WO2022138184A1

WO2022138184A1 - Active energy ray-curable resin composition, cured product, insulation material and resist member

Info

Publication number: WO2022138184A1
Application number: PCT/JP2021/045258
Authority: WO
Inventors: 駿介山田; 裕史亀山
Original assignee: Dic株式会社
Priority date: 2020-12-22
Filing date: 2021-12-09
Publication date: 2022-06-30
Also published as: JPWO2022138184A1; KR20230122013A; JP7136386B1; CN116601724A; TW202235473A

Abstract

The present invention provides an active energy ray-curable resin composition comprising a resin (A) that has an acid group and a polymerizable unsaturated group and a resin (B) that is other than the resin (A) and has a polymerizable unsaturated group and a urethane bond, said active energy ray-curable resin composition being characterized in that the resin (B) comprises, as essential starting materials, an epoxy resin (b1), an unsaturated monobasic acid (b2), a (meth)acrylate compound (b3) having a hydroxyl group and a compound (b4) having an isocyanate group. This active energy ray-curable resin composition has excellent alkali developability and a cured product thereof shows excellent elongation, high elasticity and good adhesion to a base material.

Description

Active energy ray curable resin composition, cured product, insulating material and resist member

The present invention relates to an active energy ray-curable resin composition, a cured product, an insulating material, and a resist member, which have excellent alkali developability and excellent elongation, elasticity, and substrate adhesion in a cured product.

In recent years, an acid group-containing epoxy acrylate resin obtained by reacting an epoxy resin with acrylic acid and then reacting with an acid anhydride has been widely used as a resin material for a solder resist for a printed wiring substrate. The required performance for the resin material for solder resist is that it cures with a small exposure amount, it has excellent alkali developability, and it has excellent heat resistance, strength, flexibility, elongation, dielectric properties, substrate adhesion, etc. in the cured product. Various things can be mentioned.

As a conventionally known resin material for solder resist, active energy ray curable obtained by reacting a reaction product of a novolak type epoxy resin and an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride. Although resins are known (see, for example, Patent Document 1 below), they do not satisfy the ever-increasing requirements for elongation and substrate adhesion, and are not sufficient for the recent market requirements. There wasn't.

Therefore, there has been a demand for a material that has excellent alkali developability and is more excellent in elongation, elasticity, and substrate adhesion in the cured product.

Japanese Unexamined Patent Publication No. 61-243869

The problem to be solved by the present invention is an active energy ray-curable resin composition, a cured product, an insulating material, which has excellent alkali developability and excellent elongation, elasticity, and substrate adhesion in a cured product. It is to provide a resist member.

As a result of diligent studies to solve the above problems, the present inventors have made an active energy ray-curable resin containing a resin having an acid group and a polymerizable unsaturated group and a resin having a polymerizable unsaturated group and a urethane bond. We have found that the above problems can be solved by using the composition, and have completed the present invention.

That is, the present invention is an active energy ray containing a resin (A) having an acid group and a polymerizable unsaturated group, and a resin (B) having a polymerizable unsaturated group and a urethane bond other than the resin (A). A curable resin composition in which the resin (B) has an epoxy resin (b1), an unsaturated monobasic acid (b2), a (meth) acrylate compound (b3) having a hydroxyl group, and a compound having an isocyanate group (b3). It relates to an active energy ray-curable resin composition, a cured product, an insulating material and a resist member, which are characterized by using b4) as an essential raw material.

The active energy ray-curable resin composition of the present invention has excellent alkali developability, and has excellent elongation, elasticity, and substrate adhesion in the cured product, and is therefore suitably used for insulating materials and resist members. be able to. The "excellent elasticity" in the present invention means a low elastic modulus.

The active energy ray-curable resin composition of the present invention comprises a resin (A) having an acid group and a polymerizable unsaturated group, and a resin (B) having a polymerizable unsaturated group and a urethane bond other than the resin (A). It is characterized by using and as an essential reaction raw material.

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

The resin (A) having an acid group and a polymerizable unsaturated group may be any resin (A) having an acid group and a polymerizable unsaturated group in the resin, and for example, an acid group and a polymerizable unsaturated group may be used. Epoxy resin, urethane resin having acid group and polymerizable unsaturated group, acrylic resin having acid group and polymerizable unsaturated group, amidoimide resin having acid group and polymerizable unsaturated group, acid group and polymerizable unsaturated group. Examples thereof include an acrylamide resin having a group, an ester resin having an acid group and a polymerizable unsaturated group, and the like.

Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group.

Examples of the polymerizable unsaturated group include (meth) acryloyl group, allyl group, isopropenyl group, 1-propenyl group, styryl group, styrylmethyl group, maleimide group, vinyl ether group and the like.

Examples of the epoxy resin having an acid group and a polymerizable unsaturated group include an epoxy resin, an unsaturated monobasic acid, and an epoxy (meth) acrylate resin having an acid group using a polybasic acid anhydride as an essential raw material. Examples thereof include epoxy resins, unsaturated monobasic acids, polybasic acid anhydrides, polyisocyanate compounds, and epoxy (meth) acrylate resins having acid groups and urethane bonds using a (meth) acrylate compound having a hydroxyl group as a reaction raw material. ..

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, and cresol. Novolak type epoxy resin, bisphenol novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-shrink novolak type epoxy resin, naphthol-cresol co-shrink novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, Cyclopentadiene-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 and the like can be mentioned. 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, and bisphenol S type epoxy. Examples include resin.

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. Examples include 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 and the like can be mentioned.

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

Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, β-flufurylacrylic acid and the like. Further, an esterified product of the unsaturated monobasic acid, an acid halide, an acid anhydride and the like can also be used. Further, a compound represented by the following structural formula (1) can also be used.

[In the formula (1), 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 a halogen atom in the structure. Or an alkoxy group or the like. Y is a hydrogen atom or a methyl group. ]

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

Examples of the (poly) ester chain include a (poly) ester chain represented by the following structural formula (2).

[In the formula (2), R ¹ is 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. Further, as a partial structure, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring 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 an aliphatic polybasic acid anhydride, an alicyclic polybasic acid anhydride, and an aromatic polybasic acid anhydride.

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

As the alicyclic polybasic acid anhydride, in the present invention, an alicyclic polybasic acid anhydride having an acid anhydride group bonded to an alicyclic structure is used as an alicyclic polybasic acid anhydride, and the aromatic ring in other structural parts is used. It does not matter whether it is present or not. Examples of the alicyclic polybasic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, and bicyclo [2.2.1] heptane-2. 3-Dicarboxylic acid, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid, 4- (2,5-dioxotetratetra-3-yl) -1,2,3,4-tetrahydronaphthalene- Examples thereof include acid anhydrides of 1,2-dicarboxylic acids.

Examples of the aromatic polybasic acid anhydride include phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid and biphenyltetracarboxylic acid. Examples thereof include acid anhydrides of benzophenone tetracarboxylic acid.

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

Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; norbornan diisocyanate and isophorone diisocyanate. Alicyclic diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalenedi isocyanate, 4,4'-diisocyanato-3 , 3'-Aromatic diisocyanate compounds such as dimethylbiphenyl and o-trizine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (3); these isocyanurate modified products, biuret modified products, Examples thereof include allophanate modified products. Further, these polyisocyanate compounds may be used alone or in combination of two or more.

[In the formula, R ¹ is either a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, respectively. R ² is an alkyl group having 1 to 4 carbon atoms independently, l is an integer of 0 or 1 to 3, and m is an integer of 1 to 15. ]

The (meth) acrylate compound having a hydroxyl group is not particularly limited 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 thereof include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol (meth) acrylate, and 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 Examples thereof include (meth) acrylate, ditrimethylolpropane (meth) acrylate, ditrimethylolpropane di (meth) acrylate, and ditrimethylolpropane tri (meth) acrylate. Further, a (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain was introduced into the molecular structure of the (meth) acrylate compound having various hydroxyl groups. A (poly) oxyalkylene modified product, a lactone modified product in which a (poly) lactone structure is introduced into the molecular structure of the (meth) acrylate compound having various hydroxyl groups, or the like can also be used. These (meth) acrylate compounds having a hydroxyl group may be used alone or in combination of two or more.

The method for producing the epoxy resin having the acid group and the polymerizable unsaturated group is not particularly limited, and any method may be used for producing the epoxy resin. In the production of the epoxy resin having an acid group and a polymerizable unsaturated group, it may be carried out in an organic solvent if necessary, or a basic catalyst may be used if 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 dioxolan; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; toluene, xylene and solvent. Aromatic solvents such as naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol and propylene glycol monomethyl ether; alkylene glycol monoalkyl ethers and dialkylene glycol monoalkyl ethers. , Glycol ether solvent such as dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and the like. These organic solvents may be used alone or in combination of two or more. Further, 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 because the reaction efficiency is good.

Examples of the basic catalyst include N-methylmorpholin, pyridine, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonen-. 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-( Amine compounds such as 2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, and tetramethylammonium hydroxide; quaternary such as trioctylmethylammonium chloride and trioctylmethylammonium acetate. Ammonium salt; phosphine compounds such as trimethylphosphine, tributylphosphine, triphenylphosphine; tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl (2-hydroxylpropyl) phosphonium chloride , Triphenylphosphonium chloride, phosphonium salts such as benzylphosphonium chloride; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, 1 , 1,3,3-Tetrabutyl-1,3-Dodecanoyl dystanoxane and other organic tin compounds; Zinc octylate, bismuth octylate and other organic metal compounds; Inorganic tin compounds such as tin octanate; Inorganic metal compounds and the like Can be mentioned. Further, alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydroxides and the like can also be used. In particular, alkali metal hydroxides are preferable because they are excellent in catalytic activity of the epoxy resin synthesis reaction, and for example, sodium hydroxide and potassium hydroxide are more preferable. 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 may be used in the form of a solid.

Examples of the urethane resin having an acid group and a polymerizable unsaturated group include 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. Polyisocyanate compounds obtained by reacting with polyol compounds other than polyol compounds having a carboxyl group, polyisocyanate compounds, (meth) acrylate compounds having a hydroxyl group, polybasic acid anhydrides, and polyols other than polyol compounds having a carboxyl group. Examples thereof include those obtained by reacting with a compound.

As the polyisocyanate compound, the same one as exemplified as the above-mentioned polyisocyanate compound can be used, and the polyisocyanate compound 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 for the (meth) acrylate compound having a hydroxyl group can be used, and the (meth) acrylate compound having a hydroxyl group is used alone. It is also possible to use two or more kinds together.

Examples of the polyol compound having a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolpropane valeric acid and the like. The polyol compound having a carboxyl group may be used alone or in combination of two or more.

