DE112019002493T5 - Epoxy (meth) acrylate resin composition, curable resin composition, cured product and article - Google Patents

Abstract

The present invention provides an epoxy (meth) acrylate resin composition containing an aromatic ester compound (A) and an epoxy (meth) acrylate resin (B), characterized in that the epoxy (meth) acrylate resin (B) is composed of an epoxy resin (b1 ) and a carboxyl group-containing (meth) acrylate compound (b2) is formed as indispensable reaction materials, and that the epoxy (meth) acrylate resin (B) has epoxy groups and (meth) acryloyl groups. The epoxy (meth) acrylate resin composition can form a cured product excellent in heat resistance and excellent dielectric properties.

Description

[Technical area]

The present invention relates to an epoxy (meth) acrylate resin composition excellent in heat resistance and excellent dielectric properties, a curable resin composition containing them, a cured product of the curable resin composition, and an article coated with the cured product.

[Technical background]

A photoresist process has heretofore been largely used to form solder mask patterns on circuit boards. The photoresist method is characterized in that, as a resin material for pattern formation, a resin comprising a photopolymerizable group such as a (meth) acryloyl group, etc., and an alkali-soluble group such as a carboxyl group, etc. is used, the pattern being exposed by photo-curing Split and alkaline development of unexposed parts takes place. In contrast, in recent years, as a method of forming solder mask patterns, attention is paid to an ink jet method because the number of stages of this method is smaller than that of the photoresist method.

The resin materials used in the ink jet method require not only general resist characteristics such as superior photo-curability, high heat resistance of the cured product, etc., but also a viscosity so low that ink-jet printing is possible. As resin materials suitable for ink jet printing, curable ink jet compositions, etc., which have a compound having a (meth) acryloyl group and a thermosetting functional group, and other compounds besides this compound having a (meth) acryloyl group and a thermosetting functional group, have hitherto been known , photoreactive compound and a photopolymerization initiator, wherein at least either the compound having a (meth) acryloyl group and a thermosetting functional group or the photoreactive compound has an aromatic skeleton, and the viscosity, measured at 25 ° C according to JIS K2283, 160 mPa · s or more and 1200 mPa · s or less (see, for example, Patent Document 1). However, these compositions have problems that the heat resistance of their cured product is insufficient and, in addition, the dielectric properties are poor because the formation of hydroxyl groups increases the dielectric constant and the dielectric loss factor.

Therefore, materials with both excellent heat resistance and excellent dielectric properties are sought after.

[Prior Art Document]

[Patent document]

Patent Document 1: JP2012-772989A

[Summary of the invention]

[Problem to be solved by the invention]

The object to be achieved of the invention is to provide an epoxy (meth) acrylate resin composition excellent in heat resistance and excellent dielectric properties, a curable resin composition containing them, a cured product of the curable resin composition and an article coated with the cured product.

[Means of solving the task]

After careful study to achieve the above object, the present inventors have found that the object can be achieved by using an epoxy (meth) acrylate resin composition containing an aromatic ester compound and an epoxy (meth) acrylate resin composed of an epoxy resin and a carboxyl group-containing (meth) acrylate compound is formed as indispensable reaction materials and has epoxy groups and (meth) acryloyl groups. This completed the invention.

The present invention thus relates to an epoxy (meth) acrylate resin composition containing an aromatic ester compound (A) and an epoxy (meth) acrylate resin (B), characterized in that the epoxy (meth) acrylate resin (B) consists of an epoxy resin (b1) and a carboxyl group-containing (meth) acrylate compound (b2) is formed as indispensable reaction materials, and that the epoxy (meth) acrylate resin (B) has epoxy groups and (meth) acryloyl groups; a curable resin composition containing them, a cured product of the curable resin composition, and an article having a cured coating of the cured product.

[Advantages of the invention]

The epoxy (meth) acrylate resin composition of the invention has excellent heat resistance and excellent dielectric properties, so that a curable resin composition containing the epoxy (meth) acrylate resin composition and a photopolymerization initiator can be used as a coating agent or adhesive, and particularly as a coating agent for use for Solder resists is advantageous. The “excellent dielectric properties” in the present invention are understood to mean a low dielectric constant and a low dielectric loss factor.

[Embodiments of the Invention]

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) represents a compound having a partial structure in which aromatic rings are bonded to each other through an ester bond. The other specific structures, the molecular weight, etc. do not have to be particularly taken into account, so that a wide variety of compounds can be used. It is advantageous that the aromatic ester compound (A) has one or more polymerizable unsaturated bonds in the molecular structure in order to obtain an epoxy (meth) acrylate resin composition which can form a cured product excellent in heat resistance and excellent dielectric properties.

As the aromatic ester compound (A), for. B. such aromatic compounds are listed, the reaction products of an aromatic compound with phenolic hydroxyl groups and an aromatic compound with carboxyl groups, whose acid halide and / or their esterification product are (in the present description, the aromatic compound with carboxyl groups, their acid halide and / or their esterification product possibly referred to collectively as "aromatic compound etc. with carboxyl groups").

At least one of the aromatic compound having phenolic hydroxyl groups and the aromatic compound etc. having carboxyl groups may include a substituent having a polymerizable unsaturated bond.

The aromatic compound with phenolic hydroxyl groups includes, for. B. first aromatic compounds, which have two or more phenolic hydroxyl groups, and second aromatic compounds, which have one phenolic hydroxyl group.

The first aromatic compound has two or more phenolic hydroxyl groups. Since it has two or more phenolic hydroxyl groups, it can form an ester structure by reacting it with a third or fourth aromatic compound, etc. mentioned later.

The first aromatic compounds are not particularly limited. For example, compounds having two or more phenolic hydroxyl groups on a substituted or unsubstituted first aromatic ring having a carbon number of 3 to 30 are given.

The first aromatic ring with a number of carbon atoms from 3 to 30 includes e.g. B. monocyclic aromatic rings, condensed aromatic rings, compound aromatic rings, etc.

Examples of the monocyclic aromatic rings are benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, etc.

Examples of the condensed aromatic rings are naphthalene, anthracene, phenals, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzoimidazole, benzofuran, acridine, etc.

Examples of the composite aromatic rings are biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl, etc.

The first aromatic ring having a number of carbon atoms of 3 to 30 may have a substituent. Here, as “substituent of the first aromatic ring”, for example, alkyl groups with a carbon atom number of 1 to 10, alkoxy groups with a carbon atom number of 1 to 10, halogen atoms, substituents with a polymerizable unsaturated bond, etc. are listed.

The alkyl group with a number of carbon atoms from 1 to 10 includes, for example, 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 or cyclononyl groups, etc. .

The alkoxy group with a carbon atom number of 1 to 10 includes, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, 2-ethylhexyloxy, octyloxy and nonyloxy, etc.

The halogen atom includes, for example, a fluorine, chlorine, bromine or iodine atom, etc.

By the substituent having a polymerizable unsaturated bond is meant a substituent having a carbon atom number of 2 to 30 and having at least one polymerizable unsaturated bond. “Unsaturated bond” means a carbon atom-carbon atom double bond or a carbon atom-carbon atom triple bond. As substituents with an unsaturated bond, for. B. an alkenyl or alkynyl group, etc. listed.

The alkenyl group includes, for example, vinyl, allyl, propenyl, isopropenyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-hexenyl, 2-hexenyl, 3- Hexenyl, 4-hexenyl, 5-hexenyl, 1-octenyl, 2-octenyl, 1-undecenyl, 1-pentadecenyl, 3-pentadecenyl, 7-pentadecenyl, 1-octadecenyl, 2- Octadecenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, 1,3-butadienyl, 1,4-butadienyl, hexa-1,3-dienyl, hexa-2,5-dienyl, pentadeca-4,7 dienyl, hexa-1,3,5-trienyl or pentadeca-1,4,7-trienyl group etc.

The alkynyl group includes, for example, an ethynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 3-penthynyl, 4-penthynyl or 1,3-butadiynyl group, etc.

Of these, the substituent having a polymerizable unsaturated bond is preferably an alkenyl group having a carbon number of 2 to 30, more preferably an alkenyl group having a carbon number of 2 to 10, even more preferably an alkenyl group having a carbon number of 2 to 5, particularly preferably a vinyl -, allyl, propenyl, isopropenyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl and 1,3-butadienyl groups. Allyl, propenyl, isopropenyl and 1-propenyl, respectively, are most preferred.

The first aromatic ring can contain a single substituent or a combination of two or more substituents.

As mentioned above, in the first aromatic compound, at least two of the hydrogen atoms forming the substituted or unsubstituted first aromatic ring having a number of carbon atoms of 3 to 30 are each substituted by a hydroxyl group.

Concrete examples of the compound which comprises a monocyclic aromatic ring as the first aromatic ring (in the following possibly simply referred to as "first monocyclic aromatic ring compound") are catechol, resorcinol, hydroquinone, hydroxynol, phloroglucinol, pyrogallol, 2,3-dihydroxypyridine, 2,4-dihydroxypyridine, 4,6-dihydroxypyrimidine, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, etc.

Concrete examples of the compound comprising a condensed aromatic ring as the first aromatic ring (hereinafter referred to simply as “first condensed aromatic ring compound” if necessary) are 1,3-naphthalenediol, 1,5-naphthalenediol, 2,6-naphthalenediol, 2 , 7-naphthalenediol, 1,2,4- Naphthalene triol, 1,4,5-naphthalene triol, 9,10-dihydroxyanthracene. 1,4,9,10-tetrahydroxyanthracene, 2,4-dihydroxyquinoline, 2,6-dihydroxyquinoline, 5,6-dihydroxyindole, 2-methylnaphthalene-1,4-diol, etc.

Concrete examples of the compound comprising a compound aromatic ring as the first aromatic ring (hereinafter referred to simply as “first compound aromatic ring compound” if necessary) are 2,2'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 3,4,4 '-Trihydroxybiphenyl, 2,2', 3-trihydroxybiphenyl, etc.

The first aromatic compound may have a structure in which the first aromatic rings are linked to each other through a linking group. In one embodiment, the first aromatic compound is represented by the following chemical formula (1):

In chemical formula (1), Ar ¹ each independently represents a substituted or unsubstituted first aromatic ring group, Ar ² each independently represents a substituted or unsubstituted second aromatic ring group, X each independently represents an oxygen atom, sulfur atom, substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene or aralkylene, and n is an integer from 0 to 10. At least two of the hydrogen atoms that Ar ¹ and Ar ² form are each substituted by a hydroxyl group. X corresponds to the linking group.

Ar ¹ represents the substituted or unsubstituted first aromatic ring group. As can be seen from the description of the chemical formula (1), one of the hydrogen atoms of the aromatic ring that forms the above-mentioned substituted or unsubstituted aromatic ring is bonded to “X”.

