CN113296358A - Black photosensitive resin composition, black matrix and image display device - Google Patents
Black photosensitive resin composition, black matrix and image display device Download PDFInfo
- Publication number
- CN113296358A CN113296358A CN202110193301.0A CN202110193301A CN113296358A CN 113296358 A CN113296358 A CN 113296358A CN 202110193301 A CN202110193301 A CN 202110193301A CN 113296358 A CN113296358 A CN 113296358A
- Authority
- CN
- China
- Prior art keywords
- black
- photosensitive resin
- resin composition
- black photosensitive
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
-
- 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
- G03F7/0005—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
- 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
-
- 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
- G03F7/075—Silicon-containing compounds
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Optics & Photonics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention provides a black photosensitive resin composition, a black matrix and an image display device, wherein the black photosensitive resin composition comprises a black colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, the black colorant is composed of a black organic pigment, and the reflectivity Y of a cured film formed by the black photosensitive resin composition to a standard light source D65 is less than 4.5%.
Description
Technical Field
The present invention relates to a black photosensitive resin composition, a black matrix, and an image display device, and more particularly, to a black photosensitive resin composition which reduces reflection of external light such as sunlight and a sense of reflected color, improves visibility, improves transmittance in an infrared region without inhibiting infrared sensing, and has excellent low-temperature curability, and a black matrix and an image display device formed using the same.
Background
The black photosensitive resin composition is an essential material for color filters, liquid crystal display devices, organic light-emitting elements, displays, and the like. For example, in a color filter of a color liquid crystal display, a light shielding layer is formed at a boundary portion between coloring layers such as red (red), green (green), and blue (blue), whereby display contrast and a color development effect can be improved.
Specifically, in pixels formed of red (R), green (G), and blue (B) colors, a black matrix is formed at the boundary between the colored layers of each pixel, or a columnar spacer is formed at the portion in contact with the liquid crystal, in order to prevent color mixing with other colors or to hide the electrode pattern.
In recent years, attention has been paid to development of a flexible display device which can be curled like paper. Accordingly, materials that can be used for various substrates used in display devices are limited to flexible polymer materials because they are required to have flexible characteristics. Further, due to such material limitations, the manufacturing process is also required to be performed under more mild conditions.
Therefore, the necessity for changing the curing conditions of the photosensitive resin composition from the conventional high-temperature curing to the low-temperature curing is also remarkable. However, low-temperature curing has a problem that reactivity is lowered and durability of a formed pattern is lowered.
Korean patent laid-open publication No. 2015-0062889 discloses that a photosensitive resin composition for black columnar spacers, which comprises an alkali-soluble binder resin, a polyfunctional monomer, a colorant, a solvent, and an oxime-based photoinitiator having long-wavelength band absorption, is excellent in process characteristics and post-baking characteristics.
However, the photosensitive resin composition has problems that visibility is poor due to poor external light reflection and color sensitivity, and sufficient durability is difficult to ensure at the time of low-temperature curing.
Further, development of a photosensitive resin composition which does not inhibit infrared ray sensitivity when applied to an image display device is required.
Disclosure of Invention
Problems to be solved
An object of the present invention is to provide a black photosensitive resin composition which is reduced in reflection of external light such as sunlight and color sensitivity of reflection to improve visibility, and which is improved in transmittance in an infrared region without inhibiting infrared sensitivity and is excellent in low-temperature curability.
Another object of the present invention is to provide a black matrix formed by using the black photosensitive resin composition.
Still another object of the present invention is to provide an image display device including the black matrix.
Means for solving the problems
In one aspect, the present invention provides a black photosensitive resin composition comprising a black colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the black colorant is composed of a black organic pigment, and a cured film formed from the black photosensitive resin composition has a reflectance (Y) of 4.5% or less with respect to a standard light source D65.
In one embodiment of the present invention, the cured film formed from the black photosensitive resin composition has an o.d./μm of 1.6 or more at a film thickness of 1.5 μm.
In one embodiment of the present invention, the cured film formed from the black photosensitive resin composition may have a transmittance of 80% or more at 900 nm.
The black photosensitive resin composition according to one embodiment of the present invention may further contain silica particles.
In one embodiment of the present invention, the average particle diameter of the silica particles may be 200 to 400 nm.
In one embodiment of the present invention, the content of the silica particles may be 1 to 20% by weight based on 100% by weight of the total solid content in the black photosensitive resin composition.
The black photosensitive resin composition according to one embodiment of the present invention can be used for a flexible substrate.
In another aspect, the present invention provides a black matrix formed using the black photosensitive resin composition.
In still another aspect, the present invention provides an image display device including the black matrix.
Effects of the invention
The black photosensitive resin composition of the present invention can reduce external light reflection such as sunlight and the color sensation of reflection to improve visibility, and can improve transmittance in the infrared region without interfering with infrared sensing. The black photosensitive resin composition of the present invention is excellent in low-temperature curability, and can form a pattern having excellent durability even when applied to a flexible substrate made of a polymer material.
Detailed Description
The present invention will be described in more detail below.
One embodiment of the present invention relates to a black photosensitive resin composition comprising a black colorant (a), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), wherein the black colorant is composed of a black organic pigment, and a cured film formed from the black photosensitive resin composition has a reflectance (Y) of 4.5% or less with respect to a standard light source D65.
The reflectance (Y) of the cured film formed from the black photosensitive resin composition with respect to the standard light source D65 is the reflectance (Y) measured when the light source is the standard light source D65, and the measurement method is not particularly limited, and can be measured, for example, by the method provided in the experimental examples described later.
