WO2024116596A1 - 共重合体及び感光性樹脂組成物 - Google Patents

共重合体及び感光性樹脂組成物 Download PDF

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WO2024116596A1
WO2024116596A1 PCT/JP2023/036255 JP2023036255W WO2024116596A1 WO 2024116596 A1 WO2024116596 A1 WO 2024116596A1 JP 2023036255 W JP2023036255 W JP 2023036255W WO 2024116596 A1 WO2024116596 A1 WO 2024116596A1
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structural unit
mass
group
copolymer
parts
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French (fr)
Japanese (ja)
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司 原
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Resonac Corp
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Resonac Corp
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Priority to CN202380082004.6A priority Critical patent/CN120380042A/zh
Priority to KR1020257017464A priority patent/KR20250112780A/ko
Priority to JP2024561216A priority patent/JPWO2024116596A1/ja
Publication of WO2024116596A1 publication Critical patent/WO2024116596A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • 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
    • 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
    • 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
    • C08F220/40—Esters of unsaturated alcohols, e.g. allyl (meth)acrylate
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/30—Devices specially adapted for multicolour light emission
    • H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]

Definitions

  • the present invention relates to a copolymer, a photosensitive resin composition, a photosensitive colored composition, a cured resin film, and an image display element.
  • photosensitive resin compositions that can be cured by active energy rays such as ultraviolet rays and electron beams have been widely used in fields such as various coatings, printing, paints, and adhesives.
  • photosensitive resin compositions that can be cured by active energy rays are used for solder resists and color filter resists.
  • the required properties for curable photosensitive resin compositions are becoming increasingly diverse and sophisticated, and among them, short-time curing properties that take productivity into consideration and low-temperature curing properties that suppress thermal damage to the components to which they are applied are required.
  • a color filter generally consists of a transparent substrate such as a glass substrate, red (R), green (G) and blue (B) pixels formed on the transparent substrate, a black matrix formed at the boundaries of the pixels, and a protective film formed on the pixels and the black matrix.
  • a color filter having such a configuration is usually manufactured by sequentially forming the black matrix, pixels and protective film on the transparent substrate.
  • Various methods have been proposed for forming the pixels and black matrix (hereinafter, the pixels and black matrix are referred to as "colored patterns").
  • the pigment/dye dispersion method which uses a photosensitive resin composition as a resist and is produced by a photolithography process that repeats coating, exposure, development and baking, is currently the mainstream because it gives colored patterns that are highly durable and have few defects such as pinholes.
  • photosensitive resin compositions used in photolithography contain an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a colorant, and a solvent. While the pigment/dye dispersion method has the above advantages, it requires high heat resistance because black matrices and R, G, and B patterns are repeatedly formed. Furthermore, there are often problems with restrictions such as the limited types of colorants that can be used as colorants that can withstand high baking temperatures.
  • Patent Document 1 discloses a colored composition having a specific partial structure and a hydroxyl group as a photosensitive resin composition that can give a cured product with excellent solvent resistance even under low-temperature curing conditions and can be suitably used for applications such as color filters.
  • the present invention has been made to solve the above-mentioned problems, and aims to provide a copolymer that gives a resin cured film having excellent solvent resistance, a photosensitive resin composition and a photosensitive coloring composition using the copolymer, and also aims to provide a resin cured film having excellent solvent resistance, and an image display element having the same.
  • the present invention includes the following aspects.
  • a structural unit (ma-1) having an allyl group A structural unit (ma-2) having a blocked isocyanato group, A structural unit (ma-3) having a hydroxy group, A structural unit (ma-4) having an acid group, Contains A copolymer characterized in that the content of structural units (ma-1) having an allyl group is 1 to 60 mol % of all structural units.
  • the structural unit (ma-1) having an allyl group is contained in an amount of 1 to 60 mol %
  • the structural unit (ma-2) having the blocked isocyanato group is contained in an amount of 2 to 60 mol %.
  • the weight average molecular weight is 1,000 to 50,000;
  • the molecular weight distribution (Mw/Mn) is 1.3 to 5.0.
  • a photosensitive coloring composition comprising the photosensitive resin composition according to [10] or [11] and a colorant (E).
  • the copolymer (A) is contained in an amount of 10 parts by mass to 80 parts by mass
  • the reactive diluent (B) is contained in an amount of 10 parts by mass to 80 parts by mass
  • the photopolymerization initiator (C) is contained in an amount of 0.1 to 30 parts by mass
  • the solvent (D) is contained in an amount of 30 parts by mass to 1000 parts by mass
  • the colorant (E) is contained in an amount of 4 parts by mass to 79 parts by mass.
  • a cured resin film comprising a cured product of the photosensitive resin composition according to [10] or [11].
  • a resin cured film comprising a cured product of the photosensitive coloring composition according to [12] or [13].
  • An image display element comprising the color filter according to [16].
  • the present invention can provide a copolymer that gives a cured resin film with excellent solvent resistance, and a photosensitive resin composition and a photosensitive coloring composition using the copolymer. It can also provide a cured resin film with excellent solvent resistance obtained by curing the photosensitive resin composition and the photosensitive coloring composition, a color filter, and an image display element equipped with the same.
  • FIG. 1 is a schematic cross-sectional view showing an example of a color filter according to an embodiment of the present invention.
  • Copolymer (A) contains a structural unit (ma-1) having an allyl group, a structural unit (ma-2) having a blocked isocyanato group, a structural unit (ma-3) having a hydroxyl group, and a structural unit (ma-4) having an acid group.
  • Copolymer (A) according to the present embodiment may further contain a structural unit (ma-5) other than the structural units (ma-1) to (ma-4) as necessary.
  • the structural unit (ma-1) having an allyl group, the structural unit (ma-2) having a blocked isocyanato group, the structural unit (ma-3) having a hydroxyl group, and the structural unit (ma-4) having an acid group are preferably a structural unit (ma-1) formed by radical polymerization of a (meth)acrylate (m-1) having an allyl group, a structural unit (ma-2) formed by radical polymerization of a (meth)acrylate (m-2) having a blocked isocyanato group, a structural unit (ma-3) formed by radical polymerization of a (meth)acrylate (m-3) having a hydroxyl group, and a structural unit (ma-4) formed by radical polymerization of a (meth)acrylate (m-4) having an acid group, respectively.
  • the copolymer (A) of this embodiment is preferably a copolymer of a monomer (M) having the (meth)acrylate (m-1) having the allyl group, the (meth)acrylate (m-2) having the blocked isocyanato group, the (meth)acrylate (m-3) having the hydroxyl group, and the (meth)acrylate (m-4) having the acid group.
  • the copolymer may be a random copolymer or a block copolymer.
  • the structural unit (ma-1) having an allyl group (hereinafter also simply referred to as "structural unit (ma-1)") is not particularly limited as long as it is a structural unit having an allyl group and does not have a blocked isocyanato group or a hydroxy group.
  • structural unit (ma-1) is not particularly limited as long as it is a structural unit having an allyl group and does not have a blocked isocyanato group or a hydroxy group.
  • the structural unit (ma-1) having an allyl group is preferably a structural unit derived from an allyl group-containing (meth)acrylate (m-1).
