CN112105661A

CN112105661A - Acid group-containing (meth) acrylate resin composition, curable resin composition, cured product, insulating material, resin material for solder resist, and protective member

Info

Publication number: CN112105661A
Application number: CN201980032027.XA
Authority: CN
Inventors: 山田骏介; 龟山裕史; 矢本和久; 林弘司
Original assignee: DIC Corp
Current assignee: DIC Corp
Priority date: 2018-05-15
Filing date: 2019-05-09
Publication date: 2020-12-18
Anticipated expiration: 2039-05-09
Also published as: WO2019220996A1; JPWO2019220996A1; CN112105661B; TW202003620A; TWI796478B; JP6705574B2

Abstract

The present invention provides: an acid group-containing (meth) acrylate resin composition, a curable resin composition containing the same, a cured product, and an insulating material, a resin material for a solder resist, and a protective member, each of which is formed from the curable resin composition, wherein the acid group-containing (meth) acrylate resin composition is characterized by containing a polymerizable unsaturated bond-containing aromatic ester compound (A) and an acid group-containing (meth) acrylate resin (B). The acid group-containing (meth) acrylate resin composition has high sensitivity and can form a cured product having excellent heat resistance and dielectric characteristics.

Description

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

Technical Field

The present invention relates to an acid group-containing (meth) acrylate resin composition having high sensitivity and excellent heat resistance and dielectric characteristics, a curable resin composition containing the same, a cured product, an insulating material formed from the curable resin composition, a resin material for a solder resist, and a protective member.

Background

In recent years, as a resin material for a solder resist for a printed wiring board, a curable resin composition which can be cured by an active energy ray such as an ultraviolet ray is widely used. Examples of the required properties of the resin material for a solder resist include curing with a small exposure amount, excellent alkali developability, excellent heat resistance, strength, dielectric properties, and the like of a cured product.

As a conventional resin material for a solder resist, a photosensitive resin composition containing an acid-containing epoxy acrylate resin obtained by reacting a cresol novolac type epoxy resin, an intermediate obtained by reacting acrylic acid with phthalic anhydride, and further reacting with tetrahydrophthalic anhydride has been known (for example, see patent document 1). The cured product has insufficient heat resistance, and the dielectric constant and dielectric loss tangent increase due to the formation of hydroxyl groups, which causes problems such as deterioration of dielectric properties.

Therefore, a material having high sensitivity, and a cured product having excellent heat resistance and substrate adhesion is required.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 8-259663

Disclosure of Invention

Problems to be solved by the invention

The problem to be solved by the present invention is to provide an acid group-containing (meth) acrylate resin composition having high sensitivity and excellent heat resistance and dielectric characteristics, a curable resin composition containing the same, a cured product, an insulating material formed from the photosensitive resin composition, a resin material for a solder resist, and a protective member.

Means for solving the problems

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using an acid group-containing (meth) acrylate resin composition containing a polymerizable unsaturated bond-containing aromatic ester compound and an acid group-containing (meth) acrylate resin, and have completed the present invention.

That is, the present invention relates to an acid group-containing (meth) acrylate resin composition containing a polymerizable unsaturated bond-containing aromatic ester compound (a) and an acid group-containing (meth) acrylate resin (B), a curable resin composition containing the same, a cured product, an insulating material formed from the curable resin composition, a resin material for a solder resist, and a protective member.

ADVANTAGEOUS EFFECTS OF INVENTION

The acid group-containing (meth) acrylate resin composition of the present invention can form a cured product having high sensitivity, excellent heat resistance and excellent dielectric characteristics, and therefore can be suitably used for an insulating material, a solder resist resin material, and a protective member formed from the solder resist resin. In the present invention, "excellent dielectric characteristics" mean a low dielectric constant and a low dielectric loss tangent.

Detailed Description

The acid group-containing (meth) acrylate resin composition of the present invention is characterized by containing a polymerizable unsaturated bond-containing aromatic ester compound (A) and an acid group-containing (meth) acrylate resin (B).

The polymerizable unsaturated bond-containing aromatic ester compound (a) is a compound having 1 or more polymerizable unsaturated bonds in the molecular structure and having a structural site in which aromatic rings are bonded to each other via an ester bond, and other specific structures, molecular weights, and the like are not particularly limited, and various compounds can be used.

Examples of the polymerizable unsaturated bond-containing aromatic ester compound (a) include: a reaction product of an aromatic compound having a phenolic hydroxyl group and an aromatic compound having a carboxyl group, an acid halide thereof and/or an ester thereof (in the present specification, the aromatic compound having a carboxyl group, the acid halide thereof and/or the ester thereof may be collectively referred to as "an aromatic compound having a carboxyl group" or the like), any one of the aromatic compound having a phenolic hydroxyl group and the aromatic compound having a carboxyl group or the like having a substituent having a polymerizable unsaturated bond.

Examples of the aromatic compound having a phenolic hydroxyl group include a1 st aromatic compound having 2 or more phenolic hydroxyl groups and a2 nd aromatic compound having 1 phenolic hydroxyl group.

The 1 st aromatic compound has 2 or more phenolic hydroxyl groups. Having 2 or more phenolic hydroxyl groups allows the reaction with a 3 rd aromatic compound or the like or a 4 th aromatic compound or the like described later to form an ester structure.

The 1 st aromatic compound is not particularly limited, and examples thereof include compounds having 2 or more phenolic hydroxyl groups on the 1 st aromatic ring having 3 to 30 carbon atoms which may be substituted or unsubstituted.

Examples of the 1 st aromatic ring having 3 to 30 carbon atoms include monocyclic aromatic rings, condensed ring aromatic rings, ring-aggregated aromatic rings, and the like.

Examples of the monocyclic aromatic ring include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, piperazino, pyrazine, triazine, and the like.

Examples of the fused aromatic ring include naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine.

Examples of the ring-aggregated aromatic ring include biphenyl, binaphthyl, bipyridyl, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl.

The 1 st aromatic ring having 3 to 30 carbon atoms may have a substituent. In this case, examples of the "substituent for the 1 st aromatic ring" include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, a substituent having a polymerizable unsaturated bond, and the like.

Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 1, 2-dimethylpropyl, n-hexyl, isohexyl, n-nonyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclononyl.

Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, 2-ethylhexyloxy, octyloxy, nonyloxy, and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

The polymerizable unsaturated bond-containing substituent is a substituent having 2 to 30 carbon atoms and having at least 1 polymerizable unsaturated bond. In this case, "unsaturated bond" means a carbon atom-carbon atom double bond or a carbon atom-carbon atom triple bond. Examples of the unsaturated bond-containing substituent include an alkenyl group and an alkynyl group.

Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a 1-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, a 5-hexenyl group, a 1-octenyl group, a 2-octenyl group, a 1-undecenyl group, a 1-pentadecenyl group, a 3-pentadecenyl group, a 7-pentadecenyl group, a 1-octadecenyl group, a 2-octadecenyl group, a cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, a1, 3-butadienyl group, a1, 4-butadienyl group, a hex-1, 3-dienyl group, a hex-2, 5-dienyl group, a pentadec-4, Hex-1, 3, 5-trienyl, pentadeca-1, 4, 7-trienyl, and the like.

Examples of the alkynyl group include ethynyl, propargyl, 1-butynyl, 2-butynyl, 3-pentynyl, 4-pentynyl, and 1, 3-butadiynyl.

Among these, the substituent having a polymerizable unsaturated bond is preferably an alkenyl group having 2 to 30 carbon atoms, more preferably an alkenyl group having 2 to 10 carbon atoms, still more preferably an alkenyl group having 2 to 5 carbon atoms, particularly preferably a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a 1-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a1, 3-butadienyl group, and most preferably an allyl group, a propenyl group, an isopropenyl group, or a 1-propenyl group.

The substituent for the 1 st aromatic ring may be contained singly or in combination of two or more.

The 1 st aromatic compound is a compound in which at least 2 of the hydrogen atoms constituting the 1 st substituted or unsubstituted aromatic ring having 3 to 30 carbon atoms are substituted with a hydroxyl group.

Specific examples of the compound in which the 1 st aromatic ring is a monocyclic aromatic ring (hereinafter, may be simply referred to as "the 1 st monocyclic aromatic ring compound") include catechol, resorcinol, hydroquinone, trimellitol, phloroglucinol, pyrogallol, 2, 3-dihydroxypyridine, 2, 4-dihydroxypyridine, 4, 6-dihydroxypyrimidine, 3-methylcatechol, 4-allylcatechol, and the like.

Specific examples of the compound in which the 1 st aromatic ring is a condensed ring aromatic ring (hereinafter, may be simply referred to as "1 st condensed ring aromatic ring compound") include, for example, 1, 3-naphthalenediol, 1, 5-naphthalenediol, 2, 6-naphthalenediol, 2, 7-naphthalenediol, 1,2, 4-naphthalenediol, 1,4, 5-naphthalenediol, 9, 10-dihydroxyanthracene, 1,4,9, 10-tetrahydroxyanthracene, 2, 4-dihydroxyquinoline, 2, 6-dihydroxyquinoline, 5, 6-dihydroxyindole, 2-methylnaphthalene-1, 4-diol, and the like.

Specific examples of the compound in which the 1 st aromatic ring is a ring-assembled aromatic ring (hereinafter, may be simply referred to as "1 st ring-assembled aromatic ring compound") include, for example, 2 '-dihydroxybiphenyl, 4, 4' -dihydroxybiphenyl, 3,4,4 '-trihydroxybiphenyl, 2', 3-trihydroxybiphenyl, and the like.

The 1 st aromatic compound may have a structure in which the 1 st aromatic ring is linked by a linking group. In one embodiment, the 1 st aromatic compound is represented by the following chemical formula (1).

In the above chemical formula (1), Ar¹Each independently is a substituted or unsubstituted 1 st aromatic ring radical, Ar²Each independently represents a substituted or unsubstituted 2 nd aromatic ring group, X each independently represents an oxygen atom, a sulfur atom, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, or an aralkylene group, and n is an integer of 0 to 10. In this case, Ar is constituted¹And Ar mentioned above²At least 2 of the hydrogen atoms of (a) are substituted by hydroxyl groups. In addition, the aforementioned X corresponds to a linking group.

Ar above¹Is a substituted or unsubstituted 1 st aromatic ring group. As shown in the above chemical formula (1), 1 of the hydrogen atoms constituting the aromatic ring of the substituted or unsubstituted aromatic ring is bonded to "X".

Examples of the 1 st aromatic ring group include those obtained by removing 1 hydrogen atom from a monocyclic aromatic compound such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, piperazinone, pyrazine, or triazine; and those obtained by removing 1 hydrogen atom from aromatic compounds such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine. In addition, a plurality of these aromatic compounds may be combined, and examples thereof include compounds obtained by removing 1 hydrogen atom from a ring-assembly aromatic compound such as biphenyl, binaphthyl, bipyridyl, bithiophene, phenylpyridine, phenylthiophene, terphenyl, bithiophene, and quaterphenyl.

In this case, the 1 st aromatic ring group may have a substituent, and in this case, the "substituent of the 1 st aromatic ring group" means a group in which at least 1 of hydrogen atoms of the aromatic ring constituting the 1 st aromatic ring group is substituted. Examples of the "substituent for the 1 st aromatic ring group" include an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a halogen atom, and the like.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a1, 2-dimethylpropyl group, a n-hexyl group, an isohexyl group, and a cyclohexyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group.

Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an n-butoxycarbonyl group, an isobutoxycarbonyl group, an sec-butoxycarbonyl group, and a tert-butoxycarbonyl group.

Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, a butylcarbonyloxy group, an n-butylcarbonyloxy group, an isobutylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group and the like.

Among these, Ar¹Preferably, the compound is one obtained by removing 1 hydrogen atom from benzene, naphthalene, anthracene, phenalene, phenanthrene, biphenyl, binaphthyl, quaterphenyl, allylbenzene, diallylbenzene, allylnaphthalene, diallylnaphthalene, allylbiphenyl, and diallylbiphenyl, and more preferably one obtained by removing 1 hydrogen atom from benzene, naphthalene, biphenyl, allylbenzene, diallylnaphthalene, and diallylbiphenyl.

Ar above²Each independently is a substituted or unsubstituted 2 nd aromatic ring group. As is apparent from the description of the above chemical formula (1), 2 of the hydrogen atoms constituting the aromatic ring of the above substituted or unsubstituted aromatic ring are bonded to "X".

Examples of the 2 nd aromatic ring group include those obtained by removing 2 hydrogen atoms from a monocyclic aromatic compound such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, piperazinone, pyrazine, or triazine; and those obtained by removing 2 hydrogen atoms from aromatic compounds such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine. In addition, a plurality of these aromatic compounds may be combined, and examples thereof include compounds obtained by removing 2 hydrogen atoms from a ring-assembly aromatic compound such as biphenyl, binaphthyl, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl.

In this case, the 2 nd aromatic ring group may have a substituent. Examples of the "substituent for the 2 nd aromatic ring group" include the same ones as those for the "substituent for the 1 st aromatic ring group" described above.

The aforementioned X's are each independently an oxygen atom, a sulfur atom, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, or an aralkylene group.

Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a1, 1-dimethylmethylene group, a 1-methylethylene group, a1, 1-dimethylethylene group, a1, 2-dimethylethylene group, a propylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group, and a hexylene group.

Examples of the cycloalkylene group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentyl group, a cycloheptyl group, and cycloalkylene groups represented by the following chemical formulae (2-1) to (2-4).

In the above chemical formulas (2-1) to (2-4), "Ar" represents Ar¹Or Ar²The site of bonding.

Examples of the aralkylene group include aralkylene groups represented by the following chemical formulae (3-1) to (3-8).

In the above chemical formulas (3-1) to (3-8), "Ar" represents Ar¹Or Ar²The site of bonding.

The alkylene group, cycloalkylene group and aralkylene group may have a substituent. In this case, examples of the "substituent for X" may be the same as the "substituent for the 1 st aromatic ring".

N in the chemical formula (1) is an integer of 0 to 10, preferably an integer of 0 to 8, and more preferably an integer of 0 to 5. When the compound represented by the above chemical formula (1) is an oligomer or a polymer, n represents an average value thereof.

And Ar constitutes the above-mentioned¹And Ar mentioned above²At least 2 of the hydrogen atoms of (a) are substituted by hydroxyl groups.

Specific examples of the compound represented by the following chemical formula (1) are not particularly limited, and examples thereof include various bisphenol compounds, compounds represented by the following chemical formulas (4-1) to (4-8), and compounds having 1 or more polymerizable unsaturated bond-containing substituents on the aromatic nucleus thereof.

Examples of the bisphenol compounds include bisphenol a, bisphenol AP, bisphenol B, bisphenol E, bisphenol F, bisphenol Z, and the like.

In the above chemical formulas (4-1) to (4-8), n is an integer of 0 to 10, preferably 0 to 5. In this case, when the compounds represented by the chemical formulas (4-1) to (4-8) are oligomers or polymers, n is an average value thereof. In the present specification, "oligomer" means a compound having a repeating unit of 1 to 5, and "polymer" means a compound having a repeating unit of 6 or more. The substitution position of the hydroxyl group as a substituent on the aromatic ring is arbitrary, and in the case of a naphthalene ring, a ring bonded to another structure or a ring not bonded may be used.

In one embodiment, the 1 st aromatic compound is represented by the chemical formula (1) and can be synthesized by reacting a divinyl compound or a dialkoxymethyl compound with at least 1 of the hydrogen atoms constituting the 1 st aromatic ring substituted with a hydroxyl group.