In one embodiment of the present invention, the reflectance (Y) of the cured film formed from the black photosensitive resin composition with respect to the standard light source D65 is controlled to be 4.5% or less, for example, 4.4 to 4.5%, so that external light reflection such as sunlight and reflected color sensation can be reduced to improve visibility, and transmittance in the infrared region can be improved without hindering infrared sensing.
In addition, the black photosensitive resin composition of one embodiment of the present invention can control the O.D./μm to be 1.6 or more, for example, 1.6 to 1.7, preferably 1.6 to 1.65, when the thickness of the cured film formed from the black photosensitive resin composition is 1.5 μm. If the o.d./μm is less than 1.6, light leakage by the backlight may occur.
The transmittance of a cured film formed from the black photosensitive resin composition according to one embodiment of the present invention at 900nm can be controlled to 80% or more, preferably 85% or more. If the transmittance at 900nm is less than 80%, the transmittance in the infrared region is low and infrared sensing may be hindered.
The black photosensitive resin composition satisfying the above reflectance (Y), o.d./μm and 900nm transmittance with respect to the standard light source D65 can be controlled by appropriately changing the kind or content of the components contained in the black photosensitive resin composition, the thickness of the cured film formed therefrom, and the like. Specifically, the above-described reflectance (Y), o.d./μm, and 900nm transmittance with respect to the standard light source D65 can be controlled by using a black organic pigment as a black colorant and using silica particles.
Black colorant (A)
In one embodiment of the present invention, the black colorant (a) is used for black color, and light-shielding properties are provided to the spacers, the black matrix, and the black columnar spacers. The black column spacer means that the column spacer is integrally formed with the black matrix. That is, the black matrix can prevent light leakage, and the spacer can prevent malfunction of the device due to light from the outside.
The black colorant is a substance having a light-shielding property in visible light, and a black organic pigment is used. In the present invention, the black colorant can have a high transmittance of 80% or more in a long wavelength region, for example, 900nm, by excluding a black inorganic pigment such as carbon black and using only a black organic pigment.
The black organic pigment is not particularly limited, and known black organic pigments, specifically, aniline black, lactam black, perylene black, and the like can be used. These may be used singly or in combination.
Further, the black colorant may optionally further contain a color correction agent. The colorant may be a condensed polycyclic pigment such as an anthraquinone-based pigment or a perylene-based pigment, or an organic pigment such as a phthalocyanine pigment or an azo pigment, and is preferably an anthraquinone-based pigment or a phthalocyanine pigment, and more preferably a phthalocyanine pigment. Examples of the phthalocyanine pigment include c.i. pigment blue 15:6, c.i. pigment blue 15:4, and c.i. pigment blue 16, and examples of the anthraquinone-based pigment include c.i. pigment blue 60. The phthalocyanine pigment may preferably be c.i. pigment blue 15: 6.
Among the black organic pigments, lactam black (e.g., from Pasteur corporation) is preferably used in view of optical density, dielectric constant, and transmittance
Black S 0100 CF)。
The content of the black colorant (a) may be 20 to 80% by weight, preferably 30 to 70% by weight, based on 100% by weight of the total solid content in the black photosensitive resin composition. In the case where the content of the black colorant is within the above range, the optical density may become excellent.
In the present invention, the solid content in the black photosensitive resin composition means the total amount of components obtained by removing the solvent.
The pigment is preferably a pigment dispersion liquid in which the particle size of the pigment is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method in which a pigment dispersant (a1) is added to the dispersion medium and the dispersion is performed, and according to the above method, a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained.
Pigment dispersant (a1)
The pigment dispersant (a1) is added for the purpose of disaggregation of the pigment and maintaining stability, and any pigment dispersant generally used in the art can be used without limitation. An acrylate-based dispersant (hereinafter, also referred to as "acrylic dispersant") containing Butyl Methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA) is preferably used. As the acrylic dispersant, those produced by the activity control method disclosed in Korean laid-open patent No. 2004-0014311 are preferably used, and examples of commercially available acrylic dispersants produced by the activity control method include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150 and the like.
The above-exemplified acrylic dispersants may be used each alone or in combination of two or more.
As the pigment dispersant (a1), other resin type pigment dispersants than the acrylic dispersant can be used. Examples of the other resin type pigment dispersants include oily dispersants such as polyurethanes, polycarboxylates typified by polyacrylates, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphates, esters of hydroxyl-containing polycarboxylic acids and modified products thereof, or amides or salts thereof formed by reaction of polyesters having free carboxyl groups with poly (lower alkylene imine); water-soluble resins or water-soluble polymer compounds such as (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinyl pyrrolidone; a polyester; a modified polyacrylate; ethylene oxide/propylene oxide adducts; and phosphate esters and the like. Examples of commercially available products of the resin type dispersant include trade names of BYK chemical: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, and DISPER BYK-184; trade name of BASF (BASF) corporation: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; trade name of Lubrizol (lubriun) corporation: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; trade name of Chuanjian refining company: HINACT T-6000, HINACT T-7000, HINACT T-8000; trade name of ajinomoto corporation: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; trade name of Kyoeisha chemical Co: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44, etc.
The resin type pigment dispersants other than the above-mentioned acrylic dispersant may be used alone or in combination of two or more kinds, or may be used in combination with the acrylic dispersant.
