JP7206782B2 - Acid group-containing epoxy (meth)acrylate resin, curable resin composition, cured product, insulating material, resin material for solder resist, and resist member - Google Patents

Description

The present invention provides an acid group-containing epoxy (meth)acrylate resin having excellent alkali developability and high elongation in a cured product, a curable resin composition containing the same, a cured product comprising the curable resin composition, and an insulating material. , a solder resist resin material and a resist member.

In recent years, acid group-containing epoxy acrylate resins obtained by reacting acid anhydrides after acrylated epoxy resins with acrylic acid have been widely used as resin materials for solder resists for printed wiring boards. Various properties such as excellent alkali developability and excellent elongation in a cured product are required for the solder resist resin material.

As the resin material for a solder resist excellent in alkali developability, an active energy ray obtained by reacting a reaction product of a novolak type epoxy compound and an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride Curable resins are known (see, for example, Patent Document 1 below), but they do not satisfy the ever-increasing demand for properties. There were problems such as the occurrence of

Therefore, a material having excellent alkali developability and excellent elongation in a cured product has been demanded.

JP-A-61-243869

The problem to be solved by the present invention is to provide an acid group-containing epoxy (meth)acrylate resin having excellent alkali developability and excellent elongation in a cured product, a curable resin composition containing the same, and the curability An object of the present invention is to provide a cured product, an insulating material, a solder resist resin material, and a resist member comprising a resin composition.

The inventors of the present invention have made intensive studies to solve the above problems, and have found that epoxy resins, polybasic acids, unsaturated monobasic acids, polybasic acids, unsaturated monobasic acids, which are reactants of phenolic hydroxyl group-containing compounds, alkylene oxides or alkylene carbonates, and epihalohydrin, and a polybasic acid anhydride as an essential reaction raw material, by using an acid group-containing epoxy (meth) acrylate resin, it was found that the above problems can be solved, and completed the present invention.

That is, the present invention provides an acid group-containing epoxy (meta- ) an acrylate resin, wherein the epoxy resin (A) is a reaction product of a phenolic hydroxyl group-containing compound (a1), an alkylene oxide (a2-1) or an alkylene carbonate (a2-2), and an epihalohydrin (a3); Acid group-containing epoxy (meth) acrylate resin characterized by It is.

Since the acid-group-containing epoxy (meth)acrylate resin of the present invention has excellent alkali developability and excellent elongation in a cured product, it consists of an insulating material, a solder resist resin material, and the solder resist resin. It can be suitably used for a resist member.

The acid group-containing epoxy (meth)acrylate resin of the present invention comprises an epoxy resin (A), a polybasic acid (B), an unsaturated monobasic acid (C), and a polybasic acid anhydride (D) as essential reaction raw materials. It is characterized by

In addition, in this invention, "(meth)acrylate" means an acrylate and/or a methacrylate. Moreover, "(meth)acryloyl" means acryloyl and/or methacryloyl. Furthermore, "(meth)acryl" means acryl and/or methacryl.

Examples of the acid group contained in the acid group-containing epoxy (meth)acrylate resin include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, a carboxyl group is preferred because it exhibits excellent alkali developability.

As the epoxy resin (A), a reaction product of a phenolic hydroxyl group-containing compound (a1), an alkylene oxide (a2-1) or an alkylene carbonate (a2-2), and an epihalohydrin (a3) is used.

The phenolic hydroxyl group-containing compound (a1) refers to a compound having at least two phenolic hydroxyl groups in the molecule. Examples of the compound having at least two phenolic hydroxyl groups in the molecule include compounds represented by the following structural formulas (1-1) to (1-4).

In the structural formulas (1-1) to (1-4) above, R ¹ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom. , R ² are each independently a hydrogen atom or a methyl group. In addition, p is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, still more preferably 0. q is an integer of 2 or more, preferably 2 or 3; The position of the substituent on the aromatic ring in the above structural formula is arbitrary. For example, in the naphthalene ring of structural formula (1-2), any ring may be substituted, and the structural formula ( In 1-3), any benzene ring present in one molecule may be substituted, and in structural formula (1-4), any benzene ring present in one molecule may be substituted. It indicates that it may be substituted, and indicates that the number of substituents in one molecule is p and q.

Among the compounds represented by the above structural formulas (1-1) to (1-4), an acid group-containing epoxy (meth) that has excellent alkali developability and is capable of forming a cured product having excellent elongation. A bisphenol compound represented by Structural Formula (1-4) is preferable because an acrylate resin can be obtained. Particularly, in Structural Formula (1-4), p is 0, q is 2, and R ² is Bisphenol A, which is a methyl group, is more preferred.

Further, as the phenolic hydroxyl group-containing compound (a1), for example, a compound having one phenolic hydroxyl group in the molecule and a compound represented by any of the following structural formulas (x-1) to (x-5) is an essential reaction raw material, or a compound having at least two phenolic hydroxyl groups 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 that is an essential reaction raw material can also be used. In addition, a novolac-type phenolic resin that uses one or more compounds having one phenolic hydroxyl group in the molecule as a reaction raw material, and one or more compounds having at least two phenolic hydroxyl groups in the molecule. A novolak-type phenol resin or the like used as a reaction raw material can also be used.

［式（ｘ－１）中、ｈは０または１である。式（ｘ－２）～（ｘ－５）中、Ｒ^３は、炭素原子数１～２０のアルキル基、炭素原子数１～２０のアルコキシ基、アリール基、ハロゲン原子の何れかであり、ｉは、０または１～４の整数である。式（ｘ－２）、（ｘ－３）及び（ｘ－５）中、Ｚは、ビニル基、ハロメチル基、ヒドロキシメチル基、アルキルオキシメチル基の何れかである。式（ｘ－５）中、Ｙは、炭素原子数１～４のアルキレン基、酸素原子、硫黄原子、カルボニル基の何れかであり、ｊは１～４の整数である。］

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

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

In the structural formulas (2-1) to (2-4) above, R ⁴ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom. , R ⁵ are each independently a hydrogen atom or a methyl group. In addition, p is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, still more preferably 0. The position of the substituent on the aromatic ring in the above structural formula is arbitrary. For example, the naphthalene ring of structural formula (2-2) may be substituted on any ring, and the structural formula ( In 2-3), any benzene ring present in one molecule may be substituted, and in structural formula (2-4), any benzene ring present in one molecule may be substituted. Indicates that substitution is allowed.

As the compound having at least two phenolic hydroxyl groups in the molecule, the compounds represented by the above structural formulas (1-1) to (1-4) can be used.

These phenolic hydroxyl group-containing compounds (a1) can be used alone or in combination of two or more.

Examples of the alkylene oxide (a2-1) include ethylene oxide, propylene oxide, butylene oxide and pentylene oxide. Among these, ethylene oxide and propylene oxide are preferable because they have excellent alkali developability and can form an acid group-containing epoxy (meth)acrylate resin capable of forming a cured product having excellent elongation.

The average number of added moles of the alkylene oxide (a2-1) has excellent alkali developability, and an acid group-containing epoxy (meth) acrylate resin capable of forming a cured product having excellent elongation is obtained. , preferably in the range of 1 to 20 mol, more preferably in the range of 1 to 10 mol, per 1 mol of the hydroxyl group of the phenolic hydroxyl group-containing compound (a1). The "average number of added moles of alkylene oxide (a2-1)" means the average number of moles of alkylene oxide (a2-1) added to 1 mole of hydroxyl groups of the phenolic hydroxyl group-containing compound (a1). Say.

Examples of the alkylene carbonate (a2-2) include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate and the like. Among these, ethylene carbonate or propylene carbonate is preferable because it provides an acid group-containing epoxy (meth)acrylate resin capable of forming a cured product having excellent alkali developability and excellent elongation.