In this case, examples of the divinyl compound and dialkoxymethyl compound include aliphatic diene compounds such as 1, 3-butadiene, 1, 5-hexadiene, dicyclopentadiene, tricyclopentadiene, tetracyclopentadiene, pentacyclopentadiene and hexacyclopentadiene; aromatic diene compounds such as divinylbenzene and divinylbiphenyl; and dialkoxymethyl compounds such as dimethoxymethylbenzene, dimethoxymethylbiphenyl, bisphenol A methoxy adduct, bisphenol A ethoxy adduct, bisphenol F methoxy adduct, and bisphenol F ethoxy adduct.

The 1 st aromatic compound having 2 or more phenolic hydroxyl groups may be used alone or in combination of two or more.

The hydroxyl equivalent of the 1 st aromatic compound is preferably 130 to 500 g/equivalent, more preferably 130 to 400 g/equivalent, in view of obtaining an acid group-containing (meth) acrylate resin composition capable of forming a cured product having high sensitivity, heat resistance and excellent dielectric properties.

The 1 st aromatic compound is a compound represented by the above chemical formula (1), and in view of obtaining an acid group-containing (meth) acrylate resin composition capable of forming a cured product having high sensitivity, excellent heat resistance, and excellent dielectric properties, the weight average molecular weight when n is an oligomer or a polymer is preferably 200 to 3000, more preferably 200 to 2000. In the present specification, the value of the "weight average molecular weight" is a value measured by the following method. That is, values measured by Gel Permeation Chromatography (GPC) under the following conditions were used.

Measurement conditions of GPC

A measuring device: HLC-8320GPC, manufactured by Tosoh corporation "

Column: "HXL-L" protective column manufactured by Tosoh corporation "

+ manufactured by Tosoh corporation of "TSK-GEL G4000 HXL"

+ TSK-GEL G3000HXL manufactured by Tosoh corporation "

+ TSK-GEL G2000HXL manufactured by Tosoh corporation "

A detector: RI (differential refractometer)

Data processing: "EcoSEC-WorkStation" of Tosoh corporation "

Column temperature: 40 deg.C

Developing solvent: tetrahydrofuran (THF)

Flow rate: 1.0 ml/min

The standard is as follows: the following monodisperse polystyrene having a known molecular weight was used according to the manual for measurement of "GPC-8320 GPC" mentioned above

Polystyrene used

"A-500" made by Tosoh corporation "

"A-1000" made by Tosoh corporation "

"A-2500" made by Tosoh corporation "

"A-5000" manufactured by Tosoh corporation "

"F-1" made by Tosoh corporation "

"F-2" made by Tosoh corporation "

"F-4" made by Tosoh corporation "

"F-10" made by Tosoh corporation "

"F-20" made by Tosoh corporation "

"F-40" made by Tosoh corporation "

"F-80" made by Tosoh corporation "

"F-128" made by Tosoh corporation "

Sample preparation: the resulting tetrahydrofuran solution was filtered through a microfilter at 1.0 mass% in terms of resin solid content (50. mu.l).

The 2 nd aromatic compound has 1 phenolic hydroxyl group. The 2 nd aromatic compound has 1 phenolic hydroxyl group, and thus has a function of stopping the esterification reaction.

Examples of the 2 nd aromatic compound include compounds having 1 phenolic hydroxyl group on a substituted or unsubstituted 2 nd aromatic ring having 3 to 30 carbon atoms.

Examples of the 2 nd aromatic ring having 3 to 30 carbon atoms include monocyclic aromatic rings, condensed ring aromatic rings, ring-assembled aromatic rings, and aromatic rings connected via an alkylene group. Examples of the monocyclic aromatic ring, the condensed ring aromatic ring, and the ring-aggregated aromatic ring include those similar to the 1 st aromatic ring.

Examples of the aromatic ring linked via an alkylene group include diphenylmethane, diphenylethane, 1-diphenylethane, 2-diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenylpyridinemethane, fluorene, and diphenylcyclopentane.

The 2 nd aromatic ring having 3 to 30 carbon atoms in the 2 nd aromatic compound may have a substituent. In this case, examples of the "substituent for the 2 nd aromatic ring" include the same ones as those mentioned above for the "substituent for the 1 st aromatic ring".

In the 2 nd aromatic compound, 1 of hydrogen atoms constituting the substituted or unsubstituted 2 nd aromatic ring having 3 to 30 carbon atoms is substituted with a hydroxyl group.

Examples of the 2 nd aromatic compound include compounds represented by the following chemical formulas (5-1) to (5-17).

In the above chemical formulae (5-1) to (5-17), R¹Is a substituent containing a polymerizable unsaturated bond. The substituent containing a polymerizable unsaturated bond is the same as described above. Further, p is an integer of 0 or 1 or more, preferably 1 to 3, more preferably 1 or 2, and still more preferably 1. When p is 2 or more, the bonding position on the aromatic ring is arbitrary, and for example, it may be substituted on any ring of the naphthalene ring of chemical formula (5-6) or the heterocycle of chemical formula (5-17), and in chemical formula (5-9), it is represented that it may be substituted on any ring of the benzene rings existing in 1 molecule, and the number of substituents in 1 molecule is p.

More specifically, the 2 nd aromatic compound includes compounds in which an aromatic ring is a monocyclic aromatic ring, such as phenol, cresol, xylenol, o-allylphenol, m-allylphenol, p-allylphenol, 2, 4-diallylphenol, 2, 6-diallylphenol, 2-allyl-4-methylphenol, 2-allyl-6-methylphenol, 2-allyl-4-methoxy-6-methylphenol, 2-propargylphenol, 3-propargylphenol, and 4-propargylphenol (hereinafter, may be simply referred to as "2 nd monocyclic aromatic ring compounds"); 1-naphthol, 2-allyl-1-naphthol, 3-allyl-1-naphthol, 1-allyl-2-naphthol, 3-allyl-2-naphthol, 5-allyl-1-naphthol, compounds having an aromatic ring as a condensed ring aromatic ring (hereinafter, may be referred to simply as "2 nd condensed ring aromatic ring compound"), such as 6-allyl-1-naphthol, diallylnaphthol, 2-allyl-4-methoxy-1-naphthol, 2-propargyl-1-naphthol, 3-propargyl-1-naphthol, 1-propargyl-2-naphthol, and 3-propargyl-2-naphthol; and compounds in which an aromatic ring such as allylhydroxybiphenyl or hydroxypropylbiphenyl is a ring-assembled aromatic ring (hereinafter, may be simply referred to as "ring-2-assembled aromatic ring compounds").

Among the above, the 2 nd aromatic compound is preferably a2 nd monocyclic aromatic ring compound or a2 nd fused ring aromatic ring compound, and more preferably o-allylphenol, m-allylphenol, p-allylphenol, 2-allyl-1-naphthol, 3-allyl-1-naphthol, 1-allyl-2-naphthol, 3-allyl-2-naphthol, 5-allyl-1-naphthol, or 6-allyl-1-naphthol.

In another embodiment, the 2 nd aromatic compound is preferably a2 nd fused ring aromatic ring compound (fused ring aromatic ring compound), and more preferably 2-allyl-1-naphthol, 3-allyl-1-naphthol, 1-allyl-2-naphthol, 3-allyl-2-naphthol, 5-allyl-1-naphthol, or 6-allyl-1-naphthol. When the 2 nd aromatic compound is a fused ring aromatic ring compound, the dielectric loss tangent can be reduced by suppressing the molecular movement due to steric hindrance, which is preferable. In addition, from the viewpoint of high processability and low viscosity of the polymerizable unsaturated bond-containing aromatic ester compound (a), 2-allylphenol having a benzene ring skeleton or the like is preferable, and from the viewpoint that the obtained acid group-containing (meth) acrylate resin composition can form a cured product having high sensitivity, excellent heat resistance and excellent dielectric properties, 2-allyl-1-naphthol having a naphthalene ring skeleton, 1-allyl-2-naphthol, or the like is preferable.

The 2 nd aromatic compound having 1 phenolic hydroxyl group may be used alone or in combination of two or more.

Examples of the aromatic compound having a carboxyl group include a 3 rd aromatic compound having 2 or more carboxyl groups, a 4 th aromatic compound having 1 carboxyl group, and acid halides and esters thereof.

The aforementioned 3 rd aromatic compound, its acid halide and/or its ester is an aromatic compound having 2 or more carboxyl groups, or a derivative thereof, specifically an acid halide or an ester (in the present specification, the 3 rd aromatic compound, its acid halide and/or its ester may be collectively referred to as "the 3 rd aromatic compound and the like"). The 3 rd aromatic compound or the like has 2 or more carboxyl groups and reacts with the 1 st aromatic compound or the 2 nd aromatic compound to form an ester structure.

Examples of the 3 rd aromatic compound include compounds having 2 or more carboxyl groups on a substituted or unsubstituted 3 rd aromatic ring having 3 to 30 carbon atoms.

Examples of the "carboxyl group and the like" include a carboxyl group; halogenated acyl groups such as acyl fluoride, acyl chloride and acyl bromide; alkoxycarbonyl such as methoxycarbonyl and ethoxycarbonyl; aryloxycarbonyl such as phenoxycarbonyl and naphthyloxycarbonyl. When the aromatic compound has an acyl halide group, the aromatic compound of the 3 rd group may be an acid halide compound, and when the aromatic compound has an alkoxycarbonyl group or an aryloxycarbonyl group, the aromatic compound of the 3 rd group may be an ester compound. Among these, the 3 rd aromatic compound preferably has a carboxyl group, an acyl halide group, and an aryloxycarbonyl group, more preferably has a carboxyl group and an acyl halide group, and still more preferably has a carboxyl group, an acid chloride group, and an acid bromide group.

Examples of the 3 rd aromatic ring having 3 to 30 carbon atoms include monocyclic aromatic rings, condensed ring aromatic rings, ring-assembled aromatic rings, and aromatic rings connected via an alkylene group. Examples of the monocyclic aromatic ring, the fused ring aromatic ring, the ring-aggregated aromatic ring, and the aromatic ring connected via an alkylene group include those similar to the 1 st aromatic ring and the 2 nd aromatic ring.

The 3 rd aromatic ring having 3 to 30 carbon atoms in the 3 rd aromatic compound and the like may have a substituent. In this case, examples of the "substituent for the 3 rd aromatic ring" include the same ones as those mentioned above for the "substituent for the 1 st aromatic ring".

Examples of the 3 rd aromatic compound and the like include compounds represented by the following chemical formulas (6-1) to (6-15).

In the above chemical formulae (6-1) to (6-15), R¹Is a substituent containing a polymerizable unsaturated bond. In this case, the substituent containing the polymerizable unsaturated bond is the same as described above. In addition, R²Hydroxyl, halogen atom, alkoxy and aryloxy. P is an integer of 0 or 1 or more, preferably 0 or 1 to 3, more preferably 0 or 1, and still more preferably 0. q is 2 or 3. When p and q are 2 or more, the bonding position on the aromatic ring is arbitrary, and for example, may be performed on any ring of the naphthalene ring of the formula (6-5) or the hetero ring of the formula (6-15)The substitution is represented by the formula (6-7) or the like, wherein the number of the substituents in 1 molecule is p and q, and the substitution may be carried out on any ring of the benzene rings present in 1 molecule.

More specific examples of the 3 rd aromatic compound include benzenedicarboxylic acids such as isophthalic acid, terephthalic acid, 5-allylisophthalic acid, and 2-allylterephthalic acid; benzene tricarboxylic acids such as trimellitic acid and 5-allyl trimellitic acid; naphthalenedicarboxylic acids such as naphthalene-1, 5-dicarboxylic acid, naphthalene-2, 3-dicarboxylic acid, naphthalene-2, 6-dicarboxylic acid, naphthalene-2, 7-dicarboxylic acid, 3-allylnaphthalene-1, 4-dicarboxylic acid, and 3, 7-diallylnaphthalene-1, 4-dicarboxylic acid; pyridine tricarboxylic acids such as 2,4, 5-pyridine tricarboxylic acid; triazine carboxylic acids such as 1,3, 5-triazine-2, 4, 6-tricarboxylic acid; and acid halides and esters thereof. Among these, benzene dicarboxylic acid and benzene tricarboxylic acid are preferable, isophthalic acid, terephthalic acid, isophthaloyl chloride, terephthaloyl chloride, 1,3, 5-benzenetricarboxylic acid, 1,3, 5-benzenetricarbonyl trichloride are more preferable, and isophthaloyl chloride, terephthaloyl chloride, and 1,3, 5-benzenetricarbonyl trichloride are still more preferable.

Among the above, the 3 rd aromatic compound and the like in which the aromatic ring is a monocyclic aromatic ring and the 3 rd aromatic compound and the like in which the aromatic ring is a condensed ring aromatic ring are preferable, and the benzene dicarboxylic acid, the benzene tricarboxylic acid, the naphthalene dicarboxylic acid, and acid halides thereof are preferable, the benzene dicarboxylic acid, the naphthalene dicarboxylic acid, and acid halides thereof are more preferable, and the isophthalic acid, the terephthalic acid, the naphthalene-1, 5-dicarboxylic acid, the naphthalene-2, 3-dicarboxylic acid, the naphthalene-2, 6-dicarboxylic acid, the naphthalene-2, 7-dicarboxylic acid, and acid halides thereof are further preferable.

The above-mentioned 3 rd aromatic compound and the like may be used alone or in combination of two or more.

The 4 th aromatic compound, its acid halide and/or its ester is an aromatic compound having 1 carboxyl group, or a derivative thereof, specifically an acid halide or an ester (in the present specification, the 4 th aromatic compound, its acid halide and/or its ester may be collectively referred to as "the 4 th aromatic compound and the like"). The 4 th aromatic compound and the like have 1 carboxyl group and the like, and thus have a function of stopping the esterification reaction.

Examples of the 4 th aromatic compound include compounds having 1 carboxyl group or the like on a substituted or unsubstituted 4 th aromatic ring having 3 to 30 carbon atoms.

Examples of the "carboxyl group and the like" include those similar to the "carboxyl group and the like" described above.

Examples of the 4 th aromatic ring having 3 to 30 carbon atoms include monocyclic aromatic rings, condensed ring aromatic rings, ring-assembled aromatic rings, and aromatic rings connected via an alkylene group. Examples of the monocyclic aromatic ring, the fused ring aromatic ring, the ring-aggregated aromatic ring, and the aromatic ring connected via an alkylene group include those similar to the 1 st aromatic ring, the 2 nd aromatic ring, and the 3 rd aromatic ring.

The 4 th aromatic ring having 3 to 30 carbon atoms in the 4 th aromatic compound and the like may have a substituent. In this case, examples of the "substituent for the 4 th aromatic ring" include the same ones as those mentioned above for the "substituent for the 1 st aromatic ring".

Examples of the 4 th aromatic compound include compounds represented by the following chemical formulas (7-1) to (7-15).

In the above chemical formulae (7-1) to (7-15), R¹Is a substituent containing a polymerizable unsaturated bond. In this case, the substituent containing the polymerizable unsaturated bond is the same as described above. In addition, R²Hydroxyl, halogen atom, alkoxy and aryloxy. P is an integer of 0 or 1 or more, preferably 0 or 1 to 3, more preferably 0 or 1, and still more preferably 0. q is 1. The position of the substituent on the aromatic ring in the above chemical formula is arbitrary, and for example, the substituent may be substituted on any ring of the naphthalene ring of chemical formula (7-5) or the hetero ring of chemical formula (7-15), and in chemical formula (7-7), it is shown that the substituent may be substituted on any ring of the benzene ring existing in 1 molecule, and the number of the substituents in 1 molecule is p and q.

