JP7567446B2 - Active energy ray curable resin composition, cured product, insulating material and resist member - Google Patents

Description

The present invention relates to an active energy ray-curable resin composition that has excellent alkaline developability and can form a cured product with excellent heat resistance and elasticity, a cured product of the active energy ray-curable resin composition, an insulating material, and a resist member.

In recent years, curable compositions such as active energy ray curable compositions that can be cured by active energy rays such as ultraviolet rays and heat curable compositions that can be cured by heat have been widely used in the fields of inks, paints, coating agents, adhesives, optical components, etc. In particular, for the above-mentioned coating agent applications, it is generally required that the coating agent can impart design to the surface of various substrates, has excellent curing properties, and can form a coating film that can prevent deterioration of the substrate surface. Furthermore, when used as a curable composition for solder resist for printed wiring boards, it is also required that the coating agent has excellent alkaline developability.

A known conventional curable composition for solder resist is a photosensitive resin composition containing an acid group-containing epoxy acrylate resin obtained by further reacting tetrahydrophthalic anhydride with an intermediate obtained by reacting a cresol novolac epoxy resin with acrylic acid and phthalic anhydride (see, for example, Patent Document 1). However, the cured product has problems such as insufficient heat resistance and poor elasticity.

Therefore, there was a demand for a material that had excellent alkaline developability, heat resistance, and elasticity.

Japanese Patent Application Publication No. 8-259663

The problem that the present invention aims to solve is to provide an active energy ray-curable resin composition that has excellent alkaline developability and is capable of forming a cured product having excellent heat resistance and elasticity, a cured product of the active energy ray-curable resin composition, an insulating material, and a resist member.

As a result of intensive research into solving the above problems, the inventors discovered that the above problems could be solved by using an active energy ray-curable resin composition containing an acid group-containing (meth)acrylate resin and a specific imidazole compound, and thus completed the present invention.

That is, the present invention relates to an active energy ray-curable resin composition that contains a resin (A) having an acid group and a polymerizable unsaturated group and an imidazole compound (B) represented by the following general formula (1), a cured product of the active energy ray-curable resin composition, an insulating material, and a resist member.

[In formula (1),
Ar ¹ represents an aromatic hydrocarbon group having 6 to 20 carbon atoms.
^Ar2 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms.
^Ar3 represents a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms.
^L1 represents -O-, -COO- or -OCO-.
^L2 represents a single bond or --O--.
R ¹ represents a polyoxyalkylene group or a divalent hydrocarbon group having 1 to 50 carbon atoms which may have a substituent, and --CH ₂ -- contained in the hydrocarbon group may be replaced by --O-- and/or --CO--.
R ^a1 represents a reactive group.

The active energy ray-curable resin composition of the present invention has excellent alkaline developability and can form a cured product with excellent heat resistance and elasticity, and can be used as a coating agent or adhesive. As the coating agent, it is particularly suitable for use in solder resist applications. In the present invention, "excellent elasticity" refers to high elasticity.

FIG. 1 shows the ¹ H-NMR spectrum of the imidazole compound (1). FIG. 2 shows the ¹³ C-NMR spectrum of the imidazole compound (1). FIG. 3 shows the MALDI-MS spectrum of the imidazole compound (1).

The active energy ray-curable resin composition of the present invention is characterized by containing a resin (A) having an acid group and a polymerizable unsaturated group, and an imidazole compound (B) represented by general formula (1).

In the present invention, "(meth)acrylate" means acrylate and/or methacrylate. Furthermore, "(meth)acryloyl" means acryloyl and/or methacryloyl. Furthermore, "(meth)acrylic" means acrylic and/or methacrylic.

The resin (A) having an acid group and a polymerizable unsaturated group may be any resin having an acid group and a polymerizable unsaturated group in the resin, and examples thereof include an epoxy resin having an acid group and a polymerizable unsaturated group, a urethane resin having an acid group and a polymerizable unsaturated group, an acrylic resin having an acid group and a polymerizable unsaturated group, an amide-imide resin having an acid group and a polymerizable unsaturated group, an acrylamide resin having an acid group and a polymerizable unsaturated group, and an ester resin having an acid group and a polymerizable unsaturated group.

Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, a carboxyl group is preferred.

Examples of the polymerizable unsaturated group include an allyl group, an isopropenyl group, a 1-propenyl group, a styryl group, a styrylmethyl group, a maleimide group, and a vinyl ether group.

Examples of the epoxy resin having an acid group and a polymerizable unsaturated group include epoxy (meth)acrylate resins having an acid group, which have epoxy resins, unsaturated monobasic acids, and polybasic acid anhydrides as essential raw materials, and epoxy (meth)acrylate resins having an acid group and a urethane bond, which have epoxy resins, unsaturated monobasic acids, polybasic acid anhydrides, polyisocyanate compounds, and (meth)acrylate compounds having hydroxyl groups as reaction raw materials.

Examples of the epoxy resin include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthalene 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 novolac 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 reaction type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, oxazolidone type epoxy resin, etc. These epoxy resins can be used alone or in combination of two or more.

Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, etc.

Examples of the hydrogenated bisphenol type epoxy resin include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol B type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol F type epoxy resin, and hydrogenated bisphenol S type epoxy resin.

Examples of the biphenol type epoxy resin include 4,4'-biphenol type epoxy resin, 2,2'-biphenol type epoxy resin, tetramethyl-4,4'-biphenol type epoxy resin, and tetramethyl-2,2'-biphenol type epoxy resin.

Examples of the hydrogenated biphenol type epoxy resin include hydrogenated 4,4'-biphenol type epoxy resin, hydrogenated 2,2'-biphenol type epoxy resin, hydrogenated tetramethyl-4,4'-biphenol type epoxy resin, and hydrogenated tetramethyl-2,2'-biphenol type epoxy resin.

Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, and β-furfurylacrylic acid. Esters, acid halides, and acid anhydrides of the unsaturated monobasic acids can also be used. Furthermore, compounds represented by the following structural formula (2) can also be used.

[In formula (2), X represents an alkylene chain having 1 to 10 carbon atoms, a polyoxyalkylene chain, a (poly)ester chain, an aromatic hydrocarbon chain, or a (poly)carbonate chain, and may have a halogen atom, an alkoxy group, or the like in the structure. Y represents a hydrogen atom or a methyl group.]

Examples of the polyoxyalkylene chain include polyoxyethylene chains and polyoxypropylene chains.

The (poly)ester chain may be, for example, a (poly)ester chain represented by the following structural formula (3):

[In formula (3), each R ¹ is independently an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.]

Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, and a binaphthylene chain. In addition, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring as a partial structure can also be used.

These unsaturated monobasic acids can be used alone or in combination of two or more.

Examples of the polybasic acid anhydride include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, and aromatic polybasic acid anhydrides.

Examples of the aliphatic polybasic acid anhydrides include anhydrides of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, and 1,2,3,4-butanetetracarboxylic acid. In addition, the aliphatic hydrocarbon group of the aliphatic polybasic acid anhydride may be either linear or branched, and may have an unsaturated bond in the structure.

In the present invention, the alicyclic polybasic acid anhydride is one in which an acid anhydride group is bonded to an alicyclic structure, and the presence or absence of aromatic rings in other structural parts is not important. Examples of the alicyclic polybasic acid anhydride include anhydrides of tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, and 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid.

Examples of the aromatic polybasic acid anhydrides include anhydrides of phthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, and benzophenone tetracarboxylic acid.

These polybasic acid anhydrides can be used alone or in combination of two or more.

Examples of the polyisocyanate compounds include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, Examples of the polyisocyanate include aromatic diisocyanate compounds such as silylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and o-tolidine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (4); and isocyanurate-modified, biuret-modified, and allophanate-modified versions of these compounds. These polyisocyanate compounds can be used alone or in combination of two or more types.

[In the formula, R ¹ is independently either a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ² is independently either an alkyl group having 1 to 4 carbon atoms, or a bonding point connecting the structural portion represented by structural formula (4) via a methylene group marked with *. l is 0 or an integer of 1 to 3, and m is an integer of 1 to 15.]

As the (meth)acrylate compound having a hydroxyl group, there are no particular limitations on the specific structure as long as it is a compound having a hydroxyl group and a (meth)acryloyl group in its molecular structure, and a wide variety of compounds can be used. Examples of such acrylates include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. In addition, (poly)oxyalkylene modified compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain is introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds, and lactone modified compounds in which a (poly)lactone structure is introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds can also be used. These hydroxyl group-containing (meth)acrylate compounds can be used alone or in combination of two or more.