The average number of added moles of the alkylene carbonate (a2-2) has excellent alkali developability, and an acid group-containing epoxy (meth) acrylate resin capable of forming a cured product having excellent elongation is obtained. , preferably in the range of 1 to 20 mol, more preferably in the range of 1 to 10 mol, per 1 mol of the hydroxyl group of the phenolic hydroxyl group-containing compound (a1). The "average number of added moles of alkylene carbonate (a2-2)" means the average number of moles of alkylene carbonate (a2-2) added to 1 mole of hydroxyl groups of the phenolic hydroxyl group-containing compound (a1). Say.

Examples of the epihalohydrin (a3) include epichlorohydrin and epibromohydrin. Among these, epichlorohydrin is preferable from the viewpoint of easy control of the reaction.

The amount of the epihalohydrin (a3) to be used is relative to 1 mol of hydroxyl groups generated in the reaction between the phenolic hydroxyl group-containing compound (a1) and the alkylene oxide (a2-1) or alkylene carbonate (a2-2). , preferably in the range of 1 to 15 mol, more preferably in the range of 5 to 12 mol.

The epoxy equivalent of the epoxy resin is 200 to 1000 g/equivalent because an acid group-containing epoxy (meth)acrylate resin capable of forming a cured product having excellent alkali developability and excellent elongation can be obtained. Ranges are preferred, with a range of 250-900 g/equivalent being more preferred.

The method for producing the epoxy resin (A) is not particularly limited, and any method may be used. For example, it may be produced by a method of reacting all of the reaction raw materials at once, or may be produced by a method of sequentially reacting the reaction raw materials. Among them, since the reaction is easy to control, the phenolic hydroxyl group-containing compound (a1) is first mixed with the alkylene oxide (a2-1) or the alkylene carbonate (a2-2) in the presence of a basic catalyst, After reacting at a temperature range of 80 to 200° C. for 2 to 10 hours under normal pressure to 10 kg/cm ² , epihalohydrin (a3) is added at a temperature range of 40 to 100° C. under an acidic catalyst for 1 to 10 hours. A method of reacting is preferred.

Any compound having two or more carboxyl groups in one molecule can be used as the polybasic acid (B). 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-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydro naphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and the like. be done. As the polybasic acid (B), 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 (B) can be used alone or in combination of two or more. In addition, among these, it is possible to obtain an acid group-containing epoxy (meth)acrylate resin that has excellent alkali developability and can form a cured product having excellent elongation. A copolymer having a carboxyl group in its molecule is preferred.

Examples of the copolymer of the conjugated diene-based vinyl monomer and acrylonitrile and having a carboxyl group in the molecule include a butadiene-acrylonitrile copolymer represented by the following structural formula (3-1) Half of a polymer having a carboxyl group in or a polymer having a hydroxyl group in the molecule of a butadiene-acrylonitrile copolymer represented by the following structural formula (3-2) and a polybasic acid anhydride such as maleic anhydride and esters. The position of the carboxyl group may be on either the side chain or the terminal of the molecule, but the terminal is preferred.

［構造式（３－１）中、Ｘは１～５０の整数であり、Ｙは１～５０の整数であり、Ｚは１～２０の整数である。］

[In Structural Formula (3-1), X is an integer of 1 to 50, Y is an integer of 1 to 50, and Z is an integer of 1 to 20. ]

［構造式（３－２）中、Ｘは１～５０の整数であり、Ｙは１～５０の整数であり、Ｚは１～２０の整数である。］

[In Structural Formula (3-2), X is an integer of 1 to 50, Y is an integer of 1 to 50, and Z is an integer of 1 to 20. ]

The amount of the polybasic acid (B) used has excellent alkali developability, and an acid group-containing epoxy (meth) acrylate resin capable of forming a cured product having excellent elongation is obtained. It is preferably in the range of 20 to 100 parts by mass with respect to 100 parts by mass of the resin (A).

The unsaturated monobasic acid (C) refers to a compound having a (meth)acryloyl group and a carboxyl group in one molecule, such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and α-cyanocinnamic acid. , β-styryl acrylic acid, β-furfuryl acrylic acid, and the like. Esterified products, acid halides, acid anhydrides, and the like of the unsaturated monobasic acid (C) 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 (D) include phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methyl nadic anhydride. acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, octenyl succinic anhydride, tetrapropenyl succinic anhydride and the like. These polybasic acid anhydrides can be used alone or in combination of two or more. In addition, among these, tetrahydrophthalic anhydride, succinic anhydride, since an acid group-containing epoxy (meth)acrylate resin capable of forming a cured product having excellent alkali developability and excellent elongation can be obtained. is preferred.

The acid group-containing epoxy (meth)acrylate resin of the present invention essentially comprises the epoxy resin (A), the polybasic acid (B), the unsaturated monobasic acid (C) and the polybasic acid anhydride (D). The production method is not particularly limited as long as it is used as the reaction raw material, and for example, either a method of reacting all the reaction raw materials at once or a method of sequentially reacting them may be used. Among them, the method of first reacting the epoxy resin (A) and the polybasic acid (B) and then reacting the unsaturated monobasic acid (C) is preferable because the reaction can be easily controlled. In the reaction, for example, the epoxy resin (A), the polybasic acid (B) and the unsaturated monobasic acid (C) are reacted in the presence of an esterification reaction catalyst in a temperature range of 90 to 150°C. After that, the polybasic acid anhydride (D) is added to the reaction system, and the reaction can be carried out at a temperature range of 90 to 120°C. Alternatively, the production of the epoxy resin (A) and the production of the acid group-containing epoxy (meth)acrylate resin may be carried out continuously.

Examples of the basic catalyst include alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal waters such as sodium hydroxide and potassium hydroxide. oxides; phosphorus compounds such as trimethylphosphine, tributylphosphine and triphenylphosphine; amine compounds such as triethylamine, tributylamine and dimethylbenzylamine; imidazole compounds such as 2-methylimidazole and 2-ethyl-4-methylimidazole is mentioned. These basic catalysts can be used alone or in combination of two or more. Moreover, among these, triphenylphosphine is preferable.

Moreover, you may perform this reaction in an organic solvent as needed. Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone and isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; Solvents; Alicyclic solvents such as cyclohexane and methylcyclohexane; Alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; Examples include glycol ether solvents such as alkyl ether acetate. These organic solvents can 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, since the reaction efficiency is improved.

The acid value of the acid group-containing epoxy (meth)acrylate resin of the present invention is preferably 30 to 120 mgKOH/g, and 40 because it has excellent alkali developability and can form a cured product having excellent elongation. ~100 mg KOH/g is more preferred.

In addition, the (meth)acryloyl group equivalent of the acid group-containing epoxy (meth)acrylate resin of the present invention has excellent alkali developability and can form a cured product having excellent elongation, so it is 200 to 900 g. /equivalent range is preferred, and a range of 300 to 800 g/equivalent is more preferred. The (meth)acryloyl group equivalent of the epoxy (meth)acrylate resin in the present invention is a value calculated as a theoretical value from reaction raw materials.

Since the acid group-containing epoxy (meth)acrylate resin of the present invention has a polymerizable (meth)acryloyl group in its molecular structure, it can be used as a curable resin composition by adding a photopolymerization initiator, for example. can be done.

Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy -2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2′-dimethoxy-1,2-diphenylethan-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide , 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one , 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone and the like.

