JP6705574B2 - Acid group-containing (meth)acrylate resin composition, curable resin composition, cured product, insulating material, resin material for solder resist, and resist member - Google Patents

Description

The present invention has an acid group-containing (meth)acrylate resin composition having high photosensitivity and excellent heat resistance and dielectric properties, a curable resin composition containing the same, a cured product, and the curable resin composition. And an insulating material, a resin material for a solder resist, and a resist member.

In recent years, curable resin compositions that can be cured by active energy rays such as ultraviolet rays have been widely used as resin materials for solder resists for printed wiring boards. The properties required for the resin material for solder resist include various properties such as curing with a small exposure amount, excellent alkali developability, and excellent heat resistance, strength, dielectric properties and the like of the cured product.

As a conventional solder resist resin material, an acid group-containing epoxy acrylate resin obtained by further reacting tetrahydrophthalic anhydride with an intermediate obtained by reacting a cresol novolac type epoxy resin, acrylic acid and phthalic anhydride Although a photosensitive resin composition containing a compound is known (for example, refer to Patent Document 1), the heat resistance of the cured product is not sufficient, and the dielectric constant and the dielectric loss tangent increase due to the formation of hydroxyl groups. There were problems such as deterioration of characteristics.

Therefore, there has been a demand for a material having high photosensitivity and being more excellent in heat resistance and adhesion to a substrate in a cured product.

JP-A-8-259663

The problem to be solved by the present invention has high photosensitivity, an acid group-containing (meth)acrylate resin composition having excellent heat resistance and dielectric properties, a curable resin composition containing the same, a cured product, It is intended to provide an insulating material, a resin material for a solder resist, and a resist member, which are made of the photosensitive resin composition.

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

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

The acid group-containing (meth)acrylate resin composition of the present invention has high photosensitivity and can form a cured product having excellent heat resistance and dielectric properties. Therefore, the insulating material, the resin material for solder resist, and the solder resist It can be suitably used for a resist member made of a resin for use. The "excellent dielectric property" referred to in the present invention means low dielectric constant and low dielectric loss tangent.

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

The polymerizable unsaturated bond-containing aromatic ester compound (A) is a compound having one or a plurality of polymerizable unsaturated bonds in the molecular structure and having a structural site in which aromatic rings are bonded by an ester bond. However, other specific structures and molecular weights are not particularly limited, and various compounds can be used.

Examples of the polymerizable unsaturated bond-containing aromatic ester compound (A) include an aromatic compound having a phenolic hydroxyl group, an aromatic compound having a carboxyl group, an acid halide thereof and/or an ester compound thereof (the present specification). In the specification, an aromatic compound having a carboxyl group, an acid halide thereof, and/or an esterified product thereof may be collectively referred to as “aromatic compound having a carboxyl group, etc.”). Any one of the aromatic compound having a phenolic hydroxyl group, the aromatic compound having a carboxyl group, and the like may have a polymerizable unsaturated bond-containing substituent.

Examples of the aromatic compound having a phenolic hydroxyl group include a first aromatic compound having two or more phenolic hydroxyl groups and a second aromatic compound having one phenolic hydroxyl group.

The first aromatic compound has two or more phenolic hydroxyl groups. By having two or more phenolic hydroxyl groups, an ester structure can be formed by reacting with a third aromatic compound or the like or a fourth aromatic compound or the like described later.

The first aromatic compound is not particularly limited, and examples thereof include compounds having two or more phenolic hydroxyl groups in the first aromatic ring having 3 to 30 carbon atoms, which is substituted or unsubstituted.

Examples of the first aromatic ring having 3 to 30 carbon atoms include a monocyclic aromatic ring, a condensed aromatic ring, and a ring-assembled aromatic ring.

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

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

Examples of the ring-assembled aromatic ring include biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl.

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

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

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

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

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

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

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

Among these, the polymerizable unsaturated bond-containing substituent is preferably an alkenyl group having 2 to 30 carbon atoms, more preferably an alkenyl group having 2 to 10 carbon atoms, and having 2 carbon atoms. Are more preferably alkenyl groups of 5 to 5, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, 1-propenyl groups, 1-butenyl groups, 2-butenyl groups, 3-butenyl groups, 1,3-butadienyl groups. A group is particularly preferable, and an allyl group, a propenyl group, an isopropenyl group, and a 1-propenyl group are the most preferable.

The above substituents on the first aromatic ring may be contained alone or in combination of two or more.

Then, as described above, the first aromatic compound is obtained by substituting at least two hydrogen atoms constituting the above-mentioned substituted or unsubstituted first aromatic ring having 3 to 30 carbon atoms with a hydroxyl group. Is.

Specific examples of the compound in which the first aromatic ring is a monocyclic aromatic ring (hereinafter, may be simply referred to as “first monocyclic aromatic ring compound”) include, for example, catechol, resorcinol, hydroquinone. , Hydroxynol, phloroglucinol, pyrogallol, 2,3-dihydroxypyridine, 2,4-dihydroxypyridine, 4,6-dihydroxypyrimidine, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol and the like. ..

Specific examples of the compound in which the first aromatic ring is a condensed aromatic ring (hereinafter, may be simply referred to as “first condensed aromatic ring compound”) include, for example, 1,3-naphthalene. Diol, 1,5-naphthalene diol, 2,6-naphthalene diol, 2,7-naphthalene diol, 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 and the like can be mentioned.

Specific examples of the compound in which the first aromatic ring is a ring-assembled aromatic ring (hereinafter, may be simply referred to as “first ring-assembled aromatic ring compound”) include, for example, 2,2′- Dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 3,4,4'-trihydroxybiphenyl, 2,2',3-trihydroxybiphenyl and the like can be mentioned.

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

In the chemical formula (1), Ar ¹ is independently a substituted or unsubstituted first aromatic ring group, and Ar ² is independently a substituted or unsubstituted second aromatic ring group. And X is each independently an oxygen atom, a sulfur atom, a substituted or unsubstituted alkylene, a substituted or unsubstituted cycloalkylene, or aralkylene, and n is an integer of 0 to 10. At this time, at least two hydrogen atoms constituting Ar ¹ and Ar ² are replaced with hydroxyl groups. The X corresponds to the linking group.

Ar ¹ is a substituted or unsubstituted first aromatic ring group. As is clear from the description of the above chemical formula (1), one of the hydrogen atoms of the aromatic ring that constitutes the above-mentioned substituted or unsubstituted aromatic ring is bonded to "X".

Examples of the first aromatic ring group include monocyclic aromatic compounds such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine and triazine. From which one hydrogen atom has been removed; a hydrogen atom from a condensed aromatic compound such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine, etc. Examples thereof include those obtained by removing one hydrogen atom from an aromatic compound obtained by removing one hydrogen atom. Further, a combination of a plurality of these aromatic compounds may be used, and for example, a ring-assembled aromatic compound such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl. One obtained by removing one hydrogen atom from the above.

In this case, the first aromatic ring group may have a substituent, and in this case, the “substituent of the first aromatic ring group” constitutes the first aromatic ring group. It is substituted with at least one hydrogen atom of the aromatic ring. Examples of the "substituent for the first aromatic ring group" include an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, a halogen atom and the like.

Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group. , Neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, cyclohexyl group and the like.

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

Examples of the alkyloxycarbonyl group include methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, isopropyloxycarbonyl group, butyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl. Examples thereof include an oxycarbonyl group and a tert-butyloxycarbonyl group.

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

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

Of these, Ar ¹ is benzene, naphthalene, anthracene, phenalene, phenanthrene, biphenyl, binaphthalene, quaterphenyl, allylbenzene, diallylbenzene, allylnaphthalene, diallylnaphthalene, allylbiphenyl, and one hydrogen atom is removed from diallylbiphenyl. It is preferable that one hydrogen atom is removed from benzene, naphthalene, biphenyl, allylbenzene, diallylnaphthalene, and diallylbiphenyl.

Ar ^{2 s} are each independently a substituted or unsubstituted second aromatic ring group. As is clear from the description of the chemical formula (1), two of the hydrogen atoms of the aromatic ring forming the above-mentioned substituted or unsubstituted aromatic ring are bonded to “X”.

Examples of the second aromatic ring group include monocyclic aromatic compounds such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine and triazine. From which two hydrogen atoms have been removed; a hydrogen atom from a condensed aromatic compound such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine, etc. Examples thereof include those obtained by removing two hydrogen atoms from an aromatic compound obtained by removing two hydrogen atoms. Further, a combination of a plurality of these aromatic compounds may be used, and for example, a ring-assembled aromatic compound such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl. One obtained by removing two hydrogen atoms from is mentioned.