The content of the pigment dispersant (a1) may be 5 to 60 parts by weight, and more preferably 15 to 50 parts by weight, based on 100 parts by weight of the pigment. If the content of the pigment dispersant is more than 60 parts by weight, the viscosity may be increased, and if it is less than 5 parts by weight, problems such as difficulty in microparticulation of the pigment or gelation after dispersion may be caused.
Alkali soluble resin (B)
In one embodiment of the present invention, the alkali-soluble resin (B) has reactivity and alkali solubility by the action of light or heat, and any resin known in the art can be selected and used without any particular limitation as long as it functions as a dispersion medium for solid components such as a colorant and functions as a binder resin.
Specifically, the alkali-soluble resin is preferably a copolymer of an unsaturated carboxyl group-containing monomer and another monomer copolymerizable therewith.
Examples of the unsaturated carboxyl group-containing monomer include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated carboxylic acids having 1 or more carboxyl groups in the molecule, such as unsaturated tricarboxylic acids.
Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α -chloroacrylic acid, and carnosic acid.
Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.
The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. Further, the above-mentioned unsaturated polycarboxylic acid may be a mono (2-methacryloyloxyalkyl) ester thereof, and for example, may be mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) succinate, mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate or the like. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of a dicarboxylic polymer at both ends thereof, and examples thereof include ω -carboxy polycaprolactone monoacrylate, ω -carboxy polycaprolactone monomethacrylate and the like.
The carboxyl group-containing monomers may be used alone or in combination of two or more.
Examples of the other monomer copolymerizable with the above carboxyl group-containing monomer include 3, 4-epoxytricyclo [5.2.1.02,6]Decane-9-yl acrylate, 3, 4-epoxytricyclo [5.2.1.02,6](meth) acrylic acid epoxy ester compounds such as decane-8-yl acrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether and the like; aromatic vinyl compounds such as styrene, α -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, indene and the like; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, n-butyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, n-butyl acrylate, isobutyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, 2-butyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxy-butyl acrylate, 2-hydroxy-butyl acrylate, 2-hydroxy-butyl acrylate, 2-hydroxy-butyl acrylate, and 2-butyl acrylate, 2-hydroxy-butyl acrylate, 2-hydroxy-butyl acrylate, 2-butyl acrylate, and, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, propylenePhenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, phenyl methacrylate, 2-phenoxyethyl methacrylate, phenyl methacrylate, 2-methoxyethyl acrylate, methoxyethyl methacrylate, methoxydiethylene glycol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, and mixtures thereof, Unsaturated carboxylic acid esters such as glycerol monoacrylate and glycerol monomethacrylate; aminoalkyl esters of unsaturated carboxylic acids such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α -chloroacrylonitrile, and dicyanovinylene; unsaturated amides such as acrylamide, methacrylamide, α -chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethylmethacrylamide; unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1, 3-butadiene, isoprene and chloroprene; and polymer molecular chains of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate and polysiloxaneAnd macromonomers having a monoacryloyl group or monomethacryloyl group at the terminal of (a). These monomers may be used each alone or in combination of two or more.
In the present specification, "(meth) acrylate" is a term including acrylate and/or methacrylate.
The acid value of the alkali-soluble resin (B) may be 10 to 100KOH mg/g. If the acid value is within the above range, the solubility in the developer is increased, the non-exposed portion is easily dissolved, the sensitivity is increased, and as a result, the pattern of the exposed portion is left during development to improve the film remaining ratio (film remaining ratio), which is preferable. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required for neutralizing 1g of the polymer, and can be usually determined by titration with an aqueous potassium hydroxide solution.
The alkali-soluble resin (B) may have a polystyrene-equivalent weight average molecular weight (hereinafter, simply referred to as "weight average molecular weight") of 3,000 to 200,000, preferably 5,000 to 100,000, as measured by gel permeation chromatography (GPC; with tetrahydrofuran as an eluting solvent). When the molecular weight is within the above range, the hardness of the coating film tends to be increased, the film retention rate tends to be high, the solubility of the unexposed area in the developer tends to be excellent, and the resolution tends to be improved.
The molecular weight distribution [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of the alkali-soluble resin (B) may be 1.5 to 6.0, and preferably 1.8 to 4.0. It is preferable that the molecular weight distribution is in the above range because the developability is excellent.
The content of the alkali-soluble resin (B) may be 1 to 30% by weight, preferably 4 to 20% by weight, based on 100% by weight of the total solid content in the black photosensitive resin composition. When the content of the alkali-soluble resin is within the above range, a black photosensitive resin composition having excellent developability and a cured film having excellent chemical resistance can be easily obtained.
Photopolymerizable compound (C)
In one embodiment of the present invention, the photopolymerizable compound (C) is a compound that can be polymerized by the action of light and a photopolymerization initiator described later, and is polymerized by an exposure process to improve the mechanical properties of a colored pattern or enhance the developability of the alkali-soluble resin.
Examples of the photopolymerizable compound include monofunctional monomers such as nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone; difunctional monomers such as 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol a, and 3-methylpentanediol di (meth) acrylate; and polyfunctional monomers such as trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
The photopolymerizable compound (C) may preferably contain 3 to 10 functional monomers, and more preferably contain 4 to 8 functional monomers.
The content of the photopolymerizable compound (C) may be 1 to 30% by weight, preferably 10 to 20% by weight, based on 100% by weight of the total solid content in the black photosensitive resin composition. When the content of the photopolymerizable compound is within the above range, it is preferable from the viewpoint of the intensity and smoothness of the pixel portion.