As the polybasic acid anhydride, the same ones as those exemplified as the above-mentioned polybasic acid anhydride can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. You can also.

Examples of the polyol compound other than the polyol compound 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 chains such as (poly) oxyethylene chain, (poly) oxypropylene chain and (poly) oxytetramethylene chain in the molecular structure of the various polyol compounds. (Poly) oxyalkylene modified product in which (poly) lactone structure is introduced into the molecular structure of the various polyol compounds, and the like can be mentioned. The polyol compound other than the polyol compound having a carboxyl group may be used alone or in combination of two or more.

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

As the organic solvent, the same ones as those exemplified as the above-mentioned organic solvent can be used, and the organic solvent can be used alone or in combination of two or more.

As the basic catalyst, the same catalysts as those exemplified as the above-mentioned basic catalyst can be used, and the basic catalyst may be used alone or in combination of two or more.

As the acrylic resin having an acid group and a polymerizable unsaturated group, for example, 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 is polymerized as an essential component. A reaction obtained by introducing a (meth) acryloyl group by further reacting a (meth) acrylate compound (β) having a reactive functional group capable of reacting with these functional groups with the acrylic resin intermediate obtained by the above treatment. Examples thereof include products obtained by reacting a hydroxyl group in the reaction product with a polybasic acid anhydride.

The acrylic resin intermediate may be a copolymer of the (meth) acrylate compound (α) and other compounds having a polymerizable unsaturated group, if necessary. The other compounds having a polymerizable unsaturated group include (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. ) Acrylic acid alkyl ester; alicyclic structure-containing (meth) acrylate such as cyclohexyl (meth) acrylate, isoboronyl (meth) acrylate, dicyclopentanyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate, Aromatic ring-containing (meth) acrylates such as phenoxyethyl acrylate; (meth) acrylates having a silyl group such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, α-methylstyrene and chlorostyrene can be mentioned. These can 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 combination is as follows from the viewpoint of reactivity. Is preferable. 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.

As the polybasic acid anhydride, the same ones as those exemplified as the above-mentioned polybasic acid anhydride can be used, and the polybasic acid anhydride may be used alone or in combination of two or more. can.

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

Examples of the amideimide resin having an acid group and a polymerizable unsaturated group include an amideimide resin having an acid group and / or an acid anhydride group, and a (meth) acrylate compound having a hydroxyl group and / or an epoxy group (meth). ) A compound obtained by reacting an acrylate compound 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, if necessary. Can be mentioned. The compound having a reactive functional group may or may not have a (meth) acryloyl group.

The amidimide resin may have only one of an acid group and an acid anhydride group, or may have both. From the viewpoint of reactivity with (meth) acrylate compounds having a hydroxyl group and epoxy compounds having a (meth) acryloyl group and reaction control, those having an acid anhydride group are preferable, and the acid group and the acid anhydride group are used. It is more preferable to have both of them. The solid acid value of the amideimide resin is preferably in the range of 60 to 350 mgKOH / g under neutral conditions, that is, under conditions where the acid anhydride group is not opened. On the other hand, the measured value under the condition that the acid anhydride group is opened, such as in the presence of water, is preferably in the range of 61 to 360 mgKOH / g.

Examples of the amidoimide resin include those obtained by using a polyisocyanate compound and a polybasic acid anhydride as reaction raw materials.

Further, as the amidoimide resin, a polybasic acid can be used as a reaction raw material in addition to the polyisocyanate compound and the polybasic acid anhydride, if necessary.

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, hexahydro. Phthalic 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-dioxotetratetra-3-yl) -1,2,3,4-tetrahydro Naphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid and the like can be mentioned. Will be. Further, as the polybasic acid, for example, a copolymer of a conjugated diene-based vinyl monomer and acrylonitrile, which has a carboxyl group in its molecule, can also be used. These polybasic acids can be used alone or in combination of two or more.

The (meth) acrylate compound having an epoxy group is not particularly limited as long as it has a (meth) acryloyl group and an epoxy group in its molecular structure, and a wide variety of compounds can be used. can. For example, (meth) acrylate monomers having a glycidyl group such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and epoxycyclohexylmethyl (meth) acrylate; dihydroxybenzene diglycidyl ether, dihydroxynaphthalenedi glycidyl ether. , Mono (meth) acrylates of diglycidyl ether compounds such as biphenol diglycidyl ether and bisphenol diglycidyl ether. These epoxy group-containing (meth) acrylate compounds may be used alone or in combination of two or more. Among these, one epoxy group can be obtained because an active energy ray-curable resin composition having excellent alkali developability and capable of forming a cured product having excellent elongation, elasticity and substrate adhesion can be obtained. The (meth) acrylate compound having (meth) is preferable, and an active energy ray-curable resin composition capable of forming a cured product having excellent alkali developability, excellent elongation, elasticity, and substrate adhesion can be obtained. , A (meth) acrylate monomer having a glycidyl group is preferable. Further, the molecular weight of the (meth) acrylate monomer having a glycidyl group is preferably 500 or less. Further, 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 amidoimide resin having the acid group and the polymerizable unsaturated group is not particularly limited, and any method may be used for production. In the production of the amidoimide resin having an acid group and a polymerizable unsaturated group, it may be carried out in an organic solvent if necessary, or a basic catalyst may be used if necessary.

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

As the compound having a phenolic hydroxyl group, the same compound as exemplified as the above-mentioned compound having a phenolic hydroxyl group (a1) can be used, and the compound having the phenolic hydroxyl group can be used alone. It is also possible to use more than seeds together.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. Among these, ethylene oxide or propylene oxide can be obtained because an active energy ray-curable resin composition having excellent alkali developability and capable of forming a cured product having excellent elongation, elasticity and substrate adhesion can be obtained. Is preferable. The alkylene oxide can be used alone or in combination of two or more.

Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate and the like. Among these, since an active energy ray-curable resin composition having excellent alkali developability and capable of forming a cured product having excellent elongation, elasticity and substrate adhesion can be obtained, ethylene carbonate or propylene carbonate can be obtained. Is preferable. The alkylene carbonate can be used alone or in combination of two or more.

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

As the unsaturated monobasic acid, the same as those exemplified as the above-mentioned unsaturated monobasic acid can be used, and the unsaturated monobasic acid can be used alone or in combination of two or more. ..

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

Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride and zinc chloride. And so on. Further, a solid acid catalyst having a strong acid such as a sulfonyl group can also be used. These acidic catalysts can be used alone or in combination of two or more.

As the ester resin having an acid group and a polymerizable unsaturated group, for example, a compound having a phenolic hydroxyl group, an alkylene oxide or an alkylene carbonate, an unsaturated monobasic acid, and a polybasic acid anhydride are reacted with each other. The obtained ones can be mentioned.

The compound having a phenolic hydroxyl group means 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 (4-1) to (4-5).

In the structural formulas (4-1) to (4-5), R ¹ 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. , R ² are independently hydrogen atoms or methyl groups. Further, p is 0 or an integer of 1 or more, preferably an integer of 0 or 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 above structural formula is arbitrary, and for example, in the naphthalene ring of the structural formula (4-2), it may be substituted on any ring, and the structural formula ( In 4-3), it may be substituted on any ring of the benzene ring present in one molecule, and in the structural formula (4-4), it may be substituted on any ring of the benzene ring present in one molecule. In the structural formula (4-5), it is shown that 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. Is shown to be p and q.

The compound having a phenolic hydroxyl group includes, for example, a compound having at least one phenolic hydroxyl group in the molecule and a compound represented by any of the following structural formulas (x-1) to (x-5). A reaction product or the like using the above as an essential reaction raw material can also be used. Further, a novolak type phenol resin or the like using one or more of compounds having at least one phenolic hydroxyl group in the molecule as a reaction raw material can also be used.

[In equation (x-1), h is 0 or 1. In the 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 the 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 the formula (x-5), Y is any 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 of 1 to 4. ]

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

As the alkylene oxide, the same ones as those exemplified as the above-mentioned alkylene oxide can be used. Among these, ethylene oxide or propylene oxide can be obtained because an active energy ray-curable resin composition having excellent alkali developability and capable of forming a cured product having excellent elongation, elasticity and substrate adhesion can be obtained. Is preferable. The alkylene oxide can be used alone or in combination of two or more.

As the alkylene carbonate, the same ones as those exemplified as the above-mentioned alkylene carbonate can be used. Among these, since an active energy ray-curable resin composition having excellent alkali developability and capable of forming a cured product having excellent elongation, elasticity and substrate adhesion can be obtained, ethylene carbonate or propylene carbonate can be obtained. Is preferable. The alkylene carbonate can be used alone or in combination of two or more.

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

As the acidic catalyst, the same ones as those exemplified as the above-mentioned acidic catalyst can be used, and the acidic catalyst can 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 of the present invention has excellent alkali developability, and is active energy ray curable having elongation, elasticity and substrate adhesion in a cured product. Since a resin composition can be obtained, the range of 50 to 150 mgKOH / g is preferable, and the range of 60 to 120 mgKOH / g is more preferable. 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 K0070 (1992).

The resin (B) having a polymerizable unsaturated group and a urethane bond includes an epoxy resin (b1), an unsaturated monobasic acid (b2), a (meth) acrylate compound having a hydroxyl group (b3), and a compound having an isocyanate group. It is characterized in that (b4) is used as an essential raw material. In the present invention, the resin having an acid group, a polymerizable unsaturated group, and a urethane bond is treated as the resin (A).

As the epoxy resin (b1), the same ones as those exemplified as the above-mentioned epoxy resin can be used, and the epoxy resin (b1) can be used alone or in combination of two or more. Further, among these, a novolak type epoxy resin can be obtained because an active energy ray-curable resin composition having excellent alkali developability and excellent elongation, elasticity and substrate adhesion in a cured product can be obtained. Preferably, a cresol novolac type epoxy resin is more preferable.

The epoxy resin (b1) preferably has a softening point of 78 ° C. or lower, more preferably 50 ° C. or higher and 70 ° C. or lower, and more preferably 60 ° C. or higher and 70 ° C. or lower. In the present invention, the softening point is a value measured by a method based on JIS K7234 (1986).

As the unsaturated monobasic acid (b2), the same ones as those exemplified as the above-mentioned unsaturated monobasic acid can be used, and the unsaturated monobasic acid (b2) can also be used alone. It is also possible to use more than seeds together. Further, among these, acrylic acid and methacrylic acid can be obtained because an active energy ray-curable resin composition having excellent alkali developability and excellent elongation, elasticity and substrate adhesion in a cured product can be obtained. Is preferable.

