WO2024024195A1 - 感光性樹脂組成物、樹脂硬化膜、及び画像表示素子 - Google Patents

感光性樹脂組成物、樹脂硬化膜、及び画像表示素子 Download PDF

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Publication number
WO2024024195A1
WO2024024195A1 PCT/JP2023/016723 JP2023016723W WO2024024195A1 WO 2024024195 A1 WO2024024195 A1 WO 2024024195A1 JP 2023016723 W JP2023016723 W JP 2023016723W WO 2024024195 A1 WO2024024195 A1 WO 2024024195A1
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group
meth
acrylate
resin composition
resin
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English (en)
French (fr)
Japanese (ja)
Inventor
司 原
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Resonac Corp
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Resonac Corp
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Priority to JP2024536786A priority Critical patent/JPWO2024024195A1/ja
Priority to KR1020257000491A priority patent/KR20250022137A/ko
Priority to CN202380055928.7A priority patent/CN119604818A/zh
Publication of WO2024024195A1 publication Critical patent/WO2024024195A1/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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • 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
    • C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
    • 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
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • 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
    • G03F7/004—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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • 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
    • G03F7/038—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 cured resin film, and an image display element.
  • This application claims priority based on Japanese Patent Application No. 2022-118208 filed in Japan on July 25, 2022, the contents of which are incorporated herein.
  • color filters are usually formed by baking and curing a resin composition on a substrate at a temperature of over 200°C.
  • the substrate materials for color filters are being switched from glass to organic materials such as resin.
  • the colorants used in color filters are being switched from pigments to materials such as dyes and/or fluorescent compounds and quantum dots. There is.
  • Patent Document 1 contains a photocurable compound (A), a binder resin (B), a photoinitiator (D), and a solvent (E), and the photocurable compound (A) is a carboxy group-containing dipenta
  • a colored photocurable resin composition is disclosed in which the binder resin (B) is erythritol pentaacrylate and contains one or more of a tetrahydropyran structure or a tetrahydrofuran structure in its main chain structure.
  • Organic materials used as substrate materials have inferior heat resistance compared to glass. Furthermore, dyes used as colorants for color filters have inferior heat resistance compared 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 colorant material, the heating temperature for curing the resin composition that is the color filter material may be required to be 80 to 150°C. .
  • the present invention was made in view of the above circumstances, and provides a photosensitive resin composition that has excellent developability and good low-temperature curability, and is capable of forming a cured resin film having sufficient hardness and solvent resistance.
  • the purpose is to provide a photosensitive coloring composition.
  • Another object of the present invention is to provide a cured resin film that is made of a cured product of the photosensitive resin composition of the present invention and has sufficient hardness and solvent resistance.
  • Another object of the present invention is to provide a color filter having a colored pattern made of a cured product of the photosensitive colored composition of the present invention and having sufficient hardness and solvent resistance.
  • the present invention includes the following aspects.
  • the resin (A) is an ethylenically unsaturated group- and carboxyl group-modified (meth)acrylic resin
  • the ethylenically unsaturated group- and carboxyl group-modified (meth)acrylic resin is a hydroxy group-containing (meth)acrylic resin (a-0) and a compound (a-4) containing an isocyanato group and an ethylenically unsaturated group.
  • the hydroxy group-containing (meth)acrylic resin (a-0) at least A structural unit derived from a hydroxy group-containing (meth)acrylate (m-1), A structural unit derived from a (meth)acrylate (m-2) having one or more groups selected from the group consisting of an active methylene group, an active methine group, an epoxy group, an oxetanyl group, a blocked isocyanato group, and a silyl group.
  • a photosensitive resin composition characterized by being a copolymer containing.
  • the hydroxy group-containing (meth)acrylic resin (a-0) contains the hydroxy group-containing (meth)acrylate (m-1), the (meth)acrylate (m-2), and other monomers.
  • the isocyanato group-containing (meth)acrylate (a-4a) is an isocyanato group-containing (meth)acrylate having a polyoxyalkylene structure, or an isocyanato group-containing (meth)acrylate having two or more (meth)acryloyloxy groups.
  • the amount of the compound (a-4) containing the isocyanato group and ethylenically unsaturated group added is 1 to 60 mol per 100 mol of the monomer (M)
  • the photosensitive resin composition according to any one of [10].
  • Any one of [1] to [11], wherein the amount of the polybasic acid or its anhydride (a-5) added is 1 to 60 mol per 100 mol of the monomer (M).
  • the weight average molecular weight of the resin (A) is 1000 to 50000, The photosensitive resin composition according to any one of [1] to [12], wherein the resin (A) has a molecular weight distribution (Mw/Mn) of 1.3 to 5.0.
  • Mw/Mn molecular weight distribution
  • [15] Contains the photosensitive resin composition according to any one of [1] to [14] and a colorant (E), For a total of 100 parts by mass of the components excluding the solvent (D), A photosensitive coloring composition containing 4 parts by mass to 79 parts by mass of the colorant (E).
  • a cured resin film comprising a cured product of the photosensitive resin composition according to any one of [1] to [14].
  • An image display element comprising the color filter according to [17].
  • a photosensitive resin composition and a photosensitive colored 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 that is made of a cured product of the photosensitive resin composition of the present invention and has sufficient hardness and solvent resistance.
  • a color filter having a colored pattern made of a cured product of the photosensitive colored composition of the present invention and having sufficient hardness and solvent resistance.
  • an image display element including this color filter can be provided.
  • FIG. 1 is a schematic cross-sectional view showing an example of a color filter of this embodiment.
  • (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, and
  • (meth)acryloyl means at least one selected from methacryloyl and acryloyl.
  • the photosensitive resin composition of this embodiment includes at least 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 this embodiment is an ethylenically unsaturated group- and carboxy group-modified (meth)acrylic resin.
  • an ethylenically unsaturated group-modified (meth)acrylic resin By using an ethylenically unsaturated group-modified (meth)acrylic resin, the developability of the photosensitive resin composition can be improved and a cured film having a finer pattern can be obtained.
  • a (meth)acrylic resin modified with a carboxy group the developability of the photosensitive resin composition is improved, and it is also possible to cure at a lower temperature, thereby improving the hardness and solvent resistance of the cured product. can.
  • Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, and a (meth)acryloyloxy group. It is preferable that the ethylenically unsaturated group is a (meth)acryloyloxy group.
  • “Ethylenically unsaturated group-modified” resin and “carboxy group-modified” resin are obtained by adding only an ethylenically unsaturated group-containing compound or only a carboxyl group-containing compound to a raw resin, respectively. It means a resin into which a carboxyl group has been introduced.
  • "Ethylenically unsaturated group and carboxyl group modified” resin means a resin in which ethylenically unsaturated groups and carboxyl groups are introduced by adding an ethylenically unsaturated group-containing compound and a carboxyl group-containing compound to a raw resin. do.
  • the addition reaction of the ethylenically unsaturated group-containing compound and the carboxyl group-containing compound to the raw resin may be carried out either first or simultaneously.
  • the ethylenically unsaturated group- and carboxyl group-modified (meth)acrylic resin is a hydroxy group-containing (meth)acrylic resin (a-0) and a compound (a-4) containing an isocyanato group and an ethylenically unsaturated group. and a polybasic acid or its anhydride (a-5).
  • the resin (A) is formed. Ethylenically unsaturated groups are introduced.
  • a carboxy group is introduced into the resin (A) by the reaction between the hydroxy group of the hydroxy group-containing (meth)acrylic resin (a-0) and the polybasic acid or its anhydride (a-5).
  • the amount introduced can be freely adjusted for the purpose of improving developability, low-temperature curability, hardness of a cured film, and solvent resistance.
  • a carboxyl group-containing (meth)acrylic resin in which a carboxyl group is directly introduced into the main chain of the resin can be obtained.