Photopolymerization initiator (D)
In one embodiment of the present invention, the photopolymerization initiator (D) may be used without particular limitation as long as it can polymerize the photopolymerizable compound (C). In particular, from the viewpoint of polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, and the like, it is preferable to use one or more compounds selected from the group consisting of acetophenone compounds, benzophenone compounds, triazine compounds, biimidazole compounds, oxime compounds, and thioxanthone compounds as the photopolymerization initiator (D).
Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzildimethylketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propan-1-one, and mixtures thereof, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.
Examples of the benzophenone-based compound include benzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3',4,4' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone.
Specific examples of the triazine compound include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethylene ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethylene ] -1,3, 5-triazine, and 2, 4-bis (trichloromethyl) -6- [2- (furan-2- Yl) ethylene ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethylene ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 4-dimethoxyphenyl) ethylene ] -1,3, 5-triazine, and the like.
Specific examples of the biimidazole-based compound include 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenylbiimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4',5,5' -tetraphenylbiimidazole, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (alkoxyphenyl) biimidazole, 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetrakis (trialkoxyphenyl) biimidazole, 2-bis (2, 6-dichlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole, or biimidazole compounds in which the phenyl group at the 4,4',5,5' position is substituted with an alkoxycarbonylyl group, and the like. Among them, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenyl biimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4',5,5' -tetraphenyl biimidazole, 2-bis (2, 6-dichlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole are preferably used.
Specific examples of the oxime-based compound include o-ethoxycarbonyl- α -oxyimino-1-phenylpropan-1-one, 1, 2-octanedione, -1- (4-phenylthio) phenyl, -2- (o-benzoyloxime), ethanone, -1- (9-ethyl) -6- (2-methylbenzoyl-3-yl) -,1- (o-acetyloxime), and commercially available products include CGI-124 (Ciba Geigy), CGI-224 (Ciba Geigy), Irgacure OXE-01 (Basofv), Irgacure OXE-02 (Basofv), N-1919 (ADEKA), and NCI-831 (ADEKA).
Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.
Further, other photopolymerization initiators and the like than those described above may be added and used within a range not impairing the effects of the present invention. For example, benzoin-based compounds and anthracene-based compounds may be used, and they may be used alone or in combination of two or more.
Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
Examples of the anthracene compound include 9, 10-dimethoxyanthracene, 2-ethyl-9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, and 2-ethyl-9, 10-diethoxyanthracene.
In addition, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9, 10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound, or the like may be used in combination as a photopolymerization initiator.
The content of the photopolymerization initiator (D) may be 0.01 to 10% by weight, preferably 0.01 to 5% by weight, based on 100% by weight of the total solid content in the black photosensitive resin composition. The content range takes into consideration the photopolymerization rate of the photopolymerizable compound and the physical properties of the finally obtained coating film. If the content of the photopolymerization initiator is less than the above range, the polymerization rate is low and the overall process time may be long, whereas if the content is more than the above range, the crosslinking reaction may be out of order due to excessive reaction and the physical properties of the coating film may be deteriorated, and therefore, the photopolymerization initiator is suitably used within the above range.
Further, a photopolymerization initiation aid may be used together with a photopolymerization initiator, and when the photopolymerization initiation aid is used together with the photopolymerization initiator, the black photosensitive resin composition is more highly sensitive and productivity is improved, which is preferable. As the photopolymerization initiation aid, one or more compounds selected from the group consisting of amine compounds and carboxylic acid compounds can be preferably used.
Such a photopolymerization initiator aid is preferably used in an amount of usually 10 moles or less, preferably 0.01 to 5 moles per 1 mole of the photopolymerization initiator. When the photopolymerization initiator is used in the above range, the polymerization efficiency can be improved, and the effect of improving productivity can be expected.
Solvent (E)
In one embodiment of the present invention, the solvent (E) is not particularly limited as long as it is effective in dispersing or dissolving the other components contained in the black photosensitive resin composition of the present invention, and various organic solvents used in the art can be used.
Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether, diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, ketones such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and the like, Alcohols such as glycerol, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ -butyrolactone.
Among the above solvents, from the viewpoint of coatability and drying properties, it is preferable to use an organic solvent having a boiling point of 100 to 200 ℃, more preferably an alkylene glycol alkyl ether acetate, a ketone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate or other ester, and still more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate or other ester. These solvents may be used each alone or in combination of two or more.
The content of the solvent (E) may be usually 60 to 90% by weight, preferably 70 to 85% by weight, based on 100% by weight of the total black photosensitive resin composition. When the above range is satisfied, the coating properties tend to be improved when the coating is performed by a coating apparatus such as a roll coater, a spin coater, a slit coater (also referred to as a die coater), or a spray printer, and therefore, the coating is preferable.
Silica particles (F)
The black photosensitive resin composition according to one embodiment of the present invention may further include silica particles (F).
In one embodiment of the present invention, the silica particles (F) are a component that reduces external light reflection and reflected color tone and improves visibility.
The average particle diameter of the silica particles may be preferably 200 to 400nm, and more preferably 200 to 300 nm. If the average particle diameter of the above silica particles is less than 200nm, external light reflection may increase, reflected color tone may decrease, and visibility may be deteriorated, and if it exceeds 400nm, the pattern surface may become rough.