Commercially available products of the other photopolymerization initiators include, for example, "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", and "Omnirad-379". , "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100", " Omnirad-754”, “Omnirad-784”, “Omnirad-500”, “Omnirad-81” (manufactured by IGM), “Kayacure-DETX”, “Kayacure-MBP”, “Kayacure-DMBI”, “Kayacure-EPA ”, “Kayacure-OA” (manufactured by Nippon Kayaku Co., Ltd.), “Vicure-10”, “Vicure-55” (manufactured by Stouffer Chemical), “Trigonal P1” (manufactured by Akzo), “Sunray 1000” ( Sands), "Deep" (Upjohn), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (Ward Blenkinsop), "Runtecure-1104" (Runtec company) and the like.

The amount of the photopolymerization initiator to be added is preferably, for example, in the range of 1 to 20% by mass in the curable resin composition.

The curable resin composition of the present invention may contain resin components other than the acid group-containing epoxy (meth)acrylate resin. Examples of the other resin components include an acid group-containing (meth)acrylate resin (E) and various (meth)acrylate monomers.

As the acid group-containing (meth)acrylate resin (E), any resin having an acid group and a (meth)acryloyl group may be used. For example, the acid group-containing epoxy (meth)acrylate resin of the present invention Other acid group-containing epoxy (meth) acrylate resins, acid group-containing urethane (meth) acrylate resins, acid group-containing acrylic (meth) acrylate resins, acid group-containing amideimide (meth) acrylate resins, acid group-containing acrylamide resins, etc. be done.

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

Acid group-containing epoxy (meth)acrylate resins other than the acid group-containing epoxy (meth)acrylate resin of the present invention include, for example, epoxy resins, unsaturated monobasic acids, and polybasic acid anhydrides as essential reaction raw materials. acid group-containing epoxy (meth) acrylate resins, epoxy resins, unsaturated monobasic acids, polybasic acid anhydrides, polyisocyanate compounds, and hydroxyl group-containing (meth) acrylate compounds containing acid groups and urethane groups as reaction raw materials epoxy (meth)acrylate resin and the like.

Examples of the epoxy resin include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, Bisphenol novolak type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition Examples include reactive epoxy resins. These epoxy resins can be used alone or in combination of two or more.

As the unsaturated monobasic acid, the same unsaturated monobasic acid (C) can be used.

As the polybasic acid anhydride, the same polybasic acid anhydride (D) can be used.

Examples of the polyisocyanate compounds include aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate and trimethylhexamethylene diisocyanate; polyisocyanates having an alicyclic structure such as cyclohexane diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate; - aromatic polyisocyanates such as tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, diphenylmethane-4,4-diisocyanate, 1,5-naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate; mentioned. In addition, nurate modified products, adduct modified products, biuret modified products, allophanate modified products, etc. of these polyisocyanate compounds can also be used. These polyisocyanate compounds can be used alone or in combination of two or more.

The hydroxyl group-containing (meth)acrylate compounds include, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth) Hydroxyl group-containing (meth)acrylate compounds such as acrylates and dipentaerythritol penta(meth)acrylate; A (poly)oxyalkylene modified product into which a (poly)oxyalkylene chain such as a poly)oxytetramethylene chain is introduced; a lactone modification into which a (poly)lactone structure is introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds A body etc. are mentioned.

Examples of the acid group-containing urethane (meth)acrylate resin include polyisocyanate compounds, hydroxyl group-containing (meth)acrylate compounds, carboxyl group-containing polyol compounds, and optionally polybasic acid anhydrides and the carboxyl group-containing polyol compounds. Those obtained by reacting with other polyol compounds, polyisocyanate compounds, hydroxyl group-containing (meth) acrylate compounds, polybasic acid anhydrides, and polyol compounds other than carboxyl group-containing polyol compounds obtained by reacting etc.

As the polyisocyanate compound, the same polyisocyanate compound as described above can be used.

As the hydroxyl group-containing (meth)acrylate compound, the same hydroxyl group-containing (meth)acrylate compound as described above can be used.

Examples of the carboxyl group-containing polyol compound include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid.

As the polybasic acid anhydride, the same polybasic acid anhydride (D) can be used.

Examples of polyol compounds other than the carboxyl group-containing polyol compounds include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; Aromatic polyol compounds such as biphenols and bisphenols; (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains in the molecular structures of the above-mentioned various polyol compounds Introduced (poly)oxyalkylene modified products; lactone modified products obtained by introducing a (poly)lactone structure into the molecular structure of the above-mentioned various polyol compounds, and the like.

The acid group-containing acrylic (meth)acrylate resin is obtained, for example, by polymerizing 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 as an essential component. A reaction product 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 to the acrylic resin intermediate obtained by and those obtained by reacting the hydroxyl groups in the reaction product with a polybasic acid anhydride.

The acrylic resin intermediate may be obtained by copolymerizing the (meth)acrylate compound (α) and, if necessary, other polymerizable unsaturated group-containing compounds. The other polymerizable unsaturated group-containing compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like (meth) Acrylic acid alkyl esters; Cycloring-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate; Phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl acrylate silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, α-methylstyrene and chlorostyrene; 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). From the viewpoint of reactivity, the following combinations are preferred: is preferred. That is, when a hydroxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use an isocyanate group-containing (meth)acrylate as the (meth)acrylate compound (β). When a carboxy group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a glycidyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When an isocyanate group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a hydroxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When a glycidyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a carboxy group-containing (meth)acrylate as the (meth)acrylate compound (β).

As the polybasic acid anhydride, the same polybasic acid anhydride (D) can be used.

Examples of acid group-containing amideimide (meth)acrylate resins include amideimide resins having acid groups or acid anhydride groups, hydroxyl group-containing (meth)acrylate compounds, (meth)acryloyl group-containing epoxy compounds, and polybasic acid anhydrides. and those that use a substance as an essential reaction raw material.

The amide-imide resin may have either an acid group or an acid anhydride group, or may have both. From the viewpoint of reactivity and reaction control with hydroxyl group-containing (meth)acrylate compounds and (meth)acryloyl group-containing epoxy compounds, it preferably has an acid anhydride group, and both the acid group and the acid anhydride group. It is more preferable to have The acid value of the amide-imide resin is preferably in the range of 60 to 350 mgKOH/g as measured under neutral conditions, that is, under conditions in which ring-opening of acid anhydride groups is not performed. On the other hand, it is preferable that the measured value under the condition that the acid anhydride group is ring-opened, such as in the presence of water, is in the range of 61 to 360 mgKOH/g.

The specific structure and manufacturing method of the amide-imide resin are not particularly limited, and general amide-imide resins and the like can be widely used. Examples thereof include those obtained by using a polyisocyanate compound and a polybasic acid or its acid anhydride as reaction raw materials.

As the polyisocyanate compound, the same polyisocyanate compound as described above can be used.

As the polybasic acid or its acid anhydride, the same polybasic acid (B) and polybasic acid anhydride (D) can be used.

As the hydroxyl group-containing (meth)acrylate compound, the same hydroxyl group-containing (meth)acrylate compound as described above can be used.

As the (meth)acryloyl group-containing epoxy compound, for example, other specific structures are not particularly limited as long as they have a (meth)acryloyl group and an epoxy group in the molecular structure, and a wide variety of compounds can be used. can be done. For example, glycidyl group-containing (meth)acrylate monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, epoxycyclohexylmethyl (meth)acrylate; dihydroxybenzene diglycidyl ether, dihydroxynaphthalenediglycidyl ether, Examples include mono(meth)acrylated diglycidyl ether compounds such as biphenol diglycidyl ether and bisphenol diglycidyl ether.

As the polybasic acid anhydride, the same polybasic acid anhydride (D) can be used.

Acid group-containing acrylamide resins include, for example, phenolic hydroxyl group-containing compounds, alkylene oxides or alkylene carbonates, N-alkoxyalkyl (meth)acrylamide compounds, polybasic acid anhydrides, and optionally unsaturated monobasic Examples include those obtained by reacting with an acid.