Examples of the first aromatic ring group are aromatic compounds from which a hydrogen atom has been removed, namely, monocyclic aromatic compounds such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine , Triazine, etc. from which one hydrogen atom has been removed; and condensed ring aromatic compounds such as naphthalene, anthracene, phenals, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzoimidazole, benzofuran, acridine, etc., from which a hydrogen atom has been removed. Combinations of these aromatic compounds can also be given, e.g. B. aromatic compounds of compound rings such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl, etc., from which a hydrogen atom has been removed.

The first aromatic ring group can have a substituent. The “substituent of the first aromatic ring group” here substitutes at least one of the hydrogen atoms of the aromatic ring forming the first aromatic ring group. Examples of the "substituent of the first aromatic ring group" are an alkyl, alkoxy, alkyloxycarbonyl or alkylcarbonyloxy group, a halogen atom, etc.

The alkyl group includes, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, and neopentyl -, 1,2-dimethylpropyl, n-hexyl, isohexyl or cyclohexyl group etc.

The alkoxy group includes, for example, a methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy or hexyloxy group, etc.

The alkyloxycarbonyl group includes, for example, a methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl or tert-butyloxycarbonyl group, etc.

The alkylcarbonyloxy group includes, for example, a methylcarbonyloxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, n-butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy or tert-butylcarbonyloxy group, etc.

The halogen atom includes, for example, a fluorine, chlorine, bromine or iodine atom, etc.

Of these, as Ar ^1, benzene, naphthalene, anthracene, phenals, phenanthrene, biphenyl, binaphthalene, quaterphenyl, allylbenzene, diallylbenzene, allylnaphthalene, diallylnaphthalene, allylbiphenyl and diallylbiphenyl, from which one hydrogen atom has been removed, are preferred. Benzene, naphthalene, biphenyl, allylbenzene, diallylnaphthalene and diallylbiphenyl, from which a hydrogen atom has been removed, are more preferred.

Ar ² each independently represents a substituted or unsubstituted second aromatic ring group. As can be seen from the description of the chemical formula (1), two of the hydrogen atoms of the aromatic ring that forms the substituted or unsubstituted aromatic ring are bonded to “X”.

Examples of the second aromatic ring group are e.g. B. aromatic compounds from which two hydrogen atoms have been removed, namely monocyclic aromatic compounds such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, etc. from which two hydrogen atoms have been removed; and condensed ring aromatic compounds such as naphthalene, anthracene, phenals, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzoimidazole, benzofuran, acridine, etc., from which two hydrogen atoms have been removed. Combinations of these aromatic compounds can also be given, e.g. B. aromatic compounds of composite rings such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl, etc., from which two hydrogen atoms have been removed.

The second aromatic ring group can have a substituent. As the “substituent of the second aromatic ring group”, the same substituents as for the “substituent of the first aromatic ring group” can be given.

X in each case independently represents an oxygen atom, sulfur atom, substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene or aralkylene.

The alkylene includes, for example, methylene, ethylene, propylene, 1-methylmethylene, 1,1-dimethylmethylene, 1-methylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, propylene, butylene, 1-methylpropylene, 2-methylpropylene, pentylene , Hexylene, etc.

The cycloalkylene includes, for example, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclopentylene, cycloheptylene, and cycloalkylenes, etc. having the following chemical formulas (2-1) to (2-4).

In the above chemical formulas (2-1) to (2-4), the symbol “*” means the site bonded ^{to Ar 1} or Ar ^2.

Aralkylenes include, for example, aralkylenes, etc. represented by the following chemical formulas (3-1) to (3-8).

In the above chemical formulas (3-1) to (3-8), the symbol “*” means the site bonded ^{to Ar 1} or Ar ^2.

The alkylene, the cycloalkylene and the aralkylene may have a substituent. The same substituents as for the “substituents of the first aromatic ring” can be cited as the “substituent of X”.

In the chemical formula (1), n is an integer from 0 to 10, preferably an integer from 0 to 8, more preferably an integer from 0 to 5. When the compound represented by the chemical formula (1) is an oligomer or polymer is, n means the average value.

At least two of the ^{hydrogen atoms forming Ar 1} and Ar ² are each substituted by a hydroxyl group.

Concrete examples of the compounds represented by the chemical formula (1) are not subject to any particular restriction, so that here various bisphenol compounds, compounds represented by the following chemical formulas (4-1) to (4-8) and compounds having an or have multiple substituents with a polymerizable unsaturated bond, can be cited.

Examples of the various bisphenol compounds are bisphenol A, bisphenol AP, bisphenol B, bisphenol E, bisphenol F, bisphenol Z, etc.

In the above chemical formulas (4-1) to (4-8), n is an integer of 0 to 10, preferably an integer of 0 to 5. When the compound represented by the chemical formulas (4-1) to (4 -8) an oligomer or polymer, n is the average value. In the present specification, “oligomer” means a compound comprising 1 to 5 repeating units, and “polymer” means a compound comprising 6 or more repeating units. The substitution sites of the hydroxyl groups as substituents on the aromatic ring are arbitrary. In the case of naphthalene rings, they can either be bound to another structure or not bound.

In one embodiment, the first aromatic ring having the chemical formula (1) can be synthesized by reacting the first aromatic ring, on which at least one hydrogen atom is substituted by a hydroxyl group, with a divinyl compound or dialkyloxymethyl compound.

Here fall under the divinyl compound or dialkyloxymethyl compound z. B. aliphatic diene compounds such as 1,3-butadiene, 1,5-hexadiene, dicyclopentadiene, tricyclopentadiene, tetracyclopentadiene, pentacyclopentadiene, hexacyclopentadiene, etc .; aromatic diene compounds such as divinylbenzene, divinylbiphenyl, etc .; and dialkyloxymethyl compounds such as dimethoxymethylbenzene, dimethoxymethylbiphenyl, bisphenol-A-methoxy adduct, bisphenol-A-ethoxy adduct, bisphenol-F-methoxy adduct, bisphenol-F-ethoxy adduct, etc.

The first aromatic compounds having two or more phenolic hydroxyl groups can be used individually or in combination with one another.

The hydroxyl equivalent of the first aromatic compound is preferably 130 to 500 g / equivalent, more preferably 130 to 400 g / equivalent. A hydroxyl equivalent of the first aromatic compound of 130 g / equivalent or more is preferable because it can impart heat resistance. A hydroxyl equivalent of the first aromatic compound of 500 g / equivalent or less is advantageous because it provides an excellent balance between heat resistance and dielectric loss factor.

The first aromatic compound represented by the chemical formula (1), in which n represents an oligomer or polymer, has a weight average molecular weight, preferably from 200 to 3,000, more preferably from 200 to 2,000. A weight average molecular weight of the first aromatic compound of 200 or more is advantageous because it provides an excellent dielectric loss factor. A weight average molecular weight of the first aromatic compound of 3,000 or less is advantageous because it provides excellent moldability. In the present specification, the values of “weight average molecular weight” used are those measured by the following methods. In short, values obtained by measurement by gel permeation chromatography (GPC) under the following conditions are used.

Measurement conditions for GPC

• Measuring device: "HLC-8320 GPC" from Tosoh Corp.
• Columns: Guard column "HXL-L" from Tosoh Corp.
  • + "TSK-GEL G4000HXL" from Tosoh Corp.
  • + "TSK-GEL G3000HXL" from Tosoh Corp.
  • + "TSK-GEL G2000HXL" from Tosoh Corp.
  • + "TSK-GEL G2000HXL" from Tosoh Corp.
• Detector: RI (differential refractometer)
• Data processing: "GPC Workstation EcoSEC-WorkStation" from Tosoh Corp. Column temperature: 40 ° C
• Developer solvent: tetrahydrofuran
• Flow rate: 1.0 ml / min
• Standard: According to the manual for measuring the "GPC-8320 GPC", the following monodisperse polystyrenes were used whose molecular weights were known: Polystyrenes used:
  • "A-500" from Tosoh Corp.
  • "A-1000" from Tosoh Corp.
  • "A-2500" from Tosoh Corp.
  • "A-5000" from Tosoh Corp.
  • "F-1" from Tosoh Corp.
  • "F-2" from Tosoh Corp.
  • "F-4" from Tosoh Corp.
  • "F-10" from Tosoh Corp.
  • "F-20" from Tosoh Corp.
  • "F-40" from Tosoh Corp.
  • "F-80" from Tosoh Corp.
  • "F-128" from Tosoh Corp.
• Sample: A 1% strength by weight tetrahydrofuran solution filtered through a microfilter, calculated as the solid content of the resin (50 μl).

The second aromatic compound has a phenolic hydroxyl group. Since it has a phenolic hydroxyl group, it has a function of stopping the esterification reaction.

As the second aromatic compound, for example, compounds having a phenolic hydroxyl group on a substituted or unsubstituted second aromatic ring having a carbon number of 3 to 30 are cited.

The second aromatic ring with a number of carbon atoms from 3 to 30 includes e.g. B. monocyclic aromatic rings, condensed aromatic rings, compound aromatic rings, aromatic rings linked by alkylene, etc. As the monocyclic aromatic rings, condensed aromatic rings and compound aromatic rings, the same rings as the first aromatic rings can be cited, respectively.

Examples of the aromatic rings linked by alkylene are diphenylmethane, diphenylethane, 1,1-diphenylethane, 2,2-diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenylpyridylmethane, fluorene, diphenylcyclopentane, etc.

The second aromatic ring having a number of carbon atoms of 3 to 30 in the second aromatic compound may have a substituent. The same substituents as the “substituents of the first aromatic ring” are listed as “substituents on the second aromatic ring”.

As mentioned above, in the second aromatic compound, one of the hydrogen atoms forming the substituted or unsubstituted second aromatic ring having a number of carbon atoms of 3 to 30 is substituted with a hydroxyl group.

The second aromatic compound includes, for example, compounds represented by the following chemical formulas (5-1) to (5-17).

In chemical formulas (5-1) to (5-17), R ^{1 represents} a substituent having a polymerizable unsaturated bond. This substituent having a polymerizable unsaturated bond may be any of the above-mentioned substituents. p is furthermore 0 or an integer of 1 or more, preferably 1 to 3, more preferably 1 or 2, particularly preferably 1. If p is 2 or more, the connection points on the aromatic ring are arbitrary. It is thus shown that e.g. B. on the naphthalene ring of the chemical formula (5-6) or on the heterocycle of the chemical formula (5-17) each ring can be substituted, and in the case of the chemical formula (5-9) etc. each of the benzene rings present in a molecule may be substituted, the number of substituents in a molecule being denoted by p.

