WO2023119900A1 - 感光性樹脂組成物およびカラーフィルター - Google Patents

感光性樹脂組成物およびカラーフィルター Download PDF

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WO2023119900A1
WO2023119900A1 PCT/JP2022/040995 JP2022040995W WO2023119900A1 WO 2023119900 A1 WO2023119900 A1 WO 2023119900A1 JP 2022040995 W JP2022040995 W JP 2022040995W WO 2023119900 A1 WO2023119900 A1 WO 2023119900A1
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group
mass
resin composition
parts
structural unit
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English (en)
French (fr)
Japanese (ja)
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司 原
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Resonac Corp
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Resonac Corp
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Priority to CN202280075675.5A priority Critical patent/CN118235090A/zh
Priority to JP2023569136A priority patent/JP7852652B2/ja
Priority to KR1020247015614A priority patent/KR20240074876A/ko
Publication of WO2023119900A1 publication Critical patent/WO2023119900A1/ja
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    • 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
    • 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
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • 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
    • G02F1/133514—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
    • G03F7/038—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

Definitions

  • the present invention relates to a photosensitive resin composition, a photosensitive coloring composition, a cured resin film, a color filter and an image display device.
  • This application claims priority based on Japanese Patent Application No. 2021-207178 filed in Japan on December 21, 2021, the contents of which are incorporated herein.
  • a color filter is usually formed using a method of curing a resin composition on a substrate by baking at a temperature of over 200°C.
  • substrate materials are being switched from glass to organic materials such as resins.
  • colorants used in color filters are being switched from pigments to materials such as dyes and/or fluorescent compounds and quantum dots.
  • Patent Document 1 discloses a colored photocurable resin composition containing a photocurable compound (A), a binder resin (B), a photoinitiator (D), and a solvent (E).
  • the photocurable compound (A) is a carboxy group-containing dipentaerythritol pentaacrylate.
  • the binder resin (B) contains one or more of a tetrahydropyran structure or a tetrahydrofuran structure in its main chain structure.
  • the organic material used as the substrate material is inferior to glass in heat resistance. Dyes used as colorants for color filters are inferior in heat resistance to pigments. For these reasons, it is desired to lower the heating temperature for curing resin compositions used as materials for color filters. Specifically, depending on the heat resistance of the substrate material and the colorant material, the heating temperature for curing the resin composition, which is the material of the color filter, may be required to be 80 to 150°C. .
  • the present invention has been made in view of the above circumstances, and has excellent developability and good low-temperature curability, and a photosensitive resin composition capable of forming a cured resin film having sufficient hardness and solvent resistance.
  • An object is to provide a photosensitive coloring composition.
  • Another object of the present invention is to provide a cured resin film comprising a cured product of the photosensitive resin composition of the present invention and having sufficient hardness and solvent resistance.
  • Another object of the present invention is to provide a color filter having a colored pattern formed from a cured product of the photosensitive coloring composition of the present invention and having sufficient hardness and solvent resistance.
  • a further object of the present invention is to provide an image display device comprising this color filter.
  • the present invention includes the following aspects.
  • a photosensitive resin composition comprising a structural unit (a-2) having a and a structural unit (a-3) having an acid group.
  • the structural unit (a-2) is an epoxy group, a silyl group, a blocked isocyanato group, an isocyanato group, a hydroxyl group, a mercapto group, an oxetanyl group, an amino group, a furyl group, a maleimide group, an oxazolidinyl group, an oxazolyl group,
  • the structural unit (a-2) is a structural unit (a-2-1) having an epoxy group, a structural unit (a-2-2) having a silyl group, or a structural unit having a blocked isocyanato group
  • the structural unit (a-1) is 2 to 80 mol%
  • the photosensitive resin composition according to any one of [1] to [4], wherein the structural unit (a-2) is 2 to 80 mol%.
  • R 4 represents a cyano group (—CN), nitro represents a group (-NO 2 ), a group represented by the following formula (11), or a group represented by the following formula (12).
  • * represents a binding site.
  • R 5 is a hydrogen atom or 1 carbon atom that may contain a heteroatom. represents a hydrocarbon group of ⁇ 24).
  • R 3 is a divalent group represented by the formula (8) or (10), The photosensitive resin composition according to [7], wherein R 4 is a group represented by formula (11).
  • the resin (A) has a weight average molecular weight of 1,000 to 50,000;
  • Mw/Mn molecular weight distribution
  • a photosensitive coloring composition comprising: [12] For a total of 100 parts by mass of the components excluding the solvent (D), Containing 10 parts by mass to 85 parts by mass of the resin (A), Containing 10 parts by mass to 85 parts by mass of the reactive diluent (B), 0.1 parts by mass to 30 parts by mass of the photopolymerization initiator (C), Containing 30 parts by mass to 1000 parts by mass of the solvent (D), death,
  • the photosensitive coloring composition according to [11] which contains 4 parts by mass to 85 parts by mass of the coloring agent (E).
  • a cured resin film comprising a cured product of the photosensitive resin composition according to any one of [1] to [10].
  • a color filter having a colored pattern comprising a cured product of the photosensitive coloring composition according to any one of [11] and [12].
  • An image display device comprising the color filter of [14].
  • a photosensitive resin composition and a photosensitive coloring composition that have excellent developability and good low-temperature curability and can form a cured resin film having sufficient hardness and solvent resistance.
  • a cured resin film comprising a cured product of the photosensitive resin composition of the present invention and having sufficient hardness and solvent resistance.
  • a color filter having a colored pattern formed from a cured product of the photosensitive coloring composition of the present invention and having sufficient hardness and solvent resistance.
  • an image display device equipped with this color filter is possible to provide.
  • (meth)acrylic acid means at least one selected from methacrylic acid and acrylic acid
  • (meth)acrylate means at least one selected from methacrylate and acrylate
  • (meth)acryloyl means at least one selected from methacryloyl and acryloyl.
  • the photosensitive resin composition of this embodiment contains a resin (A), a reactive diluent (B), a photopolymerization initiator (C) and a solvent (D).
  • the resin (A) contained in the photosensitive resin composition of the present embodiment includes at least one structural unit (a-1) selected from the group consisting of active methylene groups and active methine groups (hereinafter simply referred to as “structural unit ( a-1)”), a structural unit (a-2) having a group that reacts with the action of light and/or heat (hereinafter also simply referred to as “structural unit (a-2)”), and a structural unit (a-3) having an acid group (hereinafter also simply referred to as “structural unit (a-3)”).
  • the resin (A) may optionally contain a structural unit (a-4), and the number of repetitions and the order of bonding are not particularly limited.
  • the structural unit (a-1) is a structural unit having at least one group selected from the group consisting of active methylene groups and active methine groups.
  • the photosensitive resin composition has good low-temperature curability, and even when the photosensitive resin composition is cured at a low temperature, it is formed.
  • the resulting cured resin film has sufficient hardness, solvent resistance and developability.
  • the active methylene group or active methine group of the structural unit (a-1) the hydrogen atom of the methylene group is easily eliminated to promote the cross-linking reaction of the resin.
  • the methylene bond between the two carbonyls of acetoacetate is active and readily undergoes a hydrogen abstraction reaction. It may also be related to photocuring.
  • the active methylene group and active methine group in the present embodiment refer to a methylene group and a methine group having both ends bonded to any one of a carbon atom of a carbonyl group, a sulfur atom of a sulfonyl group, a cyano group, and a nitro group.
  • Structures having an active methylene group include, for example, structures having the following formula (X1).
  • the methylene groups attached to R3 and R4 are active methylene groups.
  • R 3 represents a divalent group represented by any one of the following formulas (8) to (10).
  • R 4 represents a cyano group (--CN), a nitro group (--NO 2 ), a group represented by the following formula (11), or a group represented by the following formula (12).
  • * represents a binding site. ⁇ represents an active methylene carbon.