  • the allyl group-containing (meth)acrylate (m-1) include allyl (meth)acrylate, an addition reaction product of (meth)acrylic acid and allyl glycidyl ether, and a (meth)acrylic acid ester of a compound in which an alkylene oxide is added to allyl alcohol. These may be used alone or in combination of two or more.
  • the content of the structural unit (ma-1) is preferably 1 to 60 mol %, more preferably 3 to 40 mol %, and even more preferably 5 to 20 mol % of the total structural units of the copolymer (A).
  • the content of the structural unit (ma-1) may be 1 to 20 mol %, 3 to 15 mol %, or 5 to 10 mol % of the total structural units of the copolymer (A).
  • the content of the structural unit (ma-1) is 1 mol % or more, good solvent resistance can be obtained even when the photosensitive resin composition using the copolymer (A) is cured under low temperature conditions.
  • the content of the structural unit (ma-1) is 60 mol % or less, gelation during the reaction can be prevented, and the content of the structural unit (ma-2) and the structural unit (ma-3) described below can be sufficiently ensured, and good low-temperature curing properties can be obtained as a photosensitive resin composition.
  • the content of the structural unit (ma-4) described below can be sufficiently ensured, and good developability can be obtained as a photosensitive resin composition.
  • the structural unit (ma-2) having a blocked isocyanato group (hereinafter also simply referred to as "structural unit (ma-2)") is not particularly limited as long as it is a structural unit having a blocked isocyanato group.
  • structural unit (ma-2) When the copolymer (A) has the structural unit (ma-2) having a blocked isocyanato group, crosslinking with the structural unit (ma-3) having a hydroxy group, which will be described later, progresses during thermal curing. As a result, when used in a photosensitive resin composition, good solvent resistance can be obtained even during thermal curing at low temperature conditions.
  • the structural unit (ma-2) having a blocked isocyanato group has a structure in which the isocyanato group is blocked with a blocking agent.
  • the reaction between the isocyanato group and the blocking agent can be carried out regardless of the presence or absence of a solvent. If a solvent is used, it is necessary to use a solvent that is inactive to the isocyanato group.
  • organic metal salts such as tin, zinc, and lead, and tertiary amines 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.
  • blocking agents for blocking isocyanato groups include lactams such as ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, and ⁇ -propiolactam; alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, and cyclohexanol; phenols such as phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, o-isopropylphenol, and butylphenols such as p-tert-butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, thymol,
  • active methylenes such as ethyl and acetylacetone; mercaptans such as butyl mercaptan, thiophenol and tert-dodecyl mercaptan; amines such as diphenylamine, phenylnaphthylamine, aniline and carbazole; acid amides such as acetanilide, acetanisidide, acetate amide and benzamide; acid imides such as succinimide and maleimide; imidazoles such as imidazole, 2-methylimidazole and 2-ethylimidazole;
  • suitable blocking agents include pyrazole-based blocking agents such as 3,5-dimethylpyrazole; urea-based blocking agents such as urea, thiourea, and ethyleneurea; carbamate-based blocking agents such as N-phenylcarbamate phenyl and 2-oxazolidone; imine-based blocking agents such as ethyleneimine and
  • blocking agents that have a dissociation rate of blocked isocyanato groups of 5 to 99% by mass when heated at 100° C. for 30 minutes are preferred from the viewpoint of improving low-temperature curing properties and solvent resistance as a photosensitive resin composition. More preferred are one or more selected from the group consisting of 3,5-dimethylpyrazole, methylethylketoxime, methyl4-hydroxybenzoate, methyl2-hydroxybenzoate, and 3,5-xylenol. 3,5-dimethylpyrazole is even more preferred. These blocking agents may be used alone or in combination of two or more kinds.
  • the dissociation rate of the blocked isocyanato group is the mass reduction rate of the blocked isocyanato group-containing (meth)acrylate after adding dibutyltin laurate and phenothiazine (polymerization inhibitor) to a solution of the blocked isocyanato group-containing compound and heating the solution.
  • dibutyltin laurate and phenothiazine polymerization inhibitor
  • phenothiazine polymerization inhibitor
  • the mass reduction rate of the blocked isocyanato group-containing (meth)acrylate is measured by HPLC analysis, and the value obtained is the dissociation rate of the blocked isocyanato group.
  • the structural unit (ma-2) having a blocked isocyanato group is preferably a structural unit having a carboxylic acid alkyl ester structure from the viewpoint of improving the low-temperature curing property and solvent resistance of the photosensitive resin composition.
  • the carboxylic acid alkyl ester structure means a structure having an alkyloxycarbonyl group having 10 carbon atoms. It is more preferable that the structural unit having a carboxylic acid alkyl ester structure is a structural unit having at least one type selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2).
  • R1 and R2 each independently represent an alkyl group having 1 to 10 carbon atoms.
  • n1 and n2 each independently represent an integer of 0 to 2.
  • * represents a linking site with a residue obtained by removing the blocked isocyanato group from the structural unit (ma-2).
  • R3 and R4 each independently represent an alkyl group having 1 to 10 carbon atoms.
  • n3 and n4 each independently represent an integer of 0 to 2.
  • * represents a linking site with a residue obtained by removing the blocked isocyanato group from the structural unit (ma-2).
  • the group represented by the above formula (1) or (2) undergoes ester exchange with the hydroxy group of the structural unit (ma-3) to generate a crosslinked structure by thermally curing a resin composition containing the copolymer (A). Therefore, a photosensitive resin composition using this copolymer (A) can produce a cured film with excellent solvent resistance even when cured at a low temperature of 50°C to 150°C.
  • R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms.
  • R 1 and R 2 are each independently preferably an alkyl group having 2 to 6 carbon atoms, more preferably an alkyl group having 2 to 3 carbon atoms, and most preferably both R 1 and R 2 are an ethyl group having 2 carbon atoms.
  • R 1 and R 2 are ethyl groups, when the resin composition containing the copolymer (A) is thermally cured, R 1 and R 2 undergo ester exchange with the hydroxy group of the structural unit (ma-3) to generate ethanol. This is preferable because the ethanol generated during thermal curing of the resin composition is easily evaporated and removed by heating for thermally curing the resin composition.
  • n1 and n2 each independently represent an integer of 0 to 2.
  • n1 and n2 each independently are preferably 1 or 2, and more preferably both are 1.
  • R3 and R4 in the above formula (2) are each independently an alkyl group having 1 to 10 carbon atoms.
  • R3 is preferably an alkyl group having 2 to 6 carbon atoms, more preferably an alkyl group having 2 to 3 carbon atoms, and even more preferably an ethyl group having 2 carbon atoms.
  • R 3 is an ethyl group
  • when the resin composition containing the copolymer (A) is thermally cured R 3 undergoes ester exchange with the hydroxy group of the structural unit (ma-3) to generate ethanol. This is preferable because the ethanol generated during thermal curing of the resin composition is easily evaporated and removed by heating for thermally curing the resin composition.
  • R4 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group having 1 carbon atom.
  • n3 and n4 each independently represent an integer of 0 to 2.
  • n3 and n4 each independently are preferably 1 or 2, and more preferably both are 1.
  • the group represented by formula (1) is preferred from the viewpoints of ease of transesterification with the hydroxy group in the structural unit (ma-3) and low-temperature curing properties of the photosensitive resin composition.