At this time, the second aromatic ring group may have a substituent. Examples of the “substituent of the second aromatic ring group” include the same ones as the above “substituent of the first aromatic ring group”.

The Xs are each independently an oxygen atom, a sulfur atom, a substituted or unsubstituted alkylene, a substituted or unsubstituted cycloalkylene, or an aralkylene.

Examples of the alkylene include methylene, ethylene, propylene, 1-methylmethylene, 1,1-dimethylmethylene, 1-methylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, propylene, butylene, 1- Methyl propylene, 2-methyl propylene, pentylene, hexylene, etc. are mentioned.

Examples of the cycloalkylene include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclopentylene, cycloheptylene, and cycloalkylene represented by the following chemical formulas (2-1) to (2-4). Is mentioned.

In the chemical formulas (2-1) to (2-4), “*” represents a site that binds to Ar ¹ or Ar ² .

Examples of the aralkylene include aralkylenes represented by the following chemical formulas (3-1) to (3-8).

In the chemical formulas (3-1) to (3-8), “*” represents a site that binds to Ar ¹ or Ar ² .

The alkylene, the cycloalkylene, and the aralkylene may have a substituent. In this case, as the "substituent of X", the same as the above-mentioned "substituent of the first aromatic ring" can be mentioned.

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

At least two hydrogen atoms constituting Ar ¹ and Ar ² are replaced with hydroxyl groups.

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

Examples of the various bisphenol compounds include bisphenol A, bisphenol AP, bisphenol B, bisphenol E, bisphenol F, and bisphenol Z.

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

In one embodiment, the above-mentioned first aromatic ring is represented by the above chemical formula (1), in which at least one of hydrogen atoms constituting the first aromatic ring is substituted with a hydroxyl group. With a divinyl compound or a dialkyloxymethyl compound.

At this time, examples of the divinyl compound and the dialkyloxymethyl compound include fats such as 1,3-butadiene, 1,5-hexadiene, dicyclopentadiene, tricyclopentadiene, tetracyclopentadiene, pentacyclopentadiene, and hexacyclopentadiene. Aromatic diene compounds such as divinylbenzene and divinylbiphenyl; dialkyl such as dimethoxymethylbenzene, dimethoxymethylbiphenyl, bisphenol A methoxy adduct, bisphenol A ethoxy adduct, bisphenol F methoxy adduct and bisphenol F ethoxy adduct An oxymethyl compound etc. are mentioned.

The above-mentioned first aromatic compound having two or more phenolic hydroxyl groups can be used alone or in combination of two or more kinds.

As the hydroxyl equivalent of the first aromatic compound, an acid group-containing (meth)acrylate resin composition having high photosensitivity and capable of forming a cured product excellent in heat resistance and dielectric properties is obtained, It is preferably 130 to 500 g/equivalent, and more preferably 130 to 400 g/equivalent.

When the first aromatic compound is represented by the above chemical formula (1) and n is an oligomer or a polymer, the weight average molecular weight has high photosensitivity, and excellent heat resistance and dielectric properties. Since it is possible to obtain an acid group-containing (meth)acrylate resin composition capable of forming a cured product, it is preferably 200 to 3000, and more preferably 200 to 2000. In addition, in this specification, the value of the "weight average molecular weight" shall employ the value measured by the following method. That is, the value obtained by measuring gel permeation chromatography (GPC) under the following conditions is adopted.

Measuring conditions of GPC Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation
Column: Tosoh Co., Ltd. guard column "HXL-L"
+ Tosoh Corporation “TSK-GEL G4000HXL”
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: "GPC workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation
Column temperature: 40°C
Developing solvent: Tetrahydrofuran Flow rate: 1.0 ml/min Standard: The following monodisperse polystyrene having a known molecular weight was used according to the measurement manual of "GPC-8320 GPC" Polystyrene used "A-500" manufactured by Tosoh Corporation. "
Tosoh Corporation "A-1000"
Tosoh Corporation "A-2500"
Tosoh Corporation "A-5000"
Tosoh Corporation "F-1"
Tosoh Corporation "F-2"
Tosoh Corporation "F-4"
Tosoh Corporation “F-10”
Tosoh Corporation "F-20"
Tosoh Corporation "F-40"
Tosoh Corporation “F-80”
Tosoh Corporation "F-128"
Sample: a tetrahydrofuran solution of 1.0% by mass in terms of resin solid content, filtered through a microfilter (50 μl).

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

Examples of the second aromatic compound include compounds having one phenolic hydroxyl group in the second aromatic ring having 3 to 30 carbon atoms, which is substituted or unsubstituted.

Examples of the second aromatic ring having 3 to 30 carbon atoms include a monocyclic aromatic ring, a condensed aromatic ring, a ring-assembled aromatic ring, and an aromatic ring linked by alkylene. Examples of the monocyclic aromatic ring, the condensed aromatic ring, and the ring-assembled aromatic ring include the same as the above-mentioned first aromatic ring.

Examples of the aromatic ring linked by the alkylene include diphenylmethane, diphenylethane, 1,1-diphenylethane, 2,2-diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane and phenyl. Pyridyl methane, fluorene, diphenyl cyclopentane, etc. are mentioned.

The second aromatic ring having 3 to 30 carbon atoms related to the second aromatic compound may have a substituent. In this case, as the "substituent of the second aromatic ring", the same as the above-mentioned "substituent of the first aromatic ring" can be mentioned.

Then, as described above, in the second aromatic compound, one of the hydrogen atoms constituting the above-mentioned substituted or unsubstituted second aromatic ring having 3 to 30 carbon atoms is substituted with a hydroxyl group.

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

In the above chemical formulas (5-1) to (5-17), R ¹ is a polymerizable unsaturated bond-containing substituent. The polymerizable unsaturated bond-containing substituent is the same as described above. Further, p is 0 or an integer of 1 or more, preferably 1 to 3, more preferably 1 or 2, and further preferably 1. When p is 2 or more, the bonding position on the aromatic ring is arbitrary, and for example, in the naphthalene ring of the chemical formula (5-6) or the heterocycle of the chemical formula (5-17), substitution on any ring is possible. In the chemical formula (5-9), etc., it may be substituted on any ring of the benzene ring present in one molecule, and the number of substituents in one molecule is p. It is shown that.

As the second aromatic compound, more specifically, phenol, cresol, xylenol, orthoallylphenol, methallylphenol, paraallylphenol, 2,4-diallylphenol, 2,6-diallylphenol, 2- Aromatic rings such as allyl-4-methylphenol, 2-allyl-6-methylphenol, 2-allyl-4-methoxy-6-methylphenol, 2-propargylphenol, 3-propargylphenol and 4-propargylphenol are monocyclic. A compound that is a ring aromatic ring (hereinafter, may be simply referred to as "second monocyclic aromatic ring compound"); 1-naphthol, 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, A compound in which the aromatic ring is a condensed aromatic ring such as 2-propargyl-1-naphthol, 3-propargyl-1-naphthol, 1-propargyl-2-naphthol, and 3-propargyl-2-naphthol (hereinafter, simply referred to as " A compound having an aromatic ring such as allylhydroxybiphenyl and hydroxypropargylbiphenyl is a ring-assembled aromatic ring (hereinafter, simply referred to as "second ring-assembled aromatic compound"). Sometimes referred to as "ring compound") and the like.

Of the above, the second aromatic compound is preferably a second monocyclic aromatic ring compound or a second condensed aromatic ring compound, and orthoallylphenol, methallylphenol, paraallylphenol, 2-allyl-1-naphthol, 3-allyl-1-naphthol, 1-allyl-2-naphthol, 3-allyl-2-naphthol, 5-allyl-1-naphthol, 6-allyl-1-naphthol Is more preferable.

In another embodiment, the second aromatic compound is preferably a second condensed ring aromatic ring compound (condensed aromatic ring compound), and is 2-allyl-1-naphthol, 3 -Allyl-1-naphthol, 1-allyl-2-naphthol, 3-allyl-2-naphthol, 5-allyl-1-naphthol, 6-allyl-1-naphthol are more preferred. The second aromatic compound is preferably a condensed ring aromatic ring compound because molecular motion is suppressed by steric hindrance and the dielectric loss tangent can be reduced. Further, from the viewpoint of high handling property and low viscosity of the polymerizable unsaturated bond-containing aromatic ester compound (A), 2-allylphenol or the like having a benzene ring skeleton is preferable, while the obtained acid group-containing (meth) Since the acrylate resin composition has high photosensitivity and can form a cured product having excellent heat resistance and dielectric properties, 2-allyl-1-naphthol, 1-allyl-2-naphthol having a naphthalene ring skeleton, etc. preferable.

