CN112119104A

CN112119104A - Epoxy (meth) acrylate resin composition, curable resin composition, cured product, and article

Info

Publication number: CN112119104A
Application number: CN201980032062.1A
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: 2020-12-22
Anticipated expiration: 2039-05-09
Also published as: JP6743993B2; CN112119104B; TW201946945A; WO2019220995A1; TWI845509B; JPWO2019220995A1; DE112019002493T5

Abstract

The present invention provides an epoxy (meth) acrylate resin composition comprising an aromatic ester compound (A) and an epoxy (meth) acrylate resin (B), wherein the epoxy (meth) acrylate resin (B) is obtained by using an epoxy resin (B1) and a carboxyl group-containing (meth) acrylate compound (B2) as essential reaction raw materials, and the epoxy (meth) acrylate resin (B) has an epoxy group and a (meth) acryloyl group. The epoxy (meth) acrylate resin composition can form a cured product having excellent heat resistance and dielectric characteristics.

Description

Epoxy (meth) acrylate resin composition, curable resin composition, cured product, and article

Technical Field

The present invention relates to an epoxy (meth) acrylate resin composition having excellent heat resistance and dielectric characteristics, a curable resin composition containing the resin composition, a cured product of the curable resin composition, and an article having a coating film of the cured product.

Background

In the formation of a solder resist pattern in a printed wiring board, a photoresist method has been widely used. The photoresist process is characterized in that: as a resin material for pattern formation, a resin having a photopolymerizable group such as a (meth) acryloyl group and an alkali-soluble group such as a carboxyl group is used, and patterning is performed by photocuring at exposed portions and alkali development at unexposed portions. In contrast, in recent years, an ink jet method having a smaller number of steps than the photoresist method has been attracting attention as a solder resist pattern forming method.

The resin material used in the inkjet system is required to have a low viscosity to the extent that it can be subjected to inkjet printing, in addition to general resist performance such as excellent photocurability and high heat resistance of a cured product. As a resin material suitable for conventionally known inkjet printing, there is known a curable composition for inkjet printing or the like containing a compound having a (meth) acryloyl group and a thermosetting functional group, a photoreactive compound other than the compound having a (meth) acryloyl group and a thermosetting functional group, and a photopolymerization initiator, wherein at least one of the compound having a (meth) acryloyl group and a thermosetting functional group and the photoreactive compound has an aromatic skeleton and has a viscosity of 160mPa · s or more and 1200Pa · s or less as measured at 25 ℃ in accordance with JIS K2283 (see, for example, patent document 1), but the heat resistance of a cured product is insufficient, and the generation of hydroxyl groups increases the dielectric constant and the dielectric loss tangent, resulting in problems such as deterioration of dielectric characteristics.

Therefore, a material having excellent heat resistance and excellent dielectric characteristics is required.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2012-772989

Disclosure of Invention

Problems to be solved by the invention

An object to be solved by the present invention is to provide an epoxy (meth) acrylate resin composition having excellent heat resistance and dielectric characteristics, a curable resin composition containing the epoxy (meth) acrylate resin composition, a cured product of the curable resin composition, and an article having a coating film of the cured product.

Means for solving the problems

The present inventors have intensively studied to solve the above-mentioned problems, and as a result, they have found that the above-mentioned problems can be solved by using an epoxy (meth) acrylate resin composition containing an aromatic ester compound and an epoxy (meth) acrylate resin having an epoxy group and a (meth) acryloyl group, which is an essential reaction raw material of an epoxy resin and a carboxyl group-containing (meth) acrylate compound, and have completed the present invention.

Namely, the present invention relates to: an epoxy (meth) acrylate resin composition, a curable resin composition containing the epoxy (meth) acrylate resin composition, a cured product of the curable resin composition, and an article having a cured coating film of the cured product, wherein the epoxy (meth) acrylate resin composition is characterized by containing an aromatic ester compound (A) and an epoxy (meth) acrylate resin (B), the epoxy (meth) acrylate resin (B) containing an epoxy resin (B1) and a carboxyl group-containing (meth) acrylate compound (B2) as essential reaction raw materials, and the epoxy (meth) acrylate resin (B) has an epoxy group and a (meth) acryloyl group.

ADVANTAGEOUS EFFECTS OF INVENTION

Since the epoxy (meth) acrylate resin composition of the present invention has excellent heat resistance and dielectric characteristics, a curable resin composition containing the epoxy (meth) acrylate resin composition and a photopolymerization initiator can be used as a coating agent and an adhesive, and the coating agent is particularly suitably used for solder resists. The "excellent dielectric characteristics" in the present invention mean a low dielectric constant and a low dielectric loss tangent.

Detailed Description

The epoxy (meth) acrylate resin composition of the present invention is characterized by containing an aromatic ester compound (a) and an epoxy (meth) acrylate resin (B).