The method for producing the epoxy resin having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the epoxy resin having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent as necessary, and a basic catalyst may be used as necessary.

Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, and methyl 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; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. These organic solvents can be used alone or in combination of two or more. In addition, the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials, since this improves the reaction efficiency.

Examples of the basic catalyst include amine compounds such as N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and tetramethylammonium hydroxide; trioctylmethylammonium chloride, ... Examples of the quaternary ammonium salts include octylmethylammonium acetate; phosphine compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxypropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; organic tin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; organic metal compounds such as zinc octylate and bismuth octylate; inorganic tin compounds such as tin octanoate; and inorganic metal compounds. In addition, alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides can also be used. In particular, alkali metal hydroxides are preferred because they have excellent catalytic activity in the epoxy resin synthesis reaction, and for example, sodium hydroxide and potassium hydroxide are more preferred. These basic catalysts can be used alone or in combination of two or more. When using the basic catalyst, it may be used in the form of an aqueous solution of about 10% by mass to 55% by mass, or in the form of a solid.

Examples of the urethane resin having an acid group and a polymerizable unsaturated group include those obtained by reacting a polyisocyanate compound, a (meth)acrylate compound having a hydroxyl group, a polyol compound having a carboxyl group, and, if necessary, a polybasic acid anhydride, and a polyol compound other than the polyol compound having a carboxyl group, and those obtained by reacting a polyisocyanate compound, a (meth)acrylate compound having a hydroxyl group, a polybasic acid anhydride, and a polyol compound other than a polyol compound having a carboxyl group.

The polyisocyanate compound may be the same as the polyisocyanate compounds exemplified above, and the polyisocyanate compounds may be used alone or in combination of two or more.

As the (meth)acrylate compound having a hydroxyl group, the same compounds as those exemplified as the (meth)acrylate compound having a hydroxyl group described above can be used, and the (meth)acrylate compound having a hydroxyl group can be used alone or in combination of two or more kinds.

Examples of the polyol compound having a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid. The polyol compound having a carboxyl group can be used alone or in combination of two or more kinds.

The polybasic acid anhydride may be the same as those exemplified above, and the polybasic acid anhydrides may be used alone or in combination of two or more kinds.

Examples of polyol compounds other than the polyol compounds having a carboxyl group include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; aromatic polyol compounds such as biphenol and bisphenol; (poly)oxyalkylene modified compounds in which (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains are introduced into the molecular structure of the various polyol compounds; lactone modified compounds in which (poly)lactone structures are introduced into the molecular structure of the various polyol compounds. The polyol compounds other than the polyol compounds having a carboxyl group can be used alone or in combination of two or more kinds.

The method for producing the urethane resin having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the urethane resin having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent as necessary, and a basic catalyst may be used as necessary.

The organic solvent may be the same as those exemplified above, and the organic solvent may be used alone or in combination of two or more kinds.

The basic catalyst may be the same as those exemplified above, and the basic catalyst may be used alone or in combination of two or more kinds.

Examples of the acrylic resin having an acid group and a polymerizable unsaturated group include a reaction product obtained by polymerizing an acrylic resin intermediate obtained by polymerizing an essential component of a (meth)acrylate compound (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or a glycidyl group, and then reacting the resulting intermediate with a (meth)acrylate compound (β) having a reactive functional group that can react with the functional group to introduce a (meth)acryloyl group, and a reaction product obtained by reacting a polybasic acid anhydride with the hydroxyl group in the reaction product.

The acrylic resin intermediate may be a copolymer of the (meth)acrylate compound (α) and, if necessary, other compounds having polymerizable unsaturated groups. Examples of the compounds having other polymerizable unsaturated groups include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; aromatic ring-containing (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. These may be used alone or in combination of two or more.

The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group of the (meth)acrylate compound (α), but the following combinations are preferable from the viewpoint of reactivity. That is, when a (meth)acrylate having a hydroxyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having an isocyanate group as the (meth)acrylate compound (β). When a (meth)acrylate having a carboxyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a glycidyl group as the (meth)acrylate compound (β). When a (meth)acrylate having an isocyanate group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a hydroxyl group as the (meth)acrylate compound (β). When a (meth)acrylate having a glycidyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a carboxyl group as the (meth)acrylate compound (β). The (meth)acrylate compound (β) can be used alone or in combination of two or more kinds.

The polybasic acid anhydride may be the same as those exemplified above, and the polybasic acid anhydride may be used alone or in combination of two or more kinds.

The method for producing the acrylic resin having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the acrylic resin having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent as necessary, and a basic catalyst may be used as necessary.

The organic solvent may be the same as those exemplified above, and the organic solvent may be used alone or in combination of two or more kinds.

The basic catalyst may be the same as those exemplified above, and the basic catalyst may be used alone or in combination of two or more kinds.

The amide-imide resin having an acid group and a polymerizable unsaturated group may be, for example, one obtained by reacting an amide-imide resin having an acid group and/or an acid anhydride group with a (meth)acrylate compound having a hydroxyl group and/or a (meth)acrylate compound having an epoxy group, and, if necessary, with a compound having one or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group. The compound having a reactive functional group may or may not have a (meth)acryloyl group.

The amide-imide resin may have either an acid group or an acid anhydride group, or may have both. From the viewpoint of reactivity and reaction control with a (meth)acrylate compound having a hydroxyl group or an epoxy compound having a (meth)acryloyl group, it is preferable that the resin has an acid anhydride group, and it is more preferable that the resin has both an acid group and an acid anhydride group. The solid content acid value of the amide-imide resin is preferably in the range of 60 to 350 mg KOH/g measured under neutral conditions, i.e., conditions in which the acid anhydride group is not ring-opened. On the other hand, it is preferable that the measured value under conditions in which the acid anhydride group is ring-opened, such as in the presence of water, is in the range of 61 to 360 mg KOH/g.

The amide-imide resin can be, for example, one obtained by reacting a polyisocyanate compound with a polybasic acid anhydride.

The polyisocyanate compound may be the same as the polyisocyanate compounds exemplified above, and the polyisocyanate compounds may be used alone or in combination of two or more.

The polybasic acid anhydride may be the same as those exemplified above, and the polybasic acid anhydrides may be used alone or in combination of two or more kinds.

In addition, if necessary, the amide-imide resin can be used in combination with a polybasic acid as a reaction raw material in addition to the polyisocyanate compound and polybasic acid anhydride.

As the polybasic acid, any compound having two or more carboxyl groups in one molecule can be used. For example, 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, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, 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, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, etc. In addition, as the polybasic acid, for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in the molecule, can also be used. These polybasic acids can be used alone or in combination of two or more kinds.

As the (meth)acrylate compound having a hydroxyl group, the same compounds as those exemplified as the (meth)acrylate compound having a hydroxyl group described above can be used, and the (meth)acrylate compound having a hydroxyl group can be used alone or in combination of two or more kinds.

As the (meth)acrylate compound having an epoxy group, there is no particular limitation on the specific structure 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. For example, (meth)acrylate monomers having a glycidyl group such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; mono(meth)acrylates of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether can be mentioned. These (meth)acrylate compounds having an epoxy group can be used alone or in combination of two or more kinds. Among these, (meth)acrylate compounds having one epoxy group are preferred because the reaction can be easily controlled, and (meth)acrylate monomers having a glycidyl group are preferred because an active energy ray curable resin composition having excellent alkaline developability and capable of forming a cured product having excellent heat resistance and elasticity can be obtained. In addition, the molecular weight of the (meth)acrylate monomer having a glycidyl group is preferably 500 or less. Furthermore, the ratio of the (meth)acrylate monomer having a glycidyl group to the total mass of the (meth)acrylate compound having an epoxy group is preferably 70% by mass or more, and more preferably 90% by mass or more.

The method for producing the amide-imide resin having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the amide-imide resin having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent as necessary, and a basic catalyst may be used as necessary.

The organic solvent may be the same as those exemplified above, and the organic solvent may be used alone or in combination of two or more kinds.

The basic catalyst may be the same as those exemplified above, and the basic catalyst may be used alone or in combination of two or more kinds.

Examples of the acrylamide resin having an acid group and a polymerizable unsaturated group include those obtained by reacting a compound having a phenolic hydroxyl group, an alkylene oxide or alkylene carbonate, an N-alkoxyalkyl (meth)acrylamide compound, a polybasic acid anhydride, and, if necessary, an unsaturated monobasic acid.