As the phenolic hydroxyl group-containing compound, the same phenolic hydroxyl group-containing compound (a1) as described above can be used.

As the alkylene oxide, the same alkylene oxide (a2-1) as described above can be used.

As the alkylene carbonate, the same alkylene carbonate (a2-2) as described above can be used.

As the unsaturated monobasic acid, the same unsaturated monobasic acid (C) can be used.

Examples of the N-alkoxyalkyl(meth)acrylamide compounds 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.

As the polybasic acid anhydride, the same polybasic acid anhydride (D) can be used.

The amount of the acid group-containing (meth)acrylate resin (E) used is preferably in the range of 10 to 900 parts by mass with respect to 100 parts by mass of the acid group-containing epoxy (meth)acrylate resin of the present invention.

Examples of the various (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2 - aliphatic mono (meth) acrylate compounds such as ethylhexyl (meth) acrylate and octyl (meth) acrylate; alicyclic mono (meth) acrylate compounds 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, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, benzylbenzyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate, etc. Mono (meth) acrylate compounds such as aromatic mono (meth) acrylate compounds of: (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxy in the molecular structure of the various mono (meth) acrylate monomers (Poly)oxyalkylene-modified mono(meth)acrylate compounds into which polyoxyalkylene chains such as tetramethylene chains are introduced; (Meth)acrylate compounds; aliphatics such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate Di(meth)acrylate compounds; 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornanedimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, tricyclodecanedi Alicyclic di(meth)acrylate compounds such as methanol di(meth)acrylate; Aromatic di(meth)acrylate compounds such as nord di(meth)acrylate; (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene in the molecular structure of the various di(meth)acrylate compounds polyoxyalkylene-modified di(meth)acrylate compound into which a (poly)oxyalkylene chain such as a chain is introduced; ) acrylate compound; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; (poly)oxyethylene chain in the molecular structure of the aliphatic tri(meth)acrylate compound , (poly)oxypropylene chain, (poly)oxytetramethylene chain, etc. (poly)oxyalkylene-modified tri(meth)acrylate compound introduced with (poly)oxyalkylene chain; molecule of the aliphatic tri(meth)acrylate compound Lactone-modified tri(meth)acrylate compounds having a (poly)lactone structure introduced into the structure; tetrafunctional or higher such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. Aliphatic poly (meth) acrylate compound; in the molecular structure of the aliphatic poly (meth) acrylate compound (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain such as (poly) Tetra- or more functional (poly)oxyalkylene-modified poly(meth)acrylate compound into which an oxyalkylene chain is introduced; Tetra- or more-functional lactone into which a (poly)lactone structure is introduced into the molecular structure of the aliphatic poly(meth)acrylate compound A modified poly(meth)acrylate compound and the like can be mentioned.

The curable resin composition of the present invention may optionally contain a curing agent, a curing accelerator, an organic solvent, inorganic fine particles or polymer fine particles, a pigment, an antifoaming agent, a viscosity modifier, a leveling agent, a flame retardant, Various additives such as storage stabilizers can also be contained.

The curing agent is not particularly limited as long as it has a functional group capable of reacting with the carboxyl group in the acid group-containing epoxy (meth)acrylate resin, and examples thereof include epoxy resins. Examples of the epoxy resin include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, Bisphenol novolak type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition Reactive epoxy resins, biphenylaralkyl-type epoxy resins, fluorene-type epoxy resins, xanthene-type epoxy resins, and the like can be mentioned. These epoxy resins can be used alone or in combination of two or more. Also, among these, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol cocondensation novolak type epoxy resin, due to excellent heat resistance in cured products, Novolac epoxy resins such as naphthol-cresol cocondensation novolac epoxy resins are preferred, and those having a softening point in the range of 50 to 120° C. are particularly preferred.

The curing accelerator accelerates the curing reaction of the curing agent. When an epoxy resin is used as the curing agent, examples include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Examples include Lewis acids, amine complex salts, and the like. These curing accelerators can be used alone or in combination of two or more. Further, the amount of the curing accelerator to be added is preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the curing agent.

The organic solvent is not particularly limited as long as it can dissolve various components such as the acid group-containing epoxy (meth)acrylate resin and the curing agent. Examples include ketone solvents such as methyl ethyl ketone, acetone, and isobutyl ketone; tetrahydrofuran , dioxolane and other cyclic ether solvents; methyl acetate, ethyl acetate, butyl acetate and other ester solvents; toluene, xylene, solvent naphtha and other aromatic solvents; cyclohexane, methylcyclohexane and other alicyclic solvents; carbitol, cellosolve, methanol , isopropanol, butanol and propylene glycol monomethyl ether; and glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether and dialkylene glycol monoalkyl ether acetate. These organic solvents can be used alone or in combination of two or more.

The cured product of the present invention can be obtained by irradiating the curable resin composition with an active energy ray. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, the irradiation may be performed in an atmosphere of an inert gas such as nitrogen gas or in an air atmosphere in order to efficiently perform the curing reaction using the ultraviolet rays.

An ultraviolet lamp is generally used as a source of ultraviolet light from the viewpoint of practicality and economy. Specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and LEDs.

The integrated amount of active energy rays is not particularly limited, but is preferably 50 to 5,000 mJ/cm ² , more preferably 100 to 1,000 mJ/cm ² . It is preferable that the integrated amount of light is within the above range because the generation of uncured portions can be prevented or suppressed.

The irradiation with the active energy ray may be performed in one step, or may be performed in two or more steps.

In addition, since the cured product of the present invention has excellent elongation, it can be It can be suitably used as an adhesive layer between an element and a circuit board. In addition, it can be suitably used for thin film transistor protective films, liquid crystal color filter protective films, color filter pigment resists, black matrix resists, spacers, and the like in thin display applications such as LCDs and OELDs. Among these, it can be preferably used for solder resist applications.

The resin material for solder resist of the present invention comprises the curable resin composition.

The resist member of the present invention is, for example, a photomask in which the desired pattern is formed after applying the solder resist resin material on a substrate and volatilizing and drying the organic solvent at a temperature range of about 60 to 100 ° C. It can be obtained by exposing to active energy rays through a ray, developing an unexposed portion with an alkaline aqueous solution, and further heat-curing in a temperature range of about 140 to 180°C.

Examples of the substrate include metal foil such as copper foil and aluminum foil.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples.

(Synthesis Example 1: Production of epoxy resin (A-1))
228 parts by mass of bisphenol A and 2.9 parts by mass of a 50% potassium hydroxide aqueous solution were charged into an autoclave equipped with a thermometer, a stirrer, a nitrogen introduction device and an alkylene oxide introduction device, and the system was replaced with nitrogen while stirring. Subsequently, the temperature was raised, and 349 parts by mass of propylene oxide was gradually introduced at 150° C. and reacted for 8 hours. Next, the reactant was taken out and neutralized by adding 2.6 parts by mass of a 36% hydrochloric acid aqueous solution. After filtration, the pressure was reduced to obtain 503 parts by mass of a reaction product. The hydroxyl value of this reaction product was 224.4 mgKOH/g. The number of moles of propylene oxide added to 1 mole of bisphenol A was about 2.3. In addition, in this synthesis example, the hydroxyl value is an actual value measured according to the neutralization titration method of JIS K 0070 (1992).