  • a carboxyl group-containing (meth)acrylic resin for example, it may be modified to introduce an ethylenically unsaturated group using a compound (a-4) containing an isocyanato group and an ethylenically unsaturated group, which will be described later. In this case, isocyanate dimer is generated as a by-product.
  • the by-product does not have a developing group, and is not preferable because it has disadvantages such as a reduction in the developability of the photosensitive resin composition, which is the object of the present invention.
  • the ethylenically unsaturated group- and carboxyl group-modified (meth)acrylic resin according to the present embodiment is a modified resin from the hydroxy group-containing (meth)acrylic resin (a-0) described below, and It is preferable that the hydroxy group-containing (meth)acrylic resin (a-0) does not contain a carboxy group.
  • an epoxy group-containing (meth)acrylic resin or a resin main chain in which an epoxy group is directly introduced into the main chain of the resin may be used. It is not possible to introduce an ethylenically unsaturated group into a carboxyl group-containing (meth)acrylic resin into which a carboxyl group is directly introduced using a compound other than the compound (a-4) containing an isocyanato group and an ethylenically unsaturated group. , which is not preferable because it causes various disadvantages.
  • an epoxy group contained in an epoxy group-containing (meth)acrylic resin with an epoxy group introduced directly into the main chain of the resin is reacted with (meth)acrylic acid, or a carboxyl group is introduced directly into the main chain of the resin.
  • a (meth)acryloyloxy group as an ethylenically unsaturated group is introduced into the resin by reacting the carboxy group of the carboxy group-containing (meth)acrylic resin with glycidyl (meth)acrylate, This is not preferable because it causes disadvantages such as gelation due to the reaction.
  • a polybasic acid or its anhydride (a-5) was reacted with a hydroxyl group generated by ring opening of the epoxy group of the resin into which an ethylenically unsaturated group had been introduced by the above method to introduce a carboxyl group.
  • disadvantages such as gelation due to high temperature reaction during synthesis occur, which is not preferable.
  • the hydroxy group-containing (meth)acrylic resin (a-0) at least contains a structural unit derived from the hydroxy group-containing (meth)acrylate (m-1), an active methylene group, an active methine group, an epoxy group, an oxetanyl group, Structure derived from (meth)acrylate (m-2) (hereinafter also simply referred to as (meth)acrylate (m-2)) having one or more groups selected from the group consisting of a blocked isocyanato group and a silyl group It is a copolymer containing units.
  • the hydroxy group-containing (meth)acrylic resin (a-0) may contain a structural unit derived from another monomer (m-3), if necessary.
  • the total of all monomers that are polymerization raw materials for the hydroxy group-containing (meth)acrylic resin (a-0), that is, the hydroxy group-containing (meth)acrylate (m-1) , the (meth)acrylate (m-2) and the optional other monomer (m-3) are collectively referred to as "monomer (M)".
  • the amount of monomer (M) is It means the total amount of monomers (m-1), (m-2) and (m-3).
  • a structural unit derived from a hydroxy group-containing (meth)acrylate (m-1) refers to a structural unit formed by radical polymerization of a hydroxy group-containing (meth)acrylate (m-1), and specifically Specifically, it refers to a structural unit in which a polymerizable carbon-carbon double bond of a hydroxy group-containing (meth)acrylate (m-1) becomes a carbon-carbon single bond.
  • a structural unit derived from (meth)acrylate (m-2) refers to a structural unit formed by radical polymerization of (meth)acrylate (m-2), and specifically, (meth)acrylate (m-2) is a structural unit formed by radical polymerization.
  • the hydroxy group-containing (meth)acrylate (m-1) is not particularly limited as long as it is a compound having a hydroxy group and a (meth)acryloyloxy group.
  • the hydroxy group-containing (meth)acrylate (m-1) is not particularly limited as long as it is a compound having a hydroxy group and a (meth)acryloyloxy group.
  • hydroxyalkyl (hydroxyalkyl) having a hydroxy group at the alkyl group end Meth)acrylates are preferred, hydroxyalkyl (meth)acrylates having 2 to 4 carbon atoms are particularly preferred, and 2-hydroxyethyl (meth)acrylate is most preferred.
  • the content of the hydroxy group-containing (meth)acrylate (m-1) is preferably 30 to 95 mol%, more preferably 40 to 80 mol%, based on the monomer (M). More preferably, it is 45 to 70 mol%.
  • the content is 30 mol% or more, a sufficient amount of modification can be ensured when introducing a (meth)acryloyloxy group and a carboxy group, and a photosensitive resin composition with excellent developability can be obtained. Even when cured at low temperatures, a cured film with excellent hardness and solvent resistance can be obtained.
  • the (meth)acrylate (m-2) having one or more groups selected from the group consisting of an active methylene group, an active methine group, an epoxy group, an oxetanyl group, a blocked isocyanato group, and a silyl group
  • the (meth)acrylate (m-2) according to the present embodiment is a (meth)acrylate that does not have a hydroxyl group or a carboxy group, and the (meth)acrylate (m-2-1) containing an active methylene group or an active methine group.
  • the functional group possessed by (meth)acrylate (m-2) may itself be crosslinkable by heat or light, or may react with the hydroxyl group derived from hydroxyl group-containing (meth)acrylate (m-1). This contributes to improving the hardness and solvent resistance of photosensitive resin compositions when they are cured at low temperatures, such as through crosslinking.
  • the content of (meth)acrylate (m-2) according to the present embodiment is preferably 5 to 50 mol%, more preferably 10 to 40 mol%, based on the monomer (M). It is preferably 15 to 30 mol%, and more preferably 15 to 30 mol%.
  • a sufficient amount of the functional group possessed by (meth)acrylate (m-2) can be ensured, and a photosensitive resin composition with excellent developability can be obtained. Even when cured at low temperatures, a cured film with excellent hardness and solvent resistance can be obtained.
  • blocked isocyanato group-containing (meth)acrylate (m-2-3) can improve the low-temperature curability of the photosensitive resin composition, resulting in a cured film with better hardness and solvent resistance. can be obtained.
  • silyl group-containing (meth)acrylate (m-2-4) is used, the crosslinking efficiency of the photosensitive resin composition is improved, and a finer pattern can be achieved.
  • the active methylene group or active methine group possessed by the (meth)acrylate (m-2-1) allows hydrogen atoms to be easily eliminated, allowing the crosslinking reaction of the resin to proceed.
  • the methylene bond between the two carbonyls of acetoacetate is active and easily causes a hydrogen abstraction reaction, and as is well known, acetoacetate exhibits typical keto-enol tautomerism. It is also possible that it is related to photocuring.
  • active methylene group and active methine group in this embodiment refer to a methylene group and a methine group whose both ends are bonded to either a carbon atom of a carbonyl group, a sulfur atom of a sulfonyl group, a cyano group, or a nitro group.
  • Examples of the structure having an active methylene group include a structure having the following formula (X1).
  • the methylene group bonded to R 3 and R 4 is an active methylene group.
  • R 3 represents a divalent group represented by any of the following formulas (8) to (10).
  • R 4 represents a cyano group (-CN), a nitro group (-NO 2 ), represents a group represented by the following formula (11), or the following formula (12).
  • * represents a bonding site.
  • ⁇ represents an active methylene carbon.
  • R 5 is a hydrogen atom or a carbon number 1 which may contain a hetero atom. ⁇ 24 hydrocarbon groups).
  • R 3 of formula (X1) from the viewpoint of having good low-temperature curability as a photosensitive resin composition and excellent physical properties required for a color filter, one of formula (8) and formula (10) is preferred.
  • the divalent group represented by the formula (10) is preferable, and the divalent group represented by the formula (10) is more preferable.
  • R 4 of formula (X1), formula (11) and formula (12) are preferable from the viewpoint of having good low-temperature curability as a photosensitive resin composition and excellent physical properties required for a color filter. (11) is more preferred.