The amount of the unsaturated monobasic acid (b2) used is 0.95 with respect to 1 mol of the epoxy group of the epoxy resin (b1) based on the acid group of the unsaturated monobasic acid (b2). It is preferably in the range of ~ 1.1 mol, more preferably 0.95 to 1.05.

As the (meth) acrylate compound (b3) having a hydroxyl group, the same compound as those exemplified for the (meth) acrylate compound having a hydroxyl group can be used, and the compound (b3) may be used alone. Can also be used in combination of two or more. Further, among these, hydroxyethyl (meth) can be obtained because an active energy ray-curable resin composition having excellent alkali developability and excellent elongation, elasticity and substrate adhesion in a cured product can be obtained. Acrylate, pentaerythritol di (meth) acrylate, and pentaerythritol tri (meth) acrylate are preferable.

The amount of the compound (b3) used is such that an active energy ray-curable resin composition having excellent alkali developability and excellent elongation, elasticity and substrate adhesion in a cured product can be obtained. Based on the hydroxyl group of the compound (b3), the range of 0.3 to 0.7 mol is preferable with respect to 1 mol of the isocyanate group of the compound (b4) having an isocyanate group described later, and 0.4 to 0. A range of 6 mol is more preferred.

As the compound (b4) having an isocyanate group, the same compounds as those exemplified as the above-mentioned polyisocyanate compound can be used, and the compound (b4) may be used alone or in combination of two or more. You can also. Further, among these, an active energy ray-curable resin composition having excellent alkali developability and excellent elongation, elasticity and substrate adhesion in a cured product can be obtained, and thus an aliphatic and / or an aliphatic and / or a substrate can be obtained. A compound having an isocyanate group having an alicyclic skeleton is preferable, a compound having an isocyanate group having an alicyclic skeleton is more preferable, and isophorone diisocyanate is more preferable.

The amount of the compound (b4) used is such that an active energy ray-curable resin composition having excellent alkali developability and excellent elongation, elasticity and substrate adhesion in a cured product can be obtained. Therefore, the range of 0.1 to 0.7 mol is preferable with respect to 1 mol of the epoxy group of the epoxy resin (b1), preferably 0.2 to 0, based on the isocyanate group of the compound (b4). A range of 6 mol is more preferred.

As the resin (B), an active energy ray-curable resin composition having excellent alkali developability and excellent elongation, elasticity, and substrate adhesion in a cured product can be obtained, and thus (meth). It preferably has an acryloyl group, an isocyanate group, and a urethane bond.

The method for producing the resin (B) is not particularly limited, and any method may be used for producing the resin (B). For example, it may be produced by a method of reacting all of the reaction raw materials at once, or by a method of sequentially reacting the reaction raw materials.

As a method for reacting all of the reaction raw materials at once, for example, an epoxy resin (b1), an unsaturated monobasic acid (b2), a (meth) acrylate compound having a hydroxyl group (b3), and a compound having an isocyanate group (b3) Examples thereof include a method of reacting a reaction raw material containing b4) in the presence of a basic catalyst in a temperature range of 60 to 150 ° C.

As a method for sequentially reacting the reaction raw materials, an epoxy resin (b1) and an unsaturated monobasic acid (b2) are previously reacted in the presence of a basic catalyst in a temperature range of 80 to 150 ° C. for reaction. The substance (I) is obtained, and the (meth) acrylate compound (b3) having a hydroxyl group and the compound (b4) having an isocyanate group are reacted in the presence of a basic catalyst in a temperature range of 50 to 120 ° C. After obtaining the reaction product (II), the reaction product (I) and the reaction product (II) are reacted in the presence of a basic catalyst in a temperature range of 50 to 150 ° C. and the like.

Among these production methods, an active energy ray-curable resin composition having excellent alkali developability and capable of forming a cured product having excellent elongation, elasticity and substrate adhesion can be obtained. Therefore, the reaction can be obtained. A method of sequentially reacting the raw materials is preferable, and a method of obtaining the reaction product (I) and the reaction product (II) and then reacting the reaction product (I) with the reaction product (II) to produce the reaction product (I) is preferable. More preferred.

Further, a reaction between the epoxy resin (b1), the unsaturated monobasic acid (b2), the (meth) acrylate compound (b3) having a hydroxyl group, and the compound (b4) having an isocyanate group, the epoxy resin (b1). ) And the unsaturated monobasic acid (a2), the reaction of the (meth) acrylate compound (b3) having a hydroxyl group and the compound (b4) having the isocyanate group, and the reaction product (I) and the above. The reaction with the reaction product (II) can also be carried out in an organic solvent, if necessary.

The amount of the basic catalyst used is, for example, an active energy ray-curable resin composition having excellent alkali developability and excellent elongation, elasticity and substrate adhesion in the cured product. In the reaction between the epoxy resin (b1), the unsaturated monobasic acid (b2), the (meth) acrylate compound (b3) having a hydroxyl group, and the compound (b4) having an isocyanate group, the epoxy resin (b1) ), The unsaturated monobasic acid (b2), the (meth) acrylate compound (b3) having a hydroxyl group, and the compound (b4) having an isocyanate group, 0.001 to 1.0 with respect to a total of 100 parts by mass. The range of parts by mass is preferable, and the range of 0.01 to 0.8 is more preferable.

The mass ratio of the solid content between the resin (A) and the resin (B) [(A) / (B)] has excellent alkali developability, and has excellent elongation, elasticity, and group in the cured product. Since an active energy ray-curable resin composition having material adhesion can be obtained, the range of 95/5 to 50/50 is preferable, the range of 95/5 to 60/40 is more preferable, and 95 / The range of 5 to 70/30 is more preferable.

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 production. For example, a method of mixing and producing each compounding component can be mentioned. 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 and the like may be used.

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

Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-. Hydroxy-2-methyl-1-propane-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, diphenyl (2,4,6-trimethoxybenzoyl) phosphenyl Oxide, 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphenyl oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- Examples thereof include photoradical polymerization initiators such as on, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone.

Examples of commercially available products of the other photopolymerization initiators include "Omnirad 1173", "Omnirad 184", "Omnirad 127", "Omnirad 2959", "Omnirad 369", "Omnirad 379", "Omnirad 90". "Omnirad 4265", "Omnirad 1000", "Omnirad 651", "Omnirad TPO", "Omnirad 819", "Omnirad 2022", "Omnirad 2100", "Omnirad 2100", "Omnirad", "Omnirad", "Omnirad" "Omnirad 81" (manufactured by IGM Resins); "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", "KAYACURE OA" (manufactured by Nippon Kayaku Co., Ltd.); "Vicure" Visual 55 ”(Stoffa Chemical);“ Trigonal P1 ”(Akzo Nobel),“ SANDORAY 1000 ”(SANDOZ); , "Chemistry EPD" (manufactured by Ward Brenkinsop); "Runtecure 1104" (manufactured by Runtec) and the like. These photopolymerization initiators may be used alone or in combination of two or more.

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

The active energy ray-curable resin composition of the present invention may contain other resin components other than the resin (A) and the resin (B). Examples of the other resin components include various (meth) acrylate monomers. The total content of the resin (A) and the resin (B) has excellent alkali developability, and has excellent elongation, elasticity, and substrate adhesion in the cured product, and has active energy ray curability. Since a resin composition can be obtained, 10% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and 50% by mass, based on the total components other than the solvent of the active energy ray-curable resin composition. % Or more is particularly preferable.

Examples of the various (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth) acrylate, 2 -Alipid mono (meth) acrylate compounds such as ethylhexyl (meth) acrylate and octyl (meth) acrylate; alicyclic mono (meth) such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate. Acrylate compounds; heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; benzyl (meth) acrylate, phenyl (meth) acrylate, phenylbenzyl (meth) acrylate, phenoxy (meth) acrylate, Aromatic mono (meth) such as phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxybenzyl (meth) acrylate, and phenylphenoxyethyl (meth) acrylate. Mono (meth) acrylate compounds such as acrylate compounds: Polyoxy such as (poly) oxyethylene chain, (poly) oxypropylene chain, and (poly) oxytetramethylene chain in the molecular structure of the various mono (meth) acrylate monomers. A (poly) oxyalkylene-modified mono (meth) acrylate compound having an alkylene chain introduced; a lactone-modified mono (meth) acrylate compound having a (poly) lactone structure introduced into the molecular structure of the various mono (meth) acrylate compounds; ethylene. An aliphatic di (meth) acrylate compound such as 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, norbornandi (meth) acrylate, norbornan dimethanol di (meth) acrylate, dicyclopentanyldi (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, etc. Aroma of alicyclic di (meth) acrylate compound; biphenol di (meth) acrylate, bisphenol di (meth) acrylate, etc. Group di (meth) acrylate compounds; (poly) oxyalkylenes such as (poly) oxyethylene chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains in the molecular structure of the various di (meth) acrylate compounds. Polyoxyalkylene-modified di (meth) acrylate compound having a chain introduced; lactone-modified di (meth) acrylate compound having a (poly) lactone structure introduced into the molecular structure of the various di (meth) acrylate compounds; trimethylolpropane tri An aliphatic tri (meth) acrylate compound such as (meth) acrylate and glycerin tri (meth) acrylate; a (poly) oxyethylene chain, a (poly) oxypropylene chain, etc. in the molecular structure of the aliphatic tri (meth) acrylate compound. A (poly) oxyalkylene-modified tri (meth) acrylate compound introduced with a (poly) oxyalkylene chain such as a (poly) oxytetramethylene chain; a (poly) lactone structure in the molecular structure of the aliphatic tri (meth) acrylate compound. A lactone-modified tri (meth) acrylate compound in which Compound: A tetrafunctional chain 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 aliphatic poly (meth) acrylate compound. The above (poly) oxyalkylene-modified poly (meth) acrylate compound; a tetrafunctional or higher functional lactone-modified poly (meth) acrylate compound having a (poly) lactone structure introduced into the molecular structure of the aliphatic poly (meth) acrylate compound, or the like. Can be mentioned.

Further, as the other (meth) acrylate monomer, in addition to the above-mentioned one, a (meth) acrylate monomer containing a phenol compound, a cyclic carbonate compound or a cyclic ether compound, and an unsaturated monocarboxylic acid as essential reaction raw materials. Can be used.

Examples of the phenol compound 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 Examples thereof include type diols, polynaphthylene ether type diols, phenol novolac resins, cresol novolak resins, bisphenol novolak type resins, naphthol novolak type resins, phenol aralkyl type resins, naphthol aralkyl type resins, phenol resins having a cycloring structure and the like.

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

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

As the unsaturated monocarboxylic acid, the same one as exemplified as the unsaturated monocarboxylic acid (B) described above can be used.