The aromatic ester compound (a) is a compound 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. In addition, the aromatic ester compound (a) preferably has 1 or more polymerizable unsaturated bonds in the molecular structure, from the viewpoint that an epoxy (meth) acrylate resin composition capable of forming a cured product excellent in heat resistance and dielectric characteristics can be obtained.

The aromatic ester compound (a) may be, for example, an aromatic compound which is 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 esterified product thereof (in the present specification, the aromatic compound having a carboxyl group, the acid halide thereof and/or the esterified product thereof may be collectively referred to as "an aromatic compound having a carboxyl group and the like".

At least 1 of the aromatic compound having a phenolic hydroxyl group, the aromatic compound having a carboxyl group, and the like may have 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 formation of an ester structure by reaction with a 3 rd aromatic compound or the like or a 4 th aromatic compound or the like, which will be described later.

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 obtained by substituting at least 2 of the hydrogen atoms constituting the 1 st substituted or unsubstituted aromatic ring having 3 to 30 carbon atoms with hydroxyl groups.

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 rings are 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, X is equivalent toAt the linking group.

Ar above¹Is a substituted or unsubstituted 1 st aromatic ring group. As is apparent from the description of the above chemical formula (1), 1 of the hydrogen atoms constituting the aromatic ring of the above 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; 1 hydrogen atom is removed from an aromatic compound such as a fused aromatic compound obtained by removing 1 hydrogen atom from naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, or 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 the 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; 2 hydrogen atoms are removed 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 hydrogen atoms from a ring-assembly aromatic compound such as biphenyl, binaphthyl, bipyridyl, bithiophene, phenylpyridine, phenylthiophene, terphenyl, bithiophene, 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 represents the average value thereof. In the present specification, "oligomer" includes compounds having a repeating unit of 1 to 5, and "polymer" includes compounds having a repeating unit of 6 or more. The substitution position of the substituent hydroxyl group 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 compound represented by the above chemical formula (1) as the 1 st aromatic ring can be synthesized by reacting a compound in which at least 1 of hydrogen atoms constituting the 1 st aromatic ring is substituted with a hydroxyl group, with a divinyl compound and/or a dialkoxymethyl compound.

In this case, examples of the divinyl compound and/or 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. The 1 st aromatic compound preferably has a hydroxyl group equivalent of 130 g/equivalent or more because heat resistance can be imparted. On the other hand, when the hydroxyl group equivalent of the 1 st aromatic compound is 500 g/equivalent or less, the balance between the heat resistance and the dielectric loss tangent is excellent, and therefore, it is preferable.

The 1 st aromatic compound is a compound represented by the above chemical formula (1), and when n is an oligomer or a polymer, the weight average molecular weight is preferably 200 to 3000, more preferably 200 to 2000. The 1 st aromatic compound preferably has a weight average molecular weight of 200 or more since it has an excellent dielectric loss tangent. On the other hand, the 1 st aromatic compound preferably has a weight average molecular weight of 3000 or less because of its excellent moldability. In the present specification, the value of the "weight average molecular weight" is a value measured by the following method. That is, the values obtained by Gel Permeation Chromatography (GPC) were measured under the following conditions.

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 agent: 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 tetrahydrofuran solution was filtered (50. mu.l) with a microfilter, the concentration of which was 1.0 mass% in terms of the solid content of the resin.

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 of 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".

As described above, the 2 nd aromatic compound has 1 of the hydrogen atoms constituting the substituted or unsubstituted 2 nd aromatic ring having 3 to 30 carbon atoms 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 is shown that substitution may be performed on any ring of the naphthalene ring of chemical formula (5-6) or the hetero ring of chemical formula (5-17), substitution may be performed on any ring of the benzene rings existing in 1 molecule in chemical formula (5-9) or the like, 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 molecular movement by steric hindrance, and therefore, it is preferable. In addition, 2-allylphenol having a benzene ring skeleton is preferable from the viewpoint of high processability and low viscosity of the aromatic ester compound (a), and 2-allyl-1-naphthol having a naphthalene ring skeleton, 1-allyl-2-naphthol, and the like are preferable from the viewpoint of excellent balance between heat resistance and low dielectric characteristics in the obtained cured product.

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

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 acyl halide, and when the aromatic compound has an alkoxycarbonyl group or an aryloxycarbonyl group, the aromatic compound of the 3 rd group may be an esterified 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 such as the 3 rd aromatic compound 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. 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, it is shown that substitution may be performed on any ring of the naphthalene ring of chemical formula (6-5) and the hetero ring of chemical formula (6-15), substitution may be performed on any ring of the benzene ring existing in 1 molecule in chemical formula (6-7) or the like, and the number of substituents in 1 molecule is p and q.