More concrete examples of the second aromatic compound are compounds comprising a monocyclic aromatic ring as the aromatic ring (hereinafter referred to simply as “second monocyclic aromatic ring compound”, if applicable) such as phenol, cresol, xylenol, orthoallylphenol, metaallylphenol, paraallylphenol, 2,4 -Diallylphenol, 2,6-diallylphenol, 2-allyl-4-methylphenol, 2-allyl-6-methylphenol, 2-allyl-4-methoxy-6-methylphenol, 2-propargylphenol, 3-propargylphenol, 4-propargylphenol, etc. ; Compounds which comprise a condensed aromatic ring as an aromatic ring (hereinafter referred to simply as "second condensed aromatic ring compound"), such as 1-naththol, 2-naphthol, 2-allyl-1-naphthol, 3-allyl-1- naphthol, 1-allyl-2-naphthol, 3-allyl-2-naphthol, 5-allyl-1-naphthol, 6-allyl-1-naphthol, diallylnaphthol, 2-allyl-4-methoxy-1-naphthol, 2- Propargyl-1-naphthol, 3-propargyl-1-naphthol, 1-propargyl-2-naphthol, 3-propargyl-2-naphthol, etc .; and compounds comprising, as an aromatic ring, a compound aromatic ring (hereinafter referred to simply as “second compound aromatic ring compound”, if applicable) such as allylhydroxybiphenyl, hydroxypropargylbiphenyl, etc.

Of these second aromatic compounds, the second monocyclic aromatic ring compounds or the second condensed aromatic ring compounds are advantageous. Orthoallyl phenol, Metaallylphenol, paraallylphenol, 2-allyl-1-naphthol, 3-allyl-1-naphthol, 1-allyl-2-naphthol, 3-allyl-2-naphthol, 5-allyl-1-naphthol and 6-allyl-1, respectively -naphthol are even more beneficial.

In a further embodiment, the second aromatic compound is preferably the second condensed aromatic ring compound (condensed aromatic ring compound), more preferably 2-allyl-1-naphthol, 3-allyl-1-naphthol, 1-allyl-2-naphthol, 3-allyl -2-naphthol, 5-allyl-1-naphthol and 6-allyl-1-naphthol, respectively. It is advantageous that the second aromatic compound is the condensed aromatic ring compound, since the steric hindrance suppresses the molecular movement and thereby the dielectric loss factor can be reduced. In view of the good handleability and low viscosity of the aromatic ester compound (A), 2-allyl phenol, etc. having a benzene ring structure is advantageous, and in view of the excellent balance between heat resistance and low dielectric properties of a cured product to be obtained are 2-allyl-1 -naphthol, 1-allyl-2-naphthol, etc. having a naphthalene ring structure are advantageous.

The second aromatic compounds having a phenolic hydroxyl group can be used singly or in combination with each other.

The aromatic compound with carboxyl groups includes, for. B. third aromatic compounds having two or more carboxyl groups, fourth aromatic compounds having one carboxyl group, or their acid halides and esterification products.

The third aromatic compounds, their acid halides and / or esterification products are aromatic compounds with two or more carboxyl groups or their derivatives, namely their acid halides or esterification products (in the present description, the third aromatic compound, their acid halide and / or Esterification product may be referred to collectively as "the third aromatic compound, etc."). Since the third aromatic compound, etc. has two or more carboxyl groups, etc., it can form an ester structure by reacting with the above-mentioned first or second aromatic compound.

Examples of the third aromatic compound, etc. are compounds having two or more carboxyl groups, etc. on a substituted or unsubstituted third aromatic ring having a carbon atom number of 3 to 30.

Examples of the “carboxyl groups, etc.” are carboxyl groups; Acyl halide groups such as acyl fluoride, acyl chloride or acyl bromide group, etc .; Alkyloxycarbonyl groups such as methyloxycarbonyl and ethyloxycarbonyl, etc .; and aryloxycarbonyl groups such as phenyloxycarbonyl or naphthyloxycarbonyl groups, etc. When acyl halide groups are contained, the third aromatic compound is an acid halide. When alkyloxycarbonyl or aryloxycarbonyl groups are contained, the third aromatic compound may be an esterification product. Of these, the third aromatic compound preferably has carboxyl groups, acyl halide groups or aryloxycarbonyl groups, more preferably carboxyl groups or acyl halide groups, even more preferably carboxyl groups, acyl chloride groups or acyl bromide groups.

The third aromatic ring with a number of carbon atoms from 3 to 30 includes e.g. Monocyclic aromatic rings, condensed aromatic rings, compound aromatic rings, aromatic rings linked by alkylene, etc. As the monocyclic aromatic rings, condensed aromatic rings, compound aromatic rings and alkylene linked aromatic rings are the same rings as the above-mentioned first and second aromatic rings Cite rings.

The third aromatic ring having a carbon atom number of 3 to 30 in the third aromatic compound, etc. may have a substituent. The same substituents as the “substituents of the first aromatic ring” are listed as “substituents on the third aromatic ring”.

The third aromatic compound, etc. include, for example, compounds represented by the following chemical formulas (6-1) to (6-15).

In the chemical formulas (6-1) to (6-15), R ^{1 represents} a substituent having a polymerizable unsaturated bond. This substituent with a polymerizable unsaturated bond is the same as those mentioned above. R ² stands for a hydroxyl group, a halogen atom, an alkyloxy group, aryloxy group. In addition, p is 0 or an integer of 1 or more, preferably 0 or 1 to 3, more preferably 0 or 1, particularly preferably 0. q is 2 or 3. If p and q are 2 or more, the binding sites are aromatic Any ring. It is thus shown that e.g. B. on the naphthalene ring of the chemical formula (6-5) or on the heterocycle of the chemical formula (6-15) each ring can be substituted, and in the case of the chemical formula (6-7) etc. each of the benzene rings present in a molecule may be substituted, the number of substituents in a molecule being denoted by p and q.

More concrete examples of the third aromatic compound, etc. are benzene dicarboxylic acids such as isophthalic acid, terephthalic acid, 5-allyl isophthalic acid, 2-allyl terephthalic acid, etc .; Benzenetricarboxylic acids such as trimellitic acid, 5-allyltrimellitic acid, etc .; 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, 3,7-diallylnaphthalene -1,4-dicarboxylic acid, etc .; Pyridine tricarboxylic acids such as 2,4,5-pyridine tricarboxylic acid, etc .; Triazine carboxylic acids such as 1,3,5-triazine-2,4,6-carboxylic acid, etc .; their acid halides, esterification products, etc. Of these, benzene dicarboxylic acids, benzene tricarboxylic acids are advantageous. Isophthalic acid, terephthalic acid, isophthalic acid chloride, terephthalic acid chloride, 1,3,5-benzene tricarboxylic acid and 1,3,5-benzene tricarbonyl trichloride are more advantageous. Isophthalic acid chloride, terephthalic acid chloride and 1,3,5-benzene tricarbonyl trichloride are also more advantageous.

Of these, the third aromatic compounds, etc., which have a monocyclic aromatic ring as the aromatic ring, and the third aromatic compounds, etc., which have aromatic rings fused as the aromatic rings, are advantageous. Benzenedicarboxylic acids, benzenetricarboxylic acids, naphthalenedicarboxylic acids and their acid halides are preferred Benzene dicarboxylic acids, naphthalene dicarboxylic acids, their acid halides, and even more preferably isophthalic acid, terephthalic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, their acid halides.

The third aromatic compounds, etc. can be used singly or in combination with each other.

The fourth aromatic compounds, their acid halides and / or esterification products are aromatic compounds with a carboxyl group or their derivatives, namely acid halides, esterification products (in the present description, the fourth aromatic compound, its acid halide and / or esterification product is used as a whole referred to as "the fourth aromatic compound, etc."). Since the fourth aromatic compound, etc. has a carboxyl group, etc., it has a function of stopping esterification.

Examples of the fourth aromatic compound, etc. are compounds having a carboxyl group, etc. on a substituted or unsubstituted fourth aromatic ring having a number of carbon atoms of 3 to 30.

These “carboxyl group, etc.” are the same groups as the aforementioned “carboxyl group, etc.”.

The fourth aromatic ring with a number of carbon atoms from 3 to 30 includes e.g. Monocyclic aromatic rings, condensed aromatic rings, compound aromatic rings, alkylene linked aromatic rings, etc. As the monocyclic aromatic rings, condensed aromatic rings, compound aromatic rings and alkylene linked aromatic rings, the same rings as the above-mentioned first, second and third aromatic rings.

The fourth aromatic ring having a carbon atom number of 3 to 30 in the fourth aromatic compound, etc. may have a substituent. The same substituents as the “substituents of the first aromatic ring” are listed as “substituents on the fourth aromatic ring”.

The fourth aromatic compound, etc. include, for example, compounds represented by the following chemical formulas (7-1) to (7-15).

In chemical formulas (7-1) to (7-15), R ¹ stands for a substituent having a polymerizable unsaturated bond. This substituent having a polymerizable unsaturated bond may be any of the above-mentioned substituents. R ² represents a hydroxyl group, a halogen atom, an alkyloxy group or aryloxy group. In addition, p is 0 or an integer from 1 or more, preferably 0 or 1 to 3, more preferably 0 or 1, particularly preferably 0. q is 1. In the above chemical formulas, the positions of the substituents on the aromatic ring are arbitrary. It is thus shown that e.g. B. on the naphthalene ring of the chemical formula (7-5) or on the heterocycle of the chemical formula (7-15) each ring can be substituted, and that in the case of the chemical formula (7-7), etc., each of the existing in a molecule Benzene rings can be substituted, the number of substituents in a molecule being denoted by p and q.

More concrete examples of the fourth aromatic compound, etc. are benzoic acid, benzene chloride, naphthalenecarboxylic acid, naphthalenecarbonyl chloride, etc.

[Structure of the aromatic ester compound (A)]

It is preferable that at least either the aromatic compound having phenolic hydroxyl groups or the aromatic compound, etc. having carboxyl groups has a substituent having a polymerizable unsaturated bond in order to obtain an epoxy (meth) acrylate resin composition which is a cured product having excellent heat resistance and excellent dielectric strength Properties can form. Here, it is possible that both the aromatic compound with phenolic hydroxyl groups and the aromatic compound etc. with carboxyl groups each have a substituent with a polymerizable unsaturated bond, that only the aromatic compound with phenolic hydroxyl groups has a substituent with a polymerizable unsaturated bond, or that only the aromatic compound, etc. having carboxyl groups have a substituent with a has polymerizable unsaturated bond. Further, when two or more kinds of aromatic compounds having phenolic hydroxyl groups or two or more kinds of aromatic compounds, etc. having carboxyl groups are used, only a part of these compounds has a substituent with a polymerizable unsaturated bond.

In one embodiment, it is advantageous that at least the second aromatic compound has a substituent with a polymerizable unsaturated bond. The structure derived from the second aromatic compound is at the molecular end of the aromatic ester compound (A) as mentioned above. Therefore, the substituent having a polymerizable unsaturated bond contained in the second aromatic compound is also located at the molecular end of the aromatic ester compound (A). This is advantageous because a good balance can be achieved between heat resistance and dielectric loss factor of the cured product obtained.

The aromatic ester compound (A), as mentioned above, is a reaction product of the compound having phenolic hydroxyl groups and the aromatic compound, etc., having carboxyl groups, which may include various compounds such as the first to fourth aromatic compounds and so on. It is indispensable that either the second aromatic compound or the fourth aromatic compound or these two compounds are present because they have a function of stopping esterification. The structure of the aromatic ester compound (A) can be controlled by changing the usage amounts of the first to fourth aromatic compounds, etc., reaction conditions, etc. according to circumstances.