The above-mentioned second aromatic compound having one phenolic hydroxyl group can be used alone or in combination of two or more kinds.

Examples of the aromatic compound having a carboxyl group and the like include a third aromatic compound having two or more carboxyl groups, a fourth aromatic compound having one carboxyl group, or an acid halide or ester compound thereof. Is mentioned.

The third aromatic compound, an acid halide thereof, and/or an ester compound thereof is an aromatic compound having two or more carboxyl groups, or a derivative thereof, specifically an acid halide or an ester compound (the present In the specification, the third aromatic compound, its acid halide, and/or its esterified product may be collectively referred to as "third aromatic compound or the like".). Since the third aromatic compound or the like has two or more carboxyl groups or the like, it can react with the above-mentioned first aromatic compound or second aromatic compound to form an ester structure.

Examples of the third aromatic compound and the like include compounds having two or more carboxyl groups and the like in the third aromatic ring having 3 to 30 carbon atoms, which is substituted or unsubstituted.

The “carboxyl group and the like” are, for example, a carboxyl group; a halogenated acyl group such as an acyl fluoride group, an acyl chloride group and an acyl bromide group; an alkyloxycarbonyl group such as a methyloxycarbonyl group and an ethyloxycarbonyl group; Examples thereof include aryloxycarbonyl groups such as phenyloxycarbonyl group and naphthyloxycarbonyl group. When it has an acyl halide group, the third aromatic compound is an acid halide, and when it has an alkyloxycarbonyl group or an aryloxycarbonyl group, the third aromatic compound can be an ester compound. Of these, the third aromatic compound preferably has a carboxyl group, an acyl halide group or an aryloxycarbonyl group, more preferably a carboxyl group or an acyl halide group, and a carboxyl group or an acyl chloride group. It is more preferable to have an acyl bromide group.

Examples of the third aromatic ring having 3 to 30 carbon atoms include a monocyclic aromatic ring, a condensed aromatic ring, a ring-assembled aromatic ring, and an aromatic ring linked by alkylene. The monocyclic aromatic ring, the condensed aromatic ring, the ring-assembled aromatic ring, and the aromatic ring linked by alkylene are the same as the above-mentioned first aromatic ring and second aromatic ring. There are things.

The third aromatic ring having 3 to 30 carbon atoms related to the third aromatic compound or the like may have a substituent. At this time, as the “substituent of the third aromatic ring”, the same as the above-mentioned “substituent of the first aromatic ring” can be mentioned.

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

In the above chemical formulas (6-1) to (6-15), R ¹ is a polymerizable unsaturated bond-containing substituent. At this time, the polymerizable unsaturated bond-containing substituent is the same as described above. R ² is a hydroxyl group, a halogen atom, an alkyloxy group or an aryloxy group. Further, p is 0 or an integer of 1 or more, preferably 0 or 1 to 3, more preferably 0 or 1, and further preferably 0. q is 2 or 3. In addition, when p and q are 2 or more, the bonding position on the aromatic ring is arbitrary, and for example, in the naphthalene ring of the chemical formula (6-5) or the heterocycle of the chemical formula (6-15), the bonding position is on any ring. It may be substituted, and in the chemical formula (6-7) or the like, it is shown that it may be substituted on any ring of the benzene ring present in one molecule, and the number of substituents in one molecule is p. And q.

Specific examples of the third aromatic compound and the like include benzenedicarboxylic acids such as isophthalic acid, terephthalic acid, 5-allylisophthalic acid, and 2-allylterephthalic acid; trimellitic acid and 5-allyltrimellitic acid. Such as benzenetricarboxylic acid; naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, 3-allylnaphthalene-1,4 -Naphthalenedicarboxylic acid such as dicarboxylic acid and 3,7-diallylnaphthalene-1,4-dicarboxylic acid; pyridinetricarboxylic acid such as 2,4,5-pyridinetricarboxylic acid; 1,3,5-triazine-2,4 Triazinecarboxylic acids such as 6-tricarboxylic acid; acid halides and esterified products of these. Of these, benzenedicarboxylic acid and benzenetricarboxylic acid are preferable, and isophthalic acid, terephthalic acid, isophthalic acid chloride, terephthalic acid chloride, 1,3,5-benzenetricarboxylic acid, 1,3,5-benzenetricarbonyl are preferred. Trichloride is more preferable, and isophthalic acid chloride, terephthalic acid chloride, and 1,3,5-benzenetricarbonyltrichloride are more preferable.

Among the above, a third aromatic compound whose aromatic ring is a monocyclic aromatic ring, a third aromatic compound whose aromatic ring is a condensed aromatic ring, and the like are preferable, and benzenedicarboxylic acid , Benzenetricarboxylic acid, naphthalenedicarboxylic acid, acid halides thereof are preferable, benzenedicarboxylic acid, naphthalenedicarboxylic acid, acid halides thereof are more preferable, isophthalic acid, terephthalic acid, naphthalene-1, 5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, and acid halides thereof are more preferable.

The above-mentioned third aromatic compound and the like can be used alone or in combination of two or more kinds.

The fourth aromatic compound, an acid halide thereof, and/or an ester compound thereof is an aromatic compound having one carboxyl group or a derivative thereof, specifically, an acid halide or an ester compound (the present specification). In the description, the fourth aromatic compound, its acid halide, and/or its esterified product may be collectively referred to as "fourth aromatic compound and the like".). Since the fourth aromatic compound or the like has one carboxyl group or the like, it has a function of stopping the esterification reaction.

Examples of the fourth aromatic compound and the like include compounds having one carboxyl group or the like in a substituted or substituted fourth aromatic ring having 3 to 30 carbon atoms.

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

Examples of the fourth aromatic ring having 3 to 30 carbon atoms include a monocyclic aromatic ring, a condensed aromatic ring, a ring-assembled aromatic ring, and an aromatic ring linked by alkylene. Examples of the monocyclic aromatic ring, the condensed aromatic ring, the ring-collecting aromatic ring, and the aromatic ring linked by alkylene include the above-mentioned first aromatic ring, second aromatic ring, and third aromatic ring. The same as the aromatic ring of.

The fourth aromatic ring having 3 to 30 carbon atoms related to the fourth aromatic compound or the like may have a substituent. At this time, as the “substituent of the fourth aromatic ring”, the same as the above-mentioned “substituent of the first aromatic ring” can be mentioned.

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

In the above chemical formulas (7-1) to (7-15), R ¹ is a polymerizable unsaturated bond-containing substituent. At this time, the polymerizable unsaturated bond-containing substituent is the same as described above. R ² is a hydroxyl group, a halogen atom, an alkyloxy group or an aryloxy group. Further, p is 0 or an integer of 1 or more, preferably 0 or 1 to 3, more preferably 0 or 1, and further preferably 0. q is 1. The position of the substituent on the aromatic ring in the above chemical formula is arbitrary, and for example, in the naphthalene ring of the chemical formula (7-5) or the heterocycle of the chemical formula (7-15), the substituent may be substituted on any ring. In the chemical formula (7-7) and the like, it may be substituted on any ring of the benzene ring present in one molecule, and the number of substituents in one molecule is p and q. Is shown.

More specific examples of the fourth aromatic compound and the like include benzoic acid, benzyl chloride, naphthalenecarboxylic acid, naphthalenecarbonyl chloride and the like.

[Structure of Polymerizable Unsaturated Bond-Containing Aromatic Ester Compound (A)]
At least one of the aromatic compound having a phenolic hydroxyl group and the aromatic compound having a carboxyl group has a polymerizable unsaturated bond-containing substituent having 2 to 30 carbon atoms. That is, both the aromatic compound having a phenolic hydroxyl group, and the aromatic compound having a carboxyl group may have a polymerizable unsaturated bond-containing substituent, or an aromatic compound having a phenolic hydroxyl group. Only the group compound may have a polymerizable unsaturated bond-containing substituent, or only the aromatic compound having a carboxyl group and the like may have a polymerizable unsaturated bond-containing substituent. When an aromatic compound having two or more kinds of phenolic hydroxyl groups and an aromatic compound having two or more kinds of carboxyl groups are used, only a part thereof has a polymerizable unsaturated bond-containing substituent. May be.

In one embodiment, it is preferred that at least the second aromatic compound has a polymerizable unsaturated bond-containing substituent. As described above, the structure derived from the second aromatic compound is located at the molecular end of the polymerizable unsaturated bond-containing aromatic ester compound (A). As a result, the polymerizable unsaturated bond-containing substituent contained in the second aromatic compound is also arranged at the molecular end of the aromatic ester compound (A). In this case, the obtained acid group-containing (meth)acrylate resin composition has high photosensitivity and is capable of forming a cured product having excellent heat resistance and dielectric properties, which is preferable.