In one embodiment of the present invention, the content of the silica particles (F) may be 1 to 20% by weight, preferably 2 to 15% by weight, based on 100% by weight of the total solid content in the black photosensitive resin composition. If the content of the silica particles is less than 1% by weight relative to 100% by weight of the total solid content in the black photosensitive resin composition, the external light reflectance may not be reduced, and if the content is more than 20% by weight, the pattern process may be deteriorated.
Additive (G)
The black photosensitive resin composition according to an embodiment of the present invention may further contain an additive (G) as needed, in addition to the above components.
The additive may further include one or more additives selected from the group consisting of other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-gelling agents.
Specific examples of the other polymer compounds include thermosetting resins such as epoxy resins and maleimide resins; and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.
The curing agent is used for deep-section curing and for improving mechanical strength, and specific examples thereof include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds, and the like.
Specific examples of the epoxy compound in the curing agent include bisphenol a type epoxy resins, hydrogenated bisphenol a type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol F type epoxy resins, novolac type epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester type resins, glycidyl amine type resins, brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co) polymer epoxides, isoprene (co) polymer epoxides, glycidyl (meth) acrylate (co) polymers, triglycidyl isocyanurate, and the like.
Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexane dicarboxylic acid bisoxetane, and the like.
The curing agent may be used in combination with a co-curing compound capable of ring-opening polymerizing an epoxy group of the epoxy compound or an oxetane skeleton of the oxetane compound together with the curing agent. Specific examples of the curing assistant compound include polycarboxylic acids, polycarboxylic acid anhydrides, and acid generators. The polycarboxylic acid anhydride may be a commercially available epoxy resin curing agent. Specific examples of the commercially available epoxy resin curing agent include ADEKA HARDENER EH-700 (trade name, manufactured by ADEKA industries, Ltd.), RIKACID HH (trade name, manufactured by Nissian Chemicals & Co., Ltd.), MH-700 (trade name, manufactured by Nissian Chemicals & Co., Ltd.), and the like. The curing agents exemplified above may be used alone or in combination of two or more.
The surfactant may be used for further improving the film formability of the photosensitive resin composition, and a silicone surfactant, a fluorine surfactant, or the like may be preferably used.
Examples of the silicone-based surfactant include commercially available silicone surfactants such as DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 available from dow corning dongli silicone corporation; TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 and the like of GE Toshiba Silicone company. Examples of the fluorine-based surfactant include commercially available MEGAFAC F-470, F-471, F-475, F-482, F-489 and F-554 (Dainippon ink chemical industries, Ltd.); BM-1000, BM-1100(BM Chemie Co.); FLUORAD FC-135/FC-170C/FC-430 (Sumitomo 3M strain), and the like. The above-exemplified surfactants may be used each alone or in combination of two or more.
The adhesion promoter is an additive used for improving coatability and adhesion to a substrate, and may include a silane coupling agent containing a reactive substituent selected from the group consisting of a carboxyl group, (meth) acryloyl group, isocyanate group, epoxy group, and a combination thereof.
Specific examples of the silane coupling agent include trimethoxysilylbenzoic acid, gamma-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, gamma-isocyanatopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.
Specific examples of the antioxidant include 2,2' -thiobis (4-methyl-6-tert-butylphenol) and 2, 6-di-tert-butyl-4-methylphenol.
Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.
Specific examples of the anti-gelling agent include sodium polyacrylate and the like.
The additives not contained in the above-mentioned additives may be appropriately added to the composition by those skilled in the art within a range not impairing the effects of the present invention. For example, the additive may be used in an amount of 0.05 to 10 wt%, preferably 0.1 to 10 wt%, more preferably 0.1 to 5 wt% based on 100 wt% of the entire black photosensitive resin composition, but is not limited thereto.
The black photosensitive resin composition according to one embodiment of the present invention has an advantage that it can be cured at a low temperature and is advantageous when applied to a flexible substrate.
Specifically, the black photosensitive resin composition can be cured at 100 ℃ or lower, for example, 80 to 100 ℃. The cured film obtained by curing the black photosensitive resin composition at 80 to 100 ℃ may be immersed in Propylene Glycol Monomethyl Ether Acetate (PGMEA) at 100 ℃ for 10 minutes, and the film retention may be 80% or more.
The method for producing the black photosensitive resin composition of the present invention is not particularly limited, and the method for producing the black photosensitive resin composition known in the art is used.
For example, it can be obtained by adding a colorant to a solvent, adding the remaining components and other additives, and stirring. In this case, the colorant may be added in the form of a paste in which a pigment or the like is dissolved or dispersed in a solvent or an alkali-soluble resin in advance, and the silica particles may be dispersed in advance together with the pigment in the production of the paste. When the additive is in the form of a solution, it may be previously added to the solvent together with the colorant.
The black photosensitive resin composition thus produced can be preferably used for producing a black matrix of an image display device. The black matrix is a concept including a spacer for maintaining a cell thickness (cell gap), a black column spacer (black matrix integrated spacer), or the like.
Accordingly, one embodiment of the present invention relates to a black matrix formed using the black photosensitive resin composition.
A typical patterning process for forming a black matrix according to a photolithography method includes:
a) a step of coating a substrate with a black photosensitive resin composition;
b) a pre-baking step of drying the solvent;
c) irradiating the obtained coating film with active light through a photomask to cure the exposed portion;
d) a step of performing a developing step of dissolving the unexposed portion with an alkali aqueous solution; and
e) the steps of drying and postbaking are carried out.