In one embodiment, as the aromatic ester compound (A), there are exemplified the following compounds: aromatic ester compounds as reaction products of the first aromatic compound and the fourth aromatic compound, etc .; aromatic ester compounds as reaction products of the first aromatic compound, the second aromatic compound and the third aromatic compound, etc .; aromatic ester compounds as reaction products of the first aromatic compound, the third aromatic compound and the fourth aromatic compound, etc .; aromatic ester compounds as reaction products of the first aromatic compound, the second aromatic compound, the third aromatic compound, etc. and the fourth aromatic compound, etc .; aromatic ester compounds as reaction products of the second aromatic compound and the third aromatic compound; aromatic ester compounds as reaction products of the second aromatic compound and the fourth aromatic compound.

In the aromatic ester compound (A) according to the present embodiment, no hydroxyl group is contained in principle in the molecule of the resin obtained. However, compounds having hydroxyl groups may be contained as by-products of the reaction product to such an extent that the effect of the present invention is not impaired.

In one embodiment, the aromatic ester compound (A) comprises a compound having the following chemical formula (8).

In the chemical formula (8), Ar ^{1 represents} the structure derived from the first aromatic compound, Ar ^{2 represents the} structure derived from the second aromatic compound, and Ar ^{3 represents} the structure derived from the third aromatic compound. In addition, n is an integer from 0 to 10. When the aromatic ester compound (A) is an oligomer or polymer, n represents the average value.

In the chemical formula (8), Ar ¹ each independently represents the substituted or unsubstituted first aromatic ring having a carbon atom number of 3 to 30 from which two or more hydrogen atoms have been removed or the structure of the first aromatic rings linked by a linking group from which two or more hydrogen atoms have been removed.

In the chemical formula (8), Ar ² each independently represents the substituted or unsubstituted second aromatic ring having a carbon atom number of 3 to 30 from which a hydrogen atom has been removed.

In the chemical formula (8), Ar ^{3 represents} the substituted or unsubstituted third aromatic ring having a carbon atom number of 3 to 30 from which two or more hydrogen atoms have been removed.

At least one of Ar ¹ , Ar ² and Ar ³ may have a substituent having a polymerizable unsaturated bond and having a carbon atom number of 2 to 30.

Ar ^{1 can have} a further branched structure if the first aromatic compound has three or more phenolic hydroxyl groups.

Further, when the third aromatic compound has three or more carboxyl groups and so on, ^{Ar 3 may have a more branched structure.}

In one embodiment, the aromatic ester compound (A) comprises a compound having the chemical formula (9).

In the chemical formula (9), Ar ^{1 represents} the structure derived from the first aromatic compound, Ar ^{2 represents the} structure derived from the second aromatic compound, Ar ^{3 represents the} structure derived from the third aromatic compound, and Ar ^{4 represents} that of the structure derived from the fourth aromatic compound, n is also an integer from 0 to 10. When the aromatic ester compound (A) is an oligomer or polymer, n represents the average value.

In the chemical formula (9), Ar ¹ each independently represents the substituted or unsubstituted first aromatic ring having a carbon number of 3 to 30 from which two or more hydrogen atoms have been removed, or the structure of the first aromatic rings linked by a linking group from which two or more hydrogen atoms have been removed.

In the chemical formula (9), Ar ² each independently represents the substituted or unsubstituted second aromatic ring having a carbon atom number of 3 to 30 from which a hydrogen atom has been removed.

In the chemical formula (9), Ar ^{3 represents} the substituted or unsubstituted third aromatic ring having a carbon atom number of 3 to 30 from which two or more hydrogen atoms have been removed.

In the chemical formula (9), Ar ^{4 represents} the substituted or unsubstituted fourth aromatic ring having a carbon atom number of 3 to 30 from which a hydrogen atom has been removed.

At least one of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may have a substituent having a polymerizable unsaturated bond and having a carbon atom number of 2 to 30.

Ar ^{1 can have} a further branched structure if the first aromatic compound has three or more phenolic hydroxyl groups.

Further, when the third aromatic compound, etc. has three or more carboxyl groups, etc., ^{Ar 3 may have a more branched structure.}

In one embodiment, the aromatic ester compound (A) comprises a compound having the following chemical formula (10).

In the chemical formula (10), Ar ^{1 represents} the structure derived from the first aromatic compound, Ar ^{3 represents the} structure derived from the third aromatic compound, and Ar ^{4 represents} the structure derived from the fourth aromatic compound. In addition, n is an integer from 0 to 10. When the aromatic ester compound (A) is an oligomer or polymer, n represents the average value.

In the chemical formula (10), Ar ¹ each independently represents the substituted or unsubstituted first aromatic ring having a carbon atom number of 3 to 30 from which two or more hydrogen atoms have been removed or the structure of the first aromatic rings linked by a linking group from which two or more hydrogen atoms have been removed.

In the chemical formula (10), Ar ^{3 represents} the substituted or unsubstituted third aromatic ring having a carbon atom number of 3 to 30 from which two or more hydrogen atoms have been removed.

In the chemical formula (10), Ar ^{4 represents} the substituted or unsubstituted fourth aromatic ring having a carbon atom number of 3 to 30 from which a hydrogen atom has been removed.

At least one of Ar ¹ , Ar ³ and Ar ⁴ may have a substituent having a polymerizable unsaturated bond and having a carbon atom number of 2 to 30.

Ar ^{1 can have} a further branched structure if the first aromatic compound has three or more phenolic hydroxyl groups.

Further, when the third aromatic compound, etc. has three or more carboxyl groups, etc., ^{Ar 3 may have a more branched structure.}

In one embodiment, as the compound contained in the aromatic ester compound (A), for example, compounds represented by the following chemical formulas (11-1) to (11-10) are mentioned.

In chemical formulas (11-1) to (11-10), s is an integer from 0 to 10, preferably an integer from 0 to 5. r is an integer from 1 to 10. When the compounds with the chemical Formulas (11-1) to (11-10) represent oligomers or polymers, s and r mean their average values. The dashed lines in the chemical formulas each represent a structure that is obtained by reacting the compounds corresponding to ^{Ar 3} and Ar ¹ and / or Ar ^2.

worin
Ar⁵ jeweils unabhängig für eine substituierte oder unsubstituierte aromatische Ringgruppe steht, Ar⁶ jeweils unabhängig für eine substituierte oder unsubstituierte zweite aromatische Ringgruppe steht, und n eine ganze Zahl von 1 bis 3 ist.In one embodiment, the aromatic ester compound (A) includes e.g. B. aromatic ester compounds (A-1) having the following chemical formula (a1) and aromatic ester compounds (A-2) having the following chemical formula (a2).

wherein
Each Ar ⁵ independently represents a substituted or unsubstituted aromatic ring group, ^{each Ar 6} independently represents a substituted or unsubstituted second aromatic ring group, and n is an integer from 1 to 3.

The aromatic ester compound (A-1) is represented by the chemical formula (a1).

In the chemical formula (a1), Ar ⁵ stands for a substituted or unsubstituted first aromatic ring group. Since n in the chemical formula (a1) is an integer of 1 to 3, 1 to 3 hydrogen atoms of the aromatic ring forming the first aromatic ring group are ^{substituted with “-C (O) OAr 6} ” as mentioned later.

Examples of the first aromatic ring group are e.g. B. aromatic compounds, of which two or three hydrogen atoms have been removed, namely, monocyclic aromatic compounds such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, etc., two of which or three hydrogen atoms have been removed; and condensed ring aromatic compounds such as naphthalene, anthracene, phenals, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzoimidazole, benzofuran, acridine, etc., from which two or three hydrogen atoms have been removed. Combinations of these aromatic compounds can also be given, e.g. B. compound ring aromatic compounds such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl, etc., from which two or three hydrogen atoms have been removed; and alkylene-linked aromatic compounds, etc., such as diphenylmethane, diphenylethane, 1,1-diphenylethane, 2,2-diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenylpyridylmethane, fluorene, diphenylcyclopentane, etc., of which two or three hydrogen atoms have been removed . Of these, Ar ^{5 is} preferably a substituted or unsubstituted benzene ring or naphthalene ring structure, more preferably a substituted or unsubstituted benzene ring structure, because it provides an epoxy (meth) acrylate resin composition capable of forming a cured product having excellent heat resistance and excellent dielectric properties.

The first aromatic ring group Ar ⁵ may have a substituent. The substituent of the first aromatic ring group substitutes at least one hydrogen atom of the aromatic ring forming the first aromatic ring group. Examples of the "substituent of the first aromatic ring group" are an alkyl, alkoxy, alkyloxycarbonyl or alkylcarbonyloxy group, a halogen atom, etc.

The alkyl group includes, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, and neopentyl -, 1,2-dimethylpropyl, n-hexyl, isohexyl or cyclohexyl group etc.

The alkoxy group includes, for example, a methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy or hexyloxy group, etc.

The alkyloxycarbonyl group includes, for example, a methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl or tert-butyloxycarbonyl group, etc.

The alkylcarbonyloxy group includes, for example, a methylcarbonyloxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, n-butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy or tert-butylcarbonyloxy group, etc.

The halogen atom includes, for example, a fluorine, chlorine, bromine or iodine atom, etc.

In one embodiment of the present invention, Ar ^{5 may have} a substituent with a polymerizable unsaturated bond. Concrete examples of the substituent having a polymerizable unsaturated bond are an alkenyl group, an alkynyl group, etc.

The alkenyl group includes, for example, vinyl, allyl, propenyl, isopropenyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-hexenyl, 2-hexenyl, 3- Hexenyl, 4-hexenyl, 5-hexenyl, 1-octenyl, 2-octenyl, 1-undecenyl, 1-pentadecenyl, 3-pentadecenyl, 7-pentadecenyl, 1-octadecenyl, 2- Octadecenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, 1,3-butadienyl, 1,4-butadienyl, hexa-1,3-dienyl, hexa-2,5-dienyl, pentadeca-4,7 dienyl, hexa-1,3,5-trienyl or pentadeca-1,4,7-trienyl group etc.

The alkynyl group includes, for example, an ethynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 3-penthynyl, 4-penthynyl or 1,3-butadiynyl group, etc.

The substituent with a polymerizable unsaturated bond may have another substituent. This substituent substitutes at least one of the hydrogen atoms that form the substituent with a polymerizable unsaturated bond. The substituents include, for example, an alkyloxycarbonyl or alkylcarbonyloxy group, halogen atoms, etc. The above-mentioned examples of the alkyloxycarbonyl or alkylcarbonyloxy groups and halogen atoms are given.