As described above, the polymerizable unsaturated bond-containing aromatic ester compound (A) is a reaction product of a compound having a phenolic hydroxyl group, an aromatic compound having a carboxyl group, and the like, and the first to fourth Although it may contain various compounds such as the aromatic compound of 1), since it has a function of stopping the reaction of esterification, one or both of the second aromatic compound and the fourth aromatic compound are essential. Contained as. The constitution of the polymerizable unsaturated bond-containing aromatic ester compound (A) can be controlled by appropriately changing the amounts of the first to fourth aromatic compounds and the like used and the reaction conditions.

In one embodiment, the polymerizable unsaturated bond-containing aromatic ester compound (A) is, for example, a polymerizable unsaturated bond which is a reaction product of the first aromatic compound and the fourth aromatic compound. Aromatic ester compound containing; Aromatic ester compound containing a polymerizable unsaturated bond, which is a reaction product of the first aromatic compound, the second aromatic compound, the third aromatic compound and the like; Polymerizable unsaturated bond-containing aromatic ester compound which is a reaction product of an aromatic compound, a third aromatic compound, a fourth aromatic compound and the like; a first aromatic compound and a second aroma. Polymerizable unsaturated bond-containing aromatic ester compound which is a reaction product of a group compound, a third aromatic compound and the like and a fourth aromatic compound and the like; a second aromatic compound and a third aromatic An aromatic compound that is a reaction product of a group compound; a polymerizable unsaturated bond-containing aromatic compound that is a reaction product of a second aromatic compound and a fourth aromatic compound, and the like.

In addition, as a general rule, the polymerizable unsaturated bond-containing aromatic ester compound (A) according to the present embodiment does not have a hydroxyl group in the molecule of the obtained resin. However, a compound having a hydroxyl group may be contained as a by-product of the reaction product as long as the effect of the present invention is not impaired.

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

In the above chemical formula (8), Ar ¹ is a structure derived from the first aromatic compound, Ar ² is a structure derived from the second aromatic compound, and Ar ³ is derived from the third aromatic compound. It is a structure that does. Moreover, n is an integer of 0-10. When the polymerizable unsaturated bond-containing aromatic ester compound (A) is an oligomer or a polymer, n represents its average value.

That is, in the above chemical formula (8), Ar ¹ is each independently a substituted or unsubstituted first aromatic ring having 3 to 30 carbon atoms in which two or more hydrogen atoms are removed, or Examples thereof include those having two or more hydrogen atoms removed from one having a structure in which one aromatic ring is linked by a linking group.

Further, in the above chemical formula (8), each Ar ² independently includes a substituted or unsubstituted second aromatic ring having 3 to 30 carbon atoms with one hydrogen atom removed.

In the above chemical formula (8), Ar ³ includes a substituted or unsubstituted third aromatic ring having 3 to 30 carbon atoms in which two or more hydrogen atoms are removed.

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

At this time, when the first aromatic compound has three or more phenolic hydroxyl groups, Ar ¹ may have a further branched structure.

In addition, when the third aromatic compound has three or more carboxyl groups, Ar ³ may have a branched structure.

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

In the chemical formula (9), Ar ¹ has a structure derived from the first aromatic compound, Ar ² has a structure derived from the second aromatic compound, and Ar ³ has a structure derived from the third aromatic compound. Ar ⁴ is a structure derived from the fourth aromatic compound. Moreover, n is an integer of 0-10. When the polymerizable unsaturated bond-containing aromatic ester compound (A) is an oligomer or a polymer, n represents its average value.

That is, in the chemical formula (9), Ar ¹ is each independently a substituted or unsubstituted first aromatic ring having 3 to 30 carbon atoms in which two or more hydrogen atoms are removed, or Examples thereof include those having two or more hydrogen atoms removed from one having a structure in which one aromatic ring is linked by a linking group.

Further, in the above chemical formula (9), Ar ² independently includes a substituted or unsubstituted second aromatic ring having 3 to 30 carbon atoms in which one hydrogen atom is removed.

In the chemical formula (9), Ar ³ may be a substituted or unsubstituted third aromatic ring having 3 to 30 carbon atoms in which two or more hydrogen atoms are removed.

In the above chemical formula (9), Ar ⁴ may be a substituted or unsubstituted fourth aromatic ring having 3 to 30 carbon atoms in which one hydrogen atom is removed.

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

At this time, when the first aromatic compound has three or more phenolic hydroxyl groups, Ar ¹ may have a further branched structure.

When the third aromatic compound or the like has three or more carboxyl groups and the like, Ar ³ may have a further branched structure.

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

In the above chemical formula (10), Ar ¹ is a structure derived from the first aromatic compound, Ar ³ is a structure derived from the third aromatic compound, and Ar ⁴ is derived from the fourth aromatic compound. It is a structure that does. Moreover, n is an integer of 0-10. When the polymerizable unsaturated bond-containing aromatic ester compound (A) is an oligomer or a polymer, n represents its average value.

That is, in the chemical formula (10), Ar ¹ is independently a substituted or unsubstituted first aromatic ring having 3 to 30 carbon atoms in which two or more hydrogen atoms are removed, or Examples thereof include those having two or more hydrogen atoms removed from one having a structure in which one aromatic ring is linked by a linking group.

Further, in the above chemical formula (10), Ar ³ may be a substituted or unsubstituted third aromatic ring having 3 to 30 carbon atoms in which two or more hydrogen atoms are removed.

In the above chemical formula (10), Ar ⁴ may be a substituted or unsubstituted fourth aromatic ring having 3 to 30 carbon atoms with one hydrogen atom removed.

At least one of Ar ¹ , Ar ^3, and Ar ⁴ may have a polymerizable unsaturated bond-containing substituent having 2 to 30 carbon atoms.

At this time, when the first aromatic compound has three or more phenolic hydroxyl groups, Ar ¹ may have a further branched structure.

When the third aromatic compound or the like has three or more carboxyl groups and the like, Ar ³ may have a further branched structure.

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

In said chemical formula (11-1)-(11-10), s is an integer of 0-10, Preferably it is an integer of 0-5, r is an integer of 1-10. At this time, when the compounds represented by the chemical formulas (11-1) to (11-10) are oligomers or polymers, s and r mean their average values. The broken line in the chemical formula is a structure obtained by reacting Ar ³ and a compound corresponding to Ar ¹ and/or Ar ² .

The polymerizable unsaturated bond-containing aromatic ester compound (A) may be, for example, in one embodiment, a polymerizable unsaturated bond-containing aromatic ester compound (A-1) represented by the following chemical formula (a1) or And a polymerizable unsaturated bond-containing aromatic ester compound (A-2) represented by the following chemical formula (a2).

〔式中、Ａｒ^５は、それぞれ独立して、置換または非置換の芳香族環基であり、Ａｒ^６は、それぞれ独立して、置換または非置換の第２の芳香族環基であり、前記Ａｒ^５及び前記Ａｒ^６の少なくとも１つが重合性不飽和結合含有置換基を有するものである。ｎは、１〜３の整数である。〕

[In the formula, Ar ^5's each independently represent a substituted or unsubstituted aromatic ring group, and Ar ^6's each independently represent a substituted or unsubstituted second aromatic ring group; At least one of Ar ⁵ and Ar ⁶ has a polymerizable unsaturated bond-containing substituent. n is an integer of 1 to 3. ]

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

Ar ⁵ in the chemical formula (a1) is a substituted or unsubstituted first aromatic ring group. As will be described later, since n in the chemical formula (a1) is an integer of 1 to 3, 1 to 3 of the hydrogen atoms of the aromatic ring constituting the first aromatic ring group are “-C. (O)OAr ⁶ ”.

Examples of the first aromatic ring group include monocyclic aromatic compounds such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine and triazine. From which two or three hydrogen atoms have been removed; from condensed aromatic compounds such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine, etc. Aromatic compounds such as those with two or three hydrogen atoms removed, and those with two or three hydrogen atoms removed. Further, a combination of a plurality of these aromatic compounds may be used, and for example, a ring-assembled aromatic compound such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl. From which two or three hydrogen atoms have been removed; diphenylmethane, diphenylethane, 1,1-diphenylethane, 2,2-diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenyl Examples thereof include those obtained by removing two or three hydrogen atoms from an aromatic compound linked by an alkylene such as pyridylmethane, fluorene and diphenylcyclopentane. Among these, since an acid group-containing (meth)acrylate resin composition capable of forming a cured product having high photosensitivity and excellent heat resistance and dielectric properties is obtained, Ar ⁵ is a substituted or unsubstituted benzene. It is preferably a ring structure or a naphthalene ring structure, and more preferably a substituted or unsubstituted benzene ring structure.

