WO2019198490A1 - Photosensitive resin composition, cured product, insulating material, resin material for solder resists and resist member - Google Patents

Photosensitive resin composition, cured product, insulating material, resin material for solder resists and resist member Download PDF

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Publication number
WO2019198490A1
WO2019198490A1 PCT/JP2019/012753 JP2019012753W WO2019198490A1 WO 2019198490 A1 WO2019198490 A1 WO 2019198490A1 JP 2019012753 W JP2019012753 W JP 2019012753W WO 2019198490 A1 WO2019198490 A1 WO 2019198490A1
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group
carbon atoms
meth
acid
acrylate
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PCT/JP2019/012753
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French (fr)
Japanese (ja)
Inventor
正紀 宮本
駿介 山田
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Dic株式会社
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Priority to CN201980025056.3A priority Critical patent/CN111954848B/en
Priority to JP2020513173A priority patent/JP7310802B2/en
Publication of WO2019198490A1 publication Critical patent/WO2019198490A1/en

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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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

Definitions

  • the present invention relates to a photosensitive resin composition, a cured product, an insulating material made of the photosensitive resin composition, a resin material for solder resist, and a resist member that hardly generate outgas.
  • solder resist resin materials for printed wiring boards.
  • the required properties for the solder resist resin material include various properties such as curing with a small exposure amount, excellent alkali developability, and excellent heat resistance, strength, dielectric properties, etc. in the cured product.
  • an acid group-containing epoxy acrylate resin obtained by further reacting a tetrahydrophthalic anhydride with an intermediate obtained by reacting a cresol novolak type epoxy resin, acrylic acid and phthalic anhydride Is known (for example, refer to Patent Document 1), but the photosensitivity and heat resistance of the cured product are not sufficient, and it has not satisfied the increasingly required performance.
  • the photosensitive resin composition is gasified by volatilizing components such as a photopolymerization initiator at the time of photocuring, then at the time of heat curing performed as necessary, or at the time of soldering at the time of mounting, There was an outgas problem that contaminated the surroundings.
  • the problem to be solved by the present invention is a photosensitive resin composition having high photosensitivity and excellent heat resistance in a cured product, and hardly generating outgas, a cured product, and an insulating material comprising the photosensitive resin composition It is providing the resin material for solder resists, and a resist member.
  • the present inventors have solved the above problems by using a photosensitive resin composition containing an acid group-containing (meth) acrylate resin and a specific photopolymerization initiator. The inventors have found that this can be solved and completed the present invention.
  • the present invention is a photosensitive resin composition containing an acid group-containing (meth) acrylate resin (A) and a photopolymerization initiator (B), wherein the photopolymerization initiator (B) is:
  • the present invention relates to a photosensitive resin composition, a cured product, an insulating material composed of the photosensitive resin composition, a resin material for solder resist, and a resist member, which is a compound represented by the general formula (1).
  • R 1 represents an alkyl group having 1 to 10 carbon atoms
  • R 2 represents any of an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, and an alkyl group having 2 to 4 carbon atoms substituted by an alkoxy group having 1 or 2 carbon atoms.
  • R 3 represents an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, a methoxyethyl group, or an ethoxyethyl group
  • R 2 and R 3 together form an alkylene group with a nitrogen atom to form a ring structure
  • R 2 and R 3 together form a nitrogen atom with a morpholine skeleton, N-methylpiperazine skeleton, or 2,6 -It may be a ring formation site forming a dimethylmorpholine skeleton
  • R 4 to R 7 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group
  • Y 1 is an alkyl group having 3 to 19 carbon atoms (y1-1) having no substituent, or having a halogen atom or a hydroxyl group as a substituent, aralkyl group having 7 to 19 carbon atoms (y1-2) Or
  • R 8 represents an alkylene group having 2 to 4 carbon atoms
  • R 9 represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 4 carbon atoms
  • m represents an integer of 0 to 20
  • R 8 is an alkylene group having 2 to 4 carbon atoms
  • R 9 is a hydrogen atom, a phenyl group, or an alkyl group having 1 to 4 carbon atoms
  • R 10 is a hydrogen atom or a methyl group
  • m is 0 to 20 Represents an integer.
  • R 10 represents a hydrogen atom or a methyl group
  • R 11 represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms.
  • R 12 represents an alkyl group having 1 to 18 carbon atoms.
  • R 8 represents an alkylene group having 2 to 4 carbon atoms
  • R 13 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a halogen atom
  • m represents an integer of 0 to 20
  • R 8 is independently an alkylene group having 2 to 4 carbon atoms
  • R 10 is a hydrogen atom or a methyl group
  • R 14 is a hydrocarbon group having 3 to 25 carbon atoms having a p + 1 bond
  • l represents an integer of 0 to 20
  • p represents an integer of 1 to 3.
  • R 15 represents an alkyl group having 4 to 18 carbon atoms, an aliphatic cyclic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic group.
  • X 1 represents an ethylene group, 1,3-propylene group, 1,2-propylene group, 2,3-propylene group
  • X 2 represents a hydrogen atom or a methyl group
  • X 3 represents a hydrogen atom, a methyl group, or an ethyl group.
  • X 2 and X 3 form a covalent bond at the broken line part, and integrally form an ethylene group, a 1,3-propylene group, a 1,2-propylene group, a 2,3-propylene group, or
  • X 1 , X 2 , and X 3 each represent a tetravalent aliphatic hydrocarbon group that together with the nitrogen atom forms a bicyclo ring, which is represented by the following structural formula (X-1);
  • Y 2 represents an organic nodule group having a (n + 1) bond having a nitrogen atom or an oxygen atom at the end of the structural site
  • Y 3 represents a single bond, an alkylene group having 1 to 3 carbon atoms, or carbon It represents an alkylidene group having 1 to 3 atoms
  • n represents an integer of 1 to 3.
  • the photosensitive resin composition of the present invention has high photosensitivity and excellent heat resistance in a cured product, and since it is difficult for outgas to occur, an insulating material, a resin material for solder resist, and the solder resist It can use suitably for the resist member which consists of resin.
  • the photosensitive resin composition of the present invention contains an acid group-containing (meth) acrylate resin (A) and a photopolymerizable initiator (B) represented by the following general formula (1). .
  • R 1 represents an alkyl group having 1 to 10 carbon atoms
  • R 2 represents any of an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, and an alkyl group having 2 to 4 carbon atoms substituted by an alkoxy group having 1 or 2 carbon atoms.
  • R 3 represents an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, a methoxyethyl group, or an ethoxyethyl group
  • R 2 and R 3 together form an alkylene group with a nitrogen atom to form a ring structure
  • R 2 and R 3 together form a nitrogen atom with a morpholine skeleton, N-methylpiperazine skeleton, or 2,6 -It may be a ring formation site forming a dimethylmorpholine skeleton
  • R 4 to R 7 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group
  • Y 1 is an alkyl group having 3 to 19 carbon atoms (y1-1) having no substituent, or having a halogen atom or a hydroxyl group as a substituent, aralkyl group having 7 to 19 carbon atoms (y1-2) Or
  • R 8 represents an alkylene group having 2 to 4 carbon atoms
  • R 9 represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 4 carbon atoms
  • m represents an integer of 0 to 20
  • R 8 is an alkylene group having 2 to 4 carbon atoms
  • R 9 is a hydrogen atom, a phenyl group, or an alkyl group having 1 to 4 carbon atoms
  • R 10 is a hydrogen atom or a methyl group
  • m is 0 to 20 Represents an integer.
  • R 10 represents a hydrogen atom or a methyl group
  • R 11 represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms.
  • R 12 represents an alkyl group having 1 to 18 carbon atoms.
  • R 8 represents an alkylene group having 2 to 4 carbon atoms
  • R 13 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a halogen atom
  • m represents an integer of 0 to 20
  • R 8 is independently an alkylene group having 2 to 4 carbon atoms
  • R 10 is a hydrogen atom or a methyl group
  • R 14 is a hydrocarbon group having 3 to 25 carbon atoms having a p + 1 bond
  • l represents an integer of 0 to 20
  • p represents an integer of 1 to 3.
  • R 15 represents an alkyl group having 4 to 18 carbon atoms, an aliphatic cyclic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic group.
  • X 1 represents an ethylene group, 1,3-propylene group, 1,2-propylene group, 2,3-propylene group
  • X 2 represents a hydrogen atom or a methyl group
  • X 3 represents a hydrogen atom, a methyl group, or an ethyl group.
  • X 2 and X 3 form a covalent bond at the broken line part, and integrally form an ethylene group, a 1,3-propylene group, a 1,2-propylene group, a 2,3-propylene group, or
  • X 1 , X 2 , and X 3 each represent a tetravalent aliphatic hydrocarbon group that together with the nitrogen atom forms a bicyclo ring, which is represented by the following structural formula (X-1);
  • Y 2 represents an organic nodule group having a (n + 1) bond having a nitrogen atom or an oxygen atom at the end of the structural site
  • Y 3 represents a single bond, an alkylene group having 1 to 3 carbon atoms, or carbon It represents an alkylidene group having 1 to 3 atoms
  • n represents an integer of 1 to 3.
  • (meth) acrylate resin refers to a resin having one or both of an acryloyl group and a methacryloyl group in the molecule. Further, “(meth) acryloyl group” means one or both of acryloyl group and methacryloyl group, and “(meth) acrylate” means one or both of acrylate and methacrylate.
  • the acid group-containing (meth) acrylate resin (A) will be described.
  • the acid group-containing (meth) acrylate resin (A) only needs to have an acid group and a (meth) acryloyl group, and other specific structures and molecular weights are not particularly limited, and a wide variety of resins are used. Can do.
  • Examples of the acid group contained in the acid group-containing (meth) acrylate resin (A) include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, a carboxyl group is preferable because it exhibits excellent alkali developability.
  • Examples of the acid group-containing (meth) acrylate resin (A) include [1] epoxy resin (a1-1), unsaturated monocarboxylic acid (a1-2), and polycarboxylic acid anhydride (a1-3). ) And (2) a phenolic hydroxyl group-containing resin (a2-1) and a cyclic carbonate compound (a2-2a) or a cyclic ether compound. (A2-2b), an unsaturated monocarboxylic acid (a2-3a) and / or an N-alkoxyalkyl (meth) acrylamide compound (a2-3b), and a polycarboxylic acid anhydride (a2-4) are essential.
  • Acid group-containing (meth) acrylate resin A-2
  • Acid group-containing (meth) acrylate resin comprising compound (a3-2), (meth) acryloyl group-containing epoxy compound (a3-3), and polycarboxylic acid anhydride (a3-4) as essential reaction materials ( A-3) and the like.
  • the acid group-containing (meth) acrylate resin (A-1) essentially comprises an epoxy resin (a1-1), an unsaturated monocarboxylic acid (a1-2), and a polycarboxylic acid anhydride (a1-3). Obtained as a reaction raw material.
  • the specific structure of the epoxy resin (a1-1) is not particularly limited as long as it has a plurality of epoxy groups in the resin.
  • Examples of the epoxy resin (a1-1) include bisphenol type epoxy resins, hydrogenated bisphenol type epoxy resins, biphenol type epoxy resins, hydrogenated biphenol type epoxy resins, phenylene ether type epoxy resins, naphthylene ether type epoxy resins, Phenol novolac type epoxy resin, cresol novolak type epoxy resin, bisphenol novolak type epoxy resin, naphthol novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, etc. .
  • the unsaturated monocarboxylic acid (a1-2) refers to a compound having a (meth) acryloyl group and a carboxyl group in one molecule, and examples thereof include acrylic acid and methacrylic acid. Further, esterified products, acid halides, acid anhydrides and the like of the unsaturated monocarboxylic acid (a1-2) can also be used. These unsaturated monocarboxylic acids (a1-2) can be used alone or in combination of two or more.
  • esterified product of the unsaturated monocarboxylic acid (a1-2) examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, ( (Meth) acrylic acid alkyl esters such as n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Compound; Hydroxyl group-containing (meth) acrylate compound such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate; dimethylaminoethyl (meth) acrylate, (meth) acrylic Nitrogen-containing (meth) acrylic acid ester such as dieth
  • Examples of the acid halide of the unsaturated monocarboxylic acid (a1-2) include (meth) acrylic acid chloride.
  • Examples of the acid anhydride of the unsaturated monocarboxylic acid (b1-3) include (meth) acrylic acid anhydride.
  • any acid anhydride of a compound having two or more carboxyl groups in one molecule can be used.
  • the polycarboxylic acid anhydride include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid,
  • acid anhydrides of dicarboxylic acid compounds such as terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and methylhexahydrophthalic acid.
  • the method for producing the acid group-containing (meth) acrylate resin (A-1) includes the epoxy resin (a1-1), the unsaturated monocarboxylic acid (a1-2), and the polycarboxylic acid anhydride (a1-
  • the method is not particularly limited as long as 3) is an essential reaction raw material, and any method may be used. For example, it may be produced by a method in which all of the reaction raw materials are reacted together, or may be produced by a method in which the reaction raw materials are reacted sequentially.
  • the epoxy resin (a1-1) and the unsaturated monocarboxylic acid (a1-2) are first reacted, and then the polycarboxylic acid anhydride (a1-3)
  • the method of reacting is preferred.
  • the reaction is carried out, for example, by reacting an epoxy resin (a1-1) and an unsaturated monocarboxylic acid (a1-2) in the temperature range of 100 to 150 ° C. in the presence of an esterification reaction catalyst.
  • the polycarboxylic acid anhydride (a1-3) can be added to the mixture and reacted at a temperature range of 90 to 120 ° C.
  • the reaction ratio of the epoxy resin (a1-1) to the unsaturated monocarboxylic acid (a1-2) is the amount of the unsaturated monocarboxylic acid (a1-2) relative to 1 mol of the epoxy group in the epoxy resin (a1-1). ) Is preferably used in the range of 0.9 to 1.1 mol.
  • the reaction rate of the polycarboxylic acid anhydride (a1-3) is preferably in the range of 0.2 to 1.0 mol with respect to 1 mol of the epoxy group in the epoxy resin (a1-1).
  • esterification reaction catalyst examples include phosphorus compounds such as trimethylphosphine, tributylphosphine and triphenylphosphine, amine compounds such as triethylamine, tributylamine and dimethylbenzylamine, 2-methylimidazole, 2-heptadecylimidazole, 2- Examples thereof include imidazole compounds such as ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole and 1-isobutyl-2-methylimidazole. These reaction catalysts can be used alone or in combination of two or more.
  • the amount of the reaction catalyst added is preferably in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the total reaction raw material.
  • the reaction of the epoxy resin (a1-1), the unsaturated monocarboxylic acid (a1-2), and the polycarboxylic acid anhydride (a1-3) can be performed in an organic solvent as necessary.
  • the organic solvent to be used can be appropriately selected depending on the solubility of the acid group-containing (meth) acrylate resin that is the reaction raw material and the product and the reaction temperature conditions.
  • methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone examples include methoxypropanol, cyclohexanone, methyl cellosolve, dialkylene glycol monoalkyl ether acetate, dialkylene glycol acetate and the like.
  • These organic solvents can be used alone or in combination of two or more as a mixed solvent.
  • the amount of the organic solvent used is preferably in the range of 10 to 500 parts by mass with respect to a total of 100 parts by mass of the reaction raw materials because the reaction efficiency is good.
  • the acid value of the acid group-containing (meth) acrylate resin (A-1) used in the present invention has a high photosensitivity and an acid group-containing (meth) acrylate resin composition capable of forming a cured product having excellent heat resistance Is preferably in the range of 30 to 150 mgKOH / g, more preferably in the range of 40 to 100 mgKOH / g.
  • the acid value of the acid group-containing (meth) acrylate resin is a value measured by a neutralization titration method of JIS K 0070 (1992).
  • the acid group-containing (meth) acrylate resin (A-2) includes a phenolic hydroxyl group-containing resin (a2-1), a cyclic carbonate compound (a2-2a) or a cyclic ether compound (a2-2b),
  • the carboxylic acid (a2-3a) and / or the N-alkoxyalkyl (meth) acrylamide compound (a2-3b) and the polycarboxylic acid anhydride (a2-4) are obtained as essential reaction materials.
  • the phenolic hydroxyl group-containing resin (a2-1) refers to a resin having two or more phenolic hydroxyl groups in the molecule, such as an aromatic polyhydroxy compound or a compound having one phenolic hydroxyl group in the molecule.
  • a novolak-type phenol resin using one or more kinds as a reaction raw material, a compound having one phenolic hydroxyl group, and a compound represented by any of the following structural formulas (x-1) to (x-5) ( and reaction products using x) as an essential reaction raw material.
  • R 1 is each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, or an aralkyl group, and i is 0. Or an integer of 1 to 4.
  • Z is a vinyl group, a halomethyl group, a hydroxymethyl group, or an alkyloxymethyl group, and Y is an alkylene group having 1 to 4 carbon atoms, an oxygen atom, or a sulfur atom.
  • carbonyl group, j is an integer of 1 to 4.
  • aromatic polyhydroxy compound examples include dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxyanthracene, trihydroxyanthracene, tetrahydroxyanthracene, biphenol, tetrahydroxybiphenyl, In addition to bisphenol and the like, compounds having one or more substituents on these aromatic nuclei may be mentioned.
  • substituent on the aromatic nucleus examples include a methyl group, an ethyl group, a vinyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, and a nonyl group.
  • Aliphatic hydrocarbon group such as methoxy group, ethoxy group, propyloxy group, butoxy group; halogen atom such as fluorine atom, chlorine atom, bromine atom; phenyl group, naphthyl group, anthryl group, and aromatic nucleus thereof
  • These aromatic polyhydroxy compounds can be used alone or in combination of
  • Examples of the novolac type phenol resin include those obtained by reacting one or more compounds having one phenolic hydroxyl group in the molecule with an aldehyde compound in the presence of an acidic catalyst.
  • the compound having one phenolic hydroxyl group in the molecule may be any compound as long as it is an aromatic compound having one hydroxyl group on the aromatic nucleus.
  • aromatic compound having one hydroxyl group on the aromatic nucleus For example, one or a plurality of compounds on the aromatic nucleus of phenol or phenol are used.
  • Phenol compounds having one or more substituents, naphthols or naphthol compounds having one or more substituents on the aromatic nucleus of naphthol, anthracans having one or more substituents on the aromatic nucleus of anthracenol or anthracenol Examples include a senol compound.
  • substituent on the aromatic nucleus examples include an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, and an aralkyl group, and specific examples of each are as described above. These compounds having one phenolic hydroxyl group can be used alone or in combination of two or more.
  • aldehyde compound examples include formaldehyde; alkyl aldehydes such as acetaldehyde, propyl aldehyde, butyraldehyde, isobutyraldehyde, pentyl aldehyde, hexyl aldehyde; salicyl aldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2-hydroxy-4 -Hydroxybenzaldehydes such as methylbenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde; 2-hydroxy-3-methoxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, 3 -Ethoxy-4-hydroxybenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde Benzaldehydes having both hydroxy groups and alkoxy groups; alky
  • the acidic catalyst examples include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Etc. These acidic catalysts can be used alone or in combination of two or more.
  • a compound having one phenolic hydroxyl group in the molecule and the compound (x) can be obtained by a method of heating and stirring under a temperature condition of about 80 to 200 ° C. under an acidic catalyst.
  • the reaction ratio between the compound having one phenolic hydroxyl group in the molecule and the compound (x) is 0 for the compound having one phenolic hydroxyl group in the molecule with respect to 1 mol of the compound (x).
  • the ratio is preferably 5 to 5 mol.
  • the acid catalyst is the same as described above.
  • Examples of the cyclic carbonate compound (a2-2a) include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate, and the like. These cyclic carbonate compounds can be used alone or in combination of two or more. Among these, ethylene carbonate or propylene carbonate is preferable because an acid group-containing (meth) acrylate resin composition capable of forming a cured product having high photosensitivity and excellent heat resistance can be obtained.
  • Examples of the cyclic ether compound (a2-2b) include ethylene oxide, propylene oxide, and tetrahydrofuran. These cyclic ether compounds can be used alone or in combination of two or more. Among these, ethylene oxide or propylene oxide is preferable because an acid group-containing (meth) acrylate resin composition having high photosensitivity and capable of forming a cured product having excellent heat resistance can be obtained.
  • the same unsaturated monocarboxylic acid (a1-2) as described above can be used as the unsaturated monocarboxylic acid (a1-2) as described above.
  • N-alkoxyalkyl (meth) acrylamide compound (a2-3b) examples include N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and N-methoxy. Examples include ethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide, and N-butoxyethyl (meth) acrylamide. Among these, N-methoxymethyl (meth) acrylamide is preferable because an acid group-containing (meth) acrylate resin composition having high photosensitivity and capable of forming a cured product having excellent heat resistance can be obtained. Moreover, these N-alkoxyalkyl (meth) acrylamide compounds can be used alone or in combination of two or more.
  • polycarboxylic acid anhydride (a2-4) the same polycarboxylic acid anhydride (a1-3) described above can be used.
  • the equivalent ratio [(a2-3b) / (a2-4)) to the polycarboxylic acid anhydride (a2-4)) is From the viewpoint of obtaining an acid group-containing (meth) acrylate resin composition having high photosensitivity and capable of forming a cured product excellent in heat resistance, the range of 0.2 to 7 is preferable, and 0.25 to 6 A range of .7 is more preferred.
  • the method for producing the acid group-containing (meth) acrylate resin (A-2) is not particularly limited, and any method may be used. For example, it may be produced by a method in which all of the reaction raw materials are reacted together, or may be produced by a method in which the reaction raw materials are reacted sequentially.
  • the phenolic hydroxyl group-containing resin (a2-1) is first reacted with the cyclic carbonate compound (a2-2a) or the cyclic ether compound (a2-2b), Next, after reacting the unsaturated monocarboxylic acid (a2-3a) and / or the N-alkoxyalkyl (meth) acrylamide compound (a2-3b), the polycarboxylic acid anhydride (a2-4) is reacted.
  • the reaction is performed, for example, by combining the phenolic hydroxyl group-containing resin (a2-1) with the cyclic carbonate compound (a2-2a) or the cyclic ether compound (a2-2b) in the presence of a basic catalyst.
  • the unsaturated polycarboxylic acid (b2-3a) and / or the N-alkoxyalkyl (meth) acrylamide compound (a2-3b) is heated at a temperature of 80 to 140 ° C. in the presence of an acidic catalyst.
  • the reaction can be carried out in the range, followed by the addition of polycarboxylic anhydride (a2-4) and the reaction in the temperature range of 80 to 140 ° C.
  • Examples of the basic catalyst include alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal waters such as sodium hydroxide and potassium hydroxide.
  • the acidic catalyst examples include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Etc. These acid catalysts can be used alone or in combination of two or more.
  • the reaction of the alkyl (meth) acrylamide compound (a2-3b) and the polycarboxylic acid anhydride (a2-4) can be carried out in an organic solvent as necessary.
  • the organic solvent to be used can be appropriately selected depending on the solubility of the acid group-containing (meth) acrylate resin that is the reaction raw material and the product and the reaction temperature conditions.
  • methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone examples include methoxypropanol, cyclohexanone, methyl cellosolve, dialkylene glycol monoalkyl ether acetate, dialkylene glycol acetate and the like.
  • organic solvents can be used alone or in combination of two or more kinds as a mixed solvent.
  • the amount of the organic solvent used is preferably in the range of 10 to 500 parts by mass with respect to a total of 100 parts by mass of the reaction raw materials because the reaction efficiency is good.
  • the specific structure of the acid group-containing (meth) acrylate resin (A-2) is not particularly limited, and the phenolic hydroxyl group-containing resin (a2-1) and the cyclic carbonate compound (a2-2a) or the cyclic ether compound (a2) -2b), unsaturated monocarboxylic acid (a2-3a) and / or N-alkoxyalkyl (meth) acrylamide compound (a2-3b), and polycarboxylic acid anhydride (a2-4) Any acid group and (meth) acryloyl group may be used in the resin.
  • Examples of the acid group-containing (meth) acrylate resin (A-2) to be obtained include the following structural formula (a-1): ) Having a resin structure in which a structural unit (I) represented by the following structural formula (a-2) and a structural unit (II) represented by the following structural formula (a-2) are repeated, or the following structural formula (a-3): Having a resin structure which structure represented by the site (III) and the following formula (a-4) structural moiety represented by formula (IV) and the repeating structural units and the like.
  • R 2 is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
  • R 3 is each independently a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and n is each independently 1 or 2.
  • R 4 is each independently a methylene group or a structural moiety represented by any of the following structural formulas (x′-1) to (x′-5).
  • R 5 and R 6 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R 5 and R 6 may be linked to form a saturated or unsaturated ring.
  • R 7 is a hydrocarbon group having 1 to 12 carbon atoms.
  • R 8 is a hydrogen atom or a methyl group.
  • x represents the structural site represented by R 3 or the structural site (I) represented by the structural formula (a-1) or the structural site (II) represented by the structural formula (a-2).
  • R 2 is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
  • R 3 is each independently a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and n is each independently 1 or 2.
  • R 4 is each independently a methylene group or a structural moiety represented by any of the following structural formulas (x′-1) to (x′-5).
  • R 5 and R 6 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R 5 and R 6 may be linked to form a saturated or unsaturated ring.
  • R 7 is a hydrocarbon group having 1 to 12 carbon atoms.
  • R 8 is a hydrogen atom or a methyl group.
  • x is the structural site represented by R 3 or the structural site (III) represented by the structural formula (a-3) or the structural site (IV) represented by the structural formula (a-4).
  • h is 0 or 1.
  • R 9 is independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group or an aralkyl group, and i is 0 or an integer of 1 to 4.
  • R 10 is a hydrogen atom or a methyl group.
  • W is the following structural formula (w-1) or (w-2).
  • Y is any one of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, and a carbonyl group.
  • j is an integer of 1 to 4.
  • R 11 is each independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
  • R 12 and R 13 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • R 12 and R 13 may be linked to form a saturated or unsaturated ring,
  • R 14 is a hydrocarbon group having 1 to 12 carbon atoms, and
  • R 15 is hydrogen. An atom or a methyl group.
  • the acid value of the acid group-containing (meth) acrylate resin (A-2) has high photosensitivity, and an acid group-containing (meth) acrylate resin composition capable of forming a cured product having excellent heat resistance is obtained. Therefore, the range of 30 to 150 mgKOH / g is preferable, and the range of 40 to 100 mgKOH / g is more preferable.
  • the acid value of the acid group-containing (meth) acrylate resin is a value measured based on a neutralization titration method of JIS K 0070 (1992).
  • the acid group-containing (meth) acrylate resin (A-3) includes an amideimide resin (a3-1) having an acid group or an acid anhydride group, a hydroxyl group-containing (meth) acrylate compound (a3-2), )
  • An acryloyl group-containing epoxy compound (a3-3) and a polycarboxylic acid anhydride (a3-4) are obtained as essential reaction raw materials.
  • the amideimide resin (a3-1) may have only one of an acid group or an acid anhydride group, or may have both. From the viewpoint of reactivity and reaction control with the hydroxyl group-containing (meth) acrylate compound (a3-2) and the (meth) acryloyl group-containing epoxy compound (a3-3), it may have an acid anhydride group. Preferably, it has both an acid group and an acid anhydride group.
  • the acid value of the amideimide resin (a3-1) is preferably in the range of 60 to 350 mgKOH / g under neutral conditions, that is, under conditions where the acid anhydride group is not ring-opened. On the other hand, the measured value under the condition where the acid anhydride group is opened, such as in the presence of water, is preferably in the range of 61 to 360 mgKOH / g.
  • the specific structure and production method of the amideimide resin (a3-1) are not particularly limited, and general amideimide resins and the like can be widely used.
  • amideimide resins and the like can be widely used.
  • what can be obtained by using a polyisocyanate compound and polycarboxylic acid or its acid anhydride as a reaction raw material is mentioned.
  • polyisocyanate compound examples include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; norbornane diisocyanate, isophorone diisocyanate, Cycloaliphatic diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3 , 3'-dimethylbiphenyl, o-tolidine diisocyanate, etc.
  • aliphatic diisocyanate compounds such as butane diis
  • Cyanate compound polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (i-1); these isocyanurate modified product, a biuret modified product, and the like allophanate modified product. These polyisocyanate compounds can be used alone or in combination of two or more.
  • R 1 is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
  • R 2 is each independently an alkyl group having 1 to 4 carbon atoms, or a bonding point that is linked to a structural moiety represented by the structural formula (i-1) via a methylene group marked with *. is there.
  • l is 0 or an integer of 1 to 3
  • m is an integer of 1 or more.
  • an acid group-containing (meth) acrylate resin composition having high solvent solubility is obtained, and therefore, an alicyclic diisocyanate compound or a modified product thereof, an aliphatic diisocyanate compound or a modified product thereof is used.
  • An alicyclic diisocyanate or its isocyanurate-modified product, and an aliphatic diisocyanate or its isocyanurate-modified product are more preferable.
  • the ratio of the total mass of an alicyclic diisocyanate compound or its modified body and an aliphatic diisocyanate compound or its modified body in the total mass of the said polyisocyanate compound is 70 mass% or more, and 90 mass % Or more is preferable.
  • the mass ratio of the two is preferably in the range of 30/70 to 70/30.
  • the polycarboxylic acid or its acid anhydride is not particularly limited as long as it is a compound having a plurality of carboxyl groups in its molecular structure or its acid anhydride, and a wide variety of compounds can be used.
  • the amideimide resin (a3-1) In order for the amideimide resin (a3-1) to have both an amide group and an imide group, it is necessary that both a carboxyl group and an acid anhydride group exist in the system.
  • a compound having both a carboxyl group and an acid anhydride group in the molecule may be used, or a compound having a carboxyl group and a compound having an acid anhydride group may be used in combination.
  • polycarboxylic acid or acid anhydride thereof examples include aliphatic polycarboxylic acid compounds or acid anhydrides thereof, alicyclic polycarboxylic acid compounds or acid anhydrides thereof, aromatic polycarboxylic acid compounds or acid anhydrides thereof. Etc.
  • the aliphatic hydrocarbon group may be either a linear type or a branched type, and may have an unsaturated bond in the structure.
  • Examples of the aliphatic polycarboxylic acid compound or acid anhydride thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, Examples include citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, and acid anhydrides thereof.
  • the alicyclic polycarboxylic acid compound or acid anhydride thereof is an alicyclic polycarboxylic acid compound or acid anhydride thereof in which a carboxyl group or an acid anhydride group is bonded to an alicyclic structure.
  • the presence or absence of an aromatic ring at other structural sites is not questioned.
  • the alicyclic polycarboxylic acid compound or acid anhydride thereof include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, and bicyclo [2.2.1].
  • Heptane-2,3-dicarboxylic acid methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4 -Tetrahydronaphthalene-1,2-dicarboxylic acid, and acid anhydrides thereof.
  • aromatic polycarboxylic acid compound or acid anhydride thereof examples include phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, and biphenyl.
  • aromatic polycarboxylic acid compound or acid anhydride thereof examples include phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, and biphenyl.
  • examples thereof include tetracarboxylic acid and benzophenone tetracarboxylic acid.
  • the acid group-containing (meth) acrylate resin composition having high photosensitivity and capable of forming a cured product having excellent heat resistance is obtained
  • the alicyclic polycarboxylic acid compound or its acid anhydride is obtained.
  • the aromatic polycarboxylic acid compound or acid anhydride thereof since the amideimide resin (a3-1) can be efficiently produced, it is preferable to use a tricarboxylic acid anhydride having both a carboxyl group and an acid anhydride group in the molecular structure, and cyclohexanetricarboxylic acid anhydride or It is particularly preferable to use trimellitic anhydride.
  • the ratio of the total amount of the alicyclic tricarboxylic acid anhydride and the aromatic tricarboxylic acid anhydride to the total mass of the polycarboxylic acid or acid anhydride is preferably 70% by mass or more, and 90% by mass or more. It is more preferable that
  • the amide-imide resin (a3-1) is a reaction raw material comprising the polyisocyanate compound and the polycarboxylic acid or acid anhydride thereof
  • other reaction raw materials depending on the desired resin performance and the like May be used in combination.
  • the ratio of the total mass of the polyisocyanate compound and the polycarboxylic acid or the acid anhydride thereof to the total reaction raw material mass of the amideimide resin (a3-1) Is preferably 90% by mass or more, and more preferably 95% by mass or more.
  • the amideimide resin (a3-1) is a polyisocyanate compound and polycarboxylic acid or acid anhydride thereof as reaction raw materials
  • it is not particularly limited and may be produced by any method.
  • it can be produced by the same method as a general amideimide resin. Specifically, 0.8 to 1.2 mol of polycarboxylic acid or its acid anhydride is used with 1 mol of the isocyanate group of the polyisocyanate compound, and the mixture is stirred and mixed at a temperature of about 120 to 180 ° C. The method of making it react is mentioned.
  • the reaction between the polyisocyanate compound and polycarboxylic acid or acid anhydride thereof can be performed in an organic solvent as necessary.
  • organic solvent include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, dialkylene glycol monoalkyl ether acetate, dialkylene glycol acetate and the like. These organic solvents can be used alone or in combination of two or more as a mixed solvent.
  • the amount of the organic solvent used is preferably in the range of 10 to 500 parts by mass with respect to a total of 100 parts by mass of the reaction raw materials because the reaction efficiency is good.
  • the hydroxyl group-containing (meth) acrylate compound (a3-2) is not particularly limited as long as it has a hydroxyl group and a (meth) acryloyl group in the molecular structure, and a wide variety of compounds are used. be able to.
  • those having a molecular weight of 1,000 or less are preferable because an acid group-containing (meth) acrylate resin composition capable of forming a cured product having excellent heat resistance can be obtained.
  • the weight average molecular weight (Mw) is preferably 1,000 or less.
  • the (meth) acryloyl group-containing epoxy compound (a3-3) is not particularly limited as long as it has a (meth) acryloyl group and an epoxy group in the molecular structure, and a wide variety of compounds can be used. Can be used.
  • glycidyl group-containing (meth) acrylate monomers such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and epoxycyclohexylmethyl (meth) acrylate; dihydroxybenzene diglycidyl ether, dihydroxynaphthalenediglycidyl ether, And mono (meth) acrylates of diglycidyl ether compounds such as biphenol diglycidyl ether and bisphenol diglycidyl ether.
  • a glycidyl group-containing (meth) acrylate monomer is preferable because an acid group-containing (meth) acrylate resin composition capable of forming a cured product having excellent heat resistance can be obtained. Moreover, it is preferable that the molecular weight is 500 or less. Furthermore, the proportion of the glycidyl group-containing (meth) acrylate monomer in the total mass of the (meth) acryloyl group-containing epoxy compound (a3-3) is preferably 70% by mass or more, and 90% by mass or more. Is more preferable.
  • the polycarboxylic acid anhydride (a3-4) is the same as the above-mentioned polycarboxylic acid anhydride (a1-3) and polycarboxylic acid anhydride (a2-4).
  • the acid group-containing (meth) acrylate resin (A-3) includes the amide-imide resin (a3-1) having the acid group or the acid anhydride group, the hydroxyl group-containing (meth) acrylate, depending on the desired resin performance.
  • the (meth) acryloyl group-containing epoxy compound (a3-3) and the polycarboxylic acid anhydride (a3-4) other reaction raw materials can be used in combination.
  • the ratio of the total mass of the components (a3-1) to (a3-4) in the total mass of the reaction raw material of the acid group-containing (meth) acrylate resin (A-3) is 80% by mass or more. Preferably, it is 90 mass% or more.
  • the method for producing the acid group-containing (meth) acrylate resin (A-3) is not particularly limited, and any method may be used. For example, it may be produced by a method in which all of the reaction raw materials are reacted together, or may be produced by a method in which the reaction raw materials are reacted sequentially.
  • the amide-imide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) are reacted (step 1), and the product of step 1 and the (meth) acryloyl group-containing epoxy compound (a3-3) (Step 2), and the product of Step 2 and the polycarboxylic acid anhydride (a3-4) are preferably reacted.
  • Step 1 is a step of reacting the amideimide resin (a3-1) with the hydroxyl group-containing (meth) acrylate compound (a3-2).
  • the acid group or acid anhydride group in the amideimide resin (a3-1) and the hydroxyl group in the hydroxyl group-containing (meth) acrylate compound (a3-2) mainly react. Since the hydroxyl group-containing (meth) acrylate compound (a3-2) is excellent in reactivity with an acid anhydride group, as described above, the amideimide resin (a3-1) has an acid anhydride group. It is preferable.
  • the reaction ratio between the amideimide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) is based on the total of acid groups and acid anhydride groups in the amideimide resin (a3-1).
  • the hydroxyl group-containing (meth) acrylate compound (a3-2) is preferably used in a range of 0.9 to 1.1 mol, and particularly, the total of acid anhydride groups in the amideimide resin (a3-1).
  • the hydroxyl group-containing (meth) acrylate compound (a3-2) is preferably used in the range of 0.9 to 1.1 mol.
  • the content of the acid anhydride group in the amideimide resin (a3-1) is the difference between the two acid value measurement values described above, that is, the acid value under the condition where the acid anhydride group is ring-opened, It can be calculated from the difference from the acid value under conditions where the acid anhydride group is not ring-opened.
  • the reaction between the amideimide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) is, for example, heated and stirred under a temperature condition of about 90 to 140 ° C. in the presence of an esterification reaction catalyst. Can be done.
  • esterification reaction catalyst examples include phosphorus compounds such as trimethylphosphine, tributylphosphine and triphenylphosphine, amine compounds such as triethylamine, tributylamine and dimethylbenzylamine, 2-methylimidazole, 2-heptadecylimidazole, 2- Examples thereof include imidazole compounds such as ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole and 1-isobutyl-2-methylimidazole. These reaction catalysts can be used alone or in combination of two or more.
  • the amount of the reaction catalyst added is preferably in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the total reaction raw material.
  • the reaction in Step 1 can also be performed in an organic solvent as necessary.
  • the organic solvent to be used can be appropriately selected depending on the solubility of the acid group-containing (meth) acrylate resin that is the reaction raw material and the product and the reaction temperature conditions.
  • methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone examples include methoxypropanol, cyclohexanone, methyl cellosolve, dialkylene glycol monoalkyl ether acetate, dialkylene glycol acetate and the like.
  • These organic solvents can be used alone or in combination of two or more as a mixed solvent.
  • Step 2 is a step of reacting the product obtained in Step 1 with the (meth) acryloyl group-containing epoxy compound (a3-3).
  • the (meth) acryloyl group-containing epoxy compound (a3-3) mainly reacts with the carboxyl group in the product of Step 1.
  • the reaction ratio is preferably such that the (meth) acryloyl group-containing epoxy compound (a3-3) is used in the range of 0.5 to 1.2 mol with respect to the carboxyl group in the product of Step 1. More preferably, it is used in the range of 9 to 1.1 mol.
  • the reaction in Step 2 can be performed, for example, with heating and stirring under a temperature condition of about 90 to 140 ° C. in the presence of an esterification reaction catalyst. When step 1 and step 2 are performed continuously, the esterification reaction catalyst may not be added or may be added as appropriate. Moreover, reaction can also be performed in an organic solvent as needed.
  • Step 3 is a step of reacting the product obtained in Step 2 with the polycarboxylic anhydride (a3-4).
  • the reaction mainly the polycarboxylic acid anhydride (a3-4) reacts with the hydroxyl group in the product of Step 2.
  • the reaction rate is preferably adjusted so that the acid value of the acid group-containing (meth) acrylate resin (A-3) as the final product is about 50 to 100 mgKOH / g.
  • the reaction in Step 3 can be carried out, for example, with heating and stirring under a temperature condition of about 90 to 140 ° C. in the presence of an esterification reaction catalyst.
  • the esterification reaction catalyst may not be added or may be added as appropriate.
  • reaction can also be performed in an organic solvent as needed.
  • the acid value of the acid group-containing (meth) acrylate resin (A-3) has a high photosensitivity, and an acid group-containing (meth) acrylate resin composition capable of forming a cured product having excellent heat resistance is obtained. Therefore, the range of 30 to 150 mgKOH / g is preferable, and the range of 40 to 100 mgKOH / g is more preferable.
  • the acid value of the acid group-containing (meth) acrylate resin (A-3) is a value measured by the neutralization titration method of JIS K 0070 (1992).
  • the photopolymerization initiator (B) will be described.
  • photopolymerization initiator (B) a compound represented by the following general formula (1) is used.
  • excellent curability is exhibited even though the molecular weight is relatively large and the amount of radical generation sites is relatively small.
  • R 1 represents a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group; an s-butyl group, a pentyl group, or a hexyl group.
  • An alkyl group having 1 to 10 carbon atoms such as a 1,3,3-tetramethylpentyl group and an isodecyl group is represented.
  • an ethyl group is preferable from the viewpoint of reactivity of radicals generated by light irradiation.
  • R 2 and R 3 are each independently a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, s- Linear or branched alkyl group having 1 to 12 carbon atoms such as butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group; hydroxyethyl group, hydroxy A hydroxyalkyl group having 2 to 4 carbon atoms such as a propyl group or a hydroxybutyl group; A methoxyethyl group; an ethoxyethyl group; an alkylene group in which R 2 and R 3 together form a ring structure with a nitrogen atom;
  • R 4 to R 7 are each independently a hydrogen atom; methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, s- Butyl, pentyl, hexyl, heptyl, octyl, 2-ethylbutyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, 1-methylhexyl, isoheptyl, 1,1, Alkyl groups having 1 to 8 carbon atoms such as 3,3-tetramethylbutyl group, 2,2,4,4-tetramethylbutyl group, 1-methylheptyl group, 3-methylheptyl group, 2-ethylhexyl group; Or represents a phenyl group.
  • it is preferable that all of R 4 to R 7 are hydrogen atoms from the viewpoint of easy availability of raw materials.
  • X 1 represents an ethylene group, 1,3-propylene group, 1,2-propylene group, or 2,3-propylene group
  • X 2 represents a hydrogen atom or a methyl group
  • X 3 represents a hydrogen atom, a methyl group, or an ethyl group
  • X 2 and X 3 form a covalent bond at the broken line portion, and integrally form an ethylene group, a 1,3-propylene group, or a 1,2-propylene.
  • Group, 2,3-propylene group, or X 1 , X 2 , and X 3 are integrally represented by the following structural formula (X-1)
  • the tetravalent aliphatic hydrocarbon group which comprises a bicyclo ring with a nitrogen atom represented by these is represented.
  • Y 1 represents propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, s-butyl group, pentyl group, hexyl group, heptyl group, octyl group, Nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, 2-ethylbutyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl Group, 1-methylhexyl group, isoheptyl group, 1,1,3,3-tetramethylbutyl group, 2,2,4,4-tetramethylbutyl group, 1-methylheptyl group, 3-methylheptyl group, 2 -Ethylhex
  • R 8 represents an alkylene group having 2 to 4 carbon atoms
  • R 9 represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 4 carbon atoms
  • m represents an integer of 0 to 20
  • R 8 is an alkylene group having 2 to 4 carbon atoms
  • R 9 is a hydrogen atom, a phenyl group, or an alkyl group having 1 to 4 carbon atoms
  • R 10 is a hydrogen atom or a methyl group
  • m is 0 to 20 Represents an integer.
  • R 10 represents a hydrogen atom or a methyl group
  • R 11 represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms.
  • R 12 represents an alkyl group having 1 to 18 carbon atoms.
  • R 8 represents an alkylene group having 2 to 4 carbon atoms
  • R 13 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a halogen atom
  • m represents an integer of 0 to 20
  • R 8 is an alkylene group having 2 to 4 carbon atoms
  • R 10 is a hydrogen atom or a methyl group
  • R 14 is a hydrocarbon group having 5 to 18 carbon atoms having a p + 1 bond
  • l is 0 to (An integer of 20 and p represents an integer of 1 to 3)
  • R 15 represents an alkyl group having 4 to 18 carbon atoms, an aliphatic cyclic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic group.
  • the alkylene group having 2 to 4 carbon atoms of R 8 is an n-propylene group, a 1,2-propylene group, an n-butylene group, 2-methyl-propane- 1,2-diyl group and the like
  • examples of the alkyl group having 1 to 4 carbon atoms in R 9 include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t- Examples thereof include a butyl group or a s-butyl group.
  • R 8 and R 9 in the structural moiety (y1-4) have the same meaning as in the structural formula (y1-3).
  • the alkyl group having 1 to 18 carbon atoms or the alkyl group having 1 to 18 carbon atoms of R 11 is methyl group, ethyl group, propyl group, isopropyl group, n-butyl.
  • examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a benzyl group, Phenethyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxy Phenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthio Enyl group, methylaminophenyl group, dimethylaminophenyl group,
  • alkyl group having 1 to 18 carbon atoms of R 12 a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, S-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, 2- Ethylbutyl group, isopentyl group, 1-methylpentyl group, 1,3-dimethylbutyl group, 1-methylhexyl group, isoheptyl group, 1,1,3,3-tetramethylbutyl group, 2,2,4,4- Te
  • R 8 in formula (y1-7) has the same meaning as R 8 in the structural moiety (Y1-3), the alkyl group having 1 to 6 carbon atoms R 13, a methyl group, an ethyl group, Propyl group, Isopropyl, n-butyl, isobutyl, t-butyl, s-butyl, pentyl, hexyl, 2-ethylbutyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, etc.
  • the halogen atom include a bromine atom, a chlorine atom, and a fluorine atom.
  • R 8 in the formula (y1-8) in has the same meaning as R 8 in the structural moiety (Y1-3), and a hydrocarbon group having a carbon number of 3 to 25 having a bond p + 1 in R 14 is , Aliphatic polyhydric alcohol residues such as glycerol residue, trimethylolpropane residue, pentaerythritol residue; n-propylene group, 1,2-propylene group, n-butylene group, 2-methyl-propane-1, 2-diyl group, 1,5-pentanediyl group, 1,6-hexanediyl group, 1,7-heptanediyl group, 1,8-octanediyl group, 1,9-nonanediyl group, 1,10-decandiyl group, 3 , 8-decanediyl group, 1,11-undecanediyl group, 1,12-dodecanediyl group, 1,13-tride
  • the residue refers to a hydrocarbon structure site excluding the hydroxyl group of the polyhydric alcohol.
  • the alkyl group (y1-1) having 3 to 18 carbon atoms and the structural formula (y1-4) are particularly preferable.
  • the structural moiety (y1-4), the structural moiety (y1-5) represented by the structural formula (y1-5), and the structural moiety (y1-8) represented by the structural formula (y1-8) Photosensitive resin that has high photosensitivity and excellent heat resistance in a cured product, and is less susceptible to outgassing in addition to easy introduction of Y 1 during the synthesis of the compound represented by general formula (1)
  • the structural part (y1-8) is more preferable because a composition can be obtained.
  • the structural moiety represented by the following structural formula 1a in the general formula (1) can be arbitrarily selected from the various structures described above, but the total mass number of the portion represented by the structural formula 1a is 300 to A photosensitivity resin composition having a high photosensitivity and excellent heat resistance in a cured product and having a high photosensitivity of 2000 is preferable because a photosensitive resin composition that hardly causes outgassing is obtained.
  • Y 2 is an organic nodule group having a (n + 1) bond having a nitrogen atom or an oxygen atom at the end of the structural site, as described above.
  • a (n + 1) bond having a nitrogen atom or an oxygen atom at the end of the structural site, as described above.
  • Is an amide bond-forming type structural site selected from the group consisting of structural sites (y2-1) to (y2-6) shown below, or structural sites (y2-7) to (y2-9) shown below Ester bond-forming type structural sites represented by) are preferred from the viewpoint of easy availability of raw materials and easy control of the reaction.
  • the structural part (y2-1) is a structural part represented by the following structural formula (y2-1), where n in the general formula (1) is 1.
  • R 16 is a linear or cyclic alkylene group having 2 to 18 carbon atoms, a phenylene group, a xylylene group, a phenylene group having an alkyl group having 1 to 3 carbon atoms as a nuclear substituent, or 1 carbon atom
  • R 16 represents a xylylene group having an alkyl group of ⁇ 3 as a nuclear substituent.
  • Examples of the linear or cyclic alkylene group having 2 to 18 carbon atoms constituting R 16 in the structural formula (y2-1) include an ethylene group, an n-propylene group, a 1,2-propylene group, and an n-butylene.
  • examples of the phenylene group having an alkyl group having 1 to 3 carbon atoms as a nuclear substituent include a methylphenylene group, an ethylphenylene group, an n-propylphenylene group, and i-propyl.
  • examples of the xylylene group having an alkyl group having 1 to 3 carbon atoms as a nuclear substituent include a methylxylylene group, an ethylxylylene group, an n-propylxylylene group, and an i-propylxylylene group.
  • the structural site (y2-2) is represented by the following structural formula, where n is 1 in the general formula (1).
  • R 17 is a linear or branched alkylene group or phenylene group having 2 to 6 carbon atoms
  • R 18 is a linear or branched alkylene group or phenylene group having 2 to 6 carbon atoms.
  • Q represents an integer of 0 to 12.
  • examples of the linear or branched alkylene group having 2 to 6 carbon atoms constituting R 17 and R 17 in the general formula (y2-2) include, for example, an ethylene group, an n-propylene group, , 2-propylene group, n-butylene group, 2-methyl-propane-1,2-diyl group, 1,5-pentanediyl group, 1,6-hexanediyl group.
  • the structural site (y2-3) is represented by the following structural formula (y2-3), wherein n in the general formula (1) is 1.
  • R 19 to R 22 each independently represents hydrogen or a linear or branched alkyl group having 1 to 3 carbon atoms.
  • examples of the linear or branched alkyl group having 1 to 3 carbon atoms constituting R 19 to R 22 include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • the structural site (y2-4) is one represented by the following structural formula (y2-4), where n is 1 in the general formula (1).