  • R 5 is a hydrogen atom or 1 carbon atom that may contain a heteroatom. represents a hydrocarbon group of ⁇ 24).
  • formula (X1) from the viewpoint of good low-temperature curability as a photosensitive resin composition and excellent physical properties required for color filters, either formula (8) or formula (10) A divalent group represented by the formula (10) is preferable, and a divalent group represented by the formula (10) is more preferable.
  • formulas (11) and (12) are preferred, and formula (11) is more preferred.
  • R 4 in formula (X1) represents a group represented by formula (11) or (12) above
  • the hetero atom represented by R 5 in formula (11) and formula (12) is Specific examples of hydrocarbon groups having 1 to 24 carbon atoms which may be contained include methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, methoxy group, ethoxy group, propoxy group and hexoxy group. , a cyclohexoxy group, groups represented by the following formulas (13) to (15), and the like.
  • hydrocarbon group having 1 to 24 carbon atoms which may contain a hetero atom an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 3 carbon atoms is preferable. Alkyl groups are more preferred.
  • R 5 is preferably a hydrogen atom and an alkyl group having 1 to 10 carbon atoms from the viewpoint of good low-temperature curability and excellent physical properties required for color filters, and a hydrogen atom and an alkyl group having 1 to 3 carbon atoms. More preferred are a hydrogen atom and a methyl group.
  • Structures having an active methine group include, for example, structures having the following formula (X2).
  • the methine group attached to R3 and the cyclohexane ring is the active methine group.
  • the structural unit (a-1) is preferably 2 to 80 mol%, more preferably 105 to 70 mol%, of the total structural units of the resin (A), and 4010 to 65 More preferably, it is mol %.
  • the content of the structural unit (a-1) is 2 mol% or more, the photosensitive resin composition using the resin composition containing the resin (A) as a raw material has sufficient hardness and solvent resistance. It has good low-temperature curability and can form a cured film.
  • the content of the structural unit (a-1) is 80 mol % or less, the content of the structural units (a-2) and (a-3) having functional groups in all the structural units can be sufficiently ensured.
  • a monomer (ma -1) (hereinafter also simply referred to as "monomer (ma-1)") is introduced by copolymerizing it with another ethylenically unsaturated group-containing monomer, or by polymerizing a precursor of resin (A)
  • a method of introducing an active methylene group or an active methine group later to form a resin (A) can be mentioned.
  • a precursor of the resin (A) having a hydroxy group is polymerized, and the hydroxy group of the precursor is reacted with a diketene such as 4-methyleneoxetan-2-one to convert an active methylene group.
  • the introduced resin (A) can be obtained.
  • the method for introducing the structural unit (a-1) into the resin (A) is not limited to the above.
  • the monomer (ma-1) is not particularly limited as long as it is a compound having an ethylenically unsaturated group and at least one group selected from the group consisting of an active methylene group and an active methine group.
  • ethylenically unsaturated groups include vinyl groups, allyl groups, and (meth)acryloyloxy groups.
  • a (meth)acryloyloxy group is preferable from the viewpoint of ease of polymerization for obtaining the resin (A).
  • Examples of the monomer (ma-1) include compounds represented by the following formula (1) or (2).
  • R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms which may contain a hetero atom.
  • X represents the following formulas (3) to ( 7), wherein R 2 represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and the definitions and preferred ranges of R 3 and R 4 is the same as that of formula (X1) and formula (X2). ⁇ indicates an active methylene carbon or an active methine carbon.
  • the hydrocarbon group optionally containing a heteroatom and having 1 to 24 carbon atoms represented by R 1 specifically includes a methyl group, an ethyl group, a propyl group and a butyl group. , hexyl group, cyclohexyl group, methoxy group, ethoxy group, propoxy group, hexoxy group, cyclohexoxy group, and groups represented by the following formulas (13) to (15).
  • hydrocarbon group having 1 to 24 carbon atoms which may contain a hetero atom an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 3 carbon atoms is preferable. Alkyl groups are more preferred.
  • R 1 is preferably a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom and an alkyl group having 1 to 3 carbon atoms, from the viewpoint of ease of reaction when polymerizing the resin (A).
  • a hydrogen atom and a methyl group are more preferable.
  • the monomer (ma-1) among others, a compound represented by the following formula (m1) from the viewpoint of easiness of reaction when polymerizing the resin (A), low-temperature curability as a resin composition, and physical properties of a cured resin film. is preferred.
  • R 6 represents a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms
  • R 7 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
  • the hydrocarbon group having 1 to 2 carbon atoms represented by R 6 is preferably a methyl group or an ethyl group, more preferably a methyl group, from the viewpoint of developability as a photosensitive resin composition.
  • the hydrocarbon group having 1 to 10 carbon atoms represented by R 7 may have a ring structure.
  • the hydrocarbon group represented by R 7 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms. preferable.
  • R 6 is a methyl group and R 7 has 1 to 1 carbon atoms.
  • Compounds with 4 alkyl groups are preferred.
  • Formulas (16)-(22), (31), (32), (33) and (36) are compounds with CH 3 —CH 2 ⁇ CH—, where CH 3 —CH 2 Compounds in which ⁇ CH— is replaced by H—CH 2 ⁇ CH— can also be mentioned.
  • the structural unit (a-2) of the resin (A) does not contain an active methylene group, an active methine group, or an acid group, and has a group that reacts with the action of light and/or heat.
  • the structural unit (a-2) contained in the resin (A) may be of only one type, or may be of two or more types.
  • a photosensitive resin composition using a resin composition containing the resin (A) according to the present embodiment as a raw material contains a structural unit (a-2) having a group that reacts with the action of light and/or heat.
  • the photosensitive resin composition has good low-temperature curability.
  • Low-temperature curability means a property capable of forming a cured resin film having sufficient hardness and solvent resistance.
  • the functional groups possessed by the structural unit (a-2) according to the present embodiment include an epoxy group, a silyl group, a blocked isocyanato group, a mercapto group, an isocyanato group, a hydroxyl group, an oxetanyl group, an amino group, a furyl group, a maleimide group, and an oxazolidinyl group. group, oxazolyl group, formyl group, nitro group, and halogen group.
  • a functional group that reacts by the action of heat is preferable, a group that reacts under temperature conditions of 40°C to 180°C is more preferable, and a group that reacts under temperature conditions of 50°C to 170°C is even more preferable, and 60°C. Groups that react under temperature conditions of ⁇ 160°C are most preferred. From the viewpoint of availability and reactivity when synthesizing the resin (A), the structural unit (a-2-1) having an epoxy group, the structural unit (a-2-2) having a silyl group, block Structural units (a-2-3) having an isocyanato group are more preferred.
  • the content of the structural unit (a-2) according to the present embodiment is preferably 2 to 80 mol%, more preferably 5 to 60 mol%, of the total structural units of the resin (A). More preferably 10 to 40 mol %.
  • the content of the structural unit (a-2) is 2 mol% or more, the photosensitive resin composition using the resin composition containing the resin (A) as a raw material has sufficient hardness and solvent resistance. It has good low-temperature curability and can form a cured film.
  • the content of the structural unit (a-2) is 80 mol % or less, the content of the structural units (a-1) and (a-3) having functional groups in all the structural units can be sufficiently ensured.
  • a monomer (ma-2) having an ethylenically unsaturated group and the above-described functional group (hereinafter simply referred to as "monomer (ma-2)".) can be introduced by copolymerizing it with other ethylenically unsaturated group-containing monomers, or by polymerizing the precursor of the resin (A) and then introducing the functional group described above. and the resin (A).
  • the monomer (ma-2) is not particularly limited as long as it is a compound that does not contain an active methylene group, an active methine group, or a carboxy group and has an ethylenically unsaturated group and the above-mentioned functional group.
  • ethylenically unsaturated groups include vinyl groups, allyl groups, and (meth)acryloyloxy groups.