  • formula (11) or formula (12) is included as R 4 in formula (X1)
  • the number of carbon atoms that may contain a hetero atom represented by R 5 in formula (11) and formula (12) 1 to 24 hydrocarbon groups specifically, methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, methoxy group, ethoxy group, propoxy group, hexoxy group, cyclohexoxy group, the following formula: Examples include groups represented by 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 more preferable. More preferred are alkyl groups.
  • 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; More preferred are hydrogen atoms and methyl groups.
  • Examples of the structure having an active methine group include a structure having the following formula (X2).
  • the methine group bonded to R 3 and the cyclohexane ring is the active methine group.
  • Examples of the active methylene group- or active methine group-containing (meth)acrylate (m-2-1) include compounds represented by the following formula (1) or (2).
  • R 6 represents a hydrogen atom or a methyl group.
  • R 2 represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms.
  • the definitions and preferred ranges of 3 and R 4 are the same as those of formula (X1) and formula (X2). * indicates an active methylene carbon or an active methine carbon.
  • a compound represented by the following formula (m1) is preferred.
  • R 6 represents a hydrogen atom or a methyl group
  • R 7 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
  • 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.
  • (Meth)acrylate (m-2-2) is a compound that does not contain a hydroxy group, an active methylene group, an active methine group, or a carboxy group, but has an epoxy group or an oxetanyl group and a (meth)acryloyloxy group.
  • crosslinking with the carboxy group derived from the polybasic acid or its anhydride (a-5) progresses when curing the photosensitive resin composition. Therefore, a photosensitive resin composition with good developability can be obtained, and even when cured at a low temperature, a cured film with excellent hardness and solvent resistance can be obtained.
  • epoxy group-containing (meth)acrylates include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, (meth)acrylate having an alicyclic epoxy group and its lactone adduct, 3, Examples include 4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, epoxidized products of dicyclopentenyl (meth)acrylate, and epoxidized products of dicyclopentenyloxyethyl (meth)acrylate.
  • glycidyl (meth)acrylate and (meth)acrylate having an alicyclic epoxy group are preferred from the viewpoint of availability and reactivity when synthesizing resin (A), and 3,4-epoxy Cyclohexylmethyl (meth)acrylate and glycidyl (meth)acrylate are more preferred.
  • oxetanyl group-containing (meth)acrylates include (3-ethyloxetan-3-yl)methyl (meth)acrylate, methyl (meth)acrylate, 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- Examples include methyloxetane.
  • (3-ethyloxetan-3-yl)methyl (meth)acrylate is preferred from the viewpoint of availability and reactivity when synthesizing resin (A).
  • (meth)acrylates (m-2-2) (cyclo)alkyl (meth)acrylates having 2 to 12 carbon atoms and having an epoxy group or an oxetanyl group are easy to obtain and are suitable for synthesizing resin (A). Preferred from the viewpoint of reactivity.
  • the (meth)acrylate (m-2-3) includes, for example, a compound in which the isocyanato group in an isocyanato group-containing (meth)acrylate is blocked with a blocking agent. The reaction between the isocyanato group-containing (meth)acrylate and the blocking agent can be carried out regardless of the presence or absence of a solvent.
  • organic metal salts such as tin, zinc, and lead, tertiary amines, and the like may be used as catalysts.
  • the reaction can generally be carried out at -20 to 150°C, but is preferably carried out at 0 to 100°C. Examples of the above-described 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 - (here, R 13 is an alkylene group having 1 to 6 carbon atoms) or -COO-R 14 O-CONH-R 15 - (where R 14 is an alkylene group having 2 to 6 carbon atoms, and R 15 is an alkylene group having 2 to 12 carbon atoms which may have a substituent) is an alkylene group 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.
  • the isocyanate compound represented by the above formula (XX1) includes 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.
  • Equimolar (1 mol:1 mol) reaction products of 2-hydroxyalkyl (meth)acrylates and diisocyanate compounds can also be used.
  • the alkyl group of the above-mentioned 2-hydroxyalkyl (meth)acrylate is preferably an ethyl group or an n-propyl group, and 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- Examples include 3-isocyanatomethylcyclohexyl isocyanate (IPDI), m-(or p-)xylene diisocyanate, 1,3-(or 1,4-)bis(isocyanatomethyl)cyclohexane, and lysine diisocyanate.
  • IPDI 3-isocyanatomethylcyclohexyl isocyanate
  • m-(or p-)xylene diisocyanate 1,3-(or 1,4-)bis(
  • blocking agents for blocking isocyanate groups in isocyanate compounds include lactams such as ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, and ⁇ -propiolactam; methanol, ethanol, propanol, butanol, and ethylene.
  • Alcohols such as glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, and cyclohexanol; butyl phenols such as phenol, cresol, xylenol, ethyl phenol, o-isopropylphenol, p-tert-butylphenol, etc.
  • p-tert-octylphenol nonylphenol, dinonylphenol, styrenated phenol, oxybenzoic acid ester, thymol, p-naphthol, p-nitrophenol, p-chlorophenol; dimethyl malonate, diethyl malonate, acetate Active methylene series such as methyl acetate, ethyl acetoacetate, and acetylacetone; Mercaptan series such as butyl mercaptan, thiophenol, and tert-dodecyl mercaptan; Amine series such as diphenylamine, phenylnaphthylamine, aniline, and carbazole; Acetanilide, acetanisidide, acetamide, and benzamide Acid amide systems such as succinimide and maleic imide; Imidazole systems such as imidazole, 2-methylimidazole, and 2-ethoxybenz
  • the blocking agent is preferably diethyl malonate, 3,5-dimethylpyrazole, oxybenzoic acid ester, and methyl ethyl ketoxime. From the viewpoint of low temperature curability, 3,5-dimethylpyrazole is more preferred.
  • silyl group-containing (meth)acrylate (m-2-4) does not contain a hydroxy group, an active methylene group, an active methine group, an epoxy group, an oxetanyl group, a blocked isocyanato group, or a carboxy group, and does not contain a silyl group and a (meth)acrylate.
  • ) is a compound having an acryloyloxy group.
  • Specific examples include [(meth)acryloyloxy]methyltriethoxysilane, [(meth)acryloyloxy]ethyltriethoxysilane, [(meth)acryloyloxy]propyltriethoxysilane, and [(meth)acryloyloxy]octyltriethoxysilane.
  • Examples include ethoxysilane, [(meth)acryloyloxy]propylmethyldiethoxysilane, [(meth)acryloyloxy]ethylmethyldiethoxysilane, and [(meth)acryloyloxy]nonylmethyldiethoxysilane.
  • [(meth)acryloyloxy]alkylmethyldialkoxysilane and [(meth)acryloyloxy]alkylethyldialkoxysilane are used from the viewpoint of ease of availability and reactivity when synthesizing resin (A). is preferred, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane is more preferred, and 3-(meth)acryloyloxypropylmethyldiethoxysilane is even more preferred.
  • the hydroxyl group-containing (meth)acrylic resin (a-0) may optionally contain other monomers other than the hydroxyl group-containing (meth)acrylate (m-1) and (meth)acrylate (m-2).
  • m-3) may be included as a constituent monomer.
  • the other monomer (m-3) include dienes such as butadiene, (meth)acrylic acid esters, styrenes, unsaturated dicarboxylic acid diesters, and other vinyl compounds.
  • the other monomer (m-3) does not have a carboxy group.
  • (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, tert-butyl (meth)acrylate, and pentyl (meth)acrylate.
  • Alkyl (meth)acrylates such as meth)acrylate, neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isoamyl (meth)acrylate, dodecyl (meth)acrylate; cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, ethyl Alicyclic alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate; benzyl (meth)acrylate, Aromatic-containing (meth)acrylates such as phenylmethyl (meth)acrylate, cumyl (meth)acrylate, naphthalene (meth)acrylate, anthracene (meth)acrylate; rosin (
  • styrenes include styrene and ⁇ -, o-, m-, and p-alkyl derivatives of styrene.