  • the structural unit (ma-2) having a blocked isocyanato group is preferably a structural unit derived from a monomer (ma-2) having a blocked isocyanato group and an ethylenically unsaturated bond.
  • groups having an ethylenically unsaturated bond include a vinyl group and a (meth)acryloyloxy group.
  • the ethylenically unsaturated group-containing isocyanate compound is preferably a compound represented by the following formula (3):
  • R 5 represents a hydrogen atom or a methyl group.
  • R 6 represents -CO-, -COOR 7 - (wherein R 7 is an alkylene group having 1 to 6 carbon atoms), or -COO-R 8 O-CONH-R 9 - (wherein R 8 is an alkylene group having 2 to 6 carbon atoms, and R 9 is an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms, which may have a substituent).
  • R5 represents a hydrogen atom or a methyl group.
  • R 6 in formula (3) represents -CO-, -COOR 7 - or -COO-R 8 O-CONH-R 9 -.
  • R 7 is an alkylene group having 1 to 6 carbon atoms.
  • R 8 is an alkylene group having 2 to 6 carbon atoms.
  • R 9 is an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms, which may have a substituent.
  • R 6 in formula (3) is preferably -COOR 7 -.
  • R 7 is preferably an alkylene group having 1 to 4 carbon atoms.
  • ethylenically unsaturated group-containing isocyanate compound represented by the above formula (3) include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, (meth)acryloyl isocyanate, etc.
  • an equimolar (1 mole:1 mole) reaction product of a 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound can also be used.
  • the alkyl group contained in the above 2-hydroxyalkyl (meth)acrylate is preferably an ethyl group or an n-propyl group, more preferably an ethyl group.
  • diisocyanate compound examples include hexamethylene diisocyanate, 2,4- (or 2,6-) tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 3,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate (IPDI), m- (or p-) xylylene diisocyanate, 1,3- (or 1,4-) bis (isocyanatomethyl) cyclohexane, lysine diisocyanate, etc.
  • TDI 2,4- (or 2,6-) tolylene diisocyanate
  • MDI 4,4'-diphenylmethane diisocyanate
  • IPDI 3,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate
  • m- (or p-) xylylene diisocyanate 1,3- (or 1,4-) bis (isocyana
  • These ethylenically unsaturated group-containing isocyanate compounds may be used alone or in combination of two or more.
  • the structural unit having a group represented by formula (1) or (2) is preferably a structural unit derived from a monomer having a group represented by formula (1) or (2) and an ethylenically unsaturated bond.
  • Specific examples of the group having an ethylenically unsaturated bond include a vinyl group and a (meth)acryloyloxy group.
  • Examples of monomers having a group represented by formulas (1) to (2) and an ethylenically unsaturated bond include reaction products of an isocyanate compound containing an ethylenically unsaturated group with a malonic acid diester and an acetoacetic acid ester.
  • Examples of malonic acid diesters to be reacted with the ethylenically unsaturated group-containing isocyanate compound include dimethyl malonate, diethyl malonate, di(n-propyl) malonate, and di(i-propyl) malonate. From the viewpoints of availability, cost, and quality, diethyl malonate and dimethyl malonate are preferred.
  • Specific examples of the monomer having a group represented by formula (1) and an ethylenically unsaturated bond include MOI-DEM (registered trademark, manufactured by Showa Denko KK) and AOI-DEM (registered trademark), both manufactured by Showa Denko KK.
  • Examples of the acetoacetate ester to be reacted with the ethylenically unsaturated group-containing isocyanate compound include methyl acetoacetate and ethyl acetoacetate.
  • the reaction of the ethylenically unsaturated group-containing isocyanate compound with the malonic acid diester or acetoacetate ester can be carried out regardless of the presence or absence of a solvent.
  • a solvent inactive to the isocyanato group is used.
  • an organic metal salt such as tin, zinc, or lead, or a tertiary amine may be used as a catalyst.
  • the reaction can generally be carried out at a temperature of -20 to 150°C, and is preferably carried out at a temperature of 25 to 130°C. When the reaction temperature is -20°C or higher, a sufficient reaction rate can be obtained.
  • the content of the structural unit (ma-2) is preferably 2 to 60 mol %, more preferably 5 to 50 mol %, and even more preferably 8 to 40 mol % of the total structural units of the copolymer (A).
  • the content of the structural unit (ma-2) is 2 mol % or more, the amount of crosslinking between the blocked isocyanato group of the structural unit (ma-2) and the hydroxyl group of the structural unit (ma-3) described later can be sufficiently ensured. As a result, the low-temperature curing property of the photosensitive resin composition using the copolymer (A) is improved.
  • the content of the structural unit (ma-2) is 60 mol % or less, the content of the structural unit (ma-1) can be sufficiently ensured, and sufficient solvent resistance of the cured product can be obtained.
  • the content of the structural unit (ma-3) can be sufficiently ensured, and the amount of crosslinking with the structural unit (ma-2) can be sufficiently ensured.
  • the content of the structural unit (ma-4) described later can be sufficiently ensured, and good developability can be obtained as a photosensitive resin composition.
  • the structural unit (ma-3) having a hydroxy group (hereinafter also simply referred to as "structural unit (ma-3)") is not limited as long as it is a structural unit having a hydroxy group and does not have a blocked isocyanato group.
  • structural unit (ma-3) When the copolymer (A) has the structural unit (ma-3) having a hydroxy group, crosslinking with the structural unit (ma-2) having the blocked isocyanato group described above progresses during thermal curing. As a result, when used in a photosensitive resin composition, good solvent resistance can be obtained even during thermal curing at low temperature conditions.
  • the structural unit (ma-3) having a hydroxy group is preferably a structural unit derived from a hydroxy group-containing ethylenically unsaturated group-containing compound (m-3).
  • Specific examples of the hydroxy group-containing ethylenically unsaturated group-containing compound (m-3) include (meth)acrylic acid ester derivatives having a hydroxy group, specifically, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, etc.
  • hydroxyalkyl (meth)acrylate is preferred from the viewpoints of reactivity in synthesizing the copolymer (A), low-temperature curing property of the resin composition containing the copolymer (A), and ease of availability.
  • hydroxyalkyl (meth)acrylate 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate are preferred, and from the viewpoint of reducing the glass transition temperature of the copolymer (A), 4-hydroxybutyl (meth)acrylate is more preferred. These may be used alone or in combination of two or more.
  • the content of the structural unit (ma-3) is preferably 1 to 50 mol %, more preferably 3 to 30 mol %, and even more preferably 5 to 20 mol % of the total structural units of the copolymer (A).
  • the content of the structural unit (ma-3) is 1 mol % or more, the amount of crosslinking between the hydroxyl group of the structural unit (ma-3) and the blocked isocyanato group of the structural unit (ma-2) can be sufficiently ensured. As a result, the low-temperature curing property of the photosensitive resin composition using the copolymer (A) is improved.
  • the content of the structural unit (ma-2) is 50 mol % or less, the content of the structural unit (ma-1) can be sufficiently ensured, and sufficient solvent resistance of the cured product can be obtained.
  • the content of the structural unit (ma-2) can be sufficiently ensured, and the amount of crosslinking with the structural unit (ma-3) can be sufficiently ensured.