  • R 23 represents an oxygen atom, a methylene group, an ethylene group, an ethylidene group, a 2,2-propylene group, or a 1,3-propylene group.
  • the structural portion (y2-5) is one in which n in the general formula (1) is 1, and is represented by the following structural formula (y2-5).
  • R 24 is independently a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms
  • R 25 is independently a hydrogen atom or 1 to 3 carbon atoms
  • R 26 represents an oxygen atom, a methylene group, a 2,2-propylene group, a sulfonyl group, or a carbonyl group.
  • examples of the linear or branched alkyl group having 1 to 3 carbon atoms constituting R 24 or R 25 include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • the structural moiety (y2-6) is represented by the following structural formula (y2-6) where n in the general formula (1) is 2 or 3.
  • R 27 is an alkylene group having 2 to 6 carbon atoms
  • R 28 is a (n + 1) -valent hydrocarbon group having 4 to 12 carbon atoms
  • r is an integer of 0 to 3
  • an ethylene group, an n-propylene group, a 1,2-propylene group, an n-butylene group, 2-methyl-propane-1,2- A diyl group, a 1,5-pentanediyl group, and a 1,6-hexanediyl group, and the hydrocarbon group having 4 to 12 carbon atoms constituting R 28 and having an (n + 1) -valent bond is a polyhydric alcohol.
  • examples thereof include trimethylolpropane residue, pentaerythritol residue, glyceryl residue, and ditrimethylolpropane residue.
  • the “residue” is a hydrocarbon structure site obtained by removing a hydroxyl group from the corresponding polyhydric alcohol.
  • the structural part (y2-7) which is an ester bond-forming type structural part is one in which n in the general formula (1) is 1 and represented by the following structural formula (y2-7) is there.
  • R 29 represents a linear, branched or cyclic alkylene group having 2 to 18 carbon atoms, a phenylene group or a xylylene group.
  • the linear, branched or cyclic alkylene group having 2 to 18 carbon atoms constituting R 29 includes an ethylene group, an n-propylene group, a 1,2-propylene group, an n-butylene group, 2- Methyl-propane-1,2-diyl group, 1,5-pentanediyl group, 1,6-hexanediyl group, 1,7-heptanediyl group, 1,8-octanediyl group, 1,9-nonanediyl group, 1, 10-decanediyl group, 3,8-decanediyl group, 1,11-undecanediyl group, 1,12-dodecanediyl group, 1,13-tridecanediyl group, 1,14-tetradecanediyl group, 1,15-pentadecanediyl group Group, 1,16-hexadecanediyl group, 1,17-
  • the structural moiety (y2-8) which is an ester bond-forming structural moiety, is one in which n in the general formula (1) is 1, and is represented by the following structural formula (y2-8) It is.
  • each R 30 independently represents an alkylene group having 2 to 6 carbon atoms, and q represents an integer of 1 to 20).
  • the alkylene group having 2 to 6 carbon atoms constituting R 30 includes an ethylene group, an n-propylene group, a 1,2-propylene group, an n-butylene group, 2-methyl-propane-1,2- Examples thereof include a diyl group, a 1,5-pentanediyl group, and a 1,6-hexanediyl group.
  • the structural moiety (y2-9) which is an ester bond-forming structural moiety, is represented by the following structural formula (y2-9) where n is 2 or 3 in the general formula (1). is there.
  • R 31 is a (n + 1) -valent hydrocarbon group having 4 to 12 carbon atoms
  • R 32 is an alkylene group having 2 to 6 carbon atoms
  • s is an integer of 0 to 3
  • the (n + 1) -valent hydrocarbon group having 4 to 12 carbon atoms constituting R 31 includes polyhydric alcohol residues such as trimethylolpropane residue, pentaerythritol residue. Groups, glyceryl residues, ditrimethylolpropane residues.
  • the “residue” is a hydrocarbon structure site obtained by removing a hydroxyl group from the corresponding polyhydric alcohol.
  • Examples of the alkylene group having 2 to 6 carbon atoms constituting R 32 include ethylene, n-propylene, 1,2-propylene, n-butylene, 2-methyl-propane-1,2-diyl. Group, 1,5-pentanediyl group and 1,6-hexanediyl group.
  • the amide bond forming type structural site selected from the group consisting of the structural sites (y2-1) to (y2-6) is the chemical product.
  • the structural part (y2-1), the structural part (y2-2), and the structural part (y2-3) are particularly preferred from the viewpoint of excellent stability and photocurability.
  • the structural site (y2-3) selected from the following structures is preferable because the intermediate is easily crystallized and can be easily purified in production.
  • Y 3 in the general formula (1) represents a single bond, an alkylene group having 1 to 3 carbon atoms, or an alkylidene group having 2 or 3 carbon atoms, and as an alkylene group having 1 to 3 carbon atoms, Includes a methylene group, an ethylene group, an n-propylene group, and a 1,2-propylene group, and examples of the alkylidene group having 2 or 3 carbon atoms include an ethylidene group and a propylidene group.
  • a single bond or an alkylidene group having 2 or 3 carbon atoms is preferable from the viewpoint of easy availability of a benzyl bromide derivative which is a raw material component constituting the structural part, and the safety of the decomposition product after light irradiation is particularly preferable. From these viewpoints, an alkylidene group having 2 or 3 carbon atoms is preferred.
  • examples of the compound represented by the general formula (1) detailed above include compounds M1 to M86 shown in the following Tables 1 to 12.
  • a photosensitive resin composition having high photosensitivity and excellent heat resistance in a cured product and hardly generating outgas can be obtained, and the raw materials are also available.
  • compounds of M1, M4, M7, M14, M23, M28, M31, M32, M41, M43, M45, M50, M55, M64, and M78 are preferable.
  • the compound represented by the above general formula (1) can be industrially produced through the following [Step I] to [Step VI].
  • Step I A halogenated benzene and an acid halide compound having a halide atom at the ⁇ -position are reacted to synthesize an alkyl acetophenone derivative having a halogen atom on the ⁇ -carbon atom of the carbonyl.
  • the reaction of [Step I] can be carried out by Friedel-Craft-acylation reaction in the presence of anhydrous aluminum chloride.
  • examples of the halogenated benzene include fluorinated benzene, chlorobenzene, and bromobenzene.
  • Examples of the acid halide compound having a halide atom at the ⁇ -position include 2-bromopropionic acid bromide, 2-bromopropionic acid chloride, 2-bromovaleric acid bromide, 2-bromovaleric acid chloride, 2-bromohexanoic acid. Examples thereof include bromide and 2-bromooctanoic acid bromide.
  • Step II the secondary monoamine compound (HN (R 2 ) (R 3 )) is reacted to convert the ⁇ -position to an amino group.
  • the secondary monoamine compound (HN (R 2 ) (R 3 )) used here is dimethylamine, diethylamine, methylbutylamine, methyloctylamine, methyldodecylamine, ethylhexylamine, diethanolamine, diisopropanolamine, diisobutanolamine.
  • reaction conditions can be carried out at a temperature of 0 ° C. to 80 ° C. in the presence of a base such as a carbonate such as calcium carbonate, potassium carbonate or sodium carbonate, or a tertiary amine such as triethylamine or diisopropylethylamine.
  • a base such as a carbonate such as calcium carbonate, potassium carbonate or sodium carbonate, or a tertiary amine such as triethylamine or diisopropylethylamine.
  • a base such as a carbonate such as calcium carbonate, potassium carbonate or sodium carbonate, or a tertiary amine such as triethylamine or diisopropylethylamine.
  • Step III benzyl bromide (where R is an alkyl group or a hydrogen atom) having a substituent (—Y 3 —C ( ⁇ O) —OR) as a substituent on the aromatic nucleus is converted to a tertiary amine of the acetophenone derivative.
  • the reaction is led to a quaternary ammonium salt, and then subjected to a 1.2-rearrangement reaction (Stevens transition) by alkali treatment, and an ⁇ -aminoacetophenone intermediate compound A (general formula 3) represented by general formula 3 Is synthesized.
  • the ⁇ -aminoacetophenone intermediate compound thus obtained (general formula 3) has a halogen atom on the aromatic ring of the acetophenone moiety and a carboxyl group on the aromatic ring of the benzyl group substituted at the ⁇ -position. .
  • Y 3 in benzyl bromide having a substituent (—Y 3 —C ( ⁇ O) —OR) as a substituent on the aromatic nucleus is a single bond, an alkylene group having 1 to 3 carbon atoms as described above. Or an alkylidene group having 2 or 3 carbon atoms, particularly preferably a single bond, a methylene group, or an ethylidene group from the viewpoint of easy availability of raw materials, and R is a hydrogen atom or a methyl group.
  • the quaternary ammonium conversion in [Step III] is performed at 20 to 100 ° C.
  • the subsequent 1.2-rearrangement reaction (Stevens transition) is performed at 20 to 80 ° C. using an aqueous sodium hydroxide solution as a base. Can do.
  • Step IV the carboxyl group of the ⁇ -aminoacetophenone intermediate compound (general formula 3) is subjected to a condensation reaction between a bifunctional or higher primary or secondary amine or a bifunctional or higher alcohol (general formula 4), respectively. It leads to the intermediate compound B which is a compound.
  • a bifunctional diamine is used as the compound represented by the general formula 4
  • 1 mol of the bifunctional diamine is reacted with 2 mol of the ⁇ -aminoacetophenone intermediate compound (general formula 3).
  • Intermediate compound B in which the amide group has a symmetrical molecular structure can be synthesized.
  • a bifunctional or higher functional amine is obtained after converting the carboxyl group arranged on the aromatic ring of the ⁇ -aminoacetophenone intermediate compound represented by the general formula 3 into an acid chloride using thionyl chloride or the like.
  • DCC dicyclohexylcarbodiimide
  • the synthesis method of the intermediate compound B in the case of using a bifunctional or higher alcohol as the compound represented by the general formula 4 is such that the carboxyl group arranged on the aromatic ring of the intermediate compound of the general formula 3 is substituted with thionyl chloride or the like.
  • a method of reacting with a bifunctional or higher alcohol after conversion into an acid chloride using a method a method of reacting with a bifunctional or higher alcohol by dehydration condensation using an acid catalyst such as para-toluenesulfonic acid, dicyclohexylcarbodiimide ( A method of reacting with a bifunctional or higher alcohol using an active esterification reagent such as DCC), and converting to a mixed acid anhydride using an acid anhydride such as acetic anhydride, and then reacting with a bifunctional or higher alcohol.
  • an acid catalyst such as para-toluenesulfonic acid, dicyclohexylcarbodiimide
  • DCC active esterification reagent
  • the method etc. are mentioned.
  • the primary or secondary amine for example, ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, 1, 2-diamino-2-methylpropane, 2-methyl-1,3-propanediamine, 1,5-diaminopentane, 2,2-dimethyl-1,3-propanediamine, 1,6-diaminohexane, 1,2 -Diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 2,2'-diamino-N-methyldiethylamine, 1,7-diaminoheptane, 1,3-bis (aminomethyl) cyclohexane, 1, 4-bis (aminomethyl) cyclohexane, 1,8-diaminooctane, N- (3-
  • Polyalkylene ether amine m-xylenediamine, p-xylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 1,5-diaminonaphthalene, 3,3′-dimethylbenzidine, 3,3′-diethyl Benzidine, 3,3'-dimethoxybenzidine, 3,3 ', 5,5'-tetramethylbenzidine, 2,2'-dimethylbenzidine, 1,3,5-tris (4-aminophenyl) benzene, 2,7 -Diaminofluorene, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,3'-diaminodiphenyl Methane, 4,4′-ethylenedianiline, 1,1-bis (4-aminophenyl) cyclohexane, 9,9-bis (4-aminophenyl) fluorene, 1,4-bis [2- (4-amin
  • bifunctional or higher alcohols include, for example, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1 , 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, , 16-hexadecanediol, 1,18-octadecanediol, 1,20-icosanediol and other linear alkylene diols and their ethylene oxide modified products and propylene oxide modified products such as polyoxyethylene glycol and polyoxypropylene glycol Ether glycol; Modified polyethers obtained by ring-opening polymerization
  • Such a reaction can be performed at a temperature of 60 ° C. to 160 ° C.
  • an inorganic carbonate such as potassium carbonate can be used in addition to an excessively bifunctional cyclic amine represented by the general formula 5 as a scavenger for the acid generated in the system.
  • examples of the bifunctional cyclic amine represented by the general formula 5 include piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2,3-dimethylpiperazine, 2,5-diazabicyclo [2. 2.1] heptane, homopiperazine and the like.
  • the compound represented by the general formula (1) can be produced by reacting with a halide.
  • [Step VI] can be classified into the following (Step VI-1) to (Step VI-9) depending on the compound to be reacted with the intermediate compound C.
  • Hal is a halogen atom
  • R ′ is a halogen atom or an alkyl group optionally having a hydroxyl group.
  • examples of the halogenated alkane having 3 to 18 carbon atoms represented by Hal-R ′ include 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 2-methyl-2-chloropropane, 2- Methyl-1-chloropropane, 1-chloropentane, 2-chloropentane, 3-chloropentane, 2-chloro-2-methylbutane, 1-chloro-2-ethylbutane, 1-chlorohexane, 2-chlorohexane, 3-chloro Hexane, 2-chloro-methyl-pentane, 1-chloroheptane, 2-chloroheptane, 3-chloroheptane, 1-chlorooctane, 2-chlorooctane, 3-chlorooctane, 1-chloro-1,1,3 3-tetramethylbutane, 1-chloro-2,2,4,
  • Hal-R ′ When the halogenated alkane having 3 to 18 carbon atoms represented by Hal-R ′ further has a halogen atom on the alkane structure, 1-bromo-3-fluoropropane, 1-bromo-3 -Chloropropane, 1-iodo-3-fluoropropane, 1-iodo-3-chloropropane, 1-bromo-2-fluoropropane, 1,1,1-trifluoro-3-iodopropane, 1,1,1,2 , 2-Peentafluoro-3-iodopropane, 1-bromo-4-fluorobutane, 1-bromo-3-fluorobutane, 1-bromo-4-chlororobutane, 1,1,1-trifluoro-4-iodobutane 1,1,1,2,2,3,3-pentafluoro-4-iodobutane, 1-bromo-5-fluoropentane, 1-iodo
  • halogenated alkane having 3 to 18 carbon atoms represented by Hal-R ′ further has a hydroxyl group on the alkane structure, 3-bromo-1-propanol, 3-iodo-1-propanol 4-iodo-2-methyl-2-butanol, 4-bromo-2-methyl-2-butanol, 1-iodo-2-methyl-2-propanol, 1-bromo-2-methyl-2-propanol, 1 -Iodo-4-butanol, 1-bromo-4-butanol, 1-iodo-2-butanol, 1-bromo-2-butanol, 5-iodo-1-pentanol, 5-bromo-1-pentanol, 1 -Iodo-6-hexanol, 1-bromo-6-hexanol, 5-iodo-3-methyl-1-pentanol, 5-bromo-3-methyl-1-pentanol, 1-iool,
  • the reaction in (Step VI-1) is carried out using a carbonate such as potassium carbonate as a basic catalyst in a polar solvent such as N, N-dimethylformamide, or a halogenated solvent such as dichloromethane or chloroform.
  • a carbonate such as potassium carbonate
  • a polar solvent such as N, N-dimethylformamide
  • a halogenated solvent such as dichloromethane or chloroform.
  • a tertiary amine such as triethylamine can be used as a basic catalyst.
  • Hal is a halogen atom
  • Aral is an aralkyl group.
  • the halogenated aromatic compound represented by Hal-Aral includes benzyl chloride, benzyl bromide, methoxybenzyl chloride, methoxybenzyl bromide, chlorobenzyl bromide, hydroxybenzyl bromide, and the like.
  • Phenethyl group, phenylbenzyl bromide, methoxyphenylbenzyl bromide, naphthylmethyl bromide, methoxynaphthylmethyl bromide, phenylpropyl iodide, phenylpropenyl iodide, phenoxybenzyl bromide, methylthiobenzyl bromide, terphenylmethyl bromide Can be carried out under the same reaction conditions as in (Step VI-1).
  • R 8 represents an alkylene group having 2 to 4 carbon atoms
  • R 9 represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 4 carbon atoms
  • m represents an integer of 0 to 20
  • the alkylene group having 2 to 4 carbon atoms of R 8 includes an n-propylene group, a 1,2-propylene group, an n-butylene group, 2-methyl-propane-1,2-diyl group and the like
  • examples of the alkyl group having 1 to 4 carbon atoms in R 9 include a methyl group, an ethyl group, a propyl group, an isopropyl group, and an n-butyl group.
  • the reaction conditions in the above (Step VI-3) can be carried out at 20 to 120 ° C. in the presence of a basic catalyst such as potassium carbonate.
  • R 8 is an alkylene group having 2 to 4 carbon atoms
  • R 9 is a hydrogen atom, a phenyl group, or an alkyl group having 1 to 4 carbon atoms
  • R 10 is a hydrogen atom or a methyl group
  • m is 0 to 20 Represents an integer.
  • the alkylene group having 2 to 4 carbon atoms of R 8 includes an n-propylene group, a 1,2-propylene group, an n-butylene group, 2-methyl-propane-1,2-diyl group and the like
  • examples of the alkyl group having 1 to 4 carbon atoms in R 9 include a methyl group, an ethyl group, a propyl group, an isopropyl group, and an n-butyl group.
  • the Michael addition reaction in (Step VI-4) can be carried out under known and usual reaction conditions.
  • the intermediate compound C and the compound represented by the structural formula (y1-4r) having a function as the Michael acceptor are mixed at 0 to 150 ° C. in a reaction vessel.
  • the method is mentioned and a catalyst and a solvent can also be used.
  • Examples of usable catalysts include tetrabutylammonium hydroxide, tetramethylguanidine, diazabicycloundecene, 1,4-diazabicyclo [2.2.2], sodium t-butyrate, and the like.
  • organic solvent examples include saturated hydrocarbon solvents such as pentane, hexane, heptane and cyclohexane, aromatic hydrocarbon solvents such as toluene and xylene, methanol, ethanol, isopropanol, 2-butanol, t-butanol and ethylene.
  • Alcohol solvents such as glycol and carbitol, ether solvents such as dimethyl ether, diethyl ether, 1,4-dioxane and tetrahydrofuran (THF), amide solvents such as dimethylformamide (DMF), and halogen solvents such as chloroform and dichloromethane And dimethyl sulfoxide (DMSO).
  • the mixing ratio of the intermediate compound C and the compound represented by the structural formula (y1-4r) having a function as the Michael acceptor is not particularly limited.
  • the equivalent ratio [(i) / (ii)] of the primary amino group (i) and the (meth) acryloyl group (ii) in the compound represented by the structural formula (y1-4r) is 1/1. It is preferably 5 to 1/30.
  • the equivalent ratio [(i) / (ii)] exceeds 1 / 1.5, the possibility of migration from the coating film of the intermediate compound C or a decomposition product thereof increases, and the equivalent ratio [(i) / When (ii)] is less than 1/30, the curing performance of the Michael addition reaction product tends to be inferior.
  • the equivalent ratio [(i) / (ii)] is particularly preferably from 1/2 to 1/20.
  • the structural formula (y1-4r) having a function as the Michael acceptor for example, methoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethyleneglycol (meth) acrylate, butoxypolyethyleneglycol (Meth) acrylate, methoxypolypropylene glycol (meth) acrylate, etc. are mentioned.
  • the reaction conditions can be carried out at 20 to 120 ° C. in the presence of a catalyst such as diazabicycloundecene (DBU).
  • DBU diazabicycloundecene
  • R 10 represents a hydrogen atom or a methyl group
  • R 11 represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms.
  • R 11 represents an alkyl group having 1 to 18 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group; s-butyl group, pentyl Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, 2-ethylbutyl group, isopentyl group, 1 -Methylpentyl group, 1,3-dimethylbutyl group, 1-methylhexyl group, isoheptyl group, 1,1,3,3-tetramethylbutyl group, 2,2,
  • R 12 represents an alkyl group having 1 to 18 carbon atoms.
  • the alkyl group having 1 to 18 carbon atoms of R 12 includes a methyl group, an ethyl group, a propyl group, an isopropyl group, and an n-butyl group.
  • reaction with the epoxy compound in (Step VI-6) is carried out by subjecting the intermediate compound C and the compound represented by the structural formula (y1-6r) to a temperature condition of 0 to 150 ° C. in a reaction vessel.
  • a catalyst or a solvent can also be used.
  • Examples of usable catalysts include triethylamine, diisopropylethylamine, benzyldiethylamine, imidazole, tetrabutylammonium bromide, tri-n-octylphosphine, triphenylphosphine, and the like.
  • organic solvent examples include aromatic hydrocarbon solvents such as toluene and xylene, ethers such as dimethyl ether, diethyl ether, 1,4-dioxane, and tetrahydrofuran (THF), acetone, 2-butanone, methyl isobutyl ketone, and the like.
  • aromatic hydrocarbon solvents such as toluene and xylene
  • ethers such as dimethyl ether, diethyl ether, 1,4-dioxane, and tetrahydrofuran (THF)
  • THF tetrahydrofuran
  • acetone 2-butanone
  • 2-butanone methyl isobutyl ketone
  • examples thereof include ketone solvents, amide solvents such as dimethylformamide (DMF), halogen solvents such as chloroform and dichloromethane, dimethyl sulfoxide (DMSO), and the like.
  • R 8 represents an alkylene group having 2 to 4 carbon atoms
  • R 13 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a halogen atom
  • m represents an integer of 0 to 20
  • R 8 in said formula (y1-7r) and the general formula 1-7 is synonymous with R 8 in the structural moiety (Y1-3), from 1 to 6 carbon atoms of R 13
  • the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, s-butyl group, pentyl group, hexyl group, 2-ethylbutyl group, isopentyl group, 1 -A methylpentyl group, a 1,3-dimethylbutyl group and the like can be mentioned, and examples of the halogen atom include a bromine atom, a chlorine atom and a fluorine atom.
  • reaction with the epoxy compound in Step VI-7 includes, for example, mixing the intermediate compound C and the compound represented by the structural formula (y1-7r) at 0 to 150 ° C. in a reaction vessel.
  • the method of making it react is mentioned.
  • a catalyst or a solvent can also be used.
  • Examples of usable catalysts include triethylamine, diisopropylethylamine, benzyldiethylamine, imidazole, tetrabutylammonium bromide, tri-n-octylphosphine, triphenylphosphine, and the like.
  • organic solvent examples include aromatic hydrocarbon solvents such as toluene and xylene, ether solvents such as dimethyl ether, diethyl ether, 1,4-dioxane, and tetrahydrofuran (THF), acetone, 2-butanone, and methyl isobutyl ketone.
  • ketone solvents such as dimethylformamide (DMF), halogen solvents such as chloroform and dichloromethane, and dimethyl sulfoxide (DMSO).
  • R 8 is an alkylene group having 2 to 4 carbon atoms
  • R 10 is a hydrogen atom or a methyl group
  • R 14 is a hydrocarbon group having 5 to 18 carbon atoms having a p + 1 bond
  • l is 0 to (An integer of 20 and p represents an integer of 1 to 3)
  • the structural formula (y1-8r) and the general formula in 1-8 R 8 has the same meaning as R 8 in the structural moiety (Y1-3), the number of carbon atoms with a bond p + 1 in R 14 3 to 25 hydrocarbon groups are aliphatic polyhydric alcohol residues such as glycerol residue, trimethylolpropane residue, pentaerythritol residue; n-propylene group, 1,2-propylene group, n-butylene group 2-methyl-propane-1,2-diyl group, 1,5-pentanediyl group, 1,6-hexanediyl group, 1,7-heptanediyl group, 1,8-octanediyl group, 1,9-nonanediyl group 1,10-decanediyl group, 3,8-decanediyl group, 1,11-undecanediyl group, 1,12-dodecanediyl group, 1,13-
  • the residue refers to a hydrocarbon structure site excluding the hydroxyl group of the polyhydric alcohol.
  • the Michael addition reaction in (Step VI-8) can be carried out under known and usual reaction conditions.
  • the intermediate compound C and the compound represented by the structural formula (y1-8r) having a function as the Michael acceptor are mixed at 0 to 150 ° C. in a reaction vessel.
  • the method of making it react is mentioned.
  • a catalyst or a solvent can also be used.
  • Examples of usable catalysts include tetrabutylammonium hydroxide, tetramethylguanidine, diazabicycloundecene, 1,4-diazabicyclo [2.2.2], sodium tert-butylate, and the like.
  • organic solvent examples include saturated hydrocarbon solvents such as pentane, hexane, heptane and cyclohexane, aromatic hydrocarbon solvents such as toluene and xylene, methanol, ethanol, isopropanol, 2-butanol, t-butanol and ethylene.
  • Alcohol solvents such as glycol and carbitol, ether solvents such as dimethyl ether, diethyl ether, 1,4-dioxane and tetrahydrofuran (THF), amide solvents such as dimethylformamide (DMF), and halogen solvents such as chloroform and dichloromethane And dimethyl sulfoxide (DMSO).
  • the mixing ratio of the intermediate compound C and the compound represented by the structural formula (y1-8r) having a function as the Michael acceptor is not particularly limited.
  • the equivalent ratio [(i) / (ii)] of the primary amino group (i) and the (meth) acryloyl group (ii) in the compound represented by the structural formula (y1-8r) is 1/1. It is preferably 5 to 1/30.
  • the equivalent ratio [(i) / (ii)] exceeds 1 / 1.5, the possibility of migration from the coating film of the intermediate compound C or a decomposition product thereof increases, and the equivalent ratio [(i) / When (ii)] is less than 1/30, the curing performance of the Michael addition reaction product tends to be inferior.
  • the equivalent ratio [(i) / (ii)] is particularly preferably from 1/2 to 1/20.
  • examples of the compound represented by the structural formula (y1-8r) having a function as the Michael acceptor include, for example, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and tripropylene.
  • Bifunctional acrylates such as glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentylglycol di (meth) acrylate; trimethylolpropane tri ( (Meth) acrylate and its modified alkylene oxide such as ethylene oxide and propylene oxide; pentaerythritol tri or tetra (meth) acrylate and its modified alkylene oxide such as ethylene oxide and propylene oxide Ditrimethylolpropane tetra (meth) acrylate and its alkylene oxide modified products such as ethylene oxide and propylene oxide; dipentaerythritol tetra or penta or hexa (meth) acrylate and its polyfunctional (meth) acrylate such as caprolactone modified products; bisphenol A di Epoxy (meth) acrylate obtained by reaction
  • R 15 represents an alkyl group having 4 to 18 carbon atoms, an aliphatic cyclic hydrocarbon group having 6 to 10 carbon atoms, an aromatic group, or an acryloyloxyethyl group.
  • examples of the isocyanate compound represented by the structural formula (y1-9r) include alkyl isocyanates having 4 to 18 carbon atoms such as propyl isocyanate, butyl isocyanate, hexyl isocyanate, dodecyl isocyanate, octadecyl isocyanate, and the like; cyclohexyl isocyanate, Examples thereof include an isocyanate group-containing aliphatic cyclic hydrocarbon having 6 to 10 carbon atoms such as adamantyl isocyanate; and an isocyanate group-containing aromatic hydrocarbon such as phenyl isocyanate, benzyl isocyanate, phenethyl isocyanate, and toluidyl isocyanate.
  • alkyl isocyanates having 4 to 18 carbon atoms such as propyl isocyanate, butyl isocyanate, hexyl isocyanate, dodecyl isocyanate,
  • Step VI-9 the reaction between the intermediate compound C and the isocyanate compound represented by the structural formula (y1-9r) is performed, for example, by mixing both at 0 to 150 ° C. in a reaction vessel.
  • the method of making it react is mentioned, A catalyst and a solvent can also be used.
  • Examples of usable catalysts include triethylamine, diazabicycloundecene, dibutyltin dilaurate, tri-n-octylphosphine, triphenylphosphine, and the like.
  • organic solvent examples include aromatic hydrocarbon solvents such as toluene and xylene, ether solvents such as dimethyl ether, diethyl ether, 1,4-dioxane, and tetrahydrofuran (THF), acetone, 2-butanone, and methyl isobutyl ketone.
  • ketone solvents such as dimethylformamide (DMF), halogen solvents such as chloroform and dichloromethane, and dimethyl sulfoxide (DMSO).
  • the amount of the photopolymerization initiator (B) used is preferably in the range of 1 to 20 parts by mass with respect to 100 parts by mass of the acid group-containing (meth) acrylate resin (A).
  • a photoinitiator such as a photosensitizer or a tertiary amine may be used as necessary in order to further improve the curing performance.
  • the photosensitizer include thioxanthone series such as 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone, benzophenone series such as 4,4'-bis (diethylamino) benzophenone, anthraquinone and the like.
  • examples of the tertiary amine include ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, and N, N-dimethylbenzylamine.
  • a high molecular weight compound obtained by branching a plurality of photosensitizers or tertiary amines in one molecule with a polyhydric alcohol or the like can be used as appropriate.
  • the photoinitiator aid is preferably used in an amount of 0.03 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on the total amount of the photosensitive resin composition.
  • photopolymerization initiators other than the photopolymerization initiator (B) can be used in combination as long as the effects of the present invention are not impaired.
  • Examples of the other photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl]- 2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2′-dimethoxy-1,2-diphenylethane-1-one, diphenyl (2,4,6-trimethoxybenzoyl) ) Phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4 Morpholinophenyl) -1-butanone, and the like.
  • photopolymerization initiators examples include “Omnirad-1173”, “Omnirad-184”, “Omnirad-127”, “Omnirad-2959”, “Omnirad-369”, “Omnirad-379”.
  • the photosensitive resin composition of the present invention may contain other resin components other than the acid group-containing (meth) acrylate resin (A).
  • the other resin components include (meth) acrylic acid, dicarboxylic acid anhydride, and unsaturated monocarboxylic acid anhydride, if necessary, to epoxy resin such as bisphenol type epoxy resin and novolak type epoxy resin.
  • epoxy resin such as bisphenol type epoxy resin and novolak type epoxy resin.
  • examples thereof include resins having a carboxyl group and a (meth) acryloyl group in the resin, various (meth) acrylate monomers, and the like.
  • Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and 2-ethylhexyl.
  • Aliphatic mono (meth) acrylate compounds such as (meth) acrylate and octyl (meth) acrylate; alicyclic mono (meth) acrylate compounds such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate ; Heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; benzyl (meth) acrylate, phenyl (meth) acrylate, phenylben (Meth) acrylate, phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxybenzyl (meth) acrylate, benz
  • the photosensitive resin composition of the present invention may contain an organic solvent for the purpose of adjusting the coating viscosity, and the type and addition amount thereof are appropriately selected and adjusted according to the desired performance.
  • organic solvent examples include ketone solvents such as methyl ethyl ketone, acetone and isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; and aromatics such as toluene, xylene and solvent naphtha.
  • ketone solvents such as methyl ethyl ketone, acetone and isobutyl ketone
  • cyclic ether solvents such as tetrahydrofuran and dioxolane
  • ester solvents such as methyl acetate, ethyl acetate and butyl acetate
  • aromatics such as toluene, xylene and solvent naphtha.
  • Aliphatic solvents such as cyclohexane and methylcyclohexane; Alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether; alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, dialkylene glycol Examples include glycol ether solvents such as monoalkyl ether acetate. These organic solvents can be used alone or in combination of two or more.
  • the photosensitive resin composition of the present invention may contain various additives such as inorganic fine particles and polymer fine particles, pigments, antifoaming agents, viscosity modifiers, leveling agents, flame retardants, and storage stabilizers as necessary. It can also be contained.
  • the cured product of the present invention can be obtained by irradiating the photosensitive resin composition with active energy rays.
  • the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
  • irradiation may be performed in an inert gas atmosphere such as nitrogen gas or an air atmosphere in order to efficiently perform a curing reaction with ultraviolet rays.
  • an ultraviolet lamp is generally used from the viewpoint of practicality and economy. Specific examples include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, and an LED.
  • the cured product obtained by curing the photosensitive resin composition of the present invention has excellent heat resistance and is less likely to generate outgas.
  • solder resist and interlayer insulation in semiconductor device applications It can be suitably used as a package adhesive layer such as a material, a package material, an underfill material, or a circuit element, or an adhesive layer between an integrated circuit element and a circuit board. Further, it can be suitably used for a thin film transistor protective film, a liquid crystal color filter protective film, a color filter pigment resist, a black matrix resist, a spacer, etc. in thin display applications typified by LCD and OELD.
  • the resin material for a solder resist of the present invention can be applied to the photosensitive resin composition, if necessary, for example, a curing agent, a curing accelerator, an organic solvent, inorganic fine particles or polymer fine particles, a pigment, an antifoaming agent, a viscosity modifier.
  • a curing agent for example, a curing agent, a curing accelerator, an organic solvent, inorganic fine particles or polymer fine particles, a pigment, an antifoaming agent, a viscosity modifier.
  • Various additives such as a leveling agent, a flame retardant, and a storage stabilizer can be used.
  • the curing agent is not particularly limited as long as it has a functional group capable of reacting with a carboxyl group in the acid group-containing (meth) acrylate resin (A), and examples thereof include an epoxy resin.
  • the epoxy resin include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, Bisphenol novolac type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition Examples include reactive epoxy resins.
  • epoxy resins can be used alone or in combination of two or more.
  • a phenol novolac type epoxy resin a cresol novolak type epoxy resin, a bisphenol novolak type epoxy resin, a naphthol novolak type epoxy resin, a naphthol-phenol co-condensed novolak type epoxy resin
  • a novolak type epoxy resin such as a naphthol-cresol co-condensed novolak type epoxy resin is preferable, and a softening point in the range of 50 to 120 ° C. is particularly preferable.
  • the curing accelerator is to accelerate the curing reaction of the curing agent.
  • an epoxy resin for example, a phosphorus compound, a tertiary amine, imidazole, an organic acid metal salt
  • Examples include Lewis acids and amine complex salts.
  • These curing accelerators can be used alone or in combination of two or more.
  • the addition amount of the curing accelerator is preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the curing agent, for example.
  • the organic solvent is not particularly limited as long as it can dissolve various components such as the acid group-containing (meth) acrylate resin (A) and a curing agent, and examples thereof include ketone solvents such as methyl ethyl ketone, acetone, and isobutyl ketone.
  • Cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; aromatic solvents such as toluene, xylene and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; carbitol and cellosolve Alcohol solvents such as methanol, isopropanol, butanol, propylene glycol monomethyl ether; alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether acetate Such as glycol ethers solvents over bets, and the like. These organic solvents can be used alone or in combination of two or more.
  • the resist member of the present invention is, for example, a photomask in which a desired pattern is formed after applying the resin material for solder resist on a substrate and evaporating and drying an organic solvent in a temperature range of about 60 to 100 ° C. And exposed to an active energy ray, developed in an unexposed portion with an aqueous alkali solution, and further heat-cured in a temperature range of about 140 to 180 ° C.
  • the acid content-containing (meth) acrylate resin (1) had a solid content acid value of 85 mgKOH / g.
  • This acid group-containing (meth) acrylate resin (A-2) had a solid content acid value of 80 mgKOH / g.
  • a 1 L flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, an alkali trap and a dropping funnel was charged with 121.8 g of aluminum chloride (anhydrous) and 300 mL of dehydrated dichloromethane, and ice-cooled using an ice bath in a nitrogen stream. To this was added 200 g of 2-bromobutyryl bromide.
  • a mixed solution of 83.6 g of fluorobenzene and 100 mL of dehydrated dichloromethane was dropped into the previous flask using a dropping funnel over 20 minutes. After completion of dropping, the ice bath was removed and stirring was continued for 2 hours. After completion of the stirring, the reaction solution was put into 1 L of ice water and stirring was continued for 2 hours.
  • a 1000 mL flask equipped with a stirrer, a thermometer, and a dropping funnel was charged with 35.0 g of 2-chloro-4.6-dimethoxy-1,3,5-triazine and 400 mL of dehydrated dichloromethane, and ice-cooled using an ice bath. Thereto, 80.8 g of N-methylmorpholine was added dropwise using a dropping funnel over 10 minutes. After completion of dropping, 76.0 g of intermediate (104) was added and stirred for 1 hour under ice cooling. Thereto, 200 mL of dehydrated dichloromethane in which 9.5 g of piperazine was dissolved was dropped over 20 minutes using a dropping funnel. The ice bath was removed and stirring was continued for 1 hour at room temperature.
  • reaction product was transferred to a separatory funnel, and the lower organic layer was recovered. Further, after washing twice with distilled water, it was dried overnight with magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the resulting crude product was recrystallized from ethanol to obtain an intermediate (109).
  • Example 1 Preparation of photosensitive resin composition (1)
  • 100 parts by mass of the acid group-containing (meth) acrylate resin (A-1) obtained in Synthesis Example 1 100 parts by mass of the acid group-containing (meth) acrylate resin (A-1) obtained in Synthesis Example 1, 24.6 parts by mass of an orthocresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation) as a curing agent, 6.3 parts by weight of dipentaerythritol hexaacrylate, 10 parts by weight of the photopolymerization initiator (M31) obtained in Synthesis Example 3, 13.3 parts by weight of diethylene glycol monomethyl ether acetate, 0.5 parts by weight of 2-ethyl-4-methylimidazole Part and 0.7 parts by mass of phthalocyanine green were blended and kneaded by a roll mill to obtain a photosensitive resin composition (1).
  • A-1 acid group-containing (meth) acrylate resin obtained in Synthesis Example 1
  • Examples 2 and 3 Preparation of photosensitive resin compositions (2) and (3)
  • the photosensitivity was the same as in Example 1 except that the acid group-containing (meth) acrylate resin (A-1) and the photopolymerization initiator (M31) used in Example 1 were replaced with the compositions shown in Table 13. Resin compositions (2) and (3) were obtained.
  • the drying management width was 60 minutes or more.
  • X The dry management width was less than 60 minutes.
  • Table 13 shows the compositions and evaluation results of the photosensitive resin compositions (1) to (3) prepared in Examples 1 to 3 and the photosensitive resin compositions (C1) and (C2) prepared in Comparative Examples 1 and 2. Shown in
  • Example 4 Preparation of photosensitive resin composition (4)
  • 100 parts by mass of the acid group-containing (meth) acrylate resin (A-1) obtained in Synthesis Example 1, 24.6 parts by mass of an orthocresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation) as a curing agent The photosensitive resin composition (4) was obtained by blending 10 parts by mass of the photopolymerization initiator (M31) obtained in Synthesis Example 3 and 13.3 parts by mass of diethylene glycol monomethyl ether acetate.
  • Example 5 and 6 Preparation of photosensitive resin compositions (5) and (6)
  • Photosensitivity was the same as in Example 4 except that the acid group-containing (meth) acrylate resin (A-1) and photopolymerization initiator (M31) used in Example 4 were replaced with the compositions shown in Table 14. Resin compositions (5) and (6) were obtained.
  • a 6 mm ⁇ 35 mm test piece was cut out from the cured product, and a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device “RSAII” manufactured by Rheometric Co., Ltd., tension method: frequency 1 Hz, temperature rising rate 3 ° C./min) was used.
  • the temperature at which the change in elastic modulus was maximized was evaluated as the glass transition temperature. In addition, it shows that it is excellent in heat resistance, so that glass transition temperature is high.
  • Table 14 shows the compositions and evaluation results of the photosensitive resin compositions (4) to (6) prepared in Examples 4 to 6 and the photosensitive resin compositions (C3) and (C4) prepared in Comparative Examples 3 and 4. Shown in
  • the “curing agent” in Tables 13 and 14 represents an ortho-cresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation, epoxy equivalent: 214 g / equivalent).
  • Organic solvent in Tables 13 and 14 represents diethylene glycol monomethyl ether acetate.

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Abstract

Provided are: a photosensitive resin composition comprising an acid group-containing (meth)acrylate resin (A) and a photopolymerization initiator (B), characterized in that the photopolymerization initiator (B) is a compound represented by general formula (1); a cured product that is a product of a curing reaction of the photosensitive resin composition; an insulating material; a resin material for solder resists; and a resist member. The photosensitive resin composition has a high photosensitivity and is capable of forming a cured product that has an excellent heat tolerance and generates little outgas.

Description

感光性樹脂組成物、硬化物、絶縁材料、ソルダーレジスト用樹脂材料及びレジスト部材Photosensitive resin composition, cured product, insulating material, resin material for solder resist and resist member
　本発明は、アウトガスが生じにくい感光性樹脂組成物、硬化物、前記感光性樹脂組成物からなる絶縁材料、ソルダーレジスト用樹脂材料及びレジスト部材に関する。 The present invention relates to a photosensitive resin composition, a cured product, an insulating material made of the photosensitive resin composition, a resin material for solder resist, and a resist member that hardly generate outgas.
　近年、プリント配線板向けのソルダーレジスト用樹脂材料としては、紫外線等の活性エネルギー線により硬化可能な感光性樹脂組成物が広く用いられている。前記ソルダーレジスト用樹脂材料に対する要求特性としては、少ない露光量で硬化すること、アルカリ現像性に優れること、硬化物における耐熱性や強度、誘電特性等に優れることなど様々なものが挙げられる。 In recent years, photosensitive resin compositions that can be cured by active energy rays such as ultraviolet rays have been widely used as solder resist resin materials for printed wiring boards. The required properties for the solder resist resin material include various properties such as curing with a small exposure amount, excellent alkali developability, and excellent heat resistance, strength, dielectric properties, etc. in the cured product.
　従来のソルダーレジスト用樹脂材料としては、クレゾールノボラック型エポキシ樹脂とアクリル酸と無水フタル酸とを反応させて得られる中間体に、更にテトラヒドロ無水フタル酸を反応させて得られる酸基含有エポキシアクリレート樹脂を含む感光性樹脂組成物が知られているが（例えば、特許文献１参照。）、光感度や硬化物における耐熱性が十分ではなく、昨今ますます高まる要求性能を満足するものではなかった。 As a conventional resin material for a solder resist, an acid group-containing epoxy acrylate resin obtained by further reacting a tetrahydrophthalic anhydride with an intermediate obtained by reacting a cresol novolak type epoxy resin, acrylic acid and phthalic anhydride Is known (for example, refer to Patent Document 1), but the photosensitivity and heat resistance of the cured product are not sufficient, and it has not satisfied the increasingly required performance.
　また、前記感光性樹脂組成物は、光硬化時、その後必要に応じて行われる熱硬化時、または実装時のはんだ付けの際に、光重合開始剤などの含有成分が揮発してガス化し、周囲を汚染するアウトガスの問題があった。 In addition, the photosensitive resin composition is gasified by volatilizing components such as a photopolymerization initiator at the time of photocuring, then at the time of heat curing performed as necessary, or at the time of soldering at the time of mounting, There was an outgas problem that contaminated the surroundings.
　そこで、光感度及び硬化物における耐熱性に優れ、さらに、アウトガスが生じにくい感光性樹脂組成物が求められていた。 Therefore, there has been a demand for a photosensitive resin composition that is excellent in photosensitivity and heat resistance in a cured product, and that hardly causes outgassing.
特開平８－２５９６６３号公報JP-A-8-259663
　本発明が解決しようとする課題は、高い光感度及び硬化物における優れた耐熱性を有し、かつ、アウトガスが生じにくい感光性樹脂組成物、硬化物、前記感光性樹脂組成物からなる絶縁材料、ソルダーレジスト用樹脂材料及びレジスト部材を提供することである。 The problem to be solved by the present invention is a photosensitive resin composition having high photosensitivity and excellent heat resistance in a cured product, and hardly generating outgas, a cured product, and an insulating material comprising the photosensitive resin composition It is providing the resin material for solder resists, and a resist member.
　本発明者らは、上記の課題を解決すべく鋭意研究した結果、酸基含有（メタ）アクリレート樹脂と、特定の光重合開始剤とを含む感光性樹脂組成物を用いることによって、上記課題を解決できることを見出し、本発明を完成させた。 As a result of diligent research to solve the above problems, the present inventors have solved the above problems by using a photosensitive resin composition containing an acid group-containing (meth) acrylate resin and a specific photopolymerization initiator. The inventors have found that this can be solved and completed the present invention.
　すなわち、本発明は、酸基含有（メタ）アクリレート樹脂（Ａ）と、光重合開始剤（Ｂ）とを含有する感光性樹脂組成物であって、前記光重合開始剤（Ｂ）が、下記一般式（１）で表される化合物であることを特徴とする感光性樹脂組成物、硬化物、前記感光性樹脂組成物からなる絶縁材料、ソルダーレジスト用樹脂材料及びレジスト部材に関するものである。 That is, the present invention is a photosensitive resin composition containing an acid group-containing (meth) acrylate resin (A) and a photopolymerization initiator (B), wherein the photopolymerization initiator (B) is: The present invention relates to a photosensitive resin composition, a cured product, an insulating material composed of the photosensitive resin composition, a resin material for solder resist, and a resist member, which is a compound represented by the general formula (1).
Figure JPOXMLDOC01-appb-C000010
 ［一般式（１）中、
Ｒ１は炭素原子数１～１０のアルキル基を表し、
Ｒ２は炭素原子数１～１２のアルキル基、炭素原子数２～４のヒドロキシアルキル基、炭素原子数１または２のアルコキシ基で置換された炭素原子数２～４のアルキル基のいずれかを表し、
Ｒ３は炭素原子数１～１２のアルキル基、炭素原子数２～４のヒドロキシアルキル基、メトキシエチル基、またはエトキシエチル基を表し、
またＲ２とＲ３とが一体となって窒素原子と共に環構造を形成するアルキレン基、Ｒ２とＲ３とが一体となって窒素原子と共にモルホリン骨格、Ｎ－メチルピペラジン骨格、または２，６－ジメチルモルホリン骨格を形成する環構形成部位であってもよく、
Ｒ４～Ｒ７は、それぞれ独立して水素原子、炭素原子数１～８のアルキル基、またはフェニル基を表し、
Ｙ１は、置換基を有しないか、またはハロゲン原子若しくは水酸基を置換基として有する炭素原子数３～１９のアルキル基（ｙ１－１）、炭素原子数７～１９のアラルキル基（ｙ１－２）、または下記構造式（ｙ１－３）で表される構造部位（ｙ１－３）、
Figure JPOXMLDOC01-appb-C000010
 [In general formula (1),
R 1 represents an alkyl group having 1 to 10 carbon atoms,
R 2 represents any of an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, and an alkyl group having 2 to 4 carbon atoms substituted by an alkoxy group having 1 or 2 carbon atoms. Represent,
R 3 represents an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, a methoxyethyl group, or an ethoxyethyl group,
R 2 and R 3 together form an alkylene group with a nitrogen atom to form a ring structure, R 2 and R 3 together form a nitrogen atom with a morpholine skeleton, N-methylpiperazine skeleton, or 2,6 -It may be a ring formation site forming a dimethylmorpholine skeleton,
R 4 to R 7 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group,
Y 1 is an alkyl group having 3 to 19 carbon atoms (y1-1) having no substituent, or having a halogen atom or a hydroxyl group as a substituent, aralkyl group having 7 to 19 carbon atoms (y1-2) Or a structural moiety (y1-3) represented by the following structural formula (y1-3),
Figure JPOXMLDOC01-appb-C000011
 （式中、Ｒ８は炭素原子数２～４のアルキレン基、Ｒ９は水素原子又はフェニル基又は炭素原子数１～４のアルキル基、ｍは０～２０の整数を表す。）
Figure JPOXMLDOC01-appb-C000011
 (Wherein R 8 represents an alkylene group having 2 to 4 carbon atoms, R 9 represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 0 to 20)
　下記構造式（ｙ１－４）で表される構造部位（ｙ１－４）、 A structural portion (y1-4) represented by the following structural formula (y1-4),
Figure JPOXMLDOC01-appb-C000012
 （式中、Ｒ８は炭素原子数２～４のアルキレン基、Ｒ９は水素原子、フェニル基、又は炭素数１～４のアルキル基、Ｒ１０は水素原子またはメチル基、ｍは０～２０の整数を表す。）
Figure JPOXMLDOC01-appb-C000012
 (Wherein R 8 is an alkylene group having 2 to 4 carbon atoms, R 9 is a hydrogen atom, a phenyl group, or an alkyl group having 1 to 4 carbon atoms, R 10 is a hydrogen atom or a methyl group, and m is 0 to 20) Represents an integer.)
　下記構造式（ｙ１－５）で表される構造部位（ｙ１－５）、 Structural part (y1-5) represented by the following structural formula (y1-5),
Figure JPOXMLDOC01-appb-C000013
 （式中、Ｒ１０は水素原子またはメチル基、Ｒ１１は炭素原子数１～１８のアルキル基又は炭素原子数６～１８のアリール基を表す。）
Figure JPOXMLDOC01-appb-C000013
 (Wherein R 10 represents a hydrogen atom or a methyl group, and R 11 represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms.)
　下記構造式（ｙ１－６）で表される構造部位（ｙ１－６）、 Structural part (y1-6) represented by the following structural formula (y1-6),
Figure JPOXMLDOC01-appb-C000014
 （式中、Ｒ１２は炭素原子数１～１８のアルキル基を表す。）
Figure JPOXMLDOC01-appb-C000014
 (In the formula, R 12 represents an alkyl group having 1 to 18 carbon atoms.)