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

Further, the active energy ray-curable resin composition of the present invention may contain, if necessary, a curing agent, a curing accelerator, an ultraviolet absorber, a polymerization inhibitor, an antioxidant, an organic solvent, an inorganic filler or polymer fine particles. It can also contain various additives such as pigments, defoaming agents, viscosity modifiers, leveling agents, flame retardants, and storage stabilizers.

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.

As the epoxy resin, the same ones as those exemplified as the above-mentioned epoxy resin can be used, and the epoxy resin can be used alone or in combination of two or more.

Examples of the polybasic acid 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, and 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-dioxotetraxoxy-3-yl) -1, 2,3,4-Tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, Examples thereof include benzophenone tetracarboxylic acid. Further, as the polybasic acid, for example, a copolymer of a conjugated diene-based vinyl monomer and acrylonitrile, which has a carboxyl group in its molecule, can also be used. These polybasic acids can be used alone or in combination of two or more.

As the unsaturated monobasic acid, the same ones as those exemplified as the above-mentioned unsaturated monobasic acid can be used, and the unsaturated monobasic acid may be used alone or in combination of two or more. You can also.

Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, guanidine derivative and the like. These amine compounds may be used alone or in combination of two or more.

Examples of the amide compound include a polyamide resin synthesized from a dimer of dicyandiamide and linolenic acid and ethylenediamine. These amide compounds may be used alone or in combination of two or more.

Examples of the azo compound include azobisisobutyronitrile.

Examples of the organic peroxide include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, alkyl peroxycarbonates and the like. These organic peroxides can be used alone or in combination of two or more.

Examples of the polyol compound include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1, 5-Pentanediol, Neopentylglycol, 1,6-hexanediol, Glycerin, Glycerin mono (meth) acrylate, Trimethylol ethane, Trimethylol methanemono (meth) acrylate, Trimethylol propane, Trimethylol propane mono (meth) acrylate , Pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate and other polyol monomers; , Hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, polyester polyol obtained by cocondensation with dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; , Δ-Valerolactone, 3-methyl-δ-Valerolactone and other lactone-type polyester polyols obtained by polycondensation reaction with various lactones; Examples thereof include a polyether polyol obtained by ring-opening polymerization with a cyclic ether compound such as ether. These polyol compounds may be used alone or in combination of two or more.

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

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

Examples of the polymerization inhibitor include 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) dodecanedihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine , 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinone and other phenolic compounds, hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy- Quinone compounds such as 1,4-naphthoquinone, anthraquinone and diphenoquinone, melamine, p-phenylenediamine, 4-aminodiphenylamine, N.I. 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), sylated diphenylamine, sylated diphenylamine and 2,4,4-trimethyl Penten reaction products, amine compounds such as diphenylamine and 2,4,4-trimethylpenten reaction products, phenothiazine, distearylthiodipropionate, 2,2-bis ({[3- (dodecylthio) propionyl] oxy } Methyl) -1,3-propanediyl = bis [3- (dodecylthio) propionate], ditridecane-1-yl = 3,3'-thioether compounds such as sulfandyl dipropanoate, N-nitrosodiphenylamine, N- Nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, etc., N, N-dimethylp-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitron -N, N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N- Ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholin, N-nitroso N-phenylhydroxylamine ammonium salt, ditrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide , N-nitroso-N-ethylurethane, N-nitroso-Nn-propyl urethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 1-nitroso-2-naphthol-3,6-sulfone Nitroso compounds such as sodium acid, 2-nitroso-1-naphthol-4-sulfonate sodium, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride, phosphoric acid and octadecane- 1-ol ester, triphenylphosphite, 3,9-dioctadecane-1-yl-2,4,8,10-tetraoxa-3,9-diphosph Aspiro [5.5] undecane, trisnonylphenylphosphite, phosphite- (1-methylethylidene) -di-4,1-phenylenetetra-C12-15-alkyl ester, 2-ethylhexyl = diphenyl = phosfit, Phosphite compounds such as diphenylisodecylphosphite, triisodecyl-phosfit, tris (2,4-di-tert-butylphenyl) phosphite, bis (dimethyldithiocarbamato-κ (2) S, S') zinc, Zinc compounds such as zinc diethyldithiocarbamate, zinc dibutyl / dithiocarbamate, nickel compounds such as bis (N, N-dibutylcarbamodithioato-S, S') nickel, 1,3-dihydro-2H-benzoimidazole-2 -Thion, 4,6-bis (octylthiomethyl) -o-cresol, 2-methyl-4,6-bis [(octane-1-ylsulfanyl) methyl] phenol, dilaurylthiodipropionic acid ester, 3, Examples thereof include sulfur compounds such as distearyl thiodipropionate. These polymerization inhibitors may be used alone or in combination of two or more.

As the antioxidant, the same compounds as those exemplified for the polymerization inhibitor can be used, and the antioxidant may be used alone or in combination of two or more.

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 "Smilizer BBM-S" manufactured by Sumitomo Chemical Industries, Ltd. , "Smilizer GA-80 is" and the like.

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

As the pigment, a known and commonly used inorganic pigment or organic pigment can be used.

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

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, and zinc sulfide. And so on.

Examples of the organic pigment include quinacridone pigment, quinacridone quinone pigment, dioxazine pigment, phthalocyanine pigment, anthrapyrimidine pigment, anthanthrone pigment, indanslon pigment, flavanthron pigment, perylene pigment, diketopyrrolopyrrole pigment, perinone pigment, and the like. Examples thereof include quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, and azo pigments. These organic pigments can be used alone or in combination of two or more.

Examples of the flame retardant include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphate such as ammonium polyphosphate, and inorganic phosphorus compounds such as phosphate amide; phosphoric acid ester compounds and phosphoruses. Acid compound, phosphinic acid compound, phosphin oxide compound, phosphoran compound, organonitrous-containing phosphorus compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxy) Cyclic organics such as phenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthren-10-oxide Organophosphorus compounds such as phosphorus compounds and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds and phenothiazine; silicone oils, silicone rubbers, Silicone-based flame retardants such as silicone resins; examples thereof include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and inorganic flame retardants such as low melting point glass. These flame retardants may be used alone or in combination of two or more. When these flame retardants are used, it 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 ray 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, they may be irradiated in an atmosphere of an inert gas such as nitrogen gas or in an air atmosphere in order to efficiently carry out the curing reaction by the ultraviolet rays.

As a source of ultraviolet rays, an ultraviolet lamp is generally used from the viewpoint of practicality and economy. Specific examples thereof include low pressure mercury lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, LEDs and the like.

The integrated 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 integrated light amount is in the above range, it is preferable because the generation of the uncured portion can be prevented or suppressed.

The irradiation of the active energy beam may be performed in one step or may be divided into two or more steps.

Further, since the cured product of the present invention has excellent alkali developability and is excellent in elongation, elasticity and substrate adhesion, for example, solder resist, interlayer insulating material, packaging material and undercoat in semiconductor device applications. It can be suitably used as a package adhesive layer for a fill material, a circuit element, or the like, or as an adhesive layer between an integrated circuit element and a circuit board. Further, it can be suitably used for a thin film transistor protective film, a liquid crystal color filter protective film, a pigment resist for a color filter, a resist for a black matrix, a spacer and the like in a thin display application typified by LCD and OELD. Among these, it can be particularly preferably used for solder resist applications.

The resist member of the present invention is, for example, a photomask in which the resin material for solder resist is applied onto a substrate, an organic solvent is volatilized and dried in a temperature range of about 60 to 100 ° C., and then a desired pattern is formed. It can be obtained by exposing the unexposed portion with an alkaline aqueous solution, developing the unexposed portion with an alkaline aqueous solution, and further heating and curing the unexposed portion in a temperature range of about 140 to 200 ° C.

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

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to the examples listed below.

(Synthesis Example 1: Preparation of resin (1) having an acid group and a 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, an isocyanurate-modified product of isophorone diisocyanate (“VESTANAT T-1890 / 100” manufactured by EVONIK Co., Ltd., isocyanate group content 17. 2% by mass) (hereinafter abbreviated as "T-1890") 244 parts by mass, 192 parts by mass of trimellitic anhydride and 1.0 part by mass of dibutylhydroxytoluene were added and dissolved. The reaction was carried out at 160 ° C. for 5 hours in a nitrogen atmosphere, and it was confirmed that the isocyanate group content was 0.1% by mass or less. The solid content acid value measured under the acid anhydride group non-ring-opening condition was 160 mgKOH / g. 0.3 parts by mass of methquinone, pentaerythritol polyacrylate mixture (“Aronix M-306” manufactured by Toagosei Co., Ltd., pentaerythritol triacrylate content of about 67%, hydroxyl value 159.7 mgKOH / g) 172 parts by mass and triphenylphosphine 3.6 parts by mass was added, and the mixture was reacted at 110 ° C. for 5 hours while blowing air. Then, 163 parts by mass of glycidyl methacrylate was added and reacted at 110 ° C. for 5 hours. Further, 112 parts by mass of succinic anhydride and 122 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110 ° C. for 5 hours to obtain a resin (1) having an acid group having a non-volatile content of 62% by mass and a polymerizable unsaturated group. rice field. The solid acid value of the resin (1) having the acid group and the polymerizable unsaturated group was 79 mgKOH / g. The acid value is 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)
Put 123 parts by mass of diethylene glycol monomethyl ether acetate in a flask equipped with a thermometer, a stirrer, and a reflux cooler, and orthocresol novolac type epoxy resin "EPICLON N-680" (manufactured by DIC Co., Ltd., softening point 86 ° C., epoxy). Equivalent amount: 214 g / eq,) (hereinafter abbreviated as "epoxy resin (1)") 214 parts by mass is dissolved, 0.9 parts by mass of dibutylhydroxytoluene and 0.2 parts by mass of methquinone are added, and then acrylic acid 72. A mass part and 1.4 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120 ° C. for 10 hours while blowing air. Next, 72 parts by mass of diethylene glycol monomethyl ether acetate and 76 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 3 hours to obtain a resin (2) having an acid group and a polymerizable unsaturated group. The non-volatile content of the resin (2) having an acid group and a polymerizable unsaturated group was 65% by mass, and the solid content acid value was 80 mgKOH / g.