  • a (meth)acryloyloxy group is preferable from the viewpoint of ease of polymerization for obtaining the resin (A).
  • the monomer (ma-2) is an epoxy group-containing ethylenically unsaturated compound (ma-2-1), a silyl group-containing ethylenically unsaturated compound (ma-2-2), a block isocyanato group-containing ethylenically unsaturated compound ( ma-2-3) is preferred.
  • epoxy group-containing ethylenically unsaturated compound (ma-2-1) include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and (meth)acrylate having an alicyclic epoxy group. and its lactone adduct, 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate, epoxidized dicyclopentenyl (meth)acrylate, epoxidized dicyclopentenyloxyethyl (meth)acrylate, etc. and epoxy group-containing (meth)acrylates.
  • glycidyl (meth)acrylate 3,4-epoxycyclohexylmethyl (meth)acrylate, having an alicyclic epoxy group, from the viewpoint of availability and reactivity when synthesizing the resin (A) (Meth)acrylates are preferred, and glycidyl (meth)acrylates are more preferred.
  • silyl group-containing ethylenically unsaturated compound (ma-2-2) include [(meth)acryloyloxy]methyltriethoxysilane, [(meth)acryloyloxy]ethyltriethoxysilane, [(meth)acryloyl Oxy]propyltriethoxysilane, [(meth)acryloyloxy]octyltriethoxysilane, [(meth)acryloyloxy]propylmethyldiethoxysilane, [(meth)acryloyloxy]ethylmethyldiethoxysilane, [(meth)acryloyl oxy]nonylmethyldiethoxysilane and the like.
  • 3-(meth)acryloyloxypropylmethyldimethoxysilane and 3-(meth)acryloyloxypropylmethyldiethoxysilane are preferred from the viewpoint of availability and reactivity in synthesizing the resin (A).
  • 3-(meth)acryloyloxypropylmethyldiethoxysilane is more preferred.
  • the blocked isocyanato group-containing ethylenically unsaturated compound (ma-2-3) include monomers having an ethylenically unsaturated bond and a blocked isocyanato group.
  • the monomer include compounds obtained by blocking isocyanato groups in isocyanate compounds having a vinyl group, (meth)acryloyloxy group, or the like in the molecule with a blocking agent.
  • the reaction between the isocyanate compound and the blocking agent can be carried out with or without the presence of a solvent. When using a solvent, it is necessary to use a solvent that is inert to isocyanato groups.
  • an organic metal salt such as tin, zinc or lead, or a tertiary amine may be used as a catalyst.
  • the reaction can generally be carried out at -20 to 150°C, preferably at 0 to 100°C.
  • Examples of the above isocyanate compounds include compounds represented by the following formula (XX1).
  • R 11 represents a hydrogen atom or a methyl group
  • R 12 represents -CO-, -COOR 13 -
  • R 13 is an alkylene group having 1 to 6 carbon atoms.
  • R 15 is an optionally substituted alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms.
  • R 12 is preferably —COOR 13 —, where R 13 is preferably an alkylene group having 1 to 4 carbon atoms.
  • isocyanate compound represented by the formula (XX1) examples include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2 -isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, methacryloyl isocyanate and the like.
  • An equimolar (1 mol:1 mol) reaction product of a 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound can also be used.
  • the alkyl group of the 2-hydroxyalkyl (meth)acrylate described above is preferably an ethyl group or an n-propyl group, more preferably an ethyl group.
  • diisocyanate compounds include hexamethylene diisocyanate, 2,4- (or 2,6-) tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 3,5,5-trimethyl- 3-isocyanatomethylcyclohexyl isocyanate (IPDI), m-(or p-)xylene diisocyanate, 1,3-(or 1,4-)bis(isocyanatomethyl)cyclohexane, lysine diisocyanate and the like.
  • blocking agents for blocking isocyanato groups in isocyanate compounds include lactams such as ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam and ⁇ -propiolactam; methanol, ethanol, propanol, butanol, ethylene glycol, alcohols such as methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, and cyclohexanol; Phenols such as -tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, oxybenzoic acid ester, thymol, p-naphthol, p-nitrophenol, p-chlorophenol; dimethyl malonate, diethyl malonate, methyl acetoacetate , ethyl acetoacetate, active methylene-
  • ma-2 examples include an epoxy group-containing ethylenically unsaturated compound (ma-2-1), a silyl group-containing ethylenically unsaturated compound (ma-2-2), and a blocked isocyanato group.
  • Compounds other than the containing ethylenically unsaturated compound (ma-2-3) include mercapto group-containing ethylenically unsaturated compounds such as 2-mercaptoethyl (meth)acrylate; 2-(meth)acryloyloxyethyl isocyanate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1 - isocyanato group-containing ethylenically unsaturated compounds such as dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phen
  • a maleimide group-containing ethylenically unsaturated compound oxazolidinyl group-containing ethylenically unsaturated compounds such as 2-(2-oxo-3-oxazolidinyl)ethyl (meth)acrylate; oxazolyl group-containing ethylenically unsaturated compounds such as 2-oxazolylethyl (meth)acrylate; formyl group-containing ethylenically unsaturated compounds such as formylphenyl (meth)acrylate; nitro group-containing ethylenically unsaturated compounds such as nitropropyl (meth)acrylate; 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, halogen group-containing
  • the structural unit (a-3) of the resin (A) according to the present embodiment is a structural unit other than the structural unit (a-1) and the structural unit (a-2) and has an acid group. be.
  • the structural unit (a-3) contained in the resin (A) may be of only one type, or may be of two or more types.
  • a carboxy group is preferable from the viewpoint of developability as a photosensitive resin composition.
  • the content of the structural unit (a-3) is preferably 2 to 60 mol%, more preferably 4 to 40 mol%, and 6 to 30 mol% of the total structural units of the resin (A). is more preferable.
  • the content of the structural unit (a-3) is 2 mol % or more, the effect of including a carboxy group can be sufficiently obtained.
  • the content of the structural unit (a-3) is 60 mol% or less, the content of the structural units (a-1) and (a-2) can be sufficiently ensured.
  • a monomer (ma-3) having an ethylenically unsaturated group and an acid group (hereinafter also simply referred to as "monomer (ma-3)" ) is introduced by copolymerizing it with another ethylenically unsaturated group-containing monomer, and a method of polymerizing a precursor of the resin (A) and then introducing an acid group to obtain the resin (A). be done.
  • a precursor of the resin (A) having a hydroxy group is polymerized, and a polybasic acid anhydride is added to the hydroxy group of the precursor to obtain a resin (A) into which an acid group has been introduced.
  • Examples of the monomer (ma-3) include unsaturated carboxylic acids or their anhydrides, unsaturated sulfonic acids, and unsaturated phosphonic acids. Specific examples of preferred monomers include (meth)acrylic acid, ⁇ -bromo(meth)acrylic acid, ⁇ -furyl(meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, ⁇ -cyanocinnamic acid, and maleic acid.
  • maleic anhydride monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, unsaturated carboxylic acids or anhydrides thereof such as citraconic anhydride; vinyl sulfonic acid, 2 - unsaturated sulfonic acids such as acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, p-styrenesulfonic acid; unsaturated phosphonic acids such as 2-(meth)acryloyloxyethyl acid phosphate, vinylphosphonic acid; 2-(meth)acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid and the like.
  • These monomers may be used alone or in combination of two or more.
  • (meth)acrylic acid and unsaturated carboxylic acid are preferable, and (meth)acrylic acid is more preferable, from the viewpoint of availability and reactivity when synthesizing the resin (A).
  • the resin (A) may optionally contain a structural unit (a-4) other than the structural units (a-1), (a-2) and (a-3).
  • the structural unit (a-4) contained in the resin (A) may be of only one type, or may be of two or more types.
  • the content thereof is preferably 1 to 80 mol%, more preferably 4 to 70 mol%, based on the total structural units of the resin (A). is more preferred, and 10 to 30 mol % is even more preferred.