The first aromatic ring group according to Ar ⁵ may have a substituent, and the substituent of the first aromatic ring group constitutes the first aromatic ring group. Is substituted with at least one hydrogen atom of the aromatic ring. Examples of the "substituent for the first aromatic ring group" include an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, a halogen atom and the like.

Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group. , Neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, cyclohexyl group and the like.

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

Examples of the alkyloxycarbonyl group include methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, isopropyloxycarbonyl group, butyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl. Examples thereof include an oxycarbonyl group and a tert-butyloxycarbonyl group.

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

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

In one embodiment of the present invention, Ar ⁵ may have a polymerizable unsaturated bond-containing substituent. Specific examples of the substituent containing a polymerizable unsaturated bond include an alkenyl group and an alkynyl group.

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

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

The polymerizable unsaturated bond-containing substituent may further have a substituent. The substituent is substituted with at least one hydrogen atom constituting the polymerizable unsaturated bond-containing substituent. Examples of the substituent include an alkyloxycarbonyl group, an alkylcarbonyloxy group, a halogen atom and the like. At this time, the alkyloxycarbonyl group, the alkylcarbonyloxy group, and the halogen atom include those mentioned above.

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

Examples of the preferable structure of Ar ⁵ include the following formulas (12-1) to (12-17).

In the above formulas (12-1) to (12-17), “*” indicates the position of bonding to “—C(O)OAr ⁶ ”. In addition, "-*" may be bonded to any position of the aromatic ring.

Of these, formulas (12-1) to (12-11) are preferable, and formulas (12-1), (12-2), (12-6), (12-7), and (12- 9) is more preferable, and formulas (12-1), (12-2), (12-6) and (12-7) are more preferable. Further, in view of high handling property and low viscosity of the polymerizable unsaturated bond-containing aromatic ester compound (A), formulas (12-1) and (12-2) are preferable, while the obtained acid is Since the group-containing (meth)acrylate resin composition has high photosensitivity and can form a cured product having excellent heat resistance and dielectric properties, it is represented by formulas (12-6) and (12-7). preferable.

In addition, at least one of the hydrogen atoms of the aromatic ring of the formulas (12-1) to (12-17) may be substituted with the polymerizable unsaturated bond-containing group.

Ar ⁶ in the chemical formula (a1) is a substituted or unsubstituted second aromatic ring group. As is clear from the description of the chemical formula (10), one of the hydrogen atoms of the aromatic ring constituting the second aromatic ring group is substituted with “—OC(O)Ar ⁵ ”. Become.

Examples of the second aromatic ring group include monocyclic aromatic compounds such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine and triazine. From which one hydrogen atom has been removed; a hydrogen atom from a condensed aromatic compound such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine, etc. Examples thereof include those obtained by removing one hydrogen atom from an aromatic compound obtained by removing one hydrogen atom. Further, a combination of a plurality of these aromatic compounds may be used, and for example, a ring-assembled aromatic compound such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl. From which one hydrogen atom has been removed; diphenylmethane, diphenylethane, 1,1-diphenylethane, 2,2-diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenylpyridylmethane, Examples thereof include those obtained by removing one hydrogen atom from an aromatic compound linked by alkylene such as fluorene and diphenylcyclopentane. Among these, Ar ⁶ is a substituted or unsubstituted benzene because it is possible to obtain an acid group-containing (meth)acrylate resin composition which has a high photosensitivity and can form a cured product having excellent heat resistance and dielectric properties. It is preferably a ring structure or a naphthalene ring structure.

The second aromatic ring group of Ar ⁶ may have a substituent, and the substituent of the second aromatic ring group constitutes the second aromatic ring group. Is substituted with at least one hydrogen atom of the aromatic ring. Examples of the "substituent of the second aromatic ring group" include an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, a halogen atom and the like. In this case, examples of the alkyl group, alkoxy group, alkyloxycarbonyl group, alkylcarbonyloxy group and halogen atom include those mentioned above.

In one embodiment of the present invention, Ar ⁶ may have a polymerizable unsaturated bond-containing substituent such as the above-mentioned alkenyl group or alkynyl group. The polymerizable unsaturated bond-containing substituent may be used alone or in combination of two or more kinds.

Preferred structures of Ar ⁶ include the following formulas (13-1) to (13-17).

In the above formulas (13-1) to (13-17), “*” represents a position bonded to “—OC(O)Ar ⁵ ”. In addition, "-*" may be bonded to any position of the aromatic ring.

Among these, the formulas (13-1) to (13-11) are preferable, the formulas (13-1), (13-6), and (13-9) are more preferable, and the formula (13 -1) and (13-6) are more preferable.

In addition, at least 1 of the hydrogen atom of the aromatic ring of Formula (13-1)-(13-17) may be substituted by the polymerizable unsaturated bond containing group.

According to one embodiment, Ar ⁵ is the above formula (12-1), (12-2), (12-6), (12-7), (12-9), and Ar ⁶ is the above formula (12). 13-1), (13-6) and (13-9) are more preferable, and Ar ⁵ is the above formula (12-1), (12-2), (12-6) or (12-7). It is more preferable that Ar ⁶ is the above formula (13-1) or (13-6), Ar ⁵ is the above formula (12-1), and Ar ⁶ is the above formula (13-1). , (13-6) are particularly preferable.

In the above chemical formulas (a1) and (a2), at least one of Ar ⁵ and Ar ⁶ has a polymerizable unsaturated bond-containing substituent. At this time, only Ar ⁵ may have a polymerizable unsaturated bond-containing substituent, only Ar ⁶ may have a polymerizable unsaturated bond-containing substituent, and Ar ⁵ and Ar ⁶ May each have a polymerizable unsaturated bond-containing substituent.

According to one embodiment, in the above formula (a1), preferably it has at least one of polymerizable unsaturated bond-containing substituent group of Ar ^6, that all of Ar ⁶ has a polymerizable unsaturated bond-containing substituent group Is more preferable, Ar ⁵ does not have a polymerizable unsaturated bond-containing substituent, and it is further preferable that all Ar ⁶ have a polymerizable unsaturated bond-containing substituent. When the polymerizable unsaturated bond-containing substituent is present in Ar ⁶ , an acid group-containing (meth)acrylate resin composition having high photosensitivity and capable of forming a cured product having an excellent balance between heat resistance and dielectric properties is obtained. It is preferable because it can be obtained.

According to an embodiment, in the above chemical formula (a2), at least one of preferably has a polymerizable unsaturated bond-containing substituent group, all Ar ⁵ is a polymerizable unsaturated bond-containing substituent group of Ar ⁵ It is more preferable that Ar ⁶ has no polymerizable unsaturated bond-containing substituent, and it is further preferable that all Ar ⁵ have a polymerizable unsaturated bond-containing substituent. When a polymerizable unsaturated bond-containing substituent is present in Ar ⁵ , an acid group-containing (meth)acrylate resin composition having high photosensitivity and capable of forming a cured product having an excellent balance between heat resistance and dielectric properties is obtained. It is preferable because it can be obtained.

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

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

〔式中Ｒ^１は、重合性不飽和結合含有置換基である。Ｒ^２は、それぞれ独立にアルキル基、アルコキシ基、アルキルオキシカルボニル基、アルキルカルボニルオキシ基、ハロゲン原子のいずれかである。ｈは１〜３の整数であり、ｉはそれぞれ独立に１以上の整数であり、ｊはそれぞれ独立に０または１以上の整数であり、ｉ＋ｊは５以下の整数である。ｋは１〜３の整数であり、ｌはそれぞれ独立に１以上の整数であり、ｍはそれぞれ独立に０または１以上の整数であり、ｌ＋ｍは７以下の整数である。ｉ、ｊ、ｌ、ｍが２以上の整数である場合、複数のＲ^１或いはＲ^２は互いに同一であってもよいし、異なっていてもよい。式（ａ１−２）においてＲ^１、Ｒ^２はナフタレン環上の何れの炭素原子上に置換していてもよい。〕

[In formula, R< ¹ > is a polymerizable unsaturated bond containing substituent. R ^2's are each independently an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, or a halogen atom. h is an integer of 1 to 3, i is an integer of 1 or more independently, j is 0 or an integer of 1 or more independently, and i+j is an integer of 5 or less. k is an integer of 1 to 3, l is an integer of 1 or more independently, m is an integer of 0 or 1 or more independently, and l+m is an integer of 7 or less. When i, j, l, and m are integers of 2 or more, a plurality of R ¹ or R ² may be the same as or different from each other. In formula (a1-2), R ¹ and R ² may be substituted on any carbon atom on the naphthalene ring. ]

In the formula (a1-1), particularly preferable examples of R ¹ include an allyl group, a propenyl group, an isopropenyl group, and a 1-propenyl group as described above. i is preferably 1 or 2, and more preferably 1.