  • unsaturated dicarboxylic acid diesters include diethyl citraconate, diethyl maleate, diethyl fumarate, diethyl itaconate, and the like.
  • 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]dodec-3-ene, 8-methyltetracyclo[4.4.0.12,5.
  • (meth)acrylic acid esters and other vinyl compounds are preferred from the viewpoint of availability and reactivity when synthesizing the resin (A), and alkyl (meth) having 1 to 12 carbon atoms are preferred.
  • alkyl (meth) having 1 to 12 carbon atoms are preferred.
  • acrylate, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, styrene, vinyltoluene and norbornene are preferred, and methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and dicyclopentanyl (meth)acrylate are preferred. More preferred.
  • alkyl (meth)acrylates having 6 to 12 carbon atoms and alicyclic alkyl (meth)acrylates are preferred, and 2-ethylhexyl (meth)acrylate and dicyclopentaacrylate are preferred. Nyl(meth)acrylate is more preferred.
  • the content of the other monomer (m-3) is preferably 1 to 50 mol%, more preferably 3 to 40 mol%, and 5 to 50 mol%, based on the monomer (M). More preferably, it is 35 mol%.
  • the compound (a-4) containing an isocyanato group and an ethylenically unsaturated group has an isocyanato group and an ethylenically unsaturated group, and has a hydroxy group, an active methylene group, an active methine group, an epoxy group, an oxetanyl group, a block There are no particular limitations as long as the compound does not have an isocyanato group or a silyl group.
  • the compound (a-4) containing an isocyanato group and an ethylenically unsaturated group is an isocyanato group-containing (meth)acrylate (a-4a).
  • Examples of the isocyanato group-containing (meth)acrylate (a-4a) include 2-(meth)acryloyloxyethyl isocyanate, 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, 2-(2-isocyanatoethyloxy)ethyl (meth)acrylate , 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate and the like.
  • isocyanatoalkyl (meth)acrylate is preferred, and 2-(meth)acryloyloxyethyl isocyanate is more preferred, from the viewpoint of ease of availability and ease of synthesis of resin (A).
  • the number of carbon atoms in the alkyl group of the isocyanatoalkyl (meth)acrylate is preferably 2 to 10.
  • isocyanato group-containing (meth)acrylates having a polyoxyalkylene structure are preferred, and 2-(2-isocyanatoethyloxy) Ethyl (meth)acrylate is more preferred.
  • a compound containing two or more ethylenically unsaturated groups and an isocyanato group is preferable.
  • the ethylenically unsaturated group is a (meth)acryloyloxy group
  • two or more (meth)acryloyloxy groups The isocyanato group-containing (meth)acrylate having a group is preferable, and 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate is more preferable.
  • the amount of the compound (a-4) containing an isocyanato group and an ethylenically unsaturated group is based on 100 moles of the monomer (M) constituting the hydroxy group-containing (meth)acrylic resin (a-0).
  • the amount is preferably 1 to 60 mol, more preferably 3 to 50 mol, and even more preferably 5 to 40 mol.
  • the added amount of the compound (a-4) containing an isocyanato group and an ethylenically unsaturated group is 1 mol or more, sufficient photocurability as a photosensitive resin composition can be imparted.
  • the amount added is 60 mol or less, gelation during synthesis of the resin (A) can be prevented, and a sufficient amount of the polybasic acid or its anhydride (a-5) can be ensured, resulting in photosensitive properties. Good developability as a resin composition can be obtained.
  • the added amount of the compound (a-4) containing an isocyanato group and an ethylenically unsaturated group is the same as that of the hydroxy group-containing (meth)acrylic resin (a-0).
  • the amount is preferably 30 to 50 mol per 100 mol of monomer (M).
  • the polybasic acid or its anhydride (a-5) is a compound having two or more carboxy groups or its anhydride.
  • polybasic acids include adipic acid, itaconic acid, succinic acid, oxalic acid, malonic acid, phthalic acid, fumaric acid, maleic acid, glutaric acid, tartaric acid, glutamic acid, and sebacic acid.
  • polybasic acid anhydride include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, succinic anhydride, cyclohexanetricarboxylic anhydride, and the like.
  • polybasic acid anhydrides having an alicyclic structure are preferred, such as maleic anhydride, itaconic anhydride, ethyl maleic anhydride, methyl itaconic anhydride, chloromaleic anhydride, citraconic anhydride, 2 -Norbornene-5,6-dicarboxylic anhydride, 4-[2-(methacryloyloxy)ethoxycarbonyl]phthalic anhydride, succinic anhydride, tetrahydrophthalic anhydride, and cyclohexanetricarboxylic anhydride are more preferred, and introduction of a carboxy group Tetrahydrophthalic anhydride and cyclohexanetricarboxylic anhydride are more preferred from the viewpoint of increasing the amount and improving low-temperature curability.
  • maleic anhydride such as maleic anhydride, itaconic anhydride, ethyl maleic anhydride, methyl itaconic anhydride, chloromaleic
  • the amount of the polybasic acid or its anhydride (a-5) added is 1 to 60 mol per 100 mol of the monomer (M) constituting the hydroxy group-containing (meth)acrylic resin (a-0).
  • the amount is preferably from 3 to 50 mol, and even more preferably from 5 to 45 mol.
  • the amount of the polybasic acid or its anhydride (a-5) added is 1 mol or more, sufficient developability as a photosensitive resin composition can be obtained.
  • the addition amount is 60 mol or less, a sufficient amount of the compound (a-4) containing an isocyanato group and an ethylenically unsaturated group can be ensured, and a good photosensitive resin composition can be obtained. Curability is obtained.
  • the amount of polybasic acid or its anhydride (a-5) added is preferably 35 to 60 mol.
  • the ratio of the introduced amount (total number of moles) of the polybasic acid or its anhydride (a-5) is preferably 20 to 90%, more preferably 30 to 85%, and even more preferably 45 to 80%. If the modification rate is 20% or more, a sufficient amount of ethylenically unsaturated groups and carboxyl groups can be ensured, and a photosensitive resin composition with excellent developability can be obtained, and when cured at low temperature. However, a cured film with excellent hardness and solvent resistance can be obtained.
  • the modification rate is 90% or less, it is possible to suppress gelation during resin (A) synthesis, reduce residual monomer, and suppress generation of residue during development as a photosensitive resin composition.
  • the weight average molecular weight (Mw) of the resin (A) is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and most preferably 3,500 to 25,000 in terms of polystyrene. . If the weight average molecular weight (Mw) of the resin (A) is 1000 or more, when a 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 damaged, such as chipping. A photosensitive resin composition that is less likely to cause such problems can be obtained. When the weight average molecular weight of the resin (A) is 50,000 or less, the photosensitive resin composition containing the resin (A) has a sufficiently short development time and is excellent in practical use.
  • the value of the weight average molecular weight (Mw) of the resin (A) in this embodiment is measured using gel permeation chromatography (GPC) under the following conditions and calculated in terms of polystyrene. .
  • GPC gel permeation chromatography
  • Developing solvent Tetrahydrofuran Detector: Differential refractometer (trade name: Showdex (registered trademark) RI-71S, manufactured by Showa Denko K.K.) Flow rate: 1mL/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. , most preferably from 1.7 to 3.0.
  • Mw/Mn molecular weight distribution
  • optimization of target numerical ranges such as weight average molecular weight (Mw) and acid value, and reaction when manufacturing the resin (A) are possible. Conditions etc. can be set within a certain range, allowing efficient manufacturing.
  • the molecular weight distribution (Mw/Mn) of the resin (A) is 5.0 or less, when a resin composition containing the resin (A) is used as a raw material for a photosensitive resin composition, performance such as developability may deteriorate. A photosensitive resin composition without variations can be obtained. Note that the molecular weight distribution (Mw/Mn) is calculated using the chromatogram of the above GPC measurement.