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, and isophthaloyl chloride, terephthaloyl chloride, and 1,3, 5-benzenetricarboxylic acid trichloride are 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, and 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, the acid halide thereof and/or the esterified product thereof is an aromatic compound having 1 carboxyl group, or a derivative thereof, specifically an acid halide or an esterified product thereof (in the present specification, the 4 th aromatic compound, the acid halide thereof and/or the esterified product thereof 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 such as the 4 th aromatic compound 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 positions of the substituents on the aromatic ring in the above chemical formula are arbitrary, and for example, they may be substituted on any ring of the naphthalene ring of chemical formula (7-5) or the hetero ring of chemical formula (7-15), or on any ring of the benzene ring present in 1 molecule in chemical formula (7-7), and the number of 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 aromatic ester Compound (A) ]

In view of obtaining an epoxy (meth) acrylate resin composition capable of forming a cured product excellent in heat resistance and dielectric characteristics, it is preferable that 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. That is, the aromatic compound having a phenolic hydroxyl group, the aromatic compound having a carboxyl group, and the like may have both of the substituents having a polymerizable unsaturated bond, only the aromatic compound having a phenolic hydroxyl group may have a substituent having a polymerizable unsaturated bond, only the aromatic compound having a carboxyl group, and the like may have a substituent having a polymerizable unsaturated bond. 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 thereof 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 aforementioned 2 nd aromatic compound is located at the molecular end of the aromatic ester compound (a). As a result, the substituent containing a polymerizable unsaturated bond, which the 2 nd aromatic compound has, is also arranged at the molecular end of the aromatic ester compound (a). In this case, the balance between the heat resistance and the dielectric loss tangent of the resulting cured product is preferably high.

As described above, the aromatic ester compound (a) is a reaction product of a compound having a phenolic hydroxyl group and an aromatic compound having a carboxyl group or the like, and may include various compounds such as the aromatic compounds of the above 1 to 4, and either one of the 2 nd aromatic compound and the 4 th aromatic compound or both of them is contained as an essential component in terms of having a function of stopping the esterification reaction. The composition of the aromatic ester compound (a) can be controlled by appropriately changing the amount of the aromatic compound or the like used, the reaction conditions, and the like in the above-mentioned 1 st to 4 th stages.

In one embodiment, examples of the aromatic ester compound (a) include: an aromatic ester compound which is a reaction product of a1 st aromatic compound and a 4 th aromatic compound or the like; an aromatic ester compound which is a reaction product of a1 st aromatic compound, a2 nd aromatic compound, a 3 rd aromatic compound, and the like; an aromatic ester compound which is a reaction product of a1 st aromatic compound, a 3 rd aromatic compound, a 4 th aromatic compound, and the like; aromatic ester compounds as reaction products of 1 st aromatic compounds, 2 nd aromatic compounds, 3 rd aromatic compounds, etc. and 4 th aromatic compounds, etc.; an aromatic compound which is a reaction product of the 2 nd aromatic compound and the 3 rd aromatic compound; aromatic compounds as reaction products of the 2 nd aromatic compound and the 4 th aromatic compound, and the like.

In principle, the aromatic ester compound (a) of the present embodiment has no hydroxyl group in the molecule of the obtained resin. However, a compound having a hydroxyl group as a by-product of the reaction product may be contained within a range in which the effect of the present invention is not inhibited.

In one embodiment, the 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 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 compound obtained by removing 2 or more hydrogen atoms from a1 st aromatic ring having 3 to 30 carbon atoms which may be substituted or unsubstituted, or a compound having a structure in which 1 st aromatic ring is linked via a linking group.

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 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 is³It may have a branched structure.

In one embodiment, the 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 aromatic ester compound (a) is an oligomer or a polymer, n represents an average value thereof.

That is, in the above chemical formula (9), Ar¹Each of which is independently a compound obtained by removing 2 or more hydrogen atoms from a1 st aromatic ring having 3 to 30 carbon atoms which may be substituted or unsubstituted, or a compound having a structure in which 1 st aromatic ring is linked via 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 groups may have a substituent containing a polymerizable unsaturated bond having 2 to 30 carbon atoms.

In one embodiment, the 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 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 compound obtained by removing 2 or more hydrogen atoms from a1 st aromatic ring having 3 to 30 carbon atoms which may be substituted or unsubstituted, or a compound having a structure in which 1 st aromatic ring is linked via a linking group.

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 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 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 (c) is reacted to obtain the structure.