More specific examples of the 4 th aromatic compound include benzoic acid, benzyl chloride, naphthalene carboxylic acid, and naphthoyl chloride.

[ constitution of the polymerizable unsaturated bond-containing aromatic ester Compound (A) ]

At least 1 of the aromatic compound having a phenolic hydroxyl group, the aromatic compound having a carboxyl group, and the like has a substituent having a polymerizable unsaturated bond having 2 to 30 carbon atoms. That is, both of the aromatic compound having a phenolic hydroxyl group and the aromatic compound having a carboxyl group and the like may have a substituent having a polymerizable unsaturated bond, only the aromatic compound having a phenolic hydroxyl group may have a substituent having a polymerizable unsaturated bond, or only the aromatic compound having a carboxyl group and the like may have a substituent having a polymerizable unsaturated bond. In addition, when an aromatic compound having 2 or more phenolic hydroxyl groups, an aromatic compound having 2 or more carboxyl groups, or the like is used, only a part of the aromatic compound may have a substituent having a polymerizable unsaturated bond.

In one embodiment, at least the 2 nd aromatic compound preferably has a substituent having a polymerizable unsaturated bond. As described above, the structure derived from the 2 nd aromatic compound is located at the molecular terminal of the polymerizable unsaturated bond-containing aromatic ester compound (a). As a result, the substituent containing the polymerizable unsaturated bond, which the 2 nd aromatic compound has, remains arranged at the molecular end of the aromatic ester compound (a). In this case, the obtained acid group-containing (meth) acrylate resin composition is preferable because it can form a cured product having high sensitivity, excellent heat resistance, and excellent dielectric characteristics.

The polymerizable unsaturated bond-containing aromatic ester compound (a) is a reaction product of a compound having a phenolic hydroxyl group and an aromatic compound having a carboxyl group and the like as described above, and may include various compounds such as the aromatic compounds of the above 1 to 4, but in view of having a function of stopping the esterification reaction, it is necessary to include either one of the 2 nd aromatic compound and the 4 th aromatic compound, or both of them. The composition of the polymerizable unsaturated bond-containing aromatic ester compound (a) can be controlled by appropriately changing the amount of the aromatic compound or the like of the 1 st to 4 th groups, the reaction conditions, and the like.

In one embodiment, examples of the polymerizable unsaturated bond-containing aromatic ester compound (a) include: a polymerizable unsaturated bond-containing aromatic ester compound which is a reaction product of a1 st aromatic compound and a 4 th aromatic compound or the like; a polymerizable unsaturated bond-containing aromatic ester compound which is a reaction product of a1 st aromatic compound, a2 nd aromatic compound, a 3 rd aromatic compound, or the like; a polymerizable unsaturated bond-containing aromatic ester compound which is a reaction product of a1 st aromatic compound, a 3 rd aromatic compound, a 4 th aromatic compound, or the like; a polymerizable unsaturated bond-containing aromatic ester compound which is a reaction product of a1 st aromatic compound, a2 nd aromatic compound, a 3 rd aromatic compound, or the like with a 4 th aromatic compound or the like; an aromatic compound which is a reaction product of the 2 nd aromatic compound and the 3 rd aromatic compound; and a polymerizable unsaturated bond-containing aromatic compound which is a reaction product of the 2 nd aromatic compound and the 4 th aromatic compound.

The polymerizable unsaturated bond-containing aromatic ester compound (a) of the present embodiment basically has no hydroxyl group in the molecule of the obtained resin. However, the reaction product may be a by-product containing a hydroxyl group, as long as the effect of the present invention is not impaired.

In one embodiment, the polymerizable unsaturated bond-containing aromatic ester compound (a) includes a compound represented by the following chemical formula (8).

In the above chemical formula (8), Ar¹Is a structure derived from an aromatic compound of the 1 st group, Ar²Is a structure derived from a2 nd aromatic compound, Ar³Is derived from the 3 rd aromatic compound. In addition, n is an integer of 0 to 10. When the polymerizable unsaturated bond-containing aromatic ester compound (a) is an oligomer or a polymer, n represents an average value thereof.

That is, in the above chemical formula (8), Ar¹Each of which is independently a substituted or unsubstituted aromatic ring 1 having 3 to 30 carbon atoms, or a compound having a structure in which aromatic rings 1 are linked via a linking group and 2 or more hydrogen atoms are removed.

In the above chemical formula (8), Ar²Each independently includes a substituted or unsubstituted aromatic ring 2 having 3 to 30 carbon atoms from which 1 hydrogen atom is removed.

In the above chemical formula (8), Ar³There may be mentioned those obtained by removing 2 or more hydrogen atoms from a 3 rd aromatic ring having 3 to 30 carbon atoms which may be substituted or unsubstituted.

In addition, Ar is¹、Ar²And Ar³At least 1 of the above groups may have a substituent containing a polymerizable unsaturated bond having 2 to 30 carbon atoms.

In this case, when the 1 st aromatic compound has 3 or more phenolic hydroxyl groups, Ar¹It may have a branched structure.

When the 3 rd aromatic compound has 3 or more carboxyl groups, Ar may have a branched structure.

In one embodiment, the polymerizable unsaturated bond-containing aromatic ester compound (a) includes a compound represented by the following chemical formula (9).

In the above chemical formula (9), Ar¹Is a structure derived from an aromatic compound of the 1 st group, Ar²Is a structure derived from a2 nd aromatic compound, Ar³Is a structure derived from a 3 rd aromatic compound, Ar⁴Is derived from the structure of the 4 th aromatic compound. In addition, n is an integer of 0 to 10. When the polymerizable unsaturated bond-containing aromatic ester compound (a) is an oligomer or a polymer, n represents an average value thereof.

That is, in the above chemical formula (9), Ar¹Can be separatedIndependently, the aromatic ring is obtained by removing 2 or more hydrogen atoms from a1 st aromatic ring having 3 to 30 carbon atoms which is substituted or unsubstituted, or by removing 2 or more hydrogen atoms from a substance having a structure in which the 1 st aromatic ring is linked through a linking group.

In the above chemical formula (9), Ar²Each independently includes a substituted or unsubstituted aromatic ring 2 having 3 to 30 carbon atoms from which 1 hydrogen atom is removed.

In the above chemical formula (9), Ar³There may be mentioned those obtained by removing 2 or more hydrogen atoms from a 3 rd aromatic ring having 3 to 30 carbon atoms which may be substituted or unsubstituted.

In the above chemical formula (9), Ar⁴Examples thereof include those obtained by removing 1 hydrogen atom from a substituted or unsubstituted aromatic ring 4 having 3 to 30 carbon atoms.

In addition, Ar is¹、Ar²、Ar³And Ar⁴At least 1 of the above groups may have a substituent containing a polymerizable unsaturated bond having 2 to 30 carbon atoms.

When the 3 rd aromatic compound has 3 or more carboxyl groups, Ar is³It may have a branched structure.

In one embodiment, the polymerizable unsaturated bond-containing aromatic ester compound (a) includes a compound represented by the following chemical formula (10).

In the above chemical formula (10), Ar¹Is a structure derived from an aromatic compound of the 1 st group, Ar³Is a structure derived from a 3 rd aromatic compound, Ar⁴Is derived from the structure of the 4 th aromatic compound. In addition, n is an integer of 0 to 10. When the polymerizable unsaturated bond-containing aromatic ester compound (a) is an oligomer or a polymer, n represents an average value thereof.

That is, in the above chemical formula (10), Ar¹Each of which is independently a substituted or unsubstituted aromatic ring 1 having 3 to 30 carbon atoms, or a1 st aromatic ring linked through a linking group, wherein 2 or more hydrogen atoms are removed.

In the above chemical formula (10), Ar³There may be mentioned those obtained by removing 2 or more hydrogen atoms from a 3 rd aromatic ring having 3 to 30 carbon atoms which may be substituted or unsubstituted.

In the above chemical formula (10), Ar⁴Examples thereof include those obtained by removing 1 hydrogen atom from a substituted or unsubstituted aromatic ring 4 having 3 to 30 carbon atoms.

In addition, Ar is¹、Ar³And Ar⁴At least 1 of the above groups may have a substituent containing a polymerizable unsaturated bond having 2 to 30 carbon atoms.

In one embodiment, examples of the compound contained in the polymerizable unsaturated bond-containing aromatic ester compound (A) include compounds represented by the following chemical formulas (11-1) to (11-10).

In the above chemical formulas (11-1) to (11-10), s is an integer of 0 to 10, preferably an integer of 0 to 5, and r is an integer of 1 to 10. In this case, when the compounds represented by the chemical formulas (11-1) to (11-10) are oligomers or polymers, s and r represent average values thereof. The wavy line in the formula is Ar³And Ar¹And/or Ar²The compound (4) is reacted to obtain the structure.

In one embodiment, the polymerizable unsaturated bond-containing aromatic ester compound (a) includes, for example, a polymerizable unsaturated bond-containing aromatic ester compound (a-1) represented by the following chemical formula (a1) and a polymerizable unsaturated bond-containing aromatic ester compound (a-2) represented by the following chemical formula (a 2).

[ in the formula, Ar⁵Each independently being a substituted or unsubstituted aromatic ring radical, Ar⁶Each independently is a substituted or unsubstituted 2 nd aromatic ring group, Ar⁵And Ar mentioned above⁶At least 1 of them has a substituent having a polymerizable unsaturated bond. n is an integer of 1 to 3. Angle (c)

The polymerizable unsaturated bond-containing aromatic ester compound (A-1) is represented by the chemical formula (a 1).

Ar in the above chemical formula (a1)⁵Is a substituted or unsubstituted 1 st aromatic ring group. As described later, since n in the formula (a1) is an integer of 1 to 3, 1 to 3 of hydrogen atoms in the aromatic ring constituting the 1 st aromatic ring group are substituted with a "-C (O) OAr⁶"substitution".

Examples of the 1 st aromatic ring group include those obtained by removing 2 or 3 hydrogen atoms from a monocyclic aromatic compound such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, piperazinone, pyrazine, or triazine; and those obtained by removing 2 or 3 hydrogen atoms from aromatic compounds such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine and the like fused ring aromatic compounds. In addition, a plurality of these aromatic compounds may be combined, and examples thereof include compounds obtained by removing 2 to 3 hydrogen atoms from a ring-assembly aromatic compound such as biphenyl, binaphthyl, bipyridyl, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl; from diphenylmethane, diphenylethane, 1-diphenylethane, diphenyl,2, 2-diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenylpyridinemethane, fluorene, diphenylcyclopentane and the like, in which 2 or 3 hydrogen atoms are removed from an aromatic compound bonded via an alkylene group. Among these, Ar is an acid group-containing (meth) acrylate resin composition that can form a cured product having high sensitivity, excellent heat resistance, and excellent dielectric properties⁵A substituted or unsubstituted benzene ring structure or a naphthalene ring structure is preferred, and a substituted or unsubstituted benzene ring structure is more preferred.

Ar⁵The 1 st aromatic ring group may have a substituent, and in this case, the substituent of the 1 st aromatic ring group means a group in which at least 1 of hydrogen atoms of the aromatic ring constituting the 1 st aromatic ring group is substituted. Examples of the "substituent for the 1 st aromatic ring group" include an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a halogen atom, and the like.

In one embodiment of the present invention, Ar is⁵May have a substituent having a polymerizable unsaturated bond. Specific examples of the substituent having a polymerizable unsaturated bond include an alkenyl group and an alkynyl group.

The substituent having a polymerizable unsaturated bond may further have a substituent. The substituent means a group substituted with at least 1 of hydrogen atoms constituting the substituent having a polymerizable unsaturated bond. Examples of the substituent include an alkoxycarbonyl group, an alkylcarbonyloxy group, a halogen atom and the like. In this case, examples of the alkoxycarbonyl group, the alkylcarbonyloxy group and the halogen atom include those described above.

Among these, the substituent containing a polymerizable unsaturated bond is preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, more preferably a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, still more preferably a substituted or unsubstituted alkenyl group having 2 to 5 carbon atoms, particularly preferably a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a 1-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a1, 3-butadienyl group, and most preferably an allyl group, a propenyl group, an isopropenyl group, or a 1-propenyl group.

As the aforementioned Ar⁵Preferable examples of the structure of (B) include the following formulae (12-1) to (12-17).

In the above formulas (12-1) to (12-17), "" Ar "represents a group with" -C (O) OAr⁶"bonding position". In addition, "-" may be bonded to any position of the aromatic ring.

Among these, the preferred are the formulae (12-1) to (12-11), the more preferred are the formulae (12-1), (12-2), (12-6), (12-7) and (12-9), and the still more preferred are the formulae (12-1), (12-2), (12-6) and (12-7). Further, the formulae (12-1) and (12-2) are preferable from the viewpoint of high processability and low viscosity of the polymerizable unsaturated bond-containing aromatic ester compound (A), and the formulae (12-6) and (12-7) are preferable from the viewpoint that the resulting acid group-containing (meth) acrylate resin composition can form a cured product having high sensitivity, excellent heat resistance and excellent dielectric properties.

At least 1 of the hydrogen atoms of the aromatic rings of the formulae (12-1) to (12-17) may be substituted with a group having a polymerizable unsaturated bond.

Ar in the above chemical formula (a1)⁶Is a substituted or unsubstituted 2 nd aromatic ring group. As is apparent from the description of the above chemical formula (10), 1 of the hydrogen atoms of the aromatic ring constituting the 2 nd aromatic ring group is substituted with-OC (O) Ar⁵”。

Examples of the 2 nd aromatic ring group include those obtained by removing 1 hydrogen atom from a monocyclic aromatic compound such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, piperazinone, pyrazine, or triazine; and those obtained by removing 1 hydrogen atom from aromatic compounds such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine. In addition, a plurality of these aromatic compounds may be combined, and examples thereof include compounds obtained by removing 1 hydrogen atom from a ring-assembly aromatic compound such as biphenyl, binaphthyl, bipyridyl, bithiophene, phenylpyridine, phenylthiophene, terphenyl, bithiophene, and quaterphenyl; from diphenylAnd (3) aromatic compounds bonded through an alkylene group such as methane, diphenylethane, 1-diphenylethane, 2-diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenylpyridinemethane, fluorene, and diphenylcyclopentane, from which 1 hydrogen atom has been removed. Among these, Ar is an acid group-containing (meth) acrylate resin composition that can form a cured product having high sensitivity, excellent heat resistance, and excellent dielectric properties⁶A substituted or unsubstituted benzene ring structure or naphthalene ring structure is preferred.

Ar⁶The 2 nd aromatic ring group may have a substituent, and in this case, the substituent of the 2 nd aromatic ring group is a group in which at least 1 of hydrogen atoms of the aromatic ring constituting the 2 nd aromatic ring group is substituted. Examples of the "substituent for the 2 nd aromatic ring group" include an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a halogen atom, and the like. In this case, examples of the alkyl group, alkoxy group, alkoxycarbonyl group, alkylcarbonyloxy group and halogen atom include those described above.

In one embodiment of the present invention, Ar is⁶The substituent may have a polymerizable unsaturated bond-containing substituent such as the above alkenyl group and alkynyl group. The polymerizable unsaturated bond-containing substituent may be present alone or in combination of two or more.

As the aforementioned Ar⁶Preferable examples of (3) include the following formulae (13-1) to (13-17).

