CN114730129A - Photosensitive resin composition and image display device - Google Patents

Photosensitive resin composition and image display device Download PDF

Info

Publication number
CN114730129A
CN114730129A CN202180006609.8A CN202180006609A CN114730129A CN 114730129 A CN114730129 A CN 114730129A CN 202180006609 A CN202180006609 A CN 202180006609A CN 114730129 A CN114730129 A CN 114730129A
Authority
CN
China
Prior art keywords
resin
resin composition
photosensitive resin
mass
acid
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
Application number
CN202180006609.8A
Other languages
Chinese (zh)
Inventor
柳正义
木下健宏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Holdings Corp
Original Assignee
Showa Denko KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Showa Denko KK filed Critical Showa Denko KK
Publication of CN114730129A publication Critical patent/CN114730129A/en
Pending legal-status Critical Current

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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • 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
    • G02F1/133514—Colour filters
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0385—Macromolecular compounds which are rendered insoluble or differentially wettable using epoxidised novolak resin
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/86—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • H10K50/865—Arrangements for improving contrast, e.g. preventing reflection of ambient light comprising light absorbing layers, e.g. light-blocking layers

Abstract

A photosensitive resin composition which can give a cured resin film having excellent developability and colorant dispersibility and having a high elastic recovery rate. A photosensitive resin composition comprising a resin (A), a photopolymerization initiator (B), a solvent (C), a colorant (D), and a reactive diluent (E), wherein the resin (A) is a reaction product of a polybasic acid (a3) and a reaction product of an epoxy resin (a1) and an ethylenically unsaturated monocarboxylic acid (a2), and the epoxy resin (a1) is a condensation product of a dihydric phenol compound and an aldehyde compound, and epichlorohydrin. The ratio of each structural unit derived from the components (a1) to (a3) in the resin (a) is: the amount of the structural unit derived from the ethylenically unsaturated group-containing monocarboxylic acid (a2) is 0.85 to 1.00 mol and the amount of the structural unit derived from the polybasic acid (a3) is 0.10 to 0.70 mol, based on 1.00 mol of the epoxy group-derived site of the epoxy resin (a 1).

Description

Photosensitive resin composition and image display device
Technical Field
The invention relates to a photosensitive resin composition and an image display device.
This application claims priority based on Japanese application No. 2020-.
Background
Conventionally, spacer particles have been used for a liquid crystal display panel in order to keep a constant interval (cell interval) between 2 substrates. As the spacer, glass beads, plastic beads, or the like having a predetermined particle diameter are used. Generally, the spacer particles are randomly arranged on a transparent substrate such as a glass substrate. If the spacer exists in the pixel formation region of the liquid crystal display panel, the following problem occurs: a phenomenon of reflection of the spacer occurs, or incident light is scattered to lower the contrast.
In order to solve this problem, dot-shaped or stripe-shaped spacers formed by photolithography using a photosensitive resin composition are used instead of the spacer particles. The spacer can be formed by a method in which a photosensitive resin composition is applied to a substrate, exposed to ultraviolet light through a predetermined mask, and then developed. Therefore, the spacer formed of the cured product of the photosensitive resin composition is formed only in a predetermined place other than the pixel formation region in the liquid crystal display panel. Therefore, the above-mentioned problems in the case of using the spacer can be solved by forming the spacer by photolithography using the photosensitive resin composition.
In addition, for the organic EL display panel, a resist for discriminating the partition walls of each color is used. However, since the partition walls are transparent, they are color-mixed and reflect light from the outside. In order to prevent reflection, a circularly polarizing plate needs to be mounted.
In order to solve this problem, a method of preventing light reflection is studied using a black PDL (Pixel Defining Layer) in which barrier rib portions are colored black. A foldable or foldable display can be produced as long as it can prevent reflected light without mounting a circularly polarizing plate.
As a photosensitive resin composition used as a material of a spacer provided in a liquid crystal display panel, for example, a radiation-sensitive resin composition described in patent document 1 is known.
Patent document 2 discloses a photosensitive composition that is preferably used as a resist for forming a color filter, a black matrix, a black columnar spacer, and the like.
Patent document 3 describes a photosensitive resin composition for a black columnar spacer, which contains an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a light-shielding agent.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2001-302712
Patent document 2: japanese patent laid-open publication No. 2011-
Patent document 3: japanese patent laid-open publication No. 2013-134263
Disclosure of Invention
Problems to be solved by the invention
Recently, in liquid crystal display elements and black matrixes, color filters, black columnar spacers, and the like that form the liquid crystal display elements; or black PDL forming the organic EL display panel, more strict dimensional accuracy is required. Therefore, a photosensitive resin composition used as a material for these is required to have more excellent developability. In addition, in order to improve the display characteristics of the liquid crystal display device, it is necessary that a resin cured film obtained by curing the photosensitive resin composition used in the above-mentioned applications has good colorant dispersibility. Further, in order to prevent deterioration of the liquid crystal display element due to external impact, a resin cured film obtained by curing the photosensitive resin composition used for the above-mentioned applications is required to have a high elastic recovery rate.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a photosensitive resin composition capable of obtaining a resin cured film having excellent developability, good colorant dispersibility, and high elastic recovery.
Another object of the present invention is to provide a cured resin film of the photosensitive resin composition of the present invention, and an image display device including the cured resin film.
Means for solving the problems
The present invention for solving the above problems is configured as follows.
[ 1] A photosensitive resin composition characterized by containing:
a resin (A),
A photopolymerization initiator (B),
A solvent (C),
A colorant (D), and
a reactive diluent (E) which is a mixture of,
the resin (A) has a structure (a11) derived from an epoxy resin (a1), a structure (a21) derived from an ethylenically unsaturated group-containing monocarboxylic acid (a2), and a structure (a31) derived from a polybasic acid (a3),
the resin (A) is a reaction product obtained by adding the polybasic acid (a3) to the reaction product (R1) of the epoxy resin (a1) and the ethylenically unsaturated group-containing monocarboxylic acid (a2),
the epoxy resin (a1) is a reaction product of a phenolic resin (a4) and an epihalohydrin,
the phenol resin (a4) is a condensate of a dihydric phenol compound and an aldehyde compound,
the ratio of each structural unit derived from the components (a1) to (a3) in the resin (a) is: the amount of the structural unit derived from the ethylenically unsaturated group-containing monocarboxylic acid (a2) is 0.85 to 1.00 mol and the amount of the structural unit derived from the polybasic acid (a3) is 0.10 to 0.70 mol, based on 1.00 mol of the epoxy group-derived site of the epoxy resin (a 1).
[ 2] the photosensitive resin composition according to [ 1], which contains, when the total of the resin (A), the photopolymerization initiator (B), the colorant (D) and the reactive diluent (E) is 100 parts by mass:
1 to 50 parts by mass of the resin (A),
0.01 to 5 parts by mass of the photopolymerization initiator (B),
10 to 2000 parts by mass of the solvent (C),
1 to 50 parts by mass of the colorant (D), and
1 to 60 parts by mass of the reactive diluent (E).
[ 3] the photosensitive resin composition according to [ 1] or [ 2], wherein the acid value of the resin (A) is 20 to 300KOHmg/g, and the unsaturated group equivalent is 100 to 4000 g/mol.
The photosensitive resin composition according to any one of [ 1] to [ 3], wherein the colorant (D) comprises an inorganic black pigment and an organic black pigment.
[ 5 ] the photosensitive resin composition according to any one of [ 1] to [4 ], wherein the phenolic resin (a4) is a condensate of bisphenol A and formaldehyde.
The photosensitive resin composition according to any one of [ 1] to [ 5 ], wherein the ethylenically unsaturated group-containing monocarboxylic acid (a2) is at least one member selected from the group consisting of (meth) acrylic acid and 2- (meth) acryloyloxyethylsuccinic acid.
The photosensitive resin composition according to any one of [ 1] to [ 6 ], wherein the polybasic acid (a3) is at least one selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride, and 1,2, 4-cyclohexanetricarboxylic anhydride.
A cured resin film of the photosensitive resin composition according to any one of [ 1] to [ 7 ].
An image display device characterized by comprising the cured resin film described in [ 8 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The photosensitive resin composition of the invention can obtain a resin cured film with excellent developing property, high dimensional accuracy, good colorant dispersibility and high elastic recovery rate. Therefore, the photosensitive resin composition of the present invention is suitable as a material for black PDL, black matrix, color filter, and black column spacer.
The resin cured film of the resin composition of the present invention is suitable as a black PDL, a black matrix, a color filter, and a black columnar spacer which are members of an image display device.
Detailed Description
The photosensitive resin composition of the present invention, the cured resin film thereof, and the image display device are described in detail below. The present invention is not limited to the embodiments described below.
[ photosensitive resin composition ]
The photosensitive resin composition of the present embodiment contains a resin (a), a photopolymerization initiator (B), a solvent (C), a colorant (D), and a reactive diluent (E).
[ resin (A) ]
The resin (a) has a structure (a11) derived from an epoxy resin (a1), a structure (a21) derived from an ethylenically unsaturated group-containing monocarboxylic acid (a2), and a structure (a31) derived from a polybasic acid (a 3). The resin (a) is a reaction product obtained by adding the polybasic acid (a3) to the reaction product (R1) of the epoxy resin (a1) and the ethylenically unsaturated group-containing monocarboxylic acid (a 2). The epoxy resin (a1) is a reaction product of a phenol resin (a4) and an epihalohydrin, and the phenol resin (a4) is a condensate of a dihydric phenol compound and an aldehyde compound.
The ratio of each structural unit derived from the components (a1) to (a3) in the resin (a) is as follows. The amount of the structural unit derived from the ethylenically unsaturated group-containing monocarboxylic acid (a2) is 0.85 to 1.00 mol per 1.00 mol of the epoxy group-derived site of the epoxy resin (a 1). The amount of the structural unit derived from the polybasic acid (a3) is 0.10 to 0.70 mol per 1.00 mol of the site derived from the epoxy group of the epoxy resin (a 1).
The resin (a) may contain a structural unit derived from other arbitrary components within a range not to impair the effects of the present invention.
The dihydric phenol compound is a compound containing 2 aromatic hydroxyl groups in 1 molecule. Examples thereof include bisphenol A, bisphenol F, 4' -dihydroxybenzophenone, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3-methylphenyl) ether, bis (3, 5-dimethyl-4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bisphenols such as bis (4-hydroxy-3-methylphenyl) sulfide, bis (3, 5-dimethyl-4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfone, bis (3, 5-dimethyl-4-hydroxyphenyl) sulfone, and 1, 1' -bis (3-tert-butyl-6-methyl-4-hydroxyphenyl) butane;
dioxybenzenes such as hydroquinone and resorcinol;
2-membered naphthols such as dihydroxynaphthalene, bis (hydroxynaphthyl) methane, and 1, 1' -binaphthol;
2-membered phenols having an alicyclic structure such as bis (4-hydroxyphenyl) dicyclopentane, 1-bis (4-hydroxyphenyl) cyclohexane, 1-bis (4-hydroxy-3-methylphenyl) cyclohexane and 1, 1-bis (3, 5-dimethyl-4-hydroxyphenyl) cyclohexane;
and 4,4 ' -dihydroxybiphenyl-3, 3 ', 5,5 ' -tetramethylbiphenyl, and the like, but are not particularly limited. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds. Among them, from the viewpoint of developability, colorant dispersibility, and elastic recovery when used in a photosensitive resin composition, a compound having 2 4-hydroxyphenyl groups is preferable, bisphenols are more preferable, and bisphenol a and bisphenol F are even more preferable.
The aldehyde compound is not particularly limited as long as it has 1 or more formyl groups in the molecule, and examples thereof include formaldehyde, acetaldehyde, benzaldehyde, crotonaldehyde, and hydroxybenzaldehyde. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds. Among them, formaldehyde is preferable from the viewpoint of developability, colorant dispersibility, and elastic recovery when used in a photosensitive resin composition.
As the epihalohydrin, epichlorohydrin, epiiodohydrin, epibromohydrin, β -methylepichlorohydrin, and the like can be used. From the viewpoint of reactivity with a condensate of a dihydric phenol compound and an aldehyde compound, epichlorohydrin is preferable. The reaction product of the phenolic resin (a4) and the epihalohydrin is not limited to a reaction product obtained by reacting the phenolic resin (a4) and the epihalohydrin. As long as the structure of the reactant is the same as that of the above reactant. For example, the hydroxyl group of the phenolic resin (a4) may be allyl etherified, and then the allyl group may be oxidized to produce a glycidyl ether.
The weight average molecular weight of the phenolic resin (a4) is preferably 3000 to 30000, more preferably 4000 to 20000, and further preferably 5000 to 15000.
The weight average molecular weight of the epoxy resin (a1) is preferably 4000 to 30000, more preferably 5000 to 20000, and further preferably 6000 to 15000.
The epoxy equivalent is preferably 100 to 5000, more preferably 150 to 1000, and further preferably 200 to 600.
The above monocarboxylic acid having an ethylenically unsaturated group (a2) is not particularly limited as long as it is a compound having an ethylenically unsaturated group and 1 carboxyl group in 1 molecule, and examples thereof include (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, α -bromo (meth) acrylic acid, β -furanyl (meth) acrylic acid, crotonic acid, propiolic acid, cinnamic acid, α -cyanocinnamic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, monomethyl fumarate, monoethyl itaconate and the like. They may be used alone, or 2 or more kinds thereof may be used. Among them, (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid are preferable from the viewpoints of availability and reactivity with the epoxy resin (a 1).
Examples of the polybasic acid (a3) include maleic anhydride, itaconic anhydride, citraconic anhydride, succinic anhydride, tetrahydrophthalic anhydride, and 1,2, 4-cyclohexanetricarboxylic anhydride.
The ratio of each structural unit derived from the components (a1) to (a3) in the resin (a) used in the present embodiment is as follows.
The amount of the structural unit derived from the monocarboxylic acid (a2) having an ethylenically unsaturated group is 0.85 to 1.00 mol, preferably 0.90 to 1.00 mol, and more preferably 0.95 to 1.00 mol, based on 1.00 mol of the epoxy group-derived site of the epoxy resin (a 1). It is particularly preferable that the structural unit derived from the ethylenically unsaturated group-containing monocarboxylic acid (a2) is 0.99 to 1.00 mol, that is, it is preferable that the resin (a) contains substantially no unreacted epoxy group. When the amount of the structural unit derived from the ethylenically unsaturated group-containing monocarboxylic acid (a2) is 0.85 mol or more, the resin (a) sufficiently contains an unsaturated group. Therefore, as the photosensitive resin composition, a resin cured film having excellent curability and developability, good colorant dispersibility, and high hardness and elastic recovery rate can be obtained.
The structural unit derived from the polybasic acid (a3) is preferably 0.10 to 0.70 mol, more preferably 0.15 to 0.50 mol, and still more preferably 0.20 to 0.40 mol, based on 1.00 mol of the epoxy group-derived site of the epoxy resin (a 1). If the structural unit derived from the polybasic acid (a3) is 0.10 mol or more, the acid value of the resin (a) becomes sufficiently high, and no residue of unexposed portions is generated in the developing step, and good developability as a photosensitive resin composition can be obtained. Further, if the structural unit derived from the polybasic acid (a3) is 0.70 mol or less, the exposed portion is not damaged in the developing step, and good developability can be obtained.
The "1.00 mol of a site derived from an epoxy group" means the number of moles of an unreacted epoxy group before addition of the monocarboxylic acid (a2) having an ethylenically unsaturated group and the polybasic acid (a 3).
The weight average molecular weight of the resin (A) is preferably 1000 to 20000, more preferably 3000 to 10000, and further preferably 5000 to 7500. When the weight average molecular weight is 1000 or more, a developed pattern is less likely to be broken in a developing step after application and exposure of the photosensitive resin composition, and thus it is preferable. The weight average molecular weight is preferably 20000 or less because the developing time can be adjusted to an appropriate range in the developing step after application and exposure of the photosensitive resin composition.
The weight average molecular weight was measured by Gel Permeation Chromatography (GPC) under the following conditions, and was a value in terms of standard polystyrene.
Column: ショウデックス (registered trademark) LF-804+ LF-804 (manufactured by Showa Denko K.K.)
Column temperature: 40 deg.C
Sample preparation: 0.2% by mass tetrahydrofuran solution of resin (A)
Developing solvent: tetrahydrofuran (THF)
A detector: differential refractometer (ショウデックス (registered trademark) RI-71S) (manufactured by SHOWA ELECTRIC CORPORATION)
Flow rate: 1mL/min
The acid value (JIS K69015.3) of the resin (A) is not limited as long as the desired effect of the present invention is exhibited, but is preferably 20 to 300KOHmg/g, more preferably 30 to 200KOHmg/g, and still more preferably 40 to 125 KOHmg/g. When the acid value is 20KOHmg/g or more, the developability of the photosensitive resin composition is good. On the other hand, if the acid value is 300KOHmg/g or less, the portion that is photo-cured by applying and exposing the photosensitive resin composition is not easily dissolved in the developer, and thus it is preferable.
The unsaturated group equivalent of the resin (a) in the present embodiment is not limited as long as the desired effect of the present invention is exerted, but is preferably 100 to 4000 g/mole, more preferably 200 to 2000 g/mole, and further preferably 250 to 500 g/mole. When the unsaturated group equivalent is 100 g/mole or more, the developability of the photosensitive resin composition becomes good. On the other hand, if the unsaturated group equivalent is 4000 g/mole or less, the sensitivity of the photosensitive resin composition becomes higher, and a finer pattern can be formed. In addition, the cured product of the photosensitive resin composition is improved in hardness, and a resin cured film having a high elastic recovery rate can be obtained.
The unsaturated group equivalent is the mass of the resin (a) per 1 mol of the unsaturated bond (olefinic carbon-carbon double bond) in the resin (a). The unsaturated group equivalent can be determined by dividing the mass of the resin (a) by the number of moles of unsaturated groups in the resin (a) (g/mole). In the present specification, the unsaturated group equivalent of the resin (a) is a theoretical value calculated from the amount of the ethylenically unsaturated group-containing monocarboxylic acid (a2) added to the resin (a) for introducing an unsaturated group.
[ method for producing resin (A) ]
Next, a method for producing the resin (a) of the present embodiment will be described.
As the method for producing the resin (a) of the present embodiment, the following method is preferably used. First, an epoxy resin (a1) which is a reactant of a condensate of a dihydric phenol compound and an aldehyde compound and an epihalohydrin is obtained in a solvent using a catalyst as necessary. The precursor of the resin (a) is synthesized by reacting the obtained epoxy resin (a1) with a monocarboxylic acid (a2) containing an ethylenically unsaturated group (step 1). In this step, the carboxyl group of the ethylenically unsaturated group-containing monocarboxylic acid (a2) is subjected to an addition reaction with the epoxy group of the epoxy resin (a1), and an unsaturated group derived from the ethylenically unsaturated group-containing monocarboxylic acid (a2) is introduced into the resulting resin (a) precursor. Further, an epoxy group derived from the epoxy resin (a1) generates a hydroxyl group by ring-opening addition. Next, the resin (a) is synthesized by reacting the hydroxyl group of the resin (a) precursor with a polybasic acid (a3) (step 2).
The reaction conditions in the step 1 may be appropriately set according to a conventional method. For example, the reaction temperature in the step 1 is preferably 50 to 150 ℃, more preferably 60 to 140 ℃. The reaction time in the step 1 is preferably 1 to 10 hours, for example.
The compounding ratio of the epoxy resin (a1) and the ethylenically unsaturated group-containing monocarboxylic acid (a2) can be appropriately set according to the target equivalent weight of the unsaturated group of the resin (a) and the amount of the ethylenically unsaturated group-containing monocarboxylic acid (a2) added to the epoxy group in the epoxy resin (a1) (the ratio of the unsaturated group to the epoxy group to be introduced). For example, the blending ratio of the ethylenically unsaturated group-containing monocarboxylic acid (a2) is preferably 0.85 to 1.10 mol, more preferably 0.90 to 1.00 mol, and still more preferably 0.95 to 1.00 mol, based on 1.00 mol of the epoxy group in the epoxy resin (a 1). In particular, in order to produce a resin (a) precursor in which substantially no unreacted epoxy group remains, the blending ratio of the ethylenically unsaturated group-containing monocarboxylic acid (a2) is 1.00 mol or more. When the compounding ratio of the ethylenically unsaturated group-containing monocarboxylic acid (a2) is 0.85 mol or more, an increase in molecular weight due to a reaction between epoxy groups of the epoxy resin (a1) can be suppressed. When the blending ratio of the ethylenically unsaturated group-containing monocarboxylic acid (a2) is 1.10 mol or less, good colorant dispersibility and developability and elastic recovery of a cured product can be ensured as the photosensitive resin composition.
The solvent used in the step 1 is not particularly limited, and any known solvent can be suitably used. Specific examples of the solvent include (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether and the like;
(poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate;
other ether compounds such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran;
ketone compounds such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;
methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, ethyl acetate, ethyl butyrate, ethyl acetate, ethyl butyrate, ethyl acetate, Ester compounds such as n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate;
aromatic hydrocarbon compounds such as toluene and xylene;
and carboxylic acid amide compounds such as N-methylpyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide. These solvents may be used alone, or 2 or more kinds may be used in combination.
Among the above solvents, glycol ether solvents are preferable from the viewpoint of suppressing gelation and the storage stability of the resin (a). That is, as the solvent, it is preferable to use (poly) alkylene glycol monoalkyl ether such as propylene glycol monomethyl ether, or (poly) alkylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate.
The amount of the solvent used in the step 1 is not particularly limited, but is preferably 30 to 1000 parts by mass, more preferably 50 to 800 parts by mass, when the total amount of the epoxy resin (a1) and the ethylenically unsaturated group-containing monocarboxylic acid (a2) as raw materials is 100 parts by mass. The amount of the solvent used is preferably 1000 parts by mass or less because the viscosity of the resin (a) precursor can be controlled within an appropriate range. On the other hand, if the amount of the solvent used is 30 parts by mass or more, sintering can be prevented from occurring during the reaction, and the synthesis reaction can be stably performed, which is preferable. Further, if the amount of the solvent used is 30 parts by mass or more, the coloring and gelation of the resin (a) precursor can be prevented.
In the present embodiment, a catalyst is preferably used in order to promote the reaction between the epoxy resin (a1) and the monocarboxylic acid having an ethylenically unsaturated group (a 2). The catalyst used in the present embodiment is not particularly limited, and is appropriately selected depending on the kind of the raw material and the like.
Examples of the catalyst used in the present embodiment include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and chromium chelates. These catalysts may be used alone, or 2 or more of them may be used in combination.
The amount of the catalyst used in the present embodiment is not particularly limited, and is generally 0.01 to 5 parts by mass, preferably 0.1 to 2 parts by mass, and more preferably 0.2 to 1 part by mass, when the total amount of the epoxy resin (a1) and the ethylenically unsaturated group-containing monocarboxylic acid (a2) is 100 parts by mass.
In the step 1, a polymerization inhibitor is preferably used in order to prevent gelation of the resin. The polymerization inhibitor used in step 1 is not particularly limited, and is appropriately selected depending on the raw material of the resin, etc.
Examples of the polymerization inhibitor used in step 1 include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, and butylhydroxytoluene. These polymerization inhibitors may be used alone, or 2 or more kinds may be used.
The amount of the polymerization inhibitor used is not particularly limited, but is generally 0.01 to 5 parts by mass, preferably 0.1 to 2 parts by mass, and more preferably 0.2 to 1 part by mass, when the total amount of the epoxy resin (a1) and the ethylenically unsaturated group-containing monocarboxylic acid (a2) is 100 parts by mass.
The reaction conditions in the step 2 may be appropriately set according to a conventional method. For example, the reaction temperature in the step 2 is preferably 50 to 130 ℃, more preferably 60 to 120 ℃. The reaction time in the step 1 is preferably, for example, 1 to 10 hours.
The compounding ratio of the resin (a) precursor and the polybasic acid (a3) is preferably 0.10 to 0.70 mol, more preferably 0.15 to 0.50 mol, and even more preferably 0.20 to 0.40 mol, based on 1.00 mol of hydroxyl groups in the resin (a) precursor, that is, based on 1.00 mol of the constitutional units derived from the polybasic acid (a3) in the resin (a) precursor. When the compounding ratio of the polybasic acid (a3) is 0.10 mol or more, good developability as a photosensitive resin composition can be obtained. When the compounding ratio of the polybasic acid (a3) is 0.70 mol or less, a side reaction during synthesis can be suppressed, and the developability as a photosensitive resin composition is improved, so that a finer pattern can be formed.
The compounding ratio of the polybasic acid (a3) to 1.00 mol of the site derived from the epoxy group of the epoxy resin (a1) in the resin (a) precursor is preferably 0.10 to 0.70 mol, more preferably 0.15 to 0.50 mol, and still more preferably 0.20 to 0.40 mol.
The solvent used in the 2 nd step may be the same as the solvent used in the 1 st step, and may include the solvent used in the 1 st step. That is, the 2 nd step may be continuously performed after the 1 st step is completed without removing the solvent used in the 1 st step.
The amount of the solvent used in the step 2 is not particularly limited, and is preferably 30 to 1000 parts by mass, more preferably 50 to 800 parts by mass, when the total amount of the epoxy resin (a1), the ethylenically unsaturated group-containing monocarboxylic acid (a2), and the polybasic acid (a3) is 100 parts by mass. The amount of the solvent used is preferably 1000 parts by mass or less because the viscosity of the resin (a) can be controlled to an appropriate range. On the other hand, if the amount of the solvent used is 30 parts by mass or more, sintering can be prevented from occurring during the reaction, and the synthesis reaction can be stably performed, which is preferable. Further, if the amount of the solvent used is 30 parts by mass or more, the coloring and gelation of the resin (a) can be prevented.
In the 2 nd step, the same catalyst and polymerization inhibitor as used in the 1 st step may be used. When the 2 nd step is continuously performed after the 1 st step, the catalyst and the polymerization inhibitor used in the 1 st step may be continuously used without being removed, or may be newly added in the 2 nd step.
[ photopolymerization initiator (B) ]
The photopolymerization initiator (B) is not particularly limited as long as it is a polymerization initiator that generates radicals by irradiation with light, and examples thereof include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin butyl ether;
acetophenone compounds such as acetophenone, 2-dimethoxy-2-phenylacetophenone, 1-dichloroacetophenone, 4- (1-tert-butyldioxy-1-methylethyl) acetophenone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1;
anthraquinone compounds such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone;
xanthone compounds such as xanthone, thioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diisopropylthioxanthone and 2-chlorothioxanthone;
ketal compounds such as acetophenone dimethyl ketal and benzil dimethyl ketal;
benzophenone compounds such as benzophenone, 4- (1-tert-butyldioxy-1-methylethyl) benzophenone, and 3,3 ', 4, 4' -tetrakis (tert-butyldioxycarbonyl) benzophenone;
acylphosphine oxide compounds, 1.2-octanedione, 1- [4- (phenylthio) -,2- (O-benzoyloxime) ], and the like. These photopolymerization initiators (C) may be used alone, or 2 or more kinds thereof may be used.
[ solvent (C) ]
The solvent (C) is not particularly limited as long as it is an inert solvent that can dissolve the resin (a) and does not react with the resin (a), and can be arbitrarily selected depending on the kind of the resin (a). The solvent (C) is preferably compatible with the reactive diluent (E) described later.
As the solvent (C), the same solvents as those that can be used in the production of the resin (a) can be used, and a glycol ether solvent is preferably used. That is, as the solvent (C), it is preferable to use (poly) alkylene glycol monoalkyl ether such as propylene glycol monomethyl ether, or (poly) alkylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate.
When a solution containing any component other than the solvent (C) is used as the material of the photosensitive resin composition other than the solvent (C), the solvent contained in the solution can be used as the solvent (C).
[ colorant (D) ]
The colorant (D) is not particularly limited as long as it is dissolved or dispersed in the solvent (C). Examples of the colorant (D) include dyes and pigments. As the colorant (D), only a dye may be used, only a pigment may be used, or a dye and a pigment may be used in combination. When the resin cured film of the photosensitive resin composition of the present embodiment is used as any one of a black PDL, a black matrix, a color filter, and a black columnar spacer, the colorant (D) may be used alone or in combination of 2 or more types depending on the purpose of a member formed of the resin cured film. For example, when a black colorant is used as the colorant (D), a resin cured film of the photosensitive resin composition is suitable as a black PDL, a black matrix, and a black columnar spacer.
Examples of the dye include, for example, acid alizarin violet N; acid black 1,2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; acid chromium violet K; acid fuchsin; acid green 1, 3,5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow 3 and their derivatives, and the like.
Among these dyes, azo, xanthene, anthraquinone or phthalocyanine acid dyes are preferably used.
These dyes may be used alone, or 2 or more kinds may be used in combination.
Examples of the pigment include yellow pigments such as c.i. pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214;
orange pigments such as c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
red pigments such as c.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
c.i. pigment blue 15, 15: 3. 15: 4. 15: 6. 60, etc. blue pigments;
c.i. pigment violet 1, 19, 23, 29, 32, 36, 38 and the like violet pigment;
green pigments such as c.i. pigment green 7, 36, 58;
c.i. brown pigments such as pigment brown 23, 25;
black pigments such as aniline black, perylene black, titanium black, cyanine black, lignin black, lactam-based organic black, RGB black, carbon black, and iron oxide.
These pigments may be used alone or in combination of 2 or more.
The black pigment is preferably used in combination with an inorganic black pigment and an organic black pigment, and more preferably used in combination with a lactam-based organic black, from the viewpoint of the optical density of an image display device provided with a resin cured film of the photosensitive resin composition of the present embodiment.
When a pigment is contained as the colorant (D), the photosensitive resin composition may contain a known dispersant from the viewpoint of improving the dispersibility of the pigment in the photosensitive resin composition. The content of the dispersant may be appropriately set according to the kind of the pigment and the like used.
As the dispersant, a polymer dispersant is preferably used in view of excellent dispersion stability with time. The polymeric dispersant may be arbitrarily selected, and examples thereof include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol ester dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified ester dispersant. Examples of the polymer dispersant include those commercially available under trade names such as EFKA (registered trademark, manufactured by BASF ジャパン), Disperbyk (registered trademark, manufactured by ビックケミー), ディスパロン (registered trademark, manufactured by nakeda chemical corporation), SOLSPERSE (registered trademark, manufactured by ゼネカ), and the like.
< reactive diluent (E) >
The photosensitive resin composition of the present embodiment contains a reactive diluent (E) in addition to the resin (a), the photopolymerization initiator (B), the solvent (C), and the colorant (D).
The reactive diluent (E) is a compound having at least 1 ethylenically unsaturated group in the molecule, preferably a compound having a plurality of ethylenically unsaturated groups.
By including the reactive diluent (E) in the photosensitive resin composition, the viscosity and sensitivity of the photosensitive resin composition can be easily adjusted. In addition, when a resin cured film of a photosensitive resin composition containing the reactive diluent (E) is used as a black PDL, a black matrix, a color filter, or a black columnar spacer, the strength of the resin cured film becomes good. Further, the photosensitive resin composition containing the reactive diluent (E) is applied to the surface of the resin cured film to be formed, exposed, and then developed, so that the resin cured film formed has good adhesion to the surface to be formed.
Examples of the monofunctional monomer (monomer having only 1 ethylenically unsaturated bond) used as the reactive diluent (E) include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 2-phenoxymethyl (meth) acrylate, and mixtures thereof, (meth) acrylate compounds such as glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2,2, 2-trifluoroethyl (meth) acrylate, 2,2,3, 3-tetrafluoropropyl (meth) acrylate, and hemi (meth) acrylate of phthalic acid derivative;
aromatic vinyl compounds such as styrene, α -methylstyrene, α -chloromethylstyrene and vinyltoluene;
and carboxylic acid esters such as vinyl acetate and vinyl propionate. These monofunctional monomers may be used alone, or 2 or more thereof may be used.
Examples of the polyfunctional monomer (monomer having a plurality of ethylenically unsaturated bonds) used as the reactive diluent (E) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethyleneglycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and propylene glycol di (meth) acrylate, 2, 2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, (meth) acrylate compounds such as glycerol triacrylate, glycerol polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., toluene diisocyanate), a reaction product of 2-hydroxyethyl (meth) acrylate such as trimethylhexamethylene diisocyanate and 1, 6-hexamethylene diisocyanate, and tris (meth) acrylate of tris (hydroxyethyl) isocyanurate;
aromatic vinyl compounds such as divinylbenzene, diallyl phthalate and diallyl phenylphosphonate;
dicarboxylic acid ester compounds such as divinyl adipate;
triallyl cyanurate;
and (meth) acrylamide compounds such as methylenebis (meth) acrylamide, (meth) acrylamide methylene ether, and condensates of polyhydric alcohols and N-methylol (meth) acrylamide. These polyfunctional monomers may be used alone, and 2 or more kinds thereof may be used.
< other ingredients >
The photosensitive resin composition of the present embodiment may further contain known additives such as a coupling agent, a leveling agent, and a thermal polymerization inhibitor within a range not to impair the effects of the present invention. Examples of the coupling agent include KBM-403 (3-glycidoxypropyltriethoxysilane, manufactured by shin シリコーン) and the like. The content of these additives is not particularly limited as long as the effects of the present invention are not impaired.
The content of the resin (a) is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, and still more preferably 20 to 35 parts by mass, based on 100 parts by mass of the total of the resin (a), the photopolymerization initiator (B), the colorant (D), and the reactive diluent (E) in the photosensitive resin composition. When the content of the resin (a) is 1 part by mass or more, a photosensitive resin composition having good photocurability can be obtained. When the content of the resin (A) is 50 parts by mass or less, a photosensitive resin composition having good coatability is obtained.
When the total amount of the resin (a), the photopolymerization initiator (B), the colorant (D) and the reactive diluent (E) in the photosensitive resin composition is 100 parts by mass, the content of the photopolymerization initiator (B) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and still more preferably 1 to 5 parts by mass. When the content of the photopolymerization initiator (B) is 0.01 parts by mass or more, the photocurability of the photosensitive resin composition is good. If the content of the photopolymerization initiator (B) is 10 parts by mass or less, no residue is generated in the development step after the application and exposure of the photosensitive resin composition.
When the total amount of the resin (a), the photopolymerization initiator (B), the colorant (D) and the reactive diluent (E) in the photosensitive resin composition is 100 parts by mass, the content of the solvent (C) is preferably 100 to 2000 parts by mass, more preferably 150 to 1000 parts by mass, and further preferably 200 to 500 parts by mass. If the content of the solvent (C) is 100 parts by mass or more, the photosensitive resin composition has good coatability. If the content of the solvent (C) is 2000 parts by mass or less, a coating film having a sufficient film thickness can be obtained in the step of applying the photosensitive resin composition.
When the total amount of the resin (a), the photopolymerization initiator (B), the colorant (D) and the reactive diluent (E) in the photosensitive resin composition is 100 parts by mass, the content of the colorant (D) is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, and still more preferably 20 to 30 parts by mass. When the content of the colorant (D) is 1 part by mass or more, the resin cured film of the photosensitive resin composition has sufficient color reproducibility. In addition, when a black substance is used as the colorant (D), the resin cured film has sufficient light-shielding properties. If the content of the colorant (D) is 50 parts by mass or less, a residue is less likely to be generated in the developing step after the application/exposure of the photosensitive resin composition.
When the total amount of the resin (a), the photopolymerization initiator (B), the colorant (D) and the reactive diluent (E) in the photosensitive resin composition is 100 parts by mass, the content of the reactive diluent (E) is preferably 1 to 60 parts by mass, more preferably 15 to 50 parts by mass, and still more preferably 30 to 45 parts by mass. When the content of the reactive diluent (E) is 1 part by mass or more, a photosensitive resin composition having good curability can be obtained even if the colorant (D) is contained in a large amount. If the content of the reactive diluent (E) is 60 parts by mass or less, a residue is less likely to be generated in the developing step after the application and exposure of the photosensitive resin composition.
[ method for producing photosensitive resin composition ]
Next, a method for producing the photosensitive resin composition of the present embodiment will be described.
The photosensitive resin composition of the present embodiment can be produced by a method of mixing any 1 or more of the resin (a), the photopolymerization initiator (B), the solvent (C), the colorant (D), the reactive diluent (E), and the dispersant and the additive of the present embodiment using a known mixing device.
The photosensitive resin composition of the present embodiment can be produced by preparing a composition containing the resin (a) and the solvent (C) in advance, adding 1 or more of the photopolymerization initiator (B), the colorant (D), the reactive diluent (E), and the dispersant and the additive to the composition, and mixing them.
The composition containing the resin (a) and the solvent (C) can be produced, for example, by a method of adding and mixing the solvent (C) to the resin (a) isolated from a resin solution in which a reaction for synthesizing the resin (a) has been completed.
In the present embodiment, it is not necessary to isolate the resin (a) as the target substance from the resin solution in which the reaction for synthesizing the resin (a) is completed. Therefore, as the composition containing the resin (a) and the solvent (C), the resin solution after the reaction is completed can be used as it is without separating the solvent contained in the resin solution at the time when the reaction for synthesizing the resin (a) is completed from the resin solution. In addition, as the composition containing the resin (a) and the solvent (C), a composition obtained by adding and mixing another solvent to a resin solution after the reaction is completed can be used.
The photosensitive resin composition of the present embodiment contains the resin (a) of the present embodiment, and therefore, a resin cured film having excellent developability, good colorant dispersibility, and high elastic recovery rate can be obtained. Therefore, the photosensitive resin composition of the present embodiment is suitable as a material for black PDL, black matrix, color filter, and black column spacer.
The photosensitive resin composition of the present embodiment has good dispersibility of the colorant, and can form a resin cured film having good adhesion to a surface to be formed, while satisfying general characteristics such as developability sufficiently even if the colorant (D) is black. Therefore, according to the photosensitive resin composition of the present embodiment, a black pattern having good adhesion to a surface to be formed and sufficient light-shielding properties can be formed.
[ resin cured film ]
The resin cured film of the present embodiment is a resin cured film obtained by photocuring the photosensitive resin composition of the present embodiment.
The resin cured film of the present embodiment is excellent in colorant dispersibility, solvent resistance, and elastic recovery rate, and therefore is suitable as a member of an image display device, such as a black PDL, a black matrix, a color filter, and a black columnar spacer.
[ method for producing resin cured film ]
The resin cured film of the present embodiment can be produced, for example, by the following method.
First, a photosensitive resin composition is applied to a surface of a cured resin film to be formed, thereby forming a resin layer (coating film). Next, the resin layer is exposed through a mask having a predetermined pattern, and the exposed portion is photocured. Next, the unexposed portion of the resin layer is developed with a developer to form a cured resin film having a predetermined pattern. Then, post baking (heat treatment) of the resin cured film is performed as necessary.
When the resin layer is exposed to light, a halftone mask having a predetermined pattern may be used. In this case, the unexposed portion and the half-exposed portion are developed with a developer to form a resin cured film having a predetermined pattern.
The method for applying the photosensitive resin composition is not particularly limited, and examples thereof include screen printing, roll coating, curtain coating, spray coating, and spin coating.
After the photosensitive resin composition is applied, if necessary, the solvent (C) contained in the resin layer can be volatilized by heating with a heating means such as a circulation oven, an infrared heater, or an electric heating plate. The heating conditions after coating are not particularly limited, and may be appropriately set according to the composition of the photosensitive resin composition. For example, the heating temperature after coating may be 50 to 120 ℃ and the heating time may be 30 seconds to 30 minutes.
The method of exposing the resin layer to light is not particularly limited, and examples thereof include a method of irradiating the resin layer with active energy rays such as ultraviolet rays and excimer laser light.
The amount of energy radiation irradiated to the resin layer may be appropriately set according to the composition of the photosensitive resin composition. For example, the amount of energy rays irradiated to the resin layer may be 30 to 2000mJ/cm2However, the present invention is not limited to this range.
The light source used for exposure is not particularly limited, and a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be optionally used.
As the developer used for development, an alkaline developer is preferably used in order to obtain excellent developability. Examples of the alkaline developer include aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, and the like; aqueous solutions of amine compounds such as ethylamine, diethylamine, and dimethylethanolamine; aqueous solutions of tetramethylammonium, 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- β -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- β -methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N- β -methoxyethylaniline, and their sulfates, hydrochlorides, p-toluenesulfonates, and the like; aqueous solutions of p-phenylenediamine compounds, and the like.
The developer may contain an antifoaming agent, a surfactant, and the like as needed.
After development with a developer, the resin cured film having a predetermined pattern is preferably washed with water and dried.
After development with a developer, post baking (heat treatment) of the resin cured film having a predetermined pattern is preferably performed. By performing the post-baking, the curing of the resin cured film can be further promoted. The conditions for the post-baking are not particularly limited, and may be arbitrarily selected, and may be appropriately set according to the composition of the photosensitive resin composition. For example, the post bake heating temperature may be 130 ℃ to 250 ℃. The heating time for the post-baking is preferably 10 minutes to 4 hours, and more preferably 20 minutes to 2 hours.
[ image display apparatus ]
The image display device of the present embodiment includes the resin cured film of the present embodiment. Specific examples of the image display device include a liquid crystal display device and an organic EL display device.
As the image display device, for example, 1 or more members selected from a black PDL, a black matrix, a color filter, and a black columnar spacer are preferably formed of the resin cured film of the present embodiment.
The material of the substrate on which the surface to be formed of the cured resin film is formed is not particularly limited, and examples thereof include substrates having a wiring pattern formed on the surface thereof, such as glass, silicon, polycarbonate, polyester, polyamide, polyamideimide, polyimide, aluminum, and printed wiring boards, and array substrates.
The method for manufacturing an image display device of the present embodiment may include a step of forming the cured resin film of the present embodiment by the above-described manufacturing method, and members other than the member formed of the cured resin film may be manufactured by a conventional method.
The resin cured film obtained by curing the photosensitive resin composition of the present embodiment has excellent developability, good colorant dispersibility and solvent resistance, and high elastic recovery. Therefore, the material is suitable for black PDL, black matrix, color filter, and black column spacer provided in the image display device.
Examples
The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
< Synthesis example 1 >
(step 1)
86g of propylene glycol monomethyl ether acetate as a solvent and 198g of bisphenol A novolac-type epoxy resin (product name NPPN-438, epoxy equivalent 198, manufactured by Nanyamo プラスチック) were put into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, and stirred and dissolved. Then, 72g of acrylic acid as an ethylenically unsaturated group-containing monocarboxylic acid (a2), 0.3g of methylhydroquinone as an inhibitor, and 0.7g of triphenylphosphine as a catalyst were added thereto, and the flask was stirred while blowing air, and the temperature was raised to 120 ℃ to effect a reaction for 2 hours.
(step 2)
Subsequently, 32g of succinic anhydride as an acid anhydride of the polybasic acid (a3) was added thereto, and the mixture was further stirred at 120 ℃ for 30 minutes to synthesize resin (A) of Synthesis example 1.
After the reaction, propylene glycol monomethyl ether acetate was added to the resin (a) solution as a solvent (C) and mixed to prepare a solution (solid content concentration: 40 mass%) containing the resin (a) and the solvent (C). The solid content is a heating residue obtained by heating the composition at 130 ℃ for 2 hours, and the resin (A) is the main component in the solid content of the prepared solution.
< Synthesis examples 2 to 7 >
Resin (a) was synthesized in the same manner as in synthesis example 1 except that resin (a) was synthesized and propylene glycol monomethyl ether acetate was added to prepare a preparation solution (solid content concentration: 40 mass%) containing resin (a) and solvent (C) with the composition shown in table 1.
[ Table 1]
Figure BDA0003654105480000231
As the compounds in table 1, the following compounds were used.
NPPN-438: bisphenol A novolak type epoxy resin (product name NPPN-438, manufactured by Nanzha プラスチック Co., Ltd., epoxy equivalent 198)
AA: acrylic acid
MAA: methacrylic acid
HOMS: acryloxyethyl succinic acid
And SA: succinic anhydride
THPA: tetrahydrophthalic anhydride
CHTC: 1,2, 4-Cyclohexanetricarboxylic acid
< determination of acid value >
The measurement was carried out according to JIS K69015.3.2 using a mixed indicator of bromothymol blue and phenol red. The acid value is the mg number of potassium hydroxide required for neutralizing the acidic components contained in 1g of the resin (A).
< unsaturated radical equivalent >
The mass of the resin (a) relative to the number of moles of polymerizable unsaturated bonds is a calculated value calculated based on the amounts of the components (a1) to (a3) used as raw materials.
< determination of weight average molecular weight (Mw) >)
The measurement was performed under the following conditions using Gel Permeation Chromatography (GPC) and converted to standard polystyrene.
Column: ショウデックス (registered trademark) LF-804+ LF-804 (manufactured by Showa Denko K.K.)
Column temperature: 40 deg.C
Sample preparation: 0.2% tetrahydrofuran solution of resin (A)
Developing solvent: tetrahydrofuran (THF)
A detector: differential refractometer (ショウデックス (registered trademark) RI-71S) (manufactured by SHOWA DENKO K.K.)
Flow rate: 1mL/min
Comparative Synthesis example 1
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, 71g of propylene glycol monomethyl ether acetate, 210g of cresol novolak-type epoxy resin (YDCN-704L, epoxy equivalent: 210), 72g of acrylic acid, 0.2g of triphenylphosphine as a catalyst and 0.7g of butylhydroxytoluene as a polymerization inhibitor were charged as a solvent, and the flask was stirred while blowing air, and the temperature was raised to 120 ℃ to react for two hours.
Subsequently, 28.6g of tetrahydrophthalic anhydride was put into the same flask, and the mixture was further stirred at 120 ℃ for 30 minutes to synthesize a resin.
To the resin solution after the completion of the reaction, propylene glycol monomethyl ether acetate was added as a solvent (C) and mixed to prepare a solution (solid content concentration: 40 mass%) containing the resin and the solvent (C).
The resin synthesized in comparative synthesis example 1 was measured for the acid value, weight average molecular weight, and unsaturated group equivalent of the solid content in the same manner as in synthesis example 1. As a result, the resin synthesized in comparative Synthesis example 1 had an acid value of the solid content of 36KOHmg/g, a weight average molecular weight (Mw) of 7000 and an unsaturated group equivalent of 310.
Comparative Synthesis example 2
164g of propylene glycol monomethyl ether acetate was charged into a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, and the mixture was stirred under nitrogen substitution, and the temperature was raised to 120 ℃. Subsequently, 12g of t-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by Nichikoku corporation, パーブチル (registered trademark) O) was added to a monomer mixture comprising 85g (0.6 mol) of glycidyl methacrylate, 66g (0.3 mol) of tricyclodecanyl methacrylate, and 10.4g (0.1 mol) of styrene, and the mixture was dropped from a dropping funnel over 2 hours into the flask. After the completion of the dropwise addition, the mixture was further stirred at 120 ℃ for 2 hours to effect copolymerization. Then, 42g of acrylic acid, 0.4g of hydroquinone monomethyl ether as a polymerization inhibitor, and 0.5g of triphenylphosphine as a catalyst were added to the reaction solution, and the mixture was heated at 110 ℃ for 10 hours while blowing low-oxygen air into which nitrogen gas was injected so that the oxygen concentration became 4% to 7%.
Then, it was confirmed that the acid value was 1.0KOHmg/g or less, 55g of tetrahydrophthalic anhydride was added, and the reaction was carried out at 110 ℃ for 2 hours to obtain a resin solution having a solid content of 50 mass% (solid content acid value 80.6KOHmg/g, weight average molecular weight 9500).
< comparative Synthesis examples 3 to 6 >
A resin was synthesized in the same manner as in synthesis example 1 except that the composition was changed to the composition shown in table 1, and propylene glycol monomethyl ether acetate was added to prepare a solution (solid content concentration: 40 mass%) containing the resin (a) and the solvent (C).
< examples 1 to 7, comparative examples 1 to 5 >
Photosensitive resin compositions of examples 1 to 7 and comparative examples 1 to 5 were prepared by mixing a prepared solution containing the resin (a) and the solvent (C) of synthetic examples 1 to 7 and a resin solution of comparative synthetic examples 1,2,4 to 6 in a 500ml vial with the composition (parts by mass) shown in table 2 and shaking by hand.
[ Table 2]
Figure BDA0003654105480000271
The following compounds were used as the compounds shown in table 2.
OXE-01: イルガキュア OXE01 (photopolymerization initiator, manufactured by BASF ジャパン) PGMEA: propylene glycol monomethyl ether acetate
DPHA: dipentaerythritol hexaacrylate (product name A-DPH, manufactured by Xinzhongcun Industrial Co., Ltd.)
KBM-403: 3-glycidoxypropyltriethoxysilane (coupling agent, manufactured by Xinyue シリコーン, product name KBM-403)
Black grind (mill base): the preparation was performed by the following "adjustment of abrasives".
< adjustment of abrasives >
A millbase was prepared by charging 0.6g of carbon Black, 3.6g of lactam-based Black (Irgaphor Black S0100CF, manufactured by BASF Co., Ltd.), 7.5g of アジスパー PB822 as a dispersant, 2.5g of the acrylic resin synthesized in comparative Synthesis example 2, 15g of PGMEA together with zirconia beads into a metal can and shaking the mixture for 5 hours with a paint shaker.
The photosensitive resin compositions of examples 1 to 7 and comparative examples 1 to 5 were evaluated for optical density (OD value, colorant dispersibility), elastic recovery, development morphology, and fine line adhesion by the following methods, respectively. The results are shown in table 3.
< evaluation of optical Density (OD value, colorant dispersibility) >
The photosensitive resin compositions of examples 1 to 7 and comparative examples 1 to 5 were spin-coated on IZO (In) of 10cm × 10cm so that the thickness of the coating film became 1.5 μm2O3ZnO) substrate (substrate with wiring pattern formed of IZO formed on the surface). Then, the IZO substrate was heated at 90 ℃ for 3 minutes to volatilize the solvent in the coating film. Next, the entire surface of the coating film was exposed to light (exposure amount: 50 mJ/cm) using an inhibitor マルチライト ML-251D/B manufactured by ウシオ Inc. and an irradiation optical unit PM25C-1002) And photocuring the mixture. Then, the resultant was developed with a 0.2 mass% aqueous solution of potassium hydroxide for 120 seconds, and further post-baked at 230 ℃ for 30 minutes, thereby obtaining a resin cured film having a target thickness of 1.0 μm.
The Optical Density (Optical Density: OD) of the resin cured film having a thickness of 1.0 μm was measured by using a transmission densitometer (361T, X-lite).
The higher the optical density, the more excellent the colorant dispersibility can be said to be.
< evaluation of elastic recovery >
The resin cured film used for the evaluation of optical density was measured for elastic recovery at 25 ℃ using an elasticity measuring apparatus (DUH-W201S, Shimadzu corporation) under the following measurement conditions.
As a pressing body for pressing the resin cured film, a flat pressing body having a diameter of 50 μm was used. The elastic recovery was measured by a test in which a load of 300mN was applied in order to obtain a result that could be recognized between the groups to which the comparison was made. The load speed of 3 gf/sec and the holding time of 3 seconds were kept constant. Regarding the elastic recovery rate, the load was removed after a load of 300mN for 3 seconds was applied to the flat pressing body, and the elastic recovery rate of the resin cured film before and after the load was measured by using a three-dimensional thickness measuring apparatus. The elastic recovery rate is a ratio of a distance recovered after a recovery time of 10 minutes (recovery distance) to a distance compressed when a load of 300mN was applied (compression displacement), and is represented by the following formula.
Elastic recovery rate (%) (recovery distance/compression displacement) × 100
< evaluation of development form and Fine wire adhesion >
The photosensitive resin compositions of examples 1 to 7 and comparative examples 1 to 5 were spin-coated on a glass substrate of 10cm × 10cm so that the thickness of the coating film became 2.5 μm. Then, the glass substrate was heated at 90 ℃ for 3 minutes to volatilize the solvent. Next, a pattern mask having dots with diameters of 1 μm up to 35, 30, 25, and 20 to 3 μm was placed on the coating film, and exposure was performed from above the mask using マルチライト ML-251D/B manufactured by ウシオ (manufactured by Okagaku corporation) and an irradiation optical unit PM25C-100 (exposure amount was 20 mJ/cm)2 80mJ/cm2) And photocuring the mixture. Then, the resultant was developed with a 0.2 mass% aqueous solution of potassium hydroxide for 120 seconds, and the size of the minimum pattern that can be developed was confirmed, thereby evaluating the adhesion of the thin line.
Also, the development pattern was confirmed during development. When the developing form is dissolved instead of peeling off the coating film, the developability is further improved.
[ Table 3]
Figure BDA0003654105480000301
As shown in Table 3, the cured resin films of the photosensitive resin compositions of examples 1 to 7 had high optical density (colorant dispersibility) and elastic recovery, and good evaluations of development morphology and fine line adhesion.
On the other hand, the cured resin films of the photosensitive resin compositions of comparative examples 1 to 5 are inferior to those of examples 1 to 7 in particular in the fine line adhesion and the development form.

Claims (9)

1. A photosensitive resin composition, comprising:
a resin (A),
A photopolymerization initiator (B),
A solvent (C),
A colorant (D) and
a reactive diluent (E) which is a mixture of,
the resin (A) has a structure (a11) derived from an epoxy resin (a1), a structure (a21) derived from an ethylenically unsaturated group-containing monocarboxylic acid (a2), and a structure (a31) derived from a polybasic acid (a3),
the resin (A) is a reactant obtained by adding the polybasic acid (a3) to the reactant (R1) of the epoxy resin (a1) and the ethylenically unsaturated group-containing monocarboxylic acid (a2),
the epoxy resin (a1) is a reactant of phenolic resin (a4) and epihalohydrin,
the phenolic resin (a4) is a condensate of a dihydric phenol compound and an aldehyde compound,
the resin (A) has the following structural unit ratios derived from the components (a1) to (a 3): the amount of the structural unit derived from the ethylenically unsaturated group-containing monocarboxylic acid (a2) is 0.85 to 1.00 mol and the amount of the structural unit derived from the polybasic acid (a3) is 0.10 to 0.70 mol, based on 1.00 mol of the epoxy group-derived site of the epoxy resin (a 1).
2. The photosensitive resin composition according to claim 1, which contains, when the total of the resin (a), the photopolymerization initiator (B), the colorant (D) and the reactive diluent (E) is 100 parts by mass:
1 to 50 parts by mass of the resin (A),
0.01 to 5 parts by mass of the photopolymerization initiator (B),
10 to 2000 parts by mass of the solvent (C),
1 to 50 parts by mass of the colorant (D), and
1-60 parts by mass of the reactive diluent (E).
3. The photosensitive resin composition according to claim 1 or 2, wherein the resin (A) has an acid value of 20 to 300KOHmg/g and an unsaturated group equivalent of 100 to 4000 g/mol.
4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the colorant (D) comprises an inorganic black pigment and an organic black pigment.
5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the phenolic resin (a4) is a condensate of bisphenol A and formaldehyde.
6. The photosensitive resin composition according to any one of claims 1 to 5, wherein the ethylenically unsaturated group-containing monocarboxylic acid (a2) is at least one member selected from the group consisting of (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid.
7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the polybasic acid (a3) is one or more selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride, and 1,2, 4-cyclohexanetricarboxylic anhydride.
8. A cured resin film of the photosensitive resin composition according to any one of claims 1 to 7.
9. An image display device comprising the cured resin film according to claim 8.
CN202180006609.8A 2020-02-06 2021-02-02 Photosensitive resin composition and image display device Pending CN114730129A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2020-019204 2020-02-06
JP2020019204 2020-02-06
PCT/JP2021/003688 WO2021157558A1 (en) 2020-02-06 2021-02-02 Light-sensitive resin composition and image display device

Publications (1)

Publication Number Publication Date
CN114730129A true CN114730129A (en) 2022-07-08

Family

ID=77199362

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202180006609.8A Pending CN114730129A (en) 2020-02-06 2021-02-02 Photosensitive resin composition and image display device

Country Status (5)

Country Link
JP (1) JPWO2021157558A1 (en)
KR (1) KR102594321B1 (en)
CN (1) CN114730129A (en)
TW (1) TW202142961A (en)
WO (1) WO2021157558A1 (en)

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4269480B2 (en) 2000-04-19 2009-05-27 Ｊｓｒ株式会社 Radiation sensitive resin composition
JP3830330B2 (en) * 2000-05-17 2006-10-04 三菱化学株式会社 Photosensitive material
JP5690490B2 (en) 2010-02-18 2015-03-25 東京応化工業株式会社 Photosensitive composition
JP2013134263A (en) 2011-12-22 2013-07-08 Tokyo Ohka Kogyo Co Ltd Photosensitive resin composition for black column spacer, black column spacer, display device, and method for forming black column spacer
JP6519134B2 (en) * 2014-09-25 2019-05-29 日立化成株式会社 Photosensitive resin composition
JP6620923B2 (en) * 2015-06-05 2019-12-18 Dic株式会社 (Meth) acrylate resin and resist member
CN107615114A (en) * 2015-06-15 2018-01-19 昭和电工株式会社 Color composition for color filter, colour filter and image-displaying member
KR20180109239A (en) * 2017-03-27 2018-10-08 동우 화인켐 주식회사 Colored photosensitive resin composition, color filter and image display device produced using the same
JP6958188B2 (en) * 2017-09-28 2021-11-02 昭和電工マテリアルズ株式会社 A photosensitive resin composition, a photosensitive element using the same, a method for forming a resist pattern, a solder resist, an interlayer insulating film, a method for forming an interlayer insulating film, a method for manufacturing a printed wiring board, and a printed wiring board.

Also Published As

Publication number Publication date
KR102594321B1 (en) 2023-10-26
TW202142961A (en) 2021-11-16
KR20220084093A (en) 2022-06-21
WO2021157558A1 (en) 2021-08-12
JPWO2021157558A1 (en) 2021-08-12

Similar Documents

Publication Publication Date Title
KR101473511B1 (en) Photosensitive graft polymer, and photosensitive resin composition comprising the same
JP5133658B2 (en) Photosensitive resin composition for black matrix, cured product and color filter using the same
JP3813244B2 (en) Alkali developable unsaturated resin composition and highly sensitive negative pattern forming material using the same
KR20160066482A (en) Black photosensitive resin composition, black matrix and image display device comprising thereof
KR20090097120A (en) Liquid-repellent resin composition
KR102392964B1 (en) Photosensitive resin composition for light-shielding film, display substrate having the light-shielding film obtained by curing the same, and manufacturing method of display substrate
CN111032720B (en) Resin, photosensitive resin composition, resin cured film, and image display device
JP5449666B2 (en) Alkali-soluble resin and method for producing the same, and photosensitive resin composition, cured product, and color filter using alkali-soluble resin
TWI643022B (en) Photosensitive resin composition for forming black column spacer, black column spacer and image display device
CN109471331B (en) Resin composition, photosensitive resin composition, resin cured film, and image display element
TWI794313B (en) Photosensitive resin composition for color filter, color filter, image display element and method for producing color filter
TW200530281A (en) Photosensitive resin composition and color filter using the same
KR102594321B1 (en) Photosensitive resin composition and image display device
CN116529670A (en) Photosensitive resin composition and method for producing photosensitive resin composition
JP2011093970A (en) Photosensitive resin
JP2022062515A (en) Phenolic hydroxy group-containing resin, photosensitive resin composition, cured resin film, and image display device
WO2020044677A1 (en) Photosensitive resin composition, black column spacer and image display device
JP2011099034A (en) Polycarboxylic acid resin and polycarboxylic acid resin composition
WO2020044678A1 (en) Photosensitive resin composition for forming black column spacers, black column spacer and image display device
JP2021031625A (en) Thiol resin and photosensitive resin composition comprising thiol resin
CN113166342A (en) Ethylenically unsaturated resin composition and photosensitive resin composition
JPH08337736A (en) Carbon black, resin composition and black matrix
KR20140087819A (en) Photosensitive resin composition, spacer for liquid crystal display using the same and liquid crystal display device having the spacer

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
CB02 Change of applicant information
CB02 Change of applicant information

Address after: Tokyo, Japan

Applicant after: Lishennoco Co.,Ltd.

Address before: Tokyo, Japan

Applicant before: Showa electrical materials Co.,Ltd.

TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20230506

Address after: Tokyo, Japan

Applicant after: Showa electrical materials Co.,Ltd.

Address before: Tokyo, Japan

Applicant before: SHOWA DENKO Kabushiki Kaisha