In one embodiment, the aromatic ester compound (a) includes, for example, an aromatic ester compound (a-1) represented by the following chemical formula (a1) and an 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, and n is an integer of 1 to 3. Angle (c)

The aromatic ester compound (A-1) is represented by the 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 each 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; from naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzeneAnd 2 or 3 hydrogen atoms are removed from an aromatic compound such as a fused aromatic compound such as benzimidazole, benzofuran or acridine, or 2 or 3 hydrogen atoms are removed from an aromatic compound. 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; and those obtained by removing 2 or 3 hydrogen atoms from an aromatic compound connected via an alkylene group, such as diphenylmethane, diphenylethane, 1-diphenylethane, 2-diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenylpyridinemethane, fluorene, or diphenylcyclopentane. Among these, Ar is an epoxy (meth) acrylate resin composition that can form a cured product having excellent heat resistance and dielectric characteristics⁵A 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 in which at least 1 of hydrogen atoms constituting the substituent having a polymerizable unsaturated bond is substituted. 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 aromatic ester compound (A) is preferably represented by the formulae (12-1) and (12-2) from the viewpoint of high processability and low viscosity, and the resulting cured product is preferably represented by the formulae (12-6) and (12-7) from the viewpoint of excellent balance between heat resistance and low dielectric characteristics.

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

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 in the aromatic ring constituting the 2 nd aromatic ring group is substituted with "-OC (O) Ar⁵"substitution".

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; removing 1 hydrogen from fused ring aromatic compounds such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine, etcAnd those in which 1 hydrogen atom is removed from an aromatic compound. 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; and those obtained by removing 1 hydrogen atom from an aromatic compound connected via an alkylene group, such as diphenylmethane, diphenylethane, 1-diphenylethane, 2-diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenylpyridinemethane, fluorene, or diphenylcyclopentane. Among these, Ar is an epoxy (meth) acrylate resin composition that can form a cured product having excellent heat resistance and dielectric characteristics⁶A 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 means 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 of formulae with" -OC (O) Ar⁵"bonding position". In addition, of "" with aromatic ringsBonding at any position can be carried out.

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 of 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 chemical formula (a1), Ar is preferably used in order to obtain an epoxy (meth) acrylate resin composition capable of forming a cured product having excellent heat resistance and dielectric properties⁵And 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, Ar⁵And Ar⁶May have a substituent having a polymerizable unsaturated bond.

By one embodiment, Ar is preferred⁶At least 1 of them has a substituent having a polymerizable unsaturated bond, and more preferably all Ar⁶Having a substituent containing a polymerizable unsaturated bond, more preferably Ar⁵Having no substituent containing a polymerizable unsaturated bond and all Ar⁶Having a substituent containing a polymerizable unsaturated bond. The substituent containing polymerizable unsaturated bond being present in Ar⁶In the case of (iii), an epoxy (meth) acrylate resin composition capable of forming a cured product having an excellent balance between heat resistance and dielectric characteristics is preferred.

In the chemical formula (a1), n is an integer of 1 to 3. That is, the aromatic ester compound (A-1) has 1 to 3 ester bonds to which 2 aromatic rings are bonded.

As described above, as a more preferable embodiment of the 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 independently an integer of 1 or more, j is 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 independently an integer of 1 or more, m is 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. In the formula (a1-2), R¹、R²Substitution may be made at any carbon atom on the naphthalene ring. Angle (c)

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

Specific structures of the aromatic ester compound (A-1) represented by the above chemical formula (a1) are 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 (14-47), 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 aromatic ester compound (A-1) is not particularly limited, and can be produced by an appropriately known method.

Examples of the method for producing the aromatic ester compound (A-1) include a method in which the 2 nd aromatic compound is reacted with the 3 rd aromatic compound, and the like.

The aromatic ester compound (A-2) is represented by the 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 "-C (O) OAr⁶"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)⁶Is a 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 in the aromatic ring constituting the 2 nd aromatic ring group are substituted with-OC (O) Ar⁵"substitution".

As the aforesaid chemistryAr in 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 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 aromatic ester compound (A-2) represented by the above chemical formula (a2), a compound represented by the following chemical formula (1-3) or (1-4) can be exemplified.

[ 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, particularly preferred are 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, particularly preferred are allyl, propenyl, isopropenyl and 1-propenyl. l is preferably 1 or 2, more preferably 1.

Specific structures of the aromatic ester compound (A-2) represented by the above chemical formula (a2) are not particularly limited, and examples thereof include compounds represented by the following chemical formulas (15-1) to (15-6).

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

Examples of the method for producing the aromatic ester compound (A-2) include a method in which the 1 st aromatic compound and the 4 th aromatic compound are reacted with each other.

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

For example, in view of obtaining an epoxy (meth) acrylate resin composition capable of forming a cured product excellent in heat resistance and dielectric properties, the ratio of the number of moles of carboxyl groups or the like 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 or the like/hydroxyl groups) is preferably 0.3 to 3.

In the production of the 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 epoxy (meth) acrylate resin (B) is essentially a reaction product of an epoxy resin (B1) and a carboxyl group-containing (meth) acrylate compound (B2).

