyl group, and a carboxyl group.
  • the necessary component of the adhesive resin is a carboxyl-containing acrylic resin, such as 2-methacryloxyethyl, phthalic acid, etc., and the carboxyl-containing acrylic resin can make the alkali-soluble resin develop The stage reacts with the alkaline developer to be dissolved and washed away to form a corresponding pattern.
  • the adhesive resin also contains epoxy-based acrylic resin.
  • the epoxy-based acrylic resin can generate hydroxyl groups or undergo further crosslinking reaction with other epoxy acrylates after ring opening during the baking stage, thereby improving the The compactness of the resin composition.
  • the photoinitiator includes at least one of acetophenone compounds, imidazole compounds, benzophenone compounds, benzoin compounds, and acyl phosphine oxide derivatives.
  • the photoinitiator can absorb the energy of light with a wavelength range of 270nm-400nm to generate free radicals or cations, thereby initiating monomer polymerization, crosslinking and curing.
  • the photoinitiator may include diethoxyacetophenone, 2,2-dibutoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- Acetophenone compounds such as phenylpropane-1-one, 2,2-dimethoxy-2-phenylacetophenone; 2-methylimidazole, 4-methylimidazole, 1,2-dimethyl Imidazole, benzimidazole and other imidazole compounds; benzophenone, tetraphenylbenzophenone, hydroxybenzophenone, 4,4-dimethylaminobenzophenone and other benzophenone compounds; benzophenone, 1 -(2-methylphenyl)-2-phenylethanone and other benzoin compounds; trimethylbenzoyl-diphenylphosphine oxide and other acyl phosphine oxide derivatives.
  • the photoinitiator can be irgacure369, O
  • the polymerizable monomer includes styrene, acrylate or methacrylate with unsaturated double bond structure.
  • the polymerizable monomer may be dipentaerythritol pentaacrylate or dipentaerythritol hexaacrylate.
  • the light-shielding material includes at least one of carbon black, organic black pigment, and inorganic black pigment.
  • the carbon black can be CIpigment black7, MA100 manufactured by Mitsubishi Chemicals, #1000, #2650;
  • the organic black pigment can be perylene black, aniline black, cyanine black;
  • the inorganic black The pigment may be titanium oxide, chromium oxide, iron oxide or graphite.
  • the auxiliary agent includes an adhesion auxiliary agent and a leveling auxiliary agent
  • the adhesion auxiliary agent includes a silane coupling agent.
  • the leveling aid can make the surface of the film more flat and uniform after the photoresist film is cured.
  • the adhesion assistant includes carbamate silane, vinyl silane, isocyanato silane, epoxy silane, (meth)acryloyl silane, aldimino silane, etc., as well as the oligomerization of alkanes mentioned above.
  • the leveling aid includes at least one of acrylic leveling agents, organosiloxane wetting agents, and fluorocarbon modified acrylate leveling agents.
  • the solvent includes tetrahydrofuran, cyclohexanone, propylene glycol methyl ether acetate, ethyl acetate, butyl acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, propylene glycol monomethyl Glycol ethyl acetate, acetone, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl ether acetate, ethylene glycol monomethyl ether, propylene glycol monomethyl ether Ether, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, propanol, n-butanol, toluene, xylene, ethylbenzene, dimethyl sulfoxide, dimethyl At least one of acetamide.
  • the present invention also provides a method for preparing a black matrix, as shown in Figure 1, including the following steps:
  • S101 Provide binding resins, photoinitiators, polymerizable monomers, shading materials, spiropyran derivatives, additives, and solvents.
  • the mass percentage of the binder resin in the resin composition is 5-15%
  • the mass percentage of the photoinitiator in the resin composition is 0.01-2%
  • the polymerizable monomer The mass percentage in the resin composition is 0.01-1%
  • the mass percentage of the light-shielding material in the resin composition is 5-12%
  • the spiropyran derivative is in the resin composition.
  • the mass percentage of the additive is 1-5%
  • the mass percentage of the auxiliary agent in the resin composition is 0-0.5%
  • the mass percentage of the solvent in the resin composition is 70-85%.
  • the R is: -CnH2n+1, -CmH2mOH, -Ar or -Ar-CHO, n is 1-20, m is 1-3; the spiropyran derivative is under light conditions Structural isomerism can occur under the following conditions.