  • the acid value of the resin (A) is not particularly limited, but is preferably 10KOHmg/g to 300KOHmg/g, more preferably 50KOHmg/g to 300KOHmg/g, and most preferably 100KOHmg/g to 300KOHmg/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 for the photosensitive resin composition. You can get things.
  • the acid value of the resin (A) is 300 KOHmg/g or less
  • a resin composition containing the resin (A) is used as a raw material for a photosensitive resin composition
  • the exposed portion photocurable A photosensitive resin composition having good developability without dissolving the part
  • the acid value of the resin (A) is a value measured using a mixed indicator of bromothymol blue and phenol red in accordance with 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 ethylenically unsaturated group equivalent of the resin (A) is not particularly limited, but is preferably from 200 g/mol to 5000 g/mol, more preferably from 300 g/mol to 4000 g/mol, and most preferably from 300 g/mol to It is 3000g/mol.
  • the photosensitive resin composition containing the resin (A) can form a cured resin film having better hardness.
  • the ethylenically unsaturated group equivalent of the resin (A) is 200 g/mol or more, a sufficient amount of carboxyl groups can be introduced into the resin (A), and a photosensitive material with better developability can be obtained. A synthetic resin composition is obtained. Moreover, when the ethylenically unsaturated 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 better hardness.
  • the equivalent amount of ethylenically unsaturated groups is 1500 g/mol or less.
  • the amount may be 800 g/mol or less.
  • the ethylenically unsaturated group equivalent of the resin (A) is the value obtained by dividing the molecular weight of the resin (A) by the average number of unsaturated groups per molecule.
  • the ethylenically unsaturated group equivalent of the resin (A) is a calculated value calculated based on the 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 unsaturated groups, all unsaturated groups are counted as the number of unsaturated groups, regardless of the type of unsaturated groups.
  • the functional group equivalent of the resin (A) refers to the aforementioned functional groups (active methylene group, active (methine group, epoxy group, oxetanyl group, blocked isocyanato group, and silyl group).
  • 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 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 better hardness.
  • the functional group equivalent of the resin (A) is 200 g/mol or more
  • a resin composition containing the resin (A) is used as a raw material for a photosensitive resin composition
  • a photosensitive resin composition with better developability can be obtained.
  • a synthetic resin composition is obtained.
  • the functional 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 better hardness.
  • the functional group equivalent of the resin (A) is the value obtained by dividing the molecular weight of the resin (A) by the average number of the above-mentioned functional groups contained in the (meth)acrylate (m-2)-derived structural units per molecule. It is.
  • the functional group equivalent of the resin (A) is a calculated value calculated based on the charged amount of the monomer (M) 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 type of functional group.
  • the hydroxy group-containing (meth)acrylic resin (a-0) can be produced, for example, using the production method shown below. That is, in the presence of a polymerization solvent, the monomer (M) is copolymerized using a polymerization initiator according to a radical polymerization method known in the art.
  • a polymerization initiator is added to the raw material solution, and the mixture is heated at, for example, 50°C to 130°C for 1 hour to 20 hours.
  • a method of carrying out a copolymerization reaction while stirring can be used.
  • the polymerization solvent used in producing the hydroxy group-containing (meth)acrylic resin (a-0) is not particularly limited as long as it is inert to the copolymerization reaction of the monomer (M).
  • the polymerization solvent used when producing the hydroxy group-containing (meth)acrylic resin (a-0) may be the same as the solvent contained in the solvent (D) contained in the resin composition described below. However, part or all of the solvent may be different from the solvent contained in the solvent (D).
  • the reaction solution after the copolymerization reaction is It is preferable because it can be used as a part of the solvent (D) without separating or removing the polymerization solvent from the polymerization solvent.
  • the solvent used for polymerization is not particularly limited as long as it dissolves the monomer (M) and the resulting copolymer and does not inhibit the polymerization reaction.
  • the copolymer to be produced is a (meth)acrylic acid-based polymer
  • a glycol ether solvent is preferred 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, dipropylene glycol dimethyl ether, and the like.
  • solvents may be used alone or in combination of two
  • the amount of the polymerization solvent used when producing the hydroxy group-containing (meth)acrylic resin (a-0) is not particularly limited, but is preferably 30 parts by mass based on 100 parts by mass of the monomer (M). ⁇ 1000 parts by weight, more preferably 50 parts by weight ⁇ 800 parts by weight.
  • the amount of the polymerization solvent used is 30 parts by mass or more, the copolymerization reaction of the monomer (M) can be carried out stably, and the coloring and the hydroxyl group-containing (meth)acrylic resin (a-0) can be Can prevent gelation.
  • the amount of the polymerization solvent used is 1000 parts by mass or less, it is possible to suppress a decrease in the molecular weight of the hydroxy group-containing (meth)acrylic resin (a-0) due to chain transfer, and also to keep the viscosity of the reaction solution within an appropriate range. Can be controlled.
  • the polymerization initiator that can be used in the copolymerization reaction of the monomer (M) is not particularly limited, but for example, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2 , 4-dimethylvaleronitrile), dimethyl 2,2'-azobis(isobutyrate), benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, and the like. These polymerization initiators may be used alone or in combination of two or more.
  • the amount of the polymerization initiator used is not particularly limited, but is preferably 0.1 parts by mass to 20 parts by mass, more preferably 0.5 parts by mass to 16 parts by mass, based on 100 parts by mass of the monomer (M). Part by mass.
  • the resin (A) is a compound (a-4) containing an isocyanato group and an ethylenically unsaturated group in some of the hydroxy groups of the hydroxy group-containing (meth)acrylic resin (a-0) and a polybasic acid or It can be obtained by adding the anhydride (a-5).
  • the addition reaction can be carried out according to conventional methods.
  • a compound (a-4) containing an isocyanato group and an ethylenically unsaturated group and a polybasic acid or its anhydride A method of adding a-5) and causing an addition reaction can be used.
  • this addition reaction modification reaction
  • the reaction solution contains the polymerization solvent used during copolymerization to produce the hydroxy group-containing (meth)acrylic resin (a-0).
  • the addition reaction can be carried out without removing the polymerization solvent from the reaction solution after the copolymerization reaction for producing the hydroxy group-containing (meth)acrylic resin (a-0) is completed.
  • the order in which the compound containing an isocyanato group and an ethylenically unsaturated group (a-4) and the polybasic acid or its anhydride (a-5) are added is not particularly limited, and they may be added at the same time or separately. You can also add it. From the viewpoint of suppressing the by-production of isocyanate dimers, first, a compound (a-4) containing an isocyanate group and an ethylenically unsaturated group is added and reacted, and then a polybasic acid or its anhydride (a-5) is added and reacted. ) is preferably added and reacted.
  • the reaction temperature in the addition reaction can be appropriately set depending on the type of each raw material. Specifically, the temperature is preferably 30°C to 150°C, more preferably 50°C to 120°C. By setting the reaction temperature to 30° C. or higher, the addition reaction can proceed sufficiently. Moreover, by setting the reaction temperature to 150° C. or lower, gelation of the reaction solution can be suppressed, and decomposition of bonds generated by the addition reaction can be suppressed.
  • a polymerization inhibitor When performing the addition reaction, a polymerization inhibitor may be added to the reaction solution, if necessary, in order to prevent gelation of the reaction solution due to the addition reaction.
  • the polymerization inhibitor include, but are not limited to, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, dibutylhydroxytoluene, and the like.
  • a catalyst When carrying out the addition reaction, a catalyst may be added to the reaction solution to promote the reaction, if necessary.
  • the catalyst include, but are not limited to, tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, metal chelate compounds such as chromium, Examples include metal chelate compounds such as lithium, tin compounds such as tin 2-ethylhexanoate, and dibutyltin dilaurate (DBTDL).
  • DBTDL dibutyltin dilaurate
  • 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. ⁇ 85 parts by weight, more preferably 15 parts to 75 parts by weight, and most preferably 24 parts to 60 parts by weight. When the content of the resin (A) is within the above range, the viscosity and low temperature curability of the photosensitive resin composition become more appropriate.