Of these, as the substituent having a polymerizable unsaturated bond, the substituted or unsubstituted alkenyl groups having a carbon atom number of 2 to 30 are preferred. More preferred are the substituted or unsubstituted alkenyl groups with a carbon atom number of 2 to 10. Even more preferred are the substituted or unsubstituted alkenyl groups with a carbon atom number of 2 to 5, and particularly preferred are the vinyl, allyl, propenyl, isopropenyl, 1- Propenyl, 1-butenyl, 2-butenyl, 3-butenyl and 1,3-butadienyl groups, of which the allyl, propenyl, isopropenyl and 1-propenyl groups are most preferred.

As the preferable structure of Ar ⁵ , for example, the following formulas (12-1) to (12-17), etc. are given.

In the above formulas (12-1) to (12-17), the symbol “*” represents the position that is attached to “-C (O) OAr ⁶ ”. "- *" can be attached to any position on the aromatic ring.

Of these formulas, formulas (12-1) to (12-11) are advantageous, formulas (12-1), (12-2), (12-6), (12-7) or (12-9) ) more advantageous, and the formulas (12-1), (12-2), (12-6) and (12-7) even more advantageous. Formulas (12-1) and (12-2) are advantageous in view of the good handleability and low viscosity of the aromatic ester compound (A), and in view of the excellent balance between heat resistance and low dielectric properties of a cured product to be obtained the formulas (12-6) and (12-7) are advantageous.

At least one hydrogen atom of the aromatic ring of the formulas (12-1) to (12-17) may be substituted with a group having a polymerizable unsaturated bond.

In chemical formula (a1), Ar ⁶ stands for a substituted or unsubstituted second aromatic ring group. As can be seen from the information regarding chemical formula (10), a hydrogen atom of the aromatic ring forming the second aromatic ring group is ^{substituted by “-OC (O) OAr 5} ”.

Examples of the second aromatic ring group are e.g. B. aromatic compounds from which a hydrogen atom has been removed, namely monocyclic aromatic compounds such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, etc. from which one hydrogen atom has been removed; and condensed ring aromatic compounds such as naphthalene, anthracene, phenals, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzoimidazole, benzofuran, acridine, etc., from which a hydrogen atom has been removed. Combinations of these aromatic compounds can also be given, e.g. B. composite ring aromatic compounds such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl, etc. from which a hydrogen atom has been removed; and alkylene-linked aromatic compounds, etc., such as diphenylmethane, diphenylethane, 1,1-diphenylethane, 2,2-diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenylpyridylmethane, fluorene, diphenylcyclopentane, etc., from which a hydrogen atom has been removed. Of these, Ar ^{6 is} preferably a substituted or unsubstituted benzene ring or naphthalene ring structure because it provides an epoxy (meth) acrylate resin composition capable of forming a cured product having excellent heat resistance and dielectric properties.

The second aromatic ring group Ar ⁶ may have a substituent. The substituent of the second aromatic ring group substitutes at least one hydrogen atom of the aromatic ring forming the second aromatic ring group. Examples of the “substituent of the second aromatic ring group” are an alkyl, alkoxy, alkyloxycarbonyl or alkylcarbonyloxy group, a halogen atom, etc. Here, as examples of the alkyl, alkoxy, alkyloxycarbonyl or alkylcarbonyloxy groups and halogen atoms, the above are cited.

In one embodiment of the present invention, Ar ^{6 may have} a substituent having a polymerizable unsaturated bond such as the above-mentioned alkenyl or alkynyl group, etc. The substituents having a polymerizable unsaturated bond may be contained individually or in combination with one another.

As an advantageous structure of Ar ⁶ , the following formulas (13-1) to (13-17) are given.

In the above formulas (13-1) to (13-17), the symbol “*” represents a digit that is linked to “-OC (O) OAr ⁵ ”. "- *" can be attached to any position on the aromatic ring.

Of these formulas, formulas (13-1) to (13-11) are advantageous, formulas (13-1), (13-6) and (13-9) are more advantageous, and formulas (13-1) or . (13-6) even more advantageous.

At least one hydrogen atom of the aromatic ring of the formulas (13-1) to (13-17) may be substituted with a group having a polymerizable unsaturated bond.

In one embodiment, it is more advantageous that Ar ⁵ the formulas (12-1), (12-2), (12-6), (12-7) or (12-9) and Ar ⁶ the formulas (13- 1), (13-6) or (13-9). It is even more advantageous that Ar ^{5 has} the formulas (12-1), (12-2), (12-6) or (12-7) and Ar ⁶ the formulas (13-1) or (13-6 ) represents. It is particularly advantageous that Ar ⁵ represents formula (12-1) and Ar ⁶ represents formulas (13-1) or (13-6).

It is preferable that at least one of Ar ⁵ and Ar ⁶ in the chemical formula (a1) has a substituent having a polymerizable unsaturated bond in order to obtain an epoxy (meth) acrylate resin composition which is a cured product having excellent heat resistance and excellent dielectric properties can form. Either Ar ⁵ or Ar ^{6 can have} the substituent with a polymerizable unsaturated bond, or both Ar ⁵ and Ar ⁶ can have the substituent with a polymerizable unsaturated bond.

In one embodiment, it is advantageous that at least one of the Ar ^{6 has} the substituent with a polymerizable unsaturated bond. It is more advantageous if each Ar ^{6 has} the substituent with a polymerizable unsaturated bond. It is more preferable that Ar ⁵ does not have a substituent with a polymerizable unsaturated bond and each Ar ^{6 has} the substituent with a polymerizable unsaturated bond. It is advantageous that the substituent having a polymerizable unsaturated bond is present in Ar ⁶ , since there is obtained an epoxy (meth) acrylate resin composition which can form a cured product having an excellent balance between heat resistance and dielectric properties.

In the chemical formula (a1), n is an integer of 1 to 3. That is, the aromatic ester compound (A-1) comprises 1 to 3 ester bonds for bonding two aromatic rings.

worin
R¹ für einen Substituenten mit einer polymerisierbaren ungesättigten Bindung steht, R² jeweils unabhängig für eine Alkyl-, Alkoxy-, Alkyloxycarbonyl- bzw. Alkylcarbonyloxygruppe oder ein Halogenatom steht, h eine ganze Zahl von 1 bis 3 ist, i jeweils unabhängig eine ganze Zahl von 1 oder mehr und j jeweils unabhängig 0 oder eine ganze Zahl von 1 oder mehr ist, wobei i + j eine ganze Zahl von 5 oder weniger ist, k eine ganze Zahl von 1 bis 3 ist, I jeweils unabhängig eine ganze Zahl von 1 oder mehr ist und m jeweils unabhängig 0 oder eine ganze Zahl von 1 oder mehr ist, wobei l + m eine ganze Zahl von 7 oder weniger ist. Falls i, j, I und m ganze Zahlen von 2 oder mehr sind, können mehrere R¹ oder R² miteinander identisch oder voneinander verschieden sein. In der Formel (a1-2) können R¹ und R² durch irgendein Kohlenstoffatom am Naphthalinring substituiert sein.Therefore, as more preferable forms of the aromatic ester compound (A-1) represented by the chemical formula (a1), compounds represented by the following chemical formula (a1-1) or (a1-2) are given.

wherein
R ^{1 represents} a substituent with a polymerizable unsaturated bond, R ² each independently represents an alkyl, alkoxy, alkyloxycarbonyl or alkylcarbonyloxy group or a halogen atom, h is an integer from 1 to 3, i each independently is an integer of 1 or more and each j is independently 0 or an integer of 1 or more, where i + j is an integer of 5 or less, k is an integer from 1 to 3, each I independently is an integer of 1 or more and each m is independently 0 or an integer of 1 or more, where l + m is an integer of 7 or less. If i, j, I and m are integers of 2 or more, a plurality of R ¹ or R ^{2 may} be identical to or different from one another. In the formula (a1-2), R ¹ and R ² may be substituted by any carbon atom on the naphthalene ring.

In the formula (a1-1), R ^{1 is} particularly preferably an allyl, propenyl, isopropenyl or 1-propenyl group, as mentioned above. i is preferably 1 or 2, more preferably 1.

In the formula (a1-2), R ^{1 is} particularly preferably an allyl, propenyl, isopropenyl or 1-propenyl group, as mentioned above. I is preferably 1 or 2, more preferably 1.

The concrete structure of the aromatic ester compound (A-1) represented by the chemical formula (a1) is not particularly limited, but compounds represented by the following chemical formulas (14-1) to (14-47), etc. are given as examples.

Of the chemical formulas (14-1) to (14-47), the chemical formulas (14-1) to (14-39) are preferred, the chemical formulas (14-1) to (14-3), (14- 10) to (14-13) and (14-18) to (14-39) more preferred, the chemical formulas (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 more preferred, and the chemical formulas (14-1), (14-2), (14-12), (14-13), (14-26), (14-32) and (14-37) are particularly preferred.

The method for producing the aromatic ester compound (A-1) is not particularly limited. The aromatic ester compound (A-1) can be produced by an appropriate known method.

As the method for producing the aromatic ester compound (A-1), e.g. For example, a method in which the second aromatic compound is reacted with the third aromatic compound and so on can be cited.

The aromatic ester compound (A-2) is represented by the chemical formula (a2).

In the chemical formula (a2), Ar ⁵ stands for a substituted or unsubstituted first aromatic ring group. As mentioned later, n in the chemical formula (a2) is an integer from 1 to 3, so that a hydrogen atom of the aromatic ring forming the first aromatic ring group is ^{substituted with “-C (O) OAr 6} ”.

As Ar ⁵ in the chemical formula (a2), the same ring groups are given as the above-mentioned “first aromatic ring groups” for “Ar ⁶ in the chemical formula (10)”.

In the chemical formula (a2), Ar ⁶ stands for a substituted or unsubstituted second aromatic ring group. As can be seen from the information regarding chemical formula (11), 1 to 3 hydrogen atoms of the aromatic ring forming the second aromatic ring group are ^{substituted by “-OC (O) OAr 5} ”.

As Ar ⁶ in the chemical formula (a2), the same ring groups are given as the above-mentioned “second aromatic ring groups” for “Ar ⁶ in the chemical formula (a1)”.

In the chemical formula (a2), n is an integer from 1 to 3. That is, the aromatic ester compound (A-2) comprises 1 to 3 ester bonds for bonding two aromatic rings.

worin
R¹ für einen Substituenten mit einer polymerisierbaren ungesättigten Bindung steht, R² jeweils unabhängig für eine Alkyl-, Alkoxy-, Alkyloxycarbonyl- bzw. Alkylcarbonyloxygruppe oder ein Halogenatom steht, h eine ganze Zahl von 1 bis 3 ist, i jeweils unabhängig eine ganze Zahl von 1 oder mehr ist und j jeweils unabhängig 0 oder eine ganze Zahl von 1 oder mehr ist, wobei i + j eine ganze Zahl von 5 oder weniger ist. Falls i und j ganze Zahlen von 2 oder mehr sind, können mehrere R¹ oder R² miteinander identisch oder voneinander verschieden sein.Therefore, as more preferable forms of the aromatic ester compound (A-2) represented by the chemical formula (a2), compounds represented by the following chemical formula (1-3) or (1-4) are cited.

wherein
R ^{1 represents} a substituent with a polymerizable unsaturated bond, R ² each independently represents an alkyl, alkoxy, alkyloxycarbonyl or alkylcarbonyloxy group or a halogen atom, h is an integer from 1 to 3, i each independently is an integer is of 1 or more and each j is independently 0 or an integer of 1 or more, where i + j is an integer of 5 or less. If i and j are integers of 2 or more, a plurality of R ¹ or R ^{2 may} be identical to or different from one another.