  • the content of the structural unit (ma-4) described later can be sufficiently ensured, and good developability can be obtained as a photosensitive resin composition.
  • the structural unit (ma-4) having an acid group (hereinafter also simply referred to as "structural unit (ma-4)") is not particularly limited as long as it is a structural unit having an acid group and does not have a blocked isocyanato group, a hydroxy group, or an allyl group.
  • structural unit (ma-4) When the copolymer (A) has the structural unit (ma-4) having an acid group, it can impart good alkaline developability when used in a photosensitive resin composition.
  • the acid group include a carboxy group, a sulfo group, and a phospho group. Among these acid groups, in terms of ease of availability, a carboxy group is preferred as the acid group of the structural unit (ma-4).
  • the structural unit (ma-4) having an acid group is preferably a structural unit derived from an acid group-containing ethylenically unsaturated group-containing compound (m-4).
  • the acid group-containing (meth)acrylate (m-4) include unsaturated carboxylic acids or anhydrides thereof such as (meth)acrylic acid, ⁇ -bromo(meth)acrylic acid, ⁇ -furyl(meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, ⁇ -cyanocinnamic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride; unsaturated sulfonic acids such as 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, and p
  • the content of the structural unit (ma-4) is preferably 1 to 50 mol %, more preferably 3 to 40 mol %, and even more preferably 5 to 30 mol % of all structural units of the copolymer (A).
  • the content of the structural unit (ma-4) is 1 mol % or more, good developability of the photosensitive resin composition using the copolymer (A) is obtained.
  • the content of the structural unit (ma-4) is 50 mol % or less, the content of the structural unit (ma-1) and the structural unit (ma-3) can be sufficiently ensured, and the effects attributable to the structural unit (ma-1) and the structural unit (ma-3) can be sufficiently ensured.
  • Copolymer (A) of the present embodiment may contain a structural unit (ma-5) (hereinafter, simply referred to as "structural unit (ma-5)”) other than the structural units (ma-1) to (ma-4) as necessary.
  • the structural unit (ma-5) is a structural unit other than the structural units (ma-1) to (ma-4) that does not have a blocked isocyanato group, a hydroxy group, an allyl group, or an acid group.
  • copolymer (A) contains the structural unit (ma-5), it is possible to impart additionally required functions.
  • the other structural unit (ma-5) is another ethylenically unsaturated group-containing compound (m-5) copolymerizable with the monomers (m-1) to (m-4).
  • Specific examples include aromatic vinyl compounds, cyclic olefins having a norbornene structure, dienes, (meth)acrylic acid esters, (meth)acrylic acid amides, unsaturated dicarboxylic acid diesters, monomaleimides, glycidyl (meth)acrylates, (meth)acrylic acid anilides, (meth)acrylonitrile, and acrolein.
  • aromatic vinyl compound examples include styrene, ⁇ -methylstyrene, o-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, methoxystyrene, p-nitrostyrene, p-cyanostyrene, and p-acetylaminostyrene.
  • cyclic olefins having a norbornene structure include norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.1 2,5 .
  • the dienes include butadiene, isoprene, chloroprene, and the like.
  • Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, benzyl (meth)acrylate, isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, rosin (meth)acrylate, norbornyl (meth)acrylate, 5-ethylnorbornyl (meth)acrylate, dicyclopentenyl
  • Examples of the (meth)acrylic acid amide include (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diisopropylamide, and (meth)acrylic acid anthracenylamide.
  • Examples of the vinyl compound include vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, and vinyltoluene.
  • Examples of the unsaturated dicarboxylic acid diester include diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate.
  • Examples of monomaleimides include N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide.
  • aromatic vinyl compounds, aromatic-containing (meth)acrylates, and alkyl (meth)acrylates in which the alkyl group has 1 to 12 carbon atoms are preferred, with styrene, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and methyl (meth)acrylate being more preferred, and 2-ethylhexyl (meth)acrylate and methyl (meth)acrylate being even more preferred.
  • aromatic vinyl compounds, aromatic-containing (meth)acrylates, and alkyl (meth)acrylates in which the alkyl group has 1 to 12 carbon atoms are preferred, with styrene, benzyl (meth)acrylate, dicyclopent
  • the structural unit (ma-5) When the structural unit (ma-5) is contained, its content is preferably 1 to 80 mol %, more preferably 10 to 70 mol %, and even more preferably 20 to 60 mol % of all structural units of the copolymer (A).
  • the content of the structural unit (ma-5) By setting the content of the structural unit (ma-5) within the above range, it is possible to impart additional functions by the structural unit (ma-5) while fully securing the functions of the structural units (ma-1) to (ma-4), or to adjust the functions obtained from the structural units (ma-1) to (ma-4) to an appropriate range.
  • the allyl group equivalent of the copolymer (A) of this embodiment is preferably 300 to 5000 g/mol, more preferably 500 to 4500 g/mol, and even more preferably 800 to 4000 g/mol.
  • the storage stability as a photosensitive resin composition is good.
  • it is 5000 g/mol or less the solvent resistance of the cured product is good even when cured at a low temperature.
  • the “allyl group equivalent” is the mass of a polymer per 1 mol of allyl groups in the polymer.
  • the allyl group equivalent of copolymer (A) is determined by dividing the mass of copolymer (A) by the number of moles of allyl groups contained in the copolymer (g/mol).
  • the “allyl group equivalent” is a theoretical value calculated from the amounts of monomers (m-1) to (m-5) used in producing the copolymer.
  • the acid value of the copolymer (A) of the present embodiment is preferably 10 to 300 KOHmg/g, more preferably 15 to 200 KOHmg/g, and even more preferably 20 to 150 KOHmg/g. When it is 10 KOHmg/g or more, the developability is good. When it is 300 KOHmg/g or less, the storage stability is good.
  • Acid value refers to the acid value of the curable polymer measured in accordance with JIS K6901 5.3. In other words, the acid value refers to the number of milligrams of potassium hydroxide required to neutralize the acidic components contained in 1 g of copolymer.
  • the weight average molecular weight of the copolymer (A) of this embodiment is preferably 1000 to 50000, more preferably 3000 to 40000, and even more preferably 5000 to 30000.
  • the weight average molecular weight is 1000 or more, when a resin composition containing the copolymer (A) is used as a raw material for a photosensitive resin composition, defects such as chipping are unlikely to occur in the cured resin film after development.
  • the weight average molecular weight is 50000 or less, the photosensitive resin composition containing the copolymer (A) has a sufficiently short development time and is excellent in practical use.
  • the number average molecular weight of the copolymer (A) of this embodiment is preferably 500 to 30,000, more preferably 1,000 to 15,000, and even more preferably 1,000 to 10,000.
  • 500 or more when a resin composition containing the copolymer (A) is used as a raw material for a photosensitive resin composition, defects such as chipping are unlikely to occur in the cured resin film after development.
  • the photosensitive resin composition containing the copolymer (A) has a sufficiently short development time and is excellent in practical use.
  • the molecular weight distribution of the copolymer (A) of this embodiment is preferably 1.3 to 5.0, more preferably 1.5 to 4.5, and even more preferably 1.9 to 4.0.