  • the content of the structural unit (a-4) is 1 mol % or more, the effect of including the structural unit (a-4) can be sufficiently obtained.
  • the content of the structural unit (a-4) is 80 mol % or less, the content of the structural units (a-1), (a-2) and (a-3) can be sufficiently ensured.
  • a monomer (ma -4) (hereinafter also simply referred to as "monomer (ma-4)") is introduced by copolymerizing it with another ethylenically unsaturated group-containing monomer.
  • Examples of the monomer (ma-4) include dienes such as butadiene, (meth)acrylates, styrenes, unsaturated dicarboxylic acid diesters, and other vinyl compounds.
  • (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl ( Alkyl (meth)acrylates such as meth)acrylate, neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isoamyl (meth)acrylate, dodecyl (meth)acrylate; Alicyclic compounds such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl (meth)acrylate alkyl (meth)acrylate
  • styrenes include styrene and ⁇ -, o-, m-, and p-alkyl derivatives of styrene.
  • unsaturated dicarboxylic acid diesters include diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate.
  • vinyl compounds include norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[ 2.2.1]hept-2-ene, tetracyclo[4.4.0.12,5.17,10]dodeca-3-ene, 8-methyltetracyclo[4.4.0.12,5.
  • (meth)acrylic acid esters and other vinyl compounds are preferable from the viewpoint of availability and reactivity when synthesizing the resin (A), and methyl (meth)acrylate and 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, styrene, vinyltoluene and norbornene are preferred, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and dicyclopentanyl (meth)acrylate Acrylates are more preferred.
  • the weight average molecular weight (Mw) of the resin (A) is preferably 1000 to 50000, more preferably 2000 to 30000, and most preferably 3000 to 12000 in terms of polystyrene. .
  • the weight-average molecular weight (Mw) of the resin (A) is 1000 or more
  • the resin composition containing the resin (A) is used as a raw material for a photosensitive resin composition
  • the cured resin film after development may be chipped. It is possible to obtain a photosensitive resin composition that is less likely to cause the problem of
  • the weight-average molecular weight of the resin (A) is 50,000 or less, the photosensitive resin composition containing the resin (A) has sufficiently short development time and excellent practicality.
  • the value of the weight average molecular weight (Mw) of the resin (A) in the present embodiment is measured using gel permeation chromatography (GPC) under the following conditions and calculated in terms of polystyrene. .
  • GPC gel permeation chromatography
  • Sample Tetrahydrofuran solution containing 0.2% by mass of resin (A)
  • Developing solvent Tetrahydrofuran Detector: Differential refractometer (trade name: Shodex (registered trademark) RI-71S, manufactured by Showa Denko KK) Flow rate: 1 mL/min
  • the molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the resin (A) is preferably 1.3 to 5.0, more preferably 1.5 to 4.0. , 1.5 to 3.0.
  • the weight average molecular weight (Mw) of the resin (A) is 1.3 or more, the weight average molecular weight (Mw), the optimization of the target numerical range such as the acid value, and the reaction during the production of the resin (A) Conditions, etc. can be set within a certain range, and efficient production can be achieved.
  • the molecular weight distribution (Mw/Mn) of the resin (A) is 3.0 or less, when the resin composition containing the resin (A) is used as a raw material of the photosensitive resin composition, performance such as developability is affected. A photosensitive resin composition free from variations is obtained.
  • the molecular weight distribution (Mw/Mn) is calculated using the chromatogram of the GPC measurement described above.
  • the acid value of the resin (A) is not particularly limited, but is preferably 10 KOHmg/g to 300 KOHmg/g, more preferably 20KOHmg/g to 200KOHmg/g, most preferably 25KOHmg/g to 150KOHmg/g. be.
  • the acid value of the resin (A) is 10 KOHmg/g or more, the photosensitive resin composition has better developability when the resin composition containing the resin (A) is used as a raw material of the photosensitive resin composition. you get something.
  • the acid value of the resin (A) is 300 KOHmg/g or less
  • the resin composition containing the resin (A) is used as a raw material for the photosensitive resin composition
  • the exposed portion (photocured Part) does not dissolve, and a photosensitive resin composition having good developability can be obtained.
  • the acid value of resin (A) is a value measured using a mixed indicator of bromothymol blue and phenol red according to JIS K6901 5.3.
  • the acid value of resin (A) means the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of resin (A).
  • the functional group equivalent weight of the resin (A) is the equivalent weight of the aforementioned functional group contained in the structural unit (a-2) contained in the resin (A).
  • the functional group equivalent is not particularly limited, but is preferably 200 g/mol to 5000 g/mol, more preferably 300 g/mol to 4000 g/mol, and most preferably 300 g/mol to 3000 g/mol.
  • the functional group equivalent weight of the resin (A) is 200 g/mol or more, the photosensitive resin composition containing the resin (A) can form a cured resin film having superior hardness.
  • the functional group equivalent of the resin (A) is 200 g/mol or more
  • the resin composition containing the resin (A) is used as a raw material of the photosensitive resin composition
  • the photosensitive resin composition has better developability.
  • a flexible resin composition is obtained.
  • the functional group equivalent weight of the resin (A) is 5000 g/mol or less
  • the photosensitive resin composition containing the resin (A) can form a cured resin film having superior hardness.
  • the functional group equivalent weight of the resin (A) is a value obtained by dividing the molecular weight of the resin (A) by the average number of functional groups contained in the structural unit (a-2) per molecule.
  • the functional group equivalent weight of the resin (A) is a calculated value calculated based on the charged amount of the polymerizable unsaturated compound (raw material monomer) used as a raw material when synthesizing the resin (A). When one molecule of resin (A) contains different types of functional groups, all functional groups are counted as the number of functional groups regardless of the types of functional groups.
  • active methylene group and active methine group equivalent The active methylene group and active methine group equivalents of resin (A) are not particularly limited, but are preferably 200 g/mol to 5000 g/mol, more preferably 300 g/mol to 4000 g/mol, and most preferably 300 g/mol. mol-3000 g/mol.
  • the photosensitive resin composition containing the resin (A) can form a cured resin film having superior hardness.
  • the active methylene group and active methine group equivalent of the resin (A) is 200 g/mol or more
  • the resin composition containing the resin (A) is used as a raw material of the photosensitive resin composition
  • more favorable A photosensitive resin composition having developability is obtained.
  • the active methylene group equivalent of the resin (A) is 5000 g/mol or less
  • the photosensitive resin composition containing the resin (A) can form a cured resin film having superior hardness.
  • the active methylene group and active methine group equivalents of resin (A) are values obtained by dividing the molecular weight of resin (A) by the average number of active methylene groups and active methine groups per molecule.
  • the active methylene group and active methine group equivalents of the resin (A) are calculated values calculated based on the charged amounts of the polymerizable unsaturated compounds (raw material monomers) used as raw materials when synthesizing the resin (A). .
  • one molecule of resin (A) contains different types of active methylene groups and active methine groups, all active methylene groups and active methine groups are treated regardless of the types of active methylene groups and active methine groups. Count as the number of active methylene groups and active methine groups.
  • hydroxyl equivalent When the resin (A) contains a hydroxyl group, its hydroxyl equivalent is not particularly limited, but is preferably 200 g/mol to 5000 g/mol, more preferably 300 g/mol to 4000 g/mol, most preferably 300 g/mol. mol-3000 g/mol. When the hydroxyl equivalent of the resin (A) is 200 g/mol or more, the photosensitive resin composition containing the resin (A) can form a cured resin film having superior hardness. Moreover, when the hydroxyl equivalent of the resin (A) is 5000 g/mol or less, the photosensitive resin composition containing the resin (A) can form a cured resin film having superior hardness.
  • the hydroxyl equivalent of resin (A) is a value obtained by dividing the molecular weight of resin (A) by the average number of hydroxyl groups per molecule.