　下記構造式（ｙ１－７）で表される構造部位（ｙ１－７）、 A structural portion (y1-7) represented by the following structural formula (y1-7),
Figure JPOXMLDOC01-appb-C000015
 （式中、Ｒ８は炭素原子数２～４のアルキレン基、Ｒ１３は水素原子、炭素原子数１～６のアルキル基又はハロゲン原子、ｍは０～２０の整数を表す。）
Figure JPOXMLDOC01-appb-C000015
 (Wherein R 8 represents an alkylene group having 2 to 4 carbon atoms, R 13 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a halogen atom, and m represents an integer of 0 to 20)
　下記構造式（ｙ１－８）で表される構造部位（ｙ１－８）、 Structural part (y1-8) represented by the following structural formula (y1-8),
Figure JPOXMLDOC01-appb-C000016
 （式中、Ｒ８はそれぞれ独立して炭素原子数２～４のアルキレン基、Ｒ１０は水素原子又はメチル基、Ｒ１４はｐ＋１の結合手を持つ炭素原子数３～２５の炭化水素基、ｌは０～２０の整数、ｐは１～３の整数を表す。）
Figure JPOXMLDOC01-appb-C000016
 (Wherein R 8 is independently an alkylene group having 2 to 4 carbon atoms, R 10 is a hydrogen atom or a methyl group, R 14 is a hydrocarbon group having 3 to 25 carbon atoms having a p + 1 bond, l represents an integer of 0 to 20, and p represents an integer of 1 to 3.)
　下記構造式（ｙ１－９）を表し、 Represents the following structural formula (y1-9)
Figure JPOXMLDOC01-appb-C000017
 （式中、Ｒ１５は炭素原子数４～１８のアルキル基、炭素原子数６～１０の脂肪族環状炭化水素基、芳香族基を表す。）
Figure JPOXMLDOC01-appb-C000017
 (Wherein R 15 represents an alkyl group having 4 to 18 carbon atoms, an aliphatic cyclic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic group.)
　Ｘ１はエチレン基、１，３－プロピレン基、１，２－プロピレン基、２，３－プロピレン基を、Ｘ２は水素原子又はメチル基を、Ｘ３は水素原子、メチル基、又はエチル基を、或いは、Ｘ２及びＸ３が破線部にて共有結合を形成しつつ一体的にエチレン基、１，３－プロピレン基、１，２－プロピレン基、２，３－プロピレン基を、或いは、Ｘ１、Ｘ２、及びＸ３が、一体的に下記構造式（Ｘ－１）で表される、窒素原子と共にビシクロ環を構成する４価の脂肪族炭化水素基を表し、 X 1 represents an ethylene group, 1,3-propylene group, 1,2-propylene group, 2,3-propylene group, X 2 represents a hydrogen atom or a methyl group, and X 3 represents a hydrogen atom, a methyl group, or an ethyl group. Or X 2 and X 3 form a covalent bond at the broken line part, and integrally form an ethylene group, a 1,3-propylene group, a 1,2-propylene group, a 2,3-propylene group, or X 1 , X 2 , and X 3 each represent a tetravalent aliphatic hydrocarbon group that together with the nitrogen atom forms a bicyclo ring, which is represented by the following structural formula (X-1);
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　Ｙ２は、その構造部位末端に窒素原子又は酸素原子を有する、（ｎ＋１）の結合手を持つ有機結節基を表し、Ｙ３は、単結合、炭素原子数１～３のアルキレン基、又は炭素原子数１～３のアルキリデン基を表し、かつ、ｎは１～３の整数を表す。］ Y 2 represents an organic nodule group having a (n + 1) bond having a nitrogen atom or an oxygen atom at the end of the structural site, Y 3 represents a single bond, an alkylene group having 1 to 3 carbon atoms, or carbon It represents an alkylidene group having 1 to 3 atoms, and n represents an integer of 1 to 3. ]
　本発明の感光性樹脂組成物は、高い光感度及び硬化物における優れた耐熱性を有しており、また、アウトガスが生じにくいことから、絶縁材料、ソルダーレジスト用樹脂材料、及び前記ソルダーレジスト用樹脂からなるレジスト部材に好適に用いることができる。 The photosensitive resin composition of the present invention has high photosensitivity and excellent heat resistance in a cured product, and since it is difficult for outgas to occur, an insulating material, a resin material for solder resist, and the solder resist It can use suitably for the resist member which consists of resin.
　本発明の感光性樹脂組成物は、酸基含有（メタ）アクリレート樹脂（Ａ）と、下記一般式（１）で表される光重合性開始剤（Ｂ）とを含有することを特徴とする。 The photosensitive resin composition of the present invention contains an acid group-containing (meth) acrylate resin (A) and a photopolymerizable initiator (B) represented by the following general formula (1). .
Figure JPOXMLDOC01-appb-C000019
 ［一般式（１）中、
Ｒ１は炭素原子数１～１０のアルキル基を表し、
Ｒ２は炭素原子数１～１２のアルキル基、炭素原子数２～４のヒドロキシアルキル基、炭素原子数１または２のアルコキシ基で置換された炭素原子数２～４のアルキル基のいずれかを表し、
Ｒ３は炭素原子数１～１２のアルキル基、炭素原子数２～４のヒドロキシアルキル基、メトキシエチル基、またはエトキシエチル基を表し、
またＲ２とＲ３とが一体となって窒素原子と共に環構造を形成するアルキレン基、Ｒ２とＲ３とが一体となって窒素原子と共にモルホリン骨格、Ｎ－メチルピペラジン骨格、または２，６－ジメチルモルホリン骨格を形成する環構形成部位であってもよく、
Ｒ４～Ｒ７は、それぞれ独立して水素原子、炭素原子数１～８のアルキル基、またはフェニル基を表し、
Ｙ１は、置換基を有しないか、またはハロゲン原子若しくは水酸基を置換基として有する炭素原子数３～１９のアルキル基（ｙ１－１）、炭素原子数７～１９のアラルキル基（ｙ１－２）、または下記構造式（ｙ１－３）で表される構造部位（ｙ１－３）、
Figure JPOXMLDOC01-appb-C000019
 [In general formula (1),
R 1 represents an alkyl group having 1 to 10 carbon atoms,
R 2 represents any of an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, and an alkyl group having 2 to 4 carbon atoms substituted by an alkoxy group having 1 or 2 carbon atoms. Represent,
R 3 represents an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, a methoxyethyl group, or an ethoxyethyl group,
R 2 and R 3 together form an alkylene group with a nitrogen atom to form a ring structure, R 2 and R 3 together form a nitrogen atom with a morpholine skeleton, N-methylpiperazine skeleton, or 2,6 -It may be a ring formation site forming a dimethylmorpholine skeleton,
R 4 to R 7 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group,
Y 1 is an alkyl group having 3 to 19 carbon atoms (y1-1) having no substituent, or having a halogen atom or a hydroxyl group as a substituent, aralkyl group having 7 to 19 carbon atoms (y1-2) Or a structural moiety (y1-3) represented by the following structural formula (y1-3),
Figure JPOXMLDOC01-appb-C000020
 （式中、Ｒ８は炭素原子数２～４のアルキレン基、Ｒ９は水素原子又はフェニル基又は炭素原子数１～４のアルキル基、ｍは０～２０の整数を表す。）
Figure JPOXMLDOC01-appb-C000020
 (Wherein R 8 represents an alkylene group having 2 to 4 carbon atoms, R 9 represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 0 to 20)
　下記構造式（ｙ１－４）で表される構造部位（ｙ１－４）、 A structural portion (y1-4) represented by the following structural formula (y1-4),
Figure JPOXMLDOC01-appb-C000021
 （式中、Ｒ８は炭素原子数２～４のアルキレン基、Ｒ９は水素原子、フェニル基、又は炭素数１～４のアルキル基、Ｒ１０は水素原子またはメチル基、ｍは０～２０の整数を表す。）
Figure JPOXMLDOC01-appb-C000021
 (Wherein R 8 is an alkylene group having 2 to 4 carbon atoms, R 9 is a hydrogen atom, a phenyl group, or an alkyl group having 1 to 4 carbon atoms, R 10 is a hydrogen atom or a methyl group, and m is 0 to 20) Represents an integer.)
　下記構造式（ｙ１－５）で表される構造部位（ｙ１－５）、 Structural part (y1-5) represented by the following structural formula (y1-5),
Figure JPOXMLDOC01-appb-C000022
 （式中、Ｒ１０は水素原子またはメチル基、Ｒ１１は炭素原子数１～１８のアルキル基又は炭素原子数６～１８のアリール基を表す。）
Figure JPOXMLDOC01-appb-C000022
 (Wherein R 10 represents a hydrogen atom or a methyl group, and R 11 represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms.)
　下記構造式（ｙ１－６）で表される構造部位（ｙ１－６）、 Structural part (y1-6) represented by the following structural formula (y1-6),
Figure JPOXMLDOC01-appb-C000023
 （式中、Ｒ１２は炭素原子数１～１８のアルキル基を表す。）
Figure JPOXMLDOC01-appb-C000023
 (In the formula, R 12 represents an alkyl group having 1 to 18 carbon atoms.)
　下記構造式（ｙ１－７）で表される構造部位（ｙ１－７）、 A structural portion (y1-7) represented by the following structural formula (y1-7),
Figure JPOXMLDOC01-appb-C000024
 （式中、Ｒ８は炭素原子数２～４のアルキレン基、Ｒ１３は水素原子、炭素原子数１～６のアルキル基又はハロゲン原子、ｍは０～２０の整数を表す。）
Figure JPOXMLDOC01-appb-C000024
 (Wherein R 8 represents an alkylene group having 2 to 4 carbon atoms, R 13 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a halogen atom, and m represents an integer of 0 to 20)
　下記構造式（ｙ１－８）で表される構造部位（ｙ１－８）、 Structural part (y1-8) represented by the following structural formula (y1-8),
Figure JPOXMLDOC01-appb-C000025
 （式中、Ｒ８はそれぞれ独立して炭素原子数２～４のアルキレン基、Ｒ１０は水素原子又はメチル基、Ｒ１４はｐ＋１の結合手を持つ炭素原子数３～２５の炭化水素基、ｌは０～２０の整数、ｐは１～３の整数を表す。）
Figure JPOXMLDOC01-appb-C000025
 (Wherein R 8 is independently an alkylene group having 2 to 4 carbon atoms, R 10 is a hydrogen atom or a methyl group, R 14 is a hydrocarbon group having 3 to 25 carbon atoms having a p + 1 bond, l represents an integer of 0 to 20, and p represents an integer of 1 to 3.)
　下記構造式（ｙ１－９）を表し、 Represents the following structural formula (y1-9)
Figure JPOXMLDOC01-appb-C000026
 （式中、Ｒ１５は炭素原子数４～１８のアルキル基、炭素原子数６～１０の脂肪族環状炭化水素基、芳香族基を表す。）
Figure JPOXMLDOC01-appb-C000026
 (Wherein R 15 represents an alkyl group having 4 to 18 carbon atoms, an aliphatic cyclic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic group.)
　Ｘ１はエチレン基、１，３－プロピレン基、１，２－プロピレン基、２，３－プロピレン基を、Ｘ２は水素原子又はメチル基を、Ｘ３は水素原子、メチル基、又はエチル基を、或いは、Ｘ２及びＸ３が破線部にて共有結合を形成しつつ一体的にエチレン基、１，３－プロピレン基、１，２－プロピレン基、２，３－プロピレン基を、或いは、Ｘ１、Ｘ２、及びＸ３が、一体的に下記構造式（Ｘ－１）で表される、窒素原子と共にビシクロ環を構成する４価の脂肪族炭化水素基を表し、 X 1 represents an ethylene group, 1,3-propylene group, 1,2-propylene group, 2,3-propylene group, X 2 represents a hydrogen atom or a methyl group, and X 3 represents a hydrogen atom, a methyl group, or an ethyl group. Or X 2 and X 3 form a covalent bond at the broken line part, and integrally form an ethylene group, a 1,3-propylene group, a 1,2-propylene group, a 2,3-propylene group, or X 1 , X 2 , and X 3 each represent a tetravalent aliphatic hydrocarbon group that together with the nitrogen atom forms a bicyclo ring, which is represented by the following structural formula (X-1);
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　Ｙ２は、その構造部位末端に窒素原子又は酸素原子を有する、（ｎ＋１）の結合手を持つ有機結節基を表し、Ｙ３は、単結合、炭素原子数１～３のアルキレン基、又は炭素原子数１～３のアルキリデン基を表し、かつ、ｎは１～３の整数を表す。］ Y 2 represents an organic nodule group having a (n + 1) bond having a nitrogen atom or an oxygen atom at the end of the structural site, Y 3 represents a single bond, an alkylene group having 1 to 3 carbon atoms, or carbon It represents an alkylidene group having 1 to 3 atoms, and n represents an integer of 1 to 3. ]
　なお、本発明において、「（メタ）アクリレート樹脂」とは、分子中にアクリロイル基及びメタクリロイル基の一方または両方を有する樹脂のことをいう。また、「（メタ）アクリロイル基」とは、アクリロイル基及びメタクリロイル基の一方または両方のことをいい、「（メタ）アクリレート」とは、アクリレート及びメタクリレートの一方また両方をいう。 In the present invention, “(meth) acrylate resin” refers to a resin having one or both of an acryloyl group and a methacryloyl group in the molecule. Further, “(meth) acryloyl group” means one or both of acryloyl group and methacryloyl group, and “(meth) acrylate” means one or both of acrylate and methacrylate.
　前記酸基含有（メタ）アクリレート樹脂（Ａ）について説明する。 The acid group-containing (meth) acrylate resin (A) will be described.
　前記酸基含有（メタ）アクリレート樹脂（Ａ）としては、酸基及び（メタ）アクリロイル基を有していればよく、その他の具体構造や分子量等は特に問われず、多種多様な樹脂を用いることができる。 The acid group-containing (meth) acrylate resin (A) only needs to have an acid group and a (meth) acryloyl group, and other specific structures and molecular weights are not particularly limited, and a wide variety of resins are used. Can do.
　前記酸基含有（メタ）アクリレート樹脂（Ａ）が含有する酸基としては、例えば、カルボキシル基、スルホン酸基、燐酸基等が挙げられる。これらの中でも優れたアルカリ現像性を発現することから、カルボキシル基が好ましい。 Examples of the acid group contained in the acid group-containing (meth) acrylate resin (A) include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, a carboxyl group is preferable because it exhibits excellent alkali developability.
　前記酸基含有（メタ）アクリレート樹脂（Ａ）としては、例えば、〔１〕エポキシ樹脂（ａ１－１）と、不飽和モノカルボン酸（ａ１－２）と、ポリカルボン酸無水物（ａ１－３）とを必須の反応原料とする酸基含有（メタ）アクリレート樹脂（Ａ－１）、〔２〕フェノール性水酸基含有樹脂（ａ２－１）と、環状カーボネート化合物（ａ２－２ａ）または環状エーテル化合物（ａ２－２ｂ）と、不飽和モノカルボン酸（ａ２－３ａ）及び／またはＮ－アルコキシアルキル（メタ）アクリルアミド化合物（ａ２－３ｂ）と、ポリカルボン酸無水物（ａ２－４）とを必須の反応原料とする酸基含有（メタ）アクリレート樹脂（Ａ－２）、〔３〕酸基または酸無水物基を有するアミドイミド樹脂（ａ３－１）と、水酸基含有（メタ）アクリレート化合物（ａ３－２）と、（メタ）アクリロイル基含有エポキシ化合物（ａ３－３）と、ポリカルボン酸無水物（ａ３－４）とを必須の反応原料とする酸基含有（メタ）アクリレート樹脂（Ａ－３）等が挙げられる。 Examples of the acid group-containing (meth) acrylate resin (A) include [1] epoxy resin (a1-1), unsaturated monocarboxylic acid (a1-2), and polycarboxylic acid anhydride (a1-3). ) And (2) a phenolic hydroxyl group-containing resin (a2-1) and a cyclic carbonate compound (a2-2a) or a cyclic ether compound. (A2-2b), an unsaturated monocarboxylic acid (a2-3a) and / or an N-alkoxyalkyl (meth) acrylamide compound (a2-3b), and a polycarboxylic acid anhydride (a2-4) are essential. Acid group-containing (meth) acrylate resin (A-2), [3] Amidoimide resin (a3-1) having acid group or acid anhydride group, and hydroxyl group-containing (meth) acrylate Acid group-containing (meth) acrylate resin comprising compound (a3-2), (meth) acryloyl group-containing epoxy compound (a3-3), and polycarboxylic acid anhydride (a3-4) as essential reaction materials ( A-3) and the like.
　〔１〕酸基含有（メタ）アクリレート樹脂（Ａ－１）について説明する。 [1] The acid group-containing (meth) acrylate resin (A-1) will be described.
　前記酸基含有（メタ）アクリレート樹脂（Ａ－１）は、エポキシ樹脂（ａ１－１）と、不飽和モノカルボン酸（ａ１－２）と、ポリカルボン酸無水物（ａ１－３）とを必須の反応原料として得られるものである。 The acid group-containing (meth) acrylate resin (A-1) essentially comprises an epoxy resin (a1-1), an unsaturated monocarboxylic acid (a1-2), and a polycarboxylic acid anhydride (a1-3). Obtained as a reaction raw material.
　前記エポキシ樹脂（ａ１－１）としては、樹脂中に複数のエポキシ基を有しているものであれば、その具体構造は特に限定されない。 The specific structure of the epoxy resin (a1-1) is not particularly limited as long as it has a plurality of epoxy groups in the resin.
　前記エポキシ樹脂（ａ１－１）としては、例えば、ビスフェノール型エポキシ樹脂、水添ビスフェノール型エポキシ樹脂、ビフェノール型エポキシ樹脂、水添ビフェノール型エポキシ樹脂、フェニレンエーテル型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールノボラック型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ジシクロペンタジエン－フェノール付加反応型エポキシ樹脂等が挙げられる。 Examples of the epoxy resin (a1-1) include bisphenol type epoxy resins, hydrogenated bisphenol type epoxy resins, biphenol type epoxy resins, hydrogenated biphenol type epoxy resins, phenylene ether type epoxy resins, naphthylene ether type epoxy resins, Phenol novolac type epoxy resin, cresol novolak type epoxy resin, bisphenol novolak type epoxy resin, naphthol novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, etc. .
　前記不飽和モノカルボン酸（ａ１－２）とは、一分子中に（メタ）アクリロイル基とカルボキシル基とを有する化合物をいい、例えば、アクリル酸、メタクリル酸等が挙げられる。また、前記不飽和モノカルボン酸（ａ１－２）のエステル化物、酸ハロゲン化物、酸無水物等も用いることができる。これらの不飽和モノカルボン酸（ａ１－２）は、単独で用いることも２種以上を併用することもできる。 The unsaturated monocarboxylic acid (a1-2) refers to a compound having a (meth) acryloyl group and a carboxyl group in one molecule, and examples thereof include acrylic acid and methacrylic acid. Further, esterified products, acid halides, acid anhydrides and the like of the unsaturated monocarboxylic acid (a1-2) can also be used. These unsaturated monocarboxylic acids (a1-2) can be used alone or in combination of two or more.
　前記不飽和モノカルボン酸（ａ１－２）のエステル化物としては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓｅｃ－ブチル、（メタ）アクリル酸ｔｅｒｔ－ブチル、（メタ）アクリル酸２－エチルヘキシル等の（メタ）アクリル酸アルキルエステル化合物；（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチル等の水酸基含有（メタ）アクリル酸エステル化合物；（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸ジエチルアミノエチル等の窒素含有（メタ）アクリル酸エステル化合物；（メタ）アクリル酸グリシジル、（メタ）アクリル酸テトラヒドロフルフリル、（メタ）アクリル酸モルホリル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸シクロへキシル等のその他（メタ）アクリル酸エステル化合物などが挙げられる。 Examples of the esterified product of the unsaturated monocarboxylic acid (a1-2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, ( (Meth) acrylic acid alkyl esters such as n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Compound; Hydroxyl group-containing (meth) acrylate compound such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate; dimethylaminoethyl (meth) acrylate, (meth) acrylic Nitrogen-containing (meth) acrylic acid ester such as diethylaminoethyl acid Other compounds (meth) acrylates such as glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, morpholyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate Compound etc. are mentioned.
　前記不飽和モノカルボン酸（ａ１－２）の酸ハロゲン化物としては、例えば、（メタ）アクリル酸クロライド等が挙げられる。 Examples of the acid halide of the unsaturated monocarboxylic acid (a1-2) include (meth) acrylic acid chloride.
　前記不飽和モノカルボン酸（ｂ１－３）の酸無水物としては、例えば、（メタ）アクリル酸無水物等が挙げられる。 Examples of the acid anhydride of the unsaturated monocarboxylic acid (b1-3) include (meth) acrylic acid anhydride.
　前記ポリカルボン酸無水物（ａ１－３）は、一分子中に２つ以上のカルボキシル基を有する化合物の酸無水物であれば、いずれのものも用いることができる。前記ポリカルボン酸無水物としては、例えば、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、マレイン酸、フマル酸、フタル酸、イソフタル酸、テレフタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、メチルヘキサヒドロフタル酸等のジカルボン酸化合物の酸無水物などが挙げられる。 As the polycarboxylic acid anhydride (a1-3), any acid anhydride of a compound having two or more carboxyl groups in one molecule can be used. Examples of the polycarboxylic acid anhydride include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, Examples thereof include acid anhydrides of dicarboxylic acid compounds such as terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and methylhexahydrophthalic acid.
　前記酸基含有（メタ）アクリレート樹脂（Ａ－１）の製造方法は、前記エポキシ樹脂（ａ１－１）、前記不飽和モノカルボン酸（ａ１－２）、及び前記ポリカルボン酸無水物（ａ１－３）を必須の反応原料とするものであれば特に限定されず、どのような方法にて製造してもよい。例えば、反応原料の全てを一括で反応させる方法で製造してもよいし、反応原料を順次反応させる方法で製造してもよい。なかでも、反応の制御が容易であることから、先にエポキシ樹脂（ａ１－１）と不飽和モノカルボン酸（ａ１－２）とを反応させ、次いで、ポリカルボン酸無水物（ａ１－３）を反応させる方法が好ましい。該反応は、例えば、エポキシ樹脂（ａ１－１）と不飽和モノカルボン酸（ａ１－２）とをエステル化反応触媒の存在下、１００～１５０℃の温度範囲で反応させた後、反応系中にポリカルボン酸無水物（ａ１－３）を加え、９０～１２０℃の温度範囲で反応させる方法等により行うことができる。 The method for producing the acid group-containing (meth) acrylate resin (A-1) includes the epoxy resin (a1-1), the unsaturated monocarboxylic acid (a1-2), and the polycarboxylic acid anhydride (a1- The method is not particularly limited as long as 3) is an essential reaction raw material, and any method may be used. For example, it may be produced by a method in which all of the reaction raw materials are reacted together, or may be produced by a method in which the reaction raw materials are reacted sequentially. Among these, since the reaction is easily controlled, the epoxy resin (a1-1) and the unsaturated monocarboxylic acid (a1-2) are first reacted, and then the polycarboxylic acid anhydride (a1-3) The method of reacting is preferred. The reaction is carried out, for example, by reacting an epoxy resin (a1-1) and an unsaturated monocarboxylic acid (a1-2) in the temperature range of 100 to 150 ° C. in the presence of an esterification reaction catalyst. The polycarboxylic acid anhydride (a1-3) can be added to the mixture and reacted at a temperature range of 90 to 120 ° C.
　前記エポキシ樹脂（ａ１－１）と不飽和モノカルボン酸（ａ１－２）との反応割合は、エポキシ樹脂（ａ１－１）中のエポキシ基１モルに対し、不飽和モノカルボン酸（ａ１－２）を０．９～１．１モルの範囲で用いることが好ましい。また、前記ポリカルボン酸無水物（ａ１－３）の反応割合は、エポキシ樹脂（ａ１－１）中のエポキシ基１モルに対し、０．２～１．０モルの範囲で用いることが好ましい。 The reaction ratio of the epoxy resin (a1-1) to the unsaturated monocarboxylic acid (a1-2) is the amount of the unsaturated monocarboxylic acid (a1-2) relative to 1 mol of the epoxy group in the epoxy resin (a1-1). ) Is preferably used in the range of 0.9 to 1.1 mol. The reaction rate of the polycarboxylic acid anhydride (a1-3) is preferably in the range of 0.2 to 1.0 mol with respect to 1 mol of the epoxy group in the epoxy resin (a1-1).
　前記エステル化反応触媒としては、例えば、トリメチルホスフィン、トリブチルホスフィン、トリフェニルホスフィン等のリン化合物、トリエチルアミン、トリブチルアミン、ジメチルベンジルアミン等のアミン化合物、２－メチルイミダゾール、２－ヘプタデシルイミダゾール、２－エチル－４－メチルイミダゾール、１－ベンジル－２－メチルイミダゾール、１－イソブチル－２－メチルイミダゾール等のイミダゾール化合物などが挙げられる。これらの反応触媒は、単独で用いることも２種以上を併用することもできる。 Examples of the esterification reaction catalyst include phosphorus compounds such as trimethylphosphine, tributylphosphine and triphenylphosphine, amine compounds such as triethylamine, tributylamine and dimethylbenzylamine, 2-methylimidazole, 2-heptadecylimidazole, 2- Examples thereof include imidazole compounds such as ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole and 1-isobutyl-2-methylimidazole. These reaction catalysts can be used alone or in combination of two or more.
　前記反応触媒の添加量は、反応原料の合計１００質量部に対して０．００１～５質量部の範囲が好ましい。 The amount of the reaction catalyst added is preferably in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the total reaction raw material.
　前記エポキシ樹脂（ａ１－１）、前記不飽和モノカルボン酸（ａ１－２）、及び前記ポリカルボン酸無水物（ａ１－３）の反応は、必要に応じて有機溶媒中で行うこともできる。用いる有機溶媒の選択は、反応原料及び生成物である酸基含有（メタ）アクリレート樹脂の溶解性や、反応温度条件により適宜選択し得るが、例えば、メチルエチルケトン、アセトン、ジメチルホルムアミド、メチルイソブチルケトン、メトキシプロパノール、シクロヘキサノン、メチルセロソルブ、ジアルキレングリコールモノアルキルエーテルアセテート、ジアルキレングリコールアセテート等が挙げられる。これらの有機溶媒は、単独で用いることも、２種以上を併用し混合溶媒として用いることもできる。 The reaction of the epoxy resin (a1-1), the unsaturated monocarboxylic acid (a1-2), and the polycarboxylic acid anhydride (a1-3) can be performed in an organic solvent as necessary. The organic solvent to be used can be appropriately selected depending on the solubility of the acid group-containing (meth) acrylate resin that is the reaction raw material and the product and the reaction temperature conditions. For example, methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, Examples include methoxypropanol, cyclohexanone, methyl cellosolve, dialkylene glycol monoalkyl ether acetate, dialkylene glycol acetate and the like. These organic solvents can be used alone or in combination of two or more as a mixed solvent.
　前記有機溶媒の使用量は、反応効率が良好となることから、反応原料の合計１００質量部に対して１０～５００質量部の範囲が好ましい。 The amount of the organic solvent used is preferably in the range of 10 to 500 parts by mass with respect to a total of 100 parts by mass of the reaction raw materials because the reaction efficiency is good.
　本発明に用いる酸基含有（メタ）アクリレート樹脂（Ａ－１）の酸価は、高い光感度を有し、耐熱性に優れた硬化物を形成可能な酸基含有（メタ）アクリレート樹脂組成物が得られることから、３０～１５０ｍｇＫＯＨ／ｇの範囲が好ましく、４０～１００ｍｇＫＯＨ／ｇの範囲がより好ましい。なお、本願発明において酸基含有（メタ）アクリレート樹脂の酸価は、ＪＩＳ　Ｋ　００７０（１９９２）の中和滴定法にて測定される値である。 The acid value of the acid group-containing (meth) acrylate resin (A-1) used in the present invention has a high photosensitivity and an acid group-containing (meth) acrylate resin composition capable of forming a cured product having excellent heat resistance Is preferably in the range of 30 to 150 mgKOH / g, more preferably in the range of 40 to 100 mgKOH / g. In the present invention, the acid value of the acid group-containing (meth) acrylate resin is a value measured by a neutralization titration method of JIS K 0070 (1992).
　次に、〔２〕酸基含有（メタ）アクリレート樹脂（Ａ－２）について説明する。 Next, [2] acid group-containing (meth) acrylate resin (A-2) will be described.
　前記酸基含有（メタ）アクリレート樹脂（Ａ－２）は、フェノール性水酸基含有樹脂（ａ２－１）と、環状カーボネート化合物（ａ２－２ａ）または環状エーテル化合物（ａ２－２ｂ）と、不飽和モノカルボン酸（ａ２－３ａ）及び／またはＮ－アルコキシアルキル（メタ）アクリルアミド化合物（ａ２－３ｂ）と、ポリカルボン酸無水物（ａ２－４）とを必須の反応原料として得られるものである。 The acid group-containing (meth) acrylate resin (A-2) includes a phenolic hydroxyl group-containing resin (a2-1), a cyclic carbonate compound (a2-2a) or a cyclic ether compound (a2-2b), The carboxylic acid (a2-3a) and / or the N-alkoxyalkyl (meth) acrylamide compound (a2-3b) and the polycarboxylic acid anhydride (a2-4) are obtained as essential reaction materials.
　前記フェノール性水酸基含有樹脂（ａ２－１）とは、分子内にフェノール性水酸基を２つ以上有する樹脂をいい、例えば、芳香族ポリヒドロキシ化合物や、分子内にフェノール性水酸基を１つ有する化合物の１種または２種以上を反応原料とするノボラック型フェノール樹脂や、前記フェノール性水酸基を１つ有する化合物と下記構造式（ｘ－１）～（ｘ－５）の何れかで表される化合物（ｘ）とを必須の反応原料とする反応生成物等が挙げられる。 The phenolic hydroxyl group-containing resin (a2-1) refers to a resin having two or more phenolic hydroxyl groups in the molecule, such as an aromatic polyhydroxy compound or a compound having one phenolic hydroxyl group in the molecule. A novolak-type phenol resin using one or more kinds as a reaction raw material, a compound having one phenolic hydroxyl group, and a compound represented by any of the following structural formulas (x-1) to (x-5) ( and reaction products using x) as an essential reaction raw material.
Figure JPOXMLDOC01-appb-C000028
 （式中ｈは、０または１である。Ｒ１は、それぞれ独立に脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アリールオキシ基、アラルキル基の何れかであり、ｉは、０または１～４の整数である。Ｚは、ビニル基、ハロメチル基、ヒドロキシメチル基、アルキルオキシメチル基の何れかである。Ｙは、炭素原子数１～４のアルキレン基、酸素原子、硫黄原子、カルボニル基の何れかである。ｊは１～４の整数である。）
Figure JPOXMLDOC01-appb-C000028
 (In the formula, h is 0 or 1. R 1 is each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, or an aralkyl group, and i is 0. Or an integer of 1 to 4. Z is a vinyl group, a halomethyl group, a hydroxymethyl group, or an alkyloxymethyl group, and Y is an alkylene group having 1 to 4 carbon atoms, an oxygen atom, or a sulfur atom. Or carbonyl group, j is an integer of 1 to 4.)
　前記芳香族ポリヒドロキシ化合物としては、例えば、ジヒドロキシベンゼン、トリヒドロキシベンゼン、テトラヒドロキシベンゼン、ジヒドロキシナフタレン、トリヒドロキシナフタレン、テトラヒドロキシナフタレン、ジヒドロキシアントラセン、トリヒドロキシアントラセン、テトラヒドロキシアントラセン、ビフェノール、テトラヒドロキシビフェニル、ビスフェノール等の他、これらの芳香核上に１つまたは複数の置換基を有する化合物などが挙げられる。また、芳香核上の置換基としては、例えば、メチル基、エチル基、ビニル基、プロピル基、ブチル基、ペンチル基、へキシル基、シクロへキシル基、ヘプチル基、オクチル基、ノニル基等の脂肪族炭化水素基；メトキシ基、エトキシ基、プロピルオキシ基、ブトキシ基等のアルコキシ基；フッ素原子、塩素原子、臭素原子等のハロゲン原子；フェニル基、ナフチル基、アントリル基、及びこれらの芳香核上に前記脂肪族炭化水素基、前記アルコキシ基、前記ハロゲン原子等が置換したアリール基；フェニルオキシ基、ナフチルオキシ基、及びこれらの芳香核上に前記脂肪族炭化水素基、前記アルコキシ基、前記ハロゲン原子等が置換したアリールオキシ基；フェニルメチル基、フェニルエチル基、ナフチルメチル基、ナフチルエチル基、及びこれらの芳香核上に前記脂肪族炭化水素基、前記アルコキシ基、前記ハロゲン原子等が置換したアラルキル基などが挙げられる。これらの芳香族ポリヒドロキシ化合物は、単独で用いることも２種以上を併用することもできる。これらの中でも、高い絶縁信頼性を有する酸基含有（メタ）アクリレート樹脂が得られることから、ハロゲンを含有しない化合物が好ましい。 Examples of the aromatic polyhydroxy compound include dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxyanthracene, trihydroxyanthracene, tetrahydroxyanthracene, biphenol, tetrahydroxybiphenyl, In addition to bisphenol and the like, compounds having one or more substituents on these aromatic nuclei may be mentioned. Examples of the substituent on the aromatic nucleus include a methyl group, an ethyl group, a vinyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, and a nonyl group. Aliphatic hydrocarbon group; alkoxy group such as methoxy group, ethoxy group, propyloxy group, butoxy group; halogen atom such as fluorine atom, chlorine atom, bromine atom; phenyl group, naphthyl group, anthryl group, and aromatic nucleus thereof An aryl group substituted with the aliphatic hydrocarbon group, the alkoxy group, the halogen atom or the like above; a phenyloxy group, a naphthyloxy group, and the aliphatic hydrocarbon group, the alkoxy group, Aryloxy groups substituted by halogen atoms and the like; phenylmethyl group, phenylethyl group, naphthylmethyl group, naphthylethyl group, and These aromatic nuclei wherein the aliphatic hydrocarbon group on the alkoxy group, the halogen atom and the like and aralkyl groups substituted. These aromatic polyhydroxy compounds can be used alone or in combination of two or more. Among these, a compound containing no halogen is preferable because an acid group-containing (meth) acrylate resin having high insulation reliability can be obtained.
　前記ノボラック型フェノール樹脂としては、例えば、分子内にフェノール性水酸基を１つ有する化合物の１種または２種以上と、アルデヒド化合物とを酸性触媒下で反応させて得られるものが挙げられる。 Examples of the novolac type phenol resin include those obtained by reacting one or more compounds having one phenolic hydroxyl group in the molecule with an aldehyde compound in the presence of an acidic catalyst.
　前記分子内にフェノール性水酸基を１つ有する化合物としては、芳香核上に水酸基を１つ有する芳香族化合物であれば何れの化合物でもよく、例えば、フェノール或いはフェノールの芳香核上に１つまたは複数の置換基を有するフェノール化合物、ナフトール或いはナフトールの芳香核上に１つまたは複数の置換基を有するナフトール化合物、アントラセノール或いはアントラセノールの芳香核上に１つまたは複数の置換基を有するアントラセノール化合物等が挙げられる。また、芳香核上の置換基としては、例えば、脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アリールオキシ基、アラルキル基等が挙げられ、それぞれの具体例は前述の通りである。これらのフェノール性水酸基を１つ有する化合物は、単独で用いることも、２種以上を併用することもできる。 The compound having one phenolic hydroxyl group in the molecule may be any compound as long as it is an aromatic compound having one hydroxyl group on the aromatic nucleus. For example, one or a plurality of compounds on the aromatic nucleus of phenol or phenol are used. Phenol compounds having one or more substituents, naphthols or naphthol compounds having one or more substituents on the aromatic nucleus of naphthol, anthracans having one or more substituents on the aromatic nucleus of anthracenol or anthracenol Examples include a senol compound. Examples of the substituent on the aromatic nucleus include an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, and an aralkyl group, and specific examples of each are as described above. These compounds having one phenolic hydroxyl group can be used alone or in combination of two or more.
　前記アルデヒド化合物としては、例えば、ホルムアルデヒド；アセトアルデヒド、プロピルアルデヒド、ブチルアルデヒド、イソブチルアルデヒド、ペンチルアルデヒド、へキシルアルデヒド等のアルキルアルデヒド；サリチルアルデヒド、３－ヒドロキシベンズアルデヒド、４－ヒドロキシベンズアルデヒド、２－ヒドロキシ－４－メチルベンズアルデヒド、２，４－ジヒドロキシベンズアルデヒド、３，４－ジヒドロキシベンズアルデヒド等のヒドロキシベンズアルデヒド；２－ヒドロキシ－３－メトキシベンズアルデヒド、３－ヒドロキシ－４－メトキシベンズアルデヒド、４－ヒドロキシ－３－メトキシベンズアルデヒド、３－エトキシ－４－ヒドロキシベンズアルデヒド、４－ヒドロキシ－３，５－ジメトキシベンズアルデヒド等のヒドロキシ基とアルコキシ基の両方を有するベンズアルデヒド；メトキシベンズアルデヒド、エトキシベンズアルデヒド等のアルコキシベンズアルデヒド；１－ヒドロキシ－２－ナフトアルデヒド、２－ヒドロキシ－１－ナフトアルデヒド、６－ヒドロキシ－２－ナフトアルデヒド等のヒドロキシナフトアルデヒド；ブロムベンズアルデヒド等のハロゲン化ベンズアルデヒド等が挙げられる。 Examples of the aldehyde compound include formaldehyde; alkyl aldehydes such as acetaldehyde, propyl aldehyde, butyraldehyde, isobutyraldehyde, pentyl aldehyde, hexyl aldehyde; salicyl aldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2-hydroxy-4 -Hydroxybenzaldehydes such as methylbenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde; 2-hydroxy-3-methoxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, 3 -Ethoxy-4-hydroxybenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde Benzaldehydes having both hydroxy groups and alkoxy groups; alkoxybenzaldehydes such as methoxybenzaldehyde and ethoxybenzaldehyde; 1-hydroxy-2-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 6-hydroxy-2-naphthaldehyde and the like Hydroxynaphthaldehyde; Halogenated benzaldehyde such as bromobenzaldehyde.
　前記酸性触媒としては、例えば、塩酸、硫酸、リン酸等の無機酸、メタンスルホン酸、パラトルエンスルホン酸、シュウ酸等の有機酸、三フッ化ホウ素、無水塩化アルミニウム、塩化亜鉛等のルイス酸などが挙げられる。これらの酸性触媒は、単独で用いることも２種以上を併用することもできる。 Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Etc. These acidic catalysts can be used alone or in combination of two or more.
　前記フェノール性水酸基を１つ有する化合物と前記化合物（ｘ）とを必須の反応原料とする反応生成物としては、例えば、前記分子内にフェノール性水酸基を１つ有する化合物と前記化合物（ｘ）とを、酸性触媒下で８０～２００℃程度の温度条件下で加熱撹拌する方法により得ることができる。前記分子内にフェノール性水酸基を１つ有する化合物と前記化合物（ｘ）との反応割合は、前記化合物（ｘ）１モルに対して、前記分子内にフェノール性水酸基を１つ有する化合物が、０．５～５モルとなる割合であることが好ましい。 As a reaction product using the compound having one phenolic hydroxyl group and the compound (x) as essential reaction raw materials, for example, a compound having one phenolic hydroxyl group in the molecule and the compound (x) Can be obtained by a method of heating and stirring under a temperature condition of about 80 to 200 ° C. under an acidic catalyst. The reaction ratio between the compound having one phenolic hydroxyl group in the molecule and the compound (x) is 0 for the compound having one phenolic hydroxyl group in the molecule with respect to 1 mol of the compound (x). The ratio is preferably 5 to 5 mol.
　前記酸性触媒としては、上述したものと同様である。 The acid catalyst is the same as described above.
　前記環状カーボネート化合物（ａ２－２ａ）としては、例えば、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ペンチレンカーボネート等が挙げられる。これらの環状カーボネート化合物は、単独で用いることも２種以上を併用することもできる。また、これらの中でも、高い光感度を有し、耐熱性に優れた硬化物を形成可能な酸基含有（メタ）アクリレート樹脂組成物が得られることから、エチレンカーボネート、またはプロピレンカーボネートが好ましい。 Examples of the cyclic carbonate compound (a2-2a) include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate, and the like. These cyclic carbonate compounds can be used alone or in combination of two or more. Among these, ethylene carbonate or propylene carbonate is preferable because an acid group-containing (meth) acrylate resin composition capable of forming a cured product having high photosensitivity and excellent heat resistance can be obtained.
　前記環状エーテル化合物（ａ２－２ｂ）としては、例えば、エチレンオキサイド、プロピレンオキサイド、テトラヒドロフラン等が挙げられる。これらの環状エーテル化合物は、単独で用いることも２種以上を併用することもできる。また、これらの中でも、高い光感度を有し、耐熱性に優れた硬化物を形成可能な酸基含有（メタ）アクリレート樹脂組成物が得られることから、エチレンオキサイド、またはプロピレンオキサイドが好ましい。 Examples of the cyclic ether compound (a2-2b) include ethylene oxide, propylene oxide, and tetrahydrofuran. These cyclic ether compounds can be used alone or in combination of two or more. Among these, ethylene oxide or propylene oxide is preferable because an acid group-containing (meth) acrylate resin composition having high photosensitivity and capable of forming a cured product having excellent heat resistance can be obtained.
　前記不飽和モノカルボン酸（ａ２－３ａ）としては、上述の不飽和モノカルボン酸（ａ１－２）と同様のものを用いることができる。 As the unsaturated monocarboxylic acid (a2-3a), the same unsaturated monocarboxylic acid (a1-2) as described above can be used.
　前記Ｎ－アルコキシアルキル（メタ）アクリルアミド化合物（ａ２－３ｂ）としては、例えば、Ｎ－メトキシメチル（メタ）アクリルアミド、Ｎ－エトキシメチル（メタ）アクリルアミド、Ｎ－ブトキシメチル（メタ）アクリルアミド、Ｎ－メトキシエチル（メタ）アクリルアミド、Ｎ－エトキシエチル（メタ）アクリルアミド、Ｎ－ブトキシエチル（メタ）アクリルアミド等が挙げられる。これらの中でも、高い光感度を有し、耐熱性に優れた硬化物を形成可能な酸基含有（メタ）アクリレート樹脂組成物が得られることから、Ｎ－メトキシメチル（メタ）アクリルアミドが好ましい。また、これらのＮ－アルコキシアルキル（メタ）アクリルアミド化合物は、単独で用いることも２種以上を併用することもできる。 Examples of the N-alkoxyalkyl (meth) acrylamide compound (a2-3b) include N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and N-methoxy. Examples include ethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide, and N-butoxyethyl (meth) acrylamide. Among these, N-methoxymethyl (meth) acrylamide is preferable because an acid group-containing (meth) acrylate resin composition having high photosensitivity and capable of forming a cured product having excellent heat resistance can be obtained. Moreover, these N-alkoxyalkyl (meth) acrylamide compounds can be used alone or in combination of two or more.
　前記ポリカルボン酸無水物（ａ２－４）としては、上述のポリカルボン酸無水物（ａ１－３）と同様のものを用いることができる。 As the polycarboxylic acid anhydride (a2-4), the same polycarboxylic acid anhydride (a1-3) described above can be used.
　前記Ｎ－アルコキシアルキル（メタ）アクリルアミド化合物（ａ２－３ｂ）を用いる場合、前記ポリカルボン酸無水物（ａ２－４））との当量比［（ａ２－３ｂ）／（ａ２－４））］は、高い光感度を有し、耐熱性に優れた硬化物を形成可能な酸基含有（メタ）アクリレート樹脂組成物が得られることから、０．２～７の範囲が好ましく、０．２５～６．７の範囲がより好ましい。 When the N-alkoxyalkyl (meth) acrylamide compound (a2-3b) is used, the equivalent ratio [(a2-3b) / (a2-4)) to the polycarboxylic acid anhydride (a2-4)) is From the viewpoint of obtaining an acid group-containing (meth) acrylate resin composition having high photosensitivity and capable of forming a cured product excellent in heat resistance, the range of 0.2 to 7 is preferable, and 0.25 to 6 A range of .7 is more preferred.
　前記酸基含有（メタ）アクリレート樹脂（Ａ－２）の製造方法は、特に限定されず、どのような方法にて製造してもよい。例えば、反応原料の全てを一括で反応させる方法で製造してもよいし、反応原料を順次反応させる方法で製造してもよい。なかでも、反応の制御が容易であることから、先にフェノール性水酸基含有樹脂（ａ２－１）と、環状カーボネート化合物（ａ２－２ａ）または環状エーテル化合物（ａ２－２ｂ）とを反応させて、次いで、不飽和モノカルボン酸（ａ２－３ａ）及び／またはＮ－アルコキシアルキル（メタ）アクリルアミド化合物（ａ２－３ｂ）を反応させた後、ポリカルボン酸無水物（ａ２－４）を反応させる方法が好ましい。該反応は、例えば、前記フェノール性水酸基含有樹脂（ａ２－１）と前記前記環状カーボネート化合物（ａ２－２ａ）または前記環状エーテル化合物（ａ２－２ｂ）とを塩基性触媒の存在下、１００～２００℃の温度範囲で反応させた後、酸性触媒の存在下、不飽和ポリカルボン酸（ｂ２－３ａ）及び／またはＮ－アルコキシアルキル（メタ）アクリルアミド化合物（ａ２－３ｂ）を８０～１４０℃の温度範囲で反応させ、次いで、ポリカルボン酸無水物（ａ２－４）を加え、８０～１４０℃の温度範囲で反応させる方法等により行うことができる。 The method for producing the acid group-containing (meth) acrylate resin (A-2) is not particularly limited, and any method may be used. For example, it may be produced by a method in which all of the reaction raw materials are reacted together, or may be produced by a method in which the reaction raw materials are reacted sequentially. Among these, since the reaction is easily controlled, the phenolic hydroxyl group-containing resin (a2-1) is first reacted with the cyclic carbonate compound (a2-2a) or the cyclic ether compound (a2-2b), Next, after reacting the unsaturated monocarboxylic acid (a2-3a) and / or the N-alkoxyalkyl (meth) acrylamide compound (a2-3b), the polycarboxylic acid anhydride (a2-4) is reacted. preferable. The reaction is performed, for example, by combining the phenolic hydroxyl group-containing resin (a2-1) with the cyclic carbonate compound (a2-2a) or the cyclic ether compound (a2-2b) in the presence of a basic catalyst. After the reaction in the temperature range of 0 ° C., the unsaturated polycarboxylic acid (b2-3a) and / or the N-alkoxyalkyl (meth) acrylamide compound (a2-3b) is heated at a temperature of 80 to 140 ° C. in the presence of an acidic catalyst. The reaction can be carried out in the range, followed by the addition of polycarboxylic anhydride (a2-4) and the reaction in the temperature range of 80 to 140 ° C.
　前記塩基性触媒としては、例えば、水酸化カルシウム、水酸化バリウム等のアルカリ土類金属水酸化物；炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩；水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、トリメチルホスフィン、トリブチルホスフィン、トリフェニルホスフィン等のリン化合物、トリエチルアミン、トリブチルアミン、ジメチルベンジルアミン等のアミン化合物、２－メチルイミダゾール、２－ヘプタデシルイミダゾール、２－エチル－４－メチルイミダゾール、１－ベンジル－２－メチルイミダゾール、１－イソブチル－２－メチルイミダゾール等のイミダゾール化合物などが挙げられる。これらの塩基性触媒は、単独で用いることも２種以上を併用することもできる。 Examples of the basic catalyst include alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal waters such as sodium hydroxide and potassium hydroxide. Oxides, phosphorus compounds such as trimethylphosphine, tributylphosphine, triphenylphosphine, amine compounds such as triethylamine, tributylamine, dimethylbenzylamine, 2-methylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, Examples thereof include imidazole compounds such as 1-benzyl-2-methylimidazole and 1-isobutyl-2-methylimidazole. These basic catalysts can be used alone or in combination of two or more.
　前記酸性触媒としては、例えば、塩酸、硫酸、リン酸等の無機酸、メタンスルホン酸、パラトルエンスルホン酸、シュウ酸等の有機酸、三フッ化ホウ素、無水塩化アルミニウム、塩化亜鉛等のルイス酸などが挙げられる。これらの酸触媒は、単独で用いることも２種以上を併用することもできる。 Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Etc. These acid catalysts can be used alone or in combination of two or more.
　前記フェノール性水酸基含有樹脂（ａ２－１）、前記環状カーボネート化合物（ａ２－２ａ）または前記環状エーテル化合物（ａ２－２ｂ）、前記不飽和モノカルボン酸（ａ２－３ａ）及び／または前記Ｎ－アルコキシアルキル（メタ）アクリルアミド化合物（ａ２－３ｂ）、並びに前記ポリカルボン酸無水物（ａ２－４）の反応は、必要に応じて有機溶媒中で行うこともできる。用いる有機溶媒の選択は、反応原料及び生成物である酸基含有（メタ）アクリレート樹脂の溶解性や、反応温度条件により適宜選択し得るが、例えば、メチルエチルケトン、アセトン、ジメチルホルムアミド、メチルイソブチルケトン、メトキシプロパノール、シクロヘキサノン、メチルセロソルブ、ジアルキレングリコールモノアルキルエーテルアセテート、ジアルキレングリコールアセテート等が挙げられる。これらの有機溶媒は、単独で用いることも２種以上を併用し混合溶媒として用いることもできる。 The phenolic hydroxyl group-containing resin (a2-1), the cyclic carbonate compound (a2-2a) or the cyclic ether compound (a2-2b), the unsaturated monocarboxylic acid (a2-3a) and / or the N-alkoxy The reaction of the alkyl (meth) acrylamide compound (a2-3b) and the polycarboxylic acid anhydride (a2-4) can be carried out in an organic solvent as necessary. The organic solvent to be used can be appropriately selected depending on the solubility of the acid group-containing (meth) acrylate resin that is the reaction raw material and the product and the reaction temperature conditions. For example, methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, Examples include methoxypropanol, cyclohexanone, methyl cellosolve, dialkylene glycol monoalkyl ether acetate, dialkylene glycol acetate and the like. These organic solvents can be used alone or in combination of two or more kinds as a mixed solvent.