As the compound having a phenolic hydroxyl group, the same compounds as those exemplified as the compound (a1) having a phenolic hydroxyl group described above can be used, and the compound having a phenolic hydroxyl group can be used alone or in combination of two or more kinds.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. Among these, ethylene oxide or propylene oxide is preferred because it provides an active energy ray-curable resin composition that has excellent alkaline developability and can form a cured product with excellent heat resistance and elasticity. The alkylene oxides can be used alone or in combination of two or more kinds.

Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. Among these, ethylene carbonate or propylene carbonate is preferred because it provides an active energy ray-curable resin composition that has excellent alkaline developability and can form a cured product with excellent heat resistance and elasticity. The alkylene carbonates can be used alone or in combination of two or more kinds.

Examples of the N-alkoxyalkyl (meth)acrylamide compounds include N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-methoxyethyl (meth)acrylamide, N-ethoxyethyl (meth)acrylamide, and N-butoxyethyl (meth)acrylamide. The N-alkoxyalkyl (meth)acrylamide compounds can be used alone or in combination of two or more.

The polybasic acid anhydride may be the same as those exemplified above, and the polybasic acid anhydrides may be used alone or in combination of two or more kinds.

The unsaturated monobasic acid may be the same as those exemplified above, and the unsaturated monobasic acid may be used alone or in combination of two or more kinds.

The method for producing the acrylamide resin having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the acrylamide resin having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent as necessary, and a basic catalyst and an acid catalyst may be used as necessary.

The organic solvent may be the same as those exemplified above, and the organic solvent may be used alone or in combination of two or more kinds.

The basic catalyst may be the same as those exemplified above, and the basic catalyst may be used alone or in combination of two or more kinds.

Examples of the acid 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. In addition, solid acid catalysts having strong acids such as sulfonyl groups can also be used. These acid catalysts can be used alone or in combination of two or more.

The ester resin having an acid group and a polymerizable unsaturated group may be, for example, one obtained by reacting a compound having a phenolic hydroxyl group with an alkylene oxide or alkylene carbonate, an unsaturated monobasic acid, and a polybasic acid anhydride.

The compound having a phenolic hydroxyl group refers to a compound having at least one phenolic hydroxyl group in the molecule. Examples of the compound having at least one phenolic hydroxyl group in the molecule include compounds represented by the following structural formulas (2-1) to (2-4).

In the structural formulae (5-1) to (5-4), R ¹ is any of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom, and R ² is each independently a hydrogen atom or a methyl group. Furthermore, p is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, and even more preferably 0. q is an integer of 1 or more, preferably 2 or 3. The position of the substituent on the aromatic ring in the structural formulae is arbitrary, and for example, in the naphthalene ring of structural formula (5-2), it may be substituted on any ring, in structural formula (5-3), it may be substituted on any ring of the benzene ring present in one molecule, and in structural formula (5-4), it may be substituted on any ring of the benzene ring present in one molecule, and the number of substituents in one molecule is indicated as p and q.

As the compound having a phenolic hydroxyl group, for example, a reaction product in which a compound having at least one phenolic hydroxyl group in the molecule and a compound represented by any one of the following structural formulas (x-1) to (x-5) are used as essential reaction raw materials can also be used. In addition, a novolac-type phenolic resin in which one or more compounds having at least one phenolic hydroxyl group in the molecule are used as reaction raw materials can also be used.

[In formula (x-1), h is 0 or 1. In formulas (x-2) to (x-5), R ³ is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom, and i is 0 or an integer from 1 to 4. In formulas (x-2), (x-3), and (x-5), Z is any one of a vinyl group, a halomethyl group, a hydroxymethyl group, and an alkyloxymethyl group. In formula (x-5), Y is any one of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, and a carbonyl group, and j is an integer from 1 to 4.]

These compounds having a phenolic hydroxyl group can be used alone or in combination of two or more.

As the alkylene oxide, the same alkylene oxides as those exemplified above can be used. Among these, ethylene oxide or propylene oxide is preferred because it gives an active energy ray-curable resin composition that has excellent alkaline developability and can form a cured product with excellent heat resistance and elasticity. The alkylene oxides can be used alone or in combination of two or more kinds.

As the alkylene carbonate, the same ones as those exemplified above as the alkylene carbonate can be used. Among these, ethylene carbonate or propylene carbonate is preferred because it gives an active energy ray curable resin composition that has excellent alkaline developability and can form a cured product with excellent heat resistance and elasticity. The alkylene carbonates can be used alone or in combination of two or more kinds.

The unsaturated monobasic acid may be the same as those exemplified above, and the unsaturated monobasic acid may be used alone or in combination of two or more kinds.

The polybasic acid anhydride may be the same as those exemplified above, and the polybasic acid anhydrides may be used alone or in combination of two or more kinds.

The method for producing the ester resin having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the ester resin having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent as necessary, and a basic catalyst and an acid catalyst may be used as necessary.

The organic solvent may be the same as those exemplified above, and the organic solvent may be used alone or in combination of two or more kinds.

The basic catalyst may be the same as those exemplified above, and the basic catalyst may be used alone or in combination of two or more kinds.

The acid catalyst may be the same as those exemplified above, and the acid catalyst may be used alone or in combination of two or more.

The acid value of the resin (A) having an acid group and a polymerizable unsaturated group is preferably in the range of 50 to 150 mgKOH/g, and more preferably in the range of 60 to 120 mgKOH/g, since an active energy ray-curable resin composition having excellent alkaline developability and excellent heat resistance and elasticity in the cured product can be obtained. In the present invention, the acid value of the (meth)acrylate resin having an acid group is a value measured by the neutralization titration method of JIS K 0070 (1992).

The imidazole compound (B) is a compound represented by the following general formula (1):

In formula (1), Ar ¹ represents an aromatic hydrocarbon group having 6 to 20 carbon atoms.
^Ar2 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms.
^Ar3 represents a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms.
^L1 represents -O-, -COO- or -OCO-.
^L2 represents a single bond or --O--.
R ¹ represents a polyoxyalkylene group or a divalent hydrocarbon group having 1 to 50 carbon atoms which may have a substituent, and --CH ₂ -- contained in the hydrocarbon group may be replaced by --O-- and/or --CO--.
R ^a1 represents a reactive group.

Examples of the aromatic hydrocarbon groups represented by Ar ¹ and Ar ² in formula (1) include a phenyl group, a naphthyl group, an anthracenyl group, etc. These aromatic hydrocarbon groups may have a substituent, and examples of the substituent include an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms), such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc.; an aromatic hydrocarbon group having 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group; a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.; and a hydroxy group.

The number of carbon atoms in the aromatic hydrocarbon groups represented by Ar ¹ and Ar ² in formula (1) (including the number of carbon atoms in the substituent if any) is in the range of 6 to 20, preferably 6 to 10.

Examples of the aromatic hydrocarbon group represented by ^Ar3 in formula (1) include a phenylene group, a naphthylene group, an anthracenediyl group, etc. These aromatic hydrocarbon groups may have a substituent, and examples of the substituent include the same as those exemplified as the substituents that may be possessed by ^Ar1 and ^Ar2 described above.

The aromatic hydrocarbon group represented by ^Ar3 in formula (1) has a carbon atom number (including the carbon atom number of the substituent if the group has a substituent) in the range of 6 to 20, preferably 6 to 10.

In formula (1), L ¹ is any one of -O-, -COO-, and -OCO-, and is preferably -O- or -COO-. In addition, -O-, -COO-, and -OCO- are bonded to Ar ³ via the left bond.

In formula (1), L ² is either a single bond or —O—.

Examples of the polyoxyalkylene group represented by R ¹ in formula (1) include groups having a repeating unit consisting of a combination of an alkylene group having 2 to 5 carbon atoms and -O-, such as a polyoxyethylene group, a polyoxypropylene group, or a polyoxybutylene group. The number of repeating units is preferably in the range of 2 to 50, more preferably in the range of 2 to 20, and particularly preferably in the range of 2 to 10.

Examples of the divalent hydrocarbon group represented by R ¹ in formula (1) include divalent aliphatic hydrocarbon groups having 1 to 50 carbon atoms, divalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, and groups having 4 to 50 carbon atoms that are a combination of two or more of the divalent aliphatic hydrocarbon groups, divalent alicyclic hydrocarbon groups, and divalent aromatic hydrocarbon groups.

Examples of the aliphatic hydrocarbon group include saturated or unsaturated aliphatic hydrocarbon groups, and preferred are alkanediyl groups such as methylene, ethylene, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, octanediyl, nonanediyl, decanediyl, undecanediyl, dodecanediyl, tridecanediyl, tetradecanediyl, pentadecanediyl, hexadecanediyl, heptadecanediyl, octadecanediyl, nonadecanediyl, and eicosanediyl. The aliphatic hydrocarbon group may be linear or branched.