  • the hydroxyl equivalent of the resin (A) is a calculated value calculated based on the charged amount of the polymerizable unsaturated compound (raw material monomer) used as a raw material when synthesizing the resin (A).
  • all hydroxyl groups are counted as the number of hydroxyl groups regardless of the type of hydroxyl group.
  • ⁇ Method for producing resin (A)> In order to produce the resin (A) contained in the resin composition of the present embodiment, for example, the following production method can be used. That is, a raw material monomer consisting of monomers (ma-1) to (ma-3) and other monomers (ma-4) contained as necessary is prepared using a polymerization initiator, and is known in the art. are copolymerized according to the radical polymerization method of Resin (A) is thus obtained.
  • a polymerization initiator is added to the raw material monomer solution, and stirred at 50° C. to 130° C. for 1 hour to 20 hours, for example. It is possible to use a method of conducting a copolymerization reaction while
  • the solvent for polymerization used in producing the resin (A) is not particularly limited as long as it is inert to the copolymerization reaction of the raw material monomers.
  • the solvent for polymerization used in producing the resin (A) may be the same as the solvent contained in the solvent (D) contained in the resin composition described later, or may be contained in the solvent (D). It may be partially or wholly different from the solvent.
  • the reaction solution after the completion of the copolymerization reaction It can be used as part of the solvent (D) without separating and removing the solvent for polymerization from, which is preferable.
  • the solvent used for polymerization is not particularly limited as long as it dissolves the monomers and the resulting copolymer and does not interfere with the polymerization reaction.
  • a glycol ether solvent is preferable from the viewpoint of its solubility.
  • ethylene glycol monomethyl ether diethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, propylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether , diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether and dipropylene glycol dimethyl ether.
  • solvents may be used alone, or two or more of them may be used alone
  • the amount of the polymerization solvent used in producing the resin (A) is not particularly limited, but is preferably 30 parts by mass to 1000 parts by mass, more preferably 50 parts by mass, relative to 100 parts by mass of the raw material monomer. ⁇ 800 parts by mass.
  • the amount of the polymerization solvent used is 30 parts by mass or more, the copolymerization reaction of the raw material monomers can be stably carried out, and coloration and gelation of the resin (A) can be prevented.
  • the amount of the polymerization solvent used is 1000 parts by mass or less, the decrease in the molecular weight of the resin (A) due to the chain transfer effect can be suppressed, and the viscosity of the reaction solution can be controlled within an appropriate range.
  • the polymerization initiator that can be used in the copolymerization reaction of the raw material monomers is not particularly limited. valeronitrile), 2,2′-azobis(isobutyrate)dimethyl, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate and the like. These polymerization initiators may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the amount of the polymerization initiator used is not particularly limited, but is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 16 parts by mass with respect to 100 parts by mass of the raw material monomer. .
  • the content of the resin (A) in the photosensitive resin composition of the present embodiment is preferably 10 parts by mass when the total of the components excluding the solvent (D) contained in the photosensitive resin composition is 100 parts by mass. to 85 parts by mass, more preferably 15 to 75 parts by mass, and most preferably 25 to 65 parts by mass.
  • the content of the reactive diluent (A) is within the above range, the viscosity and low-temperature curability of the photosensitive resin composition become more appropriate.
  • the (B) reactive diluent contained in the photosensitive resin composition of the present embodiment may be a low molecular weight compound having an ethylenically unsaturated group such as a vinyl group, an allyl group, or a (meth)acryloyloxy group. , is not particularly limited. Specific examples of the reactive diluent (B) include aromatic vinyl monomers; polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; monofunctional (meth)acrylates; polyfunctional (meth)acrylates; and triallyl cyanurate.
  • aromatic vinyl monomers include styrene, ⁇ -methylstyrene, ⁇ -chloromethylstyrene, vinyltoluene, divinylbenzene, diallyl phthalate, and diallylbenzene phosphonate.
  • monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, ⁇ -hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, ) acrylates and the like.
  • polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate.
  • reactive diluent (B) polyfunctional (meth)acrylates are preferable for improving curability (reactivity), particularly dipentaerythritol penta(meth)acrylate and/or dipentaerythritol. Hexa(meth)acrylate is preferred.
  • reactive diluents (B) may be used singly or in combination of two or more.
  • the content of the reactive diluent (B) in the photosensitive resin composition of the present embodiment is preferably It is 10 to 85 parts by mass, more preferably 15 to 75 parts by mass, and most preferably 25 to 65 parts by mass. When the content of the reactive diluent (B) is within the above range, the viscosity and photocurability of the photosensitive resin composition become more appropriate.
  • the photopolymerization initiator (C) contained in the photosensitive resin composition of the present embodiment is not particularly limited as long as it is a compound that generates radicals upon irradiation with light.
  • the photopolymerization initiator (C) include benzoin, benzoin methyl ether, benzoin ethyl ether and other benzoin and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, Acetophenones such as 4-(1-t-butyldioxy-1-methylethyl)acetophenone; Alkylphenones such as 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one;2 -anthraquinones such as methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinon
  • the content of the photopolymerization initiator (C) in the photosensitive resin composition of the present embodiment is preferably It is 0.1 to 30 parts by mass, more preferably 0.3 to 20 parts by mass, and most preferably 0.5 to 10 parts by mass.
  • the photosensitive resin composition has sufficient photocurability.
  • the photopolymerization initiator (C) does not adversely affect the storage stability of the photosensitive resin composition and the performance of the cured resin film.
  • the solvent (D) contained in the resin composition of the present embodiment is not particularly limited as long as it is inert to the resin (A) and capable of dissolving the resin (A).
  • the solvent (D) may or may not contain the solvent for polymerization used in producing the resin (A).
  • the solvent for polymerization is extracted from the reaction solution after the copolymerization reaction for producing the resin (A) is completed. Without removing the addition reaction for producing the resin (A), the solvent for polymerization is separated from the reaction solution after the addition reaction is completed, and the solvent (D ) can be used as part or all of
  • the case where the solvent (D) does not contain the solvent for polymerization used in producing the resin (A) means that the resin (A) used as a raw material of the resin composition produces the resin (A). This is the case where the substance is separated and removed from the reaction solution. In this case, regardless of the type and amount of the polymerization solvent used in producing the resin (A), the type of the resin (A), the type and content of the solvent (D) depending on the application of the resin composition, etc. The amount can be selected appropriately. That is, when the resin (A) is separated and removed from the reaction solution in which the resin (A) is produced, the solvent (D) is the polymerization solvent used in the production of the resin (A). The same type may be used, or different types may be used.
  • the solvent (D) is not particularly limited, but when the resin (A) is a (meth)acrylic acid-based polymer, a glycol ether solvent is preferable from the viewpoint of its solubility.
  • a glycol ether solvent is preferable from the viewpoint of its solubility.
  • the solvent (D) may contain other solvents capable of dissolving the resin (A).
  • Examples include monoalcohols and (poly)alkylene glycol monoalkyl ethers.
  • monoalcohols include primary alcohols such as propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol and dodecyl alcohol; and secondary alcohols such as benzyl alcohol.
  • secondary alcohols such as benzyl alcohol.
  • Specific examples of other solvents include tertiary alcohols such as tert-butyl alcohol and diacetone alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate.
  • (poly)alkylene glycol monoalkyl ether acetates such as; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, other ethers such as tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; -methyl hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3 -methyl ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutyl
  • the content of the solvent (D) in the resin composition of the present embodiment is preferably 30 parts by mass to 1000 parts by mass when the sum of the components excluding the solvent (D) in the resin composition is 100 parts by mass. , more preferably 50 to 800 parts by mass, most preferably 100 to 700 parts by mass.
  • the viscosity of the resin composition can be adjusted to an appropriate range.
  • the photosensitive resin composition of the present embodiment may contain one or more known additives such as leveling agents, thermal polymerization inhibitors, and sensitizers, if necessary.