　前記有機溶媒の使用量は、反応効率が良好となることから、反応原料の合計１００質量部に対して１０～５００質量部の範囲が好ましい。 The amount of the organic solvent used is preferably in the range of 10 to 500 parts by mass with respect to a total of 100 parts by mass of the reaction raw materials because the reaction efficiency is good.
　前記酸基含有（メタ）アクリレート樹脂（Ａ－２）の具体的構造は特に限定されず、フェノール性水酸基含有樹脂（ａ２－１）と、環状カーボネート化合物（ａ２－２ａ）または環状エーテル化合物（ａ２－２ｂ）と、不飽和モノカルボン酸（ａ２－３ａ）及び／またはＮ－アルコキシアルキル（メタ）アクリルアミド化合物（ａ２－３ｂ）と、ポリカルボン酸無水物（ａ２－４）とを必須の反応原料とし、樹脂中に酸基及び（メタ）アクリロイル基を有するものであればよいが、得られる前記酸基含有（メタ）アクリレート樹脂（Ａ－２）としては、例えば、下記構造式（ａ－１）で表される構造部位（Ｉ）と下記構造式（ａ－２）で表される構造部位（ＩＩ）とを繰り返し構造単位とする樹脂構造を有するものや、下記構造式（ａ－３）で表される構造部位（ＩＩＩ）と下記構造式（ａ－４）で表される構造部位（ＩＶ）とを繰り返し構造単位とする樹脂構造を有するものが挙げられる。 The specific structure of the acid group-containing (meth) acrylate resin (A-2) is not particularly limited, and the phenolic hydroxyl group-containing resin (a2-1) and the cyclic carbonate compound (a2-2a) or the cyclic ether compound (a2) -2b), unsaturated monocarboxylic acid (a2-3a) and / or N-alkoxyalkyl (meth) acrylamide compound (a2-3b), and polycarboxylic acid anhydride (a2-4) Any acid group and (meth) acryloyl group may be used in the resin. Examples of the acid group-containing (meth) acrylate resin (A-2) to be obtained include the following structural formula (a-1): ) Having a resin structure in which a structural unit (I) represented by the following structural formula (a-2) and a structural unit (II) represented by the following structural formula (a-2) are repeated, or the following structural formula (a-3): Having a resin structure which structure represented by the site (III) and the following formula (a-4) structural moiety represented by formula (IV) and the repeating structural units and the like.
Figure JPOXMLDOC01-appb-C000029
 ［式中Ｒ２は、それぞれ独立に水素原子または炭素原子数１～４の炭化水素基である。Ｒ３は、それぞれ独立に水素原子、炭素原子数１～４の炭化水素基、炭素原子数１～４のアルコキシ基、ハロゲン原子の何れかであり、ｎは、それぞれ独立に１または２である。Ｒ４は、それぞれ独立にメチレン基または下記構造式（ｘ’－１）～（ｘ’－５）の何れかで表される構造部位である。Ｒ５、Ｒ６は、それぞれ独立に水素原子または炭素原子数１～２０の炭化水素基である。また、Ｒ５とＲ６とが、連結して飽和または不飽和の環を形成してもよい。Ｒ７は、炭素原子数１～１２の炭化水素基である。Ｒ８は、水素原子またはメチル基である。ｘは、前記Ｒ３で表される構造部位、或いは、構造式（ａ－１）で表される構造部位（Ｉ）または構造式（ａ－２）で表される構造部位（ＩＩ）とが、＊印が付されたＲ４を介して連結する結合点である。］
Figure JPOXMLDOC01-appb-C000029
 [Wherein R 2 is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. R 3 is each independently a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and n is each independently 1 or 2. . R 4 is each independently a methylene group or a structural moiety represented by any of the following structural formulas (x′-1) to (x′-5). R 5 and R 6 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R 5 and R 6 may be linked to form a saturated or unsaturated ring. R 7 is a hydrocarbon group having 1 to 12 carbon atoms. R 8 is a hydrogen atom or a methyl group. x represents the structural site represented by R 3 or the structural site (I) represented by the structural formula (a-1) or the structural site (II) represented by the structural formula (a-2). , And a connecting point to be connected through R 4 marked with *. ]
Figure JPOXMLDOC01-appb-C000030
 ［式中Ｒ２は、それぞれ独立に水素原子または炭素原子数１～４の炭化水素基である。Ｒ３は、それぞれ独立に水素原子、炭素原子数１～４の炭化水素基、炭素原子数１～４のアルコキシ基、ハロゲン原子の何れかであり、ｎは、それぞれ独立に１または２である。Ｒ４は、それぞれ独立にメチレン基または下記構造式（ｘ’－１）～（ｘ’－５）の何れかで表される構造部位である。Ｒ５、Ｒ６は、それぞれ独立に水素原子または炭素原子数１～２０の炭化水素基である。また、Ｒ５とＲ６とが、連結して飽和または不飽和の環を形成してもよい。Ｒ７は、炭素原子数１～１２の炭化水素基である。Ｒ８は、水素原子またはメチル基である。ｘは、前記Ｒ３で表される構造部位、或いは、構造式（ａ－３）で表される構造部位（ＩＩＩ）または構造式（ａ－４）で表される構造部位（ＩＶ）とが、＊印が付されたＲ４を介して連結する結合点である。］
Figure JPOXMLDOC01-appb-C000030
 [Wherein R 2 is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. R 3 is each independently a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and n is each independently 1 or 2. . R 4 is each independently a methylene group or a structural moiety represented by any of the following structural formulas (x′-1) to (x′-5). R 5 and R 6 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R 5 and R 6 may be linked to form a saturated or unsaturated ring. R 7 is a hydrocarbon group having 1 to 12 carbon atoms. R 8 is a hydrogen atom or a methyl group. x is the structural site represented by R 3 or the structural site (III) represented by the structural formula (a-3) or the structural site (IV) represented by the structural formula (a-4). , And a connecting point to be connected through R 4 marked with *. ]
Figure JPOXMLDOC01-appb-C000031
 ［式中ｈは、０または１である。Ｒ９は、それぞれ独立して脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アラルキル基の何れかであり、ｉは、０または１～４の整数である。Ｒ１０は、水素原子またはメチル基である。Ｗは、下記構造式（ｗ－１）または（ｗ－２）である。Ｙは、炭素原子数１～４のアルキレン基、酸素原子、硫黄原子、カルボニル基の何れかである。ｊは、１～４の整数である。］
Figure JPOXMLDOC01-appb-C000031
 [In the formula, h is 0 or 1. R 9 is independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group or an aralkyl group, and i is 0 or an integer of 1 to 4. R 10 is a hydrogen atom or a methyl group. W is the following structural formula (w-1) or (w-2). Y is any one of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, and a carbonyl group. j is an integer of 1 to 4. ]
Figure JPOXMLDOC01-appb-C000032
 （式中Ｒ１１は、それぞれ独立に水素原子または炭素原子数１～４の炭化水素基である。Ｒ１２、Ｒ１３は、それぞれ独立に水素原子または炭素原子数１～２０の炭化水素基である。また、Ｒ１２とＲ１３とが、連結して飽和または不飽和の環を形成してもよい。Ｒ１４は、炭素原子数１～１２の炭化水素基である。Ｒ１５は、水素原子またはメチル基である。）
Figure JPOXMLDOC01-appb-C000032
 (Wherein R 11 is each independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. R 12 and R 13 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R 12 and R 13 may be linked to form a saturated or unsaturated ring, R 14 is a hydrocarbon group having 1 to 12 carbon atoms, and R 15 is hydrogen. An atom or a methyl group.)
　前記酸基含有（メタ）アクリレート樹脂（Ａ－２）の酸価は、高い光感度を有し、耐熱性に優れた硬化物を形成可能な酸基含有（メタ）アクリレート樹脂組成物が得られることから、３０～１５０ｍｇＫＯＨ／ｇの範囲が好ましく、４０～１００ｍｇＫＯＨ／ｇの範囲がより好ましい。なお、本発明において、前記酸基含有（メタ）アクリレート樹脂の酸価は、ＪＩＳ　Ｋ　００７０（１９９２）の中和滴定法に基づいて測定される値である。 The acid value of the acid group-containing (meth) acrylate resin (A-2) has high photosensitivity, and an acid group-containing (meth) acrylate resin composition capable of forming a cured product having excellent heat resistance is obtained. Therefore, the range of 30 to 150 mgKOH / g is preferable, and the range of 40 to 100 mgKOH / g is more preferable. In the present invention, the acid value of the acid group-containing (meth) acrylate resin is a value measured based on a neutralization titration method of JIS K 0070 (1992).
　次に、〔３〕酸基含有（メタ）アクリレート樹脂（Ａ－３）について説明する。 Next, [3] acid group-containing (meth) acrylate resin (A-3) will be described.
　前記酸基含有（メタ）アクリレート樹脂（Ａ－３）は、酸基または酸無水物基を有するアミドイミド樹脂（ａ３－１）と、水酸基含有（メタ）アクリレート化合物（ａ３－２）と、（メタ）アクリロイル基含有エポキシ化合物（ａ３－３）と、ポリカルボン酸無水物（ａ３－４）とを必須の反応原料として得られるものである。 The acid group-containing (meth) acrylate resin (A-3) includes an amideimide resin (a3-1) having an acid group or an acid anhydride group, a hydroxyl group-containing (meth) acrylate compound (a3-2), ) An acryloyl group-containing epoxy compound (a3-3) and a polycarboxylic acid anhydride (a3-4) are obtained as essential reaction raw materials.
　前記アミドイミド樹脂（ａ３－１）としては、酸基または酸無水物基のどちらか一方のみを有するものであってもよいし、両方を有するものであってもよい。前記水酸基含有（メタ）アクリレート化合物（ａ３－２）や前記（メタ）アクリロイル基含有エポキシ化合物（ａ３－３）との反応性や反応制御の観点から、酸無水物基を有するものであることが好ましく、酸基と酸無水物基との両方を有するものであることがより好ましい。前記アミドイミド樹脂（ａ３－１）の酸価は、中性条件下、即ち、酸無水物基を開環させない条件での測定値が６０～３５０ｍｇＫＯＨ／ｇの範囲であることが好ましい。他方、水の存在下等、酸無水物基を開環させた条件での測定値が６１～３６０ｍｇＫＯＨ／ｇの範囲であることが好ましい。 The amideimide resin (a3-1) may have only one of an acid group or an acid anhydride group, or may have both. From the viewpoint of reactivity and reaction control with the hydroxyl group-containing (meth) acrylate compound (a3-2) and the (meth) acryloyl group-containing epoxy compound (a3-3), it may have an acid anhydride group. Preferably, it has both an acid group and an acid anhydride group. The acid value of the amideimide resin (a3-1) is preferably in the range of 60 to 350 mgKOH / g under neutral conditions, that is, under conditions where the acid anhydride group is not ring-opened. On the other hand, the measured value under the condition where the acid anhydride group is opened, such as in the presence of water, is preferably in the range of 61 to 360 mgKOH / g.
　前記アミドイミド樹脂（ａ３－１）の具体構造や製造方法は特に限定されず、一般的なアミドイミド樹脂等を広く用いることができる。例えば、ポリイソシアネート化合物と、ポリカルボン酸またはその酸無水物とを反応原料として得られるものが挙げられる。 The specific structure and production method of the amideimide resin (a3-1) are not particularly limited, and general amideimide resins and the like can be widely used. For example, what can be obtained by using a polyisocyanate compound and polycarboxylic acid or its acid anhydride as a reaction raw material is mentioned.
　前記ポリイソシアネート化合物としては、例えば、ブタンジイソシアネート、ヘキサメチレンジイソシアネート、２，２，４－トリメチルヘキサメチレンジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート等の脂肪族ジイソシアネート化合物；ノルボルナンジイソシアネート、イソホロンジイソシアネート、水添キシリレンジイソシアネート、水添ジフェニルメタンジイソシアネート等の脂環式ジイソシアネート化合物；トリレンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート、ジフェニルメタンジイソシアネート、１，５－ナフタレンジイソシアネート、４，４’－ジイソシアナト－３，３’－ジメチルビフェニル、ｏ－トリジンジイソシアネート等の芳香族ジイソシアネート化合物；下記構造式（ｉ－１）で表される繰り返し構造を有するポリメチレンポリフェニルポリイソシアネート；これらのイソシアヌレート変性体、ビウレット変性体、アロファネート変性体などが挙げられる。また、これらのポリイソシアネート化合物は、単独で用いることも２種以上を併用することもできる。 Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; norbornane diisocyanate, isophorone diisocyanate, Cycloaliphatic diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3 , 3'-dimethylbiphenyl, o-tolidine diisocyanate, etc. Cyanate compound; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (i-1); these isocyanurate modified product, a biuret modified product, and the like allophanate modified product. These polyisocyanate compounds can be used alone or in combination of two or more.
Figure JPOXMLDOC01-appb-C000033
 ［式中、Ｒ１はそれぞれ独立に水素原子、炭素原子数１～６の炭化水素基の何れかである。Ｒ２はそれぞれ独立に炭素原子数１～４のアルキル基、または構造式（ｉ－１）で表される構造部位と＊印が付されたメチレン基を介して連結する結合点の何れかである。ｌは０または１～３の整数であり、ｍは１以上の整数である。］
Figure JPOXMLDOC01-appb-C000033
 [Wherein, R 1 is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R 2 is each independently an alkyl group having 1 to 4 carbon atoms, or a bonding point that is linked to a structural moiety represented by the structural formula (i-1) via a methylene group marked with *. is there. l is 0 or an integer of 1 to 3, and m is an integer of 1 or more. ]
　また、前記ポリイソシアネート化合物としては、高い溶剤溶解性を有する酸基含有（メタ）アクリレート樹脂組成物が得られることから、脂環式ジイソシアネート化合物またはその変性体、脂肪族ジイソシアネート化合物またはその変性体が好ましく、脂環式ジイソシアネートまたはそのイソシアヌレート変性体、脂肪族ジイソシアネートまたはそのイソシアヌレート変性体がより好ましい。 In addition, as the polyisocyanate compound, an acid group-containing (meth) acrylate resin composition having high solvent solubility is obtained, and therefore, an alicyclic diisocyanate compound or a modified product thereof, an aliphatic diisocyanate compound or a modified product thereof is used. An alicyclic diisocyanate or its isocyanurate-modified product, and an aliphatic diisocyanate or its isocyanurate-modified product are more preferable.
　また、前記ポリイソシアネート化合物の総質量中における、脂環式ジイソシアネート化合物またはその変性体と、脂肪族ジイソシアネート化合物またはその変性体の合計質量の割合が、７０質量％以上であることが好ましく、９０質量％以上であることが好ましい。 Moreover, it is preferable that the ratio of the total mass of an alicyclic diisocyanate compound or its modified body and an aliphatic diisocyanate compound or its modified body in the total mass of the said polyisocyanate compound is 70 mass% or more, and 90 mass % Or more is preferable.
　また、脂環式ジイソシアネート化合物またはその変性体と、脂肪族ジイソシアネート化合物またはその変性体とを併用する場合には、両者の質量比が３０／７０～７０／３０の範囲であることが好ましい。 Further, when the alicyclic diisocyanate compound or a modified product thereof and the aliphatic diisocyanate compound or the modified product thereof are used in combination, the mass ratio of the two is preferably in the range of 30/70 to 70/30.
　前記ポリカルボン酸またはその酸無水物としては、分子構造中に複数のカルボキシル基を有する化合物またはその酸無水物であれば具体構造は特に問われず、多種多様な化合物を用いることができる。なお、前記アミドイミド樹脂（ａ３－１）がアミド基とイミド基の両方を有するためには、系中にカルボキシル基及び酸無水物基の両方が存在している必要があるが、本発明においては、分子中にカルボキシル基と酸無水物基との両方を有する化合物を用いてもよいし、カルボキシル基を有する化合物と酸無水物基を有する化合物とを併用してもよい。 The polycarboxylic acid or its acid anhydride is not particularly limited as long as it is a compound having a plurality of carboxyl groups in its molecular structure or its acid anhydride, and a wide variety of compounds can be used. In order for the amideimide resin (a3-1) to have both an amide group and an imide group, it is necessary that both a carboxyl group and an acid anhydride group exist in the system. A compound having both a carboxyl group and an acid anhydride group in the molecule may be used, or a compound having a carboxyl group and a compound having an acid anhydride group may be used in combination.
　前記ポリカルボン酸またはその酸無水物としては、例えば、脂肪族ポリカルボン酸化合物またはその酸無水物、脂環式ポリカルボン酸化合物またはその酸無水物、芳香族ポリカルボン酸化合物またはその酸無水物等が挙げられる。 Examples of the polycarboxylic acid or acid anhydride thereof include aliphatic polycarboxylic acid compounds or acid anhydrides thereof, alicyclic polycarboxylic acid compounds or acid anhydrides thereof, aromatic polycarboxylic acid compounds or acid anhydrides thereof. Etc.
　前記脂肪族ポリカルボン酸化合物またはその酸無水物としては、脂肪族炭化水素基は直鎖型及び分岐型のいずれでもよく、構造中に不飽和結合を有していてもよい。 As the aliphatic polycarboxylic acid compound or an acid anhydride thereof, the aliphatic hydrocarbon group may be either a linear type or a branched type, and may have an unsaturated bond in the structure.
　前記脂肪族ポリカルボン酸化合物またはその酸無水物としては、例えば、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、マレイン酸、フマル酸、シトラコン酸、イタコン酸、グルタコン酸、１，２，３，４－ブタンテトラカルボン酸、及びこれらの酸無水物等が挙げられる。 Examples of the aliphatic polycarboxylic acid compound or acid anhydride thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, Examples include citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, and acid anhydrides thereof.
　前記脂環式ポリカルボン酸化合物またはその酸無水物としては、本発明では、カルボキシル基または酸無水物基が脂環構造に結合しているものを脂環式ポリカルボン酸化合物またはその酸無水物とし、それ以外の構造部位における芳香環の有無は問わないものとする。前記脂環式ポリカルボン酸化合物またはその酸無水物としては、例えば、テトラヒドロフタル酸、ヘキサヒドロフタル酸、メチルヘキサヒドロフタル酸、シクロヘキサントリカルボン酸、シクロヘキサンテトラカルボン酸、ビシクロ［２．２．１］ヘプタン－２，３－ジカルボン酸、メチルビシクロ［２．２．１］ヘプタン－２，３－ジカルボン酸、４－（２，５－ジオキソテトラヒドロフラン－３－イル）－１，２，３，４－テトラヒドロナフタレン－１，２－ジカルボン酸、及びこれらの酸無水物等が挙げられる。 In the present invention, the alicyclic polycarboxylic acid compound or acid anhydride thereof is an alicyclic polycarboxylic acid compound or acid anhydride thereof in which a carboxyl group or an acid anhydride group is bonded to an alicyclic structure. In addition, the presence or absence of an aromatic ring at other structural sites is not questioned. Examples of the alicyclic polycarboxylic acid compound or acid anhydride thereof include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, and bicyclo [2.2.1]. Heptane-2,3-dicarboxylic acid, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4 -Tetrahydronaphthalene-1,2-dicarboxylic acid, and acid anhydrides thereof.
　前記芳香族ポリカルボン酸化合物またはその酸無水物としては、例えば、フタル酸、トリメリット酸、ピロメリット酸、ナフタレンジカルボン酸、ナフタレントリカルボン酸、ナフタレンテトラカルボン酸、ビフェニルジカルボン酸、ビフェニルトリカルボン酸、ビフェニルテトラカルボン酸、ベンゾフェノンテトラカルボン酸等が挙げられる。 Examples of the aromatic polycarboxylic acid compound or acid anhydride thereof include phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, and biphenyl. Examples thereof include tetracarboxylic acid and benzophenone tetracarboxylic acid.
　これらの中でも、高い光感度を有し、耐熱性に優れた硬化物を形成可能な酸基含有（メタ）アクリレート樹脂組成物が得られることから、前記脂環式ポリカルボン酸化合物またはその酸無水物、或いは前記芳香族ポリカルボン酸化合物またはその酸無水物が好ましい。また、前記アミドイミド樹脂（ａ３－１）を効率的に製造できることから、分子構造中にカルボキシル基と酸無水物基との両方を有するトリカルボン酸無水物を用いることが好ましく、シクロヘキサントリカルボン酸無水物またはトリメリット酸無水物を用いることが特に好ましい。更に、前記ポリカルボン酸またはその酸無水物の総質量に対する脂環式トリカルボン酸無水物と芳香族トリカルボン酸無水物との合計量の割合が７０質量％以上であることが好ましく、９０質量％以上であることがより好ましい。 Among these, since the acid group-containing (meth) acrylate resin composition having high photosensitivity and capable of forming a cured product having excellent heat resistance is obtained, the alicyclic polycarboxylic acid compound or its acid anhydride is obtained. Or the aromatic polycarboxylic acid compound or acid anhydride thereof. In addition, since the amideimide resin (a3-1) can be efficiently produced, it is preferable to use a tricarboxylic acid anhydride having both a carboxyl group and an acid anhydride group in the molecular structure, and cyclohexanetricarboxylic acid anhydride or It is particularly preferable to use trimellitic anhydride. Furthermore, the ratio of the total amount of the alicyclic tricarboxylic acid anhydride and the aromatic tricarboxylic acid anhydride to the total mass of the polycarboxylic acid or acid anhydride is preferably 70% by mass or more, and 90% by mass or more. It is more preferable that
　前記アミドイミド樹脂（ａ３－１）が、前記ポリイソシアネート化合物と、前記ポリカルボン酸またはその酸無水物とを反応原料とするものである場合、所望の樹脂性能等に応じて、これら以外の反応原料を併用してもよい。この場合、本発明が奏する効果が十分に発揮されることから、アミドイミド樹脂（ａ３－１）の反応原料総質量に対する前記ポリイソシアネート化合物と前記ポリカルボン酸またはその酸無水物との合計質量の割合が９０質量％以上であることが好ましく、９５質量％以上であることがより好ましい。 When the amide-imide resin (a3-1) is a reaction raw material comprising the polyisocyanate compound and the polycarboxylic acid or acid anhydride thereof, other reaction raw materials depending on the desired resin performance and the like May be used in combination. In this case, since the effect exhibited by the present invention is sufficiently exhibited, the ratio of the total mass of the polyisocyanate compound and the polycarboxylic acid or the acid anhydride thereof to the total reaction raw material mass of the amideimide resin (a3-1) Is preferably 90% by mass or more, and more preferably 95% by mass or more.
　前記アミドイミド樹脂（ａ３－１）が、ポリイソシアネート化合物とポリカルボン酸またはその酸無水物とを反応原料とするものである場合、特に限定されず、どのような方法にて製造してもよい。例えば、一般的なアミドイミド樹脂と同様の方法にて製造することができる。具体的には、ポリイソシアネート化合物が有するイソシアネート基１モルに対し、０．８～１．２モルのポリカルボン酸またはその酸無水物を用い、１２０～１８０℃程度の温度条件下で撹拌混合して反応させる方法が挙げられる。 When the amideimide resin (a3-1) is a polyisocyanate compound and polycarboxylic acid or acid anhydride thereof as reaction raw materials, it is not particularly limited and may be produced by any method. For example, it can be produced by the same method as a general amideimide resin. Specifically, 0.8 to 1.2 mol of polycarboxylic acid or its acid anhydride is used with 1 mol of the isocyanate group of the polyisocyanate compound, and the mixture is stirred and mixed at a temperature of about 120 to 180 ° C. The method of making it react is mentioned.
　前記ポリイソシアネート化合物とポリカルボン酸またはその酸無水物との反応は、必要に応じて有機溶媒中で行うこともできる。前記有機溶媒としては、例えば、メチルエチルケトン、アセトン、ジメチルホルムアミド、メチルイソブチルケトン、メトキシプロパノール、シクロヘキサノン、メチルセロソルブ、ジアルキレングリコールモノアルキルエーテルアセテート、ジアルキレングリコールアセテート等が挙げられる。これらの有機溶媒は、単独で用いることも、２種以上を併用し混合溶媒として用いることもできる。 The reaction between the polyisocyanate compound and polycarboxylic acid or acid anhydride thereof can be performed in an organic solvent as necessary. Examples of the organic solvent include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, dialkylene glycol monoalkyl ether acetate, dialkylene glycol acetate and the like. These organic solvents can be used alone or in combination of two or more as a mixed solvent.
　前記有機溶媒の使用量は、反応効率が良好となることから、反応原料の合計１００質量部に対して１０～５００質量部の範囲が好ましい。 The amount of the organic solvent used is preferably in the range of 10 to 500 parts by mass with respect to a total of 100 parts by mass of the reaction raw materials because the reaction efficiency is good.
　前記水酸基含有（メタ）アクリレート化合物（ａ３－２）としては、分子構造中に水酸基と（メタ）アクリロイル基とを有する化合物であれば他の具体構造は特に限定されず、多種多様な化合物を用いることができる。例えば、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジトリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート等のヒドロキシ（メタ）アクリレート化合物；前記各種のヒドロキシ（メタ）アクリレート化合物の分子構造中に（ポリ）オキシエチレン鎖、（ポリ）オキシプロピレン鎖、（ポリ）オキシテトラメチレン鎖等の（ポリ）オキシアルキレン鎖を導入した（ポリ）オキシアルキレン変性体；前記各種のヒドロキシ（メタ）アクリレート化合物の分子構造中に（ポリ）ラクトン構造を導入したラクトン変性体等が挙げられる。これらの中でも、耐熱性に優れた硬化物を形成可能な酸基含有（メタ）アクリレート樹脂組成物が得られることから、分子量が１，０００以下のものが好ましい。また、前記水酸基含有（メタ）アクリレート化合物（ａ３－２）が、前記オキシアルキレン変性体やラクトン変性体である場合には、重量平均分子量（Ｍｗ）が１，０００以下であることが好ましい。これらの水酸基含有（メタ）アクリレート化合物は、単独で用いることも２種以上を併用することもできる。 The hydroxyl group-containing (meth) acrylate compound (a3-2) is not particularly limited as long as it has a hydroxyl group and a (meth) acryloyl group in the molecular structure, and a wide variety of compounds are used. be able to. For example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate (Poly) oxy such as (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain, etc. in the molecular structure of the various hydroxy (meth) acrylate compounds. (Poly) oxyalkylene modified products in which an alkylene chain is introduced; lactone modified products in which a (poly) lactone structure is introduced into the molecular structure of the various hydroxy (meth) acrylate compounds. Among these, those having a molecular weight of 1,000 or less are preferable because an acid group-containing (meth) acrylate resin composition capable of forming a cured product having excellent heat resistance can be obtained. Further, when the hydroxyl group-containing (meth) acrylate compound (a3-2) is the oxyalkylene-modified product or lactone-modified product, the weight average molecular weight (Mw) is preferably 1,000 or less. These hydroxyl group-containing (meth) acrylate compounds can be used alone or in combination of two or more.
　前記（メタ）アクリロイル基含有エポキシ化合物（ａ３－３）は、分子構造中に（メタ）アクリロイル基とエポキシ基とを有するものであれば他の具体構造は特に限定されず、多種多様な化合物を用いることができる。例えば、グリシジル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレートグリシジルエーテル、エポキシシクロへキシルメチル（メタ）アクリレート等のグリシジル基含有（メタ）アクリレートモノマー；ジヒドロキシベンゼンジグリシジルエーテル、ジヒドロキシナフタレンジグリシジルエーテル、ビフェノールジグリシジルエーテル、ビスフェノールジグリシジルエーテル等のジグリシジルエーテル化合物のモノ（メタ）アクリレート化物などが挙げられる。これらの中でも、耐熱性に優れた硬化物を形成可能な酸基含有（メタ）アクリレート樹脂組成物が得られることから、グリシジル基含有（メタ）アクリレートモノマーが好ましい。また、その分子量は、５００以下であることが好ましい。さらに、前記（メタ）アクリロイル基含有エポキシ化合物（ａ３－３）の総質量中の前記グリシジル基含有（メタ）アクリレートモノマーの割合が７０質量％以上であることが好ましく、９０質量％以上であることがより好ましい。 The (meth) acryloyl group-containing epoxy compound (a3-3) is not particularly limited as long as it has a (meth) acryloyl group and an epoxy group in the molecular structure, and a wide variety of compounds can be used. Can be used. For example, glycidyl group-containing (meth) acrylate monomers such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and epoxycyclohexylmethyl (meth) acrylate; dihydroxybenzene diglycidyl ether, dihydroxynaphthalenediglycidyl ether, And mono (meth) acrylates of diglycidyl ether compounds such as biphenol diglycidyl ether and bisphenol diglycidyl ether. Among these, a glycidyl group-containing (meth) acrylate monomer is preferable because an acid group-containing (meth) acrylate resin composition capable of forming a cured product having excellent heat resistance can be obtained. Moreover, it is preferable that the molecular weight is 500 or less. Furthermore, the proportion of the glycidyl group-containing (meth) acrylate monomer in the total mass of the (meth) acryloyl group-containing epoxy compound (a3-3) is preferably 70% by mass or more, and 90% by mass or more. Is more preferable.
　前記ポリカルボン酸無水物（ａ３－４）としては、上述のポリカルボン酸無水物（ａ１－３）及びポリカルボン酸無水物（ａ２－４）と同様である。 The polycarboxylic acid anhydride (a3-4) is the same as the above-mentioned polycarboxylic acid anhydride (a1-3) and polycarboxylic acid anhydride (a2-4).
　前記酸基含有（メタ）アクリレート樹脂（Ａ－３）は、所望の樹脂性能等に応じて、前記酸基または酸無水物基を有するアミドイミド樹脂（ａ３－１）、前記水酸基含有（メタ）アクリレート化合物（ａ３－２）、（メタ）アクリロイル基含有エポキシ化合物（ａ３－３）及びポリカルボン酸無水物（ａ３－４）以外に、他の反応原料を併用することもできる。この場合、酸基含有（メタ）アクリレート樹脂（Ａ－３）の反応原料総質量中の前記（ａ３－１）～（ａ３－４）成分の合計質量の割合が８０質量％以上であることが好ましく、９０質量％以上であることがより好ましい。 The acid group-containing (meth) acrylate resin (A-3) includes the amide-imide resin (a3-1) having the acid group or the acid anhydride group, the hydroxyl group-containing (meth) acrylate, depending on the desired resin performance. In addition to the compound (a3-2), the (meth) acryloyl group-containing epoxy compound (a3-3) and the polycarboxylic acid anhydride (a3-4), other reaction raw materials can be used in combination. In this case, the ratio of the total mass of the components (a3-1) to (a3-4) in the total mass of the reaction raw material of the acid group-containing (meth) acrylate resin (A-3) is 80% by mass or more. Preferably, it is 90 mass% or more.
　前記酸基含有（メタ）アクリレート樹脂（Ａ－３）の製造方法は、特に限定されず、どのような方法にて製造してもよい。例えば、反応原料の全てを一括で反応させる方法で製造してもよいし、反応原料を順次反応させる方法で製造してもよい。なかでも、アミドイミド樹脂（ａ３－１）と水酸基含有（メタ）アクリレート化合物（ａ３－２）を反応させ（工程１）、工程１の生成物と（メタ）アクリロイル基含有エポキシ化合物（ａ３－３）とを反応させ（工程２）、工程２の生成物と前記ポリカルボン酸無水物（ａ３－４）とを反応させる方法で製造することが好ましい。 The method for producing the acid group-containing (meth) acrylate resin (A-3) is not particularly limited, and any method may be used. For example, it may be produced by a method in which all of the reaction raw materials are reacted together, or may be produced by a method in which the reaction raw materials are reacted sequentially. In particular, the amide-imide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) are reacted (step 1), and the product of step 1 and the (meth) acryloyl group-containing epoxy compound (a3-3) (Step 2), and the product of Step 2 and the polycarboxylic acid anhydride (a3-4) are preferably reacted.
　前記工程１は、アミドイミド樹脂（ａ３－１）と水酸基含有（メタ）アクリレート化合物（ａ３－２）とを反応させる工程である。前記反応としては、主に、前記アミドイミド樹脂（ａ３－１）中の酸基または酸無水物基と前記水酸基含有（メタ）アクリレート化合物（ａ３－２）中の水酸基とが反応する。前記水酸基含有（メタ）アクリレート化合物（ａ３－２）は、酸無水物基との反応性に優れることから、前述の通り、前記アミドイミド樹脂（ａ３－１）は酸無水物基を有していることが好ましい。前記アミドイミド樹脂（ａ３－１）と前記水酸基含有（メタ）アクリレート化合物（ａ３－２）との反応割合は、前記アミドイミド樹脂（ａ３－１）中の酸基及び酸無水物基の合計に対して、前記水酸基含有（メタ）アクリレート化合物（ａ３－２）を０．９～１．１モルの範囲で用いることが好ましく、特に、前記アミドイミド樹脂（ａ３－１）中の酸無水物基の合計に対して、前記水酸基含有（メタ）アクリレート化合物（ａ３－２）を０．９～１．１モルの範囲で用いることが好ましい。前記アミドイミド樹脂（ａ３－１）中の酸無水物基の含有量は、前述した２通りの酸価の測定値の差分、即ち、酸無水物基を開環させた条件での酸価と、酸無水物基を開環させない条件での酸価との差分から算出することができる。 Step 1 is a step of reacting the amideimide resin (a3-1) with the hydroxyl group-containing (meth) acrylate compound (a3-2). As the reaction, the acid group or acid anhydride group in the amideimide resin (a3-1) and the hydroxyl group in the hydroxyl group-containing (meth) acrylate compound (a3-2) mainly react. Since the hydroxyl group-containing (meth) acrylate compound (a3-2) is excellent in reactivity with an acid anhydride group, as described above, the amideimide resin (a3-1) has an acid anhydride group. It is preferable. The reaction ratio between the amideimide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) is based on the total of acid groups and acid anhydride groups in the amideimide resin (a3-1). The hydroxyl group-containing (meth) acrylate compound (a3-2) is preferably used in a range of 0.9 to 1.1 mol, and particularly, the total of acid anhydride groups in the amideimide resin (a3-1). On the other hand, the hydroxyl group-containing (meth) acrylate compound (a3-2) is preferably used in the range of 0.9 to 1.1 mol. The content of the acid anhydride group in the amideimide resin (a3-1) is the difference between the two acid value measurement values described above, that is, the acid value under the condition where the acid anhydride group is ring-opened, It can be calculated from the difference from the acid value under conditions where the acid anhydride group is not ring-opened.
　前記アミドイミド樹脂（ａ３－１）と前記水酸基含有（メタ）アクリレート化合物（ａ３－２）との反応は、例えば、エステル化反応触媒の存在下、９０～１４０℃程度の温度条件下で加熱撹拌して行うことができる。前記エステル化反応触媒としては、例えば、トリメチルホスフィン、トリブチルホスフィン、トリフェニルホスフィン等のリン化合物、トリエチルアミン、トリブチルアミン、ジメチルベンジルアミン等のアミン化合物、２－メチルイミダゾール、２－ヘプタデシルイミダゾール、２－エチル－４－メチルイミダゾール、１－ベンジル－２－メチルイミダゾール、１－イソブチル－２－メチルイミダゾール等のイミダゾール化合物などが挙げられる。これらの反応触媒は、単独で用いることも２種以上を併用することもできる。 The reaction between the amideimide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) is, for example, heated and stirred under a temperature condition of about 90 to 140 ° C. in the presence of an esterification reaction catalyst. Can be done. Examples of the esterification reaction catalyst include phosphorus compounds such as trimethylphosphine, tributylphosphine and triphenylphosphine, amine compounds such as triethylamine, tributylamine and dimethylbenzylamine, 2-methylimidazole, 2-heptadecylimidazole, 2- Examples thereof include imidazole compounds such as ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole and 1-isobutyl-2-methylimidazole. These reaction catalysts can be used alone or in combination of two or more.
　前記反応触媒の添加量は、反応原料の合計１００質量部に対して０．００１～５質量部の範囲が好ましい。 The amount of the reaction catalyst added is preferably in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the total reaction raw material.
　前記工程１の反応は、必要に応じて有機溶媒中で行うこともできる。用いる有機溶媒の選択は、反応原料及び生成物である酸基含有（メタ）アクリレート樹脂の溶解性や、反応温度条件により適宜選択し得るが、例えば、メチルエチルケトン、アセトン、ジメチルホルムアミド、メチルイソブチルケトン、メトキシプロパノール、シクロヘキサノン、メチルセロソルブ、ジアルキレングリコールモノアルキルエーテルアセテート、ジアルキレングリコールアセテート等が挙げられる。これらの有機溶媒は、単独で用いることも、２種以上を併用し混合溶媒として用いることもできる。前記アミドイミド樹脂（ａ３－１）の製造と工程１とを連続して行う場合には、前記アミドイミド樹脂（ａ３－１）の製造で用いた有機溶媒中でそのまま反応を続けてもよい。 The reaction in Step 1 can also be performed in an organic solvent as necessary. The organic solvent to be used can be appropriately selected depending on the solubility of the acid group-containing (meth) acrylate resin that is the reaction raw material and the product and the reaction temperature conditions. For example, methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, Examples include methoxypropanol, cyclohexanone, methyl cellosolve, dialkylene glycol monoalkyl ether acetate, dialkylene glycol acetate and the like. These organic solvents can be used alone or in combination of two or more as a mixed solvent. When the production of the amideimide resin (a3-1) and Step 1 are carried out continuously, the reaction may be continued as it is in the organic solvent used in the production of the amideimide resin (a3-1).
　前記工程２は、前記工程１で得られた生成物と（メタ）アクリロイル基含有エポキシ化合物（ａ３－３）とを反応させる工程である。前記反応としては、主に、（メタ）アクリロイル基含有エポキシ化合物（ａ３－３）と、前記工程１の生成物中のカルボキシル基とが反応する。その反応割合は、工程１の生成物中のカルボキシル基に対して、前記（メタ）アクリロイル基含有エポキシ化合物（ａ３－３）を０．５～１．２モルの範囲で用いることが好ましく、０．９～１．１モルの範囲で用いることがより好ましい。工程２の反応は、例えば、エステル化反応触媒の存在下、９０～１４０℃程度の温度条件下で加熱撹拌して行うことができる。工程１と工程２とを連続して行う場合、エステル化反応触媒は追加しなくてもよいし、適宜追加してもよい。また、反応は必要に応じて有機溶媒中で行うこともできる。 Step 2 is a step of reacting the product obtained in Step 1 with the (meth) acryloyl group-containing epoxy compound (a3-3). As the reaction, the (meth) acryloyl group-containing epoxy compound (a3-3) mainly reacts with the carboxyl group in the product of Step 1. The reaction ratio is preferably such that the (meth) acryloyl group-containing epoxy compound (a3-3) is used in the range of 0.5 to 1.2 mol with respect to the carboxyl group in the product of Step 1. More preferably, it is used in the range of 9 to 1.1 mol. The reaction in Step 2 can be performed, for example, with heating and stirring under a temperature condition of about 90 to 140 ° C. in the presence of an esterification reaction catalyst. When step 1 and step 2 are performed continuously, the esterification reaction catalyst may not be added or may be added as appropriate. Moreover, reaction can also be performed in an organic solvent as needed.
　前記工程３は、前記工程２で得られた生成物とポリカルボン酸無水物（ａ３－４）とを反応させる工程である。前記反応としては、主に、前記ポリカルボン酸無水物（ａ３－４）と、前記工程２の生成物中の水酸基とが反応する。その反応割合は、最終生成物である酸基含有（メタ）アクリレート樹脂（Ａ－３）の酸価が５０～１００ｍｇＫＯＨ／ｇ程度になるよう調整されることが好ましい。前記工程３の反応は、例えば、エステル化反応触媒の存在下、９０～１４０℃程度の温度条件下で加熱撹拌して行うことができる。工程２と工程３とを連続して行う場合、エステル化反応触媒は追加しなくてもよいし、適宜追加してもよい。また、反応は必要に応じて有機溶媒中で行うこともできる。 Step 3 is a step of reacting the product obtained in Step 2 with the polycarboxylic anhydride (a3-4). As the reaction, mainly the polycarboxylic acid anhydride (a3-4) reacts with the hydroxyl group in the product of Step 2. The reaction rate is preferably adjusted so that the acid value of the acid group-containing (meth) acrylate resin (A-3) as the final product is about 50 to 100 mgKOH / g. The reaction in Step 3 can be carried out, for example, with heating and stirring under a temperature condition of about 90 to 140 ° C. in the presence of an esterification reaction catalyst. When step 2 and step 3 are performed continuously, the esterification reaction catalyst may not be added or may be added as appropriate. Moreover, reaction can also be performed in an organic solvent as needed.
　前記酸基含有（メタ）アクリレート樹脂（Ａ－３）の酸価は、高い光感度を有し、耐熱性に優れた硬化物を形成可能な酸基含有（メタ）アクリレート樹脂組成物が得られることから、３０～１５０ｍｇＫＯＨ／ｇの範囲が好ましく、４０～１００ｍｇＫＯＨ／ｇの範囲がより好ましい。なお、本願発明において酸基含有（メタ）アクリレート樹脂（Ａ－３）の酸価は、ＪＩＳ　Ｋ　００７０（１９９２）の中和滴定法にて測定される値である。 The acid value of the acid group-containing (meth) acrylate resin (A-3) has a high photosensitivity, and an acid group-containing (meth) acrylate resin composition capable of forming a cured product having excellent heat resistance is obtained. Therefore, the range of 30 to 150 mgKOH / g is preferable, and the range of 40 to 100 mgKOH / g is more preferable. In the present invention, the acid value of the acid group-containing (meth) acrylate resin (A-3) is a value measured by the neutralization titration method of JIS K 0070 (1992).
　前記光重合開始剤（Ｂ）について説明する。 The photopolymerization initiator (B) will be described.
　前記光重合開始剤（Ｂ）としては、下記一般式（１）で表される化合物を用いる。 As the photopolymerization initiator (B), a compound represented by the following general formula (1) is used.
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
本発明では上記した一般式（１）中、下記構造式 In the present invention, in the above general formula (1), the following structural formula
Figure JPOXMLDOC01-appb-C000035
 で表される構造部位が光照射によってラジカルを発生させることにより重合開始剤として機能するものである。本発明では比較的分子量が大きくそのラジカル発生部位の量が相対的に少なくなるにも拘わらず、優れた硬化性を発現させることは特筆すべき点である。
Figure JPOXMLDOC01-appb-C000035
 The structure part represented by these functions as a polymerization initiator by generating radicals by light irradiation. In the present invention, it should be noted that excellent curability is exhibited even though the molecular weight is relatively large and the amount of radical generation sites is relatively small.
　ここで、前記一般式（１）中、Ｒ１は、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、；ｓ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、２－エチルブチル基、イソペンチル基、１－メチルペンチル基、１，３－ジメチルブチル基、１－メチルヘキシル基、イソヘプチル基、１，１，３，３－テトラメチルブチル基、２，２，４，４－テトラメチルブチル基、１－メチルヘプチル基、３－メチルヘプチル基、２－エチルヘキシル基、１，１，３－トリメチルヘキシル基、１，１，３，３－テトラメチルペンチル基、イソデシル基等の炭素原子数１～１０のアルキル基を表す。これらの中でも光照射により発生したラジカルの反応性の点からエチル基であることが好ましい。 In the general formula (1), R 1 represents a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group; an s-butyl group, a pentyl group, or a hexyl group. Group, heptyl group, octyl group, nonyl group, decyl group, 2-ethylbutyl group, isopentyl group, 1-methylpentyl group, 1,3-dimethylbutyl group, 1-methylhexyl group, isoheptyl group, 1,1,3 , 3-tetramethylbutyl group, 2,2,4,4-tetramethylbutyl group, 1-methylheptyl group, 3-methylheptyl group, 2-ethylhexyl group, 1,1,3-trimethylhexyl group, 1, An alkyl group having 1 to 10 carbon atoms such as a 1,3,3-tetramethylpentyl group and an isodecyl group is represented. Among these, an ethyl group is preferable from the viewpoint of reactivity of radicals generated by light irradiation.
　次に、前記一般式（１）中、Ｒ２及びＲ３は、それぞれ独立して、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｓ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基等の炭素原子数１～１２の直鎖状または分岐上のアルキル基；ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基等の炭素原子数２～４のヒドロキシアルキル基；
メトキシエチル基；エトキシエチル基；Ｒ２及びＲ３が一体となって窒素原子と共に環構造を形成するアルキレン基、即ち In the general formula (1), R 2 and R 3 are each independently a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, s- Linear or branched alkyl group having 1 to 12 carbon atoms such as butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group; hydroxyethyl group, hydroxy A hydroxyalkyl group having 2 to 4 carbon atoms such as a propyl group or a hydroxybutyl group;
A methoxyethyl group; an ethoxyethyl group; an alkylene group in which R 2 and R 3 together form a ring structure with a nitrogen atom;
Figure JPOXMLDOC01-appb-C000036
 に相当する構造として、下記構造式
Figure JPOXMLDOC01-appb-C000036
 As the structure corresponding to
Figure JPOXMLDOC01-appb-C000037
 で表されるピロリジン構造やピペリジン構造を形成するブチレン基、ペンテン基；Ｒ２及びＲ３と一体となって窒素原子と共にモルホリン骨格、Ｎ－メチルピペラジン骨格、２，６－ジメチルモルホリン骨格を形成する環構形成部位、即ち
Figure JPOXMLDOC01-appb-C000037
 A butylene group or a pentene group forming a pyrrolidine structure or a piperidine structure represented by the formula: A morpholine skeleton, an N-methylpiperazine skeleton, or a 2,6-dimethylmorpholine skeleton together with a nitrogen atom together with R 2 and R 3 Ring formation site, ie
Figure JPOXMLDOC01-appb-C000038
 に相当する構造として、下記構造式
Figure JPOXMLDOC01-appb-C000038
 As the structure corresponding to
Figure JPOXMLDOC01-appb-C000039
 を形成する構造部位を表す。これらの中でも特に合成上の収率の高さの点から炭素原子数１～１２の直鎖状または分岐上のアルキル基が好ましい。
Figure JPOXMLDOC01-appb-C000039
 Represents the structural site that forms Among these, a linear or branched alkyl group having 1 to 12 carbon atoms is particularly preferable from the viewpoint of high yield in synthesis.
　前記一般式（１）中、Ｒ４～Ｒ７は、それぞれ独立して、水素原子；メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｓ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、２－エチルブチル基、イソペンチル基、１－メチルペンチル基、１，３－ジメチルブチル基、１－メチルヘキシル基、イソヘプチル基、１，１，３，３－テトラメチルブチル基、２，２，４，４－テトラメチルブチル基、１－メチルヘプチル基、３－メチルヘプチル基、２－エチルヘキシル基等の炭素原子数１～８のアルキル基；又はフェニル基を表す。これらの中でも、原料の入手の容易さの点からＲ４～Ｒ７の全てが水素原子であることが好ましい。 In the general formula (1), R 4 to R 7 are each independently a hydrogen atom; methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, s- Butyl, pentyl, hexyl, heptyl, octyl, 2-ethylbutyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, 1-methylhexyl, isoheptyl, 1,1, Alkyl groups having 1 to 8 carbon atoms such as 3,3-tetramethylbutyl group, 2,2,4,4-tetramethylbutyl group, 1-methylheptyl group, 3-methylheptyl group, 2-ethylhexyl group; Or represents a phenyl group. Among these, it is preferable that all of R 4 to R 7 are hydrogen atoms from the viewpoint of easy availability of raw materials.
　また、前記一般式（１）中、Ｘ１はエチレン基、１，３－プロピレン基、１，２－プロピレン基、又は２，３－プロピレン基を表し、Ｘ２は水素原子又はメチル基を、Ｘ３は水素原子、メチル基、又はエチル基を、或いは、Ｘ２及びＸ３が破線部にて共有結合を形成しつつ一体的にエチレン基、１，３－プロピレン基、１，２－プロピレン基、２，３－プロピレン基を、或いは、Ｘ１、Ｘ２、及びＸ３が、一体的に下記構造式（Ｘ－１） In the general formula (1), X 1 represents an ethylene group, 1,3-propylene group, 1,2-propylene group, or 2,3-propylene group, X 2 represents a hydrogen atom or a methyl group, X 3 represents a hydrogen atom, a methyl group, or an ethyl group, or X 2 and X 3 form a covalent bond at the broken line portion, and integrally form an ethylene group, a 1,3-propylene group, or a 1,2-propylene. Group, 2,3-propylene group, or X 1 , X 2 , and X 3 are integrally represented by the following structural formula (X-1)
Figure JPOXMLDOC01-appb-C000040
 で表される、窒素原子と共にビシクロ環を構成する４価の脂肪族炭化水素基を表す。
Figure JPOXMLDOC01-appb-C000040
 The tetravalent aliphatic hydrocarbon group which comprises a bicyclo ring with a nitrogen atom represented by these is represented.
　これらの中でも上記Ｘ１、Ｘ２、及びＸ３と窒素原子とにより構成される下記部分構造式 Among these, the following partial structural formulas composed of X 1 , X 2 , X 3 and a nitrogen atom
Figure JPOXMLDOC01-appb-C000041
 （式中＊は他の構造部位との結合手を表す。）
で表される構造部位として、
Figure JPOXMLDOC01-appb-C000041
 (In the formula, * represents a bond with another structural site.)
As a structural site represented by
Figure JPOXMLDOC01-appb-C000042
 （式中＊は他の構造部位との結合手を表す。）
などが挙げられるが、前記一般式（１）で表される化合物の製造方法の［工程Ｖ］における収率が高くなる点から、下記構造式
Figure JPOXMLDOC01-appb-C000042
 (In the formula, * represents a bond with another structural site.)