In the formula (a1-2), particularly preferable examples of R ¹ include an allyl group, a propenyl group, an isopropenyl group, and a 1-propenyl group as described above. l is preferably 1 or 2, and more preferably 1.

Although the specific structure of the polymerizable unsaturated bond-containing aromatic ester compound (A-1) represented by the above chemical formula (a1) is not particularly limited, for example, the following chemical formulas (14-1) to (14) -47) and the like.

Among the above chemical formulas (14-1) to (14-44), the chemical formulas (14-1) to (14-39) are preferable, and the chemical formulas (14-1) to (14-3) and (14-10). )-(14-13), (14-18)-(14-39) are more preferable, and chemical formulas (14-1)-(14-3), (14-12), (14-13) are more preferable. , (14-19) to (14-21), (14-23) to (14-26), (14-29), (14-30), (14-32) to (14-39). Is more preferable, and it is the chemical formula (14-1), (14-2), (14-12), (14-13), (14-26), (14-32), or (14-37). Is particularly preferable.

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

Examples of the method for producing the polymerizable unsaturated bond-containing aromatic ester compound (A-1) include a method of reacting the second aromatic compound with the third aromatic compound.

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

Ar ⁵ in the chemical formula (a2) is a substituted or unsubstituted first aromatic ring group. As described later, since n in the chemical formula (a2) is an integer of 1 to 3, one of the hydrogen atoms of the aromatic ring constituting the first aromatic ring group is “—C(O)”. Will be replaced with OAr ⁶ ”.

Examples of Ar ⁵ in the chemical formula (a2) include the same ones as the “first aromatic ring group” in the above “Ar ⁶ in the chemical formula (10)”.

Ar ⁶ in the chemical formula (a2) is a substituted or unsubstituted second aromatic ring group. As is clear from the description of the chemical formula (11), one to three of the hydrogen atoms of the aromatic ring constituting the second aromatic ring group are substituted with “—OC(O)Ar ⁵ ”. The Rukoto.

Examples of Ar ⁶ in the chemical formula (a2) include the same ones as the “second aromatic ring group” in the above “Ar ⁶ in the chemical formula (a1)”.

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

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

〔式中Ｒ^１は、重合性不飽和結合含有置換基である。Ｒ^２は、それぞれ独立にアルキル基、アルコキシ基、アルキルオキシカルボニル基、アルキルカルボニルオキシ基、ハロゲン原子のいずれかである。ｈは１〜３の整数であり、ｉはそれぞれ独立に１以上の整数であり、ｊはそれぞれ独立に０または１以上の整数であり、ｉ＋ｊは５以下の整数である。ｉ、ｊが２以上の整数である場合、複数のＲ^１或いはＲ^２は互いに同一であってもよいし、異なっていてもよい。〕

[In formula, R< ¹ > is a polymerizable unsaturated bond containing substituent. R ^2's are each independently an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, or a halogen atom. h is an integer of 1 to 3, i is an integer of 1 or more independently, j is 0 or an integer of 1 or more independently, and i+j is an integer of 5 or less. When i and j are integers of 2 or more, a plurality of R ¹ or R ² may be the same as or different from each other. ]

In the formula (a2-1), particularly preferable examples of R ¹ include an allyl group, a propenyl group, an isopropenyl group, and a 1-propenyl group as described above. i is preferably 1 or 2, and more preferably 1.

In the formula (a2-2), particularly preferable examples of R ¹ include an allyl group, a propenyl group, an isopropenyl group, and a 1-propenyl group as described above. l is preferably 1 or 2, and more preferably 1.

Although the specific structure of the polymerizable unsaturated bond-containing aromatic ester compound (A-2) represented by the above chemical formula (a2) is not particularly limited, for example, the following chemical formulas (15-1) to (15) -3) and the like.

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

Examples of the method of producing the polymerizable unsaturated bond-containing aromatic ester compound (A-2) include a method of reacting the first aromatic compound with the fourth aromatic compound.

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

For example, the ratio of the number of moles of a carboxyl group of an aromatic compound having a carboxyl group to the number of moles of a hydroxyl group of an aromatic compound having a phenolic hydroxyl group (carboxyl group/hydroxyl group) has high photosensitivity and heat resistance. In addition, from the viewpoint of obtaining an acid group-containing (meth)acrylate resin composition capable of forming a cured product having excellent dielectric properties, 0.3 to 3 is preferable.

In addition, the reaction of the aromatic compound having a phenolic hydroxyl group and the aromatic compound having a carboxyl group in the production of the polymerizable unsaturated bond-containing aromatic ester compound (A) is not particularly limited in terms of reaction conditions. Any known method can be adopted as appropriate.

The pH during the reaction is not particularly limited, but is preferably 11 or higher. At this time, for adjusting the pH, acids such as hydrochloric acid, sulfuric acid, nitric acid and acetic acid; and bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonia can be used.

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

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

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

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

The acid group-containing (meth)acrylate resin (B) only needs to have an acid group and a (meth)acryloyl group, and other specific structures and molecular weights are not particularly limited, and various resins are used. You can

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

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

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

Examples of the epoxy resin (B-1) having an acid group and a (meth)acryloyl group include an epoxy resin (b1-1), an unsaturated monocarboxylic acid (b1-2), and a polycarboxylic acid anhydride ( b1-3) and those obtained as essential reaction raw materials.

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

Examples of the epoxy resin (b1-1) include bisphenol type epoxy resin, hydrogenated bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, hydrogenated biphenyl type epoxy resin, triphenyl. Methane type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-contracting novolac type epoxy resin, naphthol-cresol co-contracting novolac type epoxy resin, phenol Aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin Etc.

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

Examples of the esterified product of the unsaturated monocarboxylic acid (b1-2) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( (Meth)acrylic acid alkyl esters such as n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Compounds: Hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate and the like, hydroxyl group-containing (meth)acrylate compounds; dimethylaminoethyl (meth)acrylate, (meth)acrylic Nitrogen-containing (meth)acrylic acid ester compounds such as diethylaminoethyl acid ester; glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, morpholyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylic acid Other (meth)acrylic acid ester compounds such as cyclohexyl may be mentioned.

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

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

As the polycarboxylic acid anhydride (b1-3), any acid anhydride of a compound having two or more carboxyl groups in one molecule can be used. The polycarboxylic acid anhydride, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, Glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane- 2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydro Naphthalene-1,2-dicarboxylic acid, phthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid Acid anhydrides of dicarboxylic acid compounds such as

The method for producing the epoxy resin (B-1) having the acid group and the (meth)acryloyl group includes the epoxy resin (b1-1), the unsaturated monocarboxylic acid (b1-2), and the polycarboxylic acid anhydride. The compound (b1-3) is not particularly limited as long as it is an essential reaction raw material, and may be produced by any method. For example, it may be produced by a method of reacting all the reaction raw materials at once, or may be produced by a method of sequentially reacting the reaction raw materials. Among them, the epoxy resin (b1-1) is first reacted with the unsaturated monocarboxylic acid (b1-2) because the reaction can be easily controlled, and then the polycarboxylic acid anhydride (b1-3) is used. Is preferred. In the reaction, for example, after the epoxy resin (b1-1) and the unsaturated monocarboxylic acid (b1-2) are reacted in the temperature range of 100 to 150° C. in the presence of the esterification reaction catalyst, the reaction is carried out in the reaction system. Can be carried out by a method of adding the polycarboxylic acid anhydride (b1-3) to the above and reacting in the temperature range of 80 to 120°C.

The reaction ratio between the epoxy resin (b1-1) and the unsaturated monocarboxylic acid (b1-2) is 1 mol of the epoxy group in the epoxy resin (b1-1) based on the unsaturated monocarboxylic acid (b1-2). ) Is preferably used in the range of 0.9 to 1.1 mol. The reaction ratio of the polycarboxylic acid anhydride (b1-3) is preferably within the range of 0.2 to 1.0 mol with respect to 1 mol of the epoxy group in the epoxy resin (b1-1).

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

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

The reaction of the epoxy resin (b1-1), the unsaturated monocarboxylic acid (b1-2), and the polycarboxylic acid anhydride (b1-3) can be carried out in an organic solvent, if necessary.

Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; toluene, xylene and solvent. Aromatic solvents such as naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether; alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether And glycol ether solvents such as dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and the like. These organic solvents can be used alone or in combination of two or more kinds. The amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials because the reaction efficiency is good.

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

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

Examples of the acrylamide resin (B-2) having an acid group and a (meth)acryloyl group include a phenolic hydroxyl group-containing resin (b2-1) and a cyclic carbonate compound (b2-2a) or a cyclic ether compound (b2-). 2b), unsaturated monocarboxylic acid (b2-3a) and/or N-alkoxyalkyl (meth)acrylamide compound (b2-3b), and polycarboxylic acid anhydride (b2-4) as essential reaction raw materials. The obtained products and the like can be mentioned.

The phenolic hydroxyl group-containing resin (b2-1) refers to a resin having two or more phenolic hydroxyl groups in the molecule, for example, an aromatic polyhydroxy compound or a compound having one phenolic hydroxyl group in the molecule. A novolac type phenolic resin containing one or more kinds of reaction raw materials, a compound having one of the phenolic hydroxyl groups and a compound represented by any of the following structural formulas (x-1) to (x-5) ( and a reaction product containing x) as an essential reaction raw material.

（式中ｈは、０または１である。Ｒ^１は、それぞれ独立に脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アリールオキシ基、アラルキル基の何れかであり、ｉは、０または１〜４の整数である。Ｚは、ビニル基、ハロメチル基、ヒドロキシメチル基、アルキルオキシメチル基の何れかである。Ｙは、炭素原子数１〜４のアルキレン基、酸素原子、硫黄原子、カルボニル基の何れかである。ｊは１〜４の整数である。）

(In the formula, h is 0 or 1. R ¹ is each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group or an aralkyl group, and i is 0. Or an integer of 1 to 4. Z is any of a vinyl group, a halomethyl group, a hydroxymethyl group, and an alkyloxymethyl group, and Y is an alkylene group having 1 to 4 carbon atoms, an oxygen atom, and a sulfur atom. , Or a carbonyl group, and j is an integer of 1 to 4.)

Examples of the aromatic polyhydroxy compound include dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxyanthracene, trihydroxyanthracene, tetrahydroxyanthracene, biphenol, tetrahydroxybiphenyl, In addition to bisphenol and the like, compounds having one or more substituents on these aromatic nuclei and the like can be mentioned. As the substituent on the aromatic nucleus, for example, methyl group, ethyl group, vinyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, etc. Aliphatic hydrocarbon group; alkoxy group such as methoxy group, ethoxy group, propyloxy group, butoxy group; halogen atom such as fluorine atom, chlorine atom, bromine atom; phenyl group, naphthyl group, anthryl group, and aromatic nucleus thereof The above-mentioned aliphatic hydrocarbon group, the above-mentioned alkoxy group, an aryl group substituted with the above-mentioned halogen atom; a phenyloxy group, a naphthyloxy group, and the aliphatic hydrocarbon group above the aromatic nucleus, the above-mentioned alkoxy group, the above An aryloxy group substituted with a halogen atom or the like; a phenylmethyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, and the aromatic hydrocarbon group thereof, which is substituted with the aliphatic hydrocarbon group, the alkoxy group, the halogen atom or the like. And aralkyl groups. These aromatic polyhydroxy compounds can be used alone or in combination of two or more kinds. Among these, a halogen-free compound is preferable because an acid group-containing (meth)acrylate resin having high insulation reliability can be obtained.

Examples of the novolac type phenolic resin include those obtained by reacting one or more compounds having one phenolic hydroxyl group in the molecule with an aldehyde compound under an acidic catalyst.

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

Examples of the aldehyde compound include formaldehyde; alkyl aldehydes such as acetaldehyde, propyl aldehyde, butyraldehyde, isobutyraldehyde, pentyl aldehyde, and hexyl aldehyde; salicyl aldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2-hydroxy-4. -Hydroxybenzaldehydes such as methylbenzaldehyde, 2,4-dihydroxybenzaldehyde and 3,4-dihydroxybenzaldehyde; 2-hydroxy-3-methoxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, 3 Benzaldehyde having both a hydroxy group and an alkoxy group such as ethoxy-4-hydroxybenzaldehyde and 4-hydroxy-3,5-dimethoxybenzaldehyde; alkoxybenzaldehyde such as methoxybenzaldehyde and ethoxybenzaldehyde; 1-hydroxy-2-naphthaldehyde, Examples thereof include hydroxynaphthaldehyde such as 2-hydroxy-1-naphthaldehyde and 6-hydroxy-2-naphthaldehyde; halogenated benzaldehyde such as brombenzaldehyde.

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

Examples of the reaction product using the compound having one phenolic hydroxyl group and the compound (x) as essential reaction raw materials include, for example, a compound having one phenolic hydroxyl group in the molecule and the compound (x). Can be obtained by heating and stirring under a temperature condition of about 80 to 200° C. under an acidic catalyst. The reaction ratio between the compound having one phenolic hydroxyl group in the molecule and the compound (x) is 0 for the compound having one phenolic hydroxyl group in the molecule with respect to 1 mol of the compound (x). The ratio is preferably 0.5 to 5 mol.

The acidic catalyst is the same as described above.

Examples of the cyclic carbonate compound (b2-2a) include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. These cyclic carbonate compounds can be used alone or in combination of two or more kinds. Further, among these, since it is possible to obtain an acid group-containing (meth)acrylate resin composition having high photosensitivity and capable of forming a cured product having excellent heat resistance and dielectric properties, ethylene carbonate or propylene carbonate is preferable.

Examples of the cyclic ether compound (b2-2b) include ethylene oxide, propylene oxide and tetrahydrofuran. These cyclic ether compounds may be used alone or in combination of two or more kinds. In addition, among these, since an acid group-containing (meth)acrylate resin composition having high photosensitivity and capable of forming a cured product having excellent heat resistance and dielectric properties is obtained, ethylene oxide or propylene oxide is preferable.

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

Examples of the N-alkoxyalkyl(meth)acrylamide compound (b2-3b) include N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-methoxy. Examples thereof include ethyl (meth)acrylamide, N-ethoxyethyl (meth)acrylamide, N-butoxyethyl (meth)acrylamide and the like. Among these, N-methoxymethyl (meth)acrylamide is preferable because it provides an acid group-containing (meth)acrylate resin composition having high photosensitivity and capable of forming a cured product having excellent heat resistance. Moreover, these N-alkoxyalkyl (meth)acrylamide compounds can be used individually or in combination of 2 or more types.

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

When the N-alkoxyalkyl (meth)acrylamide compound (b2-3b) is used, the equivalent ratio [(b2-3b)/(b2-4))] with the polycarboxylic acid anhydride (b2-4)) is The range of 0.2 to 7 is preferable, since an acid group-containing (meth)acrylate resin composition having high photosensitivity and capable of forming a cured product having excellent heat resistance and dielectric properties can be obtained. The range of 25 to 6.7 is more preferable.

The method for producing the acrylamide resin (B-2) having an acid group and a (meth)acryloyl group is not particularly limited, and any method may be used. For example, it may be produced by a method of reacting all the reaction raw materials at once, or may be produced by a method of sequentially reacting the reaction raw materials. Among them, since the reaction is easily controlled, the phenolic hydroxyl group-containing resin (b2-1) is first reacted with the cyclic carbonate compound (b2-2a) or the cyclic ether compound (b2-2b), Then, a method of reacting the unsaturated monocarboxylic acid (b2-3a) and/or the N-alkoxyalkyl (meth)acrylamide compound (b2-3b) and then reacting the polycarboxylic acid anhydride (b2-4) is used. preferable. In the reaction, for example, the phenolic hydroxyl group-containing resin (b2-1) and the cyclic carbonate compound (b2-2a) or the cyclic ether compound (b2-2b) are added in the presence of a basic catalyst at 100 to 200. After reacting in the temperature range of ℃, in the presence of an acidic catalyst, unsaturated monocarboxylic acid (b2-3a) and / or N-alkoxyalkyl (meth)acrylamide compound (b2-3b) at a temperature of 80 ~ 140 ℃. The reaction can be carried out in the range, then the polycarboxylic acid anhydride (b2-4) is added, and the reaction is carried out in the temperature range of 80 to 140°C.

Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[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-( Amine compounds such as 2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and tetramethylammonium hydroxide; four such as trioctylmethylammonium chloride and trioctylmethylammonium acetate. Primary ammonium salts; phosphines such as trimethylphosphine, tributylphosphine and triphenylphosphine; tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxypropyl)phosphonium Phosphonium salts such as chloride, triphenylphosphonium chloride, benzylphosphonium chloride; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, Organotin compounds such as 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; Organometallic compounds such as zinc octylate and bismuth octylate; Inorganic tin compounds such as tin octoate; Inorganic metal compounds And so on. These basic catalysts can be used alone or in combination of two or more kinds.