  • the molecular structure of the structural isomer of the spiropyran derivative is:
  • the R is: -CnH2n+1, -CmH2mOH, -Ar or -Ar-CHO, the value of n is 1-20, and the value of m is 1-3.
  • the adhesive resin includes a multifunctional acrylic resin, and the functional group includes at least one of an unsaturated double bond, an epoxy group, a hydroxyl group, and a carboxyl group.
  • the necessary component of the adhesive resin is a carboxyl-containing acrylic resin, such as 2-methacryloxyethyl, phthalic acid, etc., and the carboxyl-containing acrylic resin can make the alkali-soluble resin develop The stage reacts with the alkaline developer to be dissolved and washed away to form a corresponding pattern.
  • the adhesive resin also contains epoxy-based acrylic resin.
  • the epoxy-based acrylic resin can generate hydroxyl groups or undergo further crosslinking reaction with other epoxy acrylates after ring opening during the baking stage, thereby improving the The compactness of the resin composition.
  • the photoinitiator includes at least one of acetophenone compounds, imidazole compounds, benzophenone compounds, benzoin compounds, and acyl phosphine oxide derivatives.
  • the photoinitiator can absorb the energy of light in the wavelength range of 270nm-400nm to generate free radicals or cations, thereby initiating monomer polymerization, crosslinking and curing.
  • the photoinitiator may include diethoxyacetophenone, 2,2-dibutoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- Acetophenone compounds such as phenylpropane-1-one, 2,2-dimethoxy-2-phenylacetophenone; 2-methylimidazole, 4-methylimidazole, 1,2-dimethyl Imidazole, benzimidazole and other imidazole compounds; benzophenone, tetraphenylbenzophenone, hydroxybenzophenone, 4,4-dimethylaminobenzophenone and other benzophenone compounds; benzophenone, 1 -(2-methylphenyl)-2-phenylethanone and other benzoin compounds; trimethylbenzoyl-diphenylphosphine oxide and other acyl phosphine oxide derivatives.
  • the photoinitiator can be irgacure369, O
  • the polymerizable monomer includes styrene, acrylate or methacrylate with unsaturated double bond structure.
  • the polymerizable monomer may be dipentaerythritol pentaacrylate or dipentaerythritol hexaacrylate.
  • the light-shielding material includes at least one of carbon black, organic black pigment, and inorganic black pigment.
  • the carbon black can be CIpigment black7, MA100 manufactured by Mitsubishi Chemicals, #1000, #2650;
  • the organic black pigment can be perylene black, aniline black, cyanine black;
  • the inorganic black The pigment may be titanium oxide, chromium oxide, iron oxide or graphite.
  • the auxiliary agent includes an adhesion auxiliary agent and a leveling auxiliary agent
  • the adhesion auxiliary agent includes a silane coupling agent.
  • the leveling aid can make the surface of the film more flat and uniform after the photoresist film is formed and cured.
  • the adhesion assistant includes carbamate silane, vinyl silane, isocyanato silane, epoxy silane, (meth)acryloyl silane, aldimino silane, etc., as well as the oligomerization of alkanes mentioned above.
  • the leveling aid includes at least one of acrylic leveling agents, organosiloxane wetting agents, and fluorocarbon modified acrylate leveling agents.
  • the solvent includes tetrahydrofuran, cyclohexanone, propylene glycol methyl ether acetate, ethyl acetate, butyl acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, propylene glycol monomethyl Glycol ethyl acetate, acetone, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl ether acetate, ethylene glycol monomethyl ether, propylene glycol monomethyl ether Ether, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, propanol, n-butanol, toluene, xylene, ethylbenzene, dimethyl sulfoxide, dimethyl At least one of acetamide.
  • S102 Mix the binding resin, photoinitiator, polymerizable monomer, light-shielding material, spiropyran derivative and auxiliary agent with the solvent to form a solution.
  • the step S102 may specifically include the following steps:
  • the light shielding material is mixed with the first part of the binding resin and the first part of the solvent to form a first solution.
  • the binder resin and the solvent can be selected to be divided into the first part and the second part of the same quality, and the mixture can be continuously stirred during the mixing process, so that the light-shielding material can be uniformly dispersed in the binder resin and In the solvent.