Next, 150 parts by mass of the reaction product obtained earlier, 555 parts by mass of epichlorohydrin, and 470 parts by mass of dimethyl sulfoxide were added to a flask equipped with a thermometer, a stirrer, and a reflux condenser and dissolved. , and 70° C., and 98.4 parts by mass of flaky sodium hydroxide was added over 2 hours. After reacting at 70° C. for 3 hours, the mixture was washed with water repeatedly to neutralize the reaction mixture. Then, the excess epichlorohydrin was removed by heating under reduced pressure and dissolved in 752 parts by mass of methyl isobutyl ketone. After adding 18 parts by mass of a 20% sodium hydroxide aqueous solution at 75° C. and reacting for 1 hour, the reaction mixture was washed with water repeatedly to neutralize the reaction mixture. Methyl isobutyl ketone was distilled off by heating under reduced pressure to obtain an epoxy resin (A-1). The epoxy equivalent of this epoxy resin (A-1) was 312 g/equivalent.

(Synthesis Example 2: Production of epoxy resin (A-2))
An autoclave equipped with a thermometer, a stirrer, a nitrogen introduction device and an alkylene oxide introduction device was charged with 228 parts by mass of bisphenol A and 3.2 parts by mass of a 50% potassium hydroxide aqueous solution, and the inside of the system was replaced with nitrogen while stirring. Subsequently, the temperature was raised, and 407 parts by mass of propylene oxide was gradually introduced at 150° C. and reacted for 8 hours. Next, the reactant was taken out and neutralized by adding 2.9 parts by mass of a 36% hydrochloric acid aqueous solution. After filtration, the pressure was reduced to obtain 552 parts by mass of a reaction product. The hydroxyl value of this reaction product was 196.2 mgKOH/g. Further, the average number of added moles of propylene oxide per 1 mole of hydroxyl groups possessed by bisphenol A was about 3.0.

Then, 143 parts by mass of the reaction product obtained earlier, 463 parts by mass of epichlorohydrin, and 404 parts by mass of dimethyl sulfoxide were added to a flask equipped with a thermometer, a stirrer, and a reflux condenser and dissolved. , and 70° C., and 82.0 parts by mass of flaky sodium hydroxide was added over 2 hours. After reacting at 70° C. for 3 hours, the mixture was washed with water repeatedly to neutralize the reaction mixture. Then, the excess epichlorohydrin was distilled off by heating under reduced pressure, and dissolved with 646 parts by mass of methyl isobutyl ketone. After adding 15 parts by mass of a 20% aqueous sodium hydroxide solution at 75° C. and reacting for 1 hour, the mixture was washed repeatedly with water to neutralize the reaction mixture. Methyl isobutyl ketone was distilled off by heating under reduced pressure to obtain an epoxy resin (A-2). The epoxy equivalent of this epoxy resin (A-2) was 350 g/equivalent.

(Synthesis Example 3: Production of epoxy resin (A-3))
A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 228 parts by mass of bisphenol A, 612 parts by mass of propylene carbonate, and 4.2 parts by mass of a 50% potassium hydroxide aqueous solution, and while stirring, the inside of the system was replaced with nitrogen. bottom. Subsequently, the mixture was heated and reacted at 160° C. for 8 hours. Next, the reactant was taken out and neutralized by adding 3.8 parts by mass of a 36% hydrochloric acid aqueous solution. After filtration, the pressure was reduced to obtain 645 parts by mass of a reaction product. The hydroxyl value of this reaction product was 234.7 mgKOH/g. Further, the average number of added moles of propylene carbonate per 1 mole of hydroxyl groups possessed by bisphenol A was about 2.2.

Next, 119.5 parts by mass of the reaction product obtained earlier, 463 parts by mass of epichlorohydrin, and 388 parts by mass of dimethyl sulfoxide were added to a flask equipped with a degree meter, a stirrer, and a reflux condenser and dissolved. After that, the mixture was heated to 70° C., and 82.0 parts by mass of flaky sodium hydroxide was added over 2 hours. After reacting at 70° C. for 3 hours, the mixture was washed with water repeatedly to neutralize the reaction mixture. Then, the excess epichlorohydrin was removed by heating under reduced pressure, and dissolved with 621 parts by mass of methyl isobutyl ketone. After adding 15 parts by mass of a 20% aqueous sodium hydroxide solution at 75° C. and reacting for 1 hour, the mixture was washed repeatedly with water to neutralize the reaction mixture. Methyl isobutyl ketone was distilled off by heating under reduced pressure to obtain an epoxy resin (A-3). The epoxy equivalent of this epoxy resin (A-3) was 305 g/equivalent.

(Synthesis Example 4: Production of epoxy resin (A-4))
200 parts by mass of bisphenol F and 2.7 parts by mass of 50% potassium hydroxide aqueous solution were charged into an autoclave equipped with a thermometer, a stirrer, a nitrogen introduction device and an alkylene oxide introduction device, and the system was replaced with nitrogen while stirring. Subsequently, the temperature was raised, and 349 parts by mass of propylene oxide was gradually introduced at 150° C. and reacted for 8 hours. Next, the reactant was taken out and neutralized by adding 2.5 parts by mass of a 36% hydrochloric acid aqueous solution. After filtration, the pressure was reduced to obtain 498 parts by mass of a reaction product. The hydroxyl value of this reaction product was 229.9 mgKOH/g. Further, the average number of added moles of propylene oxide per 1 mole of hydroxyl groups possessed by bisphenol F was about 2.5.

Next, 122 parts by mass of the reaction product obtained earlier, 463 parts by mass of epichlorohydrin, and 390 parts by mass of dimethyl sulfoxide were added to a flask equipped with a thermometer, a stirrer, and a reflux condenser and dissolved. , and 70° C., and 82.0 parts by mass of flaky sodium hydroxide was added over 2 hours. After reacting at 70° C. for 3 hours, the mixture was washed with water repeatedly to neutralize the reaction mixture. Then, the excess epichlorohydrin was removed by heating under reduced pressure, and dissolved with 624 parts by mass of methyl isobutyl ketone. After adding 15 parts by mass of a 20% aqueous sodium hydroxide solution at 75° C. and reacting for 1 hour, the mixture was washed repeatedly with water to neutralize the reaction mixture. Methyl isobutyl ketone was distilled off by heating under reduced pressure to obtain an epoxy resin (A-4). The epoxy equivalent of this epoxy resin (A-4) was 316 g/equivalent.

(Synthesis Example 5: Production of epoxy resin (A-5))
An autoclave equipped with a thermometer, a stirrer, a nitrogen introduction device and an alkylene oxide introduction device was charged with 160 parts by mass of 1,5-dihydroxynaphthalene and 2.5 parts by mass of a 50% potassium hydroxide aqueous solution, and while stirring, the system was was replaced with nitrogen. Subsequently, the temperature was raised, and 349 parts by mass of propylene oxide was gradually introduced at 150° C. and reacted for 8 hours. Next, the reactant was taken out and neutralized by adding 2.3 parts by mass of a 36% hydrochloric acid aqueous solution. After filtration, the pressure was reduced to obtain 404 parts by mass of a reaction product. The hydroxyl value of this reaction product was 262.1 mgKOH/g. The average number of moles of propylene oxide added to 1 mole of hydroxyl groups of 1,5-dihydroxynaphthalene was about 2.3.

Next, 107 parts by mass of the reaction product obtained earlier, 463 parts by mass of epichlorohydrin, and 380 parts by mass of dimethylsulfoxide were added to a flask equipped with a thermometer, stirrer, and reflux condenser and dissolved. , and 70° C., and 82.0 parts by mass of flaky sodium hydroxide was added over 2 hours. After reacting at 70° C. for 3 hours, the mixture was washed with water repeatedly to neutralize the reaction mixture. Then, the excess epichlorohydrin was removed by heating under reduced pressure and dissolved with 608 parts by mass of methyl isobutyl ketone. After adding 15 parts by mass of a 20% aqueous sodium hydroxide solution at 75° C. and reacting for 1 hour, the mixture was washed repeatedly with water to neutralize the reaction mixture. Methyl isobutyl ketone was distilled off by heating under reduced pressure to obtain an epoxy resin (A-5). The epoxy equivalent of this epoxy resin (A-5) was 293 g/equivalent.