  • it is possible to optimize the target numerical range of the weight average molecular weight (Mw), acid value, etc., and to set the reaction conditions, etc., when producing the copolymer (A) with a certain range, and it is possible to produce it efficiently.
  • it is 5.0 or less, when a resin composition containing the copolymer (A) is used as a raw material for a photosensitive resin composition, a photosensitive resin composition without variation in performance such as developability can be obtained.
  • the weight average molecular weight and the number average molecular weight refer to the weight average molecular weight and the number average molecular weight measured using gel permeation chromatography (GPC) under the following conditions in terms of standard polystyrene.
  • GPC gel permeation chromatography
  • the block isocyanato group equivalent of the copolymer (A) of this embodiment is preferably 100 to 2000 g/mol, more preferably 200 to 1500 g/mol, and even more preferably 300 to 1200 g/mol.
  • the photosensitive resin composition containing the copolymer (A) can have better developability.
  • the photosensitive resin composition containing the copolymer (A) can form a cured resin film having superior hardness.
  • the "blocked isocyanato group equivalent” is the mass of a polymer per 1 mol of blocked isocyanato groups.
  • the blocked isocyanato group equivalent of copolymer (A) is determined by dividing the mass of copolymer (A) by the number of moles of blocked isocyanato groups contained in copolymer (A) (g/mol).
  • the “blocked isocyanato group equivalent” is a theoretical value calculated from the amounts of monomers (m-1) to (m-5) used in producing copolymer (A).
  • the hydroxy group equivalent of the copolymer (A) of this embodiment is preferably 200 to 5000 g/mol, more preferably 400 to 4000 g/mol, and even more preferably 800 to 3000 g/mol.
  • the photosensitive resin composition containing the copolymer (A) can have better developability.
  • the photosensitive resin composition containing the copolymer (A) can form a resin cured film having better hardness.
  • the "hydroxy group equivalent” is the mass of a polymer per 1 mol of hydroxy groups in the polymer.
  • the hydroxy group equivalent of a copolymer is determined by dividing the mass of the copolymer by the number of moles of hydroxy groups contained in the copolymer (g/mol).
  • the "hydroxy group equivalent” is a theoretical value calculated from the amounts of monomers (m-1) to (m-5) used in producing the copolymer.
  • the copolymer (A) can be produced, for example, by the following production method: In the presence of a polymerization solvent, the above-mentioned monomers (m-1) to (m-5) are copolymerized using a polymerization initiator according to a radical polymerization method known in the art.
  • the above monomers (m-1) to (m-5) are dissolved in a polymerization solvent to prepare a raw material solution, and then a polymerization initiator is added to the raw material solution, and the copolymerization reaction is carried out, for example, at 50°C to 130°C for 1 hour to 20 hours while stirring.
  • the polymerization solvent used in producing the copolymer (A) is not particularly limited as long as it is a solvent inactive to the copolymerization reaction of the monomers (m-1) to (m-5).
  • the polymerization solvent used in producing the copolymer (A) may be the same as the solvent contained in the solvent (D) contained in the photosensitive resin composition described below, or may be partially or completely different from the solvent contained in the solvent (D).
  • the polymerization solvent used in producing the copolymer (A) is partially or completely the same as the solvent contained in the solvent (D) contained in the resin composition, it can be used as a part of the solvent (D) without separating and removing the polymerization solvent from the reaction solution after the copolymerization reaction is completed, which is preferable.
  • the polymerization solvent is not particularly limited as long as it dissolves the monomers (m-1) to (m-5) and the copolymer produced and does not inhibit the polymerization reaction.
  • the copolymer produced is a (meth)acrylic acid-based polymer
  • glycol ether solvents are preferred from the viewpoint of its solubility.
  • ethylene glycol monomethyl ether examples include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, propylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether.
  • solvents may be used
  • the amount of the polymerization solvent used in producing the copolymer (A) is not particularly limited, but is preferably 30 to 1000 parts by mass, and more preferably 50 to 800 parts by mass, per 100 parts by mass of the monomers (m-1) to (m-5).
  • the amount of the polymerization solvent used is 30 parts by mass or more, the copolymerization reaction of the monomers (m-1) to (m-5) can be stably carried out, and coloring and gelation of the copolymer (A) can be prevented.
  • the amount of the polymerization solvent used is 1000 parts by mass or less, a decrease in the molecular weight of the copolymer (A) due to chain transfer can be suppressed, and the viscosity of the reaction solution can be controlled within an appropriate range.
  • the polymerization initiator that can be used in the copolymerization reaction of the above monomers (m-1) to (m-5) is not particularly limited, and examples thereof include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyrate) dimethyl, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, etc. 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, and more preferably 0.5 parts by mass to 16 parts by mass, relative to 100 parts by mass of the total amount of all monomers (M) used in the polymerization reaction.
  • the photosensitive resin composition of one embodiment of the present invention contains the copolymer (A) of the present embodiment described above, a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D).
  • the content of the copolymer (A) in the photosensitive resin composition of this embodiment is preferably 10 to 85 parts by mass, more preferably 15 to 75 parts by mass, and most preferably 24 to 60 parts by mass, when the total of the components excluding the solvent (D) contained in the photosensitive resin composition is 100 parts by mass.
  • the content of the copolymer (A) is within the above range, the viscosity and low-temperature curing property of the photosensitive resin composition become more appropriate.
  • the reactive diluent (B) contained in the photosensitive resin composition of this embodiment is not particularly limited as long as it is a low molecular weight compound having an ethylenically unsaturated group such as a vinyl group, an allyl group, or a (meth)acryloyloxy group.
  • 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; triallyl cyanurate, etc.
  • aromatic vinyl monomers include styrene, ⁇ -methylstyrene, ⁇ -chloromethylstyrene, vinyltoluene, divinylbenzene, diallylphthalate, and diallylbenzenephosphonate.
  • monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, ⁇ -hydroxyethyl (meth)acrylate, and hydroxypropyl (meth)acrylate.
  • polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tris(hydroxyethyl)isocyanurate tri(meth)acrylate.
  • reactive diluent (B) polyfunctional (meth)acrylates are preferred in order to improve curability (reactivity), and dipentaerythritol penta(meth)acrylate and/or dipentaerythritol hexa(meth)acrylate are particularly 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 this embodiment is preferably 10 parts by mass to 85 parts by mass, more preferably 15 parts by mass to 75 parts by mass, and most preferably 24 parts by mass to 60 parts by mass, when the total of the components contained in the photosensitive resin composition excluding the solvent (D) is taken as 100 parts by mass.
  • 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 by irradiation with light.
  • the photopolymerization initiator (C) include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4-(1-t-butyldioxy-1-methylethyl)acetophenone; alkylphenones such as 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one; anthraquinones such as 2-methylanthraquinone, 2-amyl anthraquinone, 2-t-butyl an
  • the content of the photopolymerization initiator (C) in the photosensitive resin composition of this embodiment is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 20 parts by mass, and most preferably 0.5 to 10 parts by mass, when the total of the components contained in the photosensitive resin composition excluding the solvent (D) is taken as 100 parts by mass.
  • 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 photosensitive resin composition of the present embodiment is not particularly limited as long as it is inactive to the copolymer (A) and the reactive diluent (B) and can dissolve the copolymer (A) and the reactive diluent (B).