(Synthesis Example 3: Preparation of Urethane-Containing Acrylate Resin (1))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, a pentaerythritol polyacrylate mixture (“Aronix M-305” manufactured by Toa Synthetic Co., Ltd., hydroxyl value 115 mgKOH / g) (hereinafter, “pentaerythritol polyacrylate mixture” (hereinafter, “pentaerythritol polyacrylate mixture”) 1) ”) 486 parts by mass, dibutyl hydroxytoluene 0.2 parts by mass, methquinone 0.2 parts by mass, dioctyl tin dineodecanoate (“Neostan U-830” manufactured by Nitto Kasei Co., Ltd.) (hereinafter, (Abbreviated as "Dioctyl tin dineodecanoate (1)")) 0.07 parts by mass was charged, and the temperature was raised to 70 ° C. while blowing air. Next, 222 parts by mass of isophorone diisocyanate was added in portions and reacted at 70 ° C. for 4 hours to obtain a urethane-containing acrylate resin (1) having an NCO% of 5.9%. The number of moles of hydroxyl groups of the pentaerythritol polyacrylate mixture was 0.5 with respect to 1 mole of the isocyanate group of isophorone diisocyanate.

(Synthesis Example 4: Preparation of Urethane-Containing Acrylate Resin (2))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, pentaerythritol polyacrylate mixture (1) 292 parts by mass, dibutyl hydroxytoluene 0.2 parts by mass, methquinone 0.2 parts by mass, dioctyl tin dineodecano Ate (1) 0.05 parts by mass was charged, and the temperature was raised to 70 ° C. while blowing air. Next, 222 parts by mass of isophorone diisocyanate was added in portions and reacted at 70 ° C. for 4 hours to obtain a urethane-containing acrylate resin (2) having an NCO% of 11.4%. The number of moles of hydroxyl groups of the pentaerythritol polyacrylate mixture was 0.3 with respect to 1 mole of the isocyanate group of isophorone diisocyanate.

(Synthesis Example 5: Preparation of Urethane-Containing Acrylate Resin (3))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, pentaerythritol polyacrylate mixture (1) 243 parts by mass, dibutyl hydroxytoluene 0.1 parts by mass, methquinone 0.1 parts by mass, dioctyl tin dineodecano Ate (1) 0.05 parts by mass was charged, and the temperature was raised to 70 ° C. while blowing air. Next, 222 parts by mass of isophorone diisocyanate was added in portions and reacted at 70 ° C. for 3 hours to obtain a urethane-containing acrylate resin (3) having an NCO% of 13.5%. The number of moles of hydroxyl groups of the pentaerythritol polyacrylate mixture was 0.25 with respect to 1 mole of the isocyanate group of isophorone diisocyanate.

(Synthesis Example 6: Preparation of Urethane-Containing Acrylate Resin (4))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, pentaerythritol polyacrylate mixture (1) 681 parts by mass, dibutylhydroxytoluene 0.3 parts by mass, methquinone 0.3 parts by mass, dioctyl tin dineodecano Ate (1) 0.09 part by mass was charged, and the temperature was raised to 70 ° C. while blowing air. Next, 222 parts by mass of isophorone diisocyanate was added in portions and reacted at 70 ° C. for 4 hours to obtain a urethane-containing acrylate resin (4) having an NCO% of 2.8%. The number of moles of hydroxyl groups of the pentaerythritol polyacrylate mixture was 0.7 with respect to 1 mole of the isocyanate group of isophorone diisocyanate.

(Synthesis Example 7: Preparation of Urethane-Containing Acrylate Resin (5))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, pentaerythritol polyacrylate mixture (1) 729 parts by mass, dibutyl hydroxytoluene 0.3 parts by mass, methquinone 0.3 parts by mass, dioctyl tin dineodecano Ate (1) 0.1 part by mass was charged, and the temperature was raised to 70 ° C. while blowing air. Next, 222 parts by mass of isophorone diisocyanate was added in portions and reacted at 70 ° C. for 4 hours to obtain a urethane-containing acrylate resin (5) having an NCO% of 2.2%. The number of moles of hydroxyl groups of the pentaerythritol polyacrylate mixture was 0.75 with respect to 1 mole of the isocyanate group of isophorone diisocyanate.

(Synthesis Example 8: Preparation of Urethane-Containing Acrylate Resin (6))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 116 parts by mass of hydroxyethyl acrylate, 0.1 part by mass of dibutyl hydroxytoluene, 0.1 part by mass of methquinone, and dioctyl tin dineodecanoate (1) 0. A 03 part by mass was charged and the temperature was raised to 70 ° C. while blowing air. Next, 222 parts by mass of isophorone diisocyanate was added in portions and reacted at 70 ° C. for 4 hours to obtain a urethane-containing acrylate resin (6) having an NCO% of 21.9%. The number of moles of hydroxyl groups of hydroxyethyl acrylate was 0.5 with respect to 1 mole of isocyanate groups of isophorone diisocyanate.

(Synthesis Example 9: Preparation of Urethane-Containing Acrylate Resin (7))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, pentaerythritol polyacrylate mixture (1) 486 parts by mass, dibutyl hydroxytoluene 0.2 parts by mass, methquinone 0.2 parts by mass, dioctyl tin dineodecano Ate (1) 0.07 parts by mass was charged, and the temperature was raised to 70 ° C. while blowing air. Next, 188 parts by mass of m-xylylene diisocyanate (“Takenate 500” manufactured by Mitsui Chemicals, Inc.) was added in portions, and the reaction was carried out at 70 ° C. for 3 hours to obtain a urethane-containing acrylate resin having an NCO% of 6.2%. 7) was obtained. The number of moles of hydroxyl groups of the pentaerythritol polyacrylate mixture was 0.5 with respect to 1 mol of isocyanate groups contained in m-xylylene diisocyanate.

(Synthesis Example 10: Preparation of resin (1) having a polymerizable unsaturated group and a urethane bond)
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 123 parts by mass of diethylene glycol monomethyl ether acetate was placed, 214 parts by mass of the epoxy resin (1) was dissolved, and 0.9 parts by mass of dibutylhydroxytoluene and 0. After adding 2 parts by mass, 72 parts by mass of acrylic acid and 1.4 parts by mass of triphenylphosphine were added, and the esterification reaction was carried out at 120 ° C. for 10 hours while blowing air. Next, 227 parts by mass of diethylene glycol monomethyl ether acetate, 285 parts by mass of the urethane-containing acrylate resin (1) obtained in Synthesis Example 3, and 0.06 parts by mass of dioctyltin dineodecanoate (1) were added, and air was blown into the mixture. The reaction was carried out at 80 ° C. for 8 hours to obtain a resin (1) having the desired polymerizable unsaturated group and urethane bond. The non-volatile content of the resin (1) having a polymerizable unsaturated group and a urethane bond was 62% by mass. Further, the number of moles of acrylic acid is 1.0 with respect to 1 mol of the epoxy group of the epoxy resin (1), and the number of moles of the isocyanate group of the urethane-containing acrylate resin (1) is 0.4. there were.

(Synthesis Example 11: Preparation of resin (2) having a polymerizable unsaturated group and a urethane bond)
Put 121 parts by mass of diethylene glycol monomethyl ether acetate in a flask equipped with a thermometer, a stirrer, and a reflux cooler, and orthocresol novolac type epoxy resin (“EPICLON N-673” manufactured by DIC Co., Ltd., softening point 78 ° C., epoxy. Equivalent: 210 g / eq,) 210 parts by mass was dissolved, 0.8 parts by mass of dibutylhydroxytoluene and 0.2 parts by mass of methquinone were added, and then 72 parts by mass of acrylic acid and 1.4 parts by mass of triphenylphosphine were added. , The esterification reaction was carried out at 120 ° C. for 10 hours while blowing air. Next, 227 parts by mass of diethylene glycol monomethyl ether acetate, 285 parts by mass of the urethane-containing acrylate resin (1) obtained in Synthesis Example 3, and 0.06 parts by mass of dioctyltin dineodecanoate (1) were added, and air was blown into the mixture. The reaction was carried out at 80 ° C. for 8 hours to obtain a resin (2) having the desired polymerizable unsaturated group and urethane bond. The non-volatile content of the resin (2) having a polymerizable unsaturated group and a urethane bond was 62% by mass. Further, the number of moles of acrylic acid is 1.0 with respect to 1 mol of epoxy group contained in the orthocresol novolak type epoxy resin, and the number of moles of isocyanate group contained in the urethane-containing acrylate resin (1) is 0.4. Met.

(Synthesis Example 12: Preparation of Resin (3) Having Polymerizable Unsaturated Group and Urethane Bond)
120 parts by mass of diethylene glycol monomethyl ether acetate was placed in a flask equipped with a thermometer, a stirrer, and a reflux cooler, and an orthocresol novolac type epoxy resin (“EPICLON N-665” manufactured by DIC Co., Ltd., epoxy equivalent: 207 g / eq). , Softening point 69 ° C.) (hereinafter abbreviated as "epoxy resin (2)") 207 parts by mass is dissolved, 0.8 parts by mass of dibutylhydroxytoluene and 0.2 parts by mass of methquinone are added, and then 72 parts by mass of acrylic acid. A part, 1.4 parts by mass of triphenylphosphine was added, and an esterification reaction was carried out at 120 ° C. for 10 hours while blowing air to obtain an epoxy acrylate resin (X1). Next, 226 parts by mass of diethylene glycol monomethyl ether acetate, 285 parts by mass of the urethane-containing acrylate resin (1) obtained in Synthesis Example 3, and 0.06 parts by mass of dioctyltin dineodecanoate (1) were added, and air was blown into the mixture. The reaction was carried out at 80 ° C. for 8 hours to obtain a resin (3) having the desired polymerizable unsaturated group and urethane bond. The non-volatile content of the resin (3) having a polymerizable unsaturated group and a urethane bond was 62% by mass. Further, the number of moles of acrylic acid is 1.0 with respect to 1 mol of the epoxy group of the epoxy resin (2), and the number of moles of the isocyanate group of the urethane-containing acrylate resin (1) is 0.4. there were.

(Synthesis Example 13: Preparation of resin (4) having a polymerizable unsaturated group and a urethane bond)
Put 120 parts by mass of diethylene glycol monomethyl ether acetate in a flask equipped with a thermometer, a stirrer, and a reflux cooler, and orthocresol novolac type epoxy resin (“EPICLON N-660” manufactured by DIC Co., Ltd., epoxy equivalent: 207 g / eq. , Softening point 65 ° C.) 207 parts by mass was dissolved, 0.8 parts by mass of dibutylhydroxytoluene and 0.2 parts by mass of methquinone were added, and then 72 parts by mass of acrylic acid and 1.4 parts by mass of triphenylphosphine were added. The esterification reaction was carried out at 120 ° C. for 10 hours while blowing air. Next, 226 parts by mass of diethylene glycol monomethyl ether acetate, 285 parts by mass of the urethane-containing acrylate resin (1) obtained in Synthesis Example 3, and 0.06 parts by mass of dioctyltin dineodecanoate (1) were added, and air was blown into the mixture. The reaction was carried out at 80 ° C. for 8 hours to obtain a resin (4) having the desired polymerizable unsaturated group and urethane bond. The non-volatile content of the resin (4) having a polymerizable unsaturated group and a urethane bond was 62% by mass. Further, the number of moles of acrylic acid is 1.0 with respect to 1 mol of epoxy groups contained in the orthocresol novolak type epoxy resin, and the number of moles of isocyanate groups contained in the urethane-containing acrylate resin (1) is 0.4. Met.