(Synthesis Example 6: Production of epoxy resin (A-6))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 228 parts by mass of bisphenol A, 528 parts by mass of ethylene carbonate, and 3.8 parts by mass of a 50% potassium hydroxide aqueous solution, and the system was replaced with nitrogen while stirring. bottom. Subsequently, the mixture was heated and reacted at 160° C. for 6 hours. Then, the reactant was taken out and neutralized by adding 3.4 parts by mass of a 36% hydrochloric acid aqueous solution. After filtration, the pressure was reduced to obtain 609 parts by mass of a reaction product. The hydroxyl value of this reaction product was 259.7 mgKOH/g. Also, the average number of added moles of ethylene carbonate per 1 mole of hydroxyl groups possessed by bisphenol A was about 2.3.

Next, 108 parts by mass of the reaction product obtained earlier, 463 parts by mass of epichlorohydrin, and 380 parts by mass of dimethyl sulfoxide were added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and dissolved. , and 70° C., and 82.0 parts by mass of flaky sodium hydroxide was added over 2 hours. After reacting at 70° C. for 3 hours, the mixture was washed with water repeatedly to neutralize the reaction mixture. Then, the excess epichlorohydrin was removed by heating under reduced pressure and dissolved with 609 parts by mass of methyl isobutyl ketone. After adding 15 parts by mass of a 20% aqueous sodium hydroxide solution at 75° C. and reacting for 1 hour, the mixture was washed repeatedly with water to neutralize the reaction mixture. Methyl isobutyl ketone was distilled off by heating under reduced pressure to obtain an epoxy resin (A-6). The epoxy equivalent of this epoxy resin (A-6) was 295 g/equivalent.

(Example 1: Preparation of acid group-containing epoxy (meth)acrylate resin (1))
A flask equipped with a thermometer, a stirrer and a reflux condenser was charged with 312 parts by mass of epoxy resin (A-1), a copolymer of butadiene and acrylonitrile having carboxyl groups at both molecular ends (CVC Thermoset Specialties Co., Ltd. "HYPRO CTBN1300X13NA" (manufactured by the Company) and 0.5 parts by mass of triphenylphosphine were added and dissolved. After reacting at 100° C. for 5 hours in a nitrogen atmosphere, it was confirmed that the acid value was 1 mkOH/g or less. 281 parts by mass of diethylene glycol monomethyl ether acetate, 1.3 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of methoquinone, 67 parts by mass of acrylic acid and 2.6 parts by mass of triphenylphosphine were added, and the mixture was heated at 120°C for 10 minutes while blowing air. reacted over time. Then, 138 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110° C. for 5 hours to obtain the desired acid group-containing epoxy (meth)acrylate resin (1). The acid group-containing epoxy (meth)acrylate resin (1) had a solid content acid value of 80 mgKOH/g and a (meth)acryloyl group equivalent of 702 g/equivalent. The acid value is an actual value measured according to the neutralization titration method of JIS K 0070 (1992), and the (meth)acryloyl group equivalent is a calculated value.

(Example 2: Preparation of acid group-containing epoxy (meth)acrylate resin (2))
A flask equipped with a thermometer, a stirrer and a reflux condenser was charged with 312 parts by mass of epoxy resin (A-1), a copolymer of butadiene and acrylonitrile having carboxyl groups at both molecular ends (CVC Thermoset Specialties Co., Ltd. "HYPRO CTBN1300X13NA" (manufactured by the Company) and 0.5 parts by mass of triphenylphosphine were added and dissolved. After reacting at 100° C. for 5 hours in a nitrogen atmosphere, it was confirmed that the acid value was 1 mkOH/g or less. 257 parts by mass of diethylene glycol monomethyl ether acetate, 1.3 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of methoquinone, 67 parts by mass of acrylic acid and 2.6 parts by mass of triphenylphosphine were added, and the mixture was heated at 120°C for 10 minutes while blowing air. reacted over time. Next, 82 parts by mass of succinic anhydride was added and reacted at 110° C. for 5 hours to obtain the desired acid group-containing (epoxymeth)acrylate resin (2). The acid group-containing epoxy (meth)acrylate resin (2) had a solid content acid value of 80 mgKOH/g and a (meth)acryloyl group equivalent of 643 g/equivalent.

(Example 3: Preparation of acid group-containing epoxy (meth)acrylate resin (3))
A flask equipped with a thermometer, a stirrer and a reflux condenser was charged with 350 parts by mass of epoxy resin (A-2), a copolymer of butadiene and acrylonitrile having carboxyl groups at both molecular ends (CVC Thermoset Specialties Co. "HYPRO CTBN1300X13NA" (manufactured by the Company) and 0.5 parts by mass of triphenylphosphine were added and dissolved. After reacting at 100° C. for 5 hours in a nitrogen atmosphere, it was confirmed that the acid value was 1 mkOH/g or less. 310 parts by mass of diethylene glycol monomethyl ether acetate, 1.4 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of methoquinone, 67 parts by mass of acrylic acid and 2.9 parts by mass of triphenylphosphine were added, and the mixture was heated at 120°C for 10 minutes while blowing air. reacted over time. Then, 151 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110° C. for 5 hours to obtain the desired acid group-containing epoxy (meth)acrylate resin (3). The acid group-containing epoxy (meth)acrylate resin (3) had a solid content acid value of 80 mgKOH/g and a (meth)acryloyl group equivalent of 777 g/equivalent.

(Example 4: Preparation of acid group-containing epoxy (meth)acrylate resin (4))
A flask equipped with a thermometer, a stirrer and a reflux condenser was charged with 305 parts by mass of epoxy resin (A-3), a copolymer of butadiene and acrylonitrile having carboxyl groups at both molecular ends (CVC Thermoset Specialties Co., Ltd. "HYPRO CTBN1300X13NA" (manufactured by the Company) and 0.4 parts by mass of triphenylphosphine were added and dissolved. After reacting at 100° C. for 5 hours in a nitrogen atmosphere, it was confirmed that the acid value was 1 mkOH/g or less. 276 parts by mass of diethylene glycol monomethyl ether acetate, 1.3 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of methoquinone, 68 parts by mass of acrylic acid and 2.5 parts by mass of triphenylphosphine were added, and the mixture was heated at 120°C for 10 minutes while blowing air. reacted over time. Then, 135 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110° C. for 5 hours to obtain the desired acid group-containing epoxy (meth)acrylate resin (4). The acid group-containing epoxy (meth)acrylate resin (4) had a solid content acid value of 80 mgKOH/g and a (meth)acryloyl group equivalent of 681 g/equivalent.

(Example 5: Preparation of acid group-containing epoxy (meth)acrylate resin (5))
A flask equipped with a thermometer, a stirrer and a reflux condenser was charged with 316 parts by mass of epoxy resin (A-4), a copolymer of butadiene and acrylonitrile having carboxyl groups at both molecular ends (CVC Thermoset Specialties Co. "HYPRO CTBN1300X13NA" (manufactured by the Company) and 0.5 parts by mass of triphenylphosphine were added and dissolved. After reacting at 100° C. for 5 hours in a nitrogen atmosphere, it was confirmed that the acid value was 1 mkOH/g or less. 284 parts by mass of diethylene glycol monomethyl ether acetate, 1.3 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of methoquinone, 68 parts by mass of acrylic acid and 2.6 parts by mass of triphenylphosphine were added, and the mixture was heated at 120°C for 10 minutes while blowing air. reacted over time. Then, 139 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110° C. for 5 hours to obtain the desired acid group-containing epoxy (meth)acrylate resin (5). The acid group-containing epoxy (meth)acrylate resin (5) had a solid content acid value of 80 mgKOH/g and a (meth)acryloyl group equivalent of 704 g/equivalent.