From the point that the yield in [Step V] of the method for producing the compound represented by the general formula (1) is increased, the following structural formula
Figure JPOXMLDOC01-appb-C000043
 で表されるものが好ましい。
Figure JPOXMLDOC01-appb-C000043
 The thing represented by these is preferable.
　次に、一般式（１）中、Ｙ１は、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｓ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、２－エチルブチル基、イソペンチル基、１－メチルペンチル基、１，３－ジメチルブチル基、１－メチルヘキシル基、イソヘプチル基、１，１，３，３－テトラメチルブチル基、２，２，４，４－テトラメチルブチル基、１－メチルヘプチル基、３－メチルヘプチル基、２－エチルヘキシル基、１，１，３－トリメチルヘキシル基、１，１，３，３－テトラメチルペンチル基、イソデシル基、１－メチルウンデシル基または１，１，３，３，５，５－ヘキサメチルヘキシル基等の直鎖状または分岐上のアルキル基、シクロヘプチル基、シクロヘキシル基、シクロペンチル基；１－フルオロプロピル基、１，１，１－トリフルオロプロピル基、１，１，１－トリフルオロブチル基、２－トリフルオロメチルプロピル基、１，１，１，２，２－ペエンタフルオロプロピル基、１，１，１，２，２－ペエンタフルオロペンチル基、１，１，１，２，２，３，３－ペンタフルオロプロピル基、１，１，１，２，２，３，３－ペンタフルオロブチル基、２－（パーフルオロブチル）エチル基、１－クロロプロピル基、１，１，１－トリクロロプロピル基、１－クロロブチル基、１，１，１－トリクロロブチル基、１－クロロヘキシル基、１，１，１－トリクロロヘキシル基、１－クロロドデシル基、１，１，１－トリクロロドデシル基、１－クロロオクタデシル基、１，１，１－トリクロロオクタデシル基；１－ヒドロキシプロピル基、２-ヒドロキシプロピル基、１－ヒドロキシブチル基、１－ヒドロキシヘキシル基、１－ヒドロキシドデシル基、１-ヒドロキシオクタデシル基等の置換基を有しないか、又はハロゲン原子若しくは水酸基を置換基として有する炭素原子数３～１８のアルキル基（ｙ１－１）；ベンジル基、メトキシベンジル基、クロロベンジル基、ヒドロキシベンジル基、フェネチル基、フェニルベンジル基、メトキシフェニルベンジル基、ナフチルメチル基、メトキシナフチルメチル基、フェニルプロピル基、フェニルプロペニル基、フェノキシベンジル基、メチルチオベンジル基、ターフェニルメチル基等の炭素原子数７～１９のアラルキル基（ｙ１－２）； Next, in the general formula (1), Y 1 represents propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, s-butyl group, pentyl group, hexyl group, heptyl group, octyl group, Nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, 2-ethylbutyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl Group, 1-methylhexyl group, isoheptyl group, 1,1,3,3-tetramethylbutyl group, 2,2,4,4-tetramethylbutyl group, 1-methylheptyl group, 3-methylheptyl group, 2 -Ethylhexyl group, 1,1,3-trimethylhexyl group, 1,1,3,3-tetramethylpentyl group, isodecyl group, 1-methyl group Linear or branched alkyl group such as ndecyl group or 1,1,3,3,5,5-hexamethylhexyl group, cycloheptyl group, cyclohexyl group, cyclopentyl group; 1-fluoropropyl group, 1,1 , 1-trifluoropropyl group, 1,1,1-trifluorobutyl group, 2-trifluoromethylpropyl group, 1,1,1,2,2-peentafluoropropyl group, 1,1,1,2 , 2-Peentafluoropentyl group, 1,1,1,2,2,3,3-pentafluoropropyl group, 1,1,1,2,2,3,3-pentafluorobutyl group, 2- ( Perfluorobutyl) ethyl group, 1-chloropropyl group, 1,1,1-trichloropropyl group, 1-chlorobutyl group, 1,1,1-trichlorobutyl group, 1-chlorohexyl group, 1,1,1- Torik Rohexyl group, 1-chlorododecyl group, 1,1,1-trichlorododecyl group, 1-chlorooctadecyl group, 1,1,1-trichlorooctadecyl group; 1-hydroxypropyl group, 2-hydroxypropyl group, 1-hydroxy An alkyl group having 3 to 18 carbon atoms having no substituent such as a butyl group, a 1-hydroxyhexyl group, a 1-hydroxydodecyl group, or a 1-hydroxyoctadecyl group, or having a halogen atom or a hydroxyl group as a substituent (y1 -1); benzyl group, methoxybenzyl group, chlorobenzyl group, hydroxybenzyl group, phenethyl group, phenylbenzyl group, methoxyphenylbenzyl group, naphthylmethyl group, methoxynaphthylmethyl group, phenylpropyl group, phenylpropenyl group, phenoxybenzyl Group, methylthiobenzyl An aralkyl group having 7 to 19 carbon atoms such as a terphenylmethyl group (y1-2);
　下記構造式（ｙ１－３）で表される構造部位（ｙ１－３）、 A structural portion (y1-3) represented by the following structural formula (y1-3),
Figure JPOXMLDOC01-appb-C000044
 （式中、Ｒ８は炭素原子数２～４のアルキレン基、Ｒ９は水素原子又はフェニル基又は炭素原子数１～４のアルキル基、ｍは０～２０の整数を表す。）
Figure JPOXMLDOC01-appb-C000044
 (Wherein R 8 represents an alkylene group having 2 to 4 carbon atoms, R 9 represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 0 to 20)
　下記構造式（ｙ１－４）で表される構造部位（ｙ１－４）、 A structural portion (y1-4) represented by the following structural formula (y1-4),
Figure JPOXMLDOC01-appb-C000045
 （式中、Ｒ８は炭素原子数２～４のアルキレン基、Ｒ９は水素原子、フェニル基、又は炭素数１～４のアルキル基、Ｒ１０は水素原子またはメチル基、ｍは０～２０の整数を表す。）
Figure JPOXMLDOC01-appb-C000045
 (Wherein R 8 is an alkylene group having 2 to 4 carbon atoms, R 9 is a hydrogen atom, a phenyl group, or an alkyl group having 1 to 4 carbon atoms, R 10 is a hydrogen atom or a methyl group, and m is 0 to 20) Represents an integer.)
下記構造式（ｙ１－５）で表される構造部位（ｙ１－５）、 A structural moiety (y1-5) represented by the following structural formula (y1-5),
Figure JPOXMLDOC01-appb-C000046
 （式中、Ｒ１０は水素原子またはメチル基、Ｒ１１は炭素原子数１～１８のアルキル基又は炭素原子数６～１８のアリール基を表す。）
Figure JPOXMLDOC01-appb-C000046
 (Wherein R 10 represents a hydrogen atom or a methyl group, and R 11 represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms.)
　下記構造式（ｙ１－６）で表される構造部位（ｙ１－６）、 Structural part (y1-6) represented by the following structural formula (y1-6),
Figure JPOXMLDOC01-appb-C000047
 （式中、Ｒ１２は炭素原子数１～１８のアルキル基を表す。）
Figure JPOXMLDOC01-appb-C000047
 (In the formula, R 12 represents an alkyl group having 1 to 18 carbon atoms.)
　下記構造式（ｙ１－７）で表される構造部位（ｙ１－７）、 A structural portion (y1-7) represented by the following structural formula (y1-7),
Figure JPOXMLDOC01-appb-C000048
 （式中、Ｒ８は炭素原子数２～４のアルキレン基、Ｒ１３は水素原子、炭素原子数１～６のアルキル基又はハロゲン原子、ｍは０～２０の整数を表す。）
Figure JPOXMLDOC01-appb-C000048
 (Wherein R 8 represents an alkylene group having 2 to 4 carbon atoms, R 13 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a halogen atom, and m represents an integer of 0 to 20)
　下記構造式（ｙ１－８）で表される構造部位（ｙ１－８）、 Structural part (y1-8) represented by the following structural formula (y1-8),
Figure JPOXMLDOC01-appb-C000049
 （式中、Ｒ８は炭素原子数２～４のアルキレン基、Ｒ１０は水素原子又はメチル基、Ｒ１４はｐ＋１の結合手を持つ炭素原子数５～１８の炭化水素基、ｌは０～２０の整数、ｐは１～３の整数を表す。）
Figure JPOXMLDOC01-appb-C000049
 Wherein R 8 is an alkylene group having 2 to 4 carbon atoms, R 10 is a hydrogen atom or a methyl group, R 14 is a hydrocarbon group having 5 to 18 carbon atoms having a p + 1 bond, and l is 0 to (An integer of 20 and p represents an integer of 1 to 3)
　下記構造式（ｙ１－９）で表される構造部位（ｙ１－９）が挙げられる。 And a structural moiety (y1-9) represented by the following structural formula (y1-9).
Figure JPOXMLDOC01-appb-C000050
 （式中、Ｒ１５は炭素原子数４～１８のアルキル基、炭素原子数６～１０の脂肪族環状炭化水素基、芳香族基を表す。）
Figure JPOXMLDOC01-appb-C000050
 (Wherein R 15 represents an alkyl group having 4 to 18 carbon atoms, an aliphatic cyclic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic group.)
　ここで前記構造式（ｙ１－３）中、Ｒ８の炭素原子数２～４のアルキレン基としては、ｎ－プロピレン基、１，２－プロプレン基、ｎ－ブチレン基、２－メチル－プロパン－１，２－ジイル基等が挙げられ、また、Ｒ９における炭素原子数１～４のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、若しくはｓ－ブチル基等が挙げられる。 In the structural formula (y1-3), the alkylene group having 2 to 4 carbon atoms of R 8 is an n-propylene group, a 1,2-propylene group, an n-butylene group, 2-methyl-propane- 1,2-diyl group and the like, and examples of the alkyl group having 1 to 4 carbon atoms in R 9 include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t- Examples thereof include a butyl group or a s-butyl group.
　前記構造部位（ｙ１－４）中のＲ８及びＲ９は前記構造式（ｙ１－３）と同義である。 R 8 and R 9 in the structural moiety (y1-4) have the same meaning as in the structural formula (y1-3).
　前記構造式（ｙ１－５）中、Ｒ１１の炭素原子数１～１８のアルキル基又は炭素原子数１～１８のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、；ｓ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、２－エチルブチル基、イソペンチル基、１－メチルペンチル基、１，３－ジメチルブチル基、１－メチルヘキシル基、イソヘプチル基、１，１，３，３－テトラメチルブチル基、２，２，４，４－テトラメチルブチル基、１－メチルヘプチル基、３－メチルヘプチル基、２－エチルヘキシル基、１，１，３－トリメチルヘキシル基、１，１，３，３－テトラメチルペンチル基、イソデシル基、１－メチルウンデシル基または１，１，３，３，５，５－ヘキサメチルヘキシル基等の直鎖状または分岐上のアルキル基、シクロヘプチル基、シクロヘキシル基、シクロペンチル基等のシクロアルキル基等が挙げられ、他方、炭素原子数６～１８のアリール基としては、フェニル基、ベンジル基、フェネチル基、ビフェニル基、ナフチル基、トリル基、キシリル基、メシチル基、クメニル基、クロロフェニル基、ブロモフェニル基、クロロメチルフェニル基、ヒドロキシフェニル基、メトキシフェニル基、エトキシフェニル基、フェノキシフェニル基、アセトキシフェニル基、ベンゾイロキシフェニル基、メチルチオフェニル基、フェニルチオフェニル基、メチルアミノフェニル基、ジメチルアミノフェニル基、アセチルアミノフェニル基、カルボキシフェニル基、メトキシカルボニルフェニル基、フェノキシカルボニルフェニル基、Ｎ－フェニルカルバモイルフェニル基、シアノフェニル基、スルホフェニル基、スルホナトフェニル基、ホスホノフェニル基、及びホスホナトフェニル基等が挙げられる。 In the structural formula (y1-5), the alkyl group having 1 to 18 carbon atoms or the alkyl group having 1 to 18 carbon atoms of R 11 is methyl group, ethyl group, propyl group, isopropyl group, n-butyl. Group, isobutyl group, t-butyl group; s-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group Group, heptadecyl group, octadecyl group, 2-ethylbutyl group, isopentyl group, 1-methylpentyl group, 1,3-dimethylbutyl group, 1-methylhexyl group, isoheptyl group, 1,1,3,3-tetramethylbutyl Group, 2,2,4,4-tetramethylbutyl group, 1-methylheptyl group, 3-methylheptyl group, 2-ethylhexyl group, 1,1,3-trimethylhexyl group, 1,1,3,3-tetramethylpentyl group, isodecyl group, 1-methylundecyl group, 1,1,3,3,5,5-hexamethylhexyl group, etc. A linear or branched alkyl group, a cycloalkyl group such as a cycloheptyl group, a cyclohexyl group, a cyclopentyl group, and the like. On the other hand, examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a benzyl group, Phenethyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxy Phenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthio Enyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl Group, phosphonophenyl group, phosphonatophenyl group and the like.
　前記構造式（ｙ１－６）中、Ｒ１２の炭素原子数１～１８のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、；ｓ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、２－エチルブチル基、イソペンチル基、１－メチルペンチル基、１，３－ジメチルブチル基、１－メチルヘキシル基、イソヘプチル基、１，１，３，３－テトラメチルブチル基、２，２，４，４－テトラメチルブチル基、１－メチルヘプチル基、３－メチルヘプチル基、２－エチルヘキシル基、１，１，３－トリメチルヘキシル基、１，１，３，３－テトラメチルペンチル基、イソデシル基、１－メチルウンデシル基または１，１，３，３，５，５－ヘキサメチルヘキシル基等の直鎖状または分岐上のアルキル基、シクロヘプチル基、シクロヘキシル基、シクロペンチル基等のシクロアルキル基等が挙げられる。 In the structural formula (y1-6), as the alkyl group having 1 to 18 carbon atoms of R 12 , a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, S-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, 2- Ethylbutyl group, isopentyl group, 1-methylpentyl group, 1,3-dimethylbutyl group, 1-methylhexyl group, isoheptyl group, 1,1,3,3-tetramethylbutyl group, 2,2,4,4- Tetramethylbutyl group, 1-methylheptyl group, 3-methylheptyl group, 2-ethylhexyl group, 1,1,3-trimethylhexyl group, Linear or branched alkyl group such as 1,1,3,3-tetramethylpentyl group, isodecyl group, 1-methylundecyl group or 1,1,3,3,5,5-hexamethylhexyl group Cycloalkyl groups such as cycloheptyl group, cyclohexyl group, and cyclopentyl group.
　前記構造式（ｙ１－７）中のＲ８は、構造部位（ｙ１－３）におけるＲ８と同義であり、Ｒ１３の炭素原子数１～６のアルキル基としては、メチル基、エチル基、プロピル基、
イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｓ－ブチル基、ペンチル基、ヘキシル基、２－エチルブチル基、イソペンチル基、１－メチルペンチル基、１，３－ジメチルブチル基等が挙げられ、ハロゲン原子としては、臭素原子、塩素原子、フッ素原子が挙げられる。 Wherein R 8 in formula (y1-7) has the same meaning as R 8 in the structural moiety (Y1-3), the alkyl group having 1 to 6 carbon atoms R 13, a methyl group, an ethyl group, Propyl group,
Isopropyl, n-butyl, isobutyl, t-butyl, s-butyl, pentyl, hexyl, 2-ethylbutyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, etc. Examples of the halogen atom include a bromine atom, a chlorine atom, and a fluorine atom.
　前記構造式（ｙ１－８）中のＲ８は、構造部位（ｙ１－３）におけるＲ８と同義であり、Ｒ１４におけるｐ＋１の結合手を持つ炭素原子数３～２５の炭化水素基とは、グリセロール残基、トリメチロールプロパン残基、ペンタエリスリトール残基等の脂肪族多価アルコール残基；ｎ－プロピレン基、１，２－プロピレン基、ｎ－ブチレン基、２－メチル－プロパン－１，２－ジイル基、１，５－ペンタンジイル基、１，６－ヘキサンジイル基、１，７－ヘプタンジイル基、１，８－オクタンジイル基、１，９－ノナンジイル基、１，１０－デカンジイル基、３，８－デカンジイル基、１，１１－ウンデカンジイル基、１，１２－ドデカンジイル基、１，１３－トリデカンジイル基、１，１４－テトラデカンジイル基、１，１５－ペンタデカンジイル基、１，１６－ヘキサデカンジイル基、１，１７－ヘプタデカンジイル基、１，１８－オクタデカンジイル基、１，１９－ノナデカンジイル基、１，２０－エイコサンジイル基、１，２１－ヘネイコサンジイル基、１，２２－ドコサンジイル基、１，２３－トリコサンジイル基、１，２４－テトラコサンジイル基、１，２５－ペンタコサンジイル基が挙げられる。 R 8 in the formula (y1-8) in has the same meaning as R 8 in the structural moiety (Y1-3), and a hydrocarbon group having a carbon number of 3 to 25 having a bond p + 1 in R 14 is , Aliphatic polyhydric alcohol residues such as glycerol residue, trimethylolpropane residue, pentaerythritol residue; n-propylene group, 1,2-propylene group, n-butylene group, 2-methyl-propane-1, 2-diyl group, 1,5-pentanediyl group, 1,6-hexanediyl group, 1,7-heptanediyl group, 1,8-octanediyl group, 1,9-nonanediyl group, 1,10-decandiyl group, 3 , 8-decanediyl group, 1,11-undecanediyl group, 1,12-dodecanediyl group, 1,13-tridecanediyl group, 1,14-tetradecanediyl group, 1,15-pentadeca Diyl group, 1,16-hexadecandiyl group, 1,17-heptadecandiyl group, 1,18-octadecandiyl group, 1,19-nonadecandiyl group, 1,20-eicosanediyl group, 1,21-henei Examples thereof include a cosanediyl group, a 1,2-docosanediyl group, a 1,3-tricosanediyl group, a 1,24-tetracosanediyl group, and a 1,25-pentacosanediyl group.
　ここで残基とは、多価アルコールの水酸基を除く炭化水素構造部位を示す。 Here, the residue refers to a hydrocarbon structure site excluding the hydroxyl group of the polyhydric alcohol.
　以上詳述した一般式（１）中のＹ１で示される構造部位の中でも特に、前記炭素原子数３～１８のアルキル基（ｙ１－１）、前記構造式（ｙ１－４）で表される構造部位（ｙ１－４）、前記構造式（ｙ１－５）で表される構造部位（ｙ１－５）、前記構造式（ｙ１－８）で表される構造部位（ｙ１－８）が、前記一般式（１）で表される化合物の合成時におけるＹ１の導入が容易であることに加え、高い光感度及び硬化物における優れた耐熱性を有し、かつ、アウトガスが生じにくい感光性樹脂組成物が得られることから好ましく、前記構造部位（ｙ１－８）がより好ましい。 Among the structural sites represented by Y 1 in the general formula (1) detailed above, the alkyl group (y1-1) having 3 to 18 carbon atoms and the structural formula (y1-4) are particularly preferable. The structural moiety (y1-4), the structural moiety (y1-5) represented by the structural formula (y1-5), and the structural moiety (y1-8) represented by the structural formula (y1-8) Photosensitive resin that has high photosensitivity and excellent heat resistance in a cured product, and is less susceptible to outgassing in addition to easy introduction of Y 1 during the synthesis of the compound represented by general formula (1) The structural part (y1-8) is more preferable because a composition can be obtained.
　次に、前記一般式（１）中の下記構造式１ａで表される構造部位は、上記した各種構造から任意に選択しうるが、該構造式１ａで示される部分の総質量数が３００～２０００であることが高い光感度及び硬化物における優れた耐熱性を有し、かつ、アウトガスが生じにくい感光性樹脂組成物が得られることから好ましい。 Next, the structural moiety represented by the following structural formula 1a in the general formula (1) can be arbitrarily selected from the various structures described above, but the total mass number of the portion represented by the structural formula 1a is 300 to A photosensitivity resin composition having a high photosensitivity and excellent heat resistance in a cured product and having a high photosensitivity of 2000 is preferable because a photosensitive resin composition that hardly causes outgassing is obtained.
Figure JPOXMLDOC01-appb-C000051
 （構造式１ａ中、Ｘ１、Ｘ２、Ｘ３、Ｒ４～Ｒ７、及びＹ１は一般式（１）と同義である。）
Figure JPOXMLDOC01-appb-C000051
 (In the structural formula 1a, X 1 , X 2 , X 3 , R 4 to R 7 , and Y 1 have the same meaning as in the general formula (1).)
　次に、前記一般式（１）中、Ｙ２は、前記した通り、該構造部位末端に窒素原子又は酸素原子を有する、（ｎ＋１）の結合手を持つ有機結節基であるが、具体的には、下記に示す構造部位（ｙ２－１）～（ｙ２－６）からなる群から選択されるアミド結合形成タイプの構造部位、又は、下記に示す構造部位（ｙ２－７）～（ｙ２－９）で表されるエステル結合形成タイプの構造部位が原料の入手が容易であり、また、反応の制御が容易である点から好ましい。 Next, in the general formula (1), as described above, Y 2 is an organic nodule group having a (n + 1) bond having a nitrogen atom or an oxygen atom at the end of the structural site, as described above. Is an amide bond-forming type structural site selected from the group consisting of structural sites (y2-1) to (y2-6) shown below, or structural sites (y2-7) to (y2-9) shown below Ester bond-forming type structural sites represented by) are preferred from the viewpoint of easy availability of raw materials and easy control of the reaction.
　ここで前記構造部位（ｙ２－１）は、前記一般式（１）中のｎが１であり、かつ、下記構造式（ｙ２－１）で表される構造部位である。 Here, the structural part (y2-1) is a structural part represented by the following structural formula (y2-1), where n in the general formula (1) is 1.
Figure JPOXMLDOC01-appb-C000052
 （式中、Ｒ１６は炭素原子数２～１８の直鎖又は環状のアルキレン基、フェニレン基、キシリレン基、炭素原子数１～３のアルキル基を核置換基として有するフェニレン基、炭素原子数１～３のアルキル基を核置換基として有するキシリレン基を表す。）
Figure JPOXMLDOC01-appb-C000052
 (Wherein R 16 is a linear or cyclic alkylene group having 2 to 18 carbon atoms, a phenylene group, a xylylene group, a phenylene group having an alkyl group having 1 to 3 carbon atoms as a nuclear substituent, or 1 carbon atom) Represents a xylylene group having an alkyl group of ˜3 as a nuclear substituent.)
　前記構造式（ｙ２－１）中のＲ１６を構成する炭素原子数２～１８の直鎖又は環状のアルキレン基としては、エチレン基、ｎ－プロピレン基、１，２－プロピレン基、ｎ－ブチレン基、２－メチル－プロパン－１，２－ジイル基、１，５－ペンタンジイル基、１，６－ヘキサンジイル基、１，７－ヘプタンジイル基、１，８－オクタンジイル基、１，９－ノナンジイル基、１，１０－デカンジイル基、３，８－デカンジイル基、１，１１－ウンデカンジイル基、１，１２－ドデカンジイル基、１，１３－トリデカンジイル基、１，１４－テトラデカンジイル基、１，１５－ペンタデカンジイル基、１，１６－ヘキサデカンジイル基、１，１７－ヘプタデカンジイル基、１，１８－オクタデカンジイル基、１，４－シクロヘキサンジイル基が挙げられる。 Examples of the linear or cyclic alkylene group having 2 to 18 carbon atoms constituting R 16 in the structural formula (y2-1) include an ethylene group, an n-propylene group, a 1,2-propylene group, and an n-butylene. Group, 2-methyl-propane-1,2-diyl group, 1,5-pentanediyl group, 1,6-hexanediyl group, 1,7-heptanediyl group, 1,8-octanediyl group, 1,9-nonanediyl Group, 1,10-decanediyl group, 3,8-decanediyl group, 1,11-undecanediyl group, 1,12-dodecanediyl group, 1,13-tridecanediyl group, 1,14-tetradecanediyl group, 1, Examples include 15-pentadecanediyl group, 1,16-hexadecanediyl group, 1,17-heptadecanediyl group, 1,18-octadecanediyl group, and 1,4-cyclohexanediyl group. I can get lost.
　また、前記構造式（ｙ２－１）中の、炭素原子数１～３のアルキル基を核置換基として有するフェニレン基としては、メチルフェニレン基、エチルフェニレン基、ｎ－プロピルフェニレン基、ｉ－プロピルフェニレン基が挙げられ、また、炭素原子数１～３のアルキル基を核置換基として有するキシリレン基としては、メチルキシリレン基、エチルキシリレン基、ｎ－プロピルキシリレン基、ｉ－プロピルキシリレン基が挙げられる。 In the structural formula (y2-1), examples of the phenylene group having an alkyl group having 1 to 3 carbon atoms as a nuclear substituent include a methylphenylene group, an ethylphenylene group, an n-propylphenylene group, and i-propyl. Examples of the xylylene group having an alkyl group having 1 to 3 carbon atoms as a nuclear substituent include a methylxylylene group, an ethylxylylene group, an n-propylxylylene group, and an i-propylxylylene group. Groups.
　これらの中でも、該構造部位（ｙ２－１）としては、具体的には、下記構造式で表されるものが、後述する前記一般式（１）で表される化合物の製造方法［工程ＩＶ］において、前記構造の構成原料となるジアミン化合物の入手が容易である点から好ましい。 Among these, as the structural site (y2-1), specifically, those represented by the following structural formula can be produced by a method for producing a compound represented by the general formula (1) described later [Step IV]. Are preferable from the viewpoint of easy availability of a diamine compound as a constituent material of the structure.
Figure JPOXMLDOC01-appb-I000053
（各構造式中＊は他構造部位との結合手を表す。）
Figure JPOXMLDOC01-appb-I000053
(* In each structural formula represents a bond with another structural site.)
　前記構造部位（ｙ２－２）は、前記一般式（１）中のｎが１であり、かつ、下記構造式で表されるものである。 The structural site (y2-2) is represented by the following structural formula, where n is 1 in the general formula (1).
Figure JPOXMLDOC01-appb-C000054
 （式中、Ｒ１７は炭素原子数２～６の直鎖状、分岐状のアルキレン基又はフェニレン基を、Ｒ１８は炭素原子数２～６の直鎖状、分岐状のアルキレン基又はフェニレン基を、ｑは０～１２の整数を表す。）
Figure JPOXMLDOC01-appb-C000054
 (Wherein R 17 is a linear or branched alkylene group or phenylene group having 2 to 6 carbon atoms, and R 18 is a linear or branched alkylene group or phenylene group having 2 to 6 carbon atoms. Q represents an integer of 0 to 12.)
　ここで、一般式（ｙ２－２）中のＲ１７及びＲ１７を構成する炭素原子数２～６の直鎖状、分岐状のアルキレン基としては、例えば、エチレン基、ｎ－プロピレン基、１，２－プロピレン基、ｎ－ブチレン基、２－メチル－プロパン－１，２－ジイル基、１，５－ペンタンジイル基、１，６－ヘキサンジイル基が挙げられる。 Here, examples of the linear or branched alkylene group having 2 to 6 carbon atoms constituting R 17 and R 17 in the general formula (y2-2) include, for example, an ethylene group, an n-propylene group, , 2-propylene group, n-butylene group, 2-methyl-propane-1,2-diyl group, 1,5-pentanediyl group, 1,6-hexanediyl group.
　斯かる構造部位（ｙ２－２）としては、具体的には、下記構造式で表されるものが、後述する前記一般式（１）で表される化合物の製造方法［工程ＩＶ］において、前記構造の構成原料となるジアミン化合物の入手が容易である点から好ましい。 As such a structural moiety (y2-2), specifically, those represented by the following structural formula can be represented by the above-described method for producing a compound represented by the general formula (1) [Step IV]. It is preferable from the viewpoint of easy availability of a diamine compound as a constituent material of the structure.
Figure JPOXMLDOC01-appb-C000055
 （各構造式中＊は他構造部位との結合手を表す。）
Figure JPOXMLDOC01-appb-C000055
 (* In each structural formula represents a bond with another structural site.)
　前記構造部位（ｙ２－３）は、前記一般式（１）中のｎが１であり、かつ、下記構造式（ｙ２－３）で表されるものである。 The structural site (y2-3) is represented by the following structural formula (y2-3), wherein n in the general formula (1) is 1.
Figure JPOXMLDOC01-appb-C000056
 （式中、Ｒ１９～Ｒ２２は、それぞれ独立して、水素又は炭素原子数1～３の直鎖状、分岐状のアルキル基を表す。）
Figure JPOXMLDOC01-appb-C000056
 (Wherein R 19 to R 22 each independently represents hydrogen or a linear or branched alkyl group having 1 to 3 carbon atoms.)
　ここでＲ１９～Ｒ２２を構成する炭素原子数1～３の直鎖状、分岐状のアルキル基とは、メチル基、エチル基、プロピル基、及びイソプロピル基が挙げられる。 Here, examples of the linear or branched alkyl group having 1 to 3 carbon atoms constituting R 19 to R 22 include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
　斯かる構造部位（ｙ２－３）としては、具体的には、下記構造式で表されるものが、後述する前記一般式（１）で表される化合物の製造方法［工程ＩＶ］において、前記構造の構成原料となるジアミン化合物の入手が容易である点から好ましい。 As such a structural moiety (y2-3), specifically, those represented by the following structural formula can be represented by the above-described method for producing a compound represented by the general formula (1) [Step IV]. It is preferable from the viewpoint of easy availability of a diamine compound as a constituent material of the structure.
Figure JPOXMLDOC01-appb-C000057
 （各構造式中＊は他構造部位との結合手を表す。）
Figure JPOXMLDOC01-appb-C000057
 (* In each structural formula represents a bond with another structural site.)
　前記構造部位（ｙ２－４）は、前記一般式（１）中のｎが１であり、かつ、下記構造式（ｙ２－４）で表されるものである。 The structural site (y2-4) is one represented by the following structural formula (y2-4), where n is 1 in the general formula (1).
Figure JPOXMLDOC01-appb-C000058
 （式中、Ｒ２３は、酸素原子、メチレン基、エチレン基、エチリデン基、２，２－プロピレン基、又は１，３－プロピレン基を表す。）
Figure JPOXMLDOC01-appb-C000058
 (Wherein R 23 represents an oxygen atom, a methylene group, an ethylene group, an ethylidene group, a 2,2-propylene group, or a 1,3-propylene group.)
　斯かる構造部位（ｙ２－４）としては、具体的には、下記構造式で表されるものが、後述する前記一般式（１）で表される化合物の製造方法［工程ＩＶ］において、前記構造の構成原料となるジアミン化合物の入手が容易である点から好ましい。 As such a structural moiety (y2-4), specifically, those represented by the following structural formula can be represented by the above-described method for producing a compound represented by the general formula (1) [Step IV]. It is preferable from the viewpoint of easy availability of a diamine compound as a constituent material of the structure.
Figure JPOXMLDOC01-appb-C000059
 （各構造式中＊は他構造部位との結合手を表す。）
Figure JPOXMLDOC01-appb-C000059
 (* In each structural formula represents a bond with another structural site.)
　前記構造部位（ｙ２－５）は、前記一般式（１）中のｎが１であり、かつ、下記構造式（ｙ２－５）で表されるものである。 The structural portion (y2-5) is one in which n in the general formula (1) is 1, and is represented by the following structural formula (y2-5).
Figure JPOXMLDOC01-appb-C000060
 （式中、Ｒ２４は、それぞれ独立して水素原子又は炭素原子数1～３の直鎖状、分岐状のアルキル基を、Ｒ２５は、それぞれ独立して水素原子又は炭素原子数1～３の直鎖状、分岐状のアルキル基を、Ｒ２６は、酸素原子、メチレン基、２，２－プロピレン基、スルホニル基、又はカルボニル基を表す。）
Figure JPOXMLDOC01-appb-C000060
 Wherein R 24 is independently a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and R 25 is independently a hydrogen atom or 1 to 3 carbon atoms. And R 26 represents an oxygen atom, a methylene group, a 2,2-propylene group, a sulfonyl group, or a carbonyl group.)
　ここでＲ２４又はＲ２５を構成する炭素原子数1～３の直鎖状、分岐状のアルキル基とは、メチル基、エチル基、プロピル基、及びイソプロピル基が挙げられる。 Here, examples of the linear or branched alkyl group having 1 to 3 carbon atoms constituting R 24 or R 25 include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
　斯かる構造部位（ｙ２－５）としては、具体的には、下記構造式で表されるものが、後述する前記一般式（１）で表される化合物の製造方法［工程ＩＶ］において、前記構造の構成原料となるジアミン化合物の入手が容易である点から好ましい。 As such a structural moiety (y2-5), specifically, those represented by the following structural formula can be represented by the above-described method for producing a compound represented by the general formula (1) [Step IV]. It is preferable from the viewpoint of easy availability of a diamine compound as a constituent material of the structure.
Figure JPOXMLDOC01-appb-C000061
 （各構造式中＊は他構造部位との結合手を表す。）
Figure JPOXMLDOC01-appb-C000061
 (* In each structural formula represents a bond with another structural site.)
　前記構造部位（ｙ２－６）は、前記一般式（１）中のｎが２又は３であり、かつ、下記構造式（ｙ２－６）で表されるものである。 The structural moiety (y2-6) is represented by the following structural formula (y2-6) where n in the general formula (1) is 2 or 3.
Figure JPOXMLDOC01-appb-C000062
 （式中、Ｒ２７は炭素原子数２～６のアルキレン基、Ｒ２８は炭素原子数４～１２の結合手数が（ｎ＋１）価の炭化水素基、ｒは０～３の整数である。）
Figure JPOXMLDOC01-appb-C000062
 (Wherein R 27 is an alkylene group having 2 to 6 carbon atoms, R 28 is a (n + 1) -valent hydrocarbon group having 4 to 12 carbon atoms, and r is an integer of 0 to 3).
　ここで、Ｒ２７を構成する炭素原子数２～６のアルキレン基としては、エチレン基、ｎ－プロピレン基、１，２－プロピレン基、ｎ－ブチレン基、２－メチル－プロパン－１，２－ジイル基、１，５－ペンタンジイル基、１，６－ヘキサンジイル基が挙げられ、Ｒ２８を構成する炭素原子数４～１２の結合手数が（ｎ＋１）価の炭化水素基としては、多価アルコールの残基が挙げられ、例えば、トリメチロールプロパン残基、ペンタエリスリトール残基、グリセリロール残基、ジトリメチロールプロパン残基が挙げられる。ここで、「残基」とは、該当する多価アルコールから水酸基を除いた炭化水素構造部位である。 Here, as the alkylene group having 2 to 6 carbon atoms constituting R 27 , an ethylene group, an n-propylene group, a 1,2-propylene group, an n-butylene group, 2-methyl-propane-1,2- A diyl group, a 1,5-pentanediyl group, and a 1,6-hexanediyl group, and the hydrocarbon group having 4 to 12 carbon atoms constituting R 28 and having an (n + 1) -valent bond is a polyhydric alcohol. Examples thereof include trimethylolpropane residue, pentaerythritol residue, glyceryl residue, and ditrimethylolpropane residue. Here, the “residue” is a hydrocarbon structure site obtained by removing a hydroxyl group from the corresponding polyhydric alcohol.
　斯かる構造部位（ｙ２－６）としては、具体的には、下記構造式で表されるものが、後述する前記一般式（１）で表される化合物の製造方法［工程ＩＶ］において、前記構造の構成原料となるジアミン化合物の入手が容易である点から好ましい。 As such a structural moiety (y2-6), specifically, those represented by the following structural formula can be used in the production method [Step IV] of the compound represented by the general formula (1) described later. It is preferable from the viewpoint of easy availability of a diamine compound as a constituent material of the structure.
Figure JPOXMLDOC01-appb-C000063
 （各構造式中＊は他構造部位との結合手を表す。）
Figure JPOXMLDOC01-appb-C000063
 (* In each structural formula represents a bond with another structural site.)
　次にエステル結合形成タイプの構造部位である構造部位（ｙ２－７）は、前記一般式（１）中のｎが１であり、かつ、下記構造式（ｙ２－７）で表されるものである。 Next, the structural part (y2-7) which is an ester bond-forming type structural part is one in which n in the general formula (1) is 1 and represented by the following structural formula (y2-7) is there.
Figure JPOXMLDOC01-appb-C000064
 （式中、Ｒ２９は炭素原子数２～１８の直鎖、分岐状又は環状のアルキレン基、フェニレン基、キシリレン基を表す。）
Figure JPOXMLDOC01-appb-C000064
 (Wherein R 29 represents a linear, branched or cyclic alkylene group having 2 to 18 carbon atoms, a phenylene group or a xylylene group.)
　ここで、Ｒ２９を構成する炭素原子数２～１８の直鎖、分岐状又は環状のアルキレン基としては、エチレン基、ｎ－プロピレン基、１，２－プロピレン基、ｎ－ブチレン基、２－メチル－プロパン－１，２－ジイル基、１，５－ペンタンジイル基、１，６－ヘキサンジイル基、１，７－ヘプタンジイル基、１，８－オクタンジイル基、１，９－ノナンジイル基、１，１０－デカンジイル基、３，８－デカンジイル基、１，１１－ウンデカンジイル基、１，１２－ドデカンジイル基、１，１３－トリデカンジイル基、１，１４－テトラデカンジイル基、１，１５－ペンタデカンジイル基、１，１６－ヘキサデカンジイル基、１，１７－ヘプタデカンジイル基、１，１８－オクタデカンジイル基、１，４－シクロヘキサンジイル基が挙げられる。 Here, the linear, branched or cyclic alkylene group having 2 to 18 carbon atoms constituting R 29 includes an ethylene group, an n-propylene group, a 1,2-propylene group, an n-butylene group, 2- Methyl-propane-1,2-diyl group, 1,5-pentanediyl group, 1,6-hexanediyl group, 1,7-heptanediyl group, 1,8-octanediyl group, 1,9-nonanediyl group, 1, 10-decanediyl group, 3,8-decanediyl group, 1,11-undecanediyl group, 1,12-dodecanediyl group, 1,13-tridecanediyl group, 1,14-tetradecanediyl group, 1,15-pentadecanediyl group Group, 1,16-hexadecanediyl group, 1,17-heptadecanediyl group, 1,18-octadecanediyl group and 1,4-cyclohexanediyl group.
　斯かる構造部位（ｙ２－７）としては、具体的には、下記構造式で表されるものが、後述する前記一般式（１）で表される化合物の製造方法［工程ＩＶ］において、前記構造の構成原料となるジオール化合物の入手が容易である点から好ましい。 As such a structural moiety (y2-7), specifically, those represented by the following structural formula can be represented by the above-described method for producing a compound represented by the general formula (1) [Step IV]. It is preferable from the viewpoint of easy availability of a diol compound as a constituent material of the structure.
Figure JPOXMLDOC01-appb-C000065
 （各構造式中＊は他構造部位との結合手を表す。）
Figure JPOXMLDOC01-appb-C000065
 (* In each structural formula represents a bond with another structural site.)
　次に、エステル結合形成タイプの構造部位である構造部位（ｙ２－８）は、前記一般式（１）中のｎが１であり、かつ、下記構造式（ｙ２－８）で表されるものである。 Next, the structural moiety (y2-8), which is an ester bond-forming structural moiety, is one in which n in the general formula (1) is 1, and is represented by the following structural formula (y2-8) It is.
Figure JPOXMLDOC01-appb-C000066
 （式中、Ｒ３０は、それぞれ独立して炭素原子数２～６のアルキレン基を、ｑは１～２０の整数を表す。）
Figure JPOXMLDOC01-appb-C000066
 (In the formula, each R 30 independently represents an alkylene group having 2 to 6 carbon atoms, and q represents an integer of 1 to 20).
　ここで、Ｒ３０を構成する炭素原子数２～６のアルキレン基としては、エチレン基、ｎ－プロピレン基、１，２－プロピレン基、ｎ－ブチレン基、２－メチル－プロパン－１，２－ジイル基、１，５－ペンタンジイル基、１，６－ヘキサンジイル基が挙げられる。 Here, the alkylene group having 2 to 6 carbon atoms constituting R 30 includes an ethylene group, an n-propylene group, a 1,2-propylene group, an n-butylene group, 2-methyl-propane-1,2- Examples thereof include a diyl group, a 1,5-pentanediyl group, and a 1,6-hexanediyl group.
　斯かる構造部位（ｙ２－８）としては、具体的には、下記構造式で表されるものが、後述する前記一般式（１）で表される化合物の製造方法［工程ＩＶ］において、前記構造の構成原料となるジオール化合物の入手が容易である点から好ましい。 As such a structural moiety (y2-8), specifically, those represented by the following structural formula are those described in the above-mentioned production method [Step IV] of the compound represented by the general formula (1). It is preferable from the viewpoint of easy availability of a diol compound as a constituent material of the structure.
Figure JPOXMLDOC01-appb-C000067
 （各構造式中＊は他構造部位との結合手を表す。）
Figure JPOXMLDOC01-appb-C000067
 (* In each structural formula represents a bond with another structural site.)
　エステル結合形成タイプの構造部位である構造部位（ｙ２－９）は、前記一般式（１）中のｎが２又は３であり、かつ、下記構造式（ｙ２－９）で表されるものである。 The structural moiety (y2-9), which is an ester bond-forming structural moiety, is represented by the following structural formula (y2-9) where n is 2 or 3 in the general formula (1). is there.
Figure JPOXMLDOC01-appb-C000068
 （式中、Ｒ３１は炭素原子数４～１２の結合手数が（ｎ＋１）価の炭化水素基、Ｒ３２は炭素原子数２～６のアルキレン基、ｓは０～３の整数である）
Figure JPOXMLDOC01-appb-C000068
 (Wherein R 31 is a (n + 1) -valent hydrocarbon group having 4 to 12 carbon atoms, R 32 is an alkylene group having 2 to 6 carbon atoms, and s is an integer of 0 to 3)
　ここで、Ｒ３１を構成する炭素原子数４～１２の結合手数が（ｎ＋１）価の炭化水素基としては、多価アルコールの残基が挙げられ、例えば、トリメチロールプロパン残基、ペンタエリスリトール残基、グリセリロール残基、ジトリメチロールプロパン残基が挙げられる。ここで、「残基」とは、該当する多価アルコールから水酸基を除いた炭化水素構造部位である。 Here, the (n + 1) -valent hydrocarbon group having 4 to 12 carbon atoms constituting R 31 includes polyhydric alcohol residues such as trimethylolpropane residue, pentaerythritol residue. Groups, glyceryl residues, ditrimethylolpropane residues. Here, the “residue” is a hydrocarbon structure site obtained by removing a hydroxyl group from the corresponding polyhydric alcohol.
　また、Ｒ３２を構成する炭素原子数２～６のアルキレン基としては、エチレン基、ｎ－プロピレン基、１，２－プロピレン基、ｎ－ブチレン基、２－メチル－プロパン－１，２－ジイル基、１，５－ペンタンジイル基、１，６－ヘキサンジイル基が挙げられる。 Examples of the alkylene group having 2 to 6 carbon atoms constituting R 32 include ethylene, n-propylene, 1,2-propylene, n-butylene, 2-methyl-propane-1,2-diyl. Group, 1,5-pentanediyl group and 1,6-hexanediyl group.
　斯かる構造部位（ｙ２－９）としては、具体的には、下記構造式で表されるものが、後述する前記一般式（１）で表される化合物の製造方法［工程ＩＶ］において、前記構造の構成原料となるジオール化合物の入手が容易である点から好ましい。 As such a structural moiety (y2-9), specifically, those represented by the following structural formula can be used in the production method [Step IV] of the compound represented by the general formula (1) described later. It is preferable from the viewpoint of easy availability of a diol compound as a constituent material of the structure.
Figure JPOXMLDOC01-appb-C000069
 （各構造式中＊は他構造部位との結合手を表す。）
Figure JPOXMLDOC01-appb-C000069
 (* In each structural formula represents a bond with another structural site.)
　以上詳述した一般式（１）中、Ｙ２の中でも、特に構造部位（ｙ２－１）～（ｙ２－６）からなる群から選択されるアミド結合形成タイプの構造部位が生成物の化学的安定性に優れる点から好ましく、特に構造部位（ｙ２－１）、構造部位（ｙ２－２）、構造部位（ｙ２－３）が原料の入手の容易さと光硬化性に優れる点から好ましい。とりわけ、下記構造から選択される構造部位（ｙ２－３）が、中間体が結晶化しやすく製造上で容易に精製が可能である点から好ましい。 In the general formula (1) detailed above, among the Y 2 , the amide bond forming type structural site selected from the group consisting of the structural sites (y2-1) to (y2-6) is the chemical product. The structural part (y2-1), the structural part (y2-2), and the structural part (y2-3) are particularly preferred from the viewpoint of excellent stability and photocurability. In particular, the structural site (y2-3) selected from the following structures is preferable because the intermediate is easily crystallized and can be easily purified in production.
Figure JPOXMLDOC01-appb-C000070
 （各構造式中＊は他構造部位との結合手を表す。）
Figure JPOXMLDOC01-appb-C000070
 (* In each structural formula represents a bond with another structural site.)
　次に、一般式（１）中のＹ３は、単結合、炭素原子数１～３のアルキレン基、又は炭素原子数２又は３のアルキリデン基を表し、炭素原子数１～３のアルキレン基としては、メチレン基、エチレン基、ｎ－プロピレン基、１，２－プロピレン基が挙げられ、炭素原子数２又は３のアルキリデン基としてはエチリデン基、プロピリデン基が挙げられる。 Next, Y 3 in the general formula (1) represents a single bond, an alkylene group having 1 to 3 carbon atoms, or an alkylidene group having 2 or 3 carbon atoms, and as an alkylene group having 1 to 3 carbon atoms, Includes a methylene group, an ethylene group, an n-propylene group, and a 1,2-propylene group, and examples of the alkylidene group having 2 or 3 carbon atoms include an ethylidene group and a propylidene group.
　これらの中でも当該構造部位を構成する原料成分であるベンジルブロミド誘導体の入手の容易さの点から単結合、または炭素原子数２若しくは３のアルキリデン基が好ましく、特に光照射後の分解物の安全性の観点からは炭素原子数２又は３のアルキリデン基が好ましい。 Among these, a single bond or an alkylidene group having 2 or 3 carbon atoms is preferable from the viewpoint of easy availability of a benzyl bromide derivative which is a raw material component constituting the structural part, and the safety of the decomposition product after light irradiation is particularly preferable. From these viewpoints, an alkylidene group having 2 or 3 carbon atoms is preferred.
　以上詳述した一般式（１）で表される化合物は、更に具体的には、例えば、以下の表１～表１２に示す化合物Ｍ１～Ｍ８６のものが挙げられる。 More specifically, examples of the compound represented by the general formula (1) detailed above include compounds M1 to M86 shown in the following Tables 1 to 12.
Figure JPOXMLDOC01-appb-T000071
Figure JPOXMLDOC01-appb-T000071
Figure JPOXMLDOC01-appb-T000072
Figure JPOXMLDOC01-appb-T000072
Figure JPOXMLDOC01-appb-T000073
Figure JPOXMLDOC01-appb-T000073
Figure JPOXMLDOC01-appb-T000074
Figure JPOXMLDOC01-appb-T000074
Figure JPOXMLDOC01-appb-T000075
Figure JPOXMLDOC01-appb-T000075
Figure JPOXMLDOC01-appb-T000076
Figure JPOXMLDOC01-appb-T000076
Figure JPOXMLDOC01-appb-T000077
Figure JPOXMLDOC01-appb-T000077
Figure JPOXMLDOC01-appb-T000078
Figure JPOXMLDOC01-appb-T000078
Figure JPOXMLDOC01-appb-T000079
Figure JPOXMLDOC01-appb-T000079
Figure JPOXMLDOC01-appb-T000080
Figure JPOXMLDOC01-appb-T000080
Figure JPOXMLDOC01-appb-T000081
Figure JPOXMLDOC01-appb-T000081
Figure JPOXMLDOC01-appb-T000082
Figure JPOXMLDOC01-appb-T000082
　上記したＭ１～Ｍ８６の化合物の中でも、特に、高い光感度及び硬化物における優れた耐熱性を有し、かつ、アウトガスが生じにくい感光性樹脂組成物を得ることができ、また、原料の入手も容易である点から、Ｍ１、Ｍ４、Ｍ７、Ｍ１４、Ｍ２３、Ｍ２８、Ｍ３１、Ｍ３２、Ｍ４１、Ｍ４３、Ｍ４５、Ｍ５０、Ｍ５５、Ｍ６４、及びＭ７８の化合物が好ましい。 Among the above-mentioned compounds M1 to M86, a photosensitive resin composition having high photosensitivity and excellent heat resistance in a cured product and hardly generating outgas can be obtained, and the raw materials are also available. From the viewpoint of ease, compounds of M1, M4, M7, M14, M23, M28, M31, M32, M41, M43, M45, M50, M55, M64, and M78 are preferable.
　上記した一般式（１）で表される化合物は、下記［工程Ｉ］～［工程ＶＩ］を経て工業的に生産することができる。 The compound represented by the above general formula (1) can be industrially produced through the following [Step I] to [Step VI].