The epoxy (meth) acrylate resin (B) has an epoxy group derived from the epoxy resin (B1) and a (meth) acryloyl group derived from the carboxyl group-containing (meth) acrylate compound (B2).

The specific structure of the epoxy resin (b1) is not particularly limited as long as it has a plurality of epoxy groups in the resin and reacts with the carboxyl group-containing (meth) acrylate compound (b2) to form an epoxy (meth) acrylate resin. Examples of the epoxy resin (b1) include bisphenol epoxy resins, hydrogenated bisphenol epoxy resins, biphenol epoxy resins, hydrogenated biphenol epoxy resins, phenyl ether epoxy resins, naphthyl ether epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol novolac epoxy resins, naphthol novolac epoxy resins, phenol aralkyl epoxy resins, naphthol aralkyl epoxy resins, dicyclopentadiene-phenol addition reaction epoxy resins, biphenyl aralkyl epoxy resins, fluorene epoxy resins, xanthene epoxy resins, dihydroxybenzene epoxy resins, trihydroxybenzene epoxy resins, and the like. These epoxy resins (b1) may be used alone or in combination of two or more. Among these, bisphenol epoxy resins, hydrogenated bisphenol epoxy resins, biphenol epoxy resins, hydrogenated biphenol epoxy resins, naphthol epoxy resins, and dihydroxybenzene epoxy resins are preferable, and bisphenol epoxy resins, hydrogenated bisphenol epoxy resins, and dihydroxybenzene epoxy resins are more preferable, from the viewpoint of obtaining an epoxy (meth) acrylate resin composition capable of forming a cured product excellent in heat resistance and dielectric properties.

Examples of the bisphenol epoxy resin include bisphenol a epoxy resin, bisphenol AP epoxy resin, bisphenol B epoxy resin, bisphenol BP epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and the like.

Examples of the hydrogenated bisphenol epoxy resin include hydrogenated bisphenol a epoxy resin, hydrogenated bisphenol B epoxy resin, hydrogenated bisphenol E epoxy resin, hydrogenated bisphenol F epoxy resin, hydrogenated bisphenol S epoxy resin, and the like.

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

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

Examples of the dihydroxybenzene epoxy resin include catechol epoxy resin, resorcinol epoxy resin, and hydroquinone epoxy resin.

When the epoxy resin (b1) is any one of the bisphenol epoxy resin, the hydrogenated bisphenol epoxy resin, the diphenol epoxy resin, the hydrogenated diphenol epoxy resin, the naphthol epoxy resin and the dihydroxybenzene epoxy resin, the epoxy equivalent of the epoxy resin (b1) is preferably in the range of 110 to 400 g/equivalent in view of obtaining an epoxy (meth) acrylate resin composition capable of forming a cured product excellent in heat resistance and dielectric properties.

The specific structure of the carboxyl group-containing (meth) acrylate compound (b2) is not particularly limited as long as it has a carboxyl group and a (meth) acryloyl group in its molecular structure, and a low molecular weight compound having a molecular weight in the range of 100 to 500 is preferable, and a compound having a molecular weight in the range of 150 to 400 is more preferable, in addition to acrylic acid and methacrylic acid. More specifically, for example, a compound represented by the following structural formula (16) and the like can be given.

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

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

Examples of the (poly) ester chain include a (poly) ester chain represented by the following structural formula (X-1).

(in the formula, R₁Is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5. )

Examples of the aromatic hydrocarbon chain include a benzene chain, a naphthalene chain, a biphenyl chain, a phenylnaphthalene chain, and a binaphthyl chain. In addition, as a partial structure, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring may be used.

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

(in the formula, R₂Is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5. )

These carboxyl group-containing (meth) acrylate compounds (b2) may be used alone or in combination of two or more.

Further, as the carboxyl group-containing (meth) acrylate compound (b2), an acid anhydride of the carboxyl group-containing (meth) acrylate compound may also be used.

Examples of the acid anhydride of the carboxyl group-containing (meth) acrylate compound include (meth) acrylic acid anhydride and the like.

The amount of the carboxyl group-containing (meth) acrylate compound (b2) used is preferably in the range of 0.2 to 0.8 mol, more preferably in the range of 0.3 to 0.7 mol, based on 1 mol of the epoxy resin (b1), from the viewpoint of obtaining an epoxy (meth) acrylate resin having excellent storage stability.

In view of obtaining an epoxy (meth) acrylate resin composition capable of forming a cured product excellent in heat resistance and dielectric properties, the epoxy (meth) acrylate resin (B) preferably has a (meth) acryloyl equivalent weight of 200 to 800 g/equivalent. The epoxy equivalent of the epoxy (meth) acrylate resin (B) is preferably in the range of 300 to 900 g/equivalent.