In the above formulae (13-1) to (13-17), "" Ar "represents a group with" -OC (O) Ar⁵"bonding position". In addition, "-" may be bonded to any position of the aromatic ring.

Among these, preferred are the formulae (13-1) to (13-11), more preferred are the formulae (13-1), (13-6) and (13-9), and still more preferred are the formulae (13-1) and (13-6).

At least 1 of the hydrogen atoms in the aromatic rings of the formulae (13-1) to (13-17) may be substituted with a polymerizable unsaturated bond-containing group.

By one embodiment, Ar is more preferred⁵Is represented by the above formula (12-1), (12-2), (12-6), (12-7), (12-9), Ar⁶Is the above-mentioned formula (13-1), (13-6) or (13-9), and Ar is more preferred⁵Is represented by the above formula (12-1), (12-2), (12-6), (12-7), Ar⁶As the above-mentioned formulae (13-1) and (13-6), Ar is particularly preferred⁵Is represented by the formula (12-1) and Ar⁶The above-mentioned formulae (13-1) and (13-6).

In the above chemical formulas (a1) and (a2), Ar is⁵And Ar mentioned above⁶At least 1 of them has a substituent having a polymerizable unsaturated bond. In this case, Ar alone may be used⁵Having a substituent containing a polymerizable unsaturated bond, may be Ar alone⁶Having a substituent containing a polymerizable unsaturated bond, and may further have Ar⁵And Ar⁶Each having a substituent having a polymerizable unsaturated bond.

In one embodiment, in the chemical formula (a1), Ar is preferred⁶At least 1 of them has a substituent having a polymerizable unsaturated bond, and more preferably all Ar⁶Each having a substituent containing a polymerizable unsaturated bond, and further preferably Ar⁵Having no substituent containing polymerizable unsaturated bond and all Ar⁶Each having a substituent having a polymerizable unsaturated bond. The substituent containing polymerizable unsaturated bond being present in Ar⁶In the case of (iii), an acid group-containing (meth) acrylate resin composition capable of forming a cured product having high sensitivity and an excellent balance between heat resistance and dielectric characteristics is preferably obtained.

In one embodiment, in the chemical formula (a2), Ar is preferably Ar⁵At least 1 of them has a substituent having a polymerizable unsaturated bond, and more preferably all Ar⁵Each having a substituent containing a polymerizable unsaturated bond, and further preferably Ar⁶Having no substituent containing polymerizable unsaturated bond and all Ar⁵Each having a substituent having a polymerizable unsaturated bond. The substituent containing polymerizable unsaturated bond being present in Ar⁵In the case of (3), a cured product having high sensitivity and an excellent balance between heat resistance and dielectric characteristics can be obtainedThe acid group-containing (meth) acrylate resin composition is preferred.

In the above chemical formulas (a1) and (a2), n is an integer of 1 to 3. That is, the polymerizable unsaturated bond-containing aromatic ester compound (a-1) has 1 to 3 ester bonds to which 2 aromatic rings are bonded.

From the above, as a more preferable embodiment of the polymerizable unsaturated bond-containing aromatic ester compound (A-1) represented by the above chemical formula (a1), a compound represented by the following chemical formula (a1-1) or (a1-2) can be mentioned.

[ in the formula, R¹Is a substituent containing a polymerizable unsaturated bond. R²Each independently represents any of an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, and a halogen atom. h is an integer of 1 to 3, i is each independently an integer of 1 or more, j is each independently an integer of 0 or 1 or more, and i + j is an integer of 5 or less. k is an integer of 1 to 3, l is each independently an integer of 1 or more, m is each independently an integer of 0 or 1 or more, and l + m is an integer of 7 or less. i. When j, l and m are integers of 2 or more, a plurality of R¹Or R²May be the same as or different from each other. R in the formula (a1-2)¹、R²Substitution may be made at any carbon atom on the naphthalene ring. Angle (c)

In the above formula (a1-1), R is¹As mentioned above, the particularly preferred group of (A) includes allyl, propenyl, isopropenyl and 1-propenyl. i is preferably 1 or 2, more preferably 1.

In the above formula (a1-2), R is¹As mentioned above, the particularly preferred group of (A) includes allyl, propenyl, isopropenyl and 1-propenyl. l is preferably 1 or 2, more preferably 1.

The specific structure of the polymerizable unsaturated bond-containing aromatic ester compound (A-1) represented by the above chemical formula (a1) is not particularly limited, and examples thereof include compounds represented by the following chemical formulas (14-1) to (14-47).

Of the above chemical formulae (14-1) to (14-44), the chemical formulae (14-1) to (14-39) are preferable, the chemical formulae (14-1) to (14-3), (14-10) to (14-13) and (14-18) to (14-39) are more preferable, the chemical formulae (14-1) to (14-3), (14-12), (14-13), (14-19) to (14-21), (14-23) to (14-26), (14-29), (14-30) and (14-32) to (14-39) are even more preferable, particularly preferred are the chemical formulae (14-1), (14-2), (14-12), (14-13), (14-26), (14-32) and (14-37).

The method for producing the polymerizable unsaturated bond-containing aromatic ester compound (a-1) is not particularly limited, and can be produced by an appropriately known method.

The method for producing the polymerizable unsaturated bond-containing aromatic ester compound (A-1) includes, for example, a method of reacting the 2 nd aromatic compound with the 3 rd aromatic compound and the like.

The polymerizable unsaturated bond-containing aromatic ester compound (A-2) is a compound represented by the chemical formula (a 2).

Ar in the above chemical formula (a2)⁵Is a substituted or unsubstituted 1 st aromatic ring group. As described later, since n in the formula (a2) is an integer of 1 to 3, 1 of hydrogen atoms in the aromatic ring constituting the 1 st aromatic ring group is substituted with an-C (O) OAr group⁶"substitution".

As Ar in the aforementioned chemical formula (a2)⁵Examples thereof include "Ar in the above chemical formula (10)⁶The "1 st aromatic ring group" in "is the same.

Ar in the above chemical formula (a2)⁶To getA substituted or unsubstituted 2 nd aromatic ring group. As is apparent from the description of the above chemical formula (11), 1 to 3 of the hydrogen atoms of the aromatic ring constituting the 2 nd aromatic ring group are substituted with "-OC (O) Ar⁵"substitution".

As Ar in the aforementioned chemical formula (a2)⁶Examples thereof include Ar in the above "chemical formula (a1)⁶The "2 nd aromatic ring group" in "is the same.

In the chemical formula (a2), n is an integer of 1 to 3. That is, the polymerizable unsaturated bond-containing aromatic ester compound (a-2) has 1 to 3 ester bonds to which 2 aromatic rings are bonded.

From the above, as a more preferable embodiment of the polymerizable unsaturated bond-containing aromatic ester compound (A-2) represented by the chemical formula (a2), a compound represented by the following chemical formula (1-3) or (1-4) can be mentioned.

[ in the formula, R¹Is a substituent containing a polymerizable unsaturated bond. R²Each independently represents any of an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, and a halogen atom. h is an integer of 1 to 3, i is each independently an integer of 1 or more, j is each independently an integer of 0 or 1 or more, and i + j is an integer of 5 or less. i. When j is an integer of 2 or more, a plurality of R¹Or R²May be the same as or different from each other. Angle (c)

In the above formula (a2-1), R is¹As mentioned above, the particularly preferred group of (A) includes allyl, propenyl, isopropenyl and 1-propenyl. i is preferably 1 or 2, more preferably 1.

In the above formula (a2-2), R is¹As mentioned above, the particularly preferred group of (A) includes allyl, propenyl, isopropenyl and 1-propenyl. l is preferably 1 or 2, more preferably 1.

The specific structure of the polymerizable unsaturated bond-containing aromatic ester compound (A-2) represented by the above chemical formula (a2) is not particularly limited, and examples thereof include compounds represented by the following chemical formulas (15-1) to (15-3).

The method for producing the polymerizable unsaturated bond-containing aromatic ester compound (a-2) is not particularly limited, and can be produced by an appropriately known method.

The method for producing the polymerizable unsaturated bond-containing aromatic ester compound (A-2) includes, for example, a method of reacting the 1 st aromatic compound with the 4 th aromatic compound and the like.

The method for producing the polymerizable unsaturated bond-containing aromatic ester compound (a) is not particularly limited, and can be produced by an appropriately known method.

For example, in view of obtaining an acid group-containing (meth) acrylate resin composition that can form a cured product having high sensitivity, heat resistance, and excellent dielectric properties, the ratio of the number of moles of carboxyl groups in the aromatic compound having carboxyl groups to the number of moles of hydroxyl groups in the aromatic compound having phenolic hydroxyl groups (carboxyl groups and the like/hydroxyl groups) is preferably 0.3 to 3.

In the production of the polymerizable unsaturated bond-containing aromatic ester compound (a), the reaction conditions for the reaction between the aromatic compound having a phenolic hydroxyl group and the aromatic compound having a carboxyl group are not particularly limited, and an appropriately known method can be employed.

The pH during the reaction is not particularly limited, but is preferably 11 or more. In this case, acids such as hydrochloric acid, sulfuric acid, nitric acid, and acetic acid can be used for adjusting the pH; alkali such as sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium, etc.

The reaction temperature is also not particularly limited, but is preferably 20 to 100 ℃ and more preferably 40 to 80 ℃.

The reaction pressure is also not particularly limited, and normal pressure is more preferable.

The reaction time is also not particularly limited, but is preferably 0.5 to 10 hours, more preferably 1 to 5 hours.

The acid group-containing (meth) acrylate resin (B) will be described.

The acid group-containing (meth) acrylate resin (B) is not particularly limited as long as it has an acid group and a (meth) acryloyl group, and various resins can be used without particular limitation to the specific structure, molecular weight, and the like.

Examples of the acid group contained in the acid group-containing (meth) acrylate resin (B) include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, a carboxyl group is preferable from the viewpoint of exhibiting excellent alkali developability.

Examples of the acid group-containing (meth) acrylate resin (B) include [ 1] an epoxy resin (B-1) having an acid group and a (meth) acryloyl group, [ 2] an acrylamide resin (B-2) having an acid group and a (meth) acryloyl group, [ 3 ] an amide imide resin (B-3) having an acid group and a (meth) acryloyl group, [4 ] an acrylic resin (B-4) having an acid group and a (meth) acryloyl group, and [5 ] a urethane resin (B-5) having an acid group and a (meth) acryloyl group.

The epoxy resin (B-1) having an acid group and a (meth) acryloyl group will be described.

Examples of the epoxy resin (B-1) having an acid group and a (meth) acryloyl group include those obtained by using, as essential reaction raw materials, an epoxy resin (B1-1), an unsaturated monocarboxylic acid (B1-2), and a polycarboxylic acid anhydride (B1-3).

The specific structure of the epoxy resin (b1-1) is not particularly limited as long as it has a plurality of epoxy groups in the resin.

Examples of the epoxy resin (b1-1) include bisphenol type epoxy resins, hydrogenated bisphenol type epoxy resins, phenyl ether type epoxy resins, naphthyl ether type epoxy resins, biphenyl type epoxy resins, hydrogenated biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol novolac type epoxy resins, naphthol novolac type epoxy resins, naphthol-phenol novolak type epoxy resin, naphthol-cresol novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, and the like.

The unsaturated monocarboxylic acid (b1-2) is a compound having a (meth) acryloyl group and a carboxyl group in one molecule, and examples thereof include acrylic acid and methacrylic acid. Further, an esterified product, an acid halide, an acid anhydride or the like of the unsaturated monocarboxylic acid (b1-2) may be used. These unsaturated monocarboxylic acids (b1-2) may be used alone or in combination of two or more.

Examples of the esterified compound of the unsaturated monocarboxylic acid (b1-2) include alkyl (meth) acrylate compounds such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; hydroxyl group-containing (meth) acrylate compounds such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate; nitrogen-containing (meth) acrylate compounds such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; other (meth) acrylate compounds such as glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, morpholinyl (meth) acrylate, isobornyl (meth) acrylate, and cyclohexyl (meth) acrylate.

Examples of the acid halide of the unsaturated monocarboxylic acid (b1-2) include (meth) acryloyl chloride.

Examples of the acid anhydride of the unsaturated monocarboxylic acid (b1-2) include (meth) acrylic anhydride and the like.

The polyvalent carboxylic acid anhydride (b1-3) may be used as it is, as long as it is an anhydride of a compound having 2 or more carboxyl groups in one molecule. Examples of the polyvalent carboxylic acid anhydride include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3, 4-butanetetracarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo [2.2.1] heptane-2, 3-dicarboxylic acid, methylbicyclo [2.2.1] heptane-2, 3-dicarboxylic acid, 4- (2, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic acid, phthalic acid, trimellitic acid, benzenetetracarboxylic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, Acid anhydrides of dicarboxylic acid compounds such as biphenyltricarboxylic acid, biphenyltetracarboxylic acid and benzophenonetetracarboxylic acid.

The method for producing the epoxy resin (B-1) having an acid group and a (meth) acryloyl group is not particularly limited as long as the epoxy resin (B1-1), the unsaturated monocarboxylic acid (B1-2), and the polycarboxylic acid anhydride (B1-3) are essential reaction raw materials, and any method may be used. For example, the catalyst may be produced by a method in which all the reaction materials are reacted at once, or may be produced by a method in which the reaction materials are reacted sequentially. Among them, a method of reacting the epoxy resin (b1-1) with the unsaturated monocarboxylic acid (b1-2) and then reacting the polycarboxylic anhydride (b1-3) is preferable from the viewpoint of easy control of the reaction. This reaction can be carried out, for example, by the following method: a method comprising reacting an epoxy resin (b1-1) and an unsaturated monocarboxylic acid (b1-2) at a temperature of 100 to 150 ℃ in the presence of an esterification catalyst, and then adding a polycarboxylic anhydride (b1-3) to the reaction system to react at a temperature of 80 to 120 ℃.

The reaction ratio of the epoxy resin (b1-1) and the unsaturated monocarboxylic acid (b1-2) is preferably in the range of 0.9 to 1.1 mol of the unsaturated monocarboxylic acid (b1-2) relative to 1 mol of the epoxy group in the epoxy resin (b 1-1). The reaction ratio of the polycarboxylic acid anhydride (b1-3) is preferably in the range of 0.2 to 1.0mol based on 1 mol of epoxy groups in the epoxy resin (b 1-1).

Examples of the esterification catalyst include phosphorus compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine, amine compounds such as triethylamine, tributylamine, and dimethylbenzylamine, and imidazole compounds such as 2-methylimidazole, 2-heptylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-isobutyl-2-methylimidazole. These reaction catalysts may be used alone or in combination of two or more.

The amount of the reaction catalyst added is preferably in the range of 0.001 to 5 parts by mass relative to 100 parts by mass of the total of the reaction raw materials.

The reaction of the epoxy resin (b1-1), the unsaturated monocarboxylic acid (b1-2), and the polycarboxylic acid anhydride (b1-3) may be carried out in an organic solvent, 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 dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, solvent naphtha and the like; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether, and the like; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and the like. These organic solvents may be used alone or in combination of two or more. In addition, from the viewpoint of good reaction efficiency, 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.

The acid value of the epoxy resin (B-1) having an acid group and a (meth) acryloyl group is preferably in the range of 30 to 150mgKOH/g, and more preferably in the range of 40 to 120mgKOH/g, from the viewpoint that an acid group-containing (meth) acrylate resin composition capable of forming a cured product having high sensitivity, heat resistance, and excellent dielectric properties can be obtained. The acid value of the epoxy resin (B-1) having an acid group and a (meth) acryloyl group in the present invention is a value measured by a neutralization titration method according to JIS K0070 (1992).