  • the content of these additives is not particularly limited as long as it does not impair the effects of the present invention.
  • the photosensitive resin composition of the present embodiment may contain amines, hydrazides, aldehydes, and metal salts as cross-linking agent species in order to enhance curability.
  • cross-linking agents include MXDA and 1,3-BAC (trade names) manufactured by Mitsubishi Gas Chemical Co., Ltd.; ADH and APA-280 (trade names) manufactured by Otsuka Chemical Co.; Trade name ZIRCOZOL ZC-2, 7 manufactured by Ikki Genso Kagaku Kogyo Co., Ltd. can be mentioned.
  • the photosensitive resin composition of the present embodiment may contain an acid generator and a base generator in order to enhance curability.
  • a photoacid generator from the viewpoint of latency, it is preferable to use a photoacid generator, a photobase generator, a thermal acid generator, and a thermal base generator.
  • a photoacid generator and a photobase generator are preferably used. More preferred.
  • the photoacid generator include sulfonium salt compounds such as CPI-200K, CPI-210S, CPI-310B, and CPI-410S manufactured by San-Apro Chemical Co., Ltd., and iodonium salt compounds such as IK-1.
  • the photobase generator include trade names WPBG-266, WPBG-300, WPBG-345 manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., and the like.
  • the viscosity of the photosensitive resin composition of the present embodiment can be appropriately adjusted according to the thickness of the cured resin film made of the cured product of the photosensitive resin composition.
  • the viscosity of the photosensitive resin composition is preferably 1 mP ⁇ s to 25 mP ⁇ s, more preferably 2 mP ⁇ s to 20 mP ⁇ s. More preferably, it is 3 mP ⁇ s to 15 mP ⁇ s.
  • the photosensitive coloring composition of the present embodiment contains the photosensitive resin composition of the present embodiment and a coloring agent (E).
  • a coloring agent E
  • Known dyes and/or pigments can be used as the colorant (E).
  • a dye is used as the colorant (E)
  • a colored pattern with high brightness can be obtained and the photosensitive colored composition exhibits good alkali developability as compared with the case of using a pigment.
  • the dye from the viewpoint of solubility in the solvent (D) and alkaline developer, interaction with other components in the photosensitive resin composition, heat resistance, etc., acid dyes having an acidic group such as a carboxy group, acid It is preferable to use salts of dyes with nitrogen compounds, sulfonamides of acid dyes, and the like.
  • Such dyes include, for example, acid alizarin violet N; acid black 1,2,24,48; acid blue1,7,9,25,29,40,45,62,70,74,80,83,90; 92, 112, 113, 120, 129, 147; solvent blue 38, 44 (VALIFAST BLUE 2620); acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; 0 , 12, 50, 51, 52, 56, 63, 74, 95; 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,
  • azo-based, xanthene-based, anthraquinone-based or phthalocyanine-based acid dyes are preferred. These dyes may be used singly or in combination of two or more, depending on the desired pixel color.
  • pigments for example, C.I. 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;
  • red pigments such as 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. Blue pigments such as Pigment Blue 15, 15:3, 15:4, 15:6, 60; C.I. I. Violet color pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38; C.I. I. Green pigments such as Pigment Green 7, 36, 58; C.I. I. Pigment Brown 23, 25 and other brown pigments; C.I. I. Pigment Black 1, 7, carbon black, titanium black, black pigments such as iron oxide, and the like. One of these pigments may be used alone, or two or more of them may be used in combination, depending on the desired pixel color.
  • a known dispersant may be added to the photosensitive coloring composition from the viewpoint of improving the dispersibility of the colorant (E).
  • the dispersant it is preferable to use a polymer dispersant that exhibits excellent dispersion stability over time.
  • polymer dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified esters. system dispersants and the like.
  • polymer dispersants include trade names such as EFKA (manufactured by EFKA Chemicals B.V.
  • the blending amount of the dispersant may be appropriately set according to the type and amount of the pigment used as the colorant (E).
  • the content of the coloring agent (E) in the photosensitive coloring composition of the present embodiment is preferably 4 parts by mass when the total of the components excluding the solvent (D) contained in the photosensitive coloring composition is 100 parts by mass. parts to 85 parts by mass, more preferably 9 to 70 parts by mass, and most preferably 15 to 49 parts by mass.
  • the content of the coloring agent (E) is 4 parts by mass or more, the effect of containing the coloring agent (E) becomes remarkable, and the photosensitive coloring composition is suitable as a material for a colored pattern of a color filter.
  • the coloring agent (E) in the photosensitive coloring composition does not interfere with the curability of the photosensitive coloring composition and can be cured at a low temperature. It will be of good quality.
  • the photosensitive coloring composition of the present embodiment may contain one or more of known additives such as leveling agents, thermal polymerization inhibitors and sensitizers, if necessary.
  • the content of these additives is not particularly limited as long as it does not impair the effects of the present invention.
  • the photosensitive coloring composition of the present embodiment may contain amines, hydrazides, aldehydes, and metal salts as crosslinking agent species in order to enhance curability.
  • cross-linking agents include MXDA and 1,3-BAC (trade names) manufactured by Mitsubishi Gas Chemical Co., Ltd.; ADH and APA-280 (trade names) manufactured by Otsuka Chemical Co., Ltd.; Trade name ZIRCOZOL ZC-2 and 7 manufactured by Kigenso Kagaku Kogyo Co., Ltd. can be mentioned.
  • the photosensitive coloring composition of the present embodiment may contain an acid generator and a base generator in order to enhance curability.
  • a photoacid generator from the viewpoint of latency, it is preferable to use a photoacid generator, a photobase generator, a thermal acid generator, and a thermal base generator.
  • a photoacid generator and a photobase generator are preferably used. More preferred.
  • the photoacid generator include sulfonium salt compounds such as CPI-200K, CPI-210S, CPI-310B, and CPI-410S manufactured by San-Apro Chemical Co., Ltd., and iodonium salt compounds such as IK-1.
  • the photobase generator include trade names WPBG-266, WPBG-300, WPBG-345 manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., and the like.
  • the viscosity of the photosensitive coloring composition of the present embodiment can be appropriately adjusted according to the thickness of the cured resin film made of the cured photosensitive coloring composition.
  • the viscosity of the photosensitive coloring composition is preferably 1 mP s to 25 mP s, preferably 2 mP s to 20 mP s. More preferably, it is 3 mP ⁇ s to 15 mP ⁇ s.
  • the photosensitive resin composition of the present embodiment includes a resin (A), a reactive diluent (B), a photopolymerization initiator (C) and a solvent (D), and additives used as necessary. can be produced by mixing using known mixing equipment.
  • the photosensitive resin composition of the present embodiment has good low-temperature curability and can form a cured resin film having sufficient hardness and solvent resistance. Moreover, since the photosensitive resin composition of the present embodiment has excellent alkali developability, a fine pattern can be formed by developing with an aqueous alkali solution. Therefore, the photosensitive resin composition of this embodiment is suitably used as a resist.
  • the photosensitive coloring composition of the present embodiment comprises a resin (A), a reactive diluent (B), a photopolymerization initiator (C), a solvent (D), a coloring agent (E), and optionally It can be produced by mixing the additives used in the above using a known mixing device.
  • the photosensitive resin composition of the present embodiment has good low-temperature curability and can form a cured resin film having sufficient hardness and solvent resistance. Moreover, since the photosensitive resin composition of the present embodiment has excellent alkali developability, a fine pattern can be formed by developing with an aqueous alkali solution. Therefore, the photosensitive resin composition of this embodiment is suitably used as a resist. In addition, the photosensitive coloring composition of the present embodiment can be suitably used as a material for colored patterns such as pixels of color filters and black matrices.
  • the cured resin film of the present embodiment is composed of a cured product of the photosensitive resin composition of the present embodiment or the photosensitive coloring composition of the present embodiment.