(Synthesis Example 14: Preparation of resin (5) having a polymerizable unsaturated group and a urethane bond)
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 118 parts by mass of diethylene glycol monomethyl ether acetate was placed, 207 parts by mass of the epoxy resin (2) was dissolved, 0.8 parts by mass of dibutylhydroxytoluene, and 0. After adding 2 parts by mass, 69 parts by mass of acrylic acid and 1.4 parts by mass of triphenylphosphine were added, and the esterification reaction was carried out at 110 ° C. for 10 hours while blowing air. Next, 225 parts by mass of diethylene glycol monomethyl ether acetate, 285 parts by mass of the urethane-containing acrylate resin (1) obtained in Synthesis Example 3, and 0.06 parts by mass of dioctyltin dineodecanoate (1) were added, and air was blown into the mixture. The reaction was carried out at 80 ° C. for 8 hours to obtain a resin (5) having the desired polymerizable unsaturated group and urethane bond. The non-volatile content of the resin (5) having a polymerizable unsaturated group and a urethane bond was 62% by mass. Further, the number of moles of acrylic acid is 0.96 with respect to 1 mol of the epoxy group of the epoxy resin (2), and the number of moles of the isocyanate group of the urethane-containing acrylate resin (1) is 0.4. there were.

(Synthesis Example 15: Preparation of resin (6) having a polymerizable unsaturated group and a urethane bond)
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 117 parts by mass of diethylene glycol monomethyl ether acetate was placed, 207 parts by mass of the epoxy resin (2) was dissolved, and 0.8 parts by mass of dibutylhydroxytoluene and 0. After adding 2 parts by mass, 69 parts by mass of acrylic acid and 1.4 parts by mass of triphenylphosphine were added, and the esterification reaction was carried out at 110 ° C. for 10 hours while blowing air. Next, 225 parts by mass of diethylene glycol monomethyl ether acetate, 285 parts by mass of the urethane-containing acrylate resin (1) obtained in Synthesis Example 3, and 0.06 parts by mass of dioctyltin dineodecanoate (1) were added, and air was blown into the mixture. The reaction was carried out at 80 ° C. for 8 hours to obtain a resin (6) having the desired polymerizable unsaturated group and urethane bond. The non-volatile content of the resin (6) having a polymerizable unsaturated group and a urethane bond was 62% by mass. Further, the number of moles of acrylic acid is 0.93 with respect to 1 mol of the epoxy group of the epoxy resin (2), and the number of moles of the isocyanate group of the urethane-containing acrylate resin (1) is 0.4. there were.

(Synthesis Example 16: Preparation of Resin (7) Having Polymerizable Unsaturated Group and Urethane Bond)
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 121 parts by mass of diethylene glycol monomethyl ether acetate was placed, 207 parts by mass of the epoxy resin (2) was dissolved, 0.8 parts by mass of dibutylhydroxytoluene, and 0. After adding 2 parts by mass, 75 parts by mass of acrylic acid and 1.4 parts by mass of triphenylphosphine were added, and the esterification reaction was carried out at 120 ° C. for 12 hours while blowing air. Next, 227 parts by mass of diethylene glycol monomethyl ether acetate, 285 parts by mass of the urethane-containing acrylate resin (1) obtained in Synthesis Example 3, and 0.06 parts by mass of dioctyltin dineodecanoate (1) were added, and air was blown into the mixture. The reaction was carried out at 80 ° C. for 8 hours to obtain a resin (7) having the desired polymerizable unsaturated group and urethane bond. The non-volatile content of the resin (7) having a polymerizable unsaturated group and a urethane bond was 62% by mass. Further, the number of moles of acrylic acid is 1.04 with respect to 1 mol of the epoxy group of the epoxy resin (2), and the number of moles of the isocyanate group of the urethane-containing acrylate resin (1) is 0.4. there were.

(Synthesis Example 17: Preparation of Resin (8) Having Polymerizable Unsaturated Group and Urethane Bond)
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 122 parts by mass of diethylene glycol monomethyl ether acetate was placed, 207 parts by mass of the epoxy resin (2) was dissolved, and 0.9 parts by mass of dibutylhydroxytoluene and 0. After adding 2 parts by mass, 78.5 parts by mass of acrylic acid and 1.4 parts by mass of triphenylphosphine were added, and an esterification reaction was carried out at 120 ° C. for 13 hours while blowing air. Next, 227 parts by mass of diethylene glycol monomethyl ether acetate, 285 parts by mass of the urethane-containing acrylate resin (1) obtained in Synthesis Example 3, and 0.06 parts by mass of dioctyltin dineodecanoate (1) were added, and air was blown into the mixture. The reaction was carried out at 80 ° C. for 8 hours to obtain a resin (8) having the desired polymerizable unsaturated group and urethane bond. The non-volatile content of the resin (8) having a polymerizable unsaturated group and a urethane bond was 62% by mass. Further, the number of moles of acrylic acid is 1.09 with respect to 1 mol of the epoxy group of the epoxy resin (2), and the number of moles of the isocyanate group of the urethane-containing acrylate resin (1) is 0.4. there were.

(Synthesis Example 18: Preparation of Resin (9) Having Polymerizable Unsaturated Group and Urethane Bond)
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 123 parts by mass of diethylene glycol monomethyl ether acetate was placed, 207 parts by mass of the epoxy resin (2) was dissolved, and 0.9 parts by mass of dibutylhydroxytoluene and 0. After adding 2 parts by mass, 80.6 parts by mass of acrylic acid and 1.4 parts by mass of triphenylphosphine were added, and an esterification reaction was carried out at 120 ° C. for 14 hours while blowing air. Next, 228 parts by mass of diethylene glycol monomethyl ether acetate, 285 parts by mass of the urethane-containing acrylate resin (1) obtained in Synthesis Example 3, and 0.06 parts by mass of dioctyltin dineodecanoate (1) were added, and air was blown into the mixture. The reaction was carried out at 80 ° C. for 8 hours to obtain a resin (9) having the desired polymerizable unsaturated group and urethane bond. The non-volatile content of the resin (9) having a polymerizable unsaturated group and a urethane bond was 62% by mass. Further, the number of moles of acrylic acid is 1.12 with respect to 1 mol of the epoxy group of the epoxy resin (2), and the number of moles of the isocyanate group of the urethane-containing acrylate resin (1) is 0.4. there were.

(Synthesis Example 19: Preparation of resin (10) having a polymerizable unsaturated group and a urethane bond)
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 111 parts by mass of diethylene glycol monomethyl ether acetate was placed, and a phenol novolac type epoxy resin (“EPICLON N-770” manufactured by DIC Co., Ltd., epoxy equivalent: 188 g / eq, (Softening point 70 ° C.) 188 parts by mass was dissolved, 0.8 parts by mass of dibutylhydroxytoluene and 0.2 parts by mass of methquinone were added, then 72 parts by mass of acrylic acid and 1.3 parts by mass of triphenylphosphine were added, and air was added. The esterification reaction was carried out at 120 ° C. for 9 hours while blowing. Next, 222 parts by mass of diethylene glycol monomethyl ether acetate, 285 parts by mass of the urethane-containing acrylate resin (1) obtained in Synthesis Example 3, and 0.05 parts by mass of dioctyltin dineodecanoate (1) were added, and air was blown into the mixture. The reaction was carried out at 80 ° C. for 8 hours to obtain a resin (10) having the desired polymerizable unsaturated group and urethane bond. The non-volatile content of the resin (10) having a polymerizable unsaturated group and a urethane bond was 62% by mass. Further, the number of moles of acrylic acid is 1.0 with respect to 1 mol of epoxy group contained in the phenol novolac type epoxy resin, and the number of moles of isocyanate group contained in the urethane-containing acrylate resin (1) is 0.4. there were.

(Synthesis Example 20: Preparation of Resin (11) Having Polymerizable Unsaturated Group and Urethane Bond)
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 119 parts by mass of diethylene glycol monomethyl ether acetate was placed, and a naphthalene-type epoxy resin (“EPICLON HP-4770” manufactured by DIC Co., Ltd., epoxy equivalent: 205 g / eq, softened. (Point 73 ° C.) 205 parts by mass was dissolved, 0.8 parts by mass of dibutylhydroxytoluene and 0.2 parts by mass of methquinone were added, and then 72 parts by mass of acrylic acid and 1.4 parts by mass of triphenylphosphine were added to add air. The esterification reaction was carried out at 110 ° C. for 12 hours while blowing. Next, 226 parts by mass of diethylene glycol monomethyl ether acetate, 285 parts by mass of the urethane-containing acrylate resin (1) obtained in Synthesis Example 3, and 0.06 parts by mass of dioctyltin dineodecanoate (1) were added, and air was blown into the mixture. The reaction was carried out at 80 ° C. for 8 hours to obtain a resin (11) having the desired polymerizable unsaturated group and urethane bond. The non-volatile content of the resin (11) having a polymerizable unsaturated group and a urethane bond was 62% by mass. Further, the number of moles of acrylic acid is 1.0 with respect to 1 mol of the epoxy group of the naphthalene type epoxy resin, and the number of moles of the isocyanate group of the urethane-containing acrylate resin (1) is 0.4. rice field.

(Synthesis Example 21: Preparation of resin (12) having a polymerizable unsaturated group and a urethane bond)
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 401 parts by mass of epoxy acrylate resin (X1), 104 parts by mass of diethylene glycol monomethyl ether acetate, and urethane-containing acrylate resin (1) 85.4 obtained in Synthesis Example 3. By mass, 0.04 part by mass of dioctyl tin dineodecanoate (1) was added, and the reaction was carried out at 80 ° C. for 6 hours while blowing air, and the resin having the desired polymerizable unsaturated group and urethane bond (12). ) Was obtained. The non-volatile content of the resin (12) having a polymerizable unsaturated group and a urethane bond was 62% by mass. Further, the number of moles of acrylic acid is 1.0 with respect to 1 mol of the epoxy group of the epoxy resin (2), and the number of moles of the isocyanate group of the urethane-containing acrylate resin (1) is 0.12. there were.