Next, the acrylamide resin (B-2) having an acid group and a (meth) acryloyl group will be described.

The acrylamide resin (B-2) having an acid group and a (meth) acryloyl group may be obtained, for example, from a phenolic hydroxyl group-containing resin (B2-1), a cyclic carbonate compound (B2-2a) or a cyclic ether compound (B2-2B), an unsaturated monocarboxylic acid (B2-3a) and/or an N-alkoxyalkyl (meth) acrylamide compound (B2-3B), and a polycarboxylic acid anhydride (B2-4) as essential reaction raw materials.

The phenolic hydroxyl group-containing resin (b2-1) is a resin having 2 or more phenolic hydroxyl groups in the molecule, and examples thereof include a novolak-type phenolic resin using 1 or 2 or more of an aromatic polyhydroxy compound and a compound having 1 phenolic hydroxyl group in the molecule as reaction raw materials, and a reaction product using the compound having 1 phenolic hydroxyl group and a compound (x) represented by any one of the following structural formulae (x-1) to (x-5) as essential reaction raw materials.

(wherein h is 0 or 1. R)¹Each independently represents an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group or an aralkyl group, and i is 0 or an integer of 1 to 4. Z is any of vinyl, halomethyl, hydroxymethyl, and alkoxymethyl. Y is any one of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, and a carbonyl group. j is an integer of 1 to 4. )

Examples of the aromatic polyhydroxy compound include dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxyanthracene, trihydroxyanthracene, tetrahydroxyanthracene, biphenol, tetrahydroxybiphenyl, and bisphenol, and compounds having 1 or more substituents on the aromatic nucleus thereof. Examples of the substituent on the aromatic nucleus include aliphatic hydrocarbon groups such as methyl, ethyl, vinyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, and nonyl groups; alkoxy groups such as methoxy, ethoxy, propoxy and butoxy; halogen atoms such as fluorine atom, chlorine atom, and bromine atom; phenyl group, naphthyl group, anthracenyl group, and aryl group in which the aromatic nucleus thereof is substituted with the aliphatic hydrocarbon group, the alkoxy group, the halogen atom, or the like; phenoxy group, naphthoxy group, and aryloxy group having the aromatic nucleus thereof substituted with the aliphatic hydrocarbon group, the alkoxy group, the halogen atom, or the like; benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, and aralkyl groups in which the aromatic nucleus thereof is substituted with the aliphatic hydrocarbon group, the alkoxy group, the halogen atom, and the like. These aromatic polyhydroxy compounds may be used alone, or two or more thereof may be used in combination. Among these, halogen-free compounds are preferable from the viewpoint that an acid group-containing (meth) acrylate resin having high insulation reliability can be obtained.

Examples of the novolak phenol resin include those obtained by reacting 1 or 2 or more compounds having 1 phenolic hydroxyl group in the molecule with an aldehyde compound in the presence of an acidic catalyst.

The compound having 1 phenolic hydroxyl group in the molecule may be any compound as long as it is an aromatic compound having 1 hydroxyl group on the aromatic nucleus, and examples thereof include phenol, a phenol compound having 1 or more substituents on the aromatic nucleus of phenol, naphthol, a naphthol compound having 1 or more substituents on the aromatic nucleus of naphthol, anthraphenol, an anthraphenol compound having 1 or more substituents on the aromatic nucleus of anthraphenol, and the like. Examples of the substituent on the aromatic nucleus include an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, and an aralkyl group, and specific examples thereof are as described above. These compounds having 1 phenolic hydroxyl group may be used alone or in combination of two or more.

Examples of the aldehyde compound include formaldehyde; alkyl aldehydes such as acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, and caproaldehyde; hydroxybenzaldehydes such as salicylaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2-hydroxy-4-methylbenzaldehyde, 2, 4-dihydroxybenzaldehyde, and 3, 4-dihydroxybenzaldehyde; benzaldehydes having both a hydroxyl group and an alkoxy group, such as 2-hydroxy-3-methoxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, and 4-hydroxy-3, 5-dimethoxybenzaldehyde; alkoxybenzaldehydes such as methoxybenzaldehyde and ethoxybenzaldehyde; hydroxy naphthaldehyde such as 1-hydroxy-2-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 6-hydroxy-2-naphthaldehyde and the like; halogenated benzaldehydes such as bromobenzaldehyde.

Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid and oxalic acid, lewis acids such as boron trifluoride, anhydrous aluminum chloride and zinc chloride. These acidic catalysts may be used alone or in combination of two or more.

The reaction product of the compound having 1 phenolic hydroxyl group and the compound (x) as essential reaction raw materials can be obtained, for example, by heating and stirring the compound having 1 phenolic hydroxyl group in the molecule and the compound (x) in an acidic catalyst at a temperature of about 80 to 200 ℃. The reaction ratio of the compound having 1 phenolic hydroxyl group in the molecule to the compound (x) is preferably 0.5 to 5 mol based on 1 mol of the compound (x) and the compound having 1 phenolic hydroxyl group in the molecule.

The acidic catalyst is the same as described above.

Examples of the cyclic carbonate compound (b2-2a) 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. Among these, ethylene carbonate and propylene carbonate are preferable from the viewpoint that an acid group-containing (meth) acrylate resin composition capable of forming a cured product having high sensitivity, heat resistance, and excellent dielectric characteristics can be obtained.

Examples of the cyclic ether compound (b2-2b) include ethylene oxide, propylene oxide, and tetrahydrofuran. These cyclic ether compounds may be used alone or in combination of two or more. Among these, ethylene oxide and propylene oxide are preferable from the viewpoint that an acid group-containing (meth) acrylate resin composition capable of forming a cured product having high sensitivity, heat resistance and excellent dielectric characteristics can be obtained.

As the unsaturated monocarboxylic acid (b2-3a), those similar to the unsaturated monocarboxylic acid (b1-2) described above can be used.

Examples of the N-alkoxyalkyl (meth) acrylamide compound (b2-3b) include N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide, and N-butoxyethyl (meth) acrylamide. Among these, N-methoxymethyl (meth) acrylamide is preferable from the viewpoint that an acid group-containing (meth) acrylate resin composition capable of forming a cured product having high sensitivity and excellent heat resistance can be obtained. These N-alkoxyalkyl (meth) acrylamide compounds may be used alone or in combination of two or more.

As the polycarboxylic anhydride (b2-4), the same one as the above-mentioned polycarboxylic anhydride (b1-3) can be used.

In view of obtaining an acid group-containing (meth) acrylate resin composition capable of forming a cured product having high sensitivity, heat resistance, and excellent dielectric characteristics, when the N-alkoxyalkyl (meth) acrylamide compound (b2-3b) is used, the equivalent ratio [ (b2-3b)/(b2-4)) ] to the polyvalent carboxylic acid anhydride (b2-4)) is preferably in the range of 0.2 to 7, and more preferably in the range of 0.25 to 6.7.

The method for producing the acrylamide resin (B-2) having an acid group and a (meth) acryloyl group is not particularly limited, and any method may be used. For example, the catalyst may be produced by a method in which all the reaction materials are reacted at once, or may be produced by a method in which the reaction materials are reacted sequentially. Among them, from the viewpoint of easy control of the reaction, a method in which the phenolic hydroxyl group-containing resin (b2-1) is reacted with the cyclic carbonate compound (b2-2a) or the cyclic ether compound (b2-2b), the unsaturated monocarboxylic acid (b2-3a) and/or the N-alkoxyalkyl (meth) acrylamide compound (b2-3b) are reacted, and then the polycarboxylic anhydride (b2-4) is reacted is preferable. The reaction can be carried out, for example, as follows: a method comprising reacting the phenolic hydroxyl group-containing resin (b2-1) with the cyclic carbonate compound (b2-2a) or the cyclic ether compound (b2-2b) in the presence of a basic catalyst at a temperature of 100 to 200 ℃, reacting the unsaturated monocarboxylic acid (b2-3a) and/or the N-alkoxyalkyl (meth) acrylamide compound (b2-3b) in the presence of an acidic catalyst at a temperature of 80 to 140 ℃, adding the polycarboxylic anhydride (b2-4), and reacting the resulting mixture at a temperature of 80 to 140 ℃.

Examples of the basic catalyst include N-methylmorpholine, pyridine, 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN), 1, 4-diazabicyclo [2.2.2] octane (DABCO), tri-N-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2, 4-dimethylimidazole, 1, 4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (N-phenyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, Amine compounds such as tetramethylammonium hydroxide; quaternary ammonium salts such as trioctylmethylammonium chloride and trioctylmethylammonium acetate; phosphines such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphorus salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl (2-hydroxypropyl) phosphonium chloride, triphenylphosphonium chloride, benzylphosphonium chloride, and the like; organic tin compounds such as butyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, 1,3, 3-tetrabutyl-1, 3-dodecanoyldistannoxane, etc.; organic metal compounds such as zinc octylate and bismuth octylate; inorganic tin compounds such as tin octylate; inorganic metal compounds, and the like. These basic catalysts may be used alone or in combination of two or more.

The reaction of the phenolic hydroxyl group-containing resin (b2-1), the cyclic carbonate compound (b2-2a) or the cyclic ether compound (b2-2b), the unsaturated monocarboxylic acid (b2-3a) and/or the N-alkoxyalkyl (meth) acrylamide compound (b2-3b), and the polycarboxylic acid anhydride (b2-4) may be carried out in an organic solvent, if necessary.

The organic solvent may be the same as the above-mentioned organic solvent, and the organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent is preferably in the range of 10 to 500 parts by mass relative to 100 parts by mass of the total of the reaction raw materials, from the viewpoint of satisfactory reaction efficiency.

The specific structure of the acrylamide resin (B-2) having an acid group and a (meth) acryloyl group is not particularly limited as long as it is obtained from an essential reaction raw material comprising a phenolic hydroxyl group-containing resin (B2-1), a cyclic carbonate compound (B2-2a) or a cyclic ether compound (B2-2B), an unsaturated monocarboxylic acid (B2-3a) and/or an N-alkoxyalkyl (meth) acrylamide compound (B2-3B), and a polycarboxylic acid anhydride (B2-4), and the resulting acrylamide resin (B-2) having an acid group and a (meth) acryloyl group has, for example, a resin structure having a repeating structural unit comprising a structural site (I) represented by the following structural formula (a-1) and a structural site (II) represented by the following structural formula (a-2), A resin structure having a repeating structural unit of a structural moiety (III) represented by the following structural formula (a-3) and a structural moiety (IV) represented by the following structural formula (a-4).

[ in the formula, R²Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. R³Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a halogen atom, and n is 1 or 2. R⁴Each independently represents a methylene group or a junction represented by any one of the following structural formulae (x '-1) to (x' -5)Structural parts. R⁵、R⁶Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. In addition, R⁵And R⁶May also be linked to form a saturated or unsaturated ring. R⁷Is a hydrocarbon group having 1 to 12 carbon atoms. R⁸Is a hydrogen atom or a methyl group. x is the aforementioned R³The structural sites shown, or by means of R with a mark⁴A bonding site formed by connecting with a structural part (I) shown by a structural formula (a-1) or a structural part (II) shown by a structural formula (a-2).]

[ in the formula, R²Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. R³Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a halogen atom, and n is 1 or 2. R⁴Each independently represents a methylene group or a structural portion represented by any one of the following structural formulae (x '-1) to (x' -5). R⁵、R⁶Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. In addition, R⁵And R⁶May also be linked to form a saturated or unsaturated ring. R⁷Is a hydrocarbon group having 1 to 12 carbon atoms. R⁸Is a hydrogen atom or a methyl group. x is the aforementioned R³The structural sites shown, or by means of R with a mark⁴A bonding site connected to a structural part (III) represented by the structural formula (a-3) or a structural part (IV) represented by the structural formula (a-4).]

[ wherein h is 0 or 1. R⁹Each independently represents an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group or an aralkyl group, and i is 0 or an integer of 1 to 4. R¹⁰Is a hydrogen atom or a methyl group. W is the following structural formula (W-1) or (W-2). Y is any one of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, and a carbonyl group. j is 1 &4, or a pharmaceutically acceptable salt thereof.]

(in the formula, R¹¹Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. R¹²、R¹³Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. In addition, R¹²And R¹³May also be linked to form a saturated or unsaturated ring. R¹⁴Is a hydrocarbon group having 1 to 12 carbon atoms. R¹⁵Is a hydrogen atom or a methyl group. )

The acid value of the acrylamide resin (B-2) having an acid group and a (meth) acryloyl group is preferably in the range of 30 to 150mgKOH/g, and more preferably in the range of 40 to 120mgKOH/g, from the viewpoint that an acid group-containing (meth) acrylate resin composition capable of forming a cured product having high sensitivity, heat resistance, and excellent dielectric properties can be obtained. In the present invention, the acid value of the acid group-containing (meth) acrylate resin is a value measured by a neutralization titration method according to JIS K0070 (1992).

Next, the amide imide resin [ 3 ] having an acid group and a (meth) acryloyl group (B-3) will be described.

Examples of the amide imide resin (B-3) having an acid group and a (meth) acryloyl group include those obtained by using an amide imide resin (B3-1) having an acid group or an acid anhydride group and a hydroxyl group-containing (meth) acrylate compound (B3-2) as essential reaction raw materials.

The amide imide resin (b3-1) may have either only an acid group or an acid anhydride group, or both. From the viewpoint of reactivity with the hydroxyl group-containing (meth) acrylate compound (b3-2) and control of the reaction, those having an acid anhydride group are preferable, and those having both an acid group and an acid anhydride group are more preferable. The acid value of the amide imide resin (b3-1) is preferably in the range of 60 to 350mgKOH/g under neutral conditions, that is, under conditions in which the acid anhydride group is not ring-opened. On the other hand, the measured value under the conditions of ring-opening the acid anhydride group in the presence of water or the like is preferably in the range of 61 to 360 mgKOH/g.

The specific structure and production method of the amide imide resin (b3-1) are not particularly limited, and a general amide imide resin and the like can be widely used. Examples thereof include those obtained by using a polyisocyanate compound and a polycarboxylic acid or an anhydride thereof as reaction raw materials.

Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, and 2,4, 4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; aromatic diisocyanate compounds such as toluene diisocyanate, xylene diisocyanate, tetramethylxylene diisocyanate, diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, 4 '-diisocyanato-3, 3' -dimethylbiphenyl, and ortho-triazine diisocyanate; a polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (i-1); these isocyanurate-modified products, biuret-modified products, allophanate-modified products, and the like. These polyisocyanate compounds may be used alone or in combination of two or more.

[ in the formula, R¹Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R²Each independently represents an alkyl group having 1 to 4 carbon atoms or a bonding site connected to the structural part represented by the formula (i-1) through a methylene group having a valency. l is 0 or an integer of 1 to 3, and m is an integer of 1 or more.]

In addition, as the polyisocyanate compound, from the viewpoint of obtaining an acid group-containing (meth) acrylate resin composition having high solvent solubility, an alicyclic diisocyanate compound or a modified product thereof, an aliphatic diisocyanate compound or a modified product thereof are preferable, and an alicyclic diisocyanate or an isocyanurate modified product thereof, and an aliphatic diisocyanate or an isocyanurate modified product thereof are more preferable.