  • the solvent (D) may or may not contain the polymerization solvent used in producing the copolymer (A).
  • the addition reaction for producing the copolymer (A) is carried out without removing the polymerization solvent from the reaction solution after the copolymerization reaction for producing the copolymer (A) is completed, and the polymerization solvent can be used as it is as a part or all of the solvent (D) of the resin composition without separating and removing it from the reaction solution after the addition reaction is completed.
  • the case where the polymerization solvent used in producing copolymer (A) is not contained in solvent (D) refers to the case where copolymer (A) used as the raw material of the resin composition is one that has been separated and removed from the reaction solution in which copolymer (A) was produced.
  • the type and content of solvent (D) can be appropriately selected according to the type of copolymer (A) and the use of the resin composition.
  • copolymer (A) that has been separated and removed from the reaction solution in which copolymer (A) was produced is used as copolymer (A)
  • the same type of polymerization solvent as that used in producing copolymer (A) may be used as solvent (D) or a different type may be used.
  • the solvent (D) is not particularly limited, but from the viewpoint of the solubility of the copolymer (A), a glycol ether solvent is preferred.
  • a glycol ether solvent is preferred.
  • Specific examples include 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,
  • the solvent (D) may contain other solvents capable of dissolving the copolymer (A) and the reactive diluent (B).
  • solvents include, for example, primary alcohols such as propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, and dodecyl alcohol; secondary alcohols such as benzyl alcohol; tertiary alcohols such as tert-butyl alcohol and diacetone alcohol; (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and
  • the content of the solvent (D) in the photosensitive resin composition of this embodiment is preferably 30 parts by mass to 1000 parts by mass, more preferably 50 parts by mass to 800 parts by mass, and most preferably 100 parts by mass to 700 parts by mass, when the total of the components in the photosensitive resin composition excluding the solvent (D) is taken as 100 parts by mass.
  • the viscosity of the photosensitive resin composition can be adjusted to an appropriate range.
  • the photosensitive resin composition of the present embodiment may contain one or more known additives such as a leveling agent, a thermal polymerization inhibitor, a sensitizer, etc., as necessary.
  • the content of these additives is not particularly limited as long as it is within a range that does not impair 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 to enhance curing properties.
  • 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., SEQUAREZ 755 manufactured by OMNOVA Solutions, and ZIRCOZOL ZC-2 and 7 manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.
  • the photosensitive resin composition of this embodiment may contain an acid generator or a base generator to enhance curing properties.
  • an acid generator or a base generator to enhance curing properties.
  • a photoacid generator, photobase generator, thermal acid generator, or thermal base generator it is preferable to use a photoacid generator, photobase generator, thermal acid generator, or thermal base generator, and from the viewpoint of storage stability, a photoacid generator or a photobase generator is even more preferable.
  • photoacid generators include sulfonium salt compounds such as CPI-200K, CPI-210S, CPI-310B, and CPI-410S manufactured by San-Apro Chemical Co., Ltd., and iodonium salt compounds such as IK-1.
  • photobase generators include WPBG-266, WPBG-300, and WPBG-345 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • the photosensitive resin composition of the present embodiment can be produced by mixing the copolymer (A), the reactive diluent (B), the photopolymerization initiator (C), the solvent (D), and additives used as necessary, using a known mixing device.
  • the photosensitive resin composition of this embodiment has good low-temperature curing properties and can form a cured resin film with sufficient solvent resistance. Furthermore, since the photosensitive resin composition of this embodiment has excellent alkaline developability, fine patterns can be formed by developing with an alkaline aqueous solution. Therefore, the photosensitive resin composition of this embodiment is suitable for use as a resist.
  • the photosensitive coloring composition of the present embodiment contains the photosensitive resin composition of the present embodiment and a colorant (E).
  • a colorant (E) a known dye and/or pigment can be used. When used in a filter, from the viewpoint of color reproducibility, it is preferable to use a dye as the colorant (E).
  • a dye is used as the colorant (E)
  • a color pattern with high brightness can be obtained compared to when a pigment is used, and the photosensitive coloring composition exhibits good alkaline developability.
  • an acid dye having an acidic group such as a carboxy group, a salt of an acid dye with a nitrogen compound, a sulfonamide of an acid dye, etc., from the viewpoint of solubility in the solvent (D) and the alkaline developer, interaction with other components in the photosensitive resin composition, heat resistance, etc.
  • 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 blue 38, 44 (VALIFA ST BLUE 2620); acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 0, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 2 74; acid violet 6B,
  • azo-based, xanthene-based, anthraquinone-based or phthalocyanine-based acid dyes are preferred. These dyes may be used alone or in combination of two or more types depending on the color of the desired pixel.
  • pigments examples include yellow pigments such as C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, and 214; orange pigments such as C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73; C.I.
  • a known dispersant may be blended into the photosensitive coloring composition in order to improve the dispersibility of the colorant (E).
  • the dispersant it is preferable to use a polymer dispersant that has excellent dispersion stability over time.
  • polymer dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic modified ester-based dispersants.
  • EFKA manufactured by EFKA Chemicals BV
  • Disperbyk manufactured by BYK-Chemie
  • Disparlon manufactured by Kusumoto Chemicals Co., Ltd.
  • SOLSPERSE manufactured by Zeneca
  • the blending amount of the dispersant may be appropriately set according to the type and amount of the pigment used as the colorant (E).
  • the content of the copolymer (A) in the photosensitive coloring composition of the present embodiment is preferably 10 parts by mass to 80 parts by mass, more preferably 15 parts by mass to 70 parts by mass, and most preferably 24 parts by mass to 55 parts by mass, when the total of the components excluding the solvent (D) contained in the photosensitive coloring composition is 100 parts by mass.
  • the content of the copolymer (A) is within the above range, the viscosity and low-temperature curing property of the photosensitive coloring composition become more appropriate.
  • the content of the reactive diluent (B) in the photosensitive coloring composition of this embodiment is preferably 10 parts by mass to 80 parts by mass, more preferably 15 parts by mass to 70 parts by mass, and most preferably 24 parts by mass to 55 parts by mass, when the total of the components excluding the solvent (D) contained in the photosensitive coloring composition is 100 parts by mass.
  • the content of the reactive diluent (B) is within the above range, the viscosity and photocurability of the photosensitive coloring composition become more appropriate.
  • the content of the photopolymerization initiator (C) in the photosensitive coloring composition of this embodiment is preferably 0.1 parts by mass to 30 parts by mass, more preferably 0.3 parts by mass to 20 parts by mass, and most preferably 0.5 parts by mass to 10 parts by mass, when the total of the components excluding the solvent (D) contained in the photosensitive coloring composition is 100 parts by mass.
  • the content of the photopolymerization initiator (C) is 0.1 parts by mass or more, the photosensitive coloring 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 coloring composition and the performance of the resin cured film.
  • the content of the colorant (E) in the photosensitive coloring composition of this embodiment is preferably 4 parts by mass to 79 parts by mass, more preferably 9 parts by mass to 69 parts by mass, and most preferably 15 parts by mass to 50 parts by mass, when the total of the components excluding the solvent (D) contained in the photosensitive coloring composition is 100 parts by mass.