The acid value of the epoxy (meth) acrylate resin (B) is preferably 3mgKOH/g or less, and more preferably 2mgKOH/g or less, from the viewpoint that an epoxy (meth) acrylate resin composition capable of forming a cured product excellent in heat resistance and dielectric properties can be obtained. The hydroxyl value is preferably 300mgKOH/g or less.

The reaction of the epoxy resin (b1) and the carboxyl group-containing (meth) acrylate compound (b2) is preferably carried out in the presence of a basic catalyst.

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- (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 diacetate, dibutyltin 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. Among these, triphenylphosphine is preferable.

The amount of the basic catalyst used is preferably in the range of 0.01 to 0.5 parts by mass, more preferably in the range of 0.01 to 0.4 parts by mass, based on 100 parts by mass of the total of the epoxy resin (b1) and the carboxyl group-containing (meth) acrylate compound (b2), from the viewpoint of obtaining an epoxy (meth) acrylate resin having a low viscosity and excellent storage stability.

When a basic catalyst is used in the reaction of the epoxy resin (b1) and the carboxyl group-containing (meth) acrylate compound (b2), the basic catalyst may be used after the reaction by being separated and removed, or the basic catalyst may be used by being deactivated with an acidic compound without being separated and removed.

Examples of the acidic compound include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid. These acidic compounds may be used alone or in combination of two or more.

The method for producing the epoxy (meth) acrylate resin (B) is not particularly limited, and any method may be used. For example, the compound can be produced by a method in which all the reaction materials are reacted at once, or by a method in which the reaction materials are reacted sequentially. Among them, from the viewpoint of easy control of the reaction, the following method can be used: a method in which the epoxy resin (b1) and the carboxyl group-containing (meth) acrylate compound (b2) are reacted at a temperature of 80 to 140 ℃ in the presence of a basic catalyst, and then an acidic compound is added thereto and mixed at a temperature of 50 to 100 ℃ to deactivate the basic catalyst.

The epoxy (meth) acrylate resin composition of the present invention contains the aromatic ester compound (a) and the epoxy (meth) acrylate resin (B).

The content of the aromatic ester compound (a) in the epoxy (meth) acrylate resin composition of the present invention is preferably in the range of 10 to 90% by mass, from the viewpoint that an epoxy (meth) acrylate resin composition capable of forming a cured product excellent in heat resistance and dielectric characteristics can be obtained.

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

In view of obtaining an epoxy (meth) acrylate resin composition capable of forming a cured product excellent in heat resistance and dielectric properties, the mass ratio [ (a)/(B) ] of the aromatic ester compound (a) to the solid content of the epoxy (meth) acrylate resin (B) is preferably in the range of 10/90 to 90/10.

The epoxy (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-hydroxymethoxy) 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 1 to 20% by mass in the curable resin composition, for example.

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

The epoxy resin (b1) can be used as an example, and the epoxy resin can be used alone or in combination of two or more.

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, 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 bisphenol 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 curable resin composition of the present invention may contain an organic solvent for the purpose of adjusting the coating viscosity, and the type and the amount of the organic solvent to be added are appropriately selected and adjusted according to the desired performance.

Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, and isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; 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. These organic solvents may be used alone or in combination of two or more.

The curable resin composition of the present invention may contain various additives such as inorganic fine particles, polymer fine particles, pigments, defoaming agents, viscosity modifiers, leveling agents, flame retardants, and storage stabilizers, as necessary.

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 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, the curing reaction by ultraviolet rays can be efficiently performed, and irradiation may be performed in an inert gas atmosphere such as nitrogen gas or in an air atmosphere.

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

The article of the present invention has a coating film formed from the cured product. Examples of the article include a semiconductor device, a display device, an imaging device, a magnetic head, and a MEMS.

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

Synthesis example 1 Synthesis of aromatic ester Compound (A-1)

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 resulting mixture was dried under reduced pressure under heating to obtain an aromatic ester compound (A-1) represented by the following chemical formula. The ester group equivalent of the 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)

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))

244 parts by mass (2.0mol) of 2, 5-xylenol and 1120 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, while controlling the temperature in the system to 60 ℃ or lower while adding 0.6 part by mass of tetrabutylammonium bromide and purging with nitrogen, 410 parts by mass of a 20% aqueous sodium hydroxide solution was added over 3 hours, 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-1) represented by the following chemical formula. The ester group equivalent of the aromatic ester compound (A-3) was 187 g/equivalent. The ester group equivalent is a calculated value calculated from the charge ratio.