R ¹ in formula (1) may be a group in which one or more -CH ₂ - contained in the aliphatic hydrocarbon group are replaced with -O- and/or -CO-. Furthermore, two or more -CH ₂ - may be replaced with -O- and/or -CO- to form an ester bond (-OCO-, -COO-) or a carbonate bond (-OCOO-). The number of -CH ₂ - replaced with -O- and/or -CO- in the aliphatic hydrocarbon group may be, for example, 1 or more, 2 or more, or 10 or less, 5 or less. However, it is preferable that adjacent -CH ₂ - are not simultaneously replaced with -O-.

The aliphatic hydrocarbon group may have bonded thereto, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a hydroxy group; a group represented by -R ² -L ³ -R ^a2 , or the like.

The number of carbon atoms in the aliphatic hydrocarbon group is preferably in the range of 1 to 50, more preferably in the range of 1 to 20, and particularly preferably in the range of 1 to 10.

Examples of the alicyclic hydrocarbon group include saturated or unsaturated alicyclic hydrocarbon groups, and preferred are monocyclic alicyclic hydrocarbon groups such as cyclopropanediyl group, cyclobutanediyl group, cyclopentanediyl group, cyclohexanediyl group, cyclooctanediyl group, cyclononanediyl group, and cyclodecanediyl group; and polycyclic alicyclic hydrocarbon groups such as bicyclo[1.1.0]butanediyl group, tricyclo[2.2.1.0]heptanediyl group, bicyclo[3.2.1]octanediyl group, bicyclo[2.2.2.]octanediyl group, adamantanediyl group, bicyclo[4.3.2]undecanediyl group, and tricyclo[5.3.1.1]dodecanediyl group.

The alicyclic hydrocarbon group may have, as a substituent, an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms), such as a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, or decyl group; an aromatic hydrocarbon group having 6 to 10 carbon atoms, such as a phenyl group or naphthyl group; a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group; or a group represented by -R ² -R ^a .

The alicyclic hydrocarbon group may have bonded thereto, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a hydroxy group; a group represented by -R ² -L ³ -R ^a2 , or the like.

The number of carbon atoms in the alicyclic hydrocarbon group (including the number of carbon atoms in the substituent if the group has a substituent) is preferably in the range of 3 to 50, more preferably in the range of 5 to 20, and particularly preferably in the range of 3 to 10.

The aromatic hydrocarbon group may be monocyclic or polycyclic, and examples thereof include a phenylene group, a naphthylene group, an anthracenediyl group, and a fluorenediyl group.

The aromatic hydrocarbon group may have, as a substituent, an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms), such as a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, or decyl group; an aromatic hydrocarbon group having 6 to 10 carbon atoms, such as a phenyl group or naphthyl group; a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group; or a group represented by -R ² -R ^a .

The aromatic hydrocarbon group may have bonded thereto, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a hydroxy group; a group represented by -R ² -L ³ -R ^a; or the like.

The number of carbon atoms in the aromatic hydrocarbon group (including the number of carbon atoms of the substituent if the group has a substituent) is preferably in the range of 6 to 50, more preferably in the range of 6 to 20, and particularly preferably in the range of 6 to 10.

As the group that combines two or more of the divalent aliphatic hydrocarbon group, the divalent alicyclic hydrocarbon group, and the divalent aromatic hydrocarbon group, a divalent group that combines an aliphatic hydrocarbon group and an alicyclic hydrocarbon group, or a divalent group that combines an aliphatic hydrocarbon group and an aromatic hydrocarbon group, is preferred.

The number of carbon atoms in the group that combines two or more of the aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group is preferably in the range of 4 to 50, more preferably in the range of 4 to 20, and particularly preferably in the range of 4 to 10.

In the group represented by -R ² -L ³ -R ^a2 which the hydrocarbon group represented by R ¹ may have as a substituent, R ² represents a polyoxyalkylene group or a divalent hydrocarbon group having 1 to 50 carbon atoms, -CH ₂ - contained in the hydrocarbon group may be replaced by -O- and/or -CO-, and a hydrogen atom contained in the hydrocarbon group may be substituted by a hydroxy group. L ³ represents a single bond or -O-. R ^a2 represents a reactive group.

Examples of the polyoxyalkylene group represented by ^R2 include the same groups as those exemplified as the polyoxyalkylene group represented by ^R1 .

Examples of the hydrocarbon group represented by ^R2 (including groups in which the -CH ₂ - contained in the hydrocarbon group is replaced by -O- and/or -CO-) include the same groups as those exemplified as the hydrocarbon group represented by ^R1 .

Examples of the substituent that the hydrocarbon group represented by ^R2 may have include a hydroxy group.

^L3 represents a single bond or --O--.

Examples of the reactive groups represented by R ^a1 and R ^a2 include groups capable of forming a polymer main chain by a polycondensation reaction, and specific examples thereof include groups containing an ethylenic double bond such as a vinyl group, a (meth)acryloyl group, or a (meth)allyl group; and groups containing a cyclic ether such as an oxetanyl group. The group containing a cyclic ether may have, as a substituent, an aliphatic hydrocarbon group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, or a propyl group. Of these, examples of the reactive groups represented by R ^a1 and R ^a2 are preferably a vinyl group, a (meth)acryloyl group, or an oxetanyl group which may have a substituent.

Examples of the imidazole compound (B) represented by the general formula (1) include compounds represented by the following formulas (1-1) to (1-68). In the formulas, n represents an integer of 2 to 10.

The method for producing the imidazole compound (B) can be, for example, the method represented by the following scheme.
Route 1: Compound (a-1) is reacted with compound (b) to obtain compound (c) (step 1), and compound (d) is reacted with compound (e) to produce compound (c).
Route 2: It can also be produced by reacting compound (a-2) with compound (d) and compound (e) (step 3), and then reacting compound (g-1) or compound (g-2) (step 4),
Route 3: Compound (a-1) can also be produced by reacting compound (h) with compound (a-1) to obtain compound (i) (step 5), hydrolyzing the ester bond of compound (i) to obtain compound (j) (step 6), reacting compound (d) with compound (e) to obtain compound (k) (step 7), and then further reacting with compound (l).

[In the above scheme,
^Ar1 , ^Ar2 , ^Ar3 , ^L1 , ^L2 , ^R1 and ^Ral are as defined above.
^A1 represents a heterocyclic group containing an oxygen atom.
R ³ represents a polyoxyalkylene group or a hydrocarbon group having 1 to 47 carbon atoms, and --CH ₂ -- contained in the hydrocarbon group may be replaced by --O-- and/or --CO--.
^R4 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
X ¹ and X ² each independently represent a halogen atom.

The heterocyclic group containing an oxygen atom represented by ^A1 may be a monocyclic or polycyclic ring, and in the case of a polycyclic ring, a plurality of monocyclic heterocyclic groups may be bonded by a covalent bond, or may be a bridged ring. Examples of the heterocyclic group containing an oxygen atom represented by ^A1 include cyclic ether groups such as oxiranyl group and oxetanyl group; epoxycycloalkyl groups such as epoxycyclohexyl group and epoxycyclopentyl group; and the like.

The oxyalkylene group represented by ^R3 may be the same as the polyoxyalkylene group represented by ^R1 , and the number of repeating units of the oxyalkylene is preferably in the range of 2 to 49, more preferably in the range of 2 to 19, and particularly preferably in the range of 2 to 9.

Examples of the hydrocarbon group represented by ^R3 include groups having 1 to 47 carbon atoms among the groups explained as the hydrocarbon group represented by ^R1 . The aliphatic hydrocarbon group represented by ^R3 may have bonded thereto, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group; a group represented by ^-R2 - ^L3 - ^Ra2 , or the like. The number of carbon atoms in the aliphatic hydrocarbon group represented by ^R3 is preferably in the range of 1 to 47, more preferably in the range of 1 to 17, and particularly preferably in the range of 1 to 7.

The alicyclic hydrocarbon group represented by ^R3 may have bonded thereto, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a group represented by ^-R2 - ^L3 - ^Ra2 , etc. The number of carbon atoms in the alicyclic hydrocarbon group represented by ^R3 is preferably in the range of 3 to 47, more preferably in the range of 3 to 17, and particularly preferably in the range of 3 to 7.

The aromatic hydrocarbon group represented by ^R3 may have bonded thereto, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a hydroxy group; a group represented by ^-R2 - ^L3 - ^Ra2 , etc. The aromatic hydrocarbon group represented by ^R3 preferably has 6 to 47 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 10 carbon atoms.