(Synthesis Example 22: Preparation of resin (13) having a polymerizable unsaturated group and a urethane bond)
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 401 parts by mass of epoxy acrylate resin (X1), 86 parts by mass of diethylene glycol monomethyl ether acetate, and 57 parts by mass of urethane-containing acrylate resin (1) obtained in Synthesis Example 3. , Dioctyl tin dineodecanoate (1) 0.03 part by mass was added, and the reaction was carried out at 80 ° C. for 5 hours while blowing air to obtain the resin (13) having the desired polymerizable unsaturated group and urethane bond. Obtained. The non-volatile content of the resin (13) having a polymerizable unsaturated group and a urethane bond was 62% by mass. Further, the number of moles of acrylic acid is 1.0 with respect to 1 mol of the epoxy group of the epoxy resin (2), and the number of moles of the isocyanate group of the urethane-containing acrylate resin (1) is 0.08. there were.

(Synthesis Example 23: Preparation of resin (14) having a polymerizable unsaturated group and a urethane bond)
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 401 parts by mass of epoxy acrylate resin (X1), 389 parts by mass of diethylene glycol monomethyl ether acetate, and 484 parts by mass of urethane-containing acrylate resin (1) obtained in Synthesis Example 3. , Dioctyl tin dineodecanoate (1) 0.08 part by mass was added, and the reaction was carried out at 80 ° C. for 10 hours while blowing air to obtain the resin (14) having the desired polymerizable unsaturated group and urethane bond. Obtained. The non-volatile content of the resin (14) having a polymerizable unsaturated group and a urethane bond was 60% by mass. Further, the number of moles of acrylic acid is 1.0 with respect to 1 mol of the epoxy group of the epoxy resin (2), and the number of moles of the isocyanate group of the urethane-containing acrylate resin (1) is 0.68. there were.

(Synthesis Example 24: Preparation of Resin (15) Having Polymerizable Unsaturated Group and Urethane Bond)
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 401 parts by mass of epoxy acrylate resin (X1), 408 parts by mass of diethylene glycol monomethyl ether acetate, and urethane-containing acrylate resin (1) 512.5 obtained in Synthesis Example 3 By mass, 0.08 part by mass of dioctyl tin dineodecanoate (1) was added, and the reaction was carried out at 80 ° C. for 12 hours while blowing air, and the resin having the desired polymerizable unsaturated group and urethane bond (15). ) Was obtained. The non-volatile content of the resin (15) having a polymerizable unsaturated group and a urethane bond was 60% by mass. Further, the number of moles of acrylic acid is 1.0 with respect to 1 mol of the epoxy group of the epoxy resin (2), and the number of moles of the isocyanate group of the urethane-containing acrylate resin (1) is 0.72. there were.

(Synthesis Example 25: Preparation of Resin (16) Having Polymerizable Unsaturated Group and Urethane Bond)
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 401 parts by mass of epoxy acrylate resin (X1), 142 parts by mass of diethylene glycol monomethyl ether acetate, and urethane-containing acrylate resin (2) 147.4 obtained in Synthesis Example 4. By mass, 0.04 part by mass of dioctyl tin dineodecanoate (1) was added, and the reaction was carried out at 80 ° C. for 10 hours while blowing air, and the resin having the desired polymerizable unsaturated group and urethane bond (16). ) Was obtained. The non-volatile content of the resin (16) having a polymerizable unsaturated group and a urethane bond was 62% by mass. Further, the number of moles of acrylic acid is 1.0 with respect to 1 mol of the epoxy group of the epoxy resin (2), and the number of moles of the isocyanate group of the urethane-containing acrylate resin (2) is 0.4. there were.

(Synthesis Example 26: Preparation of Resin (17) Having Polymerizable Unsaturated Group and Urethane Bond)
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 401 parts by mass of epoxy acrylate resin (X1), 128 parts by mass of diethylene glycol monomethyl ether acetate, and urethane-containing acrylate resin (3) 124.4 obtained in Synthesis Example 5. By mass, 0.04 part by mass of dioctyl tin dineodecanoate (1) was added, and the reaction was carried out at 80 ° C. for 11 hours while blowing air, and the resin having the desired polymerizable unsaturated group and urethane bond (17). ) Was obtained. The non-volatile content of the resin (17) having a polymerizable unsaturated group and a urethane bond was 62% by mass. Further, the number of moles of acrylic acid is 1.0 with respect to 1 mol of the epoxy group of the epoxy resin (2), and the number of moles of the isocyanate group of the urethane-containing acrylate resin (3) is 0.4. there were.

(Synthesis 27: Preparation of resin (18) having a polymerizable unsaturated group and a urethane bond)
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 401 parts by mass of epoxy acrylate resin (X1), 419 parts by mass of diethylene glycol monomethyl ether acetate, and 600 parts by mass of urethane-containing acrylate resin (4) obtained in Synthesis Example 6. , Dioctyl tin dineodecanoate (1) 0.09 part by mass was added, and the reaction was carried out at 80 ° C. for 8 hours while blowing air to obtain the resin (18) having the desired polymerizable unsaturated group and urethane bond. Obtained. The non-volatile content of the resin (18) having a polymerizable unsaturated group and a urethane bond was 62% by mass. Further, the number of moles of acrylic acid is 1.0 with respect to 1 mol of the epoxy group of the epoxy resin (2), and the number of moles of the isocyanate group of the urethane-containing acrylate resin (4) is 0.4. there were.

(Synthesis Example 28: Preparation of Resin (19) Having Polymerizable Unsaturated Group and Urethane Bond)
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 401 parts by mass of epoxy acrylate resin (X1), 519.5 parts by mass of diethylene glycol monomethyl ether acetate, and urethane-containing acrylate resin (5) 763 obtained in Synthesis Example 7. .6 parts by mass, dioctyl tin dineodecanoate (1) 0.1 part by mass was added, and the reaction was carried out at 80 ° C. for 7 hours while blowing air, and the resin having the desired polymerizable unsaturated group and urethane bond. (19) was obtained. The non-volatile content of the resin (19) having a polymerizable unsaturated group and a urethane bond was 62% by mass. Further, the number of moles of acrylic acid is 1.0 with respect to 1 mol of the epoxy group of the epoxy resin (2), and the number of moles of the isocyanate group of the urethane-containing acrylate resin (5) is 0.4. there were.

(Synthesis Example 29: Preparation of resin (20) having a polymerizable unsaturated group and a urethane bond)
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 401 parts by mass of epoxy acrylate resin (X1), 98.4 parts by mass of diethylene glycol monomethyl ether acetate, and urethane-containing acrylate resin (6) 76 obtained in Synthesis Example 8. .7 parts by mass, dioctyl tin dineodecanoate (1) 0.1 part by mass was added, and the reaction was carried out at 80 ° C. for 10 hours while blowing air, and the resin having the desired polymerizable unsaturated group and urethane bond. (20) was obtained. The non-volatile content of the resin (20) having a polymerizable unsaturated group and a urethane bond was 62% by mass. Further, the number of moles of acrylic acid is 1.0 with respect to 1 mol of the epoxy group of the epoxy resin (2), and the number of moles of the isocyanate group of the urethane-containing acrylate resin (6) is 0.4. there were.

(Synthesis Example 30: Preparation of resin (21) having a polymerizable unsaturated group and a urethane bond)
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 401 parts by mass of epoxy acrylate resin (X1), 217.5 parts by mass of diethylene glycol monomethyl ether acetate, and 0.1 parts by mass of dioctyltin dineodecanoate (1). The temperature was raised to 80 ° C. while blowing air. Next, 271 parts by mass of the urethane-containing acrylate resin (7) obtained in Synthesis Example 9 was added in portions, and the reaction was carried out at 80 ° C. for 5 hours to obtain the resin (21) having the desired polymerizable unsaturated group and urethane bond. Obtained. The non-volatile content of the resin (21) having a polymerizable unsaturated group and a urethane bond was 62% by mass. Further, the number of moles of acrylic acid is 1.0 with respect to 1 mol of the epoxy group of the epoxy resin (2), and the number of moles of the isocyanate group of the urethane-containing acrylate resin (7) is 0.4. there were.

(Synthesis Example 31: Preparation of resin (22) having a polymerizable unsaturated group and a urethane bond)
In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 125.6 parts by mass of diethylene glycol monomethyl ether acetate was placed, 207 parts by mass of the epoxy resin (2) was dissolved, and 0.9 parts by mass of dibutylhydroxytoluene and methquinone were dissolved. After adding 0.2 parts by mass, 86 parts by mass of methacrylic acid and 1.5 parts by mass of triphenylphosphine were added, and an esterification reaction was carried out at 120 ° C. for 9 hours while blowing air. Next, 228.5 parts by mass of diethylene glycol monomethyl ether acetate, 285 parts by mass of the urethane-containing acrylate resin (1) obtained in Synthesis Example 3, and 0.06 parts by mass of dioctyltin dineodecanoate (1) were added to add air. The reaction was carried out at 80 ° C. for 8 hours while blowing to obtain a resin (22) having the desired polymerizable unsaturated group and urethane bond. The non-volatile content of the resin (22) having a polymerizable unsaturated group and a urethane bond was 62% by mass. Further, the number of moles of methacrylic acid is 1.0 with respect to 1 mol of the epoxy group of the epoxy resin (2), and the number of moles of the isocyanate group of the urethane-containing acrylate resin (1) is 0.4. there were.

(Synthesis 32: Preparation of resin (23) having a polymerizable unsaturated group and a urethane bond)
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 401 parts by mass of epoxy acrylate resin (X1), 273 parts by mass of diethylene glycol monomethyl ether acetate, and 285 parts by mass of urethane-containing acrylate resin (1) obtained in Synthesis Example 3. , 0.06 part by mass of dioctyl tin dineodecanoate (1) was added, and the reaction was carried out at 80 ° C. for 8 hours while blowing air. Then, 76 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 3 hours to obtain a resin (23) having a polymerizable unsaturated group and a urethane bond. The non-volatile content of the resin (23) having a polymerizable unsaturated group and a urethane bond was 62% by mass, and the solid content acid value was 46 mgKOH / g.

(Example 1: Preparation of active energy ray-curable resin composition (1))
The resin (1) having an acid group and a polymerizable unsaturated group obtained in Synthesis Example 1, the resin (3) having a polymerizable unsaturated group and a urethane bond obtained in Synthesis Example 11, and orthocresol novolac as a curing agent. Type epoxy resin (“EPICLON N-680” manufactured by DIC Co., Ltd.), dipentaerythritol hexaacrylate, diethylene glycol monoethyl ether acetate, photopolymerization initiator (“Omnirad 907” manufactured by IGM Co., Ltd.), and 2-ethyl- 4-Methylimidazole and phthalocyanine green were blended in parts by mass shown in Tables 1 to 3 and kneaded with a roll mill to obtain an active energy ray-curable resin composition (1).