Synthesis example 4 Synthesis of epoxy (meth) acrylate resin (B-1)

In a flask equipped with a thermometer, a stirrer and a reflux condenser, 344 parts by mass of a bisphenol A type epoxy resin ("EPICLON EXA-850 CRP" manufactured by DIC corporation, epoxy equivalent: 172 g/eq), 0.21 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.21 parts by mass of hydroquinone monomethyl ether as a thermal polymerization inhibitor were added, and then 72 parts by mass of acrylic acid and 0.21 parts by mass of triphenylphosphine were added to conduct an esterification reaction at 100 ℃ for 10 hours while blowing air. Then, after confirming that the acid value was 1mgKOH/g or less, 0.42 parts by mass of oxalic acid was added thereto and the mixture was stirred at 70 ℃ for 3 hours to obtain epoxy (meth) acrylate resin (B-1). The epoxy equivalent of the epoxy (meth) acrylate resin (B-1) was 445 g/eq, and the (meth) acryloyl equivalent was 416 g/eq. The equivalent weight of the (meth) acryloyl group is a calculated value.

Synthesis example 5 Synthesis of epoxy (meth) acrylate resin (B-2)

Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 318 parts by mass of a bisphenol F-type epoxy resin ("EPICLON 830 CRP" manufactured by DIC corporation, epoxy equivalent 159 g/equivalent, hereinafter abbreviated as "bisphenol F-type epoxy resin (1)") was charged, 0.2 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.2 parts by mass of hydroquinone monomethyl ether as a thermal polymerization inhibitor were added, and then 72 parts by mass of acrylic acid and 0.2 parts by mass of triphenylphosphine were added to conduct esterification reaction at 100 ℃ for 10 hours while blowing air. Then, after confirming that the acid value was 1mgKOH/g or less, 0.2 part by mass of oxalic acid was added thereto, and the mixture was stirred at 70 ℃ for 3 hours to obtain epoxy (meth) acrylate resin (B-2). The epoxy equivalent of the epoxy (meth) acrylate resin (B-2) was 421 g/eq, and the equivalent of the (meth) acryloyl group was 390 g/eq. The equivalent weight of the (meth) acryloyl group is a calculated value.

Synthesis example 6 Synthesis of epoxy (meth) acrylate resin (B-3)

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 282 parts by mass of a naphthalene-type epoxy resin ("EPICLON 4032D" manufactured by DIC corporation, epoxy equivalent 141 g/equivalent, hereinafter abbreviated as "naphthalene-type epoxy resin (1)") was charged, 0.18 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.18 parts by mass of hydroquinone monomethyl ether as a thermal polymerization inhibitor were added, and then 72 parts by mass of acrylic acid and 0.18 parts by mass of triphenylphosphine were added to conduct esterification reaction at 100 ℃ for 10 hours while blowing air. Then, after confirming that the acid value was 1mgKOH/g or less, 0.18 parts by mass of oxalic acid was added thereto, and the mixture was stirred at 70 ℃ for 3 hours to obtain an epoxy (meth) acrylate resin (B-3). The epoxy equivalent of the epoxy (meth) acrylate resin (B-3) was 388 g/eq, and the equivalent of the (meth) acryloyl group was 354 g/eq. The equivalent weight of the (meth) acryloyl group is a calculated value.

Synthesis example 7 Synthesis of epoxy (meth) acrylate resin (B-4)

A flask equipped with a thermometer, a stirrer and a reflux condenser was charged with 18g of butyl acetate, 129g of resorcinol-type epoxy resin ("ERISYS RDGE-H" manufactured by CVC Thermoset Specialties, epoxy equivalent 129 g/equivalent), 0.1g of dibutylhydroxytoluene, 0.1g of hydroquinone monomethyl ether, 36g of acrylic acid and 0.1g of triphenylphosphine, and esterification reaction was carried out at 80 ℃ for 20 hours while blowing air. Then, after confirming that the acid value was 1mgKOH/g or less, 0.1 part by mass of oxalic acid was added thereto, and the mixture was stirred at 70 ℃ for 3 hours to obtain an epoxy (meth) acrylate resin (B-4). The epoxy equivalent of the epoxy (meth) acrylate resin (B-4) was 565 g/eq, and the (meth) acryloyl equivalent was 330 g/eq. The equivalent weight of the (meth) acryloyl group is a calculated value.

Example 1 preparation of epoxy (meth) acrylate resin composition (1)

The aromatic ester compound (A-1) obtained in Synthesis example 1, the epoxy (meth) acrylate resin (B-1) obtained in Synthesis example 4, and a photopolymerization initiator ("Omnirad 184" manufactured by IGM) were mixed in the amounts shown in Table 1 to obtain an epoxy (meth) acrylate resin composition (1).

Examples 2 to 13 preparation of epoxy (meth) acrylate resin compositions (2) to (13)

Epoxy (meth) acrylate resin compositions (2) to (13) were obtained in the same manner as in example 1, except that the components and compounding were changed as shown in Table 1.