The number of carbon atoms in the group consisting of two or more of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group represented by ^R3 is preferably in the range of 4 to 47, more preferably in the range of 4 to 17, and particularly preferably in the range of 4 to 7.

Examples of the aliphatic hydrocarbon group represented by ^R4 include a methyl group, an ethyl group, a butyl group, and a pentyl group. The number of carbon atoms in the aliphatic hydrocarbon group represented by ^R4 is preferably in the range of 1 to 5, and more preferably in the range of 1 to 3.

Examples of the halogen atom represented by X ¹ and X ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a chlorine atom is preferable.

Each step is explained below.

Regarding steps 1 and 5: In steps 1 and 5, compound (a-2) is reacted with compound (b) or compound (h) to obtain compound (c) or compound (i).

During the reaction, a tertiary organic phosphorus compound such as triphenylphosphine and an azodicarboxylate ester such as diethyl azodicarboxylate or diisopropyl azodicarboxylate are present as catalysts.

An ether solvent such as tetrahydrofuran can be used as the reaction solvent.

Regarding steps 2, 3, and 7: In steps 2, 3, and 7, compound (a-2), compound (c), or compound (j) is reacted with compound (d) and compound (e) to form an imidazole ring, thereby obtaining compound (f), imidazole compound (B) represented by general formula (1), or compound (k), respectively.

During the reaction, a catalyst such as 1,4-diazabicyclo[2.2.2]octane is present.

As the reaction solvent, in steps 2 and 7, an alcohol solvent such as methanol, ethanol, isopropyl alcohol, or butanol can be used, and in step 3, glacial acetic acid can be used.

Regarding Step 4: In step 4, compound (f) is reacted with compound (g-1) or compound (g-2) to react a carboxy group of compound (f) with a hydroxyl group of compound (g-1), or a carboxy group of compound (f) with a cyclic ether of compound (g-2), thereby obtaining imidazole compound (B) represented by general formula (1).

During the reaction, a catalyst is allowed to coexist. When reacting with compound (g-1), a tertiary organic phosphorus compound such as triphenylphosphine and an azodicarboxylate ester such as diethyl azodicarboxylate or diisopropyl azodicarboxylate are used as catalysts. As the reaction solvent, an amide solvent such as dimethylformamide or dimethylacetamide can be used.

When reacting with compound (g-2), a catalyst such as tetrabutylammonium chloride can be used. As the reaction solvent, an amide solvent such as dimethylformamide can be used.

Regarding Step 6: In step 6, the ester bond of compound (i) is hydrolyzed to give compound (j) represented by general formula (1).

During the reaction, an alkaline catalyst such as potassium hydroxide may be present. An alcohol solvent such as ethanol may be used as the reaction solvent.

Regarding Step 8: In step 8, the compound (k) is reacted with the compound (l) to give the imidazole compound (B) represented by the general formula (1).

During the reaction, an amine catalyst such as triethanolamine can be used. As the reaction solvent, an ether solvent such as tetrahydrofuran can be used.

The imidazole compound (B) may also be a dimer.

The dimer may, for example, be a compound represented by the following formula (1-69):

The amount of the solid content of the imidazole compound (B) used is preferably in the range of 1 to 200 parts by mass, more preferably 1 to 100 parts by mass, per 100 parts by mass of the resin (A) having an acid group and a polymerizable unsaturated group, since an active energy ray-curable resin composition having excellent alkaline developability and capable of forming a cured product having excellent heat resistance and elasticity can be obtained.

The method for producing the active energy ray-curable resin composition of the present invention is not particularly limited, and any method may be used. For example, the composition may be produced by mixing the components including the resin (A) having an acid group and a polymerizable unsaturated group and the imidazole compound (B). The mixing method is not particularly limited, and a paint shaker, a disper, a roll mill, a bead mill, a ball mill, an attritor, a sand mill, a bead mill, or the like may be used.

In addition, depending on the type of active energy ray used, it is preferable to use a photopolymerization initiator in the active energy ray-curable resin composition of the present invention.

Examples of the photopolymerization initiator include photoradical polymerization initiators such as 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-diphenylethan-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-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone.

Examples of commercially available photopolymerization initiators include, for example, "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) Resins); "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", "KAYACURE OA" (Nippon Kayaku Co., Ltd.); "Vicure 10", "Vicure 55" (Stoffa Chemical Co.); "Trigonal P1" (Akzo Nobel Co., Ltd.), "SANDORAY 1000" (SANDOZ Co., Ltd.); "DEAP" (Upjohn Chemical Co., Ltd.), "Quantacure PDO", "Quantacure ITX", "Quantacure EPD" (Ward Blenkinsop Co., Ltd.); "Runtecure 1104" (manufactured by Runtec). These photopolymerization initiators can be used alone or in combination of two or more.

The amount of the photopolymerization initiator added is, for example, preferably in the range of 0.05 to 15 mass % of the total components other than the solvent of the active energy ray-curable resin composition, and more preferably in the range of 0.1 to 10 mass %.

The active energy ray-curable resin composition of the present invention may contain other resin components in addition to the resin (A) having an acid group and a polymerizable unsaturated group and the imidazole compound (B). Examples of the other resin components include various (meth)acrylate monomers.

Examples of the various (meth)acrylate monomers include aliphatic mono(meth)acrylate compounds such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and octyl(meth)acrylate; cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, and adamantyl mono(meth)acrylate; Alicyclic mono(meth)acrylate compounds such as acrylate; heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate, tetrahydrofurfuryl acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds such as phenoxybenzyl (meth)acrylate and phenylphenoxyethyl (meth)acrylate; (poly)oxyalkylene-modified mono(meth)acrylate compounds in which a polyoxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the various mono(meth)acrylate monomers described above; lactone-modified mono(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various mono(meth)acrylate compounds described above; aliphatic di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate and neopentyl glycol di(meth)acrylate; 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, nor Alicyclic di(meth)acrylate compounds such as bornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate; aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; polyoxyalkylene-modified di(meth)acrylate compounds having a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain introduced into the molecular structure of the above-mentioned various di(meth)acrylate compounds; lactone-modified di(meth)acrylate compounds having a (poly)lactone structure introduced into the molecular structure of the above-mentioned various di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; aliphatic tri(meth)acrylate compounds having a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain introduced into the molecular structure of the above-mentioned various di(meth)acrylate compounds. (Poly)oxyalkylene-modified tri(meth)acrylate compounds having (poly)oxyalkylene chains such as (poly)oxytetramethylene chains; lactone-modified tri(meth)acrylate compounds having (poly)lactone structures in the molecular structure of the aliphatic tri(meth)acrylate compounds; tetrafunctional or higher aliphatic poly(meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; tetrafunctional or higher (poly)oxyalkylene-modified poly(meth)acrylate compounds having (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains in the molecular structure of the aliphatic poly(meth)acrylate compounds; tetrafunctional or higher lactone-modified poly(meth)acrylate compounds having (poly)lactone structures in the molecular structure of the aliphatic poly(meth)acrylate compounds.

In addition to the above, the other (meth)acrylate monomers that can be used include (meth)acrylate monomers that have a phenol compound, a cyclic carbonate compound or a cyclic ether compound, and an unsaturated monocarboxylic acid as essential reaction raw materials.

Examples of the phenolic compounds include cresol, xylenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1-naphthol, 2-naphthol, 1,3-naphthalenediol, 1,5-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, hydrogenated bisphenol, hydrogenated biphenol, polyphenylene ether type diol, polynaphthylene ether type diol, phenol novolac resin, cresol novolac resin, bisphenol novolac type resin, naphthol novolac type resin, phenol aralkyl type resin, naphthol aralkyl type resin, and phenol resin having a cyclo ring structure.

Examples of the cyclic carbonate compounds include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. These cyclic carbonate compounds can be used alone or in combination of two or more.

Examples of the cyclic ether compounds include ethylene oxide, propylene oxide, and tetrahydrofuran. These cyclic ether compounds can be used alone or in combination of two or more.

The unsaturated monocarboxylic acid may be the same as those exemplified above as the unsaturated monobasic acid.

The content of the other (meth)acrylate monomers is preferably 90% by mass or less in the non-volatile matter of the active energy ray-curable resin composition of the present invention.

The active energy ray-curable resin composition of the present invention may also contain various additives, such as a curing agent, a curing accelerator, an ultraviolet absorber, a polymerization inhibitor, an antioxidant, an organic solvent, an inorganic filler or polymer particles, a pigment, an antifoaming agent, a viscosity adjuster, a leveling agent, a flame retardant, and a storage stabilizer, as necessary.