  • the content of the colorant (E) is 4 parts by mass or more, the effect of containing the colorant (E) becomes significant, and the photosensitive coloring composition becomes suitable as a material for the colored 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 curing property of the photosensitive coloring composition, and the low-temperature curing property is good.
  • the photosensitive coloring composition of the present embodiment may contain other additives similar to those described in the photosensitive resin composition, if necessary.
  • the photosensitive coloring composition of the present embodiment can be produced by mixing the copolymer (A), the reactive diluent (B), the photopolymerization initiator (C), the solvent (D), the colorant (E), and additives used as necessary using a known mixing device.
  • the photosensitive resin composition of the present embodiment has good low-temperature curing properties and can form a resin cured film having sufficient solvent resistance. Moreover, since the photosensitive resin composition of the present embodiment has excellent alkaline developability, a fine pattern can be formed by developing the composition using an alkaline aqueous solution. Therefore, the photosensitive resin composition of the present embodiment is suitable for use as a resist. In addition, the photosensitive coloring composition of the present embodiment can be suitably used as a material for color patterns such as pixels and black matrices of color filters.
  • the cured resin film of the present embodiment is made of a cured product of the photosensitive resin composition of the present embodiment or the photosensitive coloring composition of the present embodiment.
  • the cured resin film of the present embodiment can be formed, for example, by the following method.
  • the formation method includes a coating step of coating the photosensitive resin composition of the present embodiment on a substrate to form a coating film, a pre-baking step of drying the coating film formed by the coating step, an exposure step of irradiating the dried coating film with light to photo-cure it, and a post-baking step of thermally curing the photo-cured coating film.
  • the method shown below can be used. That is, the coating step and pre-baking step described above are performed. Then, in the exposure step, the dried coating film is irradiated with light through a photomask having a predetermined pattern, and the exposed parts are photo-cured. After the exposure step, a post-exposure heating treatment is performed as necessary. Then, a development step is performed in which the unexposed parts of the coating film are developed by dissolving them using a developer, and a post-baking step is performed in which the photo-cured coating film is thermally cured.
  • the photosensitive resin composition of the present embodiment or the photosensitive coloring composition of the present embodiment is coated on a substrate to form a coating film.
  • a known substrate can be used as the substrate to which the photosensitive resin composition or the photosensitive coloring composition is applied, and can be appropriately determined according to the application of the resin cured film.
  • the method for applying the photosensitive resin composition or the photosensitive coloring composition is not particularly limited, and for example, a screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, a slit coating method, etc. can be used.
  • 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 has been 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.
  • the substrate on which the coating film has been formed can be heated, for example, using a hot plate.
  • the surface of the coating film dried in the pre-bake step is irradiated with light to photocure the coating film.
  • the light source used for the 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 amount of exposure in the exposure step is not particularly limited, and can be appropriately set according to the composition of the photosensitive resin composition or the photosensitive coloring composition and the thickness of the coating film.
  • the surface of the coating film dried in the pre-bake step is irradiated with light through a photomask having a predetermined pattern, and the exposed part is photocure.
  • Post-exposure baking process When forming a resin cured film having a predetermined pattern, a post-exposure baking process is performed as necessary after the exposure process. By performing this process, the dissolution contrast between the exposed and unexposed parts of the coating film becomes more pronounced.
  • the post-exposure baking process is different from the post-bake process described later, and does not completely cure the coating film.
  • the post-exposure baking process is performed to leave only the exposed parts of the coating film on the substrate and more reliably remove the unexposed parts of the coating film by performing a development process. Therefore, it is not an essential process in the method for forming a resin cured film of this embodiment.
  • the substrate after the exposure step is preferably heated, for example, at 40°C to 70°C, and more preferably at 50°C to 60°C.
  • the heating temperature is 40°C or higher, the effect of improving the dissolution contrast between the exposed and unexposed parts 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 part does not diffuse to the unexposed part, and good dissolution contrast can be obtained.
  • the heating time in the post-exposure heating step is preferably 20 seconds to 600 seconds. When the heating time is 20 seconds or more, the temperature history of the entire coating film can be made uniform.
  • the acid generated in the exposed part does not diffuse to the unexposed part, and good dissolution contrast can be obtained.
  • a hot plate, an oven, or a furnace can be used as a method for heating the substrate after the exposure step in the post-exposure heating step.
  • a post-exposure heating step is performed as necessary, and then a development step is performed to develop the unexposed parts of the coating film.
  • a developer used in the development step any aqueous alkaline solution that has been conventionally used for developing a photosensitive resin composition or a photosensitive coloring composition can be used.
  • the alkaline aqueous solution is not particularly limited, but examples thereof include aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc.; aqueous solutions of amine compounds such as ethylamine, diethylamine, dimethylethanolamine, etc.; aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide; aqueous solutions of p-phenylenediamine compounds such as 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyethylaniline, and sulfates, hydrochlorides, or p
  • one or more additives such as an antifoaming agent and a surfactant may be added to the aqueous alkaline solution.
  • the development conditions 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.
  • it is preferable to develop the unexposed portion of the coating film by dissolving it with the above-mentioned aqueous alkaline solution, followed by rinsing with water and drying.
  • a post-bake process is performed in which the photocured coating film is thermally cured to form a resin cured film.
  • the heating temperature and heating time in the post-bake process are 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, the material of the substrate, etc.
  • the heating temperature in the post-baking process can be, for example, 50°C to 210°C.
  • a material with low heat resistance can be used as the material for the color filter.
  • the heating temperature may be 150°C or less, 120°C or less, or 100°C or less.
  • a colored pattern containing a colorant (E) with poor heat resistance which has been difficult to use as a material for a colored pattern in the past, can be formed while suppressing deterioration of the colorant (E).
  • the heating temperature is 150°C or less
  • a colored pattern can be formed on a substrate with poor heat resistance, which has been difficult to use as a substrate for a color filter in the past.
  • the heating temperature is 150°C or less, 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 copolymer (A) and the reactive diluent (B) are sufficiently crosslinked, and a cured resin film having sufficient solvent resistance is obtained. Furthermore, when the heating temperature is 50°C or higher, the heating time in the post-bake 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 even more preferably 70°C or higher.
  • the heating time in the post-bake process 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, and preferably 20 minutes to 2 hours.
  • the cured resin film of the present embodiment is made of a cured product of the photosensitive resin composition of the present embodiment or the photosensitive coloring composition of the present embodiment, and therefore has sufficient solvent resistance.
  • the cured resin film of the present embodiment can be suitably used as a material for various insulating films, such as a protective film provided on the top of a color filter, an insulating film provided between electrodes of a touch panel, and an interlayer insulating film of a thin film transistor (TFT).
  • TFT thin film transistor
  • Fig. 1 is a schematic cross-sectional view showing an example of a color filter according to the present embodiment.
  • the color filter shown in Fig. 1 includes a substrate 1, RGB pixels 2 formed on one surface 1a of the substrate 1, black matrices 3 formed at the boundaries of the pixels 2, and a protective film 4 formed on the pixels 2 and the black matrix 3.
  • the substrate 1 used in the color filter shown in FIG. 1 is not particularly limited, and may be a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, a printed wiring substrate, an array substrate, a PET substrate, or the like, depending on the application.