The substrate is a glass substrate or a polymer plate. As the glass substrate, soda lime glass, barium-or strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz, or the like can be used particularly preferably. Examples of the polymer sheet include polycarbonate, acryl, polyethylene terephthalate, polyether sulfide, polysulfone, and the like.
In this case, coating can be performed by a wet coating method using a coating apparatus such as a roll coater, a spin coater, a slit coater (also referred to as a die coater), or a spray printer in order to obtain a desired thickness.
In the prebaking, heating is performed by an oven, a hot plate, or the like. In this case, the heating temperature and the heating time in the prebaking are appropriately selected depending on the solvent used, and are carried out, for example, at 80 to 150 ℃ and preferably at 80 to 100 ℃ for 1 to 30 minutes.
The exposure after the prebaking is performed by an exposure machine, and exposure is performed through a photomask, so that only a portion corresponding to the pattern is exposed to light. In this case, for example, visible light, ultraviolet light, X-rays, electron beams, and the like can be used as the light to be irradiated.
The alkali development after the exposure is performed for the purpose of removing the colored photosensitive resin composition in the non-exposed portion, and a desired pattern is formed by the development. As a developer suitable for the alkali development, for example, an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal can be used. In particular, the treatment is carried out by using an aqueous alkaline solution containing 1 to 3 wt% of a carbonate such as sodium carbonate, potassium carbonate or lithium carbonate at a temperature of 10 to 50 ℃, preferably 20 to 40 ℃ by using a developing machine, an ultrasonic cleaning machine or the like.
The post-baking is performed to improve the adhesion between the patterned film and the substrate, and is performed by performing a heat treatment at 80 to 220 ℃ for 10 to 120 minutes. The post-baking is performed by an oven, a hot plate, or the like as in the pre-baking.
One embodiment of the present invention relates to an image display device including the black matrix.
The image display device of the present invention includes a configuration known in the art, in addition to the black matrix described above. That is, the image display device to which the black matrix of the present invention is applicable is included in the present invention. For example, a transmissive liquid crystal display device is known in which a liquid crystal layer is formed by opposing counter electrode substrates each including a thin film diode (TFT element), a pixel electrode, and an alignment layer at a predetermined interval and injecting a liquid crystal material into the gap. In addition, there is also a reflective liquid crystal display device in which a reflective layer is provided between a substrate of a color filter and a colored layer. As another example, there is a liquid crystal display device including a Thin Film Transistor (TFT) substrate mounted on a transparent electrode of a color filter, and a backlight fixed at a position where the TFT substrate overlaps the color filter.
The present invention will be described in more detail below with reference to examples, comparative examples, and experimental examples. It is apparent to those skilled in the art that these examples, comparative examples, and experimental examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.
Synthesis example 1: production of alkali-soluble resin (B-1)
A1 liter separation type flask having an inner volume and equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas inlet was charged with 277g of methoxybutyl acetate, and after the temperature was raised to 80 ℃,3, 4-epoxytricyclo [5.2.1.0 ] was added dropwise over 5 hours2,6]Decane-9-yl acrylate with 3, 4-epoxytricyclo [5.2.1.02,6]Mixture of decane-8-yl acrylate [50:50 (molar ratio)]301g, 49g of methacrylic acid, and 23g of azobisdimethylvaleronitrile were dissolved in 350g of methoxybutyl acetate, and the resulting mixture was aged for 3 hours to obtain an alkali-soluble resin solution (B-1) [ solid content (NV)35.0 wt.% ]]. The acid value (dry) of the resulting alkali-soluble resin was 69.8KOH mg/g, the weight-average molecular weight (Mw) was 12,300, and the molecular weight distribution (Mw/Mn) was 2.1.
Production examples 1 to 7: colorant dispersion liquid production
The components were mixed in the following composition of table 1 to prepare a colorant dispersion (wt%).
Specifically, a colorant dispersion is produced by mixing and charging a composition comprising the following components in a weight ratio of 50:50 with a rigid grinding medium (zirconia beads) having an average particle size of 0.1mm, and then dispersing the pigment for 4 to 6 hours by a bead mill: organic black pigments (OBP, Irgaphor S100CF) or mixtures of organic black pigments (Irgaphor S100CF) and carbon black as pigments; the alkali-soluble resin synthesized in the above synthesis example 1 as a dispersion resin (solid content conversion) [ 35.0 wt% of solid content (NV) ]; an acrylic polymer dispersant (DISPERBYK-2000) (in terms of solid content) [ 40.0 wt% of solid content (NV) ], which is a dispersant; optional silica particles (Sakai Chemical) with an average particle diameter of 200nm), barium sulfate (manufacturer: Sakai Chemical with an average particle diameter of 200nm), or zirconium dioxide (manufacturer: Saka (Sakata) with an average particle diameter of 200 nm); and propylene glycol monomethyl ether acetate as a solvent.
[ Table 1]
Examples and comparative examples: production of Black photosensitive resin composition
The components were mixed according to the composition of table 2 below to produce a black photosensitive resin composition (wt%).
The obtained mixture was uniformly dissolved and dispersed in 85 wt% of propylene glycol monomethyl ether acetate so that the solid content concentration became 15 mass%, thereby obtaining a black photosensitive resin composition.
[ Table 2]
A-1 to A-7: the colorant dispersion liquids of examples 1 to 7 were prepared. The numerical values of A-1 to A-7 are the sum of the solid contents of the pigment, dispersant and dispersion resin contained in the colorant dispersion.