(Examples 2-28: Preparation of active energy ray-curable resin compositions (2)-(28))
Curable resin compositions (2) to (28) were obtained in the same manner as in Example 1 with the compositions and formulations shown in Tables 1 to 3.

(Comparative Example 1: Preparation of active energy ray-curable resin composition (R1))
The resin (2) having an acid group and a polymerizable unsaturated group obtained in Synthesis Example 2, an orthocresol novolak type epoxy resin (“EPICLON N-680” manufactured by DIC Co., Ltd.) as a curing agent, and dipentaerythritol hexaacrylate. , Diethylene glycol monoethyl ether acetate, a photopolymerization initiator (“Omnirad 907” manufactured by IGM), 2-ethyl-4-methylimidazole, and phthalocyanine green in parts by mass shown in Table 3, and then a roll mill is used. The mixture was kneaded to obtain an active energy ray-curable resin composition (R1).

(Comparative Example 2: Preparation of active energy ray-curable resin composition (R2))
The resin (21) having a polymerizable unsaturated group and a urethane bond obtained in Synthesis Example 30, an orthocresol novolak type epoxy resin (“EPICLON N-680” manufactured by DIC Co., Ltd.) as a curing agent, and a dipentaerythritol hexaacrylate. , Diethylene glycol monoethyl ether acetate, a photopolymerization initiator (“Omnirad 907” manufactured by IGM), 2-ethyl-4-methylimidazole, and phthalocyanine green in parts by mass shown in Table 3, and then a roll mill is used. The mixture was kneaded to obtain an active energy ray-curable resin composition (R2).

The following evaluations were performed using the active energy ray-curable resin compositions (1) to (28), (R1) and (R2) obtained in the above Examples and Comparative Examples.

[Evaluation method of alkaline developability]
The active energy ray-curable resin composition obtained in each Example and Comparative Example was applied onto a glass substrate using an applicator so as to have a film thickness of 50 μm, and then at 80 ° C. for 70 minutes and 80 minutes, respectively. The samples were dried for 90 minutes, 100 minutes, 110 minutes, 120 minutes, 130 minutes, and 140 minutes to prepare samples having 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 in which no residue remained on the substrate was used as the drying control range and evaluated according to the following criteria. It should be noted that the longer the drying control range, the better the alkaline developability.

A: The drying control width was over 140 minutes.
B: The drying control width was more than 120 minutes and 140 minutes or less.
C: The drying control width was more than 100 minutes and 120 minutes or less.
D: The drying control width was more than 80 minutes and 100 minutes or less.
E: The drying control width was 80 minutes or less.

Compositions of the active energy ray-curable resin compositions (1) to (28) prepared in Examples 1 to 28, and the active energy ray-curable resin compositions (R1) and (R2) prepared in Comparative Examples 1 and 2. The evaluation results are shown in Tables 1 to 3.

Note that "-" in Table 3 indicates that development is not possible.

(Example 29: Preparation of active energy ray-curable resin composition (29))
The resin (1) having an acid group and a polymerizable unsaturated group obtained in Synthesis Example 1, the resin (3) having a polymerizable unsaturated group and a urethane bond obtained in Synthesis Example 11, and orthocresol novolac as a curing agent. Type epoxy resin (“EPICLON N-680” manufactured by DIC Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (IMnirad manufactured by IGM Resins) as a photopolymerization initiator 907 ”) and diethylene glycol monomethyl ether acetate as an organic solvent were blended in parts by mass shown in Table 4 to obtain an active energy ray-curable resin composition (29).

(Examples 30 to 56: Preparation of active energy ray-curable resin compositions (30) to (56))
The active energy ray-curable resin compositions (30) to (56) were obtained in the same manner as in Example 29 with the compositions and formulations shown in Tables 4 to 6.

(Comparative Examples 3 and 4: Preparation of active energy ray-curable resin compositions (R3) and (R4))
Curable resin compositions (R3) and (R4) were obtained in the same manner as in Example 29 with the compositions and formulations shown in Table 6.

The following evaluations were performed using the active energy ray-curable resin compositions (29) to (56), (R3) and (R4) obtained in the above Examples and Comparative Examples.

[Measurement method of elongation and elastic modulus]
The measurement of elongation and the measurement of elastic modulus were performed based on the tensile test.
<Preparation of test piece 1>
The active energy ray-curable resin composition obtained in Examples and Comparative Examples was applied onto a copper foil (manufactured by Furukawa Sangyo Co., Ltd., electrolytic copper foil "F2-WS" 18 μm) with a 50 μm applicator, and a metal halide lamp was used. After irradiating with ultraviolet rays of 10 kJ / m ² , it was heated at 160 ° C. for 1 hour. The cured product was peeled off from the copper foil to obtain a test piece 1 (cured product).

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

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

A: The elongation was over 2.9%.
B: The elongation was more than 2.6% and 2.9% or less.
C: The elongation was more than 2.3% and 2.6% or less.
D: The elongation was more than 2.0% and 2.3% or less.
E: The elongation was 2.0% or less.

A: The elastic modulus was less than 2080 MPa.
B: The elastic modulus was 2080 MPa or more and less than 2160 MPa.
C: The elastic modulus was 2160 MPa or more and less than 2250 MPa.
D: The elastic modulus was 2250 MPa or more and less than 2330 MPa.
E: The elastic modulus was 2330 MPa or more.

[Evaluation method of substrate adhesion]
The substrate adhesion was evaluated by measuring the peel strength.
<Preparation of test piece 2>
The active energy ray-curable resin composition obtained in Examples and Comparative Examples was applied onto a copper foil (manufactured by Furukawa Sangyo Co., Ltd., electrolytic copper foil "F2-WS" 18 μm) with a 50 μm applicator, and a metal halide lamp was used. After irradiating with ultraviolet rays of 10 kJ / m ² , the test piece 2 was obtained by heating at 160 ° C. for 1 hour.

<Measuring method of peel strength>
The test piece 2 was cut into a size of 1 cm in width and 12 cm in length, and the 90 ° peel strength was measured using a peeling tester (“A & D Tensilon” manufactured by A & D Co., Ltd., peeling speed 50 mm / min). Evaluated according to.

A: The adhesion was 0.95 N / cm or more.
B: Adhesion was 0.90 N / cm or more and less than 0.95 N / cm.
C: Adhesion was 0.85 N / cm or more and less than 0.90 N / cm.
D: Adhesion was 0.80 N / cm or more and less than 0.85 N / cm.
E: Adhesion was less than 0.80 N / cm.

Of the active energy ray-curable resin compositions (29) to (56) prepared in Examples 29 to 56, and the active energy ray-curable resin compositions (R3) and (R4) prepared in Comparative Examples 3 and 4. The composition and evaluation results are shown in Tables 4-6.

The description of the mass part of the resin having an acid group and a polymerizable unsaturated group, the polymerizable unsaturated group and the resin having a urethane bond in Tables 1 to 6 is a solid content value.

“Curing agent” in Tables 1 to 6 indicates an orthocresol novolak type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation).

"Organic solvent" in Tables 1 to 6 indicates diethylene glycol monomethyl ether acetate.

“Photopolymerization initiator” in Tables 1 to 6 indicates “Omnirad-907” manufactured by IGM Resins.

Examples 1 to 28 shown in Tables 1 to 3 are examples of the active energy ray-curable resin composition of the present invention. It was confirmed that these active energy ray-curable resin compositions have excellent alkali developability.

Further, Examples 29 to 56 shown in Tables 4 to 6 are examples of the active energy ray-curable resin composition of the present invention. It was confirmed that the cured product of these active energy ray-curable resin compositions had excellent elongation, elasticity and adhesion.

On the other hand, Comparative Example 1 is an example of an active energy ray-curable resin composition that does not use a resin having a polymerizable unsaturated group and a urethane bond specified in the present invention. It was confirmed that this active energy ray-curable resin composition had insufficient alkali developability.

Comparative Example 2 is an example of an active energy ray-curable resin composition that does not use a resin having an acid group and a polymerizable unsaturated group specified in the present invention. It was confirmed that this active energy ray-curable resin composition had insufficient alkali developability.

Further, Comparative Example 3 is an example of an active energy ray-curable resin composition which does not use a resin having a polymerizable unsaturated group and a urethane bond defined in the present invention as in Comparative Example 1. It was confirmed that this active energy ray-curable resin composition was remarkably insufficient in elongation, elasticity and substrate adhesion.

Comparative Example 4 is an example of an active energy ray-curable resin composition that does not use a resin having an acid group and a polymerizable unsaturated group specified in the present invention as in Comparative Example 2. It was confirmed that this active energy ray-curable resin composition was remarkably insufficient in elongation, elasticity and substrate adhesion.

Claims

Resin (A) having an acid group and a polymerizable unsaturated group,
An active energy ray-curable resin composition containing a polymerizable unsaturated group other than the resin (A) and a resin (B) having a urethane bond.
The resin (B) contains an epoxy resin (b1), an unsaturated monobasic acid (b2), a (meth) acrylate compound (b3) having a hydroxyl group, and a compound (b4) having an isocyanate group as essential raw materials. An active energy ray-curable resin composition characterized by being.
The active energy ray-curable resin according to claim 1, wherein the mass ratio [(A) / (B)] of the solid content of the resin (A) and the resin (B) is in the range of 95/5 to 50/50. Composition.
The amount of the unsaturated monobasic acid (b2) used is 0.95 with respect to 1 mol of the epoxy group of the epoxy resin (b1) based on the acid group of the unsaturated monobasic acid (b2). The active energy ray-curable resin composition according to claim 1 or 2, which is in the range of ~ 1.1 mol.
The amount of the compound (b3) used is in the range of 0.3 to 0.7 mol with respect to 1 mol of the isocyanate group of the compound (b4) based on the hydroxyl group of the compound (b3). Item 3. The active energy ray-curable resin composition according to any one of Items 1 to 3.
The active energy ray-curable resin composition according to any one of claims 1 to 4, wherein the resin (B) has a (meth) acryloyl group, an isocyanate group, and a urethane bond.
The amount of the compound (b4) used is in the range of 0.1 to 0.7 mol with respect to 1 mol of the epoxy group of the epoxy resin (b1) based on the isocyanate group of the compound (b4). The active energy ray-curable resin composition according to any one of claims 1 to 3.
The active energy ray-curable resin composition according to any one of claims 1 to 6, wherein the epoxy resin (b1) has a softening point of 78 ° C. or lower.
The active energy ray-curable resin composition according to any one of claims 1 to 7, further comprising a photopolymerization initiator.
A cured product of the active energy ray-curable resin composition according to any one of claims 1 to 8.
An insulating material comprising the cured product according to claim 9.
A resist member made of the cured product according to claim 9.