  • the reactive diluent (B) contained in the photosensitive resin composition of this 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. , not particularly limited.
  • a reactive diluent having a plurality of ethylenically unsaturated groups is preferred.
  • reactive diluent (B) examples include aromatic vinyl monomers; polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; monofunctional (meth)acrylates; polyfunctional (meth)acrylates; Examples include triallyl cyanurate.
  • aromatic vinyl monomers include styrene, ⁇ -methylstyrene, ⁇ -chloromethylstyrene, vinyltoluene, divinylbenzene, diallylphthalate, diallylbenzene phosphonate, and the like.
  • monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, ⁇ -hydroxyethyl (meth)acrylate, and hydroxypropyl (meth)acrylate. ) acrylate, etc.
  • polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, and trimethylolpropane di(meth)acrylate.
  • Examples include acrylate.
  • reactive diluent (B) polyfunctional (meth)acrylates are preferable in order to improve curability (reactivity), and in particular dipentaerythritol penta(meth)acrylate and/or dipentaerythritol Hexa(meth)acrylate is preferred.
  • These reactive diluents (B) may be used alone 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 100 parts by mass when the total of the components other than the solvent (D) contained in the photosensitive resin composition is The amount is from 10 parts by weight to 85 parts by weight, more preferably from 15 parts by weight to 75 parts by weight, and most preferably from 24 parts by weight to 60 parts by weight.
  • 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 when irradiated with light.
  • the photopolymerization initiator (C) include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; 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-butylanthr
  • Benzophenones 1,2-octanedione, 1-[4-(phenylthio)-2-(o-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; 2-benzyl-2 -Dimethylamino-1-(4-morpholinophenyl)butanone-1; Acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; Xanthone etc.
  • These photopolymerization initiators (C) may be used alone or in combination of two or more.
  • the content of the photopolymerization initiator (C) in the photosensitive resin composition of the present embodiment is preferably 100 parts by mass when the total of components other than the solvent (D) contained in the photosensitive resin composition is The amount is from 0.1 parts by weight to 30 parts by weight, more preferably from 0.3 parts by weight to 20 parts by weight, and most preferably from 0.5 parts by weight to 10 parts by weight.
  • the content of the photopolymerization initiator (C) is 0.1 parts by mass or more, the photosensitive resin composition has sufficient photocurability.
  • the content of the photopolymerization initiator (C) is 30 parts by mass or less, 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 this embodiment is inert to the resin (A) and the reactive diluent (B), and is capable of dissolving the resin (A) and the reactive diluent (B). It is not particularly limited as long as it is a suitable solvent.
  • the solvent (D) may or may not contain the polymerization solvent used in producing the resin (A). If the solvent (D) contains the polymerization solvent used in producing the resin (A), the polymerization solvent is extracted from the reaction solution after the copolymerization reaction to produce the resin (A) is completed.
  • the addition reaction for producing resin (A) is carried out without removing the polymerization solvent (D) from the resin composition without separating or removing the polymerization solvent from the reaction solution after the addition reaction is completed. ) can be used as part or all of.
  • the case where the polymerization solvent used in producing the resin (A) is not contained in the solvent (D) means that the resin (A) used as a raw material for the resin composition does not produce the resin (A). This is the case when it is separated and removed from the reaction solution.
  • the type and content of the solvent (D) may be determined depending on the type of the resin (A), the use of the resin composition, etc. The amount can be selected as appropriate. That is, when the resin (A) is separated and removed from the reaction solution in which the resin (A) was produced, the solvent (D) is the same as the polymerization solvent used in producing the resin (A).
  • the same kind of material may be used, or different materials may be used.
  • the solvent (D) is not particularly limited, but when the resin (A) is a (meth)acrylic acid polymer, a glycol ether solvent is preferred from the viewpoint of its solubility.
  • a glycol ether solvent is preferred from the viewpoint of its solubility.
  • the solvent (D) may contain other solvents that can dissolve the resin (A) and the reactive diluent (B).
  • Examples include monoalcohols, (poly)alkylene glycol monoalkyl ethers, and the like.
  • 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. .
  • 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, and propylene glycol monoethyl ether acetate.
  • (Poly)alkylene glycol monoalkyl ether acetates such as; 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 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-methoxybutyl acetate,
  • 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 total of the components excluding the solvent (D) in the resin composition is 100 parts by mass.
  • the amount is more preferably 50 parts by mass to 800 parts by mass, and most preferably 100 parts by mass to 700 parts by mass.
  • the viscosity of the resin composition can be adjusted to an appropriate range.
  • the photosensitive resin composition of this embodiment may contain one or more known additives such as a leveling agent, a thermal polymerization inhibitor, and a sensitizer, if necessary.
  • the content of these additives is not particularly limited as long as it does not impede the effects of the present invention.
  • the photosensitive resin composition of this embodiment may contain an amine, hydrazide, aldehyde, or metal salt as a crosslinking agent in order to improve curability.
  • crosslinking agents include MXDA and 1,3-BAC manufactured by Mitsubishi Gas Chemical Co., Ltd., ADH and APA-280 manufactured by Otsuka Chemical Co., Ltd., and SEQUAREZ 755 and the first rare element manufactured by OMNOVA Solutions. Examples include the product name ZIRCOZOL ZC-2, 7 manufactured by Kagaku Kogyo Co., Ltd.
  • the photosensitive resin composition of this embodiment may contain an acid generator and a base generator in order to improve curability.
  • an acid generator and a base generator in order to improve curability.
  • photoacid generators include sulfonium salt compounds such as CPI-200K, CPI-210S, CPI-310B, and CPI-410S, and iodonium salt compounds such as IK-1 manufactured by San-Apro Chemical Co., Ltd.
  • photobase generators include WPBG-266, WPBG-300, WPBG-345, and the like manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
  • the viscosity of the photosensitive resin composition of this embodiment can be adjusted as appropriate depending on 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, and preferably 2 mP ⁇ s to 25 mP ⁇ s at the temperature during coating. It is more preferably 20 mP ⁇ s, and most preferably 3 mP ⁇ s to 15 mP ⁇ s.
  • the photosensitive coloring composition of this embodiment contains the photosensitive resin composition of this embodiment and a colorant (E).
  • a colorant (E) As the colorant (E), known dyes and/or pigments can be used. When used in a filter, it is preferable to use a dye as the colorant (E) from the viewpoint of color reproducibility. When a dye is used as the colorant (E), a colored pattern with higher brightness can be obtained than when a pigment is used, and the photosensitive colored composition exhibits good alkali developability.
  • 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., acidic dyes having an acidic group such as a carboxy group, acidic dyes, etc. It is preferable to use salts of dyes with nitrogen compounds, sulfonamides of acidic dyes, and the like.
  • dyes examples include acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; solvent blue38, 44 (VALIFAST BLUE2620); acid chrome violet K; acid Fuchsin; acid green1, 3, 5, 25, 27, 50; a cid orange6, 7, 8, 0 , 12, 50, 51, 52, 56, 63, 74, 95; acid red1, 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
  • azo-based, xanthene-based, anthraquinone-based, or phthalocyanine-based acid dyes are preferred. These dyes may be used singly or in combinations of two or more, depending on the desired color of the pixel.
  • pigments examples include 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, Yellow pigments such as C. 147, 148, 150, 153, 154, 166, 173, 194, 214; I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, and other orange pigments; C.I. I.
  • 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. Pigment Blue 15, 15:3, 15:4, 15:6, 60 and other blue pigments; C.I. I. Violet color pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38; C.I. I. Pigment Green 7, 36, 58 and other green pigments; C.I. I. Brown pigments such as Pigment Brown 23 and 25; C.I. I. Examples include black pigments such as Pigment Black 1 and 7, carbon black, titanium black, and iron oxide. These pigments may be used singly or in combination of two or more, depending on the desired color of the pixel.