B-1: synthesis of alkali-soluble resin of example 1
C-1: dipentaerythritol hexaacrylate
D-1: PBG-327 (made by Tronly corporation)
G-1: DIC company F554
G-2: sumitomo chemical company ESCN
Experimental example 1: evaluation of physical Properties of colored substrate
The results of evaluation of the reflectance, the color tone of reflection, the optical density, and the transmittance at 900nm after producing colored substrates using the black photosensitive resin compositions produced in the comparative examples and examples as follows are shown in table 3 below.
< production of colored substrate >
The glass substrate (Corning Corp.) having a thickness of 5 cm.times.5 cm was washed with a neutral detergent and water and then dried. The black photosensitive resin compositions produced in the comparative examples and examples were applied to the glass substrate so that the final film thickness became 1.5 μm, and the solvent was removed by pre-baking at 100 ℃, i.e., drying for 1 minute to 2 minutes and 30 seconds. Then, the exposure amount is 50-150 mJ/cm2The substrate was exposed to light to form a pattern, and the unexposed portion was removed using an aqueous alkali solution. Then, the resultant was baked at 100 ℃ for 30 to 60 minutes to produce a colored substrate.
(1) Reflectance (Y) and reflected color sensation (a)*)
After a colored substrate was produced in the same manner except that the test photomask was not used, the reflectance and the color tone of reflection with respect to a standard light source D65 were measured by an integrating sphere reflectance measuring instrument (CM-3700D, konica minolta).
(2) Optical Density (optical Density)
The optical density of the produced colored pattern substrate was measured by an optical density (o.d.) measuring instrument (X-rite 301Densitometer), and the value divided by the final film thickness of 1.5 μm, i.e., o.d./μm, was described.
(3) Transmittance at 900nm
The transmittance at 900nm (Near-infrared) was measured using an ultraviolet-visible (UV-vis) spectrophotometer (UV-2600, Shimadzu corporation).
[ Table 3]
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Example 1 | Example 2 | Example 3 | |
| OD/μm | 1.60 | 1.61 | 1.60 | 1.58 | 1.62 | 1.64 | 1.64 |
| Y(D65) | 5.0 | 5.0 | 5.0 | 4.7 | 4.5 | 4.4 | 4.4 |
| a* | 1.3 | 1.3 | 1.2 | 1.1 | 0.9 | 0.8 | 0.8 |
| Near infrared (%) | 89 | 88 | 88 | 48 | 89 | 88 | 87 |
As can be seen from Table 3, the cured films formed from the black photosensitive resin compositions of examples 1 to 3 had reduced external light reflection and reduced color tone, and thus had improved visibility. In addition, it is clear that the black photosensitive resin compositions of examples 1 to 3 have high transmittance in the infrared region, and thus do not interfere with infrared sensing.
On the other hand, it is found that the cured films formed from the black photosensitive resin compositions of comparative examples 1 to 4 have poor external light reflection and poor color sensitivity of reflection, and thus have low visibility. In particular, it is found that the black photosensitive resin composition of comparative example 4 using carbon black has low transmittance in the infrared region, and thus interferes with infrared ray sensitivity.
While certain features of the invention have been described in detail above, it will be apparent to those skilled in the art that this detailed description is merely a preferred embodiment, and that the scope of the invention is not limited thereto. Those skilled in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above-described contents.
It is therefore intended that the actual scope of the invention be defined by the scope of the appended claims and their equivalents.
Claims (9)
1. A black photosensitive resin composition comprising a black colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, the black colorant being composed of a black organic pigment,
the cured film formed from the black photosensitive resin composition has a reflectance Y of 4.5% or less with respect to a standard light source D65.
2. The black photosensitive resin composition according to claim 1, wherein the cured film formed from the black photosensitive resin composition has an O.D./μm of 1.6 or more at a film thickness of 1.5 μm.
3. The black photosensitive resin composition according to claim 1, wherein a cured film formed from the black photosensitive resin composition has a transmittance of 80% or more at 900 nm.
4. The black photosensitive resin composition according to claim 1, further comprising silica particles.
5. The black photosensitive resin composition according to claim 4, wherein the silica particles have an average particle diameter of 200 to 400 nm.
6. The black photosensitive resin composition according to claim 4, wherein the content of the silica particles is 1 to 20% by weight based on 100% by weight of the total solid content in the black photosensitive resin composition.