［工程Ｉ］
　ハロゲン化ベンゼンと、α位にハライド原子を有する酸ハライド化合物とを反応させて、カルボニルのα炭素原子上にハロゲン原子を持つアルキルアセトフェノン誘導体を合成する。［工程Ｉ］の反応は無水塩化アルミの存在下でフリーデルクラフト－アシル化反応によって行うことができる。　ここで、前記ハロゲン化ベンゼンとしては、フッ化ベンゼン、クロロベンゼン、ブロモベンゼン等が挙げられる。また、前記したα位にハライド原子を有する酸ハライド化合物としては、　２－ブロモプロピオン酸ブロミド、２－ブロモプロピオン酸クロリド、２－ブロモ吉草酸ブロミド、２－ブロモ吉草酸クロリド、２－ブロモヘキサン酸ブロミド、２－ブロモオクタン酸ブロミド等が挙げられる。 [Step I]
A halogenated benzene and an acid halide compound having a halide atom at the α-position are reacted to synthesize an alkyl acetophenone derivative having a halogen atom on the α-carbon atom of the carbonyl. The reaction of [Step I] can be carried out by Friedel-Craft-acylation reaction in the presence of anhydrous aluminum chloride. Here, examples of the halogenated benzene include fluorinated benzene, chlorobenzene, and bromobenzene. Examples of the acid halide compound having a halide atom at the α-position include 2-bromopropionic acid bromide, 2-bromopropionic acid chloride, 2-bromovaleric acid bromide, 2-bromovaleric acid chloride, 2-bromohexanoic acid. Examples thereof include bromide and 2-bromooctanoic acid bromide.
［工程ＩＩ］
　次いで、２級モノアミン化合物（ＨＮ（Ｒ２）（Ｒ３））を反応させてα位をアミノ基に変換する。ここで使用する２級モノアミン化合物（ＨＮ（Ｒ２）（Ｒ３））としては、ジメチルアミン、ジエチルアミン、メチルブチルアミン、メチルオクチルアミン、メチルドデシルアミン、エチルヘキシルアミン、ジエタノールアミン、ジイソプロパノールアミン、ジイソブタノールアミン、２，２’－ジエトキシジエチルアミン、２，２’－ジメトキシジエチルアミン、モルホリン、ピロリジン、ピペリジン、Ｎ－メチルピペラジン、２，６－ジメチルモルホリン等が挙げられる。反応条件は、例えば炭酸カルシウム、炭酸カリウム、炭酸ナトリウム等の炭酸塩や、トリエチルアミン、ジイソプロピルエチルアミン等の三級アミン等の塩基の存在下、０℃～８０℃の温度条件にて行うことができる。また、２級アミンを塩基として作用させる場合には過剰量用いて製造することができる。 [Step II]
Next, the secondary monoamine compound (HN (R 2 ) (R 3 )) is reacted to convert the α-position to an amino group. The secondary monoamine compound (HN (R 2 ) (R 3 )) used here is dimethylamine, diethylamine, methylbutylamine, methyloctylamine, methyldodecylamine, ethylhexylamine, diethanolamine, diisopropanolamine, diisobutanolamine. 2,2′-diethoxydiethylamine, 2,2′-dimethoxydiethylamine, morpholine, pyrrolidine, piperidine, N-methylpiperazine, 2,6-dimethylmorpholine and the like. The reaction conditions can be carried out at a temperature of 0 ° C. to 80 ° C. in the presence of a base such as a carbonate such as calcium carbonate, potassium carbonate or sodium carbonate, or a tertiary amine such as triethylamine or diisopropylethylamine. Moreover, when making a secondary amine act as a base, it can manufacture using excess amount.
［工程ＩＩＩ］
　次いで、置換基（－Ｙ３－Ｃ（＝Ｏ）－ＯＲ）を芳香核上の置換基として有するベンジルブロミド（ここで、Ｒはアルキル基または水素原子である）をアセトフェノン誘導体の三級アミンに反応させて四級アンモニウム塩に導き、その後、アルカリ処理によって、１．２－転位反応（スティーブンス転移）を行い、一般式３で表されるα―アミノアセトフェノン中間体化合物Ａ（一般式３）を合成する。こうして得られたα―アミノアセトフェノン中間化合物（一般式３）はアセトフェノン部の芳香環上にハロゲン原子を有し、かつ、α位に置換したベンジル基の芳香環上にカルボキシル基を有するものとなる。 [Step III]
Next, benzyl bromide (where R is an alkyl group or a hydrogen atom) having a substituent (—Y 3 —C (═O) —OR) as a substituent on the aromatic nucleus is converted to a tertiary amine of the acetophenone derivative. The reaction is led to a quaternary ammonium salt, and then subjected to a 1.2-rearrangement reaction (Stevens transition) by alkali treatment, and an α-aminoacetophenone intermediate compound A (general formula 3) represented by general formula 3 Is synthesized. The α-aminoacetophenone intermediate compound thus obtained (general formula 3) has a halogen atom on the aromatic ring of the acetophenone moiety and a carboxyl group on the aromatic ring of the benzyl group substituted at the α-position. .
Figure JPOXMLDOC01-appb-C000083
 （上記反応式中、「Ｈａｌ」はハロゲン原子を表す。）
Figure JPOXMLDOC01-appb-C000083
 (In the above reaction formula, “Hal” represents a halogen atom.)
　ここで、置換基（－Ｙ３－Ｃ（＝Ｏ）－ＯＲ）を芳香核上の置換基として有するベンジルブロミドにおけるＹ３は、前記した通り、単結合、炭素原子数１～３のアルキレン基、又は炭素原子数２又は３のアルキリデン基であるが、特に、単結合、メチレン基、又はエチリデン基であることが原料の入手の容易さの点から好ましく、Ｒは、水素原子、又は、メチル基、エチル基等のアルキル基であることが好ましく、よって、置換基（－Ｙ３－Ｃ（＝Ｏ）－ＯＲ）を芳香核上の置換基として有するベンジルブロミド化合物（ここで、Ｒはメチル基、エチル基または水素原子である）としては、例えば、ブロモメチル安息香酸メチル、２－［４－（ブロモメチル）フェニル］］プロピオン酸メチル、２－［４－（ブロモメチル）フェニル］］酢酸エチル等が挙げられる。 Here, Y 3 in benzyl bromide having a substituent (—Y 3 —C (═O) —OR) as a substituent on the aromatic nucleus is a single bond, an alkylene group having 1 to 3 carbon atoms as described above. Or an alkylidene group having 2 or 3 carbon atoms, particularly preferably a single bond, a methylene group, or an ethylidene group from the viewpoint of easy availability of raw materials, and R is a hydrogen atom or a methyl group. And a benzyl bromide compound having a substituent (—Y 3 —C (═O) —OR) as a substituent on the aromatic nucleus (where R is methyl). Group, ethyl group or hydrogen atom), for example, methyl bromomethylbenzoate, methyl 2- [4- (bromomethyl) phenyl]] propionate, 2- [4- (bromomethyl) phenyl]] Ethyl and the like.
　また、［工程ＩＩＩ］における四級アンモニウム化は２０～１００℃で行い、続く、１．２－転位反応（スティーブンス転移）は水酸化ナトリウム水溶液を塩基に用いて２０～８０℃にて行うことができる。 Further, the quaternary ammonium conversion in [Step III] is performed at 20 to 100 ° C., and the subsequent 1.2-rearrangement reaction (Stevens transition) is performed at 20 to 80 ° C. using an aqueous sodium hydroxide solution as a base. Can do.
［工程ＩＶ］
　次に、前記α―アミノアセトフェノン中間化合物（一般式３）のカルボキシル基と二官能以上の１級または２級アミンまたは二官能以上のアルコール（一般式４）を縮合反応させ、それぞれポリアミド化合物およびポリエステル化合物である中間体化合物Ｂへ誘導する。 [Step IV]
Next, the carboxyl group of the α-aminoacetophenone intermediate compound (general formula 3) is subjected to a condensation reaction between a bifunctional or higher primary or secondary amine or a bifunctional or higher alcohol (general formula 4), respectively. It leads to the intermediate compound B which is a compound.
　例えば、一般式４で表される化合物として二官能のジアミンを用いる場合は、α－アミノアセトフェノン中間化合物（一般式３）の２モルに対して二官能のジアミンの１モルを反応させ、２つのアミド基が対称的な分子構造となる中間体化合物Ｂを合成することができる。具体的には、一般式３で表されるα－アミノアセトフェノン中間化合物の芳香環上に配置されたカルボキシル基を、塩化チオニル等を使用して酸塩化物に変換してから二官能以上のアミンと反応させる方法、一般式３で表されるα－アミノアセトフェノン中間化合物をジシクロヘキシルカルボジイミド（ＤＣＣ）等の活性エステル化試剤を使用して二官能以上のアルコールと反応させる方法、一般式３で表されるα－アミノアセトフェノン中間化合物を無水酢酸等の酸無水物を使用して混合酸無水物に変換してから二官能以上のアルコールと反応させる方法などが挙げられる。 For example, when a bifunctional diamine is used as the compound represented by the general formula 4, 1 mol of the bifunctional diamine is reacted with 2 mol of the α-aminoacetophenone intermediate compound (general formula 3). Intermediate compound B in which the amide group has a symmetrical molecular structure can be synthesized. Specifically, a bifunctional or higher functional amine is obtained after converting the carboxyl group arranged on the aromatic ring of the α-aminoacetophenone intermediate compound represented by the general formula 3 into an acid chloride using thionyl chloride or the like. A method of reacting an α-aminoacetophenone intermediate compound represented by general formula 3 with a bifunctional or higher alcohol using an active esterification reagent such as dicyclohexylcarbodiimide (DCC), And a method in which an α-aminoacetophenone intermediate compound is converted to a mixed acid anhydride using an acid anhydride such as acetic anhydride and then reacted with a bifunctional or higher alcohol.
　他方、一般式４で表される化合物として二官能以上のアルコールを用いる場合の中間体化合物Ｂの合成法は、一般式３の中間化合物の芳香環上に配置されたカルボキシル基を、塩化チオニル等を使用して酸塩化物に変換してから二官能以上のアルコールと反応させる方法、パラトルエンスルホン酸等の酸触媒を使用して脱水縮合により二官能以上のアルコールと反応させる方法、ジシクロヘキシルカルボジイミド（ＤＣＣ）等の活性エステル化試剤を使用して二官能以上のアルコールと反応させる方法、無水酢酸等の酸無水物を使用して混合酸無水物に変換してから二官能以上のアルコールと反応させる方法などが挙げられる。 On the other hand, the synthesis method of the intermediate compound B in the case of using a bifunctional or higher alcohol as the compound represented by the general formula 4 is such that the carboxyl group arranged on the aromatic ring of the intermediate compound of the general formula 3 is substituted with thionyl chloride or the like. A method of reacting with a bifunctional or higher alcohol after conversion into an acid chloride using a method, a method of reacting with a bifunctional or higher alcohol by dehydration condensation using an acid catalyst such as para-toluenesulfonic acid, dicyclohexylcarbodiimide ( A method of reacting with a bifunctional or higher alcohol using an active esterification reagent such as DCC), and converting to a mixed acid anhydride using an acid anhydride such as acetic anhydride, and then reacting with a bifunctional or higher alcohol. The method etc. are mentioned.
Figure JPOXMLDOC01-appb-C000084
 （上記反応式中、「Ｈａｌ」はハロゲン原子を表す。）
Figure JPOXMLDOC01-appb-C000084
 (In the above reaction formula, “Hal” represents a halogen atom.)
　ここで、一般式４で表される化合物のうち、１級または２級アミンとしては、例えば、エチレンジアミン、１，３－ジアミノプロパン、１，２－ジアミノプロパン、１，４－ジアミノブタン、１，２－ジアミノ－２－メチルプロパン、２－メチル－１，３－プロパンジアミン、１,５-ジアミノペンタン、２，２－ジメチル－１，３－プロパンジアミン、１，６－ジアミノヘキサン、１，２－ジアミノシクロヘキサン、１，３－ジアミノシクロヘキサン、１，４－ジアミノシクロヘキサン、２，２´－ジアミノ－Ｎ－メチルジエチルアミン、１，７－ジアミノヘプタン、１，３－ビス(アミノメチル)シクロヘキサン、１，４－ビス(アミノメチル)シクロヘキサン、１，８－ジアミノオクタン、Ｎ－（３－アミノプロピル) －Ｎ－メチル－１，３－プロパンジアミン、１，１０－ジアミノドデカン、１，１１－ジアミノウンデカン、１，１２－ジアミノドデカン、１，１８－ジアミノオクタデカン、ビス（４－アミノシクロヘキシル）メタン、ピペラジン、２－メチルピペラジン、２，５－ジメチルピペラジン、２，３－ジメチルピペラジン、２，５－ジアザビシクロ［２．２．１］ヘプタン、ホモピペラジン、Ｎ，Ｎ´－ジメチルエチレンジアミン、Ｎ，Ｎ´－エチレンジエチルジアミン、Ｎ，Ｎ´－ビス［２－（メチルアミノ)エチル]メチルアミン、１，１－トリス(アミノメチル)エタン, エチリジントリス(メチルアミン) 等のアルキルアミン；２，２’―オキシビス(エチルアミン)、１，８－ジアミノ－３，６－ジオキサオクタン、３，６，９－トリオキサウンデカン－１，１１－ジアミン、４，９－ジオキサ－１，１２－ドデカンジアミン、４，７，１０－トリオキサ－１，１３－トリデカンジアミン、３，６，９，１２－テトラオキサテトラデカン－１，１４－ジアミン等のポリアルキレンエーテルアミン；ｍ－キシレンジアミン、ｐ－キシレンジアミン、１，３－フェニレンジアミン、１，４－フェニレンジアミン、１，５－ジアミノナフタレン、３，３´－ジメチルベンジジン、３，３´－ジエチルベンジジン、３，３´－ジメトキシベンジジン、３，３´，５，５´－テトラメチルベンジジン、２，２´－ジメチルベンジジン、１，３，５－トリス（４－アミノフェニル）ベンゼン、２，７－ジアミノフルオレン、４，４´－ジアミノベンゾフェノン、３，３´－ジアミノベンゾフェノン、３，３´－ジアミノジフェニルメタン、４，４´－エチレンジアニリン、１，１－ビス(４－アミノフェニル)シクロヘキサン、９，９－ビス(４－アミノフェニル)フルオレン、１，４－ビス[２－(４－アミノフェニル)－２－プロピル]ベンゼン、２，２－ビス(４－アミノフェニル)ヘキサフルオロプロパン、４，４´－ジアミノジフェニルスルホン、３，３´－ジアミノジフェニルスルホン、１，４－ビス(４－アミノフェノキシ)ベンゼン、１，３－ビス(３－アミノフェノキシ)ベンゼン、１，３－ビス(４－アミノフェノキシ)ベンゼン、２，２－ビス[４－(４－アミノフェノキシ)フェニル]ヘキサフルオロプロパン、２，２－ビス[４－(４－アミノフェノキシ)フェニル]プロパン、４，４´－ビス(４－アミノフェノキシ)ビフェニル、ビス[４－(４－アミノフェノキシ)フェニル]スルホン、１，４－ビス(４－アミノ－２－トリフルオロメチルフェノキシ)ベンゼン等の芳香族ジアミンが挙げらる。 Here, among the compounds represented by the general formula 4, as the primary or secondary amine, for example, ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, 1, 2-diamino-2-methylpropane, 2-methyl-1,3-propanediamine, 1,5-diaminopentane, 2,2-dimethyl-1,3-propanediamine, 1,6-diaminohexane, 1,2 -Diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 2,2'-diamino-N-methyldiethylamine, 1,7-diaminoheptane, 1,3-bis (aminomethyl) cyclohexane, 1, 4-bis (aminomethyl) cyclohexane, 1,8-diaminooctane, N- (3-aminopropyl) -N-methyl-1,3 Propanediamine, 1,10-diaminododecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,18-diaminooctadecane, bis (4-aminocyclohexyl) methane, piperazine, 2-methylpiperazine, 2,5 -Dimethylpiperazine, 2,3-dimethylpiperazine, 2,5-diazabicyclo [2.2.1] heptane, homopiperazine, N, N'-dimethylethylenediamine, N, N'-ethylenediethyldiamine, N, N'- Alkylamines such as bis [2- (methylamino) ethyl] methylamine, 1,1-tris (aminomethyl) ethane, ethylidintris (methylamine); 2,2′-oxybis (ethylamine), 1,8- Diamino-3,6-dioxaoctane, 3,6,9-trioxaundecane-1,11-di 4,9-dioxa-1,12-dodecanediamine, 4,7,10-trioxa-1,13-tridecanediamine, 3,6,9,12-tetraoxatetradecane-1,14-diamine, etc. Polyalkylene ether amine; m-xylenediamine, p-xylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 1,5-diaminonaphthalene, 3,3′-dimethylbenzidine, 3,3′-diethyl Benzidine, 3,3'-dimethoxybenzidine, 3,3 ', 5,5'-tetramethylbenzidine, 2,2'-dimethylbenzidine, 1,3,5-tris (4-aminophenyl) benzene, 2,7 -Diaminofluorene, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,3'-diaminodiphenyl Methane, 4,4′-ethylenedianiline, 1,1-bis (4-aminophenyl) cyclohexane, 9,9-bis (4-aminophenyl) fluorene, 1,4-bis [2- (4-aminophenyl) ) -2-propyl] benzene, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 1,4-bis (4-amino) Phenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfur Emissions, 1,4-bis (4-amino-2-trifluoromethylphenoxy) aromatic diamines such as benzene is Ageraru.
　一方、一般式４で表される化合物のうち、二官能以上のアルコールとしては、例えば、エチレングリコール、ジエチレングリコール、１，３－プロパンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、１，７－へプタンジオール、１，８－オクタンジオール、１，９－ノナンジオール、１，１０－デカンジオール、１，１２－ドデカンジオール、１，１４－テトラデカンジオール、１，１６－ヘキサデカンジオール、１，１８－オクタデカンジオール、１，２０－イコサンジオール等の直鎖のアルキレンジオールおよびこれらのエチレンオキシド変性物やプロピレンオキシド変性物；ポリオキシエチレングリコール、ポリオキシプロピレングリコール等のエーテルグリコール；前記直鎖のアルキレンジオールと、エチレンオキシド、プロピレンオキシド、テトラヒドロフラン、エチルグリシジルエーテル、プロピルグリシジルエーテル、ブチルグリシジルエーテル、フェニルグリシジルエーテル、アリルグリシジルエーテル等の種々の環状エーテル結合含有化合物との開環重合によって得られる変性ポリエーテルポリオール；前記直鎖のアルキレンジオールと、ε－カプロラクトン等の種々のラクトンとの重縮合反応によって得られるラクトン系ポリエステルポリオール等の二官能型水酸基含有化合物；トリメチロールエタン、トリメチロールプロパン、２，２，４－トリメチル－１，３－ペンタンジオール、グリセリン、ヘキサントリオール、ペンタエリスリトールおよびこれらのエチレンオキシド変性物やプロピレンオキシド変性物等の３官能以上のポリオールが挙げられる。 On the other hand, among the compounds represented by the general formula 4, bifunctional or higher alcohols include, for example, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1 , 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, , 16-hexadecanediol, 1,18-octadecanediol, 1,20-icosanediol and other linear alkylene diols and their ethylene oxide modified products and propylene oxide modified products such as polyoxyethylene glycol and polyoxypropylene glycol Ether glycol; Modified polyethers obtained by ring-opening polymerization of rangeol and various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether Polyols; Bifunctional hydroxyl group-containing compounds such as lactone polyester polyols obtained by polycondensation reaction of the linear alkylene diols with various lactones such as ε-caprolactone; trimethylolethane, trimethylolpropane, 2, 2 , 4-trimethyl-1,3-pentanediol, glycerin, hexanetriol, pentaerythritol and their ethylene oxide and propylene oxide modified products And trifunctional or higher polyols such as products.
［工程Ｖ］
　その後、中間体化合物Ｂの分子の末端部分のアリールハロゲン部を、一般式５で表される二官能性の環状アミンで置換して、分子の末端が二級アミンである中間生成物Ｃを合成する。 [Process V]
Thereafter, the aryl halogen part at the terminal part of the molecule of the intermediate compound B is substituted with a bifunctional cyclic amine represented by the general formula 5 to synthesize an intermediate product C whose terminal is a secondary amine. To do.
Figure JPOXMLDOC01-appb-C000085
Figure JPOXMLDOC01-appb-C000085
　斯かる反応は、６０℃～１６０℃の温度条件にて行うことができる。この際、系内で発生する酸の捕捉剤として過剰に一般式５で表される二官能性の環状アミンを使用することのほか、炭酸カリウムなどの無機炭酸塩を使用することができる。ここで、一般式５で表される二官能性の環状アミンとしては、例えば、ピペラジン、２－メチルピペラジン、２，５－ジメチルピペラジン、２，３－ジメチルピペラジン、２，５－ジアザビシクロ［２．２．１］ヘプタン、ホモピペラジン等が挙げられる。 Such a reaction can be performed at a temperature of 60 ° C. to 160 ° C. At this time, an inorganic carbonate such as potassium carbonate can be used in addition to an excessively bifunctional cyclic amine represented by the general formula 5 as a scavenger for the acid generated in the system. Here, examples of the bifunctional cyclic amine represented by the general formula 5 include piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2,3-dimethylpiperazine, 2,5-diazabicyclo [2. 2.1] heptane, homopiperazine and the like.
［工程ＶＩ］
　次いで、最終の反応として、［工程Ｖ］で得られた中間体化合物Ｃの構造末端に位置する二級アミンに対して、（メタ）アクリル酸エステル化合物化合物、イソシアン酸エステル、グリシジルエーテル、又はアルキルハライドと反応させることにより前記一般式（１）で表される化合物を製造することができる。具体的には、［工程ＶＩ］は、中間体化合物Ｃに反応させる化合物により以下の（工程ＶＩ－１）～（工程ＶＩ－９）に分類することができる。 [Process VI]
Next, as a final reaction, a (meth) acrylic acid ester compound compound, an isocyanate ester, a glycidyl ether, or an alkyl with respect to the secondary amine located at the structure terminal of the intermediate compound C obtained in [Step V]. The compound represented by the general formula (1) can be produced by reacting with a halide. Specifically, [Step VI] can be classified into the following (Step VI-1) to (Step VI-9) depending on the compound to be reacted with the intermediate compound C.
　（工程ＶＩ－１）
　前記中間体化合物Ｃ中の構造末端に位置する二級アミンに対して、下記反応式中、Ｈａｌ－Ｒ’で表される、炭素原子数３～１８のハロゲン化アルカンを反応させることにより（なお、該アルカンは反応に関与しないハロゲン原子又は水酸基を有していてもよい。）、Ｙ１が、置換基を有しないか、又はハロゲン原子若しくは水酸基を置換基として有する炭素原子数３～１８のアルキル基（ｙ１－１）である、下記一般式１－１で表される化合物を製造することができる。 (Process VI-1)
By reacting the secondary amine located at the structural end in the intermediate compound C with a halogenated alkane having 3 to 18 carbon atoms represented by Hal-R ′ in the following reaction formula (note that The alkane may have a halogen atom or a hydroxyl group that does not participate in the reaction.) Y 1 does not have a substituent or has 3 to 18 carbon atoms having a halogen atom or a hydroxyl group as a substituent. A compound represented by the following general formula 1-1, which is an alkyl group (y1-1), can be produced.
Figure JPOXMLDOC01-appb-C000086
 （式中、Ｈａｌはハロゲン原子、Ｒ’はハロゲン原子又は水酸基を有していてもよいアルキル基である。）
Figure JPOXMLDOC01-appb-C000086
 (In the formula, Hal is a halogen atom, and R ′ is a halogen atom or an alkyl group optionally having a hydroxyl group.)
　ここで、Ｈａｌ－Ｒ’で表される炭素原子数３～１８のハロゲン化アルカンとしては、１－クロロプロパン、２－クロロプロパン、１－クロロブタン、２－クロロブタン、２－メチル－２－クロロプロパン、２－メチル－１－クロロプロパン、１－クロロペンタン、２－クロロペンタン、３－クロロペンタン、２－クロロ－２－メチルブタン、１－クロロ－２－エチルブタン、１－クロロヘキサン、２－クロロヘキサン、３－クロロヘキサン、２－クロロ－メチル－ペンタン、１－クロロヘプタン、２－クロロヘプタン、３－クロロヘプタン、１－クロロオクタン、２－クロロオクタン、３－クロロオクタン、１－クロロ－１，１，３，３－テトラメチルブタン、１－クロロ－２，２，４，４－テトラメチルブタン、１－クロロ－３－メチルへプタン、１－クロロ－２－エチルヘキサン、１－クロロノナン、２－クロロノナン、３－クロロノナン、１－クロロ－１，１，３－トリメチルヘキサン、１－クロロ－１，１，３，３－テトラメチルペンタン、１－クロロデカン、２－クロロデカン、３－クロロデカン、１－クロロ－１，１，３，３，５，５－ヘキサメチルヘキサン、１－クロロ－８－メチル－ノナン、１－クロロウンデカン、２－クロロウンデカン、３－クロロウンデカン、１－クロロドデカン、２－クロロドデカン、３－クロロドデカン、１－クロロトリデカン、２－クロロトリデカン、３－クロロトリデカン、１－クロロテトラデカン、２－クロロテトラデカン、３－クロロテトラデカン、１－クロロペンタデカン、２－クロロペンタデカン、３－クロロペンタデカン、１－クロロヘキサデカン、２－クロロヘキサデカン、３－クロロヘキサデカン、１－クロロヘプタデカン、２－クロロヘプタデカン、３－クロロヘプタデカン、１－クロロオクタデカン、２－クロロオクタデカン、３－クロロオクタデカン等のクロロアルカン；１－プロモプロパン、２－ブロモプロパン、１－ブロモブタン、２－ブロモブタン、２－メチル－２－ブロモプロパン、２－メチル－１－ブロモプロパン、１－ブロモペンタン、２－ブロモペンタン、３－ブロモペンタン、２－ブロモ－２－メチルブタン、１－ブロモ－２－エチルブタン、１－プロモヘキサン、２－プロモヘキサン、３－ブロモヘキサン、２－ブロモ－メチル－ペンタン、１－ブロモヘプタン、２－ブロモヘプタン、３－プロモヘプタン、１－ブロモオクタン、２－ブロモオクタン、３－ブロモオクタン、１－ブロモ－１，１，３，３－テトラメチルブタン、１－ブロモ－２，２，４，４－テトラメチルブタン、１－ブロモ－３－メチルへプタン、１－ブロモ－２－エチルヘキサン、１－ブロモノナン、２－ブロモノナン、３－ブロモノナン、１－ブロモ－１，１，３－トリメチルヘキサン、１－ブロモ－１，１，３，３－テトラメチルペンタン、１－ブロモデカン、２－ブロモデカン、３－ブロモデカン、１－ブロモ－１，１，３，３，５，５－ヘキサメチルヘキサン、１－ブロモ－８－メチル－ノナン、１－ブロモウンデカン、２－ブロモウンデカン、３－ブロモウンデカン、１－ブロモドデカン、２－ブロモドデカン、３－ブロモドデカン、１－ブロモトリデカン、２－ブロモトリデカン、３－ブロモトリデカン、１－ブロモテトラデカン、２－ブロモテトラデカン、３－ブロモテトラデカン、１－ブロモペンタデカン、２－ブロモペンタデカン、３－ブロモペンタデカン、１－ブロモヘキサデカン、２－ブロモヘキサデカン、３－ブロモヘキサデカン、１－ブロモヘプタデカン、２－ブロモヘプタデカン、３－ブロモヘプタデカン、１－ブロモオクタデカン、２－ブロモオクタデカン、３－ブロモオクタデカン等のブロモアルカン；１－ヨードプロパン、２－ヨードプロパン、１－ヨードブタン、２－ヨードブタン、２－メチル－２－ヨードプロパン、２－メチル－１－ヨードプロパン、１－ヨードペンタン、２－ヨードペンタン、３－ヨードペンタン、２－ヨード－２－メチルブタン、１－ヨード－２－エチルブタン、１－ヨードヘキサン、２－ヨードヘキサン、３－ヨードヘキサン、２－ヨード－メチル－ペンタン、１－ヨードヘプタン、２－ヨードヘプタン、３－ヨードヘプタン、１－ヨードオクタン、２－ヨードオクタン、３－ヨードオクタン、１－ヨード－１，１，３，３－テトラメチルブタン、１－ヨード－２，２，４，４－テトラメチルブタン、１－ヨード－３－メチルへプタン、１－ヨード－２－エチルヘキサン、１－ヨードノナン、２－ヨードノナン、３－ヨードノナン、１－ヨード－１，１，３－トリメチルヘキサン、１－ヨード－１，１，３，３－テトラメチルペンタン、１－ヨードデカン、２－ヨードデカン、３－ヨードデカン、１－ヨード－１，１，３，３，５，５－ヘキサメチルヘキサン、１－ヨード－８－メチル－ノナン、１－ヨードウンデカン、２－ヨードウンデカン、３－ヨードウンデカン、１－ヨードドデカン、２－ヨードドデカン、３－ヨードドデカン、１－ヨードトリデカン、２－ヨードトリデカン、３－ヨードトリデカン、１－ヨードテトラデカン、２－ヨードテトラデカン、３－ヨードテトラデカン、１－ヨードペンタデカン、２－ヨードペンタデカン、３－ヨードペンタデカン、１－ヨードヘキサデカン、２－ヨードヘキサデカン、３－ヨードヘキサデカン、１－ヨードヘプタデカン、２－ヨードヘプタデカン、３－ヨードヘプタデカン、１－ヨードオクタデカン、２－ヨードオクタデカン、３－ヨードオクタデカン等のヨードアルカンが挙げられる。 Here, examples of the halogenated alkane having 3 to 18 carbon atoms represented by Hal-R ′ include 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 2-methyl-2-chloropropane, 2- Methyl-1-chloropropane, 1-chloropentane, 2-chloropentane, 3-chloropentane, 2-chloro-2-methylbutane, 1-chloro-2-ethylbutane, 1-chlorohexane, 2-chlorohexane, 3-chloro Hexane, 2-chloro-methyl-pentane, 1-chloroheptane, 2-chloroheptane, 3-chloroheptane, 1-chlorooctane, 2-chlorooctane, 3-chlorooctane, 1-chloro-1,1,3 3-tetramethylbutane, 1-chloro-2,2,4,4-tetramethylbutane, 1-chloro-3-methyl Heptane, 1-chloro-2-ethylhexane, 1-chlorononane, 2-chlorononane, 3-chlorononane, 1-chloro-1,1,3-trimethylhexane, 1-chloro-1,1,3,3-tetra Methylpentane, 1-chlorodecane, 2-chlorodecane, 3-chlorodecane, 1-chloro-1,1,3,3,5,5-hexamethylhexane, 1-chloro-8-methyl-nonane, 1-chloroundecane, 2-chloroundecane, 3-chloroundecane, 1-chlorododecane, 2-chlorododecane, 3-chlorododecane, 1-chlorotridecane, 2-chlorotridecane, 3-chlorotridecane, 1-chlorotetradecane, 2- Chlorotetradecane, 3-chlorotetradecane, 1-chloropentadecane, 2-chloropentadecane, 3-chloropentadecane 1-chlorohexadecane, 2-chlorohexadecane, 3-chlorohexadecane, 1-chloroheptadecane, 2-chloroheptadecane, 3-chloroheptadecane, 1-chlorooctadecane, 2-chlorooctadecane, 3-chlorooctadecane, etc. 1-promopropane, 2-bromopropane, 1-bromobutane, 2-bromobutane, 2-methyl-2-bromopropane, 2-methyl-1-bromopropane, 1-bromopentane, 2-bromopentane, 3-bromopentane, 2-bromo-2-methylbutane, 1-bromo-2-ethylbutane, 1-promohexane, 2-promohexane, 3-bromohexane, 2-bromo-methyl-pentane, 1-bromoheptane, 2 -Bromoheptane, 3-promoheptane, 1-bromooctane 2-bromooctane, 3-bromooctane, 1-bromo-1,1,3,3-tetramethylbutane, 1-bromo-2,2,4,4-tetramethylbutane, 1-bromo-3-methyl Heptane, 1-bromo-2-ethylhexane, 1-bromononane, 2-bromononane, 3-bromononane, 1-bromo-1,1,3-trimethylhexane, 1-bromo-1,1,3,3-tetra Methylpentane, 1-bromodecane, 2-bromodecane, 3-bromodecane, 1-bromo-1,1,3,3,5,5-hexamethylhexane, 1-bromo-8-methyl-nonane, 1-bromoundecane, 2-bromoundecane, 3-bromoundecane, 1-bromododecane, 2-bromododecane, 3-bromododecane, 1-bromotridecane, 2-bromotridecane, 3 Bromotridecane, 1-bromotetradecane, 2-bromotetradecane, 3-bromotetradecane, 1-bromopentadecane, 2-bromopentadecane, 3-bromopentadecane, 1-bromohexadecane, 2-bromohexadecane, 3-bromohexadecane, 1 Bromoalkanes such as bromoheptadecane, 2-bromoheptadecane, 3-bromoheptadecane, 1-bromooctadecane, 2-bromooctadecane, 3-bromooctadecane; 1-iodopropane, 2-iodopropane, 1-iodobutane, 2-iodobutane, 2-methyl-2-iodopropane, 2-methyl-1-iodopropane, 1-iodopentane, 2-iodopentane, 3-iodopentane, 2-iodo-2-methylbutane, 1-iodo-2 -Ethylbutane, 1-Yo Hexane, 2-iodohexane, 3-iodohexane, 2-iodo-methyl-pentane, 1-iodoheptane, 2-iodoheptane, 3-iodoheptane, 1-iodooctane, 2-iodooctane, 3-iodooctane, 1-iodo-1,1,3,3-tetramethylbutane, 1-iodo-2,2,4,4-tetramethylbutane, 1-iodo-3-methylheptane, 1-iodo-2-ethylhexane 1-iodononane, 2-iodononane, 3-iodononane, 1-iodo-1,1,3-trimethylhexane, 1-iodo-1,1,3,3-tetramethylpentane, 1-iododecane, 2-iododecane, 3-iododecane, 1-iodo-1,1,3,3,5,5-hexamethylhexane, 1-iodo-8-methyl-nonane, 1-iodoun Decane, 2-iodoundecane, 3-iodoundecane, 1-iodododecane, 2-iodododecane, 3-iodododecane, 1-iodotridecane, 2-iodotridecane, 3-iodotridecane, 1-iodotetradecane, 2-iodotetradecane, 3-iodotetradecane, 1-iodopentadecane, 2-iodopentadecane, 3-iodopentadecane, 1-iodohexadecane, 2-iodohexadecane, 3-iodohexadecane, 1-iodoheptadecane, 2-iodoheptadecane Examples include iodoalkanes such as decane, 3-iodoheptadecane, 1-iodooctadecane, 2-iodooctadecane, and 3-iodooctadecane.
　また、Ｈａｌ－Ｒ’で表される炭素原子数３～１８のハロゲン化アルカンが、該アルカン構造上に更にハロゲン原子を有する場合には、１－ブロモ－３－フルオロプロパン、１－ブロモ－３－クロロプロパン、１－ヨード－３－フルオロプロパン、１－ヨード－３－クロロプロパン、１－ブロモ－２－フルオロプロパン、１，１，１－トリフルオロ－３－ヨードプロパン、１，１，１，２，２－ペエンタフルオロ－３－ヨードプロパン、１－ブロモ－４－フルオロブタン、１－ブロモ－３－フルオロブタン、１－ブロモ－４－クロロロブタン、１，１，１－トリフルオロ－４－ヨードブタン、１，１，１，２，２，３，３－ペンタフルオロ－４－ヨードブタン、１－ブロモ－５－フルオロペンタン、１－ヨード－５－フルオロペンタン、１，１，１，２，２－ペエンタフルオロ－５－ヨードベンタン、１－ブロモ－６－フルオロヘキサン、１－ヨード－６－フルオロヘキサン、１，１，１－トリクロロ－６－ヨードヘキサン、１－ブロモ－７－フルオロヘプタン、１－ヨード－７－フルオロヘプタン、１－ブロモ－８－フルオロオクタン、１－ヨード－８－フルオロオクタン、１－ブロモ－９－フルオロノナン、１－ヨード－９－フルオロノナン、１－ブロモ－１０－フルオロデカン、１－ヨード－１０－フルオロデカン、１－ブロモ－１２－フルオロドデカン、１－ヨード－１２－フルオロドデカン、１－ブロモ－１８－フルオロオクタデカン、１－ヨード－１８－フルオロオクタデカン、１，１，１－トリクロロ－１８－ヨードオクタデカン等が挙げられる。 When the halogenated alkane having 3 to 18 carbon atoms represented by Hal-R ′ further has a halogen atom on the alkane structure, 1-bromo-3-fluoropropane, 1-bromo-3 -Chloropropane, 1-iodo-3-fluoropropane, 1-iodo-3-chloropropane, 1-bromo-2-fluoropropane, 1,1,1-trifluoro-3-iodopropane, 1,1,1,2 , 2-Peentafluoro-3-iodopropane, 1-bromo-4-fluorobutane, 1-bromo-3-fluorobutane, 1-bromo-4-chlororobutane, 1,1,1-trifluoro-4-iodobutane 1,1,1,2,2,3,3-pentafluoro-4-iodobutane, 1-bromo-5-fluoropentane, 1-iodo-5-fluoropentane, 1,1,2,2-peentafluoro-5-iodobentan, 1-bromo-6-fluorohexane, 1-iodo-6-fluorohexane, 1,1,1-trichloro-6-iodohexane, 1- Bromo-7-fluoroheptane, 1-iodo-7-fluoroheptane, 1-bromo-8-fluorooctane, 1-iodo-8-fluorooctane, 1-bromo-9-fluorononane, 1-iodo-9-fluoro Nonane, 1-bromo-10-fluorodecane, 1-iodo-10-fluorodecane, 1-bromo-12-fluorododecane, 1-iodo-12-fluorododecane, 1-bromo-18-fluorooctadecane, 1-iodo -18-fluorooctadecane, 1,1,1-trichloro-18-iodooctadecane and the like.
　更に、Ｈａｌ－Ｒ’で表される炭素原子数３～１８のハロゲン化アルカンが、該アルカン構造上に更に水酸基を有する場合には、３－ブロモ－１－プロパノール、３－ヨード－１－プロパノール、４－ヨード－２－メチル－２－ブタノール、４－ブロモ－２－メチル－２－ブタノール、１－ヨード－２－メチル－２－プロパノール、１－ブロモ－２－メチル－２－プロパノール、１－ヨード－４－ブタノール、１－ブロモ－４－ブタノール、１－ヨード－２－ブタノール、１－ブロモ－２－ブタノール、５－ヨード－１－ペンタノール、５－ブロモ－１－ペンタノール、１－ヨード－６－ヘキサノール、１－ブロモ－６－ヘキサノール、５－ヨード－３－メチル－１－ペンタノール、５－ブロモ－３－メチル－１－ペンタノール、１－ヨード－８－オクタノール、１－ブロモ－８－オクタノール、１－ヨード－１２－ドデカノール、１－ブロモ－１２－ドデカノール、１－ヨード－１８－オクタデカノール、１－ブロモ－１８－オクタデカノール等が挙げられる。 Further, when the halogenated alkane having 3 to 18 carbon atoms represented by Hal-R ′ further has a hydroxyl group on the alkane structure, 3-bromo-1-propanol, 3-iodo-1-propanol 4-iodo-2-methyl-2-butanol, 4-bromo-2-methyl-2-butanol, 1-iodo-2-methyl-2-propanol, 1-bromo-2-methyl-2-propanol, 1 -Iodo-4-butanol, 1-bromo-4-butanol, 1-iodo-2-butanol, 1-bromo-2-butanol, 5-iodo-1-pentanol, 5-bromo-1-pentanol, 1 -Iodo-6-hexanol, 1-bromo-6-hexanol, 5-iodo-3-methyl-1-pentanol, 5-bromo-3-methyl-1-pentanol, 1-iodo -8-octanol, 1-bromo-8-octanol, 1-iodo-12-dodecanol, 1-bromo-12-dodecanol, 1-iodo-18-octadecanol, 1-bromo-18-octadecanol, etc. Can be mentioned.
　また、この（工程ＶＩ－１）における反応は、Ｎ，Ｎ－ジメチルホルムアミド等の極性溶媒中、炭酸カリウム等の炭酸塩を塩基性触媒として使用するか、又は、ジクロロメタンやクロロホルム等のハロゲン化溶媒中、トリエチルアミン等の３級アミンを塩基性触媒として使用することにより行うことができる。 The reaction in (Step VI-1) is carried out using a carbonate such as potassium carbonate as a basic catalyst in a polar solvent such as N, N-dimethylformamide, or a halogenated solvent such as dichloromethane or chloroform. Among them, a tertiary amine such as triethylamine can be used as a basic catalyst.
　（工程ＶＩ－２）
　前記中間体化合物Ｃ中の構造末端に位置する二級アミンを、下記反応式中、Ｈａｌ－Ａｒａｌで表されるハロゲン化芳香族化合物と反応させることにより、Ｙ１が、アラルキル基（ｙ１－２）である化合物を製造することができる。 (Process VI-2)
By reacting a secondary amine located at the structure end in the intermediate compound C with a halogenated aromatic compound represented by Hal-Aral in the following reaction formula, Y 1 becomes an aralkyl group (y1-2). ) Can be produced.
Figure JPOXMLDOC01-appb-C000087
 （式中、Ｈａｌはハロゲン原子、Ａｒａｌはアラルキル基である。）
Figure JPOXMLDOC01-appb-C000087
 (In the formula, Hal is a halogen atom, and Aral is an aralkyl group.)
　ここで、前記反応式中、Ｈａｌ－Ａｒａｌで表されるハロゲン化芳香族化合物としては、塩化ベンジル、臭化ベンジル、塩化メトキシベンジル、臭化メトキシベンジル、臭化クロロベンジル、臭化ヒドロキシベンジル、よう化フェネチル基、臭化フェニルベンジル、臭化メトキシフェニルベンジル、臭化ナフチルメチル、臭化メトキシナフチルメチル、よう化フェニルプロピル、よう化フェニルプロペニル、臭化フェノキシベンジル、臭化メチルチオベンジル、ターフェニルメチルブロマイド等が挙げられ、（工程ＶＩ－１）と同様な反応条件で行うことができる。 Here, in the above reaction formula, the halogenated aromatic compound represented by Hal-Aral includes benzyl chloride, benzyl bromide, methoxybenzyl chloride, methoxybenzyl bromide, chlorobenzyl bromide, hydroxybenzyl bromide, and the like. Phenethyl group, phenylbenzyl bromide, methoxyphenylbenzyl bromide, naphthylmethyl bromide, methoxynaphthylmethyl bromide, phenylpropyl iodide, phenylpropenyl iodide, phenoxybenzyl bromide, methylthiobenzyl bromide, terphenylmethyl bromide Can be carried out under the same reaction conditions as in (Step VI-1).
　（工程ＶＩ－３）
　前記中間体化合物Ｃ中の構造末端に位置する二級アミンを、下記構造式（ｙ１－３ｒ）で表されるハロゲン化ポリエーテル化合物と反応させることにより、Ｙ１が、構造式（ｙ１－３）である化合物を製造することができる。 (Process VI-3)
By reacting a secondary amine located at the structural end in the intermediate compound C with a halogenated polyether compound represented by the following structural formula (y1-3r), Y 1 is converted to the structural formula (y1-3 ) Can be produced.
Figure JPOXMLDOC01-appb-C000088
 （式中、Ｒ８は炭素原子数２～４のアルキレン基、Ｒ９は水素原子又はフェニル基又は炭素原子数１～４のアルキル基、ｍは０～２０の整数を表す。）
Figure JPOXMLDOC01-appb-C000088
 (Wherein R 8 represents an alkylene group having 2 to 4 carbon atoms, R 9 represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 0 to 20)
Figure JPOXMLDOC01-appb-C000089
Figure JPOXMLDOC01-appb-C000089
　ここで前記構造式（ｙ１－３ｒ）及び一般式１－３中、Ｒ８の炭素原子数２～４のアルキレン基としては、ｎ－プロピレン基、１，２－プロプレン基、ｎ－ブチレン基、２－メチル－プロパン－１，２－ジイル基等が挙げられ、また、Ｒ９における炭素原子数１～４のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、若しくはｓ－ブチル基等が挙げられる。また、前記（工程ＶＩ－３）の反応条件は、炭酸カリウム等の塩基性触媒の存在下、２０～１２０℃にて行うことができる。 Here, in the structural formula (y1-3r) and the general formula 1-3, the alkylene group having 2 to 4 carbon atoms of R 8 includes an n-propylene group, a 1,2-propylene group, an n-butylene group, 2-methyl-propane-1,2-diyl group and the like, and examples of the alkyl group having 1 to 4 carbon atoms in R 9 include a methyl group, an ethyl group, a propyl group, an isopropyl group, and an n-butyl group. , Isobutyl group, t-butyl group, or s-butyl group. The reaction conditions in the above (Step VI-3) can be carried out at 20 to 120 ° C. in the presence of a basic catalyst such as potassium carbonate.
　（工程ＶＩ－４）
　前記中間体化合物Ｃ中の構造末端に位置する二級アミンを、下記構造式（ｙ１－４ｒ）で表される化合物の（メタ）アクリロイル基とマイケル付加反応させることにより、前記一般式（１）中のＹ１が、構造式（ｙ１－４）である化合物を製造することができる。 (Process VI-4)
A secondary amine located at the structure end in the intermediate compound C is subjected to a Michael addition reaction with a (meth) acryloyl group of a compound represented by the following structural formula (y1-4r) to thereby perform the general formula (1). A compound in which Y 1 is the structural formula (y1-4) can be produced.
Figure JPOXMLDOC01-appb-C000090
 （式中、Ｒ８は炭素原子数２～４のアルキレン基、Ｒ９は水素原子、フェニル基、又は炭素数１～４のアルキル基、Ｒ１０は水素原子またはメチル基、ｍは０～２０の整数を表す。）
Figure JPOXMLDOC01-appb-C000090
 (Wherein R 8 is an alkylene group having 2 to 4 carbon atoms, R 9 is a hydrogen atom, a phenyl group, or an alkyl group having 1 to 4 carbon atoms, R 10 is a hydrogen atom or a methyl group, and m is 0 to 20) Represents an integer.)
Figure JPOXMLDOC01-appb-C000091
Figure JPOXMLDOC01-appb-C000091
　ここで前記構造式（ｙ１－４ｒ）及び一般式１－４中、Ｒ８の炭素原子数２～４のアルキレン基としては、ｎ－プロピレン基、１，２－プロプレン基、ｎ－ブチレン基、２－メチル－プロパン－１，２－ジイル基等が挙げられ、また、Ｒ９における炭素原子数１～４のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、若しくはｓ－ブチル基等が挙げられる。 Here, in the structural formula (y1-4r) and the general formula 1-4, the alkylene group having 2 to 4 carbon atoms of R 8 includes an n-propylene group, a 1,2-propylene group, an n-butylene group, 2-methyl-propane-1,2-diyl group and the like, and examples of the alkyl group having 1 to 4 carbon atoms in R 9 include a methyl group, an ethyl group, a propyl group, an isopropyl group, and an n-butyl group. , Isobutyl group, t-butyl group, or s-butyl group.
　また、（工程ＶＩ－４）におけるマイケル付加反応は、公知慣用の反応条件で行うことができる。一般的な方法としては、前記中間体化合物Ｃと、前記マイケル受容体としての機能を有する前記構造式（ｙ１－４ｒ）で表される化合物とを、反応容器中、０～１５０℃で混合する方法が挙げられ、触媒や溶媒を使用することもできる。 Further, the Michael addition reaction in (Step VI-4) can be carried out under known and usual reaction conditions. As a general method, the intermediate compound C and the compound represented by the structural formula (y1-4r) having a function as the Michael acceptor are mixed at 0 to 150 ° C. in a reaction vessel. The method is mentioned and a catalyst and a solvent can also be used.
　使用可能な触媒としては、例えば、テトラブチルアンモニウム水酸化物、テトラメチルグアニジン、ジアザビシクロウンデセン、１，４－ジアザビシクロ［２．２．２］、ナトリウムｔ－ブチラート等が挙げられる。 Examples of usable catalysts include tetrabutylammonium hydroxide, tetramethylguanidine, diazabicycloundecene, 1,4-diazabicyclo [2.2.2], sodium t-butyrate, and the like.
　また、有機溶媒としては例えば、ペンタン、ヘキサン、ヘプタン、シクロヘキサン等の飽和炭化水素系溶剤、トルエン、キシレン等の芳香族炭化水素系溶剤、メタノール、エタノール、イソプロパノール、２－ブタノール、ｔ－ブタノール、エチレングリコール、カルビトール等のアルコール系溶剤、ジメチルエーテル、ジエチルエーテル、１，４－ジオキサン、テトラヒドロフラン（ＴＨＦ）等のエーテル系溶剤、ジメチルホルムアミド（ＤＭＦ）等のアミド系溶剤、クロロホルム、ジクロロメタン等のハロゲン系溶媒、ジメチルスルホキシド（ＤＭＳＯ）等を挙げることができる。 Examples of the organic solvent include saturated hydrocarbon solvents such as pentane, hexane, heptane and cyclohexane, aromatic hydrocarbon solvents such as toluene and xylene, methanol, ethanol, isopropanol, 2-butanol, t-butanol and ethylene. Alcohol solvents such as glycol and carbitol, ether solvents such as dimethyl ether, diethyl ether, 1,4-dioxane and tetrahydrofuran (THF), amide solvents such as dimethylformamide (DMF), and halogen solvents such as chloroform and dichloromethane And dimethyl sulfoxide (DMSO).