In addition, the ratio of the total mass of the alicyclic diisocyanate compound or its modified product to the total mass of the aliphatic diisocyanate compound or its modified product is preferably 70 mass% or more, and preferably 90 mass% or more, of the total mass of the polyisocyanate compounds.

When the alicyclic diisocyanate compound or a modified product thereof and the aliphatic diisocyanate compound or a modified product thereof are used in combination, the mass ratio of the two is preferably in the range of 30/70 to 70/30.

The polycarboxylic acid or anhydride thereof is not particularly limited in specific structure as long as it is a compound having a plurality of carboxyl groups in the molecular structure or anhydride thereof, and various compounds can be used. In order to make the amide imide resin (b3-1) have both an amide group and an imide group, both a carboxyl group and an acid anhydride group need to be present in the system, and in the present invention, a compound having both a carboxyl group and an acid anhydride group in a molecule may be used, or a compound having a carboxyl group and a compound having an acid anhydride group may be used in combination.

Examples of the polycarboxylic acid or anhydride thereof include aliphatic polycarboxylic acid compounds or anhydrides thereof, alicyclic polycarboxylic acid compounds or anhydrides thereof, and aromatic polycarboxylic acid compounds or anhydrides thereof.

The aliphatic polycarboxylic acid compound or its anhydride may have an aliphatic hydrocarbon group of a straight chain type or a branched chain type, and may have an unsaturated bond in its structure.

Examples of the aliphatic polycarboxylic acid compound or an acid anhydride thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3, 4-butanetetracarboxylic acid, and acid anhydrides thereof.

In the present invention, the alicyclic polycarboxylic acid compound or its anhydride is one in which a carboxyl group or an anhydride group is bonded to an alicyclic structure, regardless of the presence or absence of an aromatic ring in the other structural parts. Examples of the alicyclic polycarboxylic acid compound or its anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo [2.2.1] heptane-2, 3-dicarboxylic acid, methylbicyclo [2.2.1] heptane-2, 3-dicarboxylic acid, 4- (2, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic acid, and anhydrides thereof.

Examples of the aromatic polycarboxylic acid compound or an acid anhydride thereof include phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid.

Among these, the alicyclic polycarboxylic acid compound or an acid anhydride thereof, or the aromatic polycarboxylic acid compound or an acid anhydride thereof is preferable in that an acid group-containing (meth) acrylate resin composition capable of forming a cured product having high sensitivity, heat resistance, and dielectric characteristics can be obtained. In addition, from the viewpoint of efficiently producing the amide imide resin (b3-1), it is preferable to use a tricarboxylic anhydride having both a carboxyl group and an acid anhydride group in the molecular structure, and it is particularly preferable to use cyclohexanetricarboxylic anhydride or trimellitic anhydride. Further, the ratio of the total amount of the alicyclic tricarboxylic acid anhydride and the aromatic tricarboxylic acid anhydride is preferably 70% by mass or more, and more preferably 90% by mass or more, relative to the total mass of the polycarboxylic acid or anhydride thereof.

When the amide imide resin (b3-1) is a reaction material of the polyisocyanate compound and the polycarboxylic acid or anhydride thereof, other reaction materials may be used in combination depending on the desired resin performance and the like. In this case, from the viewpoint of sufficiently exerting the effect of the present invention, the ratio of the total mass of the polyisocyanate compound and the polycarboxylic acid or its anhydride to the total mass of the reaction raw materials of the amide imide resin (b3-1) is preferably 90 mass% or more, and more preferably 95 mass% or more.

The amide imide resin (b3-1) is not particularly limited when it is produced by any method, as long as it is a resin obtained by reacting a polyisocyanate compound with a polycarboxylic acid or an anhydride thereof. For example, the resin can be produced by the same method as that for a general amide imide resin. Specifically, there is a method of reacting a polyvalent carboxylic acid or an acid anhydride thereof by stirring and mixing the polyvalent carboxylic acid or the acid anhydride thereof at a temperature of about 120 to 180 ℃ with respect to 1 mole of an isocyanate group contained in a polyisocyanate compound.

The reaction of the polyisocyanate compound with the polycarboxylic acid or anhydride thereof may be carried out in the presence of a basic catalyst, if necessary. The reaction may be carried out in an organic solvent as needed.

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

The hydroxyl group-containing (meth) acrylate compound (b3-2) is not particularly limited as long as it has a hydroxyl group and a (meth) acryloyl group in its molecular structure, and various compounds can be used. Examples thereof include hydroxy (meth) acrylate compounds such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like; (poly) oxyalkylene modifications in which (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains are introduced into the molecular structures of the above various hydroxy (meth) acrylate compounds; lactone modifications having a (poly) lactone structure are introduced into the molecular structures of the above-mentioned various hydroxy (meth) acrylate compounds. Among these, the molecular weight is preferably 1000 or less from the viewpoint that an acid group-containing (meth) acrylate resin composition capable of forming a cured product having high sensitivity, excellent heat resistance and excellent dielectric characteristics can be obtained. When the hydroxyl group-containing (meth) acrylate compound (b3-2) is the oxyalkylene-modified product or the lactone-modified product, the weight-average molecular weight (Mw) is preferably 1000 or less. These hydroxyl group-containing (meth) acrylate compounds may be used alone or in combination of two or more.

Further, as the amide imide resin (B-3) having an acid group and a (meth) acryloyl group, a (meth) acryloyl group-containing epoxy compound (B3-3) may be used in combination as a reaction raw material, in addition to the amide imide resin (B3-1) and the hydroxyl group-containing (meth) acrylate compound (B3-2), as required. Further, as the amide imide resin (B-3) having an acid group and a (meth) acryloyl group, a (meth) acryloyl group-containing epoxy compound (B3-3) and a polyvalent carboxylic acid anhydride (B3-4) may be used in combination as reaction raw materials in addition to the amide imide resin (B3-1) and the hydroxyl group-containing (meth) acrylate compound (B3-2), as required.

The (meth) acryloyl group-containing epoxy compound (b3-3) is not particularly limited as long as it has a (meth) acryloyl group and an epoxy group in its molecular structure, and various compounds can be used. Examples thereof include glycidyl group-containing (meth) acrylate monomers such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and epoxycyclohexylmethyl (meth) acrylate; and mono (meth) acrylate compounds of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. Among these, the glycidyl group-containing (meth) acrylate monomer is preferable in that an acid group-containing (meth) acrylate resin composition which can form a cured product having high sensitivity, excellent heat resistance and excellent dielectric characteristics can be obtained. Further, the molecular weight thereof is preferably 500 or less. Further, the proportion of the glycidyl group-containing (meth) acrylate monomer in the total mass of the (meth) acryloyl group-containing epoxy compound (b3-3) is preferably 70 mass% or more, and more preferably 90 mass% or more.

As the polycarboxylic acid anhydride (b3-4), the polycarboxylic acid anhydride (b1-3) can be used by way of example, and the polycarboxylic acid (b3-4) can be used alone or in combination of two or more.

The amide imide resin having an acid group and a (meth) acryloyl group (B-3) may be used in combination with other reaction raw materials in addition to the amide imide resin having an acid group or an acid anhydride group (B3-1), the hydroxyl group-containing (meth) acrylate compound (B3-2), the (meth) acryloyl group-containing epoxy compound (B3-3) and the polycarboxylic acid anhydride (B3-4) according to desired resin performance and the like. In this case, the total mass ratio of the components (B3-1) to (B3-4) in the total mass of the reaction raw materials for the acid group-containing (meth) acrylate resin (B-3) is preferably 80 mass% or more, and more preferably 90 mass% or more.

The method for producing the amide imide resin (B-3) having an acid group and a (meth) acryloyl group is not particularly limited, and any method may be used. For example, the resin composition can be produced by a method in which all the reaction raw materials including the amide imide resin (b3-1) and the hydroxyl group-containing (meth) acrylate compound (b3-2) are reacted at once, or by a method in which the reaction raw materials are reacted sequentially.

The reaction between the amide imide resin (b3-1) and the hydroxyl group-containing (meth) acrylate compound (b3-2) is mainly a reaction between an acid group and/or an acid anhydride group in the amide imide resin (b3-1) and a hydroxyl group in the hydroxyl group-containing (meth) acrylate compound (b 3-2). Since the hydroxyl group-containing (meth) acrylate compound (b3-2) is particularly excellent in reactivity with an acid anhydride group, the amide imide resin (b3-1) preferably has an acid anhydride group as described above. The content of the acid anhydride group in the amide imide resin (b3-1) can be calculated from the difference between the measured values of the acid anhydride group and the acid value of the acid anhydride group, that is, the difference between the acid value under the condition of ring opening of the acid anhydride group and the acid value under the condition of not ring opening of the acid anhydride group.

The ratio of the reaction between the amide imide resin (b3-1) and the hydroxyl group-containing (meth) acrylate compound (b3-2) is preferably such that, when the amide imide resin (b3-1) has an acid group and an acid anhydride group, and when the amide imide resin (b3-1) has an acid anhydride group, the number of moles of hydroxyl groups of the hydroxyl group-containing (meth) acrylate compound (b3-2) is 0.9 to 1.1 relative to 1 mole of acid anhydride groups of the amide imide resin (b 3-1). When the amide imide resin (b3-1) has an acid group, the hydroxyl group-containing (meth) acrylate compound (b3-2) is preferably used in an amount such that the number of moles of the hydroxyl group is 0.01 to 1.0 based on 1 mole of the acid group of the amide imide resin (b 3-1).

The reaction of the amide imide resin (b3-1) with the hydroxyl group-containing (meth) acrylate compound (b3-2) may also use a basic catalyst or an acidic catalyst, as required. Among them, when the amide imide resin (b3-1) has an acid group and an acid anhydride group, and when the amide imide resin (b3-1) has an acid anhydride group, a basic catalyst is preferably used, and when the amide imide resin (b3-1) has an acid group, an acidic catalyst is preferably used.

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

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

The amount of the basic catalyst or the acidic catalyst is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total mass of the reaction raw materials.

The reaction between the amide imide resin (b3-1) and the hydroxyl group-containing (meth) acrylate compound (b3-2) can be carried out by heating and stirring at a temperature of about 80 to 140 ℃ in the presence of an appropriate catalyst.

The reaction may be carried out in an organic solvent as needed, and the same organic solvent as described above may be used as the organic solvent, and the organic solvents may be used alone or in combination of two or more. When the amide imide resin (b3-1) is continuously produced, the reaction may be continued in the organic solvent used for the production of the amide imide resin (b 3-1).

When the (meth) acryloyl group-containing epoxy compound (B3-3) is used as a reaction raw material in addition to the amide imide resin (B3-1) and the hydroxyl group-containing (meth) acrylate compound (B3-2), the amide imide resin (B-3) having an acid group and a (meth) acryloyl group can be produced by a method in which all reaction raw materials including the amide imide resin (B3-1), the hydroxyl group-containing (meth) acrylate compound (B3-2), and the (meth) acryloyl group-containing epoxy compound (B3-3) are reacted at once, or by a method in which the reaction raw materials are reacted sequentially. Among them, from the viewpoint of easy control of the reaction, it is preferable to produce the compound by a method of reacting the (meth) acryloyl group-containing epoxy compound (b3-3) with a product obtained by reacting the amide imide resin (b3-1) with the hydroxyl group-containing (meth) acrylate compound (b3-2) (hereinafter, may be referred to simply as "product (1)").

The reaction of the product (1) with the (meth) acryloyl group-containing epoxy compound (b3-3) mainly causes the acid group in the product (1) to react with the (meth) acryloyl group-containing epoxy compound (b 3-3). The reaction ratio is preferably in the range of 0.05 to 1.1 in terms of the number of moles of epoxy groups in the (meth) acryloyl group-containing epoxy compound (b3-3) per 1 mole of acid groups in the product (1). The reaction can be carried out, for example, by heating and stirring at a temperature of about 90 to 140 ℃ in the presence of an appropriate basic catalyst. When the reaction of the amide imide resin (b3-1) and the hydroxyl group-containing (meth) acrylate compound (b3-2) is continuously carried out, a basic catalyst may not be added, and may be added as appropriate. The reaction may be carried out in an organic solvent, if necessary. The basic catalyst and the organic solvent may be the same as those described above, and these may be used alone or in combination of two or more.

The amide imide resin (B-3) having an acid group and a (meth) acryloyl group can be produced by a method in which all reaction raw materials including the amide imide resin (B3-1), the hydroxyl group-containing (meth) acrylate compound (B3-2), the (meth) acryloyl group-containing epoxy compound (B3-3), and the polycarboxylic anhydride (B3-4) are reacted at once, or by a method in which the reaction raw materials are reacted sequentially, when the (meth) acryloyl group-containing epoxy compound (B3-3) and the polycarboxylic anhydride (B3-4) are used as reaction raw materials in addition to the amide imide resin (B3-1) and the hydroxyl group-containing (meth) acrylate compound (B3-2). Among them, from the viewpoint of easy control of the reaction, it is preferred to produce the (meth) acryloyl group-containing epoxy compound (b3-3) by a method comprising reacting the amide imide resin (b3-1) with the product (1) obtained by reacting the hydroxyl group-containing (meth) acrylate compound (b3-2), and further reacting the obtained product (hereinafter, sometimes simply referred to as "product (2)") with the polycarboxylic anhydride (b 3-4).

The reaction of the product (2) with the polyvalent carboxylic acid anhydride (b3-4) mainly causes the hydroxyl group in the product (2) to react with the polyvalent carboxylic acid anhydride. In this case, in the product (2), the reaction ratio between the product (1) and the (meth) acryloyl group-containing epoxy compound (b3-3) is preferably in the range of 0.1 to 1.2, more preferably 0.2 to 1.1, in terms of the number of moles of epoxy groups in the (meth) acryloyl group-containing epoxy compound (b3-3) per 1 mole of acid groups in the product (1). Here, in the product (2), for example, a hydroxyl group or the like generated by ring-opening of an epoxy group in the (meth) acryloyl group-containing epoxy compound (b3-3) is present. The reaction ratio of the polycarboxylic acid anhydride (B3-4) is preferably adjusted so that the acid value of the produced amide imide resin (B-3) having an acid group and a (meth) acryloyl group is about 50 to 120 mgKOH/g. The reaction can be carried out, for example, by heating and stirring at a temperature of about 80 to 140 ℃ in the presence of an appropriate basic catalyst. When the reaction of the product (1) with the (meth) acryloyl group-containing epoxy compound (b3-3) is continuously carried out, the basic catalyst may not be added, or may be appropriately added. The reaction may be carried out in an organic solvent as required. The basic catalyst and the organic solvent may be the same as those described above, and these may be used alone or in combination of two or more.

The acid value of the acid group-and (meth) acryloyl-containing amide imide resin (B-3) is preferably in the range of 30 to 150mgKOH/g, and more preferably in the range of 40 to 120mgKOH/g, from the viewpoint that an acid group-containing (meth) acrylate resin composition capable of forming a cured product having high sensitivity, heat resistance, and excellent dielectric properties can be obtained. In the present invention, the acid value of the amide imide resin (B-3) having an acid group and a (meth) acryloyl group is a value measured by a neutralization titration method according to JIS K0070 (1992).

Next, the acrylic resin having an acid group and a (meth) acryloyl group (B-4) will be described.

Examples of the acrylic resin (B-4) having an acid group and a (meth) acryloyl group include a reaction product obtained by introducing a (meth) acryloyl group by polymerizing an acrylic resin intermediate obtained by using, as an essential component, a (meth) acrylate compound (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, and a glycidyl group, further reacting the intermediate with a (meth) acrylate compound (β) having a reactive functional group reactive with these functional groups, and reacting the hydroxyl group in the reaction product with a polybasic acid anhydride.