Examples of the curing agent include epoxy resins, polybasic acids, unsaturated monobasic acids, amine compounds, amide compounds, azo compounds, organic peroxides, polyol compounds, and epoxy resins.

The epoxy resin may be the same as those exemplified above, and the epoxy resin may be used alone or in combination of two or more kinds.

Examples of the polybasic acids 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, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]hepta Examples of the polybasic acid include methylbicyclo[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, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, and benzophenone tetracarboxylic acid. Examples of the polybasic acid include copolymers of conjugated diene vinyl monomers and acrylonitrile, and polymers having carboxyl groups in the molecule. These polybasic acids can be used alone or in combination of two or more.

The unsaturated monobasic acid may be the same as those exemplified above as the unsaturated monobasic acid, and the unsaturated monobasic acid may be used alone or in combination of two or more kinds.

Examples of the amine compounds include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, guanidine derivatives, etc. These amine compounds can be used alone or in combination of two or more kinds.

Examples of the amide-based compounds include dicyandiamide, polyamide resins synthesized from a dimer of linoleic acid and ethylenediamine, etc. These amide compounds can be used alone or in combination of two or more kinds.

Examples of the azo compound include azobisisobutyronitrile.

Examples of the organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxy esters, peroxydicarbonates, alkyl peroxycarbonates, etc. These organic peroxides can be used alone or in combination of two or more kinds.

Examples of the polyol compounds include polyol monomers such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, glycerin, glycerin mono(meth)acrylate, trimethylolethane, trimethylolmethane mono(meth)acrylate, trimethylolpropane, trimethylolpropane mono(meth)acrylate, pentaerythritol mono(meth)acrylate, and pentaerythritol di(meth)acrylate; and mixtures of the polyol monomers with succinic acid, adipic acid, azelaic acid, sebacic acid, and the like. polyester polyols obtained by co-condensation with dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, and 1,4-cyclohexanedicarboxylic acid; lactone-type polyester polyols obtained by polycondensation reaction of the above polyol monomers with various lactones such as ε-caprolactone, δ-valerolactone, and 3-methyl-δ-valerolactone; polyether polyols obtained by ring-opening polymerization of the above polyol monomers with cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, and propyl glycidyl ether. These polyol compounds can be used alone or in combination of two or more.

The epoxy resin may be the same as those exemplified above, and the epoxy resin may be used alone or in combination of two or more kinds.

The curing accelerator accelerates the curing reaction, and examples of the accelerator include phosphorus compounds, amine compounds, imidazole, organic acid metal salts, Lewis acids, and amine complex salts. These accelerators can be used alone or in combination of two or more. The amount of the accelerator added is preferably in the range of 0.01 to 10% by mass based on the solid content of the active energy ray-curable resin composition.

Examples of the ultraviolet absorber include triazine derivatives such as 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2-xanthenecarboxy-4-dodecyloxybenzophenone, and 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone. These ultraviolet absorbers can be used alone or in combination of two or more.

Examples of the polymerization inhibitor include phenolic compounds such as p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N-salicyloyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, and 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline; quinone compounds such as hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, and diphenoquinone; melamine, p-phenylenediamine, 4-aminodiphenylamine, and N. N'-diphenyl-p-phenylenediamine, N-i-propyl-N'-phenyl-p-phenylenediamine, N-(1.3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrenated diphenylamine, reaction product of styrenated diphenylamine and 2,4,4-trimethylpentene, reaction product of diphenylamine and 2,4,4-trimethylpentene, and other amine compounds, phenothiazine, distearyl thiodipropionate, 2,2-bis({[3-(dodecylthio)propionyl]oxy}methyl)-1,3-propanediyl=bis[3-(dodecylthio)propionate], ditridecane-1-yl= Thioether compounds such as 3,3'-sulfanediyl dipropanoate, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethyl-p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso-N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-N-n-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, nitrosobenzene, N- Nitroso compounds such as nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-N-n-propylurethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 1-nitroso-2-naphthol-3,6-sodium sulfonate, 2-nitroso-1-naphthol-4-sodium sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, and 2-nitroso-5-methylaminophenol hydrochloride; esters of phosphoric acid and octadecane-1-ol; triphenyl phosphite; 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane; trisnonylphenyl phosphite; and (1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl phosphite. Examples of the polymerization inhibitor include esters, phosphite compounds such as 2-ethylhexyl diphenyl phosphite, diphenyl isodecyl phosphite, triisodecyl phosphite, and tris(2,4-di-tert-butylphenyl)phosphite, zinc compounds such as bis(dimethyldithiocarbamato-κ(2)S,S')zinc, zinc diethyldithiocarbamate, and zinc dibutyl dithiocarbamate, nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S')nickel, and sulfur compounds such as 1,3-dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, dilauryl thiodipropionate, and 3,3'-thiodipropionate distearyl. These polymerization inhibitors can be used alone or in combination of two or more.

The antioxidant may be the same as the compounds exemplified as the polymerization inhibitor, and the antioxidant may be used alone or in combination of two or more kinds.

In addition, examples of commercially available products of the polymerization inhibitor and the antioxidant include "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., and "Sumilizer BBM-S" and "Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd.

The organic solvent may be the same as those exemplified above, and the organic solvent may be used alone or in combination of two or more kinds.

Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, etc.

The pigment may be any known inorganic or organic pigment.

Examples of the inorganic pigments include white pigments, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine blue, carbon black, graphite, etc. These inorganic pigments can be used alone or in combination of two or more kinds.

Examples of the white pigment include titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, zinc sulfide, etc.

Examples of the organic pigments include quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, azo pigments, etc. These organic pigments can be used alone or in combination of two or more.

Examples of the flame retardant include inorganic phosphorus compounds such as red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and phosphoric acid amides; phosphoric acid ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxy Examples of suitable flame retardants include organic phosphorus compounds such as cyclic organic phosphorus compounds such as 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof reacted with compounds such as epoxy resins and phenolic resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine; silicone-based flame retardants such as silicone oil, silicone rubber, and silicone resin; and inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass. These flame retardants can be used alone or in combination of two or more. When using these flame retardants, the amount is preferably in the range of 0.1 to 20% by mass in the total resin composition.

The cured product of the present invention can be obtained by irradiating the active energy ray-curable 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. When ultraviolet rays are used as the active energy rays, irradiation may be performed in an inert gas atmosphere such as nitrogen gas, or in an air atmosphere in order to efficiently carry out the curing reaction by ultraviolet rays.

As a source of ultraviolet light, ultraviolet lamps are generally used from the standpoint of practicality and economy. Specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, LEDs, etc.

The cumulative light amount of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ/m ² , and more preferably 0.5 to 10 kJ/m ^2. When the cumulative light amount is within the above range, it is preferable because the occurrence of uncured portions can be prevented or suppressed.

The irradiation of the active energy rays may be carried out in one step or in two or more steps.

The cured product of the present invention has excellent alkaline developability and excellent heat resistance and elasticity, and therefore can be suitably used, for example, in semiconductor device applications as solder resist, interlayer insulating material, packaging material, underfill material, package adhesive layer for circuit elements, etc., and adhesive layer between integrated circuit elements and circuit boards. It can also be suitably used in thin display applications such as LCD and OELD as thin film transistor protective films, liquid crystal color filter protective films, pigment resists for color filters, resists for black matrices, spacers, etc. Among these, it can be particularly suitably used for solder resist applications.

The resist member of the present invention can be obtained, for example, by applying the solder resist resin material onto a substrate, evaporating and drying the organic solvent at a temperature range of about 60 to 100°C, exposing the substrate to active energy rays through a photomask on which a desired pattern has been formed, developing the unexposed areas with an alkaline aqueous solution, and further heating and curing the substrate at a temperature range of about 140 to 200°C.

Examples of the substrate include metal-clad laminates such as copper and aluminum.

The present invention will be specifically described below with reference to examples and comparative examples. Note that the present invention is not limited to the examples listed below.