In the formula (a2-1), R ^{1 is} particularly preferably an allyl, propenyl, isopropenyl or 1-propenyl group, as mentioned above. i is preferably 1 or 2, more preferably 1.

In the formula (a2-2), R ^{1 is} particularly preferably an allyl, propenyl, isopropenyl or 1-propenyl group, as mentioned above. I is preferably 1 or 2, more preferably 1.

The concrete structure of the aromatic ester compound (A-2) represented by the chemical formula (a2) is not particularly limited, but compounds represented by the following chemical formulas (15-1) to (15-6), etc. are given as examples.

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

As the method for producing the aromatic ester compound (A-2), e.g. For example, a method in which the first aromatic compound is reacted with the fourth aromatic compound and so on can be cited.

The method for producing the aromatic ester compound (A) is not particularly limited. The aromatic ester compound (A) can be produced by an appropriate known method.

For example, it is advantageous that the ratio of the number of moles of carboxyl groups, etc. of the aromatic compound having carboxyl groups to the number of moles of hydroxyl groups of the aromatic compound having phenolic hydroxyl groups (carboxyl groups, etc. / hydroxyl groups) is 0.3 to 3 in order to obtain an epoxy (meth) acrylate resin composition capable of forming a cured product excellent in heat resistance and excellent dielectric properties.

The reaction conditions in the reaction between the aromatic compound having phenolic hydroxyl groups and the aromatic compound having carboxyl groups to produce the aromatic ester compound (A) are not particularly limited. Appropriate known methods can be used.

The pH in the reaction is not particularly limited, but is preferably 11 or more. For pH regulation, acids such as hydrochloric acid, sulfuric acid, nitric acid, Acetic acid, etc., or bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, etc. can be used.

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

The reaction pressure is also not subject to any particular restriction, but is preferably normal pressure.

The reaction time is also not subject to any particular restriction, but it is preferably 0.5 to 10 hours, more preferably 1 to 5 hours.

The epoxy (meth) acrylate resin (B) is formed from an epoxy resin (b1) and a carboxyl group-containing (meth) acrylate compound (b2) as indispensable reaction materials.

The epoxy (meth) acrylate resin (B) includes epoxy groups derived from the epoxy resin (b1) and (meth) acryloyl groups derived from the carboxyl group-containing (meth) acrylate compound (b2).

The specific structure of the epoxy resin (b1) is not subject to any particular restriction as long as it has several epoxy groups and can form an epoxy (meth) acrylate resin by reaction with the (meth) acrylate compound (b2) containing carboxyl groups. As the epoxy resin (b1), there are, for example, bisphenol type, hydrogenated bisphenol type, biphenol type, hydrogenated biphenol type, phenylene ether type, naphthylene ether type, phenol novolak type, cresol novolak type, bisphenol novolak type, naphthol novolak type epoxy resin , Phenol aralkyl type, naphthol aralkyl type, dicyclopentadiene-phenol addition reaction type, biphenyl aralkyl type, fluorene type, xanthene type, dihydroxybenzene type, trihydroxybenzene type, and so on. These epoxy resins (b1) can be used individually or in combination with one another. Of these epoxy resins, the bisphenol type, hydrogenated bisphenol type, biphenol type, hydrogenated biphenol type, naphthol type and dihydroxybenzene type epoxy resins are preferred, and the bisphenol type or hydrogenated bisphenol type epoxy resins are preferred. Dihydroxybenzene type are more preferred in order to obtain an epoxy (meth) acrylate resin composition which can form a cured product having excellent heat resistance and excellent dielectric properties.

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

Examples of the hydrogenated bisphenol type epoxy resins are hydrogenated bisphenol A type epoxy resins, hydrogenated bisphenol B type, hydrogenated bisphenol E type, hydrogenated bisphenol F type, hydrogenated bisphenol S type, etc.

Examples of the biphenol type epoxy resins are 4,4'-biphenol type epoxy resins, 2,2'-biphenol type, tetramethyl-4,4'-biphenol type, tetramethyl-2,2'-biphenol type, and so on .

Examples of the hydrogenated biphenol type epoxy resins are hydrogenated 4,4'-biphenol type epoxy resins, hydrogenated 2,2'-biphenol type, hydrogenated tetramethyl-4,4'-biphenol type, hydrogenated tetramethyl-2,2 ' -Biphenol type etc.

Examples of the dihydroxybenzene type epoxy resins are catechol type epoxy resins, resorcinol type, hydroquinone type, etc.

When the epoxy resin (b1) is a bisphenol type, hydrogenated bisphenol type, biphenol type, hydrogenated biphenol type, naphthol type or dihydroxybenzene type epoxy resin, it is preferable that the epoxy equivalent of the epoxy resin (b1) is in the range is from 110 to 400 g / equivalent to obtain an epoxy (meth) acrylate resin composition which can form a cured product excellent in heat resistance and excellent dielectric properties.

worin
X für eine Alkylenkette mit einer Kohlenstoffzahl von 1 bis 10, eine Polyoxyalkylenkette, (Poly)esterkette, aromatische Kohlenwasserstoffkette oder (Poly)carbonatkette steht, wobei in der Struktur ein Halogenatom, eine Alkoxygruppe usw. enthalten sein können; und Y für ein Wasserstoffatom oder eine Methylgruppe steht.The specific structure of the (meth) acrylate compound (b2) containing carboxyl groups is not subject to any particular restriction as long as it contains carboxyl groups and (meth) acryloyl groups in the molecular structure. Not only acrylic acid and methacrylic acid but also compounds having a low molecular weight in the range of 100 to 500 are advantageous, and compounds having a molecular weight in the range of 150 to 400 are more advantageous. Specifically, compounds having the following structural formula (16), etc. are given.

wherein
X represents an alkylene chain having a carbon number of 1 to 10, a polyoxyalkylene chain, (poly) ester chain, aromatic hydrocarbon chain or (poly) carbonate chain, which structure may contain a halogen atom, an alkoxy group, etc.; and Y represents a hydrogen atom or a methyl group.

Examples of the polyoxyalkylene chain are polyoxyethylene or polyoxypropylene chain, etc.

worin
R₁ für eine Alkylengruppe mit einer Kohlenstoffatomzahl von 1 bis 10 steht und n eine ganze Zahl von 1 bis 5 ist.Examples of the (poly) ester chain are (poly) ester chains having the following structural formula (X-1).

wherein
R _{1 represents} an alkylene group having a number of carbon atoms of 1 to 10 and n is an integer of 1 to 5.

Examples of the aromatic hydrocarbon chain are phenylene chain, naphthylene chain, biphenylene chain, phenylnaphthylene chain, binaphthylene chain, etc. Also, hydrocarbon chains including, as a partial structure, an aromatic ring such as benzene ring, naphthalene ring, anthracene ring, phenantrene ring, etc. can be used.

worin
R₂ für eine Alkylengruppe mit einer Kohlenstoffatomzahl von 1 bis 10 steht und n eine ganze Zahl von 1 bis 5 ist.Examples of the (poly) carbonate chain are (poly) carbonate chains having the following structural formula (X-2).

wherein
R _{2 represents} an alkylene group having a number of carbon atoms of 1 to 10 and n is an integer of 1 to 5.

These (meth) acrylate compounds (b2) containing carboxyl groups can be used individually or in combination with one another.

Acid anhydrides of the carboxyl group-containing (meth) acrylate compounds can also be used as the (meth) acrylate compound (b2) containing carboxyl groups.

Examples of the acid anhydrides of the carboxyl group-containing (meth) acrylate compounds are (meth) acrylic anhydrides, etc.

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

The (meth) acryloyl group equivalent of the epoxy (meth) acrylate resin (B) is preferably in the range of 200 to 800 g / equivalent in order to obtain an epoxy (meth) acrylate resin composition which will form a cured product having excellent heat resistance and dielectric properties can. 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 in the range of 3 mgKOH / g or less, more preferably in the range of 2 mgKOH / g or less, in order to obtain an epoxy (meth) acrylate resin composition containing a cured product excellent heat resistance and excellent dielectric properties. The hydroxyl number is preferably 300 mgKOH / g or less.

It is advantageous that the reaction between the epoxy resin (b1) and the carboxyl group-containing (meth) acrylate compound (b2) takes place in the presence of a basic catalyst.

Examples of the basic catalyst are amine compounds such as N-methylmorpholine, pyridine, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicylo [4.3.0] nonene-5 (DBN), 1, 4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (N-phenyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyl-dimethoxysilane, tetramethylammonium hydroxide, etc .; quaternary ammonium salts such as trioctylmethylammonium chloride, trioctylmethylammonium acetate, etc .: phosphines such as trimethylphosphine, tributylphosphine, triphenylphosphine, etc .; Phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl (2-hydroxypropyl) phosphonium chloride, triphenylphosphonium chloride, benzylphosphonium chloride, etc .; and organic tin compounds such as dibutyl tin dilaurate, octyl tin trilaurate, octyl tin diacetate, dioctyl tin diacetate, dioctyl tin dineodecanoate, dibutyl tin diacetate, tin octylate, 1,1,3,3-tetrabutyl-1,3-dodecanoyl distannoxane, etc .; organic metal compounds such as zinc octylate, bismuth octylate, etc .; inorganic tin compounds such as tin octanoate, etc .; inorganic metal compounds, etc. These basic catalysts can be used individually or in combination with each other. Of these, triphenylphosphine is advantageous.

The amount of the basic catalyst used, based on 100 parts by mass of the sum of the epoxy resin (b1) and the (meth) acrylate compound (b2) containing carboxyl groups, is preferably in the range from 0.01 to 0.5 parts by mass, more preferably in the range of 0, 01 to 0.4 parts by mass to obtain an epoxy (meth) acrylate resin having low viscosity and excellent storage stability.

If the basic catalyst is used in the reaction between the epoxy resin (b1) and the carboxyl-containing (meth) acrylate compound (b2), the basic catalyst can be separated off and removed after the reaction or, instead of being separated off and removed, it can be mixed with an acidic catalyst Connection can be deactivated.

Examples of the acidic compound are inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, etc .; and organic acids such as methanesulfonic acid, paratoluenesulfonic acid, oxalic acid, etc. These acidic compounds can be used singly or in combination.

The method for producing the epoxy (meth) acrylate resin (B) is not particularly limited. The epoxy (meth) acrylate resin (B) can be produced by any method. For example, it can be produced by a method in which all of the reaction materials are reacted at once or by a method in which the reaction materials are reacted in turn. In order to facilitate the regulation of the reaction, a process can be carried out in which first the epoxy resin (b1) is reacted with the carboxyl-containing (meth) acrylate compound (b2) in the presence of a basic catalyst in a temperature range of 80 to 140 ° C and then the basic catalyst is deactivated by mixing in an acidic compound in a temperature range from 50 to 100 ° C.