7. The black photosensitive resin composition according to claim 1, which is used for a flexible substrate.
8. A black matrix formed using the black photosensitive resin composition according to any one of claims 1 to 7.
9. An image display device comprising the black matrix of claim 8.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2020-0021838 | 2020-02-21 | ||
| KR1020200021838A KR20210106824A (en) | 2020-02-21 | 2020-02-21 | Black Photosensitive Resin Composition, Black Matrix and Display Device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113296358A true CN113296358A (en) | 2021-08-24 |
Family
ID=77318964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110193301.0A Pending CN113296358A (en) | 2020-02-21 | 2021-02-20 | Black photosensitive resin composition, black matrix and image display device |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR20210106824A (en) |
| CN (1) | CN113296358A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024092524A1 (en) * | 2022-11-01 | 2024-05-10 | Materion Precision Optics (Shanghai) Limited | Black adhesion film for lidar cover window structure |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0844049A (en) * | 1994-08-01 | 1996-02-16 | Sekisui Chem Co Ltd | Colored resist film |
| WO2013027936A2 (en) * | 2011-08-22 | 2013-02-28 | 성균관대학교 산학협력단 | Black photosensitive resin composition and image display device having same |
| WO2014208348A1 (en) * | 2013-06-24 | 2014-12-31 | 東レ株式会社 | Black resin composition for touch panels |
| CN107526249A (en) * | 2016-06-15 | 2017-12-29 | 山阳色素株式会社 | Black pigment compositions and the black coating film formation composition containing it |
| KR20180086132A (en) * | 2017-01-20 | 2018-07-30 | 동우 화인켐 주식회사 | A photo sensitive resin composition, a color filter comprising a black metrics, a column spacer or black column spacer prepared by using the composition, and a display devide comprising the color filter |
| KR20190053131A (en) * | 2017-11-09 | 2019-05-17 | 동우 화인켐 주식회사 | Colored photosensitive resin composition, color filter prepared by using the same, and display device comprising the color filter |
| CN109765756A (en) * | 2017-11-09 | 2019-05-17 | 东友精细化工有限公司 | Photosensitive composition, colour filter and display device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150062889A (en) | 2013-11-29 | 2015-06-08 | 주식회사 엘지화학 | Photo-sensitive resin composition for black column spacer |
-
2020
- 2020-02-21 KR KR1020200021838A patent/KR20210106824A/en not_active Application Discontinuation
-
2021
- 2021-02-20 CN CN202110193301.0A patent/CN113296358A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0844049A (en) * | 1994-08-01 | 1996-02-16 | Sekisui Chem Co Ltd | Colored resist film |
| WO2013027936A2 (en) * | 2011-08-22 | 2013-02-28 | 성균관대학교 산학협력단 | Black photosensitive resin composition and image display device having same |
| WO2014208348A1 (en) * | 2013-06-24 | 2014-12-31 | 東レ株式会社 | Black resin composition for touch panels |
| CN107526249A (en) * | 2016-06-15 | 2017-12-29 | 山阳色素株式会社 | Black pigment compositions and the black coating film formation composition containing it |
| KR20180086132A (en) * | 2017-01-20 | 2018-07-30 | 동우 화인켐 주식회사 | A photo sensitive resin composition, a color filter comprising a black metrics, a column spacer or black column spacer prepared by using the composition, and a display devide comprising the color filter |
| KR20190053131A (en) * | 2017-11-09 | 2019-05-17 | 동우 화인켐 주식회사 | Colored photosensitive resin composition, color filter prepared by using the same, and display device comprising the color filter |
| CN109765756A (en) * | 2017-11-09 | 2019-05-17 | 东友精细化工有限公司 | Photosensitive composition, colour filter and display device |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024092524A1 (en) * | 2022-11-01 | 2024-05-10 | Materion Precision Optics (Shanghai) Limited | Black adhesion film for lidar cover window structure |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20210106824A (en) | 2021-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111399340B (en) | Colored photosensitive resin composition, color filter comprising same, and display device | |
| CN107229183B (en) | Red photosensitive resin composition, color filter manufactured using the same, and display device including the color filter | |
| KR100994633B1 (en) | Black-colored photosensitive resin composition, black matrix prepared by using thereof and color filter comprising the black matrix | |
| JP6722742B2 (en) | Colored dispersion liquid, colored photosensitive resin composition containing the same, pattern layer produced using the resin composition, color filter containing the pattern layer, and display device containing the color filter | |
| KR101910674B1 (en) | A black photosensitive resin composition, color filter and display device comprising the same | |
| CN107272337B (en) | Cyan photosensitive resin composition, cyan color filter comprising same, and display element | |
| KR20120021752A (en) | A colored photosensitive resin composition, color filter and liquid crystal display device having the same | |
| KR20140104768A (en) | Colored photosensitive resin composition comprising the same | |
| KR20140008033A (en) | Colored photosensitive resin composition and color filter using the same | |
| KR20150109952A (en) | Colored Photosensitive Resin Composition and Color Filter Comprising the Same | |
| CN113296358A (en) | Black photosensitive resin composition, black matrix and image display device | |
| CN108333871B (en) | Colored photosensitive resin composition, color filter and display device comprising same | |
| KR101420868B1 (en) | A colored photosensitive resin composition, color filter and liquid crystal display device having the same | |
| KR20140020495A (en) | A colored photosensitive resin composition, color filter and liquid crystal display device having the same | |
| KR101805197B1 (en) | A colored photosensitive resin composition, colored pattern,color filter and liquid crystal display device having the same | |
| KR102012520B1 (en) | A colored photosensitive resin composition, colored pattern,color filter and liquid crystal display device having the same | |
| CN109696800B (en) | Colored photosensitive resin composition, pattern layer, color filter and display device | |
| JP4872233B2 (en) | Colored photosensitive resin composition and color filter formed using the same | |
| CN104898373B (en) | Colored photosensitive resin composition and color filter using same | |
| KR20110120816A (en) | Colored photosensitive resin composition, color filter and display device having the same | |
| KR20140020502A (en) | A colored photosensitive resin composition, color filter and liquid crystal display device having the same | |
| KR102028489B1 (en) | A black photosensitive resin composition, color filter and display device comprising the same | |
| KR101403242B1 (en) | A colored photosensitive resin composition, color filter and liquid crystal display device having the same | |
| KR101897925B1 (en) | A photo sensitive resin composition, a color filter comprising a black metrics, a column spacer or black column spacer prepared by using the composition, and a display device comprising the color filter | |
| CN105988290B (en) | Colored photosensitive resin composition, color filter and display device comprising the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |