CN111615650B - Photosensitive resin composition for color filter, image display element, and method for producing color filter - Google Patents

Photosensitive resin composition for color filter, image display element, and method for producing color filter Download PDF

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Publication number
CN111615650B
CN111615650B CN201880086882.4A CN201880086882A CN111615650B CN 111615650 B CN111615650 B CN 111615650B CN 201880086882 A CN201880086882 A CN 201880086882A CN 111615650 B CN111615650 B CN 111615650B
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China
Prior art keywords
color filter
photosensitive resin
resin composition
structural unit
meth
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CN111615650A (en
Inventor
永井英理
木下健宏
川口恭章
柳正义
仓本拓树
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Lishennoco Co ltd
Resonac Holdings Corp
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Showa Denko KK
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    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • 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
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • 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
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/18—Oxetanes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—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
    • 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
    • G03F7/027—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
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Optics & Photonics (AREA)
  • Optical Filters (AREA)
  • Materials For Photolithography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

A photosensitive resin composition for a color filter, comprising: the composition comprises a copolymer (A) containing a structural unit (a) having an acid group and a structural unit (B) having a cyclic ether group, a compound (B) which generates an acid by heat and/or ultraviolet irradiation, a solvent (C), a reactive diluent (D), a photopolymerization initiator (E), and a colorant (F).

Description

Photosensitive resin composition for color filter, image display element, and method for producing color filter
Technical Field
The present invention relates to a photosensitive resin composition for a color filter, an image display element having the color filter, and a method for manufacturing the color filter.
Background
In recent years, photosensitive resin compositions that can be cured by active energy rays such as ultraviolet rays and electron beams have been widely used in the fields of various coatings, printing, paints, adhesives, and the like from the viewpoints of resource saving and energy saving. In the field of electronic materials such as printed wiring boards, photosensitive resin compositions that can be cured by active energy rays are also used for solder resists, resists for color filters, and the like. Further, the properties required for curable photosensitive resin compositions are increasingly diversified and are becoming higher, and among them, short-time curability in view of productivity and low-temperature curability to suppress thermal damage of members to be applied are required.
The color filter is generally composed of a transparent substrate such as a glass substrate, red (R), green (G), and blue (B) pixels formed on the transparent substrate, a black matrix formed at the boundary of the pixels, and a protective film formed on the pixels and the black matrix. A color filter having such a configuration is generally manufactured by sequentially forming a black matrix, pixels, and a protective film on a transparent substrate. Various methods have been proposed as methods for forming pixels and black matrices (hereinafter, pixels and black matrices are referred to as "colored patterns"). Among them, the pigment/dye dispersion method, which is produced by using a photosensitive resin composition as a resist and repeating a photolithography process of coating, exposure, development and baking, is now the mainstream because it provides a colored pattern having excellent durability and few defects such as pin holes (Pinhole).
Generally, a photosensitive resin composition used in a photolithography process contains an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a colorant, and a solvent. The pigment/dye dispersion method has the above-mentioned advantages, but on the other hand, high heat resistance is required because a black matrix and R, G, B patterns are repeatedly formed, and there are limitations such as limitation in the types of usable colorants as a colorant capable of withstanding high baking temperatures, which is often a problem.
Patent document 1 discloses a coloring composition that can be cured at a low temperature and has improved storage stability by using an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated bond, a radiation-sensitive (radiation-sensitive) polymerization initiator, a colorant, and a compound such as ethyl 3-aminobenzenesulfonate.
In patent document 2, low-temperature curing is enabled by using a photosensitive resin composition containing a polymer precursor which promotes a reaction to a final product by an alkaline substance or by heating in the presence of an alkaline substance, and a specific alkali-generating agent which generates an alkali by irradiation of electromagnetic waves and heating.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2013-68843
Patent document 2: japanese patent laid-open No. 2014-70148
Disclosure of Invention
Problems to be solved by the invention
In recent years, flexible displays such as electronic paper have become popular. As a substrate of the flexible display, a plastic substrate such as polyethylene terephthalate is studied. This substrate has a property of extending or contracting during baking, and requires a low temperature in the baking step. However, at the level achieved by patent document 1, it is not sufficient to satisfy the above-described requirements. In addition, in patent document 2, low-temperature curability is improved, but on the other hand, storage stability is low, and practical use is difficult.
The present invention has been made to solve the above problems, and an object of the present invention is to provide a photosensitive resin composition for a color filter, which is excellent in developability and storage stability and provides a colored pattern having excellent solvent resistance even when cured at a low temperature of about 100 ℃, and a copolymer useful for production of the photosensitive resin composition.
Another object of the present invention is to provide a color filter having a colored pattern with excellent solvent resistance, a method for manufacturing the color filter, and an image display device including the color filter.
Means for solving the problems
That is, the present invention is as shown in the following [1] to [16 ].
[1] A photosensitive resin composition for a color filter, comprising: the composition comprises a copolymer (A) containing a structural unit (a) having an acid group and a structural unit (B) having a cyclic ether group, a compound (B) which generates an acid by heat and/or ultraviolet irradiation, a solvent (C), a reactive diluent (D), a photopolymerization initiator (E), and a colorant (F).
[2] The photosensitive resin composition for a color filter according to [1], wherein the structural unit (a) having an acid group is a structural unit derived from an ethylenically unsaturated compound having a carboxyl group.
[3] The photosensitive resin composition for a color filter according to [1] or [2], wherein the structural unit (b) having a cyclic ether group is a structural unit derived from at least one selected from the group consisting of an epoxy group-containing (meth) acrylate and an oxetanyl group-containing (meth) acrylate.
[4] The photosensitive resin composition for a color filter according to any one of [1] to [3], wherein the copolymer (A) contains the structural unit (a) having an acid group in a proportion of 5 to 40 mol% and the structural unit (b) having a cyclic ether group in a proportion of 60 to 95 mol%.
[5] The photosensitive resin composition for a color filter according to any one of [1] to [3], wherein the copolymer (A) further contains a structural unit (c) derived from a radical polymerizable compound having an ethylenically unsaturated group.
[6] The photosensitive resin composition for a color filter according to [5], wherein the copolymer (A) contains the structural unit (a) having an acid group in a proportion of 5 to 60 mol%, the structural unit (b) having a cyclic ether group in a proportion of 5 to 70 mol%, and the structural unit (c) derived from a radical polymerizable compound having an ethylenically unsaturated group in a proportion of more than 0 to 80 mol%.
[7] The photosensitive resin composition for a color filter according to any one of [1] to [6], wherein the acid group of the structural unit (a) having an acid group is a carboxyl group.
[8] The photosensitive resin composition for a color filter according to any one of [1] to [7], wherein the cyclic ether group of the structural unit (b) having a cyclic ether group is at least one selected from the group consisting of an epoxy group and an oxetanyl group.
[9] The photosensitive resin composition for a color filter according to any one of [1] to [8], wherein the compound (B) that generates an acid by heat and/or ultraviolet irradiation is 0.05 to 20 parts by mass with respect to 100 parts by mass of a polymerizable monomer that provides the structural unit (B) having a cyclic ether group used in synthesizing the copolymer (A).
[10] The photosensitive resin composition for a color filter according to any one of [1] to [9], wherein the compound (B) generating an acid by heat and/or ultraviolet irradiation is a sulfonium salt.
[11] The photosensitive resin composition for a color filter according to any one of [1] to [10], wherein the copolymer (A) has a weight average molecular weight of 1000 to 50000 and an acid value of 20 to 300 KOHmg/g.
[12] The photosensitive resin composition for a color filter according to any one of [1] to [11], wherein the colorant (F) comprises a pigment.
[13] The photosensitive resin composition for a color filter according to any one of [1] to [12], wherein the total of the copolymer (A) and the compound (B) that generates an acid by heat and/or ultraviolet irradiation is 1 to 50 mass%, the reactive diluent (D) is 1 to 60 mass%, the photopolymerization initiator (E) is 0.01 to 15 mass%, and the colorant (F) is 20 to 80 mass%, and the solvent (C) is 10 to 800 parts by mass, when the total of the components other than the solvent (C) in the photosensitive resin composition for a color filter is 100 parts by mass.
[14] A color filter characterized by having a colored pattern formed from a cured product of the photosensitive resin composition for a color filter according to any one of [1] to [13 ].
[15] An image display device comprising the color filter according to [14 ].
[16] A method for manufacturing a color filter, comprising: a step of applying the photosensitive resin composition for a color filter according to any one of [1] to [13] to a substrate, exposing and alkali-developing the composition, and then baking the composition at a temperature of 150 ℃ or lower to form a colored pattern.
Effects of the invention
According to the present invention, there can be provided a photosensitive resin composition for a color filter which is excellent in developability and storage stability and which provides a colored pattern excellent in solvent resistance even when cured at a low temperature of about 100 ℃, and a copolymer useful for production of the photosensitive resin composition.
Further, according to the present invention, a color filter having a colored pattern with excellent solvent resistance, a method for manufacturing the same, and an image display element having the color filter can be provided.
Detailed Description
< photosensitive resin composition for color Filter >
The photosensitive resin composition for a color filter of the present invention comprises: the composition comprises a copolymer (A) containing a structural unit (a) having an acid group and a structural unit (B) having a cyclic ether group, a compound (B) which generates an acid by heat and/or ultraviolet irradiation, a solvent (C), a reactive diluent (D), a photopolymerization initiator (E), and a colorant (F).
< copolymer (A) >
< structural unit (a) having acid group >
The structural unit (a) having an acid group contained in the copolymer (A) is a structural unit derived from a polymerizable monomer having an acid group.Examples of the acid group include: carboxyl group (-COOH), phosphate group (-PO (OH)2) Sulfo (-SO)3H) And the like. Among them, a carboxyl group is preferable from the viewpoint of easiness of raw material acquisition and solvent resistance in the case of using the compound for color filter production. Examples of the polymerizable monomer that provides the structural unit (a) having an acid group include: carboxyl group-containing ethylenically unsaturated compounds such as (meth) acrylic acid, crotonic acid, cinnamic acid, vinylsulfonic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, and 2- (meth) acryloyloxyethyl acid phosphate. These polymerizable monomers may be used alone, or two or more of them may be used in combination. Among them, (meth) acrylic acid is preferable from the viewpoint of ease of acquisition and reactivity. The structural unit is also referred to as a monomer unit.
In the present invention, the copolymer (a) contains the structural unit (a) having an acid group, and thus the alkali developability is greatly improved when the copolymer (a) is used as a photosensitive material.
When the copolymer (a) contains the structural unit (a) having an acid group and the structural unit (b) having a cyclic ether group, the proportion of the structural unit (a) having an acid group contained in the copolymer (a) is preferably 5 to 40 mol%, more preferably 10 to 35 mol%, and most preferably 15 to 30 mol%. When the proportion of the structural unit (a) having an acid group is 5 to 40 mol%, the rate of alkali development is appropriate, and a fine colored pattern can be formed.
When the copolymer (a) further contains another structural unit (c) described later, the proportion of the structural unit (a) having an acid group contained in the copolymer (a) is preferably 5 to 60 mol%, more preferably 8 to 50 mol%, and most preferably 10 to 40 mol%. When the proportion of the structural unit (a) having an acid group is 5 to 60 mol%, the rate of alkali development is appropriate, and a fine colored pattern can be formed.
< structural unit (b) having a cyclic ether group >
The structural unit (b) having a cyclic ether group contained in the copolymer (a) is a structural unit derived from a polymerizable monomer having a cyclic ether group (with the exception of the structural unit corresponding to the structural unit (a) having an acid group). Examples of the cyclic ether group include: epoxy, oxetane, and the like. Specific examples of the epoxy group-containing polymerizable monomer include: glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate having an alicyclic epoxy group, and lactone adducts thereof (for example, CYCLOMERs (registered trademark) a200 and M100, manufactured by DAICEL corporation), mono (meth) acrylate of 3, 4-epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexanecarboxylate, epoxide of dicyclopentenyl (meth) acrylate, epoxide of dicyclopentenyloxyethyl (meth) acrylate, and the like. Among them, from the viewpoint of ease of acquisition and reactivity, an epoxy group-containing (meth) acrylate is preferable, and glycidyl (meth) acrylate is more preferable. Specific examples of the polymerizable monomer having an oxetanyl group include: (meth) acrylic acid (3-ethyloxetan-3-yl) methyl ester, 4- [ 3- (3-ethyloxetan-3-ylmethoxy) propoxy ] styrene, 4- [ 6- (3-ethyloxetan-3-ylmethoxy) hexyloxy ] styrene, 4- [ 5- (3-ethyloxetan-3-ylmethoxy) pentyloxy ] styrene, 2-vinyl-2-methyloxetane and the like. Among them, from the viewpoint of ease of acquisition and reactivity, an oxetanyl group-containing (meth) acrylate is preferred, and (3-ethyloxetan-3-yl) methyl (meth) acrylate is more preferred. These polymerizable monomers may be used alone, or two or more of them may be used in combination.
In the present invention, the copolymer (a) contains the structural unit (b) having a cyclic ether group, and thus the solvent resistance when the copolymer (a) is used as a photosensitive material is greatly improved.
When the copolymer (a) contains a structural unit (a) having an acid group and a structural unit (b) having a cyclic ether group, the proportion of the structural unit (b) having a cyclic ether group contained in the copolymer (a) is preferably 60 to 95 mol%, more preferably 65 to 90 mol%, and most preferably 70 to 85 mol%. When the proportion of the structural unit (b) having a cyclic ether group is 60 to 95 mol%, both the solvent resistance of the cured coating film and the storage stability of the copolymer (a) can be satisfied.
When the copolymer (a) further contains another structural unit (c) described later, the proportion of the structural unit (b) having a cyclic ether group contained in the copolymer (a) is preferably 5 to 70 mol%, more preferably 8 to 60 mol%, and most preferably 10 to 50 mol%. When the proportion of the structural unit (b) having a cyclic ether group is 5 to 70 mol%, both the solvent resistance of the cured coating film and the storage stability of the copolymer (a) can be satisfied.
< other structural Unit (c) >)
In the present invention, the copolymer (a) may further contain a structural unit (c) other than the structural unit (a) having an acid group and the structural unit (b) having a cyclic ether group (with the exception of structural units corresponding to the structural unit (a) having an acid group and the structural unit (b) having a cyclic ether group). The polymerizable monomer providing the other structural unit (c) is usually a radical polymerizable compound having an ethylenically unsaturated group, and examples of the radical polymerizable compound having an ethylenically unsaturated group include: dienes such as butadiene; methyl (meth) acrylate, ethyl (meth) acrylate, N-propyl (meth) acrylate, isopropyl (meth) acrylate, N-butyl (meth) acrylate, benzyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, 1, 4-cyclohexanedimethanol mono (meth) acrylate, rosin ester (meth) acrylate, norbornyl (meth) acrylate, allyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 1, 1, 1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, isopropyl (meth) acrylate, N-butyl (meth) acrylate, benzyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, 1, 1, 1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, N-butyl (meth) acrylate, benzyl (meth) acrylate, methyl (meth) acrylate, N-butyl acrylate, benzyl (meth) acrylate, methyl acrylate, ethyl (meth) acrylate, methyl (2-ethyl (meth) acrylate, methyl acrylate, ethyl acrylate, methyl acrylate, ethyl (2, methyl acrylate, ethyl (meth) acrylate, methyl acrylate, ethyl acrylate, and methyl acrylate, ethyl acrylate, Glycerol mono (meth) acrylate, butanetriol mono (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate(meth) acrylates such as esters, adamantyl (meth) acrylate, naphthyl (meth) acrylate, and anthracenyl (meth) acrylate; norbornene (bicyclo [2.2.1 ]]Hept-2-ene), 5-methylbicyclo [2.2.1]Hept-2-ene, tetracyclo [4.4.0.12，5.17，10]Dodec-3-ene, dicyclopentadiene, tricyclo [5.2.1.02，6]Dec-8-ene, tetracyclo [4.4.0.12，5.17，10.01，6]Dodec-3-ene, pentacyclic [6.5.1.1 ]3，6.02,7.09，13](meth) acrylic acid amides such as pentadecene-4-ene, 5-norbornene-2, 3-dicarboxylic acid, 5-norbornene-2, 3-dicarboxylic anhydride, (meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid anthranylamide, N-isopropyl (meth) acrylamide, (meth) acryloyl morpholine, diacetone (meth) acrylamide, and the like; vinyl compounds such as (Meth) acrylic acid anilide, (Meth) acrylic acid nitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, and vinyl toluene; styrene, alpha-, o-, m-, p-alkyl, nitro, cyano, amide derivatives of styrene; unsaturated dicarboxylic acid diesters such as diethyl citraconate, diethyl maleate, diethyl fumarate and diethyl itaconate; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N- (4-hydroxyphenyl) maleimide; unsaturated polybasic acid anhydrides such as maleic anhydride and itaconic anhydride. These radical polymerizable compounds having an ethylenically unsaturated group may be used alone, or two or more of them may be used in combination. Among these, methyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentyl (meth) acrylate, styrene, vinyltoluene, isobornyl (meth) acrylate, adamantyl (meth) acrylate, norbornene, N-isopropyl (meth) acrylamide, (meth) acryloylmorpholine, and diacetone (meth) acrylamide are preferable from the viewpoint of heat resistance and transparency, and methyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentyl (meth) acrylate, styrene, ethylene, and diacetone (meth) acrylamide are more preferableToluene, isobornyl (meth) acrylate, adamantyl (meth) acrylate, and norbornene.
The proportion of the other structural unit (c) contained in the copolymer (a) is not particularly limited, but is preferably from more than 0 mol% to 80 mol%, more preferably from 5 mol% to 70 mol%, and most preferably from 10 mol% to 60 mol%. In the present invention, the other structural unit (c) is not essential, but the copolymer (A) containing the other structural unit (c) can suitably improve solvent resistance and coating film characteristics.
In the present specification, the term (meth) acrylate means any of acrylate and methacrylate, and the term (meth) acrylic acid means any of acrylic acid and methacrylic acid.
< method for producing copolymer (A) >
The proportion of the acid group-containing polymerizable monomer (a0) providing the structural unit (a) having an acid group and the cyclic ether group-containing polymerizable monomer (b0) providing the structural unit (b) having a cyclic ether group used in the production of the copolymer (a) containing the structural unit (a) having an acid group and the structural unit (b) having a cyclic ether group is not particularly limited, but is preferably (a0)5 to 40 mol% and (b0)60 to 95 mol%, more preferably (a0)10 to 35 mol% and (b0)65 to 90 mol%, most preferably (a0)15 to 30 mol% and (b0)70 to 85 mol%.
The proportions of the acid group-containing polymerizable monomer (a0) providing the structural unit (a) having an acid group, the cyclic ether group-containing polymerizable monomer (b0) providing the structural unit (b) having a cyclic ether group, and the other polymerizable monomer (c0) providing the other structural unit (c) used in the production of the copolymer (a) containing the structural unit (a) having an acid group, the structural unit (b) having a cyclic ether group, and the other structural unit (c) are not particularly limited, however, (a0) is preferably 5 to 60 mol%, (b0) is preferably 5 to 70 mol%, and (c0) exceeds 0 to 80 mol%, more preferably (a0) is 8 to 50 mol%, (b0) is 8 to 60 mol%, and (c0) is 5 to 70 mol%, and most preferably (a0) is 10 to 40 mol%, (b0) is 10 to 50 mol%, and (c0) is 10 to 60 mol%.
The copolymerization reaction of the acid group-containing polymerizable monomer (a0), the cyclic ether group-containing polymerizable monomer (b0), and the polymerizable monomer (c0) providing the other structural unit (c) may be carried out in the presence or absence of a polymerization solvent according to a radical polymerization method known in the art. For example, if desired, these polymerizable monomers may be dissolved in a solvent, and then a polymerization initiator may be added to the solution to carry out a polymerization reaction at 50 to 130 ℃ for 1 to 20 hours.
The solvent usable in the copolymerization reaction is not particularly limited as long as it is inert to the reaction, and examples thereof 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, and tripropylene glycol monoethyl ether; (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 ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones 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, esters such as isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; carboxylic acid amides such as N-methylpyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide; diethylene glycol, and the like. These solvents may be used alone, or two or more of them may be used in combination.
Among these solvents, ether solvents are preferred, and propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ether, and ethylene glycol monomethyl ether are more preferred, because they can be used as the component (C) of the photosensitive resin composition for a color filter of the present invention without removing the solvent after completion of the copolymerization reaction.
The amount of the solvent used for the copolymerization reaction is not particularly limited, but is usually 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, when the total charge amount of the polymerizable monomer is 100 parts by mass. In particular, by setting the amount of the solvent to 1000 parts by mass or less, the viscosity of the copolymer (a) can be controlled within an appropriate range while suppressing a decrease in the molecular weight of the copolymer (a) due to chain transfer. Further, by setting the amount of the solvent to 30 parts by mass or more, an abnormal polymerization reaction can be prevented, a polymerization reaction can be stably performed, and coloring and gelation of the copolymer (a) can also be prevented.
The radical polymerization initiator that can be used in the copolymerization reaction is not particularly limited, and examples thereof include: azo radical polymerization initiators such as azobisisobutyronitrile and 2, 2' -azobis (2, 4-dimethylvaleronitrile); and organic peroxide-based radical polymerization initiators such as benzoyl peroxide and t-butylperoxy-2-ethylhexanoate. These radical polymerization initiators may be used alone, or two or more kinds may be used in combination. When the total charge amount of the polymerizable monomer is 100 parts by mass, the amount of the radical polymerization initiator used is usually 0.5 to 20 parts by mass, preferably 1.0 to 10 parts by mass.
The weight average molecular weight of the copolymer (A) in terms of polystyrene is preferably 1000 to 50000, more preferably 3000 to 40000. When the weight average molecular weight of the copolymer (a) is 1000 or more, a defect in a colored pattern is less likely to occur after alkali development when the copolymer (a) is used as a photosensitive resin composition. On the other hand, when the weight average molecular weight of the copolymer (a) is 50000 or less, the development time becomes appropriate, and the practicability is ensured.
The acid value (JIS K69015.3) of the copolymer (A) is preferably 20 to 300KOHmg/g, more preferably 30 to 200 KOHmg/g. When the acid value of the copolymer (A) is 20KOHmg/g or more, the photosensitive resin composition for a color filter has good alkali developability. On the other hand, when the acid value of the copolymer (A) is 300KOHmg/g or less, the exposed portion (photocurable portion) is not easily dissolved in an alkali developing solution, and thus the pattern shape is good.
The cyclic ether group equivalent of the copolymer (A) is not particularly limited, but is usually in the range of 200 to 2000g/mol, preferably 300 to 1500g/mol, and more preferably 480 to 900 g/mol. When the cyclic ether group equivalent of the copolymer (A) is 200g/mol or more, the stability is good. On the other hand, if the cyclic ether group equivalent of the copolymer (A) is 2000g/mol or less, the solvent resistance is sufficiently ensured. The equivalent weight of the cyclic ether group means the mass of the polymer corresponding to 1 mole of the cyclic ether group in the polymer, and can be determined by dividing the mass of the polymer by the amount of the cyclic ether group in the polymer (g/mol). In the present invention, the cyclic ether group equivalent of the copolymer (a) is a theoretical value calculated from the charged amount of the polymerizable monomer.
< Compound (B) generating acid by Heat and/or ultraviolet irradiation >
Hereinafter, the compound which generates an acid by heat is referred to as "(B-1) thermal acid generator", and the compound which generates an acid by ultraviolet irradiation is referred to as "(B-2) photoacid generator". The (B-1) thermal acid generator and the (B-2) photoacid generator are not particularly limited as long as they can generate an acid by heat and/or ultraviolet irradiation, and examples thereof include: onium salts such as Iodonium salt (Iodonium salt), sulfonium salt, phosphonium salt, and diazonium salt, and sulfonium salt is preferable. Among them, as the thermal acid generator (B-1), TA-100 and TA-120 manufactured by San-Apro Ltd, which generate an acid under heating at 100 ℃ or higher and can be obtained, are preferable. The (B-2) photoacid generator is preferably a triarylsulfonium salt type photoacid generator having a small amount of impurities and high sensitivity to i-line, and of these, CPI-210 series, CPI-100 series, CPI-300 series, and CPI-400 series manufactured by San-Apro Ltd are more preferable. These (B-1) thermal acid generator and (B-2) photoacid generator may be used alone or in combination of two or more.
The amount of the compound (B) generating an acid by heat and/or ultraviolet irradiation is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and most preferably 1 to 10 parts by mass, based on 100 parts by mass of the polymerizable monomer (B0) providing the structural unit (B) having a cyclic ether group used in synthesizing the copolymer (a). When the amount of the compound (B) is 0.05 parts by mass or more, the curing reaction of the photosensitive resin composition is easily progressed. On the other hand, when the amount of the compound (B) is 20 parts by mass or less, the storage stability of the photosensitive resin composition becomes high.
The total of the copolymer (a) and the compound (B) that generates an acid by heat and/or ultraviolet irradiation is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and most preferably 10 to 30% by mass, when the total of the components other than the solvent (C) in the photosensitive resin composition for a color filter is 100% by mass. When the amount is in this range, the solvent resistance of the cured coating film can be improved and the storage stability can be maintained.
< solvent (C) >
The photosensitive resin composition for a color filter of the present invention can be prepared by appropriately mixing a desired solvent (C) with the copolymer (a) separated from the copolymerization reaction system, but the copolymer (a) does not necessarily need to be separated, and the solvent contained at the end of the copolymerization reaction may be used as it is as the solvent (C), and in this case, a desired solvent may be further added as necessary. Further, a solvent contained in other components used in the production of the photosensitive resin composition for a color filter may be used as the solvent (C).
The amount of the solvent (C) is usually 10 to 800 parts by mass, preferably 50 to 500 parts by mass, and more preferably 100 to 300 parts by mass, based on 100 parts by mass of the total of the components other than the solvent (C) in the photosensitive resin composition for a color filter. If the amount is within this range, the photosensitive resin composition for a color filter has an appropriate viscosity.
< reactive diluent (D) >
The reactive diluent (D) is a compound having at least one polymerizable ethylenically unsaturated group as a polymerizable functional group in the molecule, and among them, a compound having a plurality of polymerizable functional groups is preferable. When the photosensitive resin composition for a color filter contains the reactive diluent (D), the strength and adhesion to a substrate of the formed cured product are improved.
Examples of monofunctional monomers to be used as reactive diluent (D) 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, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2, 2, 2-trifluoroethyl (meth) acrylate, propylene glycol mono (meth) acrylate, 2, propylene glycol mono (meth) acrylate, propylene glycol (meth) acrylate, 2, 2, 2-fluoro (meth) acrylate, 2-ethyl (meth) acrylate, 2-fluoro-ethyl acrylate, 2-fluoro-2-fluoro-ethyl acrylate, 2-ethyl acrylate, or a mixture of (meth) acrylate, (meth) acrylic acid esters such as 2, 2, 3, 3-tetrafluoropropyl (meth) acrylate and hemi (meth) acrylate of a 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 monomers may be used alone or in combination of two or more.
As the polyfunctional monomer used as the reactive diluent (D), there can be mentioned: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butanediol 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, 2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 2-bis (meth) acryloyloxydethoxyphenyl) acrylate, 2-4- (meth) acryloyloxydethoxyphenyl) acrylate, 2-1, 2-1-bis (meth) acrylate, 2-acrylate, and (meth) acrylate, 2-acrylate, and/or-acrylate, (meth) acrylates such as ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, 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 hexamethylene diisocyanate, and tri (meth) acrylate such as tri (hydroxyethyl) isocyanurate; aromatic vinyl compounds such as divinylbenzene, diallyl phthalate and diallyl phenylphosphonate; dicarboxylic acid esters such as divinyl adipate; triallyl cyanurate, methylenebis (meth) acrylamide, (meth) acrylamidomethylene ether, a condensate of a polyhydric alcohol and N-methylol (meth) acrylamide, and the like. These monomers may be used alone or in combination of two or more.
The amount of the reactive diluent (D) is usually 1 to 60 mass%, preferably 5 to 50 mass%, and more preferably 10 to 40 mass% when the total of the components other than the solvent (C) in the photosensitive resin composition for a color filter is 100 mass%. When the amount is within this range, the photosensitive resin composition for a color filter has an appropriate viscosity and photocurability.
< photopolymerization initiator (E) >
The photopolymerization initiator (E) is not particularly limited, and examples thereof include: benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin butyl ether; acetophenones 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 and the like; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; thioxanthones such as xanthone, thioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diisopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4- (1-tert-butyldioxy-1-methylethyl) benzophenone, and 3, 3 ', 4, 4' -tetrakis (tert-butyldioxycarbonyl) benzophenone; acylphosphine oxides; oxime esters such as 1, 2-octanedione and 1- [ 4- (phenylthio) -, 2- (O-benzoyloxime) ]. These photopolymerization initiators (E) may be used alone or in combination of two or more.
The amount of the photopolymerization initiator (E) is usually 0.01 to 15% by mass, preferably 0.05 to 10% by mass, and more preferably 0.1 to 5% by mass, based on 100% by mass of the total of the components other than the solvent (C) in the photosensitive resin composition for a color filter. If the amount is within this range, the photosensitive resin composition for a color filter has appropriate photocurability.
The photosensitive resin composition for a color filter of the present invention may contain, in addition to the above components, known additives such as a known coupling agent, a leveling agent, and a thermal polymerization inhibitor in order to impart predetermined characteristics. The amount of these additives is not particularly limited as long as the effects of the present invention are not hindered.
< colorant (F) >)
The colorant (F) is not particularly limited as long as it is dissolved or dispersed in the solvent (C), and examples thereof include dyes and pigments. As the dye, an acid dye having an acid group such as carboxylic acid or sulfonic acid, a salt of an acid dye with a nitrogen compound, a sulfonamide compound of an acid dye, or the like is preferably used from the viewpoints of solubility in a solvent (C) or an alkali developer, interaction with other components in the photosensitive resin composition, heat resistance, and the like.
Examples of such dyes include: alizarin violet (acid alizarin violet) N; acid black (acid black)1, 2, 24, 48; acid blue (acid blue)1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; acid chrome violet (acid chrome violet) K; acid Fuchsin (acid Fuchsin); acid green (acid green)1, 3, 5, 25, 27, 50; acid orange (acid orange)6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red (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 (acid violet)6B, 7, 9, 17, 19; acid yellow (acid yellow)1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; edible yellow (food yellow)3 and derivatives thereof, and the like. Among them, azo, xanthene, anthraquinone or phthalocyanine acid dyes are preferable. These dyes may be used alone or in combination of two or more depending on the color of the target pixel.
Examples of pigments include: 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 and the like; 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, 59; c.i. brown pigments such as pigment brown 23, 25, etc.; c.i. pigment black 1, 7, carbon black, titanium black, iron oxide, and other black pigments; and the like. These pigments may be used alone or in combination of two or more depending on the color of the target pixel.
The colorant (F) may be a combination of the above-mentioned dye and pigment depending on the color of the target pixel.
When a pigment is used as the colorant (F), a known dispersant may be blended into the photosensitive resin composition for a color filter from the viewpoint of improving the dispersibility of the pigment. As the dispersant, a polymer dispersant having excellent dispersion stability with time is preferably used. Examples of the polymeric dispersant include: urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic modified ester-based dispersants. As such a polymer dispersant, commercially available products such as EFKA (EFKA Chemical b.v. (EFKA)), Disperbyk (BYK Chemie), Disparlon (manufactured by nankeka corporation) and SOLSPERSE (manufactured by Zaneca) can be used. The blending amount of the dispersant may be appropriately set according to the kind of the pigment and the like used.
The content of the colorant (F) is appropriately adjusted depending on the dye and pigment used, but is usually preferably 20 to 80 mass%, more preferably 30 to 75 mass%, and most preferably 40 to 70 mass% when the total of the components other than the solvent (C) in the photosensitive resin composition for a color filter is 100 mass%. If the amount is within this range, the photosensitive resin composition for a color filter has appropriate photocurability.
The amounts of the copolymer (A), the compound (B) which generates an acid upon heat and/or ultraviolet irradiation, the solvent (C), the reactive diluent (D), the photopolymerization initiator (E) and the colorant (F) to be blended in the photosensitive resin composition for a color filter are such that, assuming that the total of the components other than the solvent (C) in the photosensitive resin composition for a color filter is 100% by mass, the total of the copolymer (A) and the compound (B) which generates an acid upon heat and/or ultraviolet irradiation is 1% by mass to 50% by mass, the reactive diluent (D) is 1% by mass to 60% by mass, the photopolymerization initiator (E) is 0.01% by mass to 15% by mass, and the colorant (F) is 20% by mass to 80% by mass, assuming that the total of the components other than the solvent (C) in the photosensitive resin composition for a color filter is 100 parts by mass, the amount of the solvent (C) is 10 to 800 parts by mass, and the amount of the compound (B) that generates an acid by heat and/or ultraviolet irradiation is 0.05 to 20 parts by mass per 100 parts by mass of the polymerizable monomer (B0) that provides the structural unit (B) having a cyclic ether group used in synthesizing the copolymer (a). Preferably, when the total of the components other than the solvent (C) in the photosensitive resin composition for a color filter is 100% by mass, the total amount of the copolymer (A) and the compound (B) which generates an acid by heat and/or ultraviolet irradiation is 5 to 40% by mass, the amount of the reactive diluent (D) is 5 to 50% by mass, the amount of the photopolymerization initiator (E) is 0.05 to 10% by mass, the amount of the colorant (F) is 30 to 75% by mass, the amount of the solvent (C) is 50 to 500 parts by mass based on 100 parts by mass of the total amount of the components other than the solvent (C) in the photosensitive resin composition for a color filter, and the amount of the compound (B) which generates an acid by heat and/or ultraviolet irradiation is 0.1 to 15 parts by mass per 100 parts by mass of the polymerizable monomer (B0). More preferably, when the total of the components other than the solvent (C) in the photosensitive resin composition for a color filter is 100% by mass, the total amount of the copolymer (A) and the compound (B) which generates an acid by heat and/or ultraviolet irradiation is 10 to 30% by mass, the amount of the reactive diluent (D) is 10 to 40% by mass, the amount of the photopolymerization initiator (E) is 0.1 to 5% by mass, the amount of the colorant (F) is 40 to 70% by mass, the total amount of the components other than the solvent (C) in the photosensitive resin composition for a color filter is 100 parts by mass, the solvent (C) is 100 to 300 parts by mass, and the amount of the compound (B) generating an acid by heat and/or ultraviolet irradiation is 1 to 10 parts by mass per 100 parts by mass of the polymerizable monomer (B0). If the amount is within this range, the photosensitive resin composition for a color filter has an appropriate viscosity. In addition, even in the case of a photosensitive resin composition containing no colorant (F), the amounts of the copolymer (a), the compound (B) that generates an acid upon irradiation with heat and/or ultraviolet rays, the solvent (C), the reactive diluent (D), and the photopolymerization initiator (E) can be within the above-mentioned numerical ranges, and can be used for various coatings, adhesives, binders for printing inks, and the like.
< production of photosensitive resin composition for color Filter >
The photosensitive resin composition for a color filter of the present invention can be produced by mixing the above components using a known mixing device. If desired, the polymer composition containing the copolymer (a), the compound (B) generating an acid by heat and/or ultraviolet irradiation, and the solvent (C) may be prepared in advance, and then the reactive diluent (D), the photopolymerization initiator (E), and the colorant (F) may be mixed.
The photosensitive resin composition for a color filter obtained as described above is preferably used as a resist because it has alkali developability. The curing of the photosensitive resin composition for a color filter may be carried out at a baking temperature appropriately selected within a range of 250 ℃ or lower, but the copolymer (a) used in the present invention has excellent curability at a low temperature, and therefore the baking temperature can be reduced as compared with conventional materials. When a pigment is used as the colorant (F) in the photosensitive resin composition for a color filter, curing is sufficiently performed even when the baking temperature is 150 ℃. The photosensitive resin composition for a color filter of the present invention is advantageous in terms of energy consumption because the crosslinking reaction sufficiently proceeds even when the baking temperature is lowered. Further, even the colorant (F) having poor heat resistance and the substrate can be used, and the intrinsic characteristics of the colorant can be obtained, and the colorant can be applied to various substrates. From such a viewpoint, the baking temperature is preferably 80 to 210 ℃, more preferably 90 to 180 ℃, and most preferably 100 to 150 ℃. If the baking temperature is too low, it is difficult to sufficiently improve the solvent resistance of the coating film. The baking time may be appropriately selected, but is usually 10 minutes to 4 hours, preferably 20 minutes to 2 hours.
The photosensitive resin composition for a color filter of the present invention is preferably used as a resist for producing a color filter to be incorporated into a solid-state imaging device such as an organic EL display, a liquid crystal display device, a CCD, or a CMOS.
The photosensitive resin composition for a color filter of the present invention is excellent in developability and storage stability, and can form a colored pattern having excellent solvent resistance even when the baking temperature in pattern formation is lowered, and therefore, is extremely useful as a photosensitive material for a color filter. The photosensitive resin composition for a color filter of the present invention can also contribute to the development of flexible displays accompanied by low-temperature curing, the reduction of energy consumption in the production process, and the alleviation of restrictions on the colorant used.
< color filter >
Next, a color filter having a colored pattern formed from a cured product of the photosensitive resin composition for a color filter of the present invention will be described. The color filter of the invention has a colored pattern formed by using the photosensitive resin composition for the color filter. The color filter is generally composed of a substrate, RGB pixels formed on the substrate, a black matrix formed at the boundary of each pixel, and a protective film formed on the pixels and the black matrix. In this configuration, one or more color patterns selected from R, G and B constituting pixels and a black matrix (color pattern) are formed using the above-described photosensitive resin composition for a color filter, and other configurations may be adopted as well.
Next, an embodiment of a method for manufacturing a color filter will be described. First, a colored pattern is formed on a substrate. Specifically, a black matrix and RGB pixels are sequentially formed on a substrate. The material of the substrate is not particularly limited, and a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, a printed wiring substrate, an array substrate, or the like can be used as appropriate.
The colored pattern may be formed by photolithography. Specifically, after the photosensitive resin composition for a color filter is applied to a substrate to form a coating film, the coating film is exposed through a photomask (photo mask) having a predetermined pattern, and the exposed portion is photocured. Then, the unexposed portion is developed with an aqueous alkali solution and then baked, whereby a predetermined colored pattern can be formed.
The method of applying the photosensitive resin composition for a color filter is not particularly limited, and screen printing, roll coating, Curtain coating (curing method), spray coating, spin coating, and the like can be used. After the photosensitive resin composition for a color filter is applied, the solvent (C) may be volatilized by heating using a heating means such as a circulation oven, an infrared heater, or a hot plate, if necessary. The heating conditions are not particularly limited, and may be appropriately set according to the composition of the photosensitive resin composition for a color filter to be used. Usually, the heating is carried out at a temperature of 50 to 120 ℃ for 30 seconds to 30 minutes.
Next, the formed coating film is irradiated with an active energy ray such as ultraviolet ray or excimer laser through a Negative-type mask (Negative-type mask) to be locally exposed. The dose of the energy ray to be irradiated may be appropriately selected depending on the composition of the photosensitive resin composition for a color filter, and is, for example, preferably 30mJ/cm2～2000mJ/cm2. The light source used for exposure is not particularly limited, and it is possible to use: low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, metal halide lamps, and the like.
The aqueous alkali solution used for the development is not particularly limited, and it is possible to use: 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; and aqueous solutions of p-phenylenediamine compounds such as 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 sulfates, hydrochlorides, and p-toluenesulfonates thereof. To these aqueous solutions, an antifoaming agent and a surfactant may be added as necessary. Further, it is preferable that the developing is performed with the alkali aqueous solution, and then the developing is washed with water and dried.
The baking conditions are not particularly limited, and the baking may be performed by heat treatment depending on the composition of the photosensitive resin composition for a color filter to be used. In the conventional photosensitive resin composition, if the baking temperature is 200 ℃ or lower, the solvent resistance of the colored pattern is insufficient, but in the photosensitive resin composition for a color filter of the present invention, even when baking is performed at a temperature of 150 ℃ or lower, a colored pattern exhibiting sufficient solvent resistance can be formed. Therefore, the baking temperature can be reduced, and in the case of baking at a high temperature, the processing time can be shortened, which is a great advantage in terms of manufacturing. From such a viewpoint, the baking temperature is usually 210 ℃ or lower, preferably 180 ℃ or lower, more preferably 150 ℃ or lower, and most preferably 120 ℃ or lower, and the baking time is usually 10 minutes to 4 hours, preferably 20 minutes to 2 hours.
The desired colored pattern can be formed by repeating the above-described application, exposure, development and baking in this order using the photosensitive resin composition for a black matrix of a color filter and the photosensitive resin compositions for red, green and blue pixels of a color filter. In the above description, the method of forming a colored pattern by photocuring was described, but if a photosensitive resin composition containing a curing accelerator and a known epoxy resin in place of the photopolymerization initiator (E) is used, a desired colored pattern can be formed by applying the composition by an ink jet method and then heating the composition. Finally, a protective film is formed on the coloring pattern (RGB pixels and black matrix). The protective film is not particularly limited, and may be formed using a known material.
The color filter thus produced is produced using a photosensitive resin composition for a color filter which is excellent in sensitivity (sensitivity) and developability and which provides a colored pattern excellent in solvent resistance, and therefore has an excellent colored pattern with little color change.
< image display element >
The image display device of the present invention is an image display device including the above color filter, and specific examples thereof include: and solid-state imaging devices such as liquid crystal display devices, organic EL display devices, CCD devices, and CMOS devices. The image display element of the present invention may be manufactured by a conventional method, except for using the color filter. For example, in the case of manufacturing a liquid crystal display element, the above-described color filter is formed on a substrate, and then an electrode, a spacer (spacer), and the like are sequentially formed. Then, electrodes and the like are formed on the other substrate, and the two substrates are bonded to each other, and a predetermined amount of liquid crystal is injected to seal the two substrates.
Examples
The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the examples, all parts and percentages are by mass unless otherwise specified. Further, the acid value and the weight average molecular weight were determined as follows.
(1) The acid value is the acid value of the copolymer (A) measured in accordance with JIS K69015.3, and indicates the mg number of potassium hydroxide required for neutralizing the acidic components contained in 1g of the copolymer (A).
(2) The weight average molecular weight (Mw) represents a standard polystyrene-equivalent weight average molecular weight measured under the following conditions using Gel Permeation Chromatography (GPC).
Column: SHODEX (registered trademark) LF-804 + LF-804 (manufactured by SHOWA ELECTRIC CORPORATION)
Column temperature: 40 deg.C
Sample preparation: 0.2% tetrahydrofuran solution of copolymer
Developing solvent: tetrahydrofuran (THF)
A detector: differential refractometer (SHODEX RI-71S) (manufactured by SHOWA DENKO K.K.)
Flow rate: 1mL/min
[ Synthesis example 1]
175.5g of propylene glycol monomethyl ether was charged into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and then stirred while being replaced with nitrogen, and the temperature was raised to 78 ℃. Subsequently, a monomer mixture composed of 128.9g of (3-ethyloxetan-3-yl) methyl methacrylate as the polymerizable monomer having a cyclic ether group (b0) and 25.8g of methacrylic acid as the polymerizable monomer having an acid group (a0), and a solution obtained by adding and dissolving 13.9g of 2, 2' -azobis (2, 4-dimethylvaleronitrile) (a radical polymerization initiator) into 54.3g of propylene glycol monomethyl ether were added from a dropping funnel to the flask, respectively. After completion of the dropwise addition, 10.3g of propylene glycol monomethyl ether was added, and the mixture was stirred at 78 ℃ for 3 hours to effect a copolymerization reaction, thereby producing a copolymer, and finally, 1 part by mass of CPI-210S manufactured by San-Apro Ltd was added to 100 parts by mass of the cyclic ether group-containing polymerizable monomer (b0), thereby obtaining a polymer composition of sample No.1 (concentration of components other than the solvent was 35% by mass). The obtained polymer composition was diluted by about 100 times, and the weight average molecular weight of the copolymer in the polymer composition was 6800 as measured by the GPC. Further, using the obtained polymer composition, the acid value of the copolymer in the polymer composition measured in accordance with JIS K69015.3 was 120.5 KOHmg/g.
[ Synthesis examples 2 to 8 and comparative Synthesis examples 1 to 3]
Copolymerization was carried out under the same conditions as in Synthesis example 1 except that the raw materials shown in tables 1 and 2 were used, to obtain polymer compositions (concentration of components other than solvent: 35% by mass) of samples No.2 to 11. In comparative synthesis example 2, since the cyclic ether group-containing polymerizable monomer (B0) was not added, the amount of the compound (B) that generates an acid by heat and/or ultraviolet irradiation was the same as that of synthesis example 3 (sample No. 3). The weight average molecular weight and acid value of the copolymer in the obtained polymer composition are shown in tables 1 and 2. In addition, the cyclic ether group equivalent calculated from the charged amount of the polymerizable monomer is also shown in tables 1 and 2.
[ Table 1]
Figure BDA0002589159970000211
[ Table 2]
Figure BDA0002589159970000221
Examples 1 to 8 and comparative examples 1 to 3
< preparation of photosensitive resin composition (pigment type) for color Filter >
Into a stainless steel container filled with 200 parts by mass of zirconia beads having a diameter of 0.5mm, 100 parts by mass of c.i. pigment green 36 (colorant), 45 parts by mass of propylene glycol monomethyl ether acetate (solvent), and 25 parts by mass of Disperbyk-161 (dispersant) manufactured by BYKChemie Japan corporation were charged and mixed for 2 hours by a pigment shaker (Paint shaker) to disperse the mixture, thereby preparing a green pigment dispersion.
The green pigment dispersion was mixed with a polymer composition, a reactive diluent, a photopolymerization initiator, and a solvent to prepare a photosensitive resin composition for a color filter in the blending amounts shown in table 3. The blending amount of the polymer composition in table 3 is the blending amount (the sum of the copolymer (a) and the compound (B) that generates an acid by heat and/or ultraviolet irradiation) other than the solvent used in the preparation of the polymer composition, and the blending amount of the solvent in table 3 is the blending amount obtained by adding the solvent used in the preparation of the polymer composition, propylene glycol monomethyl ether additionally blended, and the solvent used in the preparation of the green pigment dispersion liquid. As can be seen from the amounts blended in table 3, assuming that the total of the components other than the solvent (C) in the photosensitive resin composition for a color filter is 100 mass%, the total of the copolymer (a) and the compound (B) that generates an acid by heat and/or ultraviolet irradiation is 24.4 mass%, the reactive diluent (D) is 24.4 mass%, the photopolymerization initiator (E) is 1.2 mass%, and the colorant (F) is 40.0 mass%, and assuming that the total of the components other than the solvent (C) in the photosensitive resin composition for a color filter is 100 mass%, the solvent (C) is 130.2 parts by mass.
The photosensitive resin compositions for color filters of examples 1 to 8 were prepared using the polymer compositions of samples No.1 to 8, respectively, and the photosensitive resin compositions for color filters of comparative examples 1 to 3 were prepared using the polymer compositions of samples No.9 to 11, respectively.
[ Table 3]
Figure BDA0002589159970000231
< evaluation of photosensitive resin composition for color Filter >
(1) Alkali developability
The photosensitive resin compositions for color filters of examples 1 to 8 and comparative examples 1 to 3 were each spin-coated onto a 5 cm-square glass substrate (alkali-free glass substrate) so that the thickness after exposure was 2.5 μm, and then heated at 90 ℃ for 3 minutes to volatilize the solvent. Next, a photomask having a predetermined pattern was placed at a distance of 100 μm from the coating film, and the coating film was exposed through the photomask (exposure amount: 150 mJ/cm)2) The exposed portion is photocured. Next, an aqueous solution containing 0.1 mass% of sodium carbonate was sprayed (spray) at a temperature of 23 ℃ and a pressure of 0.3MPa to dissolve and develop the unexposed portion, and then baked at 100 ℃ for 20 minutes, thereby forming a predetermined pattern. The residue after the alkali development was confirmed by observing the pattern after the alkali development with an electron microscope S-3400 manufactured by Hitachi High Technologies, Ltd. The criteria for this evaluation are as follows.
O: without residue
X: with residues
The evaluation results of alkali developability are shown in table 4.
(2) Evaluation of solvent resistance
The photosensitive resin compositions for color filters of examples 1 to 8 and comparative examples 1 to 3 were each spun to a thickness of 2.5 μm after bakingAfter coating the resultant coating on a glass substrate (alkali-free glass substrate) having a square width of 5cm, the coating was heated at 90 ℃ for 3 minutes to volatilize the solvent. Subsequently, the coating film was exposed to light having a wavelength of 365nm to cure the exposed portion, and then the cured coating film was left in a desiccator at a baking temperature of 100 ℃ for 20 minutes to produce a cured coating film. 200mL of propylene glycol monomethyl ether acetate was put into a glass bottle with a cap having a capacity of 500mL, and the mixture was allowed to stand at 80 ℃. The test piece with the cured coating film was immersed in the above solution and then allowed to stand for 5 minutes while maintaining the temperature at 80 ℃. The color change (. DELTA.E) of the test piece before and after immersion in propylene glycol monomethyl ether acetate was measured by a spectrophotometer UV-1650 PC (Shimadzu corporation)*ab). Will be Delta E*The results of ab measurements are shown in Table 4. If Δ E*When ab is 1.5 or less, the solvent resistance is said to be excellent.
(3) Evaluation of storage stability
The photosensitive resin compositions for color filters of examples 1 to 8 and comparative examples 1 to 3 were each measured in equal amounts into a glass container, and the container was sealed with an aluminum foil so as to prevent the entry of dust and the like. Next, these samples were each left to stand in a thermostat maintained at 23 ℃, and the weight average molecular weight (Mw) of the sample after 1 month was measured, and the storage stability was evaluated according to the following criteria.
Change in Mw (%) < 100 × (Mw before storage-Mw after storage)/Mw before storage
O: the ratio of change in Mw after 1 month from Mw before storage is within. + -. 20%
X: the change rate of Mw after 1 month from Mw before storage exceeds. + -. 20%
The evaluation results of storage stability are shown in table 4.
[ Table 4]
Figure BDA0002589159970000251
As shown in Table 4, the photosensitive resin compositions for color filters of examples 1 to 8 were excellent in all of alkali developability, solvent resistance and storage stability. In contrast, the photosensitive resin compositions for color filters of comparative examples 1 to 3 had insufficient solvent resistance, and the photosensitive resin composition for color filters of comparative example 3 had insufficient alkali developability.
From the above results, it is understood that the present invention provides a photosensitive resin composition for a color filter, which has good developability and is excellent in solvent resistance and storage stability under low-temperature curing conditions.

Claims (12)

1. A photosensitive resin composition for a color filter, characterized in that,
comprises the following components: a copolymer (A) containing a structural unit (a) having an acid group and a structural unit (B) having a cyclic ether group, a compound (B) which generates an acid by heat and/or ultraviolet irradiation, a solvent (C), a reactive diluent (D), a photopolymerization initiator (E), and a colorant (F),
the structural unit (b) having a cyclic ether group is a structural unit derived from glycidyl (meth) acrylate,
the amount of the compound (B) generating an acid by heat and/or ultraviolet irradiation is 0.05 to 20 parts by mass per 100 parts by mass of the polymerizable monomer,
the polymerizable monomer is a substance which provides the structural unit (b) having a cyclic ether group, and is used for synthesizing the copolymer (a).
2. The photosensitive resin composition for a color filter according to claim 1, wherein,
the structural unit (a) having an acid group is a structural unit derived from an ethylenically unsaturated compound having a carboxyl group.
3. The photosensitive resin composition for a color filter according to claim 1 or 2, wherein,
the copolymer (A) contains the structural unit (a) having an acid group in a proportion of 5 to 40 mol%, and the structural unit (b) having a cyclic ether group in a proportion of 60 to 95 mol%.
4. The photosensitive resin composition for a color filter according to claim 1 or 2, wherein,
the copolymer (A) further contains a structural unit (c) derived from a radical polymerizable compound having an ethylenically unsaturated group.
5. The photosensitive resin composition for a color filter according to claim 4, wherein,
the copolymer (A) contains the structural unit (a) having an acid group in a proportion of 5 to 60 mol%, the structural unit (b) having a cyclic ether group in a proportion of 5 to 70 mol%, and the structural unit (c) derived from a radical polymerizable compound having an ethylenically unsaturated group in a proportion of more than 0 to 80 mol%.
6. The photosensitive resin composition for a color filter according to claim 1 or 2, wherein,
the compound (B) generating an acid by heat and/or ultraviolet irradiation is a sulfonium salt.
7. The photosensitive resin composition for a color filter according to claim 1 or 2, wherein,
the weight average molecular weight of the copolymer (A) is 1000-50000, and the acid value is 20-300 KOHmg/g.
8. The photosensitive resin composition for a color filter according to claim 1 or 2, wherein,
the colorant (F) includes a pigment.
9. The photosensitive resin composition for a color filter according to claim 1 or 2, wherein,
the total amount of the copolymer (A) and the compound (B) generating an acid by heat and/or ultraviolet irradiation is 1 to 50% by mass, the reactive diluent (D) is 1 to 60% by mass, the photopolymerization initiator (E) is 0.01 to 15% by mass, and the colorant (F) is 20 to 80% by mass, when the total amount of the components other than the solvent (C) in the photosensitive resin composition for a color filter is 100% by mass, the solvent (C) is 10 to 800 parts by mass, when the total amount of the components other than the solvent (C) in the photosensitive resin composition for a color filter is 100 parts by mass.
10. A color filter is characterized in that,
has a colored pattern formed by a cured product of the photosensitive resin composition for a color filter according to any one of claims 1 to 9.
11. An image display element is characterized in that,
the color filter according to claim 10.
12. A method for manufacturing a color filter is characterized in that,
the method comprises the following steps: a step of forming a colored pattern by applying the photosensitive resin composition for a color filter according to any one of claims 1 to 9 to a substrate, exposing and alkali-developing the composition, and then baking the composition at a temperature of 150 ℃ or lower.
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