  • the cured resin film of the present embodiment includes, for example, a coating step of applying the photosensitive resin composition of the present embodiment onto a substrate to form a coating film, and a pre-baking step of drying the coating film formed by the coating step. , an exposure step of irradiating the dried coating film with light to photo-cure it, and a post-baking step of thermally curing the photo-cured coating film.
  • the following method can be used. That is, the coating process and the pre-baking process described above are performed. After that, in the exposure step, the dried coating film is irradiated with light through a photomask having a predetermined pattern, and the exposed portion is photocured. After the exposure step, post-exposure heat treatment is performed as necessary. After that, a developing step of dissolving and developing the unexposed portion of the coating film using a developer, and a post-baking step of thermally curing the photo-cured coating film are performed.
  • the photosensitive resin composition of the present embodiment or the photosensitive coloring composition of the present embodiment is applied onto a substrate to form a coating film.
  • the substrate for coating the photosensitive resin composition or the photosensitive coloring composition known substrates can be used, and the substrate can be appropriately determined according to the intended use of the cured resin film.
  • the method of applying the photosensitive resin composition or photosensitive coloring composition is not particularly limited, and examples thereof include screen printing, roll coating, curtain coating, spray coating, spin coating, slit coating, and the like. can be used.
  • pre-baking process In the pre-baking (pre-heat treatment) step, the coating film formed in the coating step is dried to reduce the amount of residual solvent in the coating film.
  • the substrate on which the coating film is formed is heated, for example, at a temperature of 50° C. to 120° C., preferably 70° C. to 110° C., for 10 seconds to 600 seconds, preferably 120 seconds to 180 seconds.
  • a method of heating the substrate on which the coating film is formed for example, a method using a hot plate can be used as a method of heating the substrate on which the coating film is formed.
  • the surface of the coating film dried in the pre-baking step is irradiated with light to photo-cure the coating film.
  • a light source used for light irradiation is not particularly limited, and for example, 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 used.
  • the amount of exposure in the exposure step is not particularly limited, and can be appropriately set according to the composition of the photosensitive resin composition or the photosensitive coloring composition, the thickness of the coating film, and the like.
  • the surface of the coating film dried in the prebaking step is irradiated with light through a photomask having a predetermined pattern, and the exposed portion is exposed to light. Harden.
  • Post-exposure heating process When forming a cured resin film having a predetermined pattern, a post-exposure baking process is performed after the exposure process, if necessary. By performing this step, the dissolution contrast between the exposed portion and the unexposed portion of the coating film becomes more pronounced.
  • the post-exposure heating process does not completely cure the coating film, unlike the post-baking process described below.
  • the post-exposure heating step is performed in order to leave only the exposed portion of the coating film on the substrate and more reliably remove the unexposed portion of the coating film by performing the developing step. Therefore, it is not an essential step in the method for forming a cured resin film of the present embodiment.
  • the substrate after the exposure step is preferably heated, for example, at 40°C to 70°C, more preferably at 50°C to 60°C.
  • the heating temperature is 40° C. or higher, the effect of improving the dissolution contrast between the exposed portion and the unexposed portion of the coating film can be sufficiently obtained by performing the post-exposure heating step.
  • the heating temperature is 70° C. or less, the acid generated in the exposed portion does not diffuse to the unexposed portion, and good dissolution contrast can be obtained.
  • the heating time in the post-exposure heating step is preferably 20 seconds to 600 seconds. When the heating time is 20 seconds or more, the temperature history of the entire coating film can be made uniform.
  • the heating time is 600 seconds or less, the acid generated in the exposed portion does not diffuse to the unexposed portion, and a good dissolution contrast can be obtained.
  • a hot plate, an oven, or a furnace can be used as a method for heating the substrate after the exposure step in the post-exposure heating step.
  • the alkaline aqueous solution is not particularly limited, but for example, aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide; aqueous solutions of amine compounds such as ethylamine, diethylamine, dimethylethanolamine; Aqueous solutions of quaternary ammonium salts such as methylammonium; 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl -4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyethylaniline and their sulfates, hydrochlorides or p-toluene Examples thereof include aqueous solutions of p-phenylenediamine compounds such as sulf
  • one or more additives such as antifoaming agents and surfactants may be added to the alkaline aqueous solution.
  • Development conditions such as development temperature and development time in the development step can be appropriately determined according to the composition of the photosensitive resin composition, the composition of the developer, the thickness of the coating film, and the like.
  • a post-baking process is performed in which the photocured coating film is thermally cured to form a cured resin film.
  • the heating temperature and heating time in the post-baking step are not particularly limited, and can be appropriately set according to the composition of the photosensitive resin composition or photosensitive coloring composition, the thickness of the coating film, the material of the substrate, and the like.
  • the heating temperature in the post-baking process can be, for example, 50°C to 210°C.
  • a material with low heat resistance can be used as the material for the color filter.
  • the heating temperature may be, for example, 150° C. or lower, 120° C. or lower, or 100° C. when forming a colored pattern of a color filter using a resin substrate as a base material for forming a cured resin film. °C or lower.
  • the heating temperature is 150° C. or less, it is possible to form a colored pattern containing the coloring agent (E) with poor heat resistance, which has been difficult to use as a material for conventional colored patterns, while suppressing deterioration of the coloring agent (E).
  • the heating temperature is 150° C. or lower, a colored pattern can be formed on a substrate having poor heat resistance, which has been difficult to use as a substrate for conventional color filters. Further, when the heating temperature is set to 150° C. or less, the amount of energy required for curing the coating film is small, which is preferable.
  • the heating temperature in the post-baking step is 50°C or higher, the resin (A) and the reactive diluent (B) are sufficiently crosslinked, so that a cured resin film having sufficient hardness and solvent resistance can be obtained. Moreover, when the heating temperature is 50° C. or higher, the heating time in the post-baking step can be shortened, and a cured resin film can be efficiently formed.
  • the heating temperature in the post-baking step is more preferably 60° C. or higher, still more preferably 70° C. or higher.
  • the heating time in the post-baking step can be appropriately selected according to the heating temperature, the thickness of the coating film, the composition of the photosensitive resin composition, etc. For example, it can be 10 minutes to 4 hours, preferably 20 minutes to 2 hours.
  • the cured resin film of the present embodiment is composed of a cured product of the photosensitive resin composition of the present embodiment or the photosensitive coloring composition of the present embodiment. Therefore, it has sufficient hardness and solvent resistance.
  • the cured resin film of the present embodiment is preferably used as a material for various insulating films such as a protective film provided on a color filter or the like, an insulating film provided between electrodes of a touch panel, and an interlayer insulating film of a thin film transistor (TFT). can be done.
  • FIG. 1 is a schematic cross-sectional view showing an example of the color filter of this embodiment.
  • the substrate 1 used for the color filter shown in FIG. 1 is not particularly limited, and includes a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, and printed wiring.
  • a substrate, an array substrate, or the like can be appropriately used depending on the application.
  • the pixels 2 and the black matrix 3 in the color filter shown in FIG. It is a colored pattern made of a cured product of the photosensitive colored composition of the present embodiment containing a coloring agent (E) and optionally containing additives.
  • a coloring agent E
  • the protective film 4 one made of a known material can be used.
  • the protective film 4 comprises a resin composition containing a resin (A) and a solvent (D), a reactive diluent (B), a photopolymerization initiator (C), and additives contained as necessary. It may be a resin cured film made of a cured product of the photosensitive coloring composition of the present embodiment containing.
  • the configuration other than the materials of the pixels 2 and the black matrix 3 can employ known ones.
  • the color filter shown in FIG. 1 is an example of the color filter of the present invention, and the present invention is not limited to the example shown in FIG.
  • pixels 2 of RGB and a black matrix 3 are sequentially formed on one surface 1a of the substrate 1 shown in FIG.