Comparative examples 1 and 2 preparation of epoxy (meth) acrylate resin compositions (C1) and (C2)

Epoxy (meth) acrylate resin (B-1) obtained in Synthesis example 4, EO-modified diacrylate of bisphenol A ("Miramer M-240" manufactured by Miwon Commercial Co., Ltd.), and a photopolymerization initiator ("Omnirad 184" manufactured by IGM) were mixed in the compounding amounts shown in Table 1 to obtain epoxy (meth) acrylate resin compositions (C1) and (C2).

The epoxy (meth) acrylate resin compositions obtained in the above examples and comparative examples were used to perform the following evaluations.

[ method for evaluating Heat resistance ]

The epoxy (meth) acrylate resin compositions obtained in examples and comparative examples were applied to a glass substrate with a film thickness of 50 μm using an applicator, and 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. A test piece of 6 mm. times.35 mm was cut out of the cured product, and evaluated using a viscoelasticity measuring apparatus (DMA: solid viscoelasticity measuring apparatus "RSAII" manufactured by Rheometrics, tensile method: frequency 1Hz, temperature rise rate 3 ℃/min) with the temperature at which the elastic modulus change is the largest as the glass transition temperature. The higher the glass transition temperature, the more excellent the heat resistance.

[ method for measuring dielectric constant ]

The epoxy (meth) acrylate resin compositions obtained in examples and comparative examples were applied to a glass substrate with a film thickness of 50 μm using an applicator, and dried at 80 ℃ for 30 minutes. Then, using metal halogenationObject lamp irradiating 1000mJ/cm²After 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 the cavity resonator method using "Network analyzer E8362C" manufactured by Agilent Technologies, Inc.

[ method for measuring dielectric loss tangent ]

The epoxy (meth) acrylate resin compositions obtained in examples and comparative examples were applied to a glass substrate with a film thickness of 50 μm using an applicator, and 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 resonator method using "Network analyzer E8362C" manufactured by Agilent Technologies, Inc.

The evaluation results of the epoxy (meth) acrylate resin compositions (1) to (13) prepared in examples 1 to 13 and the epoxy (meth) acrylate resin compositions (C1) and (C2) prepared in comparative examples 1 and 2 are shown in table 1.

[ Table 1]

The "epoxy resin" in Table 1 represents a bisphenol A type epoxy resin ("EPICLON EXA-850 CRP" manufactured by DIC corporation, epoxy equivalent: 172 g/equivalent).

Examples 1 to 13 shown in table 1 are examples of the epoxy (meth) acrylate resin composition of the present invention, and it was confirmed that a cured product of the epoxy (meth) acrylate resin composition of the present invention has excellent heat resistance, and also has low dielectric constant and dielectric loss tangent and excellent dielectric characteristics.

On the other hand, comparative examples 1 and 2 are examples of epoxy (meth) acrylate resin compositions not using an aromatic ester compound, and it was confirmed that the cured products of the epoxy (meth) acrylate resin compositions were high in both dielectric constant and dielectric loss tangent, and the dielectric characteristics were remarkably insufficient.

Claims

1. An epoxy (meth) acrylate resin composition comprising an aromatic ester compound (A) and an epoxy (meth) acrylate resin (B),

the epoxy (meth) acrylate resin (B) is obtained by using an epoxy resin (B1) and a carboxyl group-containing (meth) acrylate compound (B2) as essential reaction raw materials,

the epoxy (meth) acrylate resin (B) has an epoxy group and a (meth) acryloyl group.

2. The epoxy (meth) acrylate resin composition according to claim 1, wherein the aromatic ester compound (a) is:

aromatic compound having phenolic hydroxyl group, and

aromatic compound having carboxyl group, acid halide thereof and/or esterified product thereof

The reaction product of (1).

3. The epoxy (meth) acrylate resin composition according to claim 1, wherein the 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, and n is an integer of 1 to 3.

4. The epoxy (meth) acrylate resin composition according to claim 2 wherein at least one of the aromatic compound having a phenolic hydroxyl group and the aromatic compound having a carboxyl group, an acid halide thereof and/or an esterified product thereof has a substituent having a polymerizable unsaturated bond.

5. The epoxy (meth) acrylate resin composition according to claim 3, wherein the Ar is⁵And said Ar⁶At least one of them has a substituent having a polymerizable unsaturated bond.

6. The epoxy (meth) acrylate resin composition according to claim 1, wherein a mass ratio [ (A)/(B) ] of the aromatic ester compound (A) to the solid content of the epoxy (meth) acrylate resin (B) is in a range of 10/90 to 90/10.

7. A curable resin composition comprising the epoxy (meth) acrylate resin composition according to any one of claims 1 to 6 and a photopolymerization initiator.

8. The curable resin composition according to claim 7, further comprising a (meth) acrylate monomer.

9. The curable resin composition according to claim 7, further comprising an epoxy resin.

10. A cured product of the curable resin composition according to claim 7 to 9.

11. An article having a coating film formed from the cured product according to claim 10.