(Example 6: Preparation of acid group-containing epoxy (meth)acrylate resin (6))
In a flask equipped with a thermometer, a stirrer and a reflux condenser, 293 parts by mass of epoxy resin (A-5), a copolymer of butadiene and acrylonitrile having carboxyl groups at both molecular ends (CVC Thermoset Specialties Co. "HYPRO CTBN1300X13NA" (manufactured by the Company) and 0.4 parts by mass of triphenylphosphine were added and dissolved. After reacting at 100° C. for 5 hours in a nitrogen atmosphere, it was confirmed that the acid value was 1 mkOH/g or less. 266 parts by mass of diethylene glycol monomethyl ether acetate, 1.2 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of methoquinone, 68 parts by mass of acrylic acid and 2.5 parts by mass of triphenylphosphine were added, and the mixture was heated at 120°C for 10 minutes while blowing air. reacted over time. Then, 130 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110° C. for 5 hours to obtain the desired acid group-containing epoxy (meth)acrylate resin (6). The acid group-containing epoxy (meth)acrylate resin (6) had a solid content acid value of 80 mgKOH/g and a (meth)acryloyl group equivalent of 655 g/equivalent.

(Example 7: Preparation of acid group-containing epoxy (meth)acrylate resin (7))
A flask equipped with a thermometer, a stirrer and a reflux condenser was charged with 295 parts by mass of epoxy resin (A-6), a copolymer of butadiene and acrylonitrile having carboxyl groups at both molecular ends (CVC Thermoset Specialties Co. "HYPRO CTBN1300X13NA" (manufactured by the Company) and 0.4 parts by mass of triphenylphosphine were added and dissolved. After reacting at 100° C. for 5 hours in a nitrogen atmosphere, it was confirmed that the acid value was 1 mkOH/g or less. 269 parts by mass of diethylene glycol monomethyl ether acetate, 1.2 parts by mass of dibutylhydroxytoluene, 0.3 parts by mass of methoquinone, 68 parts by mass of acrylic acid and 2.5 parts by mass of triphenylphosphine were added, and the mixture was heated at 120°C for 10 minutes while blowing air. reacted over time. Then, 133 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110° C. for 5 hours to obtain the desired acid group-containing epoxy (meth)acrylate resin (7). The acid group-containing epoxy (meth)acrylate resin (7) had a solid content acid value of 80 mgKOH/g and a (meth)acryloyl group equivalent of 662 g/equivalent.

(Example 8: Preparation of acid group-containing epoxy (meth)acrylate resin (8))
312 parts by mass of epoxy resin (A-1), 34 parts by mass of 1,4-cyclohexadicarboxylic acid, and 0.3 parts by mass of triphenylphosphine were added to a flask equipped with a thermometer, stirrer, and reflux condenser. Dissolved. After reacting at 120° C. for 3 hours in a nitrogen atmosphere, it was confirmed that the acid value was 1 mkOH/g or less. 211 parts by mass of diethylene glycol monomethyl ether acetate, 1.0 parts by mass of dibutylhydroxytoluene, 0.2 parts by mass of methoquinone, 43 parts by mass of acrylic acid and 2.0 parts by mass of triphenylphosphine were added, and the mixture was heated at 120°C for 8 hours while blowing air. reacted over time. Then, 103 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110° C. for 5 hours to obtain the desired acid group-containing epoxy (meth)acrylate resin (8). The acid group-containing epoxy (meth)acrylate resin (8) had a solid content acid value of 80 mgKOH/g and a (meth)acryloyl group equivalent of 821 g/equivalent.

(Example 9: Preparation of acid group-containing epoxy (meth)acrylate resin (9))
A flask equipped with a thermometer, a stirrer and a reflux condenser was charged with 312 parts by mass of epoxy resin (A-1), a copolymer of butadiene and acrylonitrile having carboxyl groups at both molecular ends (CVC Thermoset Specialties Co., Ltd. "HYPRO CTBN1300X13NA" (manufactured by the Company) and 0.4 parts by mass of triphenylphosphine were added and dissolved. After reacting at 100° C. for 3 hours in a nitrogen atmosphere, it was confirmed that the acid value was 1 mkOH/g or less. 233 parts by mass of diethylene glycol monomethyl ether acetate, 1.1 parts by mass of dibutylhydroxytoluene, 0.2 parts by mass of methoquinone, 71 parts by mass of acrylic acid and 2.2 parts by mass of triphenylphosphine were added, and the mixture was heated at 120°C for 10 minutes while blowing air. reacted over time. Then, 114 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110° C. for 5 hours to obtain the desired acid group-containing epoxy (meth)acrylate resin (9). The acid group-containing epoxy (meth)acrylate resin (9) had a solid content acid value of 80 mgKOH/g and a (meth)acryloyl group equivalent of 549 g/equivalent.

(Comparative Example 1: Preparation of acid group-containing epoxy (meth)acrylate resin (10))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 188 parts by mass of bisphenol A type epoxy resin ("EPICLON 850S" manufactured by DIC Corporation, epoxy equivalent: 188 g/eq), molecules of a copolymer of butadiene and acrylonitrile. 83 parts by mass of a polymer having carboxyl groups at both ends (“HYPRO CTBN1300X13NA” manufactured by CVC Thermoset Specialties) and 0.3 parts by mass of triphenylphosphine were added and dissolved. After reacting at 100° C. for 5 hours in a nitrogen atmosphere, it was confirmed that the acid value was 1 mkOH/g or less. 185 parts by mass of diethylene glycol monomethyl ether acetate, 0.9 parts by mass of dibutylhydroxytoluene, 0.2 parts by mass of methoquinone, 70 parts by mass of acrylic acid and 1.7 parts by mass of triphenylphosphine were added, and the mixture was heated to 120°C for 7 hours while blowing air. reacted over time. Next, 91 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110° C. for 5 hours to obtain the desired acid group-containing epoxy (meth)acrylate resin (10). The acid group-containing epoxy (meth)acrylate resin (10) had a solid content acid value of 80 mgKOH/g and a (meth)acryloyl group equivalent of 443 g/equivalent.

(Example 10: Preparation of curable resin composition (1))
100 parts by mass of the acid group-containing epoxy (meth)acrylate resin (1) obtained in Example 1, 24 parts by mass of an ortho-cresol novolac type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation) as a curing agent, and dipentaerythritol 10 parts by weight of hexaacrylate, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one as a photopolymerization initiator ("Omnirad 907" manufactured by IGM) 5 parts by weight, 2 as a curing accelerator - 0.5 parts by mass of ethyl-4-methylimidazole, 13 parts by mass of diethylene glycol monomethyl ether acetate as an organic solvent, and 0.65 parts by mass of phthalocyanine green as a pigment are blended and kneaded by a roll mill to form a curable resin composition (1 ).

(Examples 11 to 18: Preparation of curable resin compositions (2) to (9))
Instead of the acid group-containing epoxy (meth)acrylate resin (1) used in Example 10, the acid group-containing epoxy (meth)acrylate resins (2) to (9) obtained in Examples 2 to 9 were used, respectively. Curable resin compositions (2) to (9) were obtained in the same manner as in Example 10, except for the above.

(Comparative Example 2: Preparation of curable resin composition (C1))
In the same manner as in Example 10, except that the acid group-containing epoxy (meth)acrylate resin (1) used in Example 10 was replaced with the acid group-containing epoxy acrylate resin (10) obtained in Comparative Example 1. A curable resin composition (C1) was obtained.