(Synthesis Example 1: Preparation of Resin (1) Having Acid Group and Polymerizable Unsaturated Group)
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 123 parts by mass of diethylene glycol monomethyl ether acetate was placed, and 214 parts by mass of orthocresol novolac epoxy resin "EPICLON N-680" (manufactured by DIC Corporation, softening point 86°C, epoxy equivalent: 214g/eq) (hereinafter abbreviated as "epoxy resin (1)") was dissolved therein, and 0.9 parts by mass of dibutylhydroxytoluene and 0.2 parts by mass of methoquinone were added, followed by addition of 72 parts by mass of acrylic acid and 1.4 parts by mass of triphenylphosphine, and the mixture was reacted at 120°C for 10 hours while blowing in air. Next, 72 parts by mass of diethylene glycol monomethyl ether acetate and 76 parts by mass of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours to obtain a resin (1) having an acid group and a polymerizable unsaturated group. The resin (1) having an acid group and a polymerizable unsaturated group had a non-volatile content of 65% by mass and an acid value of 80 mgKOH/g on the solid content basis, the acid value being a value measured based on the neutralization titration method of JIS K 0070 (1992).

(Synthesis Example 2: Preparation of Resin (2) Having Acid Group and Polymerizable Unsaturated Group)
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 392 parts by mass of diethylene glycol monomethyl ether acetate, 244 parts by mass of an isocyanurate modified product of isophorone diisocyanate ("VESTANAT T-1890/100" manufactured by EVONIK, isocyanate group content 17.2% by mass) (hereinafter abbreviated as "T-1890"), 192 parts by mass of trimellitic anhydride, and 1.0 part by mass of dibutylhydroxytoluene were added and dissolved. The mixture was reacted at 160°C for 5 hours under a nitrogen atmosphere, and it was confirmed that the isocyanate group content was 0.1% by mass or less. The solid acid value measured under acid anhydride group non-ring-opening conditions was 160 mgKOH/g. 0.3 parts by mass of methoquinone, 172 parts by mass of a pentaerythritol polyacrylate mixture ("Aronix M-306" manufactured by Toa Gosei Co., Ltd., pentaerythritol triacrylate content about 67%, hydroxyl value 159.7 mg KOH / g) and 3.6 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110 ° C. for 5 hours while blowing air. Next, 163 parts by mass of glycidyl methacrylate was added, and the mixture was reacted at 110 ° C. for 5 hours. Furthermore, 112 parts by mass of succinic anhydride and 122 parts by mass of diethylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110 ° C. for 5 hours to obtain a resin (2) having an acid group and a polymerizable unsaturated group with a non-volatile content of 62% by mass. The solid content acid value of this resin (2) having an acid group and a polymerizable unsaturated group was 79 mg KOH / g.

(Synthesis Example 3: Synthesis of Compound A)

14.17 parts by mass (98.26 mmol) of 4-hydroxybutyl acrylate (Osaka Organic Chemical Industry Co., Ltd. "4HBA"), 140 parts by mass of tetrahydrofuran (THF), 25.77 g (98.26 mmol) of triphenylphosphine (Ph3P), and 10.00 parts by mass (81.89 mmol) of 4-hydroxybenzaldehyde were added to a 100 mL four-neck flask equipped with a stirrer, thermometer, and reflux condenser and stirred. A pale yellow transparent solution was obtained. Next, 19.87 parts by mass (98.26 mmol) of diisopropyl azodicarboxylate (DIAD) diluted with 20 parts by mass of tetrahydrofuran was added dropwise over 30 minutes in an ice bath. The orange transparent reaction solution was stirred at room temperature for 10 hours. Hexane was added to the reaction solution, and by-products such as triphenylphosphine were precipitated and removed, followed by extraction with chloroform, washing with water and saturated saline, and drying with magnesium sulfate. The solvent was removed using an evaporator, and the resulting red viscous liquid was purified by column chromatography (developing solvent: n-hexane:ethyl acetate = 80:20) to obtain the target compound A.

(Synthesis Example 4: Synthesis of imidazole compound (1))

In a 100 mL four-neck flask equipped with a stirrer, a thermometer, and a reflux condenser, 4.87 parts by mass (19.62 mmol) of Compound A obtained in Synthesis Example 3, 15 parts by mass of methanol (MeOH), 0.00154 parts by mass (0.137 mmol) of 1,4-diazabicyclo[2.2.2]octane (DABCO), 4.948 parts by mass (23.54 mmol) of benzil, 3.629 parts by mass (47.08 mmol) of ammonium acetate (NH ₄ OAc), 1500 ppm of methoquinone, and 500 ppm of BHT were placed, and nitrogen gas was blown from above, air was bubbled through the liquid, and the mixture was stirred at 65°C for 24 hours. The mixture gradually became a reddish brown solution, and after several hours, a yellow solid precipitated on the wall. After cooling to around room temperature, the mixture was extracted with ethyl acetate, washed with water and saturated saline, and then dried over magnesium sulfate. The solvent was removed by distillation using an evaporator, and the resulting red viscous liquid was purified by column chromatography (developing solvent: n-hexane:ethyl acetate=80:20) to obtain imidazole compound (1).

[Method of identifying structure]
The structure of the product was identified by ¹ H-NMR, ¹³ C-NMR and MALDI-MS measured under the following conditions: ¹ H-NMR spectrum is shown in FIG. 1, ¹³ C-NMR spectrum in FIG. 2 and MALDI-MS spectrum in FIG.

¹ H-NMR was measured using a JEOL RESONANCE "JNM-ECM400S" under the following conditions.

Magnetic field strength: 400MHz
Number of times of accumulation: 16 Solvent: Deuterated chloroform Sample concentration: 2 mg/0.5 ml

¹³ C-NMR was measured using a JEOL RESONANCE "JNM-ECM400S" under the following conditions.

Magnetic field strength: 100MHz
Number of times of accumulation: 1000 Solvent: Deuterated chloroform Sample concentration: 2 mg/0.5 ml

The MALDI-MS was performed using Shimadzu Corporation/KRATOS "AXIMA-QIT" under the following conditions.
Device name: AXIMA-QIT
Manufacturer: Shimadzu Corporation

Measurement range: m / z = 50.00 to 2000.00
Rate of change: 25.6mA/min
Final current value: 40mA
Cathode voltage: -10 kV
Measurement mode m/z ~300: extraLow
300-750: Low
750～:Mid

(Synthesis Example 5: Synthesis of Compound B)

Compound B represented by the above structural formula was obtained in the same manner as in Synthesis Example 3, except that hydroxyethyl acrylate ("HEA" manufactured by Osaka Organic Chemical Industry Co., Ltd.) was used instead of 4-hydroxybutyl acrylate.

(Synthesis Example 6: Synthesis of imidazole compound (2))

The procedure was the same as in Synthesis Example 4, except that Compound B obtained in Synthesis Example 5 was used instead of Compound A, to obtain imidazole compound (2) represented by the above structural formula.

(Synthesis Example 7: Synthesis of Compound C)

Compound C represented by the above structural formula was obtained in the same manner as in Synthesis Example 3, except that unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone (Daicel Corporation's "Placcel FA2D") was used instead of 4-hydroxybutyl acrylate.

(Synthesis Example 8: Synthesis of imidazole compound (3))

The procedure was the same as in Synthesis Example 4, except that Compound C obtained in Synthesis Example 7 was used instead of Compound A, to obtain imidazole compound (3) represented by the above structural formula.

(Synthesis Example 9: Synthesis of Compound D)

17.85 parts by mass (118.91 mmol) of terephthalaldehyde acid, 285 parts by mass of glacial acetic acid, 0.0934 parts by mass (0.832 mmol) of 1,4-diazabicyclo[2.2.2]octane (DABCO), 25.00 parts by mass (118.91 mmol) of benzil, and 27.50 parts by mass (356.75 mmol) of ammonium acetate were placed in a 500 mL four-neck flask equipped with a stirrer, thermometer, and reflux condenser, and stirred at 105°C for 6 hours. After cooling to near room temperature, the mixture was added to ice water, and the resulting solid was filtered and washed with chloroform to obtain the target compound D.

(Synthesis Example 10: Synthesis of imidazole compound (4))

5.00 parts by mass (14.689 mmol) of compound D, 2.54 parts by mass (17.63 mmol) of 4-hydroxybutyl acrylate ("4HBA" manufactured by Osaka Organic Chemical Industry Co., Ltd.), 4.62 parts by mass (17.63 mmol), and 15.66 parts by mass of DMF were added to a 100 mL four-neck flask equipped with a stirrer, thermometer, and reflux condenser, and stirred. A pale yellow transparent solution was obtained. Next, 3.56 parts by mass (17.63 mmol) of diisopropyl azodicarboxylate diluted with 3.56 parts by mass of DMF was added dropwise over 30 minutes in an ice bath. The orange transparent reaction solution was stirred at room temperature for 10 hours. The reaction solution was dried up, chloroform and hexane were added, and by-products such as triphenylphosphine were precipitated and removed, followed by extraction with chloroform, washing with water and saturated saline, and drying with magnesium sulfate. The solvent was removed using an evaporator, and the resulting red viscous liquid was purified by column chromatography (developing solvent: n-hexane:ethyl acetate = 80:20) to obtain imidazole compound (4).