  • a known dispersant may be blended into 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 has excellent dispersion stability over time.
  • polymeric dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified esters. Examples include system dispersants and the like.
  • Such polymer dispersants include product names such as EFKA (manufactured by EFKA), Disperbyk (manufactured by BYK Chemie), Disparon (manufactured by Kusumoto Kasei Co., Ltd.), and SOLSPERSE (manufactured by Zeneca). You may use what is commercially available.
  • the amount of the dispersant to be blended may be appropriately set depending on the type and amount of the pigment used as the colorant (E).
  • the content of the colorant (E) in the photosensitive coloring composition of the present embodiment is preferably 4 parts by mass when the total amount of components other than the solvent (D) contained in the photosensitive coloring composition is 100 parts by mass. parts to 79 parts by weight, more preferably 9 parts to 69 parts by weight, and most preferably 15 parts to 50 parts by weight.
  • the content of the colorant (E) is 4 parts by mass or more, the effect of containing the colorant (E) becomes significant, resulting in a photosensitive coloring composition suitable as a material for a color pattern of a color filter.
  • the content of the colorant (E) is 85 parts by mass or less, the colorant (E) in the photosensitive coloring composition does not interfere with the curability of the photosensitive coloring composition and can be cured at low temperatures. It has good sex.
  • the photosensitive coloring composition of this embodiment may contain other additives similar to those described for the photosensitive resin composition, if necessary.
  • the viscosity of the photosensitive coloring composition of this embodiment can be adjusted as appropriate depending on the thickness of the cured resin film made of the cured product of the photosensitive coloring composition.
  • the viscosity of the photosensitive coloring composition is preferably 1 mP ⁇ s to 25 mP ⁇ s, and preferably 2 mP ⁇ s to 20 mP ⁇ s. More preferably, it is between 3 mP ⁇ s and 15 mP ⁇ s.
  • the photosensitive resin composition of this embodiment includes a resin (A), a reactive diluent (B), a photopolymerization initiator (C), a solvent (D), and additives used as necessary. can be produced by mixing them using a known mixing device.
  • the photosensitive resin composition of this embodiment has good low-temperature curability and can form a cured resin film with sufficient hardness and solvent resistance. Furthermore, since the photosensitive resin composition of this embodiment has excellent alkali developability, a fine pattern can be formed by developing it using an alkaline aqueous solution. Therefore, the photosensitive resin composition of this embodiment is suitably used as a resist.
  • the photosensitive coloring composition of this embodiment includes a resin (A), a reactive diluent (B), a photopolymerization initiator (C), a solvent (D), a colorant (E), and optionally It can be produced by mixing the additives used in the above-mentioned process using a known mixing device.
  • the photosensitive resin composition of this embodiment has good low-temperature curability and can form a cured resin film having sufficient hardness and solvent resistance. Furthermore, since the photosensitive resin composition of this embodiment has excellent alkali developability, a fine pattern can be formed by developing it using an alkaline aqueous solution. Therefore, the photosensitive resin composition of this embodiment is suitably used as a resist. Moreover, the photosensitive coloring composition of this embodiment can be suitably used as a material for coloring patterns such as pixels of color filters and black matrices.
  • the cured resin film of this embodiment is made of a cured product of the photosensitive resin composition of this embodiment or the photosensitive coloring composition of this embodiment.
  • the cured resin film of this embodiment can be produced by, for example, a coating process in which the photosensitive resin composition of this embodiment is applied onto a base material to form a coating film, and a pre-bake process in which the coating film formed by the coating process is dried. It can be formed by a method of performing an exposure step in which the dried coating film is irradiated with light and photocured, and a post-baking step in which the photocured coating film is thermally cured.
  • the method shown below can be used. That is, the above-mentioned coating process and pre-bake process are performed. Thereafter, in an exposure step, the dried coating film is irradiated with light through a photomask having a predetermined pattern to photocure the exposed portions. After the exposure step, post-exposure heat treatment is performed as necessary. Thereafter, a development process is performed in which the unexposed portion of the coating film is dissolved and developed using a developer, and a post-baking process is performed in which the photocured coating film is thermally cured.
  • the photosensitive resin composition of this embodiment or the photosensitive coloring composition of this embodiment is coated on a substrate to form a coating film.
  • the base material to which the photosensitive resin composition or the photosensitive coloring composition is applied can be any known material, and can be determined as appropriate depending on the intended use of the cured resin film.
  • the method for applying the photosensitive resin composition or the photosensitive coloring composition is not particularly limited, and examples thereof include screen printing, roll coating, curtain coating, spray coating, spin coating, slit coating, etc. can be used.
  • prebaking (preheating treatment) step the coating film formed in the coating step is dried to reduce the amount of solvent remaining 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.
  • examples of the method for heating the base material on which the coating film is formed include a method using a hot plate.
  • the surface of the coating film dried in the prebaking step is irradiated with light to photocure the coating film.
  • the light source used for light irradiation is not particularly limited, but for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, etc. can be used.
  • the exposure amount in the exposure step is not particularly limited, and can be appropriately set depending on 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 process is irradiated with light through a photomask having a predetermined pattern, and the exposed portion is exposed to light. Let it harden.
  • Post-exposure heating process When forming a cured resin film having a predetermined pattern, a post-exposure baking step is performed as necessary after the exposure step. By performing this step, the dissolution contrast between the exposed and unexposed portions of the coating film becomes more pronounced.
  • the post-exposure heating step unlike the post-bake step described below, does not completely cure the coating film.
  • the post-exposure heating step is performed in order to more reliably remove the unexposed portions of the coating film while leaving only the exposed portions of the coating film on the substrate by performing the development step. Therefore, it is not an essential step in the method for forming a cured resin film of this embodiment.
  • the substrate after the exposure step is preferably heated at, for example, 40°C to 70°C, more preferably 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 lower, the acid generated in the exposed area will not diffuse to the unexposed area, and a 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 area will not diffuse to the unexposed area, and a good dissolution contrast can be obtained.
  • a hot plate, an oven, a furnace, or the like can be used as a method for heating the substrate after the exposure step in the post-exposure heating step.
  • a post-exposure heating step is performed if necessary, and then a development step is performed to develop the unexposed portions of the coating film.
  • a developer used in the development step any alkaline aqueous solution conventionally used for developing photosensitive resin compositions or photosensitive coloring compositions can be used.
  • alkaline aqueous solutions include, but are not limited to, aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc.; aqueous solutions of amine compounds such as ethylamine, diethylamine, dimethylethanolamine; and tetrahydroxide.
  • 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 depending on the composition of the photosensitive resin composition, the composition of the developer, the thickness of the coating film, and the like.
  • the developing step it is preferable that the unexposed portion of the coating film is developed by dissolving it using the aqueous alkali solution, followed by washing with water and drying.
  • a post-bake step is performed in which the photo-cured 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 depending on the composition of the photosensitive resin composition or photosensitive coloring composition, the thickness of the coating film, the material of the substrate, etc.
  • the heating temperature in the post-bake step can be, for example, 50°C to 210°C.
  • a material with low heat resistance can be used as the color filter material.
  • the heating temperature may be 150°C or lower, 120°C or lower, or 100°C or lower. The temperature may be below °C.
  • a colored pattern containing a coloring agent (E) with poor heat resistance which has been difficult to use as a material for conventional colored patterns, can be formed 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 with poor heat resistance, which has conventionally been difficult to use as a substrate for color filters. Moreover, when the heating temperature is 150° C. or lower, the amount of energy required to cure the coating film is small, which is preferable.
  • the heating temperature in the post-bake 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 is short, and a cured resin film can be efficiently formed.
  • the heating temperature in the post-bake step is more preferably 60°C or higher, and still more preferably 70°C or higher.