The following evaluations were performed using the curable resin compositions (1) to (9) and (C1) obtained in the above examples and comparative examples.

[Evaluation method for alkali developability]
After applying the curable resin composition obtained in each example and comparative example using an applicator to a film thickness of 50 μm on a glass substrate, the coating was performed at 80° C. for 100 minutes, 110 minutes, and 120 minutes, respectively. Samples with different drying times were prepared by drying for 130 minutes, 140 minutes, 150 minutes, 160 minutes, 170 minutes, 180 minutes, 190 minutes, and 200 minutes. These samples were developed with a 1% sodium carbonate aqueous solution at 30° C. for 180 seconds, and the drying time at 80° C. for samples that left no residue on the substrate was evaluated as the drying control range. It should be noted that the longer the drying control width, the better the alkali developability.

Table 1 shows the evaluation results of the curable resin compositions (1) to (9) prepared in Examples 10 to 18 and the curable resin composition (C1) prepared in Comparative Example 2.

(Example 19: Preparation of curable resin composition (10))
100 parts by mass of the acid group-containing epoxy (meth)acrylate resin (1) obtained in Example 1, 24 parts by mass of an ortho-cresol novolac type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation) as a curing agent, and photopolymerization initiation. 5 parts by mass of 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one ("Omnirad 907" manufactured by IGM) as an agent, and 13 parts by mass of diethylene glycol monomethyl ether acetate as an organic solvent. , and kneaded by a roll mill to obtain a curable resin composition (8).

(Examples 20 to 27: Preparation of curable resin compositions (10) to (18))
Instead of the acid group-containing epoxy (meth)acrylate resin (1) used in Example 19, the acid group-containing epoxy (meth)acrylate resins (2) to (9) obtained in Examples 2 to 9 were used, respectively. Except for this, curable resin compositions (10) to (18) were obtained in the same manner as in Example 19.

(Comparative Example 3: Preparation of curable resin composition (C2))
In the same manner as in Example 19, except that the acid group-containing epoxy (meth)acrylate resin (1) used in Example 19 was replaced with the acid group-containing epoxy acrylate resin (10) obtained in Comparative Example 1. A curable resin composition (C2) was obtained.

The following evaluations were performed using the curable resin compositions (10) to (18) and (C2) obtained in the above examples and comparative examples.

[Method for measuring elongation]
Elongation measurements were based on tensile tests.
<Preparation of test piece>
A curable resin composition was applied onto a glass substrate with a 50 μm applicator and dried at 80° C. for 30 minutes. After irradiating with ultraviolet rays of 1000 mJ/cm ² using a metal halide lamp, it was heated at 160° C. for 1 hour. The cured product was peeled off from the glass substrate to obtain a test piece.

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

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

Table 1 shows the evaluation results of the curable resin compositions (10) to (18) prepared in Examples 19 to 27 and the curable resin composition (C2) prepared in Comparative Example 3.

Examples 10 to 27 shown in Tables 1 and 2 are examples of curable resin compositions using the acid group-containing epoxy (meth)acrylate resin of the present invention. It was confirmed that this curable resin composition had excellent alkali developability, and that the cured product of the curable resin composition had excellent elongation.

On the other hand, Comparative Examples 2 and 3 are examples of curable resin compositions using epoxy (meth)acrylate resins that do not use alkylene oxide or alkylene carbonate as raw materials for the epoxy resin. It was confirmed that this curable resin composition had insufficient alkali developability and that the cured product of the curable resin composition also had insufficient elongation.

Claims (9)

An acid group-containing epoxy (meth)acrylate resin containing an epoxy resin (A), a polybasic acid (B), an unsaturated monobasic acid (C), and a polybasic acid anhydride (D) as essential reaction raw materials, ,
The epoxy resin (A) is a reaction product of a phenolic hydroxyl group-containing compound (a1), an alkylene oxide (a2-1) or an alkylene carbonate (a2-2), and an epihalohydrin (a3) ,
The phenolic hydroxyl group-containing compound (a1) is selected from compounds represented by the following structural formulas (1-1) to (1-4),

(R ¹ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom; each R ² is independently a hydrogen atom or a methyl group; In addition, p is 0 or an integer of 1 to 3. q is 2 or 3. The position of the substituent on the aromatic ring in the above structural formula is arbitrary, and one molecule indicates that the number of substituents in is p and q.)
A curable resin containing an acid group-containing epoxy (meth)acrylate resin, wherein the polybasic acid (B) is a copolymer of a conjugated diene-based vinyl monomer and acrylonitrile, and a photopolymerization initiator. An insulating material comprising the composition. In the acid group-containing epoxy (meth)acrylate resin according to claim 1, the amount of the polybasic acid (B) used is in the range of 20 to 100 parts by mass with respect to 100 parts by mass of the epoxy resin (A). An insulating material comprising a curable resin composition containing the acid group-containing epoxy (meth)acrylate resin according to claim 1 and a photopolymerization initiator . 2. The acid group-containing epoxy (meth)acrylate resin according to claim 1, wherein the alkylene oxide (a2-1) is ethylene oxide or propylene oxide ; An insulating material comprising a curable resin composition containing a polymerization initiator . In the acid group-containing epoxy (meth)acrylate resin according to claim 1, the average number of added moles of the alkylene oxide (a2-1) is 1 per 1 mole of the hydroxyl group of the phenolic hydroxyl group-containing compound (a1). An insulating material comprising a curable resin composition containing the acid group-containing epoxy (meth)acrylate resin according to claim 1 in an amount of up to 20 mol and a photopolymerization initiator . An acid group-containing epoxy (meth)acrylate resin containing an epoxy resin (A), a polybasic acid (B), an unsaturated monobasic acid (C), and a polybasic acid anhydride (D) as essential reaction raw materials, ,
The epoxy resin (A) is a reaction product of a phenolic hydroxyl group-containing compound (a1), an alkylene oxide (a2-1) or an alkylene carbonate (a2-2), and an epihalohydrin (a3),
The phenolic hydroxyl group-containing compound (a1) is selected from compounds represented by the following structural formulas (1-1) to (1-4),

(R ¹ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom; ² are each independently a hydrogen atom or a methyl group. In addition, p is 0 or an integer of 1-3. q is 2 or 3; The positions of the substituents on the aromatic ring in the above structural formula are arbitrary, and the number of substituents in one molecule is p and q. )
A curable resin containing an acid group-containing epoxy (meth)acrylate resin, wherein the polybasic acid (B) is a copolymer of a conjugated diene-based vinyl monomer and acrylonitrile, and a photopolymerization initiator. A resin material for solder resist comprising the composition. In the acid group-containing epoxy (meth)acrylate resin according to claim 5, the amount of the polybasic acid (B) used is in the range of 20 to 100 parts by mass with respect to 100 parts by mass of the epoxy resin (A). A resin material for a solder resist, comprising a curable resin composition containing the acid group-containing epoxy (meth)acrylate resin according to claim 5 and a photopolymerization initiator. 6. The acid group-containing epoxy (meth)acrylate resin according to claim 5, wherein the alkylene oxide (a2-1) is ethylene oxide or propylene oxide, and an acid group-containing epoxy (meth)acrylate resin according to claim 5; A resin material for a solder resist, comprising a curable resin composition containing a polymerization initiator. In the acid group-containing epoxy (meth)acrylate resin according to claim 5, the average number of added moles of the alkylene oxide (a2-1) is 1 per 1 mole of the hydroxyl group of the phenolic hydroxyl group-containing compound (a1). A resin material for a solder resist, comprising a curable resin composition containing the acid group-containing epoxy (meth)acrylate resin according to claim 5 in an amount of up to 20 mol, and a photopolymerization initiator. A resist member comprising the solder resist resin material according to any one of claims 5 to 8.