(Synthesis Example 11: Synthesis of imidazole compound (5))

The same procedure as in Synthesis Example 10 was carried out except that a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Aronix M-305, Toagosei Co., Ltd., hydroxyl value 116 mg KOH/g) was used instead of 4-hydroxybutyl acrylate (4HBA, Osaka Organic Chemical Industry Co., Ltd.), to obtain the imidazole compound (5) represented by the above structural formula.

(Example 1: Preparation of curable resin composition (1))
The resin (1) having an acid group and a polymerizable unsaturated group obtained in Synthesis Example 1 and the imidazole compound (1) obtained in Synthesis Example 4 were mixed to obtain an active energy ray curable resin composition, and then an orthocresol novolac type epoxy resin (EPICLON N-680 manufactured by DIC Corporation) as a curing agent, diethylene glycol monoethyl ether acetate, a photopolymerization initiator (Omnirad 907 manufactured by IGM), 2-ethyl-4-methylimidazole, dipentaerythritol hexaacrylate, and phthalocyanine green were blended in the parts by mass shown in Table 1, and kneaded with a roll mill to obtain a curable resin composition (1). Note that the parts by mass of the resin having an acid group and a polymerizable unsaturated group in Table 1 are solid content values.

(Examples 2 to 10: Preparation of curable resin compositions (2) to (10))
Using the compositions and blendings shown in Table 1, curable resin compositions (2) to (10) were obtained in the same manner as in Example 1.

(Comparative Example 1: Preparation of Curable Resin Composition (R1))
Resin (1) having an acid group and a polymerizable unsaturated group obtained in Synthesis Example 1, an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation) as a curing agent, diethylene glycol monoethyl ether acetate, a photopolymerization initiator (Omnirad 907 manufactured by IGM), 2-ethyl-4-methylimidazole, dipentaerythritol hexaacrylate, and phthalocyanine green were mixed in the parts by mass shown in Table 1 and kneaded with a roll mill to obtain a curable resin composition (R1).

The following evaluations were carried out using the curable resin compositions (1) to (10) and (R1) obtained in the above examples and comparative examples.

[Method for evaluating alkaline developability]
The curable resin composition obtained in each Example and Comparative Example was applied to a glass substrate using an applicator to a film thickness of 50 μm, and then dried at 80° C. for 50, 60, 70, 80, 90, 100, 110, 120, and 130 minutes, respectively, to prepare samples with different drying times. These were developed with a 1% aqueous sodium carbonate solution at 30° C. for 180 seconds, and the drying time at 80° C. of the sample that did not leave any residue on the substrate was evaluated as the drying control width. Note that a longer drying control width indicates better alkaline developability.

The compositions and evaluation results of the curable resin compositions (1) to (10) and (R1) obtained in the above examples and comparative examples are shown in Table 1.

(Example 11: Preparation of curable resin composition (11))
The resin (1) having an acid group and a polymerizable unsaturated group obtained in Synthesis Example 1 and the imidazole compound (1) obtained in Synthesis Example 4 were mixed to obtain an active energy ray-curable resin composition. Then, an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation) as a curing agent, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (Omnirad 907 manufactured by IGM Resins) as a photopolymerization initiator, and diethylene glycol monomethyl ether acetate as an organic solvent were mixed in the parts by mass shown in Table 2 to obtain a curable resin composition (11).

(Examples 12 to 20: Preparation of curable resin compositions (12) to (20))
Curable resin compositions (12) to (20) were obtained using the compositions and blendings shown in Table 2 in the same manner as in Example 11.

(Comparative Example 2: Preparation of Curable Resin Composition (R2))
The resin (1) having an acid group and a polymerizable unsaturated group obtained in Synthesis Example 1, an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation) as a curing agent, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (Omnirad 907 manufactured by IGM Resins) as a photopolymerization initiator, and diethylene glycol monomethyl ether acetate as an organic solvent were mixed in the parts by mass shown in Table 2 to obtain a curable resin composition (R2).

The following evaluations were carried out using the curable resin compositions (11) to (20) and (R2) obtained in the above examples and comparative examples.

[Method for evaluating heat resistance]
The curable resin composition obtained in each Example and Comparative Example was applied to a copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Co., Ltd.) using an applicator so as to have a film thickness of 50 μm, and dried at 80 ° C. for 30 minutes. Next, after irradiating with ultraviolet light of 10 kJ / m ² using a metal halide lamp, it was heated at 160 ° C. for 1 hour to obtain a cured coating film. Next, the cured coating film was peeled off from the copper foil to obtain a cured product. A test piece of 6 mm x 35 mm was cut out from the cured product, and the temperature at which the change in elastic modulus was maximum was evaluated as the glass transition temperature using a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device "RSAII" manufactured by Rheometrics Co., Ltd., tensile method: frequency 1 Hz, heating rate 3 ° C. / min). Note that a higher glass transition temperature indicates better heat resistance.

[Method of measuring elastic modulus]
The elastic modulus was measured based on a tensile test.
<Preparation of Test Piece 1>
The active energy ray curable resin compositions obtained in the Examples and Comparative Examples were applied onto copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Co., Ltd.) using a 50 μm applicator, irradiated with ultraviolet light of 10 kJ/ ^m2 using a metal halide lamp, and then heated at 160° C. for 1 hour. The cured product was peeled off from the copper foil to obtain test piece 1 (cured product).

<Tensile test>
The test piece 1 was cut into a size of 10 mm x 80 mm, and a tensile test was performed on the test piece 1 under the following measurement conditions using a precision universal testing machine "AG-IS" manufactured by Shimadzu Corporation. The elastic modulus (MPa) until the test piece broke was measured and evaluated according to the following criteria.

Measurement conditions: temperature 23°C, humidity 50%, distance between gauge lines 20mm, distance between fulcrums 20mm, tensile speed 10mm/min

The compositions and evaluation results of the curable resin compositions (11) to (20) and (R2) obtained in the above examples and comparative examples are shown in Table 2.

The "hardener" in Tables 1 and 2 refers to orthocresol novolac epoxy resin (EPICLON N-680, manufactured by DIC Corporation).

"Organic solvent" in Tables 1 and 2 refers to diethylene glycol monomethyl ether acetate.

The "photopolymerization initiator" in Tables 1 and 2 refers to "Omnirad-907" manufactured by IGM Resins.

Examples 1 to 10 shown in Table 1 are examples of curable resin compositions using the active energy ray-curable resin composition of the present invention. It was confirmed that these curable resin compositions have excellent alkaline developability.

In addition, Examples 11 to 20 shown in Table 2 are examples of curable resin compositions using the active energy ray-curable resin composition of the present invention. It was confirmed that the cured products of these curable resin compositions have excellent heat resistance and elasticity.

On the other hand, Comparative Examples 1 and 2 are examples of curable resin compositions that do not contain an imidazole compound. It was confirmed that the cured products of these curable resin compositions were significantly insufficient in terms of heat resistance and elasticity.

Claims (7)

An active energy ray-curable resin composition comprising (A) a resin having an acid group and a polymerizable unsaturated group, and (B) an imidazole compound represented by the following general formula (1):

In formula (1), Ar ¹ represents an aromatic hydrocarbon group having 6 to 20 carbon atoms.
^Ar2 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms.
^Ar3 represents a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms.
^L1 represents -O-, -COO- or -OCO-.
^L2 represents a single bond or --O--.
R ¹ represents a polyoxyalkylene group or a divalent hydrocarbon group having 1 to 50 carbon atoms which may have a substituent, and --CH ₂ -- contained in the hydrocarbon group may be replaced by --O-- and/or --CO--.
R ^a1 represents a reactive group. 2. The active energy ray-curable resin composition according to claim 1, wherein R ^a1 is a vinyl group, a (meth)acryloyl group, or an oxetanyl group which may have a substituent. The active energy ray-curable resin composition according to claim 1 or 2, wherein the amount of the imidazole compound (B) used in solid form is in the range of 1 to 200 parts by mass per 100 parts by mass of the resin (A) having an acid group and a polymerizable unsaturated group. The curable resin composition according to any one of claims 1 to 3, further comprising a photopolymerization initiator. A cured product of the active energy ray-curable resin composition according to any one of claims 1 to 4. An insulating material comprising the active energy ray-curable resin composition according to any one of claims 1 to 4. A resist member comprising the active energy ray-curable resin composition according to any one of claims 1 to 4.