  • S10213 Mix the first solution with the photoinitiator, the polymerizable monomer, the spiropyran derivative, the auxiliary agent, the second part of the binding resin and the second part of the solvent to form a solution.
  • the mixture can be continuously stirred during the mixing process, so that the mixture can be uniformly mixed.
  • the step S102 may specifically include the following steps.
  • the solvent can be selected to be divided into a first part and a second part of the same quality, and the solvent can be heated while stirring the solvent, so that the solvent can be fully homogenized.
  • the polymerizable monomer, the binding resin, the light-shielding material, the spiropyran derivative, the auxiliary agent, and the photoinitiator can be sequentially added to the container, and the stirring time is 4-10 hours, so that The mixture can be sufficiently homogenized.
  • stirring time is 4-6 hours.
  • S104 The film is etched to form a black matrix, the constituent materials of the black matrix include structural isomers of spiropyran derivatives, and the molecular structure of the structural isomers of spiropyran derivatives is:
  • the step S104 may specifically include the following steps:
  • a high-pressure mercury lamp may be used as the exposure light source, the dominant wavelength of the light emitted by the high-pressure mercury lamp is 365nm, the exposure may be 1 minute, and the spiropyran derivative is in the process of exposing Structural isomerism will occur to the structural isomer of the spiropyran derivative.
  • S1042 developing, hard-baking, etching, and peeling the exposed film to form the black matrix.
  • the structural isomers of the spiropyran derivatives can drive the polymer chains and doping molecules in the solution to rearrange in the subsequent annealing process, eliminating the gap between the film and the substrate.
  • the cavities and gaps can improve the adhesion of the interface between the film and the substrate.
  • the present invention also provides a display panel.
  • the display panel 700 includes a first substrate 701, a thin film transistor layer 702 provided on the first substrate, and a passivation layer provided on the thin film transistor layer.
  • the black matrix 707 is made of the resin composition, and the constituent materials of the black matrix 70 include structural isomers of spiropyran derivatives, and molecules of the structural isomers of spiropyran derivatives
  • the structure is:
  • the R is: -CnH2n+1, -CnH2nOH, -Ar or -Ar-CHO, n is 1-20, and m is 1-3.
  • the structural isomers of the spiropyran derivatives can drive polymer chains and dopant molecules to rearrange in the subsequent annealing process, eliminating the cavities and cavities between the black matrix and the substrate.
  • the gap can improve the adhesion of the interface between the black matrix and the substrate.
  • the present invention provides a resin composition, a black matrix and a preparation method thereof, and a display panel.
  • the resin composition includes a spiropyran derivative, an adhesive resin, a photoinitiator, a Polymeric monomers, shading materials, additives and solvents, the molecular structure of the spiropyran derivative is:
  • the R is: -CnH2n+1, -CnH2nOH, -Ar or -Ar-CHO, the value of n is 1-20, and the value of m is 1-3.
  • the spiropyran derivative can drive the rearrangement of polymer chains and doping molecules after structural isomerization, eliminate the gap between the black matrix and the substrate, and improve the yield of the display panel.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
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  • Materials For Photolithography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une matrice noire, un procédé de préparation associé et un panneau d'affichage. La matrice noire est préparée à l'aide d'une composition de résine. La composition de résine comprend un dérivé de spiropyrane, une résine de liaison, un photo-initiateur, un monomère polymérisable, un matériau de blocage de lumière, un additif et un solvant, la formule structurale moléculaire du dérivé de spiropyrane étant : (I), où R représente -CnH2n+1, -CmH2mOH, -Ar ou -Ar-CHO, n a une valeur de 1 à 20, et m a une valeur de 1 à 3.
PCT/CN2019/102517 2019-05-16 2019-08-26 Matrice noire, procédé de préparation associé, et panneau d'affichage WO2020228176A1 (fr)

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CN201910404619.1A CN110161742B (zh) 2019-05-16 2019-05-16 黑色矩阵及其制备方法、显示面板

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CN112445019A (zh) * 2019-09-05 2021-03-05 咸阳彩虹光电科技有限公司 一种功能基板、液晶显示面板及显示器

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