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

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

Examples of the polybasic acid anhydride include phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, octenyl succinic anhydride, tetrapropenyl succinic anhydride, and the like. These polybasic acid anhydrides may be used alone or in combination of two or more.

The method for producing the acrylic resin (B-4) having an acid group and a (meth) acryloyl group is not particularly limited, and any method may be used. The acrylic resin (B-4) having an acid group and a (meth) acryloyl group may be produced in an organic solvent if necessary, or a basic catalyst may be used if necessary.

The acid value of the acrylic resin (B-4) having an acid group and a (meth) acryloyl group is preferably in the range of 30 to 150mgKOH/g, and more preferably in the range of 40 to 120mgKOH/g, from the viewpoint that an acid group-containing (meth) acrylate resin composition capable of forming a cured product having high sensitivity, heat resistance, and excellent dielectric properties can be obtained. In the present invention, the acid value of the acrylic resin (B-4) having an acid group and a (meth) acryloyl group is a value measured by a neutralization titration method according to JIS K0070 (1992).

Next, the urethane resin having an acid group and a (meth) acryloyl group (B-5) will be described.

Examples of the urethane resin (B-5) having an acid group and a (meth) acryloyl group include: a polyisocyanate compound, a hydroxyl group-containing (meth) acrylate compound, a carboxyl group-containing polyol compound, and if necessary, a polybasic acid anhydride, and a polyol compound other than the carboxyl group-containing polyol compound; a polyisocyanate compound, a hydroxyl group-containing (meth) acrylate compound, a polybasic acid anhydride, and a polyol compound other than a carboxyl group-containing polyol compound; and an epoxy resin, an unsaturated monobasic acid, a polybasic acid anhydride, a polyisocyanate compound, and a hydroxyl group-containing (meth) acrylate compound.

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

The hydroxyl group-containing (meth) acrylate compound may be the same as the hydroxyl group-containing (meth) acrylate compound (b3-2), and the hydroxyl group-containing (meth) acrylate compound may be used alone or in combination of two or more.

Examples of the carboxyl group-containing polyol compound include 2, 2-dimethylolpropionic acid, 2-dimethylolbutanoic acid, and 2, 2-dimethylolpentanoic acid. The carboxyl group-containing polyol compounds may be used alone or in combination of two or more.

The polybasic acid anhydrides mentioned above can be used as exemplified, and the polybasic acid anhydrides mentioned above can be used alone or in combination of two or more.

Examples of the polyol compound other than the carboxyl group-containing polyol compound include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol and the like; aromatic polyhydric alcohol compounds such as biphenol and bisphenol; (poly) oxyalkylene modifications in which (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains are introduced into the molecular structures of the above-mentioned various polyol compounds; lactone modifications having a (poly) lactone structure introduced into the molecular structure of the above-mentioned various polyol compounds, and the like. The polyol compounds other than the above-mentioned carboxyl group-containing polyol compound may be used alone or in combination of two or more.

The epoxy resin (b1-1) can be exemplified as the epoxy resin, and the epoxy resins can be used alone or in combination of two or more.

Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α -cyanocinnamic acid, β -styrylacrylic acid, β -furfurylacrylic acid, and the like. Further, esters, acid halides, acid anhydrides, and the like of the above-mentioned unsaturated monocarboxylic acids can also be used. These unsaturated monobasic acids may be used alone or in combination of two or more.

The method for producing the urethane resin (B-5) having an acid group and a (meth) acryloyl group is not particularly limited, and any method may be used. The production of the polyurethane resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent if necessary, and a basic catalyst may be used if necessary.

The acid group-containing (meth) acrylate resin composition of the present invention contains the polymerizable unsaturated bond-containing aromatic ester compound (a) and the acid group-containing (meth) acrylate resin (B).

The content of the polymerizable unsaturated bond-containing aromatic ester compound (a) in the acid group-containing (meth) acrylate resin composition of the present invention is preferably in the range of 10 to 90% by mass, from the viewpoint that the acid group-containing (meth) acrylate resin composition capable of forming a cured product having high sensitivity, heat resistance and excellent dielectric properties can be obtained.

The content of the acid group-containing (meth) acrylate resin (B) in the acid group-containing (meth) acrylate resin composition of the present invention is preferably in the range of 90 to 10 mass%.

The mass ratio [ (a)/(B) ] of the polymerizable unsaturated bond-containing aromatic ester compound (a) to the solid content of the acid group-containing (meth) acrylate resin (B) is preferably in the range of 50/50 to 95/5, from the viewpoint that an acid group-containing (meth) acrylate resin composition capable of forming a cured product having high sensitivity, heat resistance and excellent dielectric characteristics can be obtained.

The acid group-containing (meth) acrylate resin composition of the present invention can be used as a curable resin composition by adding a photopolymerization initiator.

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

Examples of commercially available products of the other photopolymerization initiators include "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", "Omnirad-379", "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100", "Omnirad-754", "Omnirad-784", "Omnirad-500", "Omnirad-81" (manufactured by IGM), "Kayakure-DETX", "Kayakure-MBP", "Kayakure-DMBI", "Kayakure-EPA", "Kayakure-OA" (manufactured by Nippon Chemicals, Inc.), "Viyakure-10", "Violure-Cm-55" (manufactured by Akancure 1) "," manufactured by Akyakure-Co., and "Triyakure-26" (manufactured by Japan Chemical Co., Ltd., "Kogyu Shikura-1 "Sandoray 1000" (manufactured by SANDOZ), "DEAP" (manufactured by Upjohn), "Quanta cure-PDO", "Quanta cure-ITX", "Quanta cure-EPD" (manufactured by Ward Blenkinson), "Runtercure-1104" (manufactured by Runtec), and the like.

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

The curable resin composition of the present invention may contain other resin components than the acid group-containing (meth) acrylate resin (B). Examples of the other resin component include resins having a carboxyl group and a (meth) acryloyl group in the resin obtained by reacting an epoxy resin such as a bisphenol epoxy resin or a novolak epoxy resin with (meth) acrylic acid, a dicarboxylic anhydride, and, if necessary, an unsaturated monocarboxylic acid anhydride, and various (meth) acrylate monomers.

Examples of the (meth) acrylate ester monomer include aliphatic mono (meth) acrylate ester compounds such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and octyl (meth) acrylate; alicyclic mono (meth) acrylate compounds such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl mono (meth) acrylate; heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; mono (meth) acrylate compounds such as aromatic mono (meth) acrylate compounds including benzyl (meth) acrylate, phenyl (meth) acrylate, phenylbenzyl (meth) acrylate, phenoxy ester (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxybenzyl (meth) acrylate, benzylbenzyl (meth) acrylate, and phenylphenoxyethyl (meth) acrylate: (poly) oxyalkylene-modified mono (meth) acrylate compounds obtained by introducing a polyoxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain into the molecular structure of each of the above-mentioned mono (meth) acrylate monomers; lactone-modified mono (meth) acrylate compounds having a (poly) lactone structure introduced into the molecular structure of each of the above mono (meth) acrylate compounds; aliphatic di (meth) acrylate compounds such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate; alicyclic di (meth) acrylate compounds such as 1, 4-cyclohexanedimethanol di (meth) acrylate, norbornanedimethanol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, and tricyclodecanedimethanol di (meth) acrylate; aromatic di (meth) acrylate compounds such as biphenol di (meth) acrylate and bisphenol di (meth) acrylate; polyoxyalkylene-modified di (meth) acrylate compounds 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 each of the above di (meth) acrylate compounds; lactone-modified di (meth) acrylate compounds having a (poly) lactone structure introduced into the molecular structure of each of the above di (meth) acrylate compounds; aliphatic tri (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate and glycerol tri (meth) acrylate; a (poly) oxyalkylene-modified tri (meth) acrylate compound having a (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain introduced into the molecular structure of the aliphatic tri (meth) acrylate compound; a lactone-modified tri (meth) acrylate compound having a (poly) lactone structure introduced into the molecular structure of the aliphatic tri (meth) acrylate compound; aliphatic poly (meth) acrylate compounds having 4 or more functions such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate; a (poly) oxyalkylene-modified poly (meth) acrylate compound having 4 or more functional groups, 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; a lactone-modified poly (meth) acrylate compound having 4 or more functions, in which a (poly) lactone structure is introduced into the molecular structure of the aliphatic poly (meth) acrylate compound. The various (meth) acrylate monomers mentioned above may be used alone or in combination of two or more.

The curable resin composition of the present invention may further contain various additives such as a curing agent, a curing accelerator, an organic solvent, inorganic fine particles, polymer fine particles, a pigment, an antifoaming agent, a viscosity modifier, a leveling agent, a flame retardant, and a storage stabilizer, if necessary.

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 (meth) acrylate resin, and examples thereof include epoxy resins. Examples of the epoxy resin include bisphenol type epoxy resins, phenyl ether type epoxy resins, naphthyl ether type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol novolac type epoxy resins, naphthol-phenol condensed novolac type epoxy resins, naphthol-cresol condensed novolac type epoxy resins, phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, dicyclopentadiene-phenol addition reaction type epoxy resins, biphenyl aralkyl type epoxy resins, fluorene type epoxy resins, xanthene type epoxy resins, dihydroxybenzene type epoxy resins, trihydroxybenzene type epoxy resins, and the like. These epoxy resins may be used alone or in combination of two or more. Among these, novolac-type epoxy resins such as phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, bisphenol novolac-type epoxy resin, naphthol-phenol co-condensed novolac-type epoxy resin, and naphthol-cresol co-condensed novolac-type epoxy resin are preferable from the viewpoint that a curable resin composition capable of forming a cured product having excellent alkali developability, high sensitivity, and excellent elongation can be obtained, and a material having a softening point in the range of 20 to 120 ℃ is particularly preferable.

When an epoxy resin is used as the curing agent for accelerating the curing reaction of the curing agent, examples of the curing accelerator include phosphorus compounds, amine compounds, imidazoles, organic acid metal salts, lewis acids, and amine complex salts. These curing accelerators may be used alone or in combination of two or more. The amount of the curing accelerator added is preferably in the range of 1 to 10 parts by mass per 100 parts by mass of the curing agent, for example.

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 ray include ionizing radiation rays such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. In the case of using ultraviolet rays as the active energy rays, irradiation may be performed in an inert gas atmosphere such as nitrogen gas or in an air atmosphere as long as curing reaction by ultraviolet rays is efficiently performed.

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

The cumulative amount of the active energy rays is not particularly limited, but is preferably 10 to 5000mJ/cm²More preferably 50 to 1000mJ/cm². When the accumulated light amount is in the above range, occurrence of uncured portions can be prevented or suppressed, which is preferable.

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

Further, a cured product obtained by curing the curable resin composition of the present invention is excellent in heat resistance and dielectric properties, and therefore can be suitably used as, for example, a solder resist layer, an interlayer insulating material, a sealing material, a potting material, a circuit element, and the like for semiconductor devices, and a sealing adhesive layer for integrated circuit elements and circuit boards. In addition, the composition can be suitably used for a protective film of a thin film transistor, a protective film of a liquid crystal color filter, a pigment protective layer for a color filter, a protective layer for a black matrix, a spacer, and the like in applications of thin displays represented by LCDs and OELDs.

The resin material for a solder resist of the present invention is formed from the curable resin composition.

The protective member of the present invention can be obtained, for example, by the following method: the resin material for solder resist is coated on a substrate, an organic solvent is evaporated and dried at a temperature of about 60 to 100 ℃, then the substrate is exposed to active energy rays through a photomask having a desired pattern formed thereon, an unexposed portion is developed with an aqueous alkali solution, and the substrate is heated and cured at a temperature of about 140 to 180 ℃.

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

Examples

Hereinafter, the present invention will be specifically described by way of comparative examples and comparative examples.

The acid value of the acid group-containing (meth) acrylate resin in the examples of the present application was measured by neutralization titration according to JIS K0070 (1992).

The weight average molecular weight of the acid group-containing (meth) acrylate resin in the examples of the present application was measured by GPC under the following conditions.

A measuring device: HLC-8320GPC, manufactured by Tosoh corporation "

Column: "HXL-L" protective column manufactured by Tosoh corporation "

+ manufactured by Tosoh corporation of "TSK-GEL G4000 HXL"

+ TSK-GEL G3000HXL manufactured by Tosoh corporation "

+ TSK-GEL G2000HXL manufactured by Tosoh corporation "

A detector: RI (differential refractometer)

Data processing: "EcoSEC-WorkStation" of Tosoh corporation "

Column temperature: 40 deg.C

Developing solvent: tetrahydrofuran (THF)

Flow rate: 1.0 ml/min

Polystyrene used

"A-500" made by Tosoh corporation "

"A-1000" made by Tosoh corporation "

"A-2500" made by Tosoh corporation "

"A-5000" manufactured by Tosoh corporation "

"F-1" made by Tosoh corporation "

"F-2" made by Tosoh corporation "

"F-4" made by Tosoh corporation "

"F-10" made by Tosoh corporation "

"F-20" made by Tosoh corporation "

"F-40" made by Tosoh corporation "

"F-80" made by Tosoh corporation "

"F-128" made by Tosoh corporation "

Sample preparation: the tetrahydrofuran solution was filtered through a microfilter at 1.0 mass% in terms of resin solid content (50. mu.l).

(Synthesis example 1 Synthesis of aromatic ester Compound (A-1) containing polymerizable unsaturated bond)

268 parts by mass (2.0mol) of o-allylphenol and 1200 parts by mass of toluene were put into a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirrer, and the inside of the system was replaced with nitrogen under reduced pressure. Then, 203 parts by mass (1.0mol) of isophthaloyl dichloride was charged into the system, and the inside of the system was replaced with nitrogen under reduced pressure. Then, 0.6 part by mass of tetrabutylammonium bromide was added, and while controlling the temperature in the system to 60 ℃ or lower, 412 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours, followed by stirring for 1 hour after the completion of the addition. After the reaction, the aqueous layer was removed by standing and separating. Water was further added to the toluene layer obtained, and the mixture was stirred for 15 minutes, and the aqueous layer was removed by standing and liquid separation. This operation was repeated until the pH of the aqueous layer became 7. Then, the resultant was dried under reduced pressure by heating to obtain a polymerizable unsaturated bond-containing aromatic ester compound (A-1) represented by the following chemical formula. The ester group equivalent of the polymerizable unsaturated bond-containing aromatic ester compound (A-1) was 199 g/equivalent. The ester group equivalent is a calculated value calculated from the charge ratio.

Synthesis example 2 Synthesis of aromatic ester Compound (A-2) containing polymerizable unsaturated bond

134 parts by mass (1.0mol) of o-allylphenol and 711 parts by mass of toluene were put into a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirrer, and the inside of the system was replaced with nitrogen under reduced pressure. Then, 140 parts by mass (1.0mol) of benzyl chloride was charged, and the inside of the system was replaced with nitrogen under reduced pressure. Then, while controlling the temperature in the system to 60 ℃ or lower while adding 0.4 parts by mass of tetrabutylammonium bromide and purging with nitrogen, 205 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours, and after the completion of the addition, the mixture was stirred for 1 hour. After the reaction, the aqueous layer was removed by standing and separating. Water was further added to the toluene layer obtained, and the mixture was stirred for 15 minutes, and the aqueous layer was removed by standing and liquid separation. This operation was repeated until the pH of the aqueous layer became 7. Then, the resulting mixture was dried under reduced pressure under heating to obtain an aromatic ester compound (A-2) represented by the following chemical formula. The ester group equivalent of the aromatic ester compound (A-2) was 119 g/equivalent. The ester group equivalent is a calculated value calculated from the charge ratio.