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 mass% in order to obtain an epoxy (meth) acrylate resin composition which is a cured product excellent in heat resistance and excellent dielectric properties can form.

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 from 90 to 10 mass%.

The mass ratio of the solid content between the aromatic ester compound (A) and the epoxy (meth) acrylate resin (B) [(A) / (B)] is preferably in the range of 10/90 to 90/10 around an epoxy (meth) acrylate resin composition which can form a cured product with excellent heat resistance and excellent dielectric properties.

By adding a photopolymerization initiator, the epoxy (meth) acrylate resin composition of the present invention can be used as a curable resin composition.

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

Examples of further commercially available photopolymerization initiators are “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 "(from IGM)," Kayacure-DETX "," Kayacure-MBP "," Kayacure-DMBI "," Kayacure-EPA "," Kayacure-OA "(From Nippon Kayaku Co., Ltd.)," Bicure-10 "," Bicure-55 "(from Stauffer Chemical Co.)," Trigonal P1 "(from Akzo)," Sandoray 1000 ”(from Sandoz),“ Deep ”(from Upjohn),“ Quantacure PDO ”,“ Quantacure ITX ”,“ Quantacure EPD ”(from Ward Blenkinsop),“ Runtecure -1104 "(from Runtec) etc.

It is preferable that the amount of the photopolymerization initiator used in, for example, the curable resin composition is in the range of 1 to 20 mass%.

The curable resin composition according to the invention can contain further resin components in addition to the epoxy (meth) acrylate resin (B). Examples of the other resin components are epoxy resins, various (meth) acrylate monomers, etc. As the other resin components, there can also be used resins made by reacting an epoxy resin such as bisphenol type epoxy resin, novolak type, etc. with a (meth) acrylic acid, Dicarboxylic anhydride or optionally an unsaturated monocarboxylic anhydride, etc., and contain carboxyl groups and (meth) acryloyl groups.

As the epoxy resins, the above-mentioned examples of the epoxy resins (b1) can be used. The epoxy resins can be used individually or in combination with one another.

Examples of the (meth) acrylate monomers are mono (meth) acrylate compounds, i.e. aliphatic mono (meth) acrylate compounds such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, etc .; alicyclic mono (meth) acrylate compounds such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl mono (meth) acrylate, etc .; heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate, tetrahydrofurfuryl acrylate, etc .; and aromatic mono (meth) acrylate compounds such as benzyl (meth) acrylate, phenyl (meth) acrylate, phenylbenzyl (meth) acrylate, phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3 -phenoxypropyl (meth) acrylate, phenoxybenzyl (meth) acrylate, phenylphenoxyethyl (meth) acrylate, etc .: as well as (poly) oxyalkylene-modified mono (meth) acrylate compounds in which the molecular structure of the various mono (meth) acrylate monomers has a polyoxyalkylene chain, such as a (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain, etc. has been introduced; lactone-modified mono (meth) acrylate compounds, in which the molecular structure of the various mono (meth) acrylate compounds a (poly) lactone structure was introduced; aliphatic di (meth) acrylate compounds such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentylglycol di (meth) acrylate, etc .; alicyclic di (meth) acrylate compounds such as 1,4-cyclohexane dimethanol di (meth) acrylate, norbornane di (meth) acrylate, norbornane dimethanol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, etc .; aromatic di (meth) acrylate compounds such as biphenol di (meth) acrylate, bisphenol di (meth) acrylate, etc .; polyoxyalkylene-modified di (meth) acrylate compounds in which a (poly) oxyalkylene chain such as (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain, etc. is introduced into the molecular structure of various di (meth) acrylate compounds; lactone-modified di (meth) acrylate compounds in which a (poly) lactone structure has been introduced into the molecular structure of the various di (meth) acrylate compounds; aliphatic tri (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, etc .; (Poly) oxyalkylene-modified tri (meth) acrylate compounds in which a (poly) oxyalkylene chain such as (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain, etc. is introduced into the molecular structure of the aliphatic tri (meth) acrylate compounds ; lactone-modified tri (meth) acrylate compounds in which a (poly) lactone structure has been introduced into the molecular structure of the aliphatic tri (meth) acrylate compounds; 4- or more-functional aliphatic poly (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc .; (Poly) oxyalkylene-modified 4- or more-functional poly (meth) acrylate compounds, in which the molecular structure of the aliphatic poly (meth) acrylate compounds contains a (poly) oxyalkylene chain, such as a (poly) oxyethylene chain, (poly) oxypropylene chain, (poly ) oxytetramethylene chain, etc. has been introduced; and lactone-modified 4- or more-functional poly (meth) acrylate compounds in which a (poly) lactone structure has been introduced into the molecular structure of the aliphatic poly (meth) acrylate compounds.

The curable resin composition of the present invention may contain organic solvents for controlling application viscosity, etc. Their type and amount used are suitably selected and regulated according to the desired properties.

Examples of the organic solvents are ketone solvents such as methyl ethyl ketone, acetone, isobutyl ketone, etc .; cyclic ether solvents such as tetrahydrofuran, dioxolane, etc .; Ester solvents such as methyl acetate, ethyl acetate, butyl acetate, etc .; aromatic solvents such as toluene, xylene, solvent naphtha, etc .; alicyclic solvents such as cyclohexane, methylcyclohexane, etc .; Alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether, etc .; and glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether acetate, etc. These organic solvents can be used singly or in combination.

The curable resin composition of the present invention may contain various additives such as inorganic fine particles, polymer fine particles, pigments, defoamers, viscosity regulators, leveling agents, flame retardants, storage stabilizers, etc., as required.

The cured product of the present invention can be obtained by irradiating the curable resin composition with active energy rays. Examples of the active energy radiation are ionizing radiation such as UV radiation, electron beam, α-, β-, γ-ray, etc. If the UV radiation is used as active energy radiation, the radiation can be in an inert gas atmosphere of nitrogen gas, etc. or in a Air atmosphere so that the curing reaction is carried out efficiently by the UV radiation.

A UV lamp is common as a source for generating UV radiation in view of its practical applicability and economy. Specifically, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, LEDs, etc. are listed.

The cured products obtained by curing the curable resin composition of the present invention can e.g. B. for semiconductor applications, such as solder resists, interlaminar insulation materials, packaging materials, underfill materials, package adhesive layers for circuit elements, etc. and as adhesive layers between integrated circuit elements and printed circuit boards are advantageously used. In addition, they can be used for thin-film display applications, typically LCDs or OELDs, e.g. B. as thin-film transistor protective films, liquid crystal color filter protective films, pigment coatings for color filters, black matrix protective coatings, spacers, etc. are advantageously used.

The article according to the invention has a coating made from the cured product. Examples of the item are semiconductor devices, display devices, image capture devices, magnetic heads, MEMS, etc.

The present invention is explained in more detail below with reference to the exemplary embodiments and comparative examples.

(Synthesis Example 1: Synthesis of an Aromatic Ester Compound (A-1))

Into a flask to which a thermometer, a dropping funnel, a cooling tube, a fractionating column and a stirrer were attached, 268 parts by mass (2.0 mol) of orthoallylphenol and 1200 parts by mass of toluene were placed, and then the inside of the system was filled with nitrogen under reduced pressure substituted. Then 203 parts by mass (1.0 mol) of isophthalic acid chloride was charged, and then the inside of the system was substituted with nitrogen under reduced pressure. Then, 0.6 part by mass of tetrabutylammonium bromide was added and the inside of the system was controlled to 60 ° C or lower while purging with nitrogen gas, whereupon 412 parts by mass of a 20% sodium hydroxide aqueous solution was dropped over 3 hours and stirred for one hour after the completion of the dropping. After the completion of the reaction, the aqueous layer was removed by stationary liquid separation. In the obtained toluene layer, water was additionally introduced and stirred for 15 minutes. Thereafter, the aqueous layer was removed by stationary liquid separation. This treatment was repeated until the pH of the aqueous layer reached 7. Then, by heating, evacuating and drying, an aromatic ester compound (A-1) having the following chemical formula was obtained. The ester group equivalent of the aromatic ester compound (A-1) was 199 g / equivalent. The ester group equivalent is a calculated value determined from the ratio of the components introduced.

(Synthesis Example 2: Synthesis of an Aromatic Ester Compound (A-2))

Into a flask to which a thermometer, a dropping funnel, a cooling tube, a fractionating column and a stirrer were attached, 134 parts by mass (1.0 mol) of orthoallylphenol and 711 parts by mass of toluene were placed, and then the inside of the system was blown by nitrogen under reduced pressure substituted. Then, 140 parts by mass (1.0 mol) of benzyl chloride was charged, and then the inside of the system was substituted with nitrogen under reduced pressure. Thereafter, 0.4 part by mass of tetrabutylammonium bromide was added and the inside of the system was controlled to 60 ° C or lower while purging with nitrogen gas, whereupon 205 parts by mass of a 20% sodium hydroxide aqueous solution was dropped over 3 hours and stirred for one hour after the completion of the dropping. After the completion of the reaction, the aqueous layer was removed by stationary liquid separation. In the obtained toluene layer, water was additionally introduced and stirred for 15 minutes. Thereafter, the aqueous layer was removed by stationary liquid separation. This treatment was repeated until the pH of the aqueous layer reached 7. Then, by heating, evacuating and drying, an aromatic ester compound (A-2) having the following chemical formula was obtained. The ester group equivalent of the aromatic ester compound (A-2) was 119 g / equivalent. The ester group equivalent is a calculated value determined from the ratio of the components introduced.

(Synthesis example 3: Synthesis of an aromatic ester compound (A-3))

Into a flask to which a thermometer, a dropping funnel, a cooling pipe, a fractionating column and a stirrer were attached, 244 parts by mass (2.0 mol) of 2,5-xylenol and 1120 parts by mass of toluene were placed, and then the inside of the system was placed substituted by nitrogen under reduced pressure. Then 203 parts by mass (1.0 mol) of isophthalic acid chloride was charged, and then the inside of the system was substituted with nitrogen under reduced pressure. Then, 0.6 part by mass of tetrabutylammonium bromide was added and the inside of the system was controlled to 60 ° C or lower while purging with nitrogen gas, whereupon 410 parts by mass of a 20% sodium hydroxide aqueous solution was dropped over 3 hours and stirred for one hour after the completion of the dropping. After the completion of the reaction, the aqueous layer was removed by stationary liquid separation. In the obtained toluene layer, water was additionally introduced and stirred for 15 minutes. Thereafter, the aqueous layer was removed by stationary liquid separation. This treatment was repeated until the pH of the aqueous layer reached 7. Then, by heating, evacuating and drying, an aromatic ester compound (A-1) having the following chemical formula was obtained. The ester group equivalent of the aromatic ester compound (A-3) was 187 g / equivalent. The ester group equivalent is a calculated value determined from the ratio of the components introduced.