  • the heating time in the post-bake step can be appropriately selected depending on the heating temperature, the thickness of the coating film, the composition of the photosensitive resin composition, etc., and can be, for example, 10 minutes to 4 hours, preferably It takes 20 minutes to 2 hours.
  • the cured resin film of this embodiment is made of a cured product of the photosensitive resin composition of this embodiment or the photosensitive coloring composition of this embodiment. Therefore, it has sufficient hardness and solvent resistance.
  • the cured resin film of this embodiment can be suitably used as a material for various insulating films such as a protective film provided above a color filter, 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 a color filter of this embodiment.
  • the color filter shown in FIG. 1 consists of a base material 1, RGB pixels 2 formed on one surface 1a of the base material 1, a black matrix 3 formed at the boundaries of each pixel 2, and a black matrix 3 formed on each pixel 2. and a protective film 4 formed on the black matrix 3.
  • the base material 1 used for the color filter shown in FIG. 1 is not particularly limited, and may include a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamide-imide substrate, a polyimide substrate, an aluminum substrate, and a printed wiring.
  • a substrate, an array substrate, a PET substrate, etc. can be used as appropriate depending on the purpose.
  • an organic material substrate such as a resin substrate
  • a low-temperature heat treatment process is essential, and the photosensitive resin composition of this embodiment and the photosensitive coloring composition of this embodiment can exhibit even greater effects.
  • the base material 1 used in the color filter shown in FIG. 1 is a polycarbonate substrate, a polyester substrate, a polyamide substrate.
  • a color filter using a resin substrate such as a polyamide-imide substrate, a polyimide substrate, a PET substrate, etc. is suitable.
  • At least one of the pixels 2 and the black matrix 3 in the color filter shown in FIG. 1 is made of a resin composition containing a resin (A) and a solvent (D), a reactive diluent (B), and a photoinitiator ( This is a colored pattern made of a cured product of the photosensitive coloring composition of this embodiment, which includes C), a colorant (E), and optionally contained additives.
  • the protective film 4 one made of a known material can be used.
  • the protective film 4 is made of 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 cured resin film made of a cured product of the photosensitive coloring composition of this embodiment containing.
  • 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.
  • RGB pixels 2 and a black matrix 3 are sequentially formed on one surface 1a of the base material 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 formation method.
  • the protective film 4 can be manufactured using the method for manufacturing a cured resin film of this embodiment described above.
  • the color filter of this embodiment has a colored pattern (pixels 2 and black matrix 3) made of the 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 includes the color filter of this embodiment that has 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 image sensor, and the like.
  • the image display element of this embodiment is capable of high-brightness display by being provided with the above-mentioned color filter.
  • DBTDL dibutyltin acid
  • methyl hydroquinone polymerization inhibitor
  • propylene glycol monomethyl ether acetate 0.27 g of dibutyltin acid (DBTDL) (addition reaction catalyst), 0.53 g of methyl hydroquinone (polymerization inhibitor), and 5.3 g of propylene glycol monomethyl ether acetate were added, and an addition reaction was carried out at 60° C. for 2 hours.
  • (meth)acryloyloxy groups were introduced into some of the hydroxy groups derived from 2-hydroxyethyl methacrylate.
  • the mixture was stirred at 98° C. for 3 hours to carry out a copolymerization reaction to produce a functional group-containing resin (ca) as a comparison copolymer.
  • the inside of the flask was replaced with air, and 52.7 g (0.17 mol) of 1,2,3,6-tetrahydrophthalic anhydride was added to the reaction solution in which the functional group-containing resin (ca) was synthesized.
  • 1.3 g of lithium naphthenate (addition reaction catalyst), 0.53 g of methyl hydroquinone (polymerization inhibitor), and 44.8 g of propylene glycol monomethyl ether acetate were added, and an addition reaction was carried out at 78° C. for 3 hours.
  • the blending 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 (D) solvent 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. It's the amount.
  • 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 performed by setting a photomask at a position 100 ⁇ m apart from the coating film.
  • the photomask used had a line and space pattern with a width of 3 to 100 ⁇ m.
  • a semi-clean DL-A10 developer manufactured by Yokohama Yushi Kogyo Co., Ltd.
  • the glass substrate having the coating film after the development step was left standing in a dryer at 100° C. for 30 minutes to thermally cure the coating film (post-bake step) to obtain a colored pattern.
  • the pencil hardness of the cured resin film thus produced was measured according to JIS K5600-5-4 using a pencil hardness meter (No. 553-M, manufactured by Yasuda Seiki Seisakusho), and evaluated according to the following criteria. .
  • the results are shown in Table 4 or Table 5.
  • ⁇ Pencil hardness less than 3H
  • a glass substrate with a cured resin film was prepared in the same manner as in (2) above for evaluating pencil hardness, and the cured resin film was measured using a spectrophotometer (UV-1650PC, manufactured by Shimadzu Corporation). The absorption spectrum was measured. Further, 200 mL of propylene glycol monomethyl ether acetate was placed in a 500 mL glass bottle with a lid, and the bottle was left standing at a temperature of 23°C. A glass substrate having a cured resin film was placed in this glass bottle, immersed in propylene glycol monomethyl ether acetate, and left at 23° C. for 15 minutes.
  • the glass substrate with the cured resin film was taken out, and the absorption spectrum of the cured resin film was measured using a spectrophotometer (UV-1650PC, manufactured by Shimadzu Corporation) in the same manner as before immersing it in propylene glycol monomethyl ether acetate. did.
  • the photosensitive coloring compositions R1 to R18 of Examples 1 to 18 all have a minimum developed size of 15 ⁇ m or less, and there is no residue in the unexposed areas between the developed patterns, and the compositions are excellent. It was confirmed that the film had alkali developability.
  • the coating film formed using the photosensitive coloring compositions R1 to R18 of Examples 1 to 18 was photocured, and then the cured product was 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 cured resin film was evaluated as ⁇ in terms of solvent resistance, confirming that it had excellent solvent resistance.
  • the photosensitive coloring compositions cR1 to cR5 of Comparative Examples 1 to 5 had insufficient alkali developability, pencil hardness, or solvent resistance.
  • the copolymers cP1 to cP3 obtained in Comparative Synthesis Examples 1 to 3 contained in the photosensitive coloring compositions cR1 to cR3 of Comparative Examples 1 to 3 have an ethylenically unsaturated group equivalent of 0. It is. For this reason, the result was that the cured resin film was inferior in either alkali developability, hardness, or solvent resistance. Furthermore, in the copolymer cP4 obtained in Comparative Synthesis Example 4, which is included in the photosensitive resin composition cR4 of Comparative Example 4, a dimer of 2-acryloyloxyethyl isocyanate is generated as a by-product during synthesis.
  • the photosensitive resin composition cR5 of Comparative Example 5 was prepared by adding a dimer of 2-acryloyloxyethyl isocyanate to the copolymer P2 obtained in Synthesis Example 2. Therefore, similarly to Comparative Example 4, Comparative Example 5 also resulted in poor alkali developability, hardness, and solvent resistance of the cured resin film. Furthermore, when we checked the changes over time in the resin composition obtained this time, we found that the order of the structural units is as follows: structural units having an active methylene group, structural units having a blocked isocyanate group, structural units having a silyl group, and structural units having an epoxy group. A trend was observed.
  • a photosensitive resin composition and a photosensitive colored composition that have excellent developability and good low-temperature curability, and can form a cured resin film having sufficient hardness and solvent resistance. Further, according to the present invention, it is possible to provide a cured resin film that is made of a cured product of a photosensitive resin composition and has sufficient hardness and solvent resistance. It is possible to provide a color filter having a colored pattern made of a cured product of the photosensitive colored composition of the present invention and having sufficient hardness and solvent resistance. Furthermore, an image display element including this color filter can be provided.
  • the photosensitive resin composition and photosensitive coloring composition of the present invention can be preferably used, for example, as resists for transparent films, protective films, insulating films, overcoats, photo spacers, black matrices, black column spacers, and color filters. can.

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