(Synthesis example 3 Synthesis of aromatic ester Compound (A-3))

216 parts by mass (2.0mol) of o-cresol and 1200 parts by mass of toluene were put into a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirrer, and the inside of the system was replaced with nitrogen under reduced pressure. Then, 203 parts by mass (1.0mol) of isophthaloyl dichloride was charged into the system, and the inside of the system was replaced with nitrogen under reduced pressure. Then, 0.5 part by mass of tetrabutylammonium bromide was added, and while purging with nitrogen, 412 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while controlling the temperature in the system to 60 ℃ or lower, and after the completion of the dropwise addition, the mixture was stirred for 1 hour. After the reaction, the aqueous layer was removed by standing and separating. Water was further added to the toluene layer obtained, and the mixture was stirred for 15 minutes, and the aqueous layer was removed by standing and liquid separation. This operation was repeated until the pH of the aqueous layer became 7. Then, the resulting mixture was dried under reduced pressure under heating to obtain an aromatic ester compound (A-3) represented by the following chemical formula. The ester equivalent of the aromatic ester compound (A-3) was 173 g/equivalent. The ester group equivalent is a calculated value calculated from the charge ratio.

Synthesis example 4 Synthesis of acid group-containing (meth) acrylate resin (B-1)

In a flask equipped with a thermometer, a stirrer and a reflux condenser, 101 parts by mass of diethylene glycol monomethyl ether acetate was added, 428 parts by mass of an o-cresol novolak-type epoxy resin ("EPICLON N-680", epoxy equivalent: 214, manufactured by DIC corporation) was dissolved, 4 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 part by mass of hydroquinone monomethyl ether as a thermal polymerization inhibitor were added, 144 parts by mass of acrylic acid and 1.6 parts by mass of triphenylphosphine were added, and esterification reaction was carried out at 120 ℃ for 10 hours while blowing air. Then, 311 parts by mass of diethylene glycol monomethyl ether acetate and 160 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ℃ for 2.5 hours to obtain an acid group-containing (meth) acrylate resin (B-1) having a solid content of 64.0 mass%. The acid group-containing (meth) acrylate resin (B-1) had an acid value of the solid content of 85mgKOH/g and a weight-average molecular weight of 8850.

Synthesis example 5 Synthesis of acid group-containing (meth) acrylate resin (B-2)

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 244 parts by mass of diethylene glycol monomethyl ether acetate, an isocyanurate-modified product of isophorone diisocyanate ("VESTANAT T-1890/100" manufactured by EVONIK corporation, isocyanate group content 17.2 mass%) (hereinafter, abbreviated as "T-1890"), 192 parts by mass of trimellitic anhydride, and 1.0 part by mass of dibutylhydroxytoluene were added and dissolved. The reaction was carried out at 160 ℃ for 5 hours under a nitrogen atmosphere, and it was confirmed that the isocyanate group content was 0.1 mass% or less. The acid value of the solid content measured under the condition of non-ring-opening of the acid anhydride group was 160 mgKOH/g. 0.3 part by mass of hydroquinone monomethyl ether, 172 parts by mass of a pentaerythritol polyacrylate mixture (made by Toyo Seiyaku K.K. "Aronix M-306", having a pentaerythritol triacrylate content of about 67%, and a hydroxyl value of 159.7mgKOH/g) (hereinafter abbreviated as "M-306"), and 3.6 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110 ℃ for 5 hours while blowing air. Then, 163 parts by mass of glycidyl methacrylate was added thereto, and the mixture was reacted at 110 ℃ 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 ℃ for 5 hours to obtain an acid group-containing (meth) acrylate resin (B-2) having a solid content of 62.1% by mass. The acid group-containing (meth) acrylate resin (B-2) had an acid value of the solid content of 79mgKOH/g and a weight-average molecular weight of 3790.

Example 1 preparation of acid group-containing (meth) acrylate resin composition (1)

The aromatic ester compound having a polymerizable unsaturated bond (a-1) obtained in synthesis example 1, the (meth) acrylate resin having an acid group (B-1) obtained in synthesis example 4, an o-cresol novolac-type epoxy resin (product of DIC corporation, "EPICLON N-680"), dipentaerythritol hexaacrylate, diethylene glycol monoethylether acetate, a photopolymerization initiator (product of IGM "Omnirad 907"), 2-ethyl-4-methylimidazole and phthalocyanine green were mixed in the parts by mass shown in table 1, and kneaded by a roll mill to obtain the (meth) acrylate resin composition (1) having an acid group.

Examples 2 to 7 preparation of acid group-containing (meth) acrylate resin compositions (2) to (7)

Acid group-containing (meth) acrylate resin compositions (2) to (7) were obtained according to the compositions and formulations shown in Table 1 in the same manner as in example 1.

Comparative example 1 preparation of acid group-containing (meth) acrylate resin composition (C1)

The aromatic ester compound (a-3) obtained in synthesis example 3, the acid group-containing (meth) acrylate resin (B-1) obtained in synthesis example 4, an o-cresol novolac type epoxy resin ("EPICLON N-680" manufactured by DIC corporation) as a curing agent, dipentaerythritol hexaacrylate, diethylene glycol monoethylether acetate, a photopolymerization initiator ("Omnirad 907" manufactured by IGM corporation), 2-ethyl-4-methylimidazole and phthalocyanine green were blended in the mass parts shown in table 1, and kneaded by a roll mill to obtain an acid group-containing (meth) acrylate resin composition (C1).

Comparative example 2 preparation of acid group-containing (meth) acrylate resin composition (C2)

An acid group-containing (meth) acrylate resin composition (C2) was obtained in the same manner as in comparative example 1, except that the acid group-containing (meth) acrylate resin (B-2) obtained in synthesis example 4 was used in place of the acid group-containing (meth) acrylate resin (B-1) used in comparative example 1.

The following evaluations were carried out using the acid group-containing (meth) acrylate resin compositions obtained in the above examples and comparative examples.

[ method for evaluating sensitivity ]

The acid group-containing (meth) acrylate resin compositions obtained in examples and comparative examples were applied to a glass substrate with an applicator so that the film thickness became 50 μm, and were dried at 80 ℃ for 30 minutes. Then, the dried coating film was placed on a "Step tablet No. 2" manufactured by Kodak corporation, and irradiated with ultraviolet rays at 1000mJ/cm2 using a metal halide lamp. The resultant was developed with a 1% aqueous solution of sodium carbonate at 30 ℃ for 180 seconds, and the number of remaining stages in Step tablet was evaluated by the Step tablet method. The higher the number of residual segments, the higher the sensitivity.

The compositions and evaluation results of the acid group-containing (meth) acrylate resin compositions (1) to (7) prepared in examples 1 to 7 and the acid group-containing (meth) acrylate resin compositions (C1) and (C2) prepared in comparative examples 1 and 2 are shown in table 1.

[ Table 1]

The evaluation "-" of comparative example 2 in table 1 indicates that the evaluation was impossible. This is because the aromatic ester compound is not compatible with the acid group-containing (meth) acrylate resin, and therefore, when mixed, it is clouded, and thus cannot be evaluated.

Example 8 preparation of acid group-containing (meth) acrylate resin composition (8)

The aromatic ester compound having a polymerizable unsaturated bond (a-1) obtained in synthesis example 1, the (meth) acrylate resin having an acid group (B-1) obtained in synthesis example 4, an o-cresol novolac-type epoxy resin (EPICLON N-680, manufactured by DIC corporation) as a curing agent, dimethylaminopyridine as a curing accelerator, a photopolymerization initiator (Omnirad 907, manufactured by IGM), and diethylene glycol monomethyl ether acetate as an organic solvent were mixed in parts by mass shown in table 2, and kneaded by a roll mill to obtain an acid group-containing (meth) acrylate resin composition (8).

Examples 9 to 14 preparation of acid group-containing (meth) acrylate resin compositions (9) to (14)

Acid group-containing (meth) acrylate resin compositions (9) to (14) were obtained according to the compositions and formulations shown in Table 2 in the same manner as in example 8.

Comparative example 3 preparation of acid group-containing (meth) acrylate resin composition (C3)

The aromatic ester compound (a-3) obtained in synthesis example 3, the acid group-containing (meth) acrylate resin (B-1) obtained in synthesis example 4, an o-cresol novolac type epoxy resin ("EPICLON N-680" manufactured by DIC corporation) as a curing agent, dimethylaminopyridine as a curing accelerator, a photopolymerization initiator ("Omnirad 907" manufactured by IGM corporation) and diethylene glycol monomethyl ether acetate as an organic solvent were mixed in the mass parts shown in table 2, and kneaded by a roll mill to obtain an acid group-containing (meth) acrylate resin composition (C3).

Comparative example 4 preparation of acid group-containing (meth) acrylate resin composition (C4)

An acid group-containing (meth) acrylate resin composition (C4) was obtained in the same manner as in comparative example 3, except that the acid group-containing (meth) acrylate resin (B-2) obtained in synthesis example 5 was used in place of the acid group-containing (meth) acrylate resin (B-1) used in comparative example 3.

[ method for evaluating Heat resistance ]

The acid group-containing (meth) acrylate resin compositions obtained in examples and comparative examples were applied to a glass substrate with an applicator so that the film thickness became 50 μm, and were dried at 80 ℃ for 30 minutes. Then, 1000mJ/c of irradiation was carried out using a metal halide lampm²After the UV ray (2), the glass substrate was heated at 160 ℃ for 1 hour to peel the cured product from the glass substrate, thereby obtaining a cured product. A test piece of 6 mm. times.35 mm was cut out of the cured product, and the temperature at which the change in elastic modulus reached the maximum was evaluated as the glass transition temperature using a viscoelasticity measuring apparatus (DMA: solid viscoelasticity measuring apparatus "RSAII" manufactured by Rheometric Co., Ltd., tensile method: frequency 1Hz, temperature rising rate 3 ℃/min). The higher the glass transition temperature, the more excellent the heat resistance.

[ method for measuring dielectric constant ]

The acid group-containing (meth) acrylate resin compositions obtained in examples and comparative examples were applied to a glass substrate with an applicator so that the film thickness became 50 μm, and were dried at 80 ℃ for 30 minutes. Then, the resultant was irradiated with 1000mJ/cm using a metal halide lamp²After the UV ray (2), the glass substrate was heated at 160 ℃ for 1 hour to peel the cured product from the glass substrate, thereby obtaining a cured product. Then, the sample was stored in a room at a temperature of 23 ℃ and a humidity of 50% for 24 hours, and the dielectric constant of the sample at 1GHz was measured by a cavity resonance method using "Network analyzer E8362C" manufactured by Agilent Technologies, Inc.

[ method for measuring dielectric loss tangent ]

The acid group-containing (meth) acrylate resin compositions obtained in examples and comparative examples were applied to a glass substrate with an applicator so that the film thickness became 50 μm, and were dried at 80 ℃ for 30 minutes. Then, the resultant was irradiated with 1000mJ/cm using a metal halide lamp²After the UV ray (2), the glass substrate was heated at 160 ℃ for 1 hour to peel the cured product from the glass substrate, thereby obtaining a cured product. Then, the sample was stored in a room at a temperature of 23 ℃ and a humidity of 50% for 24 hours, and the dielectric loss tangent at 1GHz of the sample was measured by the cavity resonance method using "Network analyzer E8362C" manufactured by Agilent Technologies, Inc.

The compositions and evaluation results of the acid group-containing (meth) acrylate resin compositions (8) to (14) prepared in examples 8 to 14 and the acid group-containing (meth) acrylate resin compositions (C3) and (C4) prepared in comparative examples 3 and 4 are shown in table 2.

[ Table 2]

The amounts of the acid group-containing (meth) acrylate resins (B-1) and (B-2) in tables 1 and 2 were set to solid content values.

The evaluation "-" of comparative example 4 in table 2 indicates that the evaluation was impossible. This is because the aromatic ester compound is not compatible with the acid group-containing (meth) acrylate resin, and cloudiness occurs during mixing, which cannot be evaluated.

The "curing agent" in tables 1 and 2 represents an o-cresol novolac type epoxy resin ("EPICLON-680" manufactured by DIC corporation, epoxy equivalent: 214).

The "curing accelerator" in Table 2 represents dimethylaminopyridine.

The "organic solvent" in tables 1 and 2 represents diethylene glycol monomethyl ether acetate.

The "photopolymerization initiator" in tables 1 and 2 is "Omnirad-907" manufactured by IGM Co.

Examples 1 to 14 shown in tables 1 and 2 are examples of the acid group-containing (meth) acrylate resin composition of the present invention, and the acid group-containing (meth) acrylate resin composition of the present invention has excellent sensitivity, and a cured product of the acid group-containing (meth) acrylate resin composition of the present invention has excellent heat resistance, and it was confirmed that the dielectric constant and the dielectric loss tangent are both low, and the dielectric characteristics are also excellent.

On the other hand, comparative examples 1 to 4 are examples of acid group-containing (meth) acrylate resin compositions using an aromatic ester compound having no polymerizable unsaturated bond, and it was confirmed that the cured products of the acid group-containing (meth) acrylate resin compositions had high dielectric constants and dielectric loss tangents, and the dielectric properties were remarkably insufficient.

Claims

1. An acid group-containing (meth) acrylate resin composition characterized by containing: an aromatic ester compound (A) having a polymerizable unsaturated bond and an acid group-containing (meth) acrylate resin (B).

2. The acid group-containing (meth) acrylate resin composition according to claim 1, wherein the polymerizable unsaturated bond-containing aromatic ester compound (A) is

Aromatic compound having phenolic hydroxyl group and

a reaction product of an aromatic compound having a carboxyl group, an acid halide thereof and/or an ester thereof,

at least one of the aromatic compound having a phenolic hydroxyl group, the aromatic compound having a carboxyl group, the acid halide thereof and/or the ester thereof has a substituent having a polymerizable unsaturated bond.

3. The acid group-containing (meth) acrylate resin composition according to claim 1, wherein the polymerizable unsaturated bond-containing aromatic ester compound (A) is a compound represented by the following chemical formula (a1) or the following chemical formula (a2),

in the formula, Ar⁵Each independently is a substituted or unsubstituted 1 st aromatic ring radical, Ar⁶Each independently is a substituted or unsubstituted 2 nd aromatic ring group, Ar⁵And said Ar⁶At least one of the above groups has a substituent having a polymerizable unsaturated bond, and n is an integer of 1 to 3.

4. The acid group-containing (meth) acrylate resin composition according to claim 1, wherein the mass ratio [ (A)/(B) ] of the polymerizable unsaturated bond-containing aromatic ester compound (A) to the solid content of the acid group-containing (meth) acrylate resin (B) is in the range of 50/50 to 95/5.

5. A curable resin composition characterized by containing: the acid group-containing (meth) acrylate resin composition according to any one of claims 1 to 3, and a photopolymerization initiator.

6. The curable resin composition according to claim 5, further comprising an organic solvent and a curing agent.

7. A cured product of the curable resin composition according to claim 5 or 6.

8. An insulating material comprising the curable resin composition according to claim 5 or 6.

9. A resin material for a solder resist, characterized by being formed from the curable resin composition according to claim 5 or 6.

10. A protective member comprising the resin material for a solder resist according to claim 9.