  • the pixels 2 and the black matrix 3 can be manufactured using the method for manufacturing a cured resin film (photolithography method) of the present embodiment described above.
  • a protective film 4 is formed on the pixels 2 and the black matrix 3 .
  • the protective film 4 can be formed using a known forming method.
  • the protective film 4 can be manufactured using the method for manufacturing a cured resin film of the present embodiment described above.
  • the color filter of this embodiment has a colored pattern (pixels 2 and black matrix 3) made of a cured product of the photosensitive coloring composition described above. Therefore, the colored pattern in the color filter of this embodiment has sufficient hardness and solvent resistance.
  • the image display element of this embodiment comprises the color filter of this embodiment having sufficient hardness and solvent resistance.
  • Examples of the image display device of this embodiment include a liquid crystal display device, an organic EL display device, a solid-state imaging device, and the like.
  • the image display device of the present embodiment is capable of high brightness display by being equipped with the color filter described above.
  • ethylene glycol monoacetoacetate monomethacrylate 215.9 g (0.545 mol), methyl methacrylate 25.9 g (0.14 mol), glycidyl methacrylate 51.3 g (0.195 mol), methacrylic acid 19.1 g (0.120 mol), 37.8 g of 2,2′-azobis(isobutyrate)dimethyl (polymerization initiator), and 143.6 g of propylene glycol monomethyl ether acetate were added from the dropping funnel into the flask for 3 hours. dripped over.
  • the amount of the copolymer in the resin composition in Table 3 does not include the polymerization solvent used when synthesizing the copolymer.
  • the blending amount of the solvent (D) in Table 3 is the sum of the polymerization solvent used when synthesizing the copolymer in the resin composition and the solvent additionally added when preparing the resin composition. quantity.
  • the surface of the dried coating film was irradiated with light of 200 mJ/cm 2 using an ultra-high pressure mercury lamp through a photomask (exposure step).
  • the exposure process was carried out by setting the photomask at a position separated from the coating film by 100 ⁇ m. A photomask having a line-and-space pattern with a width of 3 to 100 ⁇ m was used.
  • semi-clean DL-A10 developer manufactured by Yokohama Yushi Kogyo Co., Ltd.
  • development step After the development step, the glass substrate having the coating film was placed in a drier at 100° C. for 30 minutes to thermally cure the coating film (post-baking step) to obtain a colored pattern.
  • the pencil hardness of the cured resin film thus prepared was measured using a pencil hardness tester (No. 553-M, manufactured by Yasuda Seiki Seisakusho) according to JIS K5600-5-4 and evaluated according to the following criteria. . The results are shown in Table 4 or Table 5.
  • a glass substrate having a cured resin film was prepared in the same manner as in (2) Evaluation of pencil hardness, and a cured resin film was measured using a spectrophotometer (UV-1650PC, manufactured by Shimadzu Corporation). was measured.
  • a spectrophotometer UV-1650PC, manufactured by Shimadzu Corporation.
  • 200 mL of propylene glycol monomethyl ether acetate was placed in a 500 mL capacity glass bottle with a lid and allowed to stand at a temperature of 23°C.
  • a glass substrate having a cured resin film was placed in the glass bottle, immersed in propylene glycol monomethyl ether acetate, and allowed to stand at 23° C. for 15 minutes.
  • the glass substrate having the cured resin film is taken out, and the absorption spectrum of the cured resin film is measured using a spectrophotometer (UV-1650PC, manufactured by Shimadzu Corporation) in the same manner as before immersion in propylene glycol monomethyl ether acetate. bottom.
  • a spectrophotometer UV-1650PC, manufactured by Shimadzu Corporation
  • the photosensitive coloring compositions R1 to R16 of Examples 1 to 16 all have a minimum development size of 15 ⁇ m or less, and there is no residue in the unexposed area between the developed patterns, which is excellent. It was confirmed that it had good alkali developability.
  • the coating film formed using the photosensitive coloring compositions R1 to R16 of Examples 1 to 16 it consists of a cured product thermally cured at a low temperature of 100 ° C.
  • the cured resin film had a pencil hardness of 3H or more, and had excellent hardness.
  • the above-mentioned cured resin film was evaluated as ⁇ in terms of solvent resistance, and it was confirmed that it had excellent solvent resistance.
  • the photosensitive coloring compositions cR1 to cR9 of Comparative Examples 1 to 9 were insufficient in alkali developability, pencil hardness or solvent resistance.
  • the copolymers cP1 to cP8 obtained in Comparative Synthesis Examples 1 to 8 contained in the photosensitive coloring compositions cR1 to cR8 of Comparative Examples 1 to 8 have an active methylene group equivalent of 0. .
  • any one of alkali developability, hardness and solvent resistance of the cured resin film was inferior.
  • the copolymer cP9 obtained in Comparative Synthesis Example 9 contained in the photosensitive resin composition cR9 of Comparative Example 9 has a functional group equivalent of 0.
  • the hardness and solvent resistance of the cured resin film were inferior.
  • a photosensitive resin composition and a photosensitive coloring composition that have excellent developability and good low-temperature curability and are capable of forming a cured resin film having sufficient hardness and solvent resistance. Furthermore, according to the present invention, it is possible to provide a resin cured film made of a cured product of a photosensitive resin composition and having sufficient hardness and solvent resistance, and a colored pattern made of a cured product of the photosensitive coloring composition of the present invention It is possible to provide a color filter having sufficient hardness and solvent resistance, and further to provide an image display device comprising this color filter.
  • the photosensitive resin composition and photosensitive coloring composition of the present invention are preferably used as, for example, transparent films, protective films, insulating films, overcoats, photospacers, black matrices, black column spacers, and color filter resists. can.

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WO2025063731A1 (ko) * 2023-09-21 2025-03-27 동우 화인켐 주식회사 착색 감광성 수지 조성물, 이를 이용하여 제조된 컬러필터 및 화상표시장치

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007034134A (ja) * 2005-07-29 2007-02-08 Sumitomo Chemical Co Ltd 感光性樹脂組成物
JP2012073604A (ja) * 2010-09-01 2012-04-12 Sumitomo Chemical Co Ltd 感光性樹脂組成物
JP2016029151A (ja) * 2014-07-18 2016-03-03 株式会社日本触媒 硬化性樹脂組成物及びその用途
JP2018009059A (ja) * 2016-07-11 2018-01-18 株式会社日本触媒 硬化性樹脂組成物及びその用途
JP2018106172A (ja) * 2016-12-27 2018-07-05 住友化学株式会社 液晶表示装置用樹脂組成物、液晶表示装置用膜及び共重合体
WO2019156000A1 (ja) * 2018-02-08 2019-08-15 日産化学株式会社 感光性樹脂組成物

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101917406B1 (ko) 2014-03-21 2018-11-09 동우 화인켐 주식회사 고색재현이 가능한 착색 광경화성 수지조성물, 컬러필터 및 이를 구비한 액정표시장치

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007034134A (ja) * 2005-07-29 2007-02-08 Sumitomo Chemical Co Ltd 感光性樹脂組成物
JP2012073604A (ja) * 2010-09-01 2012-04-12 Sumitomo Chemical Co Ltd 感光性樹脂組成物
JP2016029151A (ja) * 2014-07-18 2016-03-03 株式会社日本触媒 硬化性樹脂組成物及びその用途
JP2018009059A (ja) * 2016-07-11 2018-01-18 株式会社日本触媒 硬化性樹脂組成物及びその用途
JP2018106172A (ja) * 2016-12-27 2018-07-05 住友化学株式会社 液晶表示装置用樹脂組成物、液晶表示装置用膜及び共重合体
WO2019156000A1 (ja) * 2018-02-08 2019-08-15 日産化学株式会社 感光性樹脂組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025063731A1 (ko) * 2023-09-21 2025-03-27 동우 화인켐 주식회사 착색 감광성 수지 조성물, 이를 이용하여 제조된 컬러필터 및 화상표시장치

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