(Synthesis example 4: Synthesis of an 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-850CRP” from DIC Corporation; epoxy equivalent: 172 g / equivalent) were placed, 0.21 parts by mass of dibutylhydroxytoluene added as an antioxidant and 0.21 parts by mass of methoquinone as a thermopolymerization inhibitor and then 72 parts by mass of acrylic acid and 0.21 parts by mass Triphenylphosphine added. Then, the esterification reaction was carried out under a bubbled air at 100 ° C. for 10 hours. Then, after the acid value was found to be 1 mgKOH / g or less, 0.42 part by mass of oxalic acid was added and stirred at 70 ° C. for 3 hours, thereby obtaining an epoxy (meth) acrylate resin (B-1). The epoxy (meth) acrylate resin (B-1) had an epoxy equivalent of 445 g / equivalent and a (meth) acryloyl group equivalent of 416 g / equivalent. The (meth) acryloyl group equivalent is a calculated value.

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

In a flask with a thermometer, a stirrer and a reflux condenser, 318 parts by mass of a bisphenol F-type epoxy resin (“EPICLON 830CRP” from DIC Corporation; epoxy equivalent: 159 g / equivalent; hereinafter referred to as “bisphenol F epoxy resin”) Type (1) "abbreviated), 0.2 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.2 parts by mass of methoquinone as thermopolymerization inhibitor were added, and then 72 parts by mass of acrylic acid and 0.2 parts by mass of triphenylphosphine were added. Then, the esterification reaction was carried out under a bubbled air at 100 ° C. for 10 hours. Subsequently, after the acid value was found to be 1 mgKOH / g or less, 0.2 part by mass of oxalic acid was added and stirred at 70 ° C for 3 hours, thereby obtaining an epoxy (meth) acrylate resin (B-2). The epoxy (meth) acrylate resin (B-2) had an epoxy equivalent of 421 g / equivalent and a (meth) acryloyl group equivalent of 390 g / equivalent. The (meth) acryloyl group equivalent is a calculated value.

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

Into a flask equipped with a thermometer, a stirrer and a reflux condenser, 282 parts by mass of a naphthalene-type epoxy resin ("EPICLON 4032D" from DIC Corporation; epoxy equivalent: 141 g / equivalent; hereinafter referred to as "naphthalene-type epoxy resin ( 1) "abbreviated), 0.18 part by mass of dibutylhydroxytoluene as an antioxidant and 0.18 part by mass of methoquinone as a thermopolymerization inhibitor were added and then 72 parts by mass of acrylic acid and 0.18 parts by mass of triphenylphosphine were added. Then, the esterification reaction was carried out under a bubbled air at 100 ° C. for 10 hours. Then, after the acid value was found to be 1 mgKOH / g or less, 0.18 part by mass of oxalic acid was added and stirred at 70 ° C for 3 hours, thereby obtaining an epoxy (meth) acrylate resin (B-3). The epoxy (meth) acrylate resin (B-3) had an epoxy equivalent of 388 g / equivalent and a (meth) acryloyl group equivalent of 354 g / equivalent. The (meth) acryloyl group equivalent is a calculated value.

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

18 g of butyl acetate, 129 g of an epoxy resin of the resorcinol type (“ERISYS RDGE-H” from CVC Thermoset Specialties; epoxy equivalent: 129 g / equivalent) were placed in a flask with a thermometer, a stirrer and a reflux condenser and 0 , 1 g of dibutylhydroxytoluene, 0.1 g of methoquinone, 36 g of acrylic acid and 0.1 g of triphenylphosphine were added. Then, the esterification reaction was carried out under blown air at 80 ° C for 20 hours. Then, after the acid value was found to be 1 mgKOH / g or less, 0.1 part by mass of oxalic acid was added and stirred at 70 ° C for 3 hours, thereby obtaining an epoxy (meth) acrylate resin (B-4). The epoxy (meth) acrylate resin (B-4) had an epoxy equivalent of 565 g / equivalent and a (meth) acryloyl group equivalent of 330 g / equivalent. The (meth) acryloyl group equivalent is a calculated value.

(Embodiment 1: Preparation of an epoxy (meth) acrylate resin composition (1))

An epoxy (meth) acrylate resin composition (1) was obtained by using 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" of from IGM) were mixed in the amounts given in Table 1.

(Working examples 2 to 13: production of epoxy (meth) acrylate resin compositions (2) to (13))

Epoxy (meth) acrylate resin compositions (2) to (13) were obtained by the same method as in Working Example 1 using the compositions and use amounts shown in Table 1.

(Comparative Examples 1 and 2: Preparation of Epoxy (meth) acrylate resin compositions (C1) and (C2))

Epoxy (meth) acrylate resin compositions (C1) and (C2) were obtained by using the epoxy (meth) acrylate resin (B-1) obtained in Synthesis Example 4, an ethylene oxide-modified diacrylate of bisphenol A (“Miramer M-240” from Miwon ) and a photopolymerization initiator ("Omnirad 184" from IGM) in the amounts given in Table 1 were mixed.

The epoxy (meth) acrylate resin compositions obtained in the above working and comparative examples were evaluated in the following items.

[Method of evaluating heat resistance]

The epoxy (meth) acrylate resin compositions obtained in the individual exemplary and comparative examples were each applied to a layer up to 50 μm thick by means of an applicator Glass substrate applied and dried at 80 ° C for 30 minutes. Subsequently, they were irradiated with UV radiation of 1000 mJ / cm ² by means of a metal halide lamp, thereafter heated at 160 ° C. for one hour, and then the obtained hardened product was peeled off from the glass substrate, whereby the hardened product was obtained. A test piece measuring 6 mm × 35 mm was cut out from the cured product. A viscoelasticity meter (DMA: solid viscoelasticity meter “RSAII” from Rheometric; drawing method: frequency number 1 Hz; temperature rise rate 3 ° C / min) was used, the temperature at which the maximum change in elasticity was observed being evaluated as the glass transition temperature. It has been shown that the higher the glass transition temperature, the better the heat resistance.

[Method of evaluating dielectric constant]

The epoxy (meth) acrylate resin compositions obtained in the individual exemplary and comparative examples were each applied to a glass substrate up to a layer thickness of 50 μm by means of an applicator and dried at 80 ° C. for 30 minutes. Subsequently, they were irradiated with UV radiation of 1000 mJ / cm ² by means of a metal halide lamp, thereafter heated at 160 ° C. for one hour, and then the obtained hardened product was peeled off from the glass substrate, whereby the hardened product was obtained. It was then stored for 24 hours in a room with a temperature of 23 ° C and a humidity of 50%. The test piece obtained in this way was measured for the dielectric constant at 1 GHz by the cavity resonance method using a “Network Analyzer E8362C” from Agilent Technologies Inc.

[Method for evaluating the dielectric loss factor]

The epoxy (meth) acrylate resin compositions obtained in the individual exemplary and comparative examples were each applied to a glass substrate up to a layer thickness of 50 μm by means of an applicator and dried at 80 ° C. for 30 minutes. Subsequently, they were irradiated with ultraviolet rays of 1000 mJ / cm ³ by means of a metal halide lamp, thereafter heated at 160 ° C. for one hour, and then the obtained hardened product was peeled off from the glass substrate, whereby the hardened product was obtained. It was then stored for 24 hours in a room with a temperature of 23 ° C and a humidity of 50%. The test piece obtained in this way was measured by the cavity resonance method using a “Network Analyzer E8362C” from Agilent Technologies Inc. with regard to the dielectric loss factor at 1 GHz.

Table 1 shows the evaluation results of the epoxy (meth) acrylate resin compositions (1) to (13) produced in Working Examples 1 to 13 and the epoxy (meth) acrylate resin compositions (C1) and (C2) produced in Comparative Examples 1 and 2.

The "epoxy resin" in Table 1 represents the bisphenol A-type epoxy resin ("EPICLON EXA-850CRP" from DIC Corporation; epoxy equivalent: 172 g / equivalent).

Examples 1 to 13 according to Table 1 correspond to the examples of the epoxy (meth) acrylate resin compositions according to the invention. It has been confirmed that, in the cured products of the epoxy (meth) acrylate resin compositions of the present invention, the heat resistance is excellent and, besides, both the dielectric constant and the dielectric loss factor are low; H. the dielectric properties are also excellent.

On the other hand, Comparative Examples 1 and 2 are examples of epoxy (meth) acrylate resin compositions in which no aromatic ester compound is used. It has been confirmed that, in the cured products of these epoxy (meth) acrylate resin compositions, both the dielectric constant and the dielectric loss factor are high; H. the dielectric properties are considerably insufficient.

QUOTES INCLUDED IN THE DESCRIPTION

This list of the documents listed by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent literature cited

• JP 2012772989 A [0005]

Claims (11)

Epoxy (meth) acrylate resin composition containing an aromatic ester compound (A) and an epoxy (meth) acrylate resin (B), characterized in that the epoxy (meth) acrylate resin (B) consists of an epoxy resin (b1) and a carboxyl group-containing (meth) acrylate compound (b2) is formed as indispensable reaction materials, and that the epoxy (meth) acrylate resin (B) has epoxy groups and (meth) acryloyl groups. Epoxy (meth) acrylate resin composition according to Claim 1 wherein the aromatic ester compound (A) is a reaction product of an aromatic compound having phenolic hydroxyl groups and an aromatic compound having carboxyl groups, the acid halide and / or the esterification product thereof. Epoxy (meth) acrylate resin composition according to Claim 1 in which the aromatic ester compound (A) is represented by a following chemical formula (a1) or (a2): [Chem. 1]

wherein ^{each Ar 5} independently represents a substituted or unsubstituted first aromatic ring group, ^{each Ar 6} independently represents a substituted or unsubstituted second aromatic ring group, and n is an integer from 1 to 3. Epoxy (meth) acrylate resin composition according to Claim 2 in which at least either the aromatic compound having phenolic hydroxyl groups or the aromatic compound having carboxyl groups, its acid halide and / or its esterification product comprises a substituent having a polymerizable unsaturated bond. Epoxy (meth) acrylate resin composition according to Claim 3 wherein at least one of Ar ⁵ and Ar ⁶ comprises a substituent having a polymerizable unsaturated bond. Epoxy (meth) acrylate resin composition according to Claim 1 wherein the mass ratio of the solid content between the aromatic ester compound (A) and the epoxy (meth) acrylate resin (B) [(A) / (B)] is in the range of 10/90 to 90/10. A curable resin composition characterized by being an epoxy (meth) acrylate resin composition according to any one of Claims 1 to 6th and contains a photopolymerization initiator. Curable resin composition according to Claim 7 which further contains a (meth) acrylate monomer. Curable resin composition according to Claim 7 , which also contains an epoxy resin. A cured product characterized by being a curing reaction product according to the curable resin composition Claims 7 to 9 is. Article characterized in that it has a coating made from the cured product after Claim 10 having.