　前記中間体化合物Ｃと、前記マイケル受容体としての機能を有する前記構造式（ｙ１－４ｒ）で表される化合物と混合比は、特に限定されることはないが、中間体化合物Ｃ中の二級アミノ基（ｉ）と、前記構造式（ｙ１－４ｒ）で表される化合物中の（メタ）アクリロイル基（ii）との当量比［（ｉ）／（ｉｉ）］が、１／１．５～１／３０であることが好ましい。当量比［（ｉ）／（ｉｉ）］が１／１．５を超えると、前記中間体化合物Ｃ又はその分解物の塗膜からのマイグレーションが生じる可能性が上がり、当量比［（ｉ）／（ｉｉ）］が１／３０未満であるとマイケル付加反応物の硬化性能が劣る傾向がある。得られるマイケル付加反応物の硬化性能と塗膜溶出物量の観点から、当量比［（ｉ）／（ｉｉ）］は、特に１／２～１／２０であることが好ましい。 The mixing ratio of the intermediate compound C and the compound represented by the structural formula (y1-4r) having a function as the Michael acceptor is not particularly limited. The equivalent ratio [(i) / (ii)] of the primary amino group (i) and the (meth) acryloyl group (ii) in the compound represented by the structural formula (y1-4r) is 1/1. It is preferably 5 to 1/30. When the equivalent ratio [(i) / (ii)] exceeds 1 / 1.5, the possibility of migration from the coating film of the intermediate compound C or a decomposition product thereof increases, and the equivalent ratio [(i) / When (ii)] is less than 1/30, the curing performance of the Michael addition reaction product tends to be inferior. From the viewpoint of the curing performance of the resulting Michael addition reaction product and the amount of coating film eluate, the equivalent ratio [(i) / (ii)] is particularly preferably from 1/2 to 1/20.
　ここで、前記マイケル受容体としての機能を有する前記構造式（ｙ１－４ｒ）としては、例えばメトキシエチル（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、エトキシポリエチレングリコール（メタ）アクリレート、ブトキシポリエチレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート等が挙げられる。また、反応条件は、ジアザビシクロウンデセン（ＤＢＵ）等の触媒の存在下、２０～１２０℃にて行うことができる。 Here, as the structural formula (y1-4r) having a function as the Michael acceptor, for example, methoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethyleneglycol (meth) acrylate, butoxypolyethyleneglycol (Meth) acrylate, methoxypolypropylene glycol (meth) acrylate, etc. are mentioned. The reaction conditions can be carried out at 20 to 120 ° C. in the presence of a catalyst such as diazabicycloundecene (DBU).
　（工程ＶＩ－５）
　前記中間体化合物Ｃ中の構造末端に位置する二級アミンを、下記構造式（ｙ１－５ｒ）で表される化合物の（メタ）アクリロイル基と反応させることにより、前記一般式（１）中のＹ１が、構造式（ｙ１－５）である化合物を製造することができる。 (Process VI-5)
By reacting the secondary amine located at the structure end in the intermediate compound C with the (meth) acryloyl group of the compound represented by the following structural formula (y1-5r), A compound in which Y 1 is the structural formula (y1-5) can be produced.
Figure JPOXMLDOC01-appb-C000092
 （式中、Ｒ１０は水素原子またはメチル基、Ｒ１１は炭素原子数１～１８のアルキル基又は炭素原子数６～１８のアリール基を表す。）
Figure JPOXMLDOC01-appb-C000092
 (Wherein R 10 represents a hydrogen atom or a methyl group, and R 11 represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms.)
Figure JPOXMLDOC01-appb-C000093
Figure JPOXMLDOC01-appb-C000093
　ここで、Ｒ１１は炭素原子数１～１８のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、；ｓ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、２－エチルブチル基、イソペンチル基、１－メチルペンチル基、１，３－ジメチルブチル基、１－メチルヘキシル基、イソヘプチル基、１，１，３，３－テトラメチルブチル基、２，２，４，４－テトラメチルブチル基、１－メチルヘプチル基、３－メチルヘプチル基、２－エチルヘキシル基、１，１，３－トリメチルヘキシル基、１，１，３，３－テトラメチルペンチル基、イソデシル基、１－メチルウンデシル基または１，１，３，３，５，５－ヘキサメチルヘキシル基等の直鎖状または分岐上のアルキル基、シクロヘプチル基、シクロヘキシル基、シクロペンチル基等のシクロアルキル基等が挙げられ、他方、炭素原子数６～１８のアリール基としては、フェニル基、ベンジル基、フェネチル基、ビフェニル基、ナフチル基、トリル基、キシリル基、メシチル基、クメニル基、クロロフェニル基、ブロモフェニル基、クロロメチルフェニル基、ヒドロキシフェニル基、メトキシフェニル基、エトキシフェニル基、フェノキシフェニル基、アセトキシフェニル基、ベンゾイロキシフェニル基、メチルチオフェニル基、フェニルチオフェニル基、メチルアミノフェニル基、ジメチルアミノフェニル基、アセチルアミノフェニル基、カルボキシフェニル基、メトキシカルボニルフェニル基、フェノキシカルボニルフェニル基、Ｎ－フェニルカルバモイルフェニル基、シアノフェニル基、スルホフェニル基、スルホナトフェニル基、ホスホノフェニル基、ホスホナトフェニル基等が挙げられる。 Here, R 11 represents an alkyl group having 1 to 18 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group; s-butyl group, pentyl Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, 2-ethylbutyl group, isopentyl group, 1 -Methylpentyl group, 1,3-dimethylbutyl group, 1-methylhexyl group, isoheptyl group, 1,1,3,3-tetramethylbutyl group, 2,2,4,4-tetramethylbutyl group, 1- Methylheptyl group, 3-methylheptyl group, 2-ethylhexyl group, 1,1,3-trimethylhexyl group, 1,1,3,3-te Linear or branched alkyl group such as tramethylpentyl group, isodecyl group, 1-methylundecyl group or 1,1,3,3,5,5-hexamethylhexyl group, cycloheptyl group, cyclohexyl group, A cycloalkyl group such as a cyclopentyl group and the like, and examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a benzyl group, a phenethyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, Cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, Methylaminophenyl group, dimethylaminophenyl Nyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, phosphonatophenyl Groups and the like.
　（工程ＶＩ－６）
　前記中間体化合物Ｃ中の構造末端に位置する二級アミンを、下記構造式（ｙ１－６ｒ）で表されるエポキシ化合物のエポキシ基と反応させることにより、Ｙ１が、構造式（ｙ１－６）である化合物を製造することができる。 (Process VI-6)
By reacting a secondary amine located at the structural end in the intermediate compound C with an epoxy group of an epoxy compound represented by the following structural formula (y1-6r), Y 1 is converted to the structural formula (y1-6). ) Can be produced.
Figure JPOXMLDOC01-appb-C000094
 （式中、Ｒ１２は炭素原子数１～１８のアルキル基を表す。）
Figure JPOXMLDOC01-appb-C000094
 (In the formula, R 12 represents an alkyl group having 1 to 18 carbon atoms.)
Figure JPOXMLDOC01-appb-C000095
Figure JPOXMLDOC01-appb-C000095
　ここで、前記構造式（ｙ１－６ｒ）及び一般式１－６中、Ｒ１２の炭素原子数１～１８のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、；ｓ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、２－エチルブチル基、イソペンチル基、１－メチルペンチル基、１，３－ジメチルブチル基、１－メチルヘキシル基、イソヘプチル基、１，１，３，３－テトラメチルブチル基、２，２，４，４－テトラメチルブチル基、１－メチルヘプチル基、３－メチルヘプチル基、２－エチルヘキシル基、１，１，３－トリメチルヘキシル基、１，１，３，３－テトラメチルペンチル基、イソデシル基、１－メチルウンデシル基または１，１，３，３，５，５－ヘキサメチルヘキシル基等の直鎖状または分岐上のアルキル基、シクロヘプチル基、シクロヘキシル基、シクロペンチル基等のシクロアルキル基等が挙げられる。 Here, in the structural formula (y1-6r) and the general formula 1-6, the alkyl group having 1 to 18 carbon atoms of R 12 includes a methyl group, an ethyl group, a propyl group, an isopropyl group, and an n-butyl group. , Isobutyl group, t-butyl group; s-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group , Heptadecyl group, octadecyl group, 2-ethylbutyl group, isopentyl group, 1-methylpentyl group, 1,3-dimethylbutyl group, 1-methylhexyl group, isoheptyl group, 1,1,3,3-tetramethylbutyl group 2,2,4,4-tetramethylbutyl group, 1-methylheptyl group, 3-methylheptyl group, 2-ethylhexyl group, 1,1, Linear such as 3-trimethylhexyl group, 1,1,3,3-tetramethylpentyl group, isodecyl group, 1-methylundecyl group or 1,1,3,3,5,5-hexamethylhexyl group Alternatively, a branched alkyl group, a cycloheptyl group, a cyclohexyl group, a cycloalkyl group such as a cyclopentyl group, and the like can be given.
　また、（工程ＶＩ－６）におけるエポキシ化合物との反応は、前記中間体化合物Ｃと、前記構造式（ｙ１－６ｒ）で表される化合物とを、反応容器中、０～１５０℃なる温度条件下に混合し反応させる方法が挙げられる。この際、触媒や溶媒を使用することもできる。 Further, the reaction with the epoxy compound in (Step VI-6) is carried out by subjecting the intermediate compound C and the compound represented by the structural formula (y1-6r) to a temperature condition of 0 to 150 ° C. in a reaction vessel. The method of mixing and making it react below is mentioned. At this time, a catalyst or a solvent can also be used.
　使用可能な触媒としては、例えば、トリエチルアミン、ジイソプロピルエチルアミン、ベンジルジエチルアミン、イミダゾール、テトラブチルアンモニウムブロミド、トリ－ｎ－オクチルホスフィン、トリフェニルホスフィン等が挙げられる。 Examples of usable catalysts include triethylamine, diisopropylethylamine, benzyldiethylamine, imidazole, tetrabutylammonium bromide, tri-n-octylphosphine, triphenylphosphine, and the like.
　また、有機溶媒としては例えば、トルエン、キシレン等の芳香族炭化水素系溶剤、ジメチルエーテル、ジエチルエーテル、１，４－ジオキサン、テトラヒドロフラン（ＴＨＦ）等のエーテル、アセトン、２－ブタノン、メチルイソブチルケトン等のケトン系溶剤、ジメチルホルムアミド（ＤＭＦ）等のアミド系溶剤、クロロホルム、ジクロロメタン等のハロゲン系溶媒、ジメチルスルホキシド（ＤＭＳＯ）等を挙げることができる。 Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, ethers such as dimethyl ether, diethyl ether, 1,4-dioxane, and tetrahydrofuran (THF), acetone, 2-butanone, methyl isobutyl ketone, and the like. Examples thereof include ketone solvents, amide solvents such as dimethylformamide (DMF), halogen solvents such as chloroform and dichloromethane, dimethyl sulfoxide (DMSO), and the like.
　（工程ＶＩ－７）
　前記中間体化合物Ｃ中の構造末端に位置する二級アミンを、下記構造式（ｙ１－７ｒ）で表されるエポキシ化合物のエポキシ基と反応させることにより、Ｙ１が、構造式（ｙ１－７）である化合物を製造することができる。 (Process VI-7)
By reacting a secondary amine located at the structural end in the intermediate compound C with an epoxy group of an epoxy compound represented by the following structural formula (y1-7r), Y 1 is converted to the structural formula (y1-7). ) Can be produced.
Figure JPOXMLDOC01-appb-C000096
 （式中、Ｒ８は炭素原子数２～４のアルキレン基、Ｒ１３は水素原子、炭素原子数１～６のアルキル基又はハロゲン原子、ｍは０～２０の整数を表す。）
Figure JPOXMLDOC01-appb-C000096
 (Wherein R 8 represents an alkylene group having 2 to 4 carbon atoms, R 13 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a halogen atom, and m represents an integer of 0 to 20)
Figure JPOXMLDOC01-appb-C000097
Figure JPOXMLDOC01-appb-C000097
　ここで、前記構造式（ｙ１－７ｒ）及び一般式１－７中の中のＲ８は、構造部位（ｙ１－３）におけるＲ８と同義であり、Ｒ１３の炭素原子数１～６のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｓ－ブチル基、ペンチル基、ヘキシル基、２－エチルブチル基、イソペンチル基、１－メチルペンチル基、１，３－ジメチルブチル基等が挙げられ、ハロゲン原子としては、臭素原子、塩素原子、フッ素原子が挙げられる。 Here, R 8 in said formula (y1-7r) and the general formula 1-7 is synonymous with R 8 in the structural moiety (Y1-3), from 1 to 6 carbon atoms of R 13 Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, s-butyl group, pentyl group, hexyl group, 2-ethylbutyl group, isopentyl group, 1 -A methylpentyl group, a 1,3-dimethylbutyl group and the like can be mentioned, and examples of the halogen atom include a bromine atom, a chlorine atom and a fluorine atom.
　また、工程ＶＩ－７におけるエポキシ化合物との反応は、例えば、前記中間体化合物Ｃと、前記構造式（ｙ１－７ｒ）で表される化合物とを、反応容器中、０～１５０℃で混合し、反応させる方法が挙げられる。この際、触媒や溶媒を使用することもできる。 In addition, the reaction with the epoxy compound in Step VI-7 includes, for example, mixing the intermediate compound C and the compound represented by the structural formula (y1-7r) at 0 to 150 ° C. in a reaction vessel. The method of making it react is mentioned. At this time, a catalyst or a solvent can also be used.
　使用可能な触媒としては、例えば、トリエチルアミン、ジイソプロピルエチルアミン、ベンジルジエチルアミン、イミダゾール、テトラブチルアンモニウムブロミド、トリ－ｎ－オクチルホスフィン、トリフェニルホスフィン等が挙げられる。 Examples of usable catalysts include triethylamine, diisopropylethylamine, benzyldiethylamine, imidazole, tetrabutylammonium bromide, tri-n-octylphosphine, triphenylphosphine, and the like.
　また、有機溶媒としては例えば、トルエン、キシレン等の芳香族炭化水素系溶剤、ジメチルエーテル、ジエチルエーテル、１，４－ジオキサン、テトラヒドロフラン（ＴＨＦ）等のエーテル系溶剤、アセトン、２－ブタノン、メチルイソブチルケトン等のケトン系溶剤、ジメチルホルムアミド（ＤＭＦ）等のアミド系溶剤、クロロホルム、ジクロロメタン等のハロゲン系溶媒、ジメチルスルホキシド（ＤＭＳＯ）等を挙げることができる。 Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, ether solvents such as dimethyl ether, diethyl ether, 1,4-dioxane, and tetrahydrofuran (THF), acetone, 2-butanone, and methyl isobutyl ketone. And ketone solvents such as dimethylformamide (DMF), halogen solvents such as chloroform and dichloromethane, and dimethyl sulfoxide (DMSO).
　（工程ＶＩ－８） (Process VI-8)
　前記中間体化合物Ｃ中の構造末端に位置する二級アミンを、下記構造式（ｙ１－８ｒ）で表される化合物の（メタ）アクリロイル基と反応させることにより、前記一般式（１）中のＹ１が、構造式（ｙ１－８）である化合物を製造することができる。 By reacting the secondary amine located at the structure end in the intermediate compound C with the (meth) acryloyl group of the compound represented by the following structural formula (y1-8r), A compound in which Y 1 is the structural formula (y1-8) can be produced.
Figure JPOXMLDOC01-appb-C000098
 （式中、Ｒ８は炭素原子数２～４のアルキレン基、Ｒ１０は水素原子又はメチル基、Ｒ１４はｐ＋１の結合手を持つ炭素原子数５～１８の炭化水素基、ｌは０～２０の整数、ｐは１～３の整数を表す。）
Figure JPOXMLDOC01-appb-C000098
 Wherein R 8 is an alkylene group having 2 to 4 carbon atoms, R 10 is a hydrogen atom or a methyl group, R 14 is a hydrocarbon group having 5 to 18 carbon atoms having a p + 1 bond, and l is 0 to (An integer of 20 and p represents an integer of 1 to 3)
Figure JPOXMLDOC01-appb-C000099
Figure JPOXMLDOC01-appb-C000099
　ここで、前記構造式（ｙ１－８ｒ）及び一般式１－８中のＲ８は、構造部位（ｙ１－３）におけるＲ８と同義であり、Ｒ１４におけるｐ＋１の結合手を持つ炭素原子数３～２５の炭化水素基とは、グリセロール残基、トリメチロールプロパン残基、ペンタエリスリトール残基等の脂肪族多価アルコール残基；ｎ－プロピレン基、１，２－プロピレン基、ｎ－ブチレン基、２－メチル－プロパン－１，２－ジイル基、１，５－ペンタンジイル基、１，６－ヘキサンジイル基、１，７－ヘプタンジイル基、１，８－オクタンジイル基、１，９－ノナンジイル基、１，１０－デカンジイル基、３，８－デカンジイル基、１，１１－ウンデカンジイル基、１，１２－ドデカンジイル基、１，１３－トリデカンジイル基、１，１４－テトラデカンジイル基、１，１５－ペンタデカンジイル基、１，１６－ヘキサデカンジイル基、１，１７－ヘプタデカンジイル基、１，１８－オクタデカンジイル基、１，１９－ノナデカンジイル基、１，２０－エイコサンジイル基、１，２１－ヘネイコサンジイル基、１，２２－ドコサンジイル基、１，２３－トリコサンジイル基、１，２４－テトラコサンジイル基、１，２５－ペンタコサンジイル基が挙げられる。 Here, the structural formula (y1-8r) and the general formula in 1-8 R 8 has the same meaning as R 8 in the structural moiety (Y1-3), the number of carbon atoms with a bond p + 1 in R 14 3 to 25 hydrocarbon groups are aliphatic polyhydric alcohol residues such as glycerol residue, trimethylolpropane residue, pentaerythritol residue; n-propylene group, 1,2-propylene group, n-butylene group 2-methyl-propane-1,2-diyl group, 1,5-pentanediyl group, 1,6-hexanediyl group, 1,7-heptanediyl group, 1,8-octanediyl group, 1,9-nonanediyl group 1,10-decanediyl group, 3,8-decanediyl group, 1,11-undecanediyl group, 1,12-dodecanediyl group, 1,13-tridecanediyl group, 1,14-tetradecanedi Group, 1,15-pentadecandiyl group, 1,16-hexadecandiyl group, 1,17-heptadecandiyl group, 1,18-octadecandiyl group, 1,19-nonadecandiyl group, 1,20-eicosanediyl group 1,2-heneicosanediyl group, 1,2-docosanediyl group, 1,23-tricosanediyl group, 1,24-tetracosanediyl group, 1,25-pentacosanediyl group.
　ここで残基とは、多価アルコールの水酸基を除く炭化水素構造部位を示す。 Here, the residue refers to a hydrocarbon structure site excluding the hydroxyl group of the polyhydric alcohol.
　（工程ＶＩ－８）における、マイケル付加反応は、公知慣用の反応条件で行うことができる。一般的な方法としては、前記中間体化合物Ｃと、前記マイケル受容体としての機能を有する前記構造式（ｙ１－８ｒ）で表される化合物とを、反応容器中、０～１５０℃で混合し、反応させる方法が挙げられる。この際、触媒や溶媒を使用することもできる。 The Michael addition reaction in (Step VI-8) can be carried out under known and usual reaction conditions. As a general method, the intermediate compound C and the compound represented by the structural formula (y1-8r) having a function as the Michael acceptor are mixed at 0 to 150 ° C. in a reaction vessel. The method of making it react is mentioned. At this time, a catalyst or a solvent can also be used.
　使用可能な触媒としては、例えば、テトラブチルアンモニウム水酸化物、テトラメチルグアニジン、ジアザビシクロウンデセン、１，４－ジアザビシクロ［２．２．２］、ナトリウム ｔ－ブチラート等が挙げられる。 Examples of usable catalysts include tetrabutylammonium hydroxide, tetramethylguanidine, diazabicycloundecene, 1,4-diazabicyclo [2.2.2], sodium tert-butylate, and the like.
　また、有機溶媒としては例えば、ペンタン、ヘキサン、ヘプタン、シクロヘキサン等の飽和炭化水素系溶剤、トルエン、キシレン等の芳香族炭化水素系溶剤、メタノール、エタノール、イソプロパノール、２－ブタノール、ｔ－ブタノール、エチレングリコール、カルビトール等のアルコール系溶剤、ジメチルエーテル、ジエチルエーテル、１，４－ジオキサン、テトラヒドロフラン（ＴＨＦ）等のエーテル系溶剤、ジメチルホルムアミド（ＤＭＦ）等のアミド系溶剤、クロロホルム、ジクロロメタン等のハロゲン系溶媒、ジメチルスルホキシド（ＤＭＳＯ）等を挙げることができる。 Examples of the organic solvent include saturated hydrocarbon solvents such as pentane, hexane, heptane and cyclohexane, aromatic hydrocarbon solvents such as toluene and xylene, methanol, ethanol, isopropanol, 2-butanol, t-butanol and ethylene. Alcohol solvents such as glycol and carbitol, ether solvents such as dimethyl ether, diethyl ether, 1,4-dioxane and tetrahydrofuran (THF), amide solvents such as dimethylformamide (DMF), and halogen solvents such as chloroform and dichloromethane And dimethyl sulfoxide (DMSO).
　前記中間体化合物Ｃと、前記マイケル受容体としての機能を有する前記構造式（ｙ１－８ｒ）で表される化合物と混合比は、特に限定されることはないが、中間体化合物Ｃ中の二級アミノ基（ｉ）と、前記構造式（ｙ１－８ｒ）で表される化合物中の（メタ）アクリロイル基（ii）との当量比［（ｉ）／（ｉｉ）］が、１／１．５～１／３０であることが好ましい。当量比［（ｉ）／（ｉｉ）］が１／１．５を超えると、前記中間体化合物Ｃ又はその分解物の塗膜からのマイグレーションが生じる可能性が上がり、当量比［（ｉ）／（ｉｉ）］が１／３０未満であるとマイケル付加反応物の硬化性能が劣る傾向がある。得られるマイケル付加反応物の硬化性能と塗膜溶出物量の観点から、当量比［（ｉ）／（ｉｉ）］は、特に１／２～１／２０であることが好ましい。 The mixing ratio of the intermediate compound C and the compound represented by the structural formula (y1-8r) having a function as the Michael acceptor is not particularly limited. The equivalent ratio [(i) / (ii)] of the primary amino group (i) and the (meth) acryloyl group (ii) in the compound represented by the structural formula (y1-8r) is 1/1. It is preferably 5 to 1/30. When the equivalent ratio [(i) / (ii)] exceeds 1 / 1.5, the possibility of migration from the coating film of the intermediate compound C or a decomposition product thereof increases, and the equivalent ratio [(i) / When (ii)] is less than 1/30, the curing performance of the Michael addition reaction product tends to be inferior. From the viewpoint of the curing performance of the resulting Michael addition reaction product and the amount of coating film eluate, the equivalent ratio [(i) / (ii)] is particularly preferably from 1/2 to 1/20.
　ここで、前記マイケル受容体としての機能を有する前記構造式（ｙ１－８ｒ）で表される化合物の例としては、例えば、ジエチレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、３－メチル－１，５－ペンタンジオールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート等の二官能アクリレート；トリメチロールプロパントリ（メタ）アクリレートおよびそのエチレンオキシドやプロピレンオキシド等のアルキレンオキシド変性物；ペンタエリスリトールトリ又はテトラ（メタ）アクリレートおよびそのエチレンオキシドやプロピレンオキシド等のアルキレンオキシド変性物；ジトリメチロールプロパンテトラ（メタ）アクリレートおよびそのエチレンオキシドやプロピレンオキシド等のアルキレンオキシド変性物；ジペンタエリスリトールテトラ又はペンタ又はヘキサ（メタ）アクリレートおよびそのカプロラクトン変性物等の多官能（メタ）アクリレート；ビスフェノールＡジグリシジルエーテルやトリメチロールプロパントリグリシジルエーテル等のポリグリシジルエーテルと（メタ）アクリル酸との反応により得られるエポキシ（メタ）アクリレート；イソホロンジイソシアネートやヘキサメチレンジイソシアネート三量体等のポリイソシアナート化合物と、ヒドロキシエチル（メタ）アクリレートやペンタエリスリトールトリ（メタ）アクリレート等の水酸基を有するアクリレートとの反応により得られるウレタン（メタ）アクリレート；トリメリット酸やコハク酸等の多塩基酸と、エチレングリコールやネオペンチルグリコール等のポリオールと、ヒドロキシエチル（メタ）アクリレートやペンタエリスリトールトリ（メタ）アクリレート等の水酸基を有する（メタ）アクリレートとの反応により得られるポリエステル（メタ）アクリレート；グリシジル（メタ）アクリレートと単官能（メタ）アクリレートとの重合物と、（メタ）アクリル酸との反応により得られる高分子量型のポリ（メタ）アクリレート等が挙げられるが、これらに限定されるものではない。またこれらの反応性化合物は、単独で使用してもよく、複数を混合して使用してもよい。 Here, examples of the compound represented by the structural formula (y1-8r) having a function as the Michael acceptor include, for example, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and tripropylene. Bifunctional acrylates such as glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentylglycol di (meth) acrylate; trimethylolpropane tri ( (Meth) acrylate and its modified alkylene oxide such as ethylene oxide and propylene oxide; pentaerythritol tri or tetra (meth) acrylate and its modified alkylene oxide such as ethylene oxide and propylene oxide Ditrimethylolpropane tetra (meth) acrylate and its alkylene oxide modified products such as ethylene oxide and propylene oxide; dipentaerythritol tetra or penta or hexa (meth) acrylate and its polyfunctional (meth) acrylate such as caprolactone modified products; bisphenol A di Epoxy (meth) acrylate obtained by reaction of polyglycidyl ether such as glycidyl ether or trimethylolpropane triglycidyl ether with (meth) acrylic acid; polyisocyanate compound such as isophorone diisocyanate or hexamethylene diisocyanate trimer, and hydroxy Obtained by reaction with acrylates with hydroxyl groups such as ethyl (meth) acrylate and pentaerythritol tri (meth) acrylate Urethane (meth) acrylate; having a polybasic acid such as trimellitic acid or succinic acid, a polyol such as ethylene glycol or neopentyl glycol, and a hydroxyl group such as hydroxyethyl (meth) acrylate or pentaerythritol tri (meth) acrylate ( Polyester (meth) acrylate obtained by reaction with (meth) acrylate; polymer of glycidyl (meth) acrylate and monofunctional (meth) acrylate, and high molecular weight type poly (obtained by reaction with (meth) acrylic acid Examples thereof include, but are not limited to, (meth) acrylate. These reactive compounds may be used alone or in combination.
　（工程ＶＩ－９）
　前記中間体化合物Ｃ中の構造末端に位置する二級アミンを、下記構造式（ｙ１－９ｒ）で表されるイソシアネート化合物のイソシアネート基と反応させることにより、Ｙ１が、構造式（ｙ１－９）である化合物を製造することができる。 (Process VI-9)
By reacting a secondary amine located at the structural end in the intermediate compound C with an isocyanate group of an isocyanate compound represented by the following structural formula (y1-9r), Y 1 is converted to the structural formula (y1-9 ) Can be produced.
Figure JPOXMLDOC01-appb-C000100
 （式中、Ｒ１５は炭素原子数４～１８のアルキル基、炭素原子数６～１０の脂肪族環状炭化水素基、芳香族基、アクリロイルオキシエチル基を表す。）
Figure JPOXMLDOC01-appb-C000100
 (Wherein R 15 represents an alkyl group having 4 to 18 carbon atoms, an aliphatic cyclic hydrocarbon group having 6 to 10 carbon atoms, an aromatic group, or an acryloyloxyethyl group.)
Figure JPOXMLDOC01-appb-C000101
Figure JPOXMLDOC01-appb-C000101
　ここで、前記構造式（ｙ１－９ｒ）で表されるイソシアネート化合物としては、例えばプロピルイソシアネート、ブチルイソシアネート、ヘキシルイソシアネート、ドデシルイソシアネート、オクタデシルイソシアネート等の炭素原子数４～１８のアルキルイソシアネート；シクロヘキシルイソシアネート、アダマンチルイソシアネート等の炭素原子数６～１０のイソシアネート基含有脂肪族環状炭化水素；フェニルイソシアネート、ベンジルイソシアネート、フェネチルイソシアネート、トルイジルイソシアネート等のイソシアネート基含有芳香族炭化水素が挙げられる。 Here, examples of the isocyanate compound represented by the structural formula (y1-9r) include alkyl isocyanates having 4 to 18 carbon atoms such as propyl isocyanate, butyl isocyanate, hexyl isocyanate, dodecyl isocyanate, octadecyl isocyanate, and the like; cyclohexyl isocyanate, Examples thereof include an isocyanate group-containing aliphatic cyclic hydrocarbon having 6 to 10 carbon atoms such as adamantyl isocyanate; and an isocyanate group-containing aromatic hydrocarbon such as phenyl isocyanate, benzyl isocyanate, phenethyl isocyanate, and toluidyl isocyanate.
　また、（工程ＶＩ－９）における、中間体化合物Ｃと、前記構造式（ｙ１－９ｒ）で表されるイソシアネート化合物との反応は、例えば、両者を反応容器中、０～１５０℃で混合し、反応させる方法が挙げられ、触媒や溶媒を使用することもできる。 In (Step VI-9), the reaction between the intermediate compound C and the isocyanate compound represented by the structural formula (y1-9r) is performed, for example, by mixing both at 0 to 150 ° C. in a reaction vessel. The method of making it react is mentioned, A catalyst and a solvent can also be used.
　使用可能な触媒としては、例えば、トリエチルアミン、ジアザビシクロウンデセン、ジブチルすずジラウリレート、トリ－ｎ－オクチルホスフィン、トリフェニルホスフィン等が挙げられる。 Examples of usable catalysts include triethylamine, diazabicycloundecene, dibutyltin dilaurate, tri-n-octylphosphine, triphenylphosphine, and the like.
　また、有機溶媒としては例えば、トルエン、キシレン等の芳香族炭化水素系溶剤、ジメチルエーテル、ジエチルエーテル、１，４－ジオキサン、テトラヒドロフラン（ＴＨＦ）等のエーテル系溶剤、アセトン、２－ブタノン、メチルイソブチルケトン等のケトン系溶剤、ジメチルホルムアミド（ＤＭＦ）等のアミド系溶剤、クロロホルム、ジクロロメタン等のハロゲン系溶媒、ジメチルスルホキシド（ＤＭＳＯ）等を挙げることができる。 Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, ether solvents such as dimethyl ether, diethyl ether, 1,4-dioxane, and tetrahydrofuran (THF), acetone, 2-butanone, and methyl isobutyl ketone. And ketone solvents such as dimethylformamide (DMF), halogen solvents such as chloroform and dichloromethane, and dimethyl sulfoxide (DMSO).
　前記光重合開始剤（Ｂ）の使用量は、前記酸基含有（メタ）アクリレート樹脂（Ａ）１００質量部に対して、１～２０質量部の範囲が好ましい。 The amount of the photopolymerization initiator (B) used is preferably in the range of 1 to 20 parts by mass with respect to 100 parts by mass of the acid group-containing (meth) acrylate resin (A).
　本発明の感光性樹脂組成物は、更に硬化性能を高めるため、必要に応じて、光増感剤や三級アミン類等の光開始助剤を使用しても良い。前記光増感剤としては、例えば、２，４－ジエチルチオキサントン、２，４－ジイソプロピルチオキサントン等のチオキサントン系、４，４’－ビス（ジエチルアミノ）ベンゾフェノン等のベンゾフェノン系、アントラキノン等が挙げられる。一方、三級アミンとしては、例えば、ｐ－ジメチルアミノ安息香酸エチル、ｐ－ジメチルアミノ安息香酸イソアミル、Ｎ，Ｎ－ジメチルベンジルアミン等が挙げられる。また、１分子内に複数の光増感剤や三級アミン類を多価アルコール等で分岐させた高分子量化合物も適宜使用することができる。前記光開始助剤は、感光性樹脂組成物の全量に対し０．０３～２０質量部で使用することが好ましく、０．１～１０質量部で使用することがなお好ましい。 In the photosensitive resin composition of the present invention, a photoinitiator such as a photosensitizer or a tertiary amine may be used as necessary in order to further improve the curing performance. Examples of the photosensitizer include thioxanthone series such as 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone, benzophenone series such as 4,4'-bis (diethylamino) benzophenone, anthraquinone and the like. On the other hand, examples of the tertiary amine include ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, and N, N-dimethylbenzylamine. In addition, a high molecular weight compound obtained by branching a plurality of photosensitizers or tertiary amines in one molecule with a polyhydric alcohol or the like can be used as appropriate. The photoinitiator aid is preferably used in an amount of 0.03 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on the total amount of the photosensitive resin composition.
　また、本発明の効果を損なわない範囲で、前記光重合開始剤（Ｂ）以外のその他の光重合開始剤を併用することもできる。 Further, other photopolymerization initiators other than the photopolymerization initiator (B) can be used in combination as long as the effects of the present invention are not impaired.
　前記その他の光重合開始剤としては、例えば、１－ヒドロキシシクロヘキシルフェニルケトン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－〔４－（２－ヒドロキシエトキシ）フェニル〕－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、チオキサントン及びチオキサントン誘導体、２，２′－ジメトキシ－１，２－ジフェニルエタン－１－オン、ジフェニル（２，４，６－トリメトキシベンゾイル）ホスフィンオキシド、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキシド、ビス（２，４，６－トリメチルベンゾイル）フェニルホスフィンオキシド、２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－１－ブタノン等が挙げられる。 Examples of the other photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl]- 2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2′-dimethoxy-1,2-diphenylethane-1-one, diphenyl (2,4,6-trimethoxybenzoyl) ) Phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4 Morpholinophenyl) -1-butanone, and the like.
　前記その他の光重合開始剤の市販品としては、例えば、「Ｏｍｎｉｒａｄ－１１７３」、「Ｏｍｎｉｒａｄ－１８４」、「Ｏｍｎｉｒａｄ－１２７」、「Ｏｍｎｉｒａｄ－２９５９」、「Ｏｍｎｉｒａｄ－３６９」、「Ｏｍｎｉｒａｄ－３７９」、「Ｏｍｎｉｒａｄ－９０７」、「Ｏｍｎｉｒａｄ－４２６５」、「Ｏｍｎｉｒａｄ－１０００」、「Ｏｍｎｉｒａｄ－６５１」、「Ｏｍｎｉｒａｄ－ＴＰＯ」、「Ｏｍｎｉｒａｄ－８１９」、「Ｏｍｎｉｒａｄ－２０２２」、「Ｏｍｎｉｒａｄ－２１００」、「Ｏｍｎｉｒａｄ－７５４」、「Ｏｍｎｉｒａｄ－７８４」、「Ｏｍｎｉｒａｄ－５００」、「Ｏｍｎｉｒａｄ－８１」（ＩＧＭ社製）、「カヤキュア－ＤＥＴＸ」、「カヤキュア－ＭＢＰ」、「カヤキュア－ＤＭＢＩ」、「カヤキュア－ＥＰＡ」、「カヤキュア－ＯＡ」（日本化薬株式会社製）、「バイキュア－１０」、「バイキュア－５５」（ストウファ・ケミカル社製）、「トリゴナルＰ１」（アクゾ社製）、「サンドレイ１０００」（サンドズ社製）、「ディープ」（アプジョン社製）、「クオンタキュア－ＰＤＯ」、「クオンタキュア－ＩＴＸ」、「クオンタキュア－ＥＰＤ」（ワードブレンキンソップ社製）、「Ｒｕｎｔｅｃｕｒｅ－１１０４」（Ｒｕｎｔｅｃ社製）等が挙げられる。 Examples of other commercially available photopolymerization initiators include “Omnirad-1173”, “Omnirad-184”, “Omnirad-127”, “Omnirad-2959”, “Omnirad-369”, “Omnirad-379”. , “Omnirad-907”, “Omnirad-4265”, “Omnirad-1000”, “Omnirad-651”, “Omnirad-TPO”, “Omnirad-819”, “Omnirad-2022”, “Omnirad-2100” “ Omnirad-754, Omnirad-784, Omnirad-500, Omnirad-81 (manufactured by IGM), Kayacure-DETX, Kayacure-MBP, Kayacure-DMBI, Kayacyu -EPA "," Kayacure-OA "(manufactured by Nippon Kayaku Co., Ltd.)," Bicure-10 "," Bicure-55 "(manufactured by Stofa Chemical)," Trigonal P1 "(manufactured by Akzo)," Sandray 1000 "Sands", "Deep" (Apjon), "QuantaCure-PDO", "QuantaCure-ITX", "QuantaCure-EPD" (Ward Brenkinsop), "Runtecure-1104" (Manufactured by Runtec).
　本発明の感光性樹脂組成物は、前記酸基含有（メタ）アクリレート樹脂（Ａ）以外のその他の樹脂成分を含有しても良い。前記その他の樹脂成分としては、例えば、ビスフェノール型エポキシ樹脂、ノボラック型エポキシ樹脂等のエポキシ樹脂に、（メタ）アクリル酸、ジカルボン酸無水物、必要に応じて不飽和モノカルボン酸無水物等を反応させて得られる、樹脂中にカルボキシル基と（メタ）アクリロイル基とを有する樹脂、各種の（メタ）アクリレートモノマー等が挙げられる。 The photosensitive resin composition of the present invention may contain other resin components other than the acid group-containing (meth) acrylate resin (A). Examples of the other resin components include (meth) acrylic acid, dicarboxylic acid anhydride, and unsaturated monocarboxylic acid anhydride, if necessary, to epoxy resin such as bisphenol type epoxy resin and novolak type epoxy resin. Examples thereof include resins having a carboxyl group and a (meth) acryloyl group in the resin, various (meth) acrylate monomers, and the like.
　前記（メタ）アクリレートモノマーとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート等の脂肪族モノ（メタ）アクリレート化合物；シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、アダマンチルモノ（メタ）アクリレート等の脂環型モノ（メタ）アクリレート化合物；グリシジル（メタ）アクリレート、テトラヒドロフルフリルアクリレート等の複素環型モノ（メタ）アクリレート化合物；ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、フェニルベンジル（メタ）アクリレート、フェノキシ（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシエトキシエチル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、フェノキシベンジル（メタ）アクリレート、ベンジルベンジル（メタ）アクリレート、フェニルフェノキシエチル（メタ）アクリレート等の芳香族モノ（メタ）アクリレート化合物等のモノ（メタ）アクリレート化合物：前記各種のモノ（メタ）アクリレートモノマーの分子構造中に（ポリ）オキシエチレン鎖、（ポリ）オキシプロピレン鎖、（ポリ）オキシテトラメチレン鎖等のポリオキシアルキレン鎖を導入した（ポリ）オキシアルキレン変性モノ（メタ）アクリレート化合物；前記各種のモノ（メタ）アクリレート化合物の分子構造中に（ポリ）ラクトン構造を導入したラクトン変性モノ（メタ）アクリレート化合物；エチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ブタンジオールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート等の脂肪族ジ（メタ）アクリレート化合物；１，４－シクロヘキサンジメタノールジ（メタ）アクリレート、ノルボルナンジ（メタ）アクリレート、ノルボルナンジメタノールジ（メタ）アクリレート、ジシクロペンタニルジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート等の脂環型ジ（メタ）アクリレート化合物；ビフェノールジ（メタ）アクリレート、ビスフェノールジ（メタ）アクリレート等の芳香族ジ（メタ）アクリレート化合物；前記各種のジ（メタ）アクリレート化合物の分子構造中に（ポリ）オキシエチレン鎖、（ポリ）オキシプロピレン鎖、（ポリ）オキシテトラメチレン鎖等の（ポリ）オキシアルキレン鎖を導入したポリオキシアルキレン変性ジ（メタ）アクリレート化合物；前記各種のジ（メタ）アクリレート化合物の分子構造中に（ポリ）ラクトン構造を導入したラクトン変性ジ（メタ）アクリレート化合物；トリメチロールプロパントリ（メタ）アクリレート、グリセリントリ（メタ）アクリレート等の脂肪族トリ（メタ）アクリレート化合物；前記脂肪族トリ（メタ）アクリレート化合物の分子構造中に（ポリ）オキシエチレン鎖、（ポリ）オキシプロピレン鎖、（ポリ）オキシテトラメチレン鎖等の（ポリ）オキシアルキレン鎖を導入した（ポリ）オキシアルキレン変性トリ（メタ）アクリレート化合物；前記脂肪族トリ（メタ）アクリレート化合物の分子構造中に（ポリ）ラクトン構造を導入したラクトン変性トリ（メタ）アクリレート化合物；ペンタエリスリトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等の４官能以上の脂肪族ポリ（メタ）アクリレート化合物；前記脂肪族ポリ（メタ）アクリレート化合物の分子構造中に（ポリ）オキシエチレン鎖、（ポリ）オキシプロピレン鎖、（ポリ）オキシテトラメチレン鎖等の（ポリ）オキシアルキレン鎖を導入した４官能以上の（ポリ）オキシアルキレン変性ポリ（メタ）アクリレート化合物；前記脂肪族ポリ（メタ）アクリレート化合物の分子構造中に（ポリ）ラクトン構造を導入した４官能以上のラクトン変性ポリ（メタ）アクリレート化合物などが挙げられる。 Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and 2-ethylhexyl. Aliphatic mono (meth) acrylate compounds such as (meth) acrylate and octyl (meth) acrylate; alicyclic mono (meth) acrylate compounds such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate ; Heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; benzyl (meth) acrylate, phenyl (meth) acrylate, phenylben (Meth) acrylate, phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxybenzyl (meth) acrylate, benzylbenzyl ( Mono (meth) acrylate compounds such as aromatic mono (meth) acrylate compounds such as meth) acrylate and phenylphenoxyethyl (meth) acrylate: (poly) oxyethylene chains in the molecular structure of the various mono (meth) acrylate monomers , (Poly) oxypropylene-modified (poly) oxyalkylene-modified (poly) oxyalkylene-modified (poly) oxyalkylene-modified mono (meth) acrylate compounds; Lactone-modified mono (meth) acrylate compounds in which (poly) lactone structure is introduced into the molecular structure of the compound; ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol Aliphatic di (meth) acrylate compounds such as di (meth) acrylate and neopentyl glycol di (meth) acrylate; 1,4-cyclohexanedimethanol di (meth) acrylate, norbornane di (meth) acrylate, norbornane dimethanol di ( Alicyclic di (meth) acrylate compounds such as (meth) acrylate, dicyclopentanyl di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate; biphenol di (meth) acrylate, bisphenol Aromatic di (meth) acrylate compounds such as rudi (meth) acrylate; in the molecular structure of the various di (meth) acrylate compounds, (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene A polyoxyalkylene-modified di (meth) acrylate compound in which a (poly) oxyalkylene chain such as a chain is introduced; a lactone-modified di (meta) compound in which a (poly) lactone structure is introduced into the molecular structure of the various di (meth) acrylate compounds ) Acrylate compound; Aliphatic tri (meth) acrylate compound such as trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, etc .; (poly) oxyethylene chain in the molecular structure of the aliphatic tri (meth) acrylate compound , (Poly) oxypropylene chain, (poly) oxyte (Poly) oxyalkylene-modified tri (meth) acrylate compound in which (poly) oxyalkylene chain such as lamethylene chain is introduced; lactone modification in which (poly) lactone structure is introduced into the molecular structure of the aliphatic tri (meth) acrylate compound Tri (meth) acrylate compounds; tetra- or higher functional aliphatic poly (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; the aliphatic (Poly) having at least four functional groups in which a (poly) oxyalkylene chain such as a (poly) oxyethylene chain, (poly) oxypropylene chain, or (poly) oxytetramethylene chain is introduced into the molecular structure of the poly (meth) acrylate compound Oxyalkylene modified poly Meth) acrylate compound; and the aliphatic poly (meth) acrylate compound in the molecular structure of (poly) lactone 4 or more functional introducing the lactone structure-modified poly (meth) acrylate compounds.
　本発明の感光性樹脂組成物は、塗工粘度調節等の目的で有機溶剤を含有してもよく、その種類や添加量は、所望の性能に応じて適宜選択及び調整される。 The photosensitive resin composition of the present invention may contain an organic solvent for the purpose of adjusting the coating viscosity, and the type and addition amount thereof are appropriately selected and adjusted according to the desired performance.
　前記有機溶剤としては、例えば、メチルエチルケトン、アセトン、イソブチルケトン等のケトン溶剤；テトラヒドロフラン、ジオキソラン等の環状エーテル溶剤；酢酸メチル、酢酸エチル、酢酸ブチル等のエステル溶剤；トルエン、キシレン、ソルベントナフサ等の芳香族溶剤；シクロヘキサン、メチルシクロヘキサン等の脂環族溶剤；カルビトール、セロソルブ、メタノール、イソプロパノール、ブタノール、プロピレングリコールモノメチルエーテル等のアルコール溶剤；アルキレングリコールモノアルキルエーテル、ジアルキレングリコールモノアルキルエーテル、ジアルキレングリコールモノアルキルエーテルアセテート等のグリコールエーテル溶剤などが挙げられる。これらの有機溶剤は、単独で用いることも２種以上を併用することもできる。 Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone and isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; and aromatics such as toluene, xylene and solvent naphtha. Aliphatic solvents such as cyclohexane and methylcyclohexane; Alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether; alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, dialkylene glycol Examples include glycol ether solvents such as monoalkyl ether acetate. These organic solvents can be used alone or in combination of two or more.
　また、本発明の感光性樹脂組成物には、必要に応じて、無機微粒子やポリマー微粒子、顔料、消泡剤、粘度調整剤、レベリング剤、難燃剤、保存安定化剤等の各種添加剤を含有することもできる。 In addition, the photosensitive resin composition of the present invention may contain various additives such as inorganic fine particles and polymer fine particles, pigments, antifoaming agents, viscosity modifiers, leveling agents, flame retardants, and storage stabilizers as necessary. It can also be contained.
　本発明の硬化物は、前記感光性樹脂組成物に、活性エネルギー線を照射することで得ることができる。前記活性エネルギー線としては、例えば、紫外線、電子線、α線、β線、γ線等の電離放射線が挙げられる。また、前記活性エネルギー線として、紫外線を用いる場合、紫外線による硬化反応を効率よく行う上で、窒素ガス等の不活性ガス雰囲気下で照射してもよく、空気雰囲気下で照射してもよい。 The cured product of the present invention can be obtained by irradiating the photosensitive resin composition with active energy rays. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. In addition, when ultraviolet rays are used as the active energy rays, irradiation may be performed in an inert gas atmosphere such as nitrogen gas or an air atmosphere in order to efficiently perform a curing reaction with ultraviolet rays.
　紫外線発生源としては、実用性、経済性の面から紫外線ランプが一般的に用いられている。具体的には、低圧水銀ランプ、高圧水銀ランプ、超高圧水銀ランプ、キセノンランプ、ガリウムランプ、メタルハライドランプ、太陽光、ＬＥＤ等が挙げられる。 As an ultraviolet ray generation source, an ultraviolet lamp is generally used from the viewpoint of practicality and economy. Specific examples include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, and an LED.
　また、本発明の感光性樹脂組成物を硬化させて得られた硬化物は、優れた耐熱性を有しており、アウトガスが生じにくいことから、例えば、半導体デバイス用途における、ソルダーレジスト、層間絶縁材料、パッケージ材、アンダーフィル材、回路素子等のパッケージ接着層や、集積回路素子と回路基板の接着層として好適に用いることができる。また、ＬＣＤ、ＯＥＬＤに代表される薄型ディスプレイ用途における、薄膜トランジスタ保護膜、液晶カラーフィルタ保護膜、カラーフィルタ用顔料レジスト、ブラックマトリックス用レジスト、スペーサー等に好適に用いることができる。 In addition, the cured product obtained by curing the photosensitive resin composition of the present invention has excellent heat resistance and is less likely to generate outgas. For example, solder resist and interlayer insulation in semiconductor device applications It can be suitably used as a package adhesive layer such as a material, a package material, an underfill material, or a circuit element, or an adhesive layer between an integrated circuit element and a circuit board. Further, it can be suitably used for a thin film transistor protective film, a liquid crystal color filter protective film, a color filter pigment resist, a black matrix resist, a spacer, etc. in thin display applications typified by LCD and OELD.
　本発明のソルダーレジスト用樹脂材料は、前記感光性樹脂組成物に、必要に応じて、例えば、硬化剤、硬化促進剤、有機溶剤、無機微粒子やポリマー微粒子、顔料、消泡剤、粘度調整剤、レベリング剤、難燃剤、保存安定化剤等の各種添加剤等を用いることができる。 The resin material for a solder resist of the present invention can be applied to the photosensitive resin composition, if necessary, for example, a curing agent, a curing accelerator, an organic solvent, inorganic fine particles or polymer fine particles, a pigment, an antifoaming agent, a viscosity modifier. Various additives such as a leveling agent, a flame retardant, and a storage stabilizer can be used.
　前記硬化剤としては、前記酸基含有（メタ）アクリレート樹脂（Ａ）中のカルボキシル基と反応し得る官能基を有するものであれば特に制限されず、例えば、エポキシ樹脂が挙げられる。前記エポキシ樹脂としては、例えば、ビスフェノール型エポキシ樹脂、フェニレンエーテル型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、ビフェニル型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールノボラック型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ナフトール－フェノール共縮ノボラック型エポキシ樹脂、ナフトール－クレゾール共縮ノボラック型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ジシクロペンタジエン－フェノール付加反応型エポキシ樹脂等が挙げられる。これらのエポキシ樹脂は、単独で用いることも２種以上を併用することもできる。また、これらの中でも、硬化物における耐熱性に優れることから、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールノボラック型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ナフトール－フェノール共縮ノボラック型エポキシ樹脂、ナフトール－クレゾール共縮ノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂が好ましく、軟化点が５０～１２０℃の範囲であるものが特に好ましい。 The curing agent is not particularly limited as long as it has a functional group capable of reacting with a carboxyl group in the acid group-containing (meth) acrylate resin (A), and examples thereof include an epoxy resin. Examples of the epoxy resin include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, Bisphenol novolac type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition Examples include reactive epoxy resins. These epoxy resins can be used alone or in combination of two or more. Among these, since it has excellent heat resistance in a cured product, a phenol novolac type epoxy resin, a cresol novolak type epoxy resin, a bisphenol novolak type epoxy resin, a naphthol novolak type epoxy resin, a naphthol-phenol co-condensed novolak type epoxy resin, A novolak type epoxy resin such as a naphthol-cresol co-condensed novolak type epoxy resin is preferable, and a softening point in the range of 50 to 120 ° C. is particularly preferable.