  • 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 be even more effective.
  • a color filter using a resin substrate such as a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, or a PET substrate is preferable.
  • At least one of the pixels 2 and the black matrix 3 in the color filter shown in FIG. 1 is a colored pattern made of a cured product of the photosensitive coloring composition of the present embodiment, which contains a resin composition containing a copolymer (A) and a solvent (D), a reactive diluent (B), a photopolymerization initiator (C), a colorant (E), and additives contained as necessary.
  • a known material can be used as the protective film 4.
  • the protective film 4 may be a resin cured film made of a cured product of the photosensitive coloring composition of the present embodiment, which contains a resin composition containing a copolymer (A) and a solvent (D), a reactive diluent (B), a photopolymerization initiator (C), and additives contained as necessary.
  • the configuration other than the materials of the pixels 2 and the black matrix 3 can be known.
  • the color filter shown in FIG. 1 is one example of the color filter of the present invention, and the present invention is not limited to the example shown in FIG. 1.
  • the RGB pixels 2 and the black matrix 3 are sequentially formed on one surface 1a of the substrate 1 shown in Fig. 1.
  • the pixels 2 and the black matrix 3 can be manufactured by using the above-mentioned method for manufacturing a cured resin film (photolithography method) of this embodiment.
  • the protective film 4 is formed on the pixels 2 and the black matrix 3.
  • the protective film 4 can be formed by a known forming method.
  • the protective film 4 can be manufactured by the above-mentioned method for manufacturing a cured resin film according to this embodiment.
  • the color filter of this embodiment has a color pattern (pixels 2 and black matrix 3) made of the cured product of the above-mentioned photosensitive coloring composition. Therefore, the color pattern in the color filter of this embodiment has sufficient solvent resistance.
  • the image display element of this embodiment is equipped with the color filter of this embodiment having sufficient solvent resistance.
  • Examples of the image display element of this embodiment include a liquid crystal display element, an organic EL display element, and a solid-state imaging element.
  • the image display element of this embodiment is capable of high brightness display by being equipped with the above-mentioned color filter.
  • Example 1 Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, 237.6 g of propylene glycol monomethyl ether was placed as a polymerization solvent, and the mixture was stirred while replacing with nitrogen and heated to 78°C.
  • Example 2 to 9 Copolymers P2 to P9 of Examples 2 to 9 were obtained in the same manner as in Example 1, except that the raw materials shown in Table 1 were used in the ratios shown in Table 1. In Examples 11 to 19 described later, the reaction solution was not removed, and the resin solutions containing the copolymers P2 to P9 of Examples 2 to 9 were used.
  • 2-Hydroxyethyl methacrylate manufactured by Tokyo Chemical Industry Co., Ltd. 4-Hydroxybutyl acrylate: manufactured by Tokyo Chemical Industry Co., Ltd. Methacrylic acid: manufactured by Tokyo Chemical Industry Co., Ltd. Acrylic acid: manufactured by Tokyo Chemical Industry Co., Ltd. 2-Ethylhexyl acrylate: manufactured by Tokyo Chemical Industry Co., Ltd. Methyl methacrylate: manufactured by Tokyo Chemical Industry Co., Ltd. Propylene glycol monomethyl ether acetate: manufactured by Tokyo Chemical Industry Co., Ltd. Propylene glycol monomethyl ether: manufactured by Tokyo Chemical Industry Co., Ltd.
  • the amount of copolymer in the resin composition in Table 3 does not include the polymerization solvent used when synthesizing the copolymer.
  • the amount of (D) solvent in Table 3 is the total amount of the polymerization solvent used when synthesizing the copolymer (A) in the photosensitive colored resin composition and the solvent added when preparing the photosensitive colored resin composition.
  • the surface of the dried coating film was irradiated with 200 mJ/ cm2 light using an ultra-high pressure mercury lamp through a photomask (exposure step).
  • the exposure step was performed by placing a photomask at a position 100 ⁇ m away from the coating film.
  • the photomask used had a line and space pattern with a width of 3 to 100 ⁇ m.
  • Semiclean DL-A10 developer manufactured by Yokohama Yushi Kogyo Co., Ltd.
  • the glass substrate having the coating film after the development step was left in a dryer at 100°C for 30 minutes to thermally cure the coating film (post-bake step), thereby obtaining a colored pattern.
  • the pencil hardness of the cured resin film thus produced was measured using a pencil hardness tester (No. 553-M, manufactured by Yasuda Seiki Seisakusho) in accordance with JIS K5600-5-4 and evaluated according to the following criteria. The results are shown in Table 4 or Table 5.
  • a glass substrate having a resin cured film was prepared in the same manner as in the evaluation of the pencil hardness in (2) above, and the absorption spectrum of the resin cured film was measured using a spectrophotometer (UV-1650PC, manufactured by Shimadzu Corporation).
  • UV-1650PC UV-1650PC
  • 200 mL of propylene glycol monomethyl ether acetate was placed in a lidded glass bottle having a capacity of 500 mL and allowed to stand under a temperature condition of 23 ° C.
  • a glass substrate having a resin cured film was placed in this glass bottle, immersed in propylene glycol monomethyl ether acetate, and allowed to stand at 23 ° C. for 15 minutes.
  • the glass substrate having the resin cured film was taken out, and the absorption spectrum of the resin cured film was measured using a spectrophotometer (UV-1650PC, manufactured by Shimadzu Corporation) in the same manner as before immersion in propylene glycol monomethyl ether acetate.
  • the resin cured film made of the cured product obtained by photocuring the coating film formed using the photosensitive coloring compositions R1 to R9 of Examples 11 to 19 and then heat curing at a low temperature of 100°C had a pencil hardness of 3H or more and excellent hardness.
  • the solvent resistance of the above-mentioned resin cured film was evaluated as ⁇ , confirming that it has excellent solvent resistance.
  • the copolymer cP1 of Comparative Example 1 contained in the photosensitive coloring composition cR1 of Comparative Example 11 has an allyl group equivalent of 0.
  • the copolymer cP2 of Comparative Example 2 contained in the photosensitive coloring composition cR2 of Comparative Example 12 has a blocked isocyanato group equivalent of 0.
  • the copolymer cP3 of Comparative Example 3 contained in the photosensitive coloring composition cR3 of Comparative Example 13 has a hydroxyl group equivalent of 0. As a result, either the hardness or the solvent resistance was inferior.
  • the present invention provides a photosensitive resin composition that gives a resin cured film with excellent solvent resistance and has good developability. It also provides a resin cured film with excellent solvent resistance and an image display element that includes the same.
  • the photosensitive resin composition can be preferably used as a transparent film, a protective film, an insulating film, an overcoat, a photospacer, a black matrix, a black column spacer, and a resist for a color filter.

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WO2013141163A1 (ja) * 2012-03-23 2013-09-26 昭和電工株式会社 化合物、該化合物の製造方法、重合体、硬化性組成物および硬化物
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JP2007270216A (ja) * 2006-03-30 2007-10-18 Fujifilm Corp 金属膜形成方法、それを用いた金属膜、金属膜形成用基板、金属パターン形成方法、及びそれを用いた金属パターン、金属パターン形成用基板、ポリマー前駆体層形成用塗布液組成物
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