　前記硬化促進剤とは、前記硬化剤の硬化反応を促進するものであり、前記硬化剤としてエポキシ樹脂を用いる場合には、例えば、リン系化合物、第３級アミン、イミダゾール、有機酸金属塩、ルイス酸、アミン錯塩等が挙げられる。これらの硬化促進剤は、単独で用いることも２種以上を併用することもできる。また、前記硬化促進剤の添加量は、例えば、前記硬化剤１００質量部に対して１～１０質量部の範囲で用いることが好ましい。 The curing accelerator is to accelerate the curing reaction of the curing agent. When an epoxy resin is used as the curing agent, for example, a phosphorus compound, a tertiary amine, imidazole, an organic acid metal salt, Examples include Lewis acids and amine complex salts. These curing accelerators can be used alone or in combination of two or more. The addition amount of the curing accelerator is preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the curing agent, for example.
　前記有機溶剤としては、前記酸基含有（メタ）アクリレート樹脂（Ａ）や硬化剤等の各種成分を溶解し得るものであれば特に限定されず、例えば、メチルエチルケトン、アセトン、イソブチルケトン等のケトン溶剤；テトラヒドロフラン、ジオキソラン等の環状エーテル溶剤；酢酸メチル、酢酸エチル、酢酸ブチル等のエステル溶剤；トルエン、キシレン、ソルベントナフサ等の芳香族溶剤；シクロヘキサン、メチルシクロヘキサン等の脂環族溶剤；カルビトール、セロソルブ、メタノール、イソプロパノール、ブタノール、プロピレングリコールモノメチルエーテルなどのアルコール溶剤；アルキレングリコールモノアルキルエーテル、ジアルキレングリコールモノアルキルエーテル、ジアルキレングリコールモノアルキルエーテルアセテート等のグリコールエーテル溶剤などが挙げられる。これらの有機溶剤は、単独で用いることも２種以上を併用することもできる。 The organic solvent is not particularly limited as long as it can dissolve various components such as the acid group-containing (meth) acrylate resin (A) and a curing agent, and examples thereof include ketone solvents such as methyl ethyl ketone, acetone, and isobutyl ketone. Cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; aromatic solvents such as toluene, xylene and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; carbitol and cellosolve Alcohol solvents such as methanol, isopropanol, butanol, propylene glycol monomethyl ether; alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether acetate Such as glycol ethers solvents over bets, and the like. These organic solvents can be used alone or in combination of two or more.
　本発明のレジスト部材は、例えば、前記ソルダーレジスト用樹脂材料を基材上に塗布し、６０～１００℃程度の温度範囲で有機溶媒を揮発乾燥させた後、所望のパターンが形成されたフォトマスクを通して活性エネルギー線にて露光させ、アルカリ水溶液にて未露光部を現像し、更に１４０～１８０℃程度の温度範囲で加熱硬化させて得ることができる。 The resist member of the present invention is, for example, a photomask in which a desired pattern is formed after applying the resin material for solder resist on a substrate and evaporating and drying an organic solvent in a temperature range of about 60 to 100 ° C. And exposed to an active energy ray, developed in an unexposed portion with an aqueous alkali solution, and further heat-cured in a temperature range of about 140 to 180 ° C.
　以下、実施例と比較例とにより、本発明を具体的に説明する。 Hereinafter, the present invention will be specifically described by way of examples and comparative examples.
（合成例１：酸基含有（メタ）アクリレート樹脂（Ａ－１）の合成）
　温度計、攪拌器、及び還流冷却器を備えたフラスコに、ジエチレングリコールモノメチルエーテルアセテート１０１質量部を入れ、オルソクレゾールノボラック型エポキシ樹脂（ＤＩＣ株式会社製「ＥＰＩＣＬＯＮ　Ｎ－６８０」、エポキシ当量；２１４ｇ／ｅｑ）４２８質量部を溶解し、酸化防止剤としてジブチルヒドロキシトルエン４質量部、熱重合禁止剤としてメトキノン０．４質量部加えた後、アクリル酸１４４質量部、トリフェニルホスフィン１．６質量部を添加し、空気を吹き込みながら１２０℃で１０時間エステル化反応を行なった。その後、ジエチレングリコールモノメチルエーテルアセテート３１１質量部、テトラヒドロ無水フタル酸１６０質量部を加え１１０℃で２．５時間反応させて、酸基含有（メタ）アクリレート樹脂（１）を得た。この酸基含有（メタ）アクリレート樹脂（１）の固形分酸価は８５ｍｇＫＯＨ／ｇであった。 (Synthesis Example 1: Synthesis of acid group-containing (meth) acrylate resin (A-1))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 101 parts by mass of diethylene glycol monomethyl ether acetate, and an orthocresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation, epoxy equivalent; 214 g / eq) ) Dissolve 428 parts by mass, add 4 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of methoquinone as a thermal polymerization inhibitor, then add 144 parts by mass of acrylic acid and 1.6 parts by mass of triphenylphosphine Then, the esterification reaction was carried out at 120 ° C. for 10 hours while blowing air. Thereafter, 311 parts by mass of diethylene glycol monomethyl ether acetate and 160 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 2.5 hours to obtain an acid group-containing (meth) acrylate resin (1). The acid content-containing (meth) acrylate resin (1) had a solid content acid value of 85 mgKOH / g.
（合成例２：酸基含有（メタ）アクリレート樹脂（Ａ－２）の合成）
　温度計、攪拌器、及び還流冷却器を備えたフラスコに、ジエチレングリコールモノメチルエーテルアセテート３７９質量部、イソホロンジイソシアネートのイソシアヌレート変性体（ＥＶＯＮＩＫ社製「ＶＥＳＴＡＮＡＴ　Ｔ－１８９０／１００」、イソシアネート基含有量１７．２質量％）１８５質量部、無水トリメリット酸１４６質量部、ジブチルヒドロキシトルエン１．６質量部を加えて溶解させた。窒素雰囲気下、１６０℃で５時間反応させ、イソシアネート基含有量が０．１質量％以下となっていることを確認した。次いで、メトキノン０．３質量部、ペンタエリスリトールポリアクリレート混合物（東亜合成株式会社製「アロニックスＭ－３０６」、ペンタエリスリトールトリアクリレート含有量約６７％、水酸基価１５９．７ｍｇＫＯＨ／ｇ）１１２質量部及びトリフェニルホスフィン３．１質量部を添加し、空気を吹き込みながら１１０℃で５時間反応させた。次いで、グリシジルメタクリレート１２５質量部を添加し、１１０℃で５時間反応させた。更に、無水コハク酸８７質量部を加えて１１０℃で５時間反応させて、酸基含有（メタ）アクリレート樹脂（Ａ－２）を得た。この酸基含有（メタ）アクリレート樹脂（Ａ－２）の固形分酸価は８０ｍｇＫＯＨ／ｇであった。 (Synthesis Example 2: Synthesis of acid group-containing (meth) acrylate resin (A-2))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 379 parts by mass of diethylene glycol monomethyl ether acetate, an isocyanurate-modified form of isophorone diisocyanate (“VESTANAT T-1890 / 100” manufactured by EVONIK, isocyanate group content 17. 2% by mass) 185 parts by mass, 146 parts by mass of trimellitic anhydride, and 1.6 parts by mass of dibutylhydroxytoluene were added and dissolved. It was made to react at 160 degreeC under nitrogen atmosphere for 5 hours, and it confirmed that isocyanate group content was 0.1 mass% or less. Next, 0.3 parts by weight of methoquinone, 112 parts by weight of pentaerythritol polyacrylate mixture (“Aronix M-306” manufactured by Toa Gosei Co., Ltd., pentaerythritol triacrylate content of about 67%, hydroxyl value of 159.7 mg KOH / g) and tri 3.1 parts by mass of phenylphosphine was added and reacted at 110 ° C. for 5 hours while blowing air. Next, 125 parts by mass of glycidyl methacrylate was added and reacted at 110 ° C. for 5 hours. Furthermore, 87 parts by mass of succinic anhydride was added and reacted at 110 ° C. for 5 hours to obtain an acid group-containing (meth) acrylate resin (A-2). This acid group-containing (meth) acrylate resin (A-2) had a solid content acid value of 80 mgKOH / g.
（合成例３：光重合開始剤（Ｍ３１）の合成） (Synthesis Example 3: Synthesis of photopolymerization initiator (M31))
［工程Ｉ］ [Step I]
Figure JPOXMLDOC01-appb-C000102
Figure JPOXMLDOC01-appb-C000102
　撹拌機、温度計、窒素導入管、アルカリトラップ及び滴下ロートを備えた１Ｌフラスコに塩化アルミニウム（無水）１２１．８ｇと脱水ジクロロメタン３００ｍＬを仕込み、窒素気流下、氷浴を用いて氷冷した。これに２－ブロモブチリルブロミドの２００ｇを添加した。フルオロベンゼン８３．６ｇと脱水ジクロロメタン１００ｍＬを混合溶液を滴下ロートを用いて先のフラスコ中へ２０分かけて滴下した。滴下終了後、氷浴を外し、そのまま、２時間攪拌を続けた。攪拌終了後、反応液を氷水１Ｌ中へ投入し、２時間攪拌を続けた。靜置後分液し、下層を回収した。２Ｎ塩酸で２回洗浄し、飽和炭酸水素ナトリウム水溶液で１回洗浄し、飽和食塩水で２回洗浄した。硫酸マグネシウムで一昼夜乾燥させた後、ジクロロメタンを減圧留去し、２－ブロモ－１－（４－フルオロフェニル）－１－ブタノン（１０１）を得た。 A 1 L flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, an alkali trap and a dropping funnel was charged with 121.8 g of aluminum chloride (anhydrous) and 300 mL of dehydrated dichloromethane, and ice-cooled using an ice bath in a nitrogen stream. To this was added 200 g of 2-bromobutyryl bromide. A mixed solution of 83.6 g of fluorobenzene and 100 mL of dehydrated dichloromethane was dropped into the previous flask using a dropping funnel over 20 minutes. After completion of dropping, the ice bath was removed and stirring was continued for 2 hours. After completion of the stirring, the reaction solution was put into 1 L of ice water and stirring was continued for 2 hours. After placing the solution, the solution was separated and the lower layer was collected. Washed twice with 2N hydrochloric acid, washed once with saturated aqueous sodium hydrogen carbonate solution, and washed twice with saturated brine. After drying overnight with magnesium sulfate, dichloromethane was distilled off under reduced pressure to obtain 2-bromo-1- (4-fluorophenyl) -1-butanone (101).
　収量：２１４．３ｇ、収率：１００％ Yield: 214.3 g, Yield: 100%
［工程ＩＩ］ [Step II]
Figure JPOXMLDOC01-appb-C000103
Figure JPOXMLDOC01-appb-C000103
　攪拌機、温度計を備えた２Ｌフラスコに中間体（１０１）１５７．７ｇとメチルエチルケトン７５０ｍＬを仕込み氷浴を用いて氷冷した。そこに５０質量％ジメチルアミン水溶液１７４ｇを、滴下ロートを用いて３０分かけて滴下した。滴下終了後、氷浴を外し、そのまま、一昼夜攪拌を続けた。薄層クロマトグラフィーを用いて中間体（１０１）の消失を確認した後、メチルエチルケトンとジメチルアミンを減圧留去し、残渣にトルエンを投入した。水で２回洗浄し、さらに飽和食塩水で１回洗浄した後、上層を回収し、硫酸マグネシウムで一昼夜乾燥させた。トルエンを減圧留去し、中間体（１０２）を得た。 In a 2 L flask equipped with a stirrer and a thermometer, 157.7 g of intermediate (101) and 750 mL of methyl ethyl ketone were charged and ice-cooled using an ice bath. 174 g of 50 mass% dimethylamine aqueous solution was dripped there over 30 minutes using the dropping funnel. After completion of the dropwise addition, the ice bath was removed and stirring was continued for a whole day and night. After confirming the disappearance of intermediate (101) using thin layer chromatography, methyl ethyl ketone and dimethylamine were distilled off under reduced pressure, and toluene was added to the residue. After washing twice with water and once with saturated saline, the upper layer was recovered and dried with magnesium sulfate for a whole day and night. Toluene was distilled off under reduced pressure to obtain an intermediate (102).
　収量：１３３．３ｇ、収率：９９％ Yield: 133.3 g, Yield: 99%
［工程ＩＩＩ］ [Step III]
Figure JPOXMLDOC01-appb-C000104
Figure JPOXMLDOC01-appb-C000104
　攪拌機、温度計、冷却管を備えた５００ｍＬフラスコに中間体（１０２）７９．５ｇと４－（ブロモメチル）安息香酸メチル（１０３）８７．０ｇとイソプロパノール（以下「ＩＰＡ」と略記する。）１２０ｍＬを仕込み、５０℃で一昼夜、攪拌した。その後、８Ｍ水酸化ナトリウム水溶液１０５ｍＬを添加し、５０℃で１時間攪拌した。攪拌終了後、ＩＰＡを留去し、１２Ｎ塩酸を用いてｐＨ５．５に調製した後、酢酸エチルで抽出した。抽出液にヘキサンを加え、析出した結晶をろ別して中間体（１０４）を得た。 A 500 mL flask equipped with a stirrer, a thermometer, and a condenser tube was charged with 79.5 g of the intermediate (102), 87.0 g of methyl 4- (bromomethyl) benzoate (103) and 120 mL of isopropanol (hereinafter abbreviated as “IPA”). The mixture was stirred and stirred at 50 ° C. all day and night. Thereafter, 105 mL of an 8M aqueous sodium hydroxide solution was added and stirred at 50 ° C. for 1 hour. After completion of the stirring, IPA was distilled off, adjusted to pH 5.5 with 12N hydrochloric acid, and then extracted with ethyl acetate. Hexane was added to the extract, and the precipitated crystals were filtered off to obtain an intermediate (104).
　収量：９４．５ｇ、収率：６５．５％ Yield: 94.5g, Yield: 65.5%
［工程ＩＶ］ [Step IV]
Figure JPOXMLDOC01-appb-C000105
Figure JPOXMLDOC01-appb-C000105
　攪拌機、温度計、滴下ロートを備えた１０００ｍＬフラスコに２－クロロ－４．６－ジメトキシ－１，３，５－トリアジン３５．０ｇと脱水ジクロロメタン４００ｍＬを仕込み、氷浴を用いて氷冷した。そこにＮ－メチルモルホリン８０．８ｇを、滴下ロートを用いて１０分かけて滴下した。滴下終了後、中間体（１０４）７６．０ｇを添加し、氷冷下で１時間攪拌した。そこにピペラジン９．５ｇを溶解した脱水ジクロロメタン２００ｍＬを、滴下ロートを用いて２０分かけて滴下した。氷浴を外し、室温下、１時間攪拌を続けた。薄層クロマトグラフィーにて反応の終了を確認し、水を加えて反応を停止させた。分液ロートに反応物を移し、下層の有機層を回収した。さらに蒸留水で２回洗浄した後、硫酸マグネシウムで、一昼夜乾燥させた。ジクロロメタンを減圧留去し、得られた粗生成物をエタノールにて再結晶して中間体（１０５）を得た。 A 1000 mL flask equipped with a stirrer, a thermometer, and a dropping funnel was charged with 35.0 g of 2-chloro-4.6-dimethoxy-1,3,5-triazine and 400 mL of dehydrated dichloromethane, and ice-cooled using an ice bath. Thereto, 80.8 g of N-methylmorpholine was added dropwise using a dropping funnel over 10 minutes. After completion of dropping, 76.0 g of intermediate (104) was added and stirred for 1 hour under ice cooling. Thereto, 200 mL of dehydrated dichloromethane in which 9.5 g of piperazine was dissolved was dropped over 20 minutes using a dropping funnel. The ice bath was removed and stirring was continued for 1 hour at room temperature. The completion of the reaction was confirmed by thin layer chromatography, and water was added to stop the reaction. The reaction product was transferred to a separatory funnel, and the lower organic layer was recovered. Further, after washing twice with distilled water, it was dried overnight with magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the resulting crude product was recrystallized from ethanol to obtain an intermediate (105).
　収量：５７．５ｇ、収率：７８％ Yield: 57.5g, Yield: 78%
［工程Ｖ］ [Process V]
Figure JPOXMLDOC01-appb-C000106
Figure JPOXMLDOC01-appb-C000106
　攪拌機、温度計、冷却管を備えた５００ｍＬフラスコに中間体（１０５）３８．０ｇとピペラジン２２．２ｇとジメチルスルホキシド（ＤＭＳＯ）１２０ｍＬを仕込み、１００℃で４０時間攪拌した。反応終了後、蒸留水と塩化メチレンを添加し、塩化メチレン層を水で３回、飽和食塩水で１回洗浄し、硫酸マグネシウムで一昼夜乾燥させた。ジクロロメタンを減圧留去し、中間体（１０６）を得た。 A 500 mL flask equipped with a stirrer, a thermometer, and a condenser was charged with 38.0 g of intermediate (105), 22.2 g of piperazine and 120 mL of dimethyl sulfoxide (DMSO), and stirred at 100 ° C. for 40 hours. After completion of the reaction, distilled water and methylene chloride were added, and the methylene chloride layer was washed 3 times with water and once with saturated brine, and dried with magnesium sulfate all day and night. Dichloromethane was distilled off under reduced pressure to obtain an intermediate (106).
　収量：４３．９ｇ、収率：９８％ Yield: 43.9g, Yield: 98%
［工程ＶＩ］ [Process VI]
　撹拌機、コンデンサ及び温度計を備えた３００ｍＬのフラスコに、中間体（１０６）１７．４ｇとのエチレンオキシド変性トリメチロールプロパントリアクリレート（ＭＩＷＯＮ社製Ｍ３１３０）２５．７ｇとｐ－メトキシフェノール４３ｍｇとエタノール１５０ｍＬを加え、５０℃で２４時間撹拌した。減圧留去により溶媒を除去して、下記構造式で表される光重合開始剤（Ｍ３１）を得た。 Into a 300 mL flask equipped with a stirrer, condenser and thermometer, 17.4 g of intermediate (106), 25.7 g of ethylene oxide-modified trimethylolpropane triacrylate (M3130 manufactured by MIWON), 43 mg of p-methoxyphenol and 150 mL of ethanol And stirred at 50 ° C. for 24 hours. The solvent was removed by distillation under reduced pressure to obtain a photopolymerization initiator (M31) represented by the following structural formula.
　収量：４２．７ｇ、収率：９９％ Yield: 42.7g, Yield: 99%
Figure JPOXMLDOC01-appb-C000107
Figure JPOXMLDOC01-appb-C000107
（合成例４：光重合開始剤（Ｍ３２）の合成） (Synthesis Example 4: Synthesis of Photopolymerization Initiator (M32))
［工程ＩＩＩ］ [Step III]
Figure JPOXMLDOC01-appb-C000108
Figure JPOXMLDOC01-appb-C000108
　攪拌機、温度計、冷却管を備えた５００ｍＬフラスコに、合成例３の工程Ｉ及び工程ＩＩを経て得られた中間体（１０２）４１．９ｇと２－［４－（ブロモメチル）フェニル］プロピオン酸（１０７）５３．５ｇとＩＰＡ１００ｍＬを仕込み、８Ｍ水酸化ナトリウム水溶液２７．５ｍＬを室温で添加し、さらに５０℃で２時間攪拌して四級アンモニウム塩を形成させた。続いて、８Ｍ水酸化ナトリウム水溶液４１ｍＬを添加し、５０℃で１時間攪拌した。攪拌終了後、ＩＰＡを留去し、６Ｎ塩酸を用いてｐＨ５．５に調製した後、トルエンで抽出した。抽出液を水洗し、溶媒を減圧留去して得られた粗反応物をシリカゲルクロマトグラフィーにて精製して中間体（１０８）を得た。 In a 500 mL flask equipped with a stirrer, thermometer, and condenser, 41.9 g of intermediate (102) obtained through Step I and Step II of Synthesis Example 3 and 2- [4- (bromomethyl) phenyl] propionic acid ( 107) 53.5 g and IPA 100 mL were charged, 8M aqueous sodium hydroxide solution 27.5 mL was added at room temperature, and the mixture was further stirred at 50 ° C. for 2 hours to form a quaternary ammonium salt. Subsequently, 41 mL of an 8M aqueous sodium hydroxide solution was added and stirred at 50 ° C. for 1 hour. After completion of stirring, IPA was distilled off, and the pH was adjusted to 5.5 using 6N hydrochloric acid, followed by extraction with toluene. The extract was washed with water, the solvent was distilled off under reduced pressure, and the resulting crude reaction product was purified by silica gel chromatography to obtain an intermediate (108).
　収量：３９．０ｇ、収率：５２．５％ Yield: 39.0 g, Yield: 52.5%
［工程ＩＶ］ [Step IV]
Figure JPOXMLDOC01-appb-C000109
Figure JPOXMLDOC01-appb-C000109
　攪拌機、温度計、滴下ロートを備えた５００ｍＬフラスコに、中間体（１０８）１９．０ｇとジクロロメタン８０ｍＬとＮ，Ｎ－ジメチルホルムアミド０．５ｍＬを仕込み、これに塩化チオニル６．７ｇをゆっくりと滴下し、３０分間撹拌した。ピペラジン２．２ｇを溶解した脱水ジクロロメタン５０ｍＬの溶液を、滴下ロートを用いて滴下し、続いて、トリエチルアミン１１．４ｇを滴下し、室温で１時間撹拌した。薄層クロマトグラフィーにて反応の終了を確認し、水を加えて反応を停止させた。分液ロートに反応物を移し、下層の有機層を回収した。さらに蒸留水で２回洗浄した後、硫酸マグネシウムで、一昼夜乾燥させた。ジクロロメタンを減圧留去し、得られた粗生成物をエタノールにて再結晶して中間体（１０９）を得た。 A 500 mL flask equipped with a stirrer, thermometer and dropping funnel was charged with 19.0 g of intermediate (108), 80 mL of dichloromethane, and 0.5 mL of N, N-dimethylformamide, and 6.7 g of thionyl chloride was slowly added dropwise thereto. And stirred for 30 minutes. A solution of 50 mL of dehydrated dichloromethane in which 2.2 g of piperazine was dissolved was added dropwise using a dropping funnel, and then 11.4 g of triethylamine was added dropwise and stirred at room temperature for 1 hour. The completion of the reaction was confirmed by thin layer chromatography, and water was added to stop the reaction. The reaction product was transferred to a separatory funnel, and the lower organic layer was recovered. Further, after washing twice with distilled water, it was dried overnight with magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the resulting crude product was recrystallized from ethanol to obtain an intermediate (109).
　収量：１７．２ｇ、収率：８５％ Yield: 17.2 g, Yield: 85%
［工程Ｖ］ [Process V]
Figure JPOXMLDOC01-appb-C000110
Figure JPOXMLDOC01-appb-C000110
　攪拌機、温度計、冷却管を備えた３００ｍＬフラスコに中間体（１０９）の１４．８ｇとピペラジンの８．６ｇと無水炭酸カリウムの５．５ｇとジメチルスルホキシド（ＤＭＳＯ）の３０ｍＬを仕込み、１００℃で２４時間攪拌した。反応終了後、蒸留水と塩化メチレンを添加し、塩化メチレン層を水で３回、飽和食塩水で１回洗浄し、硫酸マグネシウムで一昼夜乾燥させた。ジクロロメタンを減圧留去し、中間体（１１０）を得た。 A 300 mL flask equipped with a stirrer, thermometer, and condenser is charged with 14.8 g of intermediate (109), 8.6 g of piperazine, 5.5 g of anhydrous potassium carbonate, and 30 mL of dimethyl sulfoxide (DMSO) at 100 ° C. Stir for 24 hours. After completion of the reaction, distilled water and methylene chloride were added, and the methylene chloride layer was washed 3 times with water and once with saturated brine, and dried with magnesium sulfate all day and night. Dichloromethane was distilled off under reduced pressure to obtain an intermediate (110).
　収量：１８．０ｇ、収率：９７．５％ Yield: 18.0 g, Yield: 97.5%
［工程ＶＩ］ [Process VI]
撹拌機、コンデンサ及び温度計を備えた３００ｍＬのフラスコに、中間体（１１０）１８．５ｇとのエチレンオキシド変性トリメチロールプロパントリアクリレート（ＭＩＷＯＮ社製「Ｍ３１３０」）２５．７ｇとｐ－メトキシフェノール４４ｍｇとエタノール１５０ｍＬを加え、５０℃で２４時間撹拌した。減圧留去により溶媒を除去して、下記構造式で表される光重合開始剤（Ｍ３２）を得た。 In a 300 mL flask equipped with a stirrer, a condenser and a thermometer, 15.7 g of intermediate (110) and 25.7 g of ethylene oxide-modified trimethylolpropane triacrylate (“M3130” manufactured by MIWON) and 44 mg of p-methoxyphenol were added. Ethanol 150mL was added and it stirred at 50 degreeC for 24 hours. The solvent was removed by distillation under reduced pressure to obtain a photopolymerization initiator (M32) represented by the following structural formula.
収量：４３．４ｇ、収率：９８．３％ Yield: 43.4 g, Yield: 98.3%
Figure JPOXMLDOC01-appb-C000111
Figure JPOXMLDOC01-appb-C000111
（実施例１：感光性樹脂組成物（１）の調製）
　合成例１で得た酸基含有（メタ）アクリレート樹脂（Ａ－１）１００質量部、硬化剤としてオルソクレゾールノボラック型エポキシ樹脂（ＤＩＣ株式会社製「ＥＰＩＣＬＯＮ　Ｎ－６８０」）２４．６質量部、ジペンタエリスリトールヘキサアクリレート６．３質量部、合成例３で得た光重合開始剤（Ｍ３１）１０質量部、ジエチレングリコールモノメチルエーテルアセテート１３．３質量部、２－エチル－４－メチルイミダゾール０．５質量部、フタロシアニングリーン０．７質量部を配合し、ロールミルにより混錬して感光性樹脂組成物（１）を得た。 (Example 1: Preparation of photosensitive resin composition (1))
100 parts by mass of the acid group-containing (meth) acrylate resin (A-1) obtained in Synthesis Example 1, 24.6 parts by mass of an orthocresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation) as a curing agent, 6.3 parts by weight of dipentaerythritol hexaacrylate, 10 parts by weight of the photopolymerization initiator (M31) obtained in Synthesis Example 3, 13.3 parts by weight of diethylene glycol monomethyl ether acetate, 0.5 parts by weight of 2-ethyl-4-methylimidazole Part and 0.7 parts by mass of phthalocyanine green were blended and kneaded by a roll mill to obtain a photosensitive resin composition (1).
（実施例２及び３：感光性樹脂組成物（２）及び（３）の調製）
　実施例１で用いた酸基含有（メタ）アクリレート樹脂（Ａ－１）及び光重合開始剤（Ｍ３１）を、表１３に示した組成に代えた以外は、実施例１と同様にして感光性樹脂組成物（２）及び（３）を得た。 (Examples 2 and 3: Preparation of photosensitive resin compositions (2) and (3))
The photosensitivity was the same as in Example 1 except that the acid group-containing (meth) acrylate resin (A-1) and the photopolymerization initiator (M31) used in Example 1 were replaced with the compositions shown in Table 13. Resin compositions (2) and (3) were obtained.
（比較例１及び２：感光性樹脂組成物（Ｃ１）及び（Ｃ２）の調製）
　実施例１で用いた光重合開始剤（Ｍ３１）の代わりに、２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン（ＩＧＭ社製「Ｏｍｎｉｒａｄ９０７」）、または２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－１－ブタノン（ＩＧＭ社製「Ｏｍｎｉｒａｄ３６９」）を表１３に示した配合量で用いた以外は、実施例１と同様にして感光性樹脂組成物（Ｃ１）及び（Ｃ２）を得た。 (Comparative Examples 1 and 2: Preparation of photosensitive resin compositions (C1) and (C2))
Instead of the photopolymerization initiator (M31) used in Example 1, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (“Omnirad 907” manufactured by IGM) or 2 Photosensitization in the same manner as in Example 1 except that -benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone ("Omnirad 369" manufactured by IGM) was used in the amount shown in Table 13. Resin compositions (C1) and (C2) were obtained.
　上記の実施例１～３で得られた感光性樹脂組成物（１）～（３）、並びに比較例１及び２で得られた感光性樹脂組成物（Ｃ１）及び（Ｃ２）を用いて、下記の評価を行った。 Using the photosensitive resin compositions (1) to (3) obtained in Examples 1 to 3 and the photosensitive resin compositions (C1) and (C2) obtained in Comparative Examples 1 and 2, The following evaluation was performed.
［光感度の評価方法］
　各実施例及び比較例で得られた感光性樹脂組成物を、アプリケーターを用いてガラス基材上に膜厚５０μｍとなるように塗布し、８０℃で３０分乾燥させた。次いで、乾燥させた塗膜上にコダック社製「ステップタブレットＮｏ．２」を乗せ、メタルハライドランプを用いて５００ｍＪ／ｃｍ２の紫外線を照射した。これを１％の炭酸ナトリウム水溶液で３０℃１８０秒間現像し、ステップタブレット法に基づきステップタブレットの残存段数にて評価した。なお、残存段数が多いほど光感度が高いことを示す。 [Evaluation method of photosensitivity]
The photosensitive resin composition obtained by each Example and the comparative example was apply | coated so that it might become a film thickness of 50 micrometers on a glass base material using the applicator, and it was made to dry at 80 degreeC for 30 minutes. Next, “Step Tablet No. 2” manufactured by Kodak Co., Ltd. was placed on the dried coating film, and irradiated with ultraviolet rays of 500 mJ / cm 2 using a metal halide lamp. This was developed with a 1% aqueous sodium carbonate solution at 30 ° C. for 180 seconds, and evaluated by the number of remaining steps of the step tablet based on the step tablet method. In addition, it shows that photosensitivity is so high that there are many remaining steps.
［アルカリ現像性の評価方法］
　各実施例及び比較例で得られた感光性樹脂組成物を、アプリケーターを用いてガラス基材上に膜厚５０μｍとなるように塗布した後、８０℃でそれぞれ３０分間、４０分間、５０分間、６０分間、７０分間、８０分間、９０分間、１００分間乾燥させ、乾燥時間が異なるサンプルを作成した。これらを１％炭酸ナトリウム水溶液で３０℃１８０秒間現像し、基板上に残渣が残らなかったサンプルの８０℃での乾燥時間を乾燥管理幅として下記の評価基準で評価した。なお、乾燥管理幅が長いほどアルカリ現像性が優れていることを示す。 [Evaluation method of alkali developability]
After applying the photosensitive resin composition obtained in each Example and Comparative Example to a film thickness of 50 μm on a glass substrate using an applicator, 30 minutes, 40 minutes, and 50 minutes, respectively, at 80 ° C. Samples with different drying times were prepared by drying for 60 minutes, 70 minutes, 80 minutes, 90 minutes, and 100 minutes. These were developed with a 1% aqueous sodium carbonate solution at 30 ° C. for 180 seconds, and the drying time at 80 ° C. of a sample in which no residue remained on the substrate was evaluated based on the following evaluation criteria as the drying control width. In addition, it shows that alkali developability is excellent, so that the dry management width | variety is long.
　○：乾燥管理幅が、６０分以上であった。
　×：乾燥管理幅が、６０分未満であった。 ○: The drying management width was 60 minutes or more.
X: The dry management width was less than 60 minutes.
　実施例１～３で調製した感光性樹脂組成物（１）～（３）、並びに比較例１及び２で調製した感光性樹脂組成物（Ｃ１）及び（Ｃ２）の組成及び評価結果を表１３に示す。 Table 13 shows the compositions and evaluation results of the photosensitive resin compositions (1) to (3) prepared in Examples 1 to 3 and the photosensitive resin compositions (C1) and (C2) prepared in Comparative Examples 1 and 2. Shown in
Figure JPOXMLDOC01-appb-T000112
Figure JPOXMLDOC01-appb-T000112
（実施例４：感光性樹脂組成物（４）の調製）
　合成例１で得た酸基含有（メタ）アクリレート樹脂（Ａ－１）１００質量部、硬化剤としてオルソクレゾールノボラック型エポキシ樹脂（ＤＩＣ株式会社製「ＥＰＩＣＬＯＮ　Ｎ－６８０」）２４．６質量部、合成例３で得た光重合開始剤（Ｍ３１）１０質量部、ジエチレングリコールモノメチルエーテルアセテート１３．３質量部を配合して感光性樹脂組成物（４）を得た。 (Example 4: Preparation of photosensitive resin composition (4))
100 parts by mass of the acid group-containing (meth) acrylate resin (A-1) obtained in Synthesis Example 1, 24.6 parts by mass of an orthocresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation) as a curing agent, The photosensitive resin composition (4) was obtained by blending 10 parts by mass of the photopolymerization initiator (M31) obtained in Synthesis Example 3 and 13.3 parts by mass of diethylene glycol monomethyl ether acetate.
（実施例５及び６：感光性樹脂組成物（５）及び（６）の調製）
　実施例４で用いた酸基含有（メタ）アクリレート樹脂（Ａ－１）及び光重合開始剤（Ｍ３１）を、表１４に示した組成に代えた以外は、実施例４と同様にして感光性樹脂組成物（５）及び（６）を得た。 (Examples 5 and 6: Preparation of photosensitive resin compositions (5) and (6))
Photosensitivity was the same as in Example 4 except that the acid group-containing (meth) acrylate resin (A-1) and photopolymerization initiator (M31) used in Example 4 were replaced with the compositions shown in Table 14. Resin compositions (5) and (6) were obtained.
（比較例３及び４：感光性樹脂組成物（Ｃ３）及び（Ｃ４）の調製）
　実施例４で用いた光重合開始剤（Ｍ３１）の代わりに、２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン（ＩＧＭ社製「Ｏｍｎｉｒａｄ９０７」）、または２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－１－ブタノン（ＩＧＭ社製「Ｏｍｎｉｒａｄ３６９」）を表１４に示した配合量で用いた以外は、実施例４と同様にして感光性樹脂組成物（Ｃ３）及び（Ｃ４）を得た。 (Comparative Examples 3 and 4: Preparation of photosensitive resin compositions (C3) and (C4))
In place of the photopolymerization initiator (M31) used in Example 4, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (“Omnirad 907” manufactured by IGM) or 2 Photosensitization was carried out in the same manner as in Example 4 except that -benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone ("Omnirad 369" manufactured by IGM) was used in the amount shown in Table 14. Resin compositions (C3) and (C4) were obtained.
　上記の実施例４～６で得られた感光性樹脂組成物（４）～（６）、並びに比較例３及び４で得られた感光性樹脂組成物（Ｃ３）及び（Ｃ４）を用いて、下記の評価を行った。 Using the photosensitive resin compositions (4) to (6) obtained in Examples 4 to 6 and the photosensitive resin compositions (C3) and (C4) obtained in Comparative Examples 3 and 4, The following evaluation was performed.
［耐熱性の評価方法］
　各実施例及び比較例で得られた感光性樹脂組成物を、アプリケーターを用いてガラス基材上に膜厚５０μｍとなるように塗布し、８０℃で３０分乾燥させた。次いで、メタルハライドランプを用いて５００ｍＪ／ｃｍ２の紫外線を照射した後、２００℃で１時間加熱して、硬化物をガラス基材から剥離し、硬化物を得た。前記硬化物から６ｍｍ×３５ｍｍの試験片を切り出し、粘弾性測定装置（ＤＭＡ：レオメトリック社製固体粘弾性測定装置「ＲＳＡＩＩ」、引張り法：周波数１Ｈｚ、昇温速度３℃／分）を用いて、弾性率変化が最大となる温度をガラス転移温度として評価した。なお、ガラス転移温度が高いほど耐熱性に優れていることを示す。 [Evaluation method of heat resistance]
The photosensitive resin composition obtained by each Example and the comparative example was apply | coated so that it might become a film thickness of 50 micrometers on a glass base material using the applicator, and it was made to dry at 80 degreeC for 30 minutes. Subsequently, after irradiating 500 mJ / cm < 2 > of ultraviolet-rays using a metal halide lamp, it heated at 200 degreeC for 1 hour, the hardened | cured material was peeled from the glass base material, and hardened | cured material was obtained. A 6 mm × 35 mm test piece was cut out from the cured product, and a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device “RSAII” manufactured by Rheometric Co., Ltd., tension method: frequency 1 Hz, temperature rising rate 3 ° C./min) was used. The temperature at which the change in elastic modulus was maximized was evaluated as the glass transition temperature. In addition, it shows that it is excellent in heat resistance, so that glass transition temperature is high.
［アウトガスの測定方法］
　各実施例及び比較例で得られた感光性樹脂組成物を、アプリケーターを用いてガラス基材上に膜厚５０μｍとなるように塗布し、８０℃で３０分乾燥させた。次いで、メタルハライドランプを用いて５００ｍＪ／ｃｍ２の紫外線を照射した後、２００℃で１時間加熱して、硬化物をガラス基材から剥離し、硬化物を得た。前記硬化物より粉末サンプルを採取し、ゲステル社製加熱脱着装置（ＴＤＵ）に入れた。その後（１）１５０℃の熱抽出温度で１０分間アウトガス成分を、（２）２６０℃の熱抽出温度で１０分間アウトガス成分を、それぞれ液体窒素を用いて－６０℃で捕集した。捕集したアウトガス成分は、アジレントテクノロジー社製ガスクロマトグラフィー質量分析装置（６８９０Ｎ／５９７３Ｎ）で分離分析を行い、ｎ－ドデカン換算で定量し、以下の評価基準で評価した。 [Measurement method of outgas]
The photosensitive resin composition obtained by each Example and the comparative example was apply | coated so that it might become a film thickness of 50 micrometers on a glass base material using the applicator, and it was made to dry at 80 degreeC for 30 minutes. Subsequently, after irradiating 500 mJ / cm < 2 > of ultraviolet-rays using a metal halide lamp, it heated at 200 degreeC for 1 hour, the hardened | cured material was peeled from the glass base material, and hardened | cured material was obtained. A powder sample was collected from the cured product and placed in a heat desorption apparatus (TDU) manufactured by GUSTER. Thereafter, (1) an outgas component at a heat extraction temperature of 150 ° C. for 10 minutes and (2) an outgas component at a heat extraction temperature of 260 ° C. for 10 minutes were collected at −60 ° C. using liquid nitrogen. The collected outgas component was subjected to separation analysis with a gas chromatography mass spectrometer (6890N / 5973N) manufactured by Agilent Technologies, quantified in terms of n-dodecane, and evaluated according to the following evaluation criteria.
　◎：アウトガス成分はほとんど確認されなかった。
　○：アウトガス成分が少し確認された。
　△：アウトガス成分が確認された。
　×：多量のアウトガス成分が確認された。 A: Almost no outgas component was confirmed.
○: Some outgas components were confirmed.
(Triangle | delta): The outgas component was confirmed.
X: A large amount of outgas components were confirmed.
　実施例４～６で調製した感光性樹脂組成物（４）～（６）、並びに比較例３及び４で調製した感光性樹脂組成物（Ｃ３）及び（Ｃ４）の組成及び評価結果を表１４に示す。 Table 14 shows the compositions and evaluation results of the photosensitive resin compositions (4) to (6) prepared in Examples 4 to 6 and the photosensitive resin compositions (C3) and (C4) prepared in Comparative Examples 3 and 4. Shown in
Figure JPOXMLDOC01-appb-T000113
Figure JPOXMLDOC01-appb-T000113
　なお、表１３及び１４中の「硬化剤」は、オルソクレゾールノボラック型エポキシ樹脂（ＤＩＣ株式会社製「ＥＰＩＣＬＯＮ　Ｎ－６８０」、エポキシ当量：２１４ｇ／当量）を示す。 The “curing agent” in Tables 13 and 14 represents an ortho-cresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation, epoxy equivalent: 214 g / equivalent).
　表１３及び１４中の「有機溶剤」は、ジエチレングリコールモノメチルエーテルアセテートを示す。 “Organic solvent” in Tables 13 and 14 represents diethylene glycol monomethyl ether acetate.

Claims (5)

  1. 　酸基含有（メタ）アクリレート樹脂（Ａ）と、光重合開始剤（Ｂ）とを含有する感光性樹脂組成物であって、
    前記光重合開始剤（Ｂ）が、下記一般式（１）で表される化合物であることを特徴とする感光性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     ［一般式（１）中、
    Ｒ１は炭素原子数１～１０のアルキル基を表し、
    Ｒ２は炭素原子数１～１２のアルキル基、炭素原子数２～４のヒドロキシアルキル基、炭素原子数１または２のアルコキシ基で置換された炭素原子数２～４のアルキル基のいずれかを表し、
    Ｒ３は炭素原子数１～１２のアルキル基、炭素原子数２～４のヒドロキシアルキル基、メトキシエチル基、またはエトキシエチル基を表し、
    またＲ２とＲ３とが一体となって窒素原子と共に環構造を形成するアルキレン基、Ｒ２とＲ３とが一体となって窒素原子と共にモルホリン骨格、Ｎ－メチルピペラジン骨格、または２，６－ジメチルモルホリン骨格を形成する環構形成部位であってもよく、
    Ｒ４～Ｒ７は、それぞれ独立して水素原子、炭素原子数１～８のアルキル基、またはフェニル基を表し、
    Ｙ１は、置換基を有しないか、またはハロゲン原子若しくは水酸基を置換基として有する炭素原子数３～１９のアルキル基（ｙ１－１）、炭素原子数７～１９のアラルキル基（ｙ１－２）、下記構造式（ｙ１－３）で表される構造部位（ｙ１－３）、
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ８は炭素原子数２～４のアルキレン基、Ｒ９は水素原子又はフェニル基又は炭素原子数１～４のアルキル基、ｍは０～２０の整数を表す。）
    下記構造式（ｙ１－４）で表される構造部位（ｙ１－４）、
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｒ８は炭素原子数２～４のアルキレン基、Ｒ９は水素原子、フェニル基、又は炭素数１～４のアルキル基、Ｒ１０は水素原子またはメチル基、ｍは０～２０の整数を表す。）
    下記構造式（ｙ１－５）で表される構造部位（ｙ１－５）、
    Figure JPOXMLDOC01-appb-C000004
     （式中、Ｒ１０は水素原子またはメチル基、Ｒ１１は炭素原子数１～１８のアルキル基又は炭素原子数６～１８のアリール基を表す。）
    下記構造式（ｙ１－６）で表される構造部位（ｙ１－６）、
    Figure JPOXMLDOC01-appb-C000005
     （式中、Ｒ１２は炭素原子数１～１８のアルキル基を表す。）
    下記構造式（ｙ１－７）で表される構造部位（ｙ１－７）、
    Figure JPOXMLDOC01-appb-C000006
     （式中、Ｒ８は炭素原子数２～４のアルキレン基、Ｒ１３は水素原子、炭素原子数１～６のアルキル基又はハロゲン原子、ｍは０～２０の整数を表す。）
    下記構造式（ｙ１－８）で表される構造部位（ｙ１－８）、または、
    Figure JPOXMLDOC01-appb-C000007
     （式中、Ｒ８はそれぞれ独立して炭素原子数２～４のアルキレン基、Ｒ１０は水素原子又はメチル基、Ｒ１４はｐ＋１の結合手を持つ炭素原子数３～２５の炭化水素基、ｌは０～２０の整数、ｐは１～３の整数を表す。）
    下記構造式（ｙ１－９）で表される構造部位（ｙ１－９）を表し、
    Figure JPOXMLDOC01-appb-C000008
     （式中、Ｒ１５は炭素原子数４～１８のアルキル基、炭素原子数６～１０の脂肪族環状炭化水素基、芳香族基を表す。）
    Ｘ１はエチレン基、１，３－プロピレン基、１，２－プロピレン基、２，３－プロピレン基を、Ｘ２は水素原子又はメチル基を、Ｘ３は水素原子、メチル基、又はエチル基を、或いは、Ｘ２及びＸ３が破線部にて共有結合を形成しつつ一体的にエチレン基、１，３－プロピレン基、１，２－プロピレン基、２，３－プロピレン基を、或いは、Ｘ１、Ｘ２、及びＸ３が、一体的に下記構造式（Ｘ－１）で表される、窒素原子と共にビシクロ環を構成する４価の脂肪族炭化水素基を表し、
    Figure JPOXMLDOC01-appb-C000009
     Ｙ２は、その構造部位末端に窒素原子又は酸素原子を有する、（ｎ＋１）の結合手を持つ有機結節基を表し、Ｙ３は、単結合、炭素原子数１～３のアルキレン基、又は炭素原子数１～３のアルキリデン基を表し、かつ、ｎは１～３の整数を表す。］     A photosensitive resin composition containing an acid group-containing (meth) acrylate resin (A) and a photopolymerization initiator (B),
    The said photoinitiator (B) is a compound represented by following General formula (1), The photosensitive resin composition characterized by the above-mentioned.
    Figure JPOXMLDOC01-appb-C000001
     [In general formula (1),
    R 1 represents an alkyl group having 1 to 10 carbon atoms,
    R 2 represents any of an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, and an alkyl group having 2 to 4 carbon atoms substituted by an alkoxy group having 1 or 2 carbon atoms. Represent,
    R 3 represents an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, a methoxyethyl group, or an ethoxyethyl group,
    R 2 and R 3 together form an alkylene group with a nitrogen atom to form a ring structure, R 2 and R 3 together form a nitrogen atom with a morpholine skeleton, N-methylpiperazine skeleton, or 2,6 -It may be a ring formation site forming a dimethylmorpholine skeleton,
    R 4 to R 7 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group,
    Y 1 is an alkyl group having 3 to 19 carbon atoms (y1-1) having no substituent, or having a halogen atom or a hydroxyl group as a substituent, aralkyl group having 7 to 19 carbon atoms (y1-2) A structural moiety (y1-3) represented by the following structural formula (y1-3),
    Figure JPOXMLDOC01-appb-C000002
     (Wherein R 8 represents an alkylene group having 2 to 4 carbon atoms, R 9 represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 0 to 20)
    A structural moiety (y1-4) represented by the following structural formula (y1-4),
    Figure JPOXMLDOC01-appb-C000003
     (Wherein R 8 is an alkylene group having 2 to 4 carbon atoms, R 9 is a hydrogen atom, a phenyl group, or an alkyl group having 1 to 4 carbon atoms, R 10 is a hydrogen atom or a methyl group, and m is 0 to 20) Represents an integer.)
    A structural moiety (y1-5) represented by the following structural formula (y1-5),
    Figure JPOXMLDOC01-appb-C000004
     (Wherein R 10 represents a hydrogen atom or a methyl group, and R 11 represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms.)
    A structural moiety (y1-6) represented by the following structural formula (y1-6),
    Figure JPOXMLDOC01-appb-C000005
     (In the formula, R 12 represents an alkyl group having 1 to 18 carbon atoms.)
    A structural moiety (y1-7) represented by the following structural formula (y1-7);
    Figure JPOXMLDOC01-appb-C000006
     (Wherein R 8 represents an alkylene group having 2 to 4 carbon atoms, R 13 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a halogen atom, and m represents an integer of 0 to 20)
    A structural moiety (y1-8) represented by the following structural formula (y1-8), or
    Figure JPOXMLDOC01-appb-C000007
     (Wherein R 8 is independently an alkylene group having 2 to 4 carbon atoms, R 10 is a hydrogen atom or a methyl group, R 14 is a hydrocarbon group having 3 to 25 carbon atoms having a p + 1 bond, l represents an integer of 0 to 20, and p represents an integer of 1 to 3.)
    Represents a structural moiety (y1-9) represented by the following structural formula (y1-9),
    Figure JPOXMLDOC01-appb-C000008
     (Wherein R 15 represents an alkyl group having 4 to 18 carbon atoms, an aliphatic cyclic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic group.)
    X 1 represents an ethylene group, 1,3-propylene group, 1,2-propylene group, 2,3-propylene group, X 2 represents a hydrogen atom or a methyl group, and X 3 represents a hydrogen atom, a methyl group, or an ethyl group. Or X 2 and X 3 form a covalent bond at the broken line part, and integrally form an ethylene group, a 1,3-propylene group, a 1,2-propylene group, a 2,3-propylene group, or X 1 , X 2 , and X 3 each represent a tetravalent aliphatic hydrocarbon group that together with the nitrogen atom forms a bicyclo ring, which is represented by the following structural formula (X-1);
    Figure JPOXMLDOC01-appb-C000009
     Y 2 represents an organic nodule group having a (n + 1) bond having a nitrogen atom or an oxygen atom at the end of the structural site, Y 3 represents a single bond, an alkylene group having 1 to 3 carbon atoms, or carbon It represents an alkylidene group having 1 to 3 atoms, and n represents an integer of 1 to 3. ]
  2. 　請求項１記載の感光性樹脂組成物の硬化反応物であることを特徴とする硬化物。 A cured product, which is a cured reaction product of the photosensitive resin composition according to claim 1.
  3. 　請求項１記載の感光性樹脂組成物からなることを特徴とする絶縁材料。 An insulating material comprising the photosensitive resin composition according to claim 1.
  4. 　請求項１記載の感光性樹脂組成物からなることを特徴とするソルダーレジスト用樹脂材料。 A resin material for a solder resist comprising the photosensitive resin composition according to claim 1.
  5. 　請求項４記載のソルダーレジスト用樹脂材料からなることを特徴とするレジスト部材。 A resist member comprising the resin material for solder resist according to claim 4.
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