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

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

As the organic solvent, the same organic solvents as described above can be used, and the organic solvent can be used alone or in combination of two or more kinds.

The amount of the organic solvent used is preferably in the range of 10 to 500 parts by mass with respect to 100 parts by mass of the total amount of the reaction raw materials, because the reaction efficiency becomes good.

The specific structure of the acrylamide resin (B-2) having an acid group and a (meth)acryloyl group is not particularly limited, and the phenolic hydroxyl group-containing resin (b2-1) and the cyclic carbonate compound (b2-2a) or cyclic An ether compound (b2-2b), an unsaturated monocarboxylic acid (b2-3a) and/or an N-alkoxyalkyl (meth)acrylamide compound (b2-3b), and a polycarboxylic acid anhydride (b2-4). As an essential reaction raw material, a resin having an acid group and a (meth)acryloyl group may be used, and the obtained acrylamide resin (B-2) having an acid group and a (meth)acryloyl group is, for example, A resin having a resin structure in which the structural moiety (I) represented by the following structural formula (a-1) and the structural moiety (II) represented by the following structural formula (a-2) are repeating structural units, Examples thereof include those having a resin structure in which the structural moiety (III) represented by the following structural formula (a-3) and the structural moiety (IV) represented by the following structural formula (a-4) are repeating structural units. ..

［式中Ｒ^２は、それぞれ独立に水素原子または炭素原子数１〜４の炭化水素基である。Ｒ^３は、それぞれ独立に水素原子、炭素原子数１〜４の炭化水素基、炭素原子数１〜４のアルコキシ基、ハロゲン原子の何れかであり、ｎは、それぞれ独立に１または２である。Ｒ^４は、それぞれ独立にメチレン基または下記構造式（ｘ’−１）〜（ｘ’−５）の何れかで表される構造部位である。Ｒ^５、Ｒ^６は、それぞれ独立に水素原子または炭素原子数１〜２０の炭化水素基である。また、Ｒ^５とＲ^６とが、連結して飽和または不飽和の環を形成してもよい。Ｒ^７は、炭素原子数１〜１２の炭化水素基である。Ｒ^８は、水素原子またはメチル基である。ｘは、前記Ｒ^３で表される構造部位、或いは、構造式（ａ−１）で表される構造部位（Ｉ）または構造式（ａ−２）で表される構造部位（ＩＩ）とが、＊印が付されたＲ^４を介して連結する結合点である。］

[In formula, R< ² > is a hydrogen atom or a C1-C4 hydrocarbon group each independently. R ³ is independently a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and n is 1 or 2 each independently. .. R ⁴ is a methylene group or a structural moiety independently represented by any of the following structural formulas (x′-1) to (x′-5). R ⁵ and R ⁶ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ⁵ and R ⁶ may combine to form a saturated or unsaturated ring. R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms. R ⁸ is a hydrogen atom or a methyl group. x represents the structural moiety represented by R ³ or the structural moiety (I) represented by the structural formula (a-1) or the structural moiety (II) represented by the structural formula (a-2). , * Is the point of attachment that connects via R ⁴ marked. ]

［式中Ｒ^２は、それぞれ独立に水素原子または炭素原子数１〜４の炭化水素基である。Ｒ^３は、それぞれ独立に水素原子、炭素原子数１〜４の炭化水素基、炭素原子数１〜４のアルコキシ基、ハロゲン原子の何れかであり、ｎは、それぞれ独立に１または２である。Ｒ^４は、それぞれ独立にメチレン基または下記構造式（ｘ’−１）〜（ｘ’−５）の何れかで表される構造部位である。Ｒ^５、Ｒ^６は、それぞれ独立に水素原子または炭素原子数１〜２０の炭化水素基である。また、Ｒ^５とＲ^６とが、連結して飽和または不飽和の環を形成してもよい。Ｒ^７は、炭素原子数１〜１２の炭化水素基である。Ｒ^８は、水素原子またはメチル基である。ｘは、前記Ｒ^３で表される構造部位、或いは、構造式（ａ−３）で表される構造部位（ＩＩＩ）または構造式（ａ−４）で表される構造部位（ＩＶ）とが、＊印が付されたＲ^４を介して連結する結合点である。］

[In formula, R< ² > is a hydrogen atom or a C1-C4 hydrocarbon group each independently. R ³ is independently a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and n is 1 or 2 each independently. .. R ⁴ is a methylene group or a structural moiety independently represented by any of the following structural formulas (x′-1) to (x′-5). R ⁵ and R ⁶ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ⁵ and R ⁶ may combine to form a saturated or unsaturated ring. R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms. R ⁸ is a hydrogen atom or a methyl group. x is the structural moiety represented by R ³ or the structural moiety (III) represented by the structural formula (a-3) or the structural moiety (IV) represented by the structural formula (a-4). , * Is the point of attachment that connects via R ⁴ marked. ]

［式中ｈは、０または１である。Ｒ^９は、それぞれ独立して脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アラルキル基の何れかであり、ｉは、０または１〜４の整数である。Ｒ^１０は、水素原子またはメチル基である。Ｗは、下記構造式（ｗ−１）または（ｗ−２）である。Ｙは、炭素原子数１〜４のアルキレン基、酸素原子、硫黄原子、カルボニル基の何れかである。ｊは、１〜４の整数である。］

[In the formula, h is 0 or 1. R ⁹ is independently any one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group and an aralkyl group, and i is 0 or an integer of 1 to 4. R ¹⁰ is a hydrogen atom or a methyl group. W is the following structural formula (w-1) or (w-2). Y is any of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom and a carbonyl group. j is an integer of 1 to 4. ]

（式中Ｒ^１１は、それぞれ独立に水素原子または炭素原子数１〜４の炭化水素基である。Ｒ^１２、Ｒ^１３は、それぞれ独立に水素原子または炭素原子数１〜２０の炭化水素基である。また、Ｒ^１２とＲ^１３とが、連結して飽和または不飽和の環を形成してもよい。Ｒ^１４は、炭素原子数１〜１２の炭化水素基である。Ｒ^１５は、水素原子またはメチル基である。）

(In formula, R< ¹¹ > is a hydrogen atom or a C1-C4 hydrocarbon group each independently. R< ¹² >, R< ¹³ > is a hydrogen atom or a C1-C20 hydrocarbon group each independently. R ¹² and R ¹³ may combine to form a saturated or unsaturated ring, R ¹⁴ is a hydrocarbon group having 1 to 12 carbon atoms, and R ¹⁵ is hydrogen. Atom or methyl group.)

The acid value of the acrylamide resin (B-2) having an acid group and a (meth)acryloyl group has a high photosensitivity and contains an acid group (meth) capable of forming a cured product having excellent heat resistance and dielectric properties. Since the acrylate resin composition is obtained, the range of 30 to 150 mgKOH/g is preferable, and the range of 40 to 120 mgKOH/g is more preferable. In the present invention, the acid value of the acid group-containing (meth)acrylate resin is a value measured based on the neutralization titration method of JIS K 0070 (1992).

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

Examples of the amideimide resin (B-3) having an acid group and a (meth)acryloyl group include an amideimide resin (b3-1) having an acid group or an acid anhydride group and a hydroxyl group-containing (meth)acrylate compound (b3). -2) and those obtained as essential reaction raw materials can be mentioned.

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

The specific structure and manufacturing method of the amide imide resin (b3-1) are not particularly limited, and general amide imide resins and the like can be widely used. For example, those obtained by using a polyisocyanate compound and a polycarboxylic acid or an acid anhydride thereof as a reaction raw material may be mentioned.

Examples of the polyisocyanate compound include, butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and aliphatic diisocyanate compounds such as 2,4,4-trimethylhexamethylene diisocyanate; norbornane diisocyanate, isophorone diisocyanate, Alicyclic diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3 , 3'-dimethylbiphenyl, aromatic diisocyanate compounds such as o-tolidine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (i-1); modified isocyanurates thereof, biuret modified Body, modified allophanate, and the like. In addition, these polyisocyanate compounds can be used alone or in combination of two or more kinds.

［式中、Ｒ^１はそれぞれ独立に水素原子、炭素原子数１〜６の炭化水素基の何れかである。Ｒ^２はそれぞれ独立に炭素原子数１〜４のアルキル基、または構造式（ｉ−１）で表される構造部位と＊印が付されたメチレン基を介して連結する結合点の何れかである。ｌは０または１〜３の整数であり、ｍは１以上の整数である。］

[In the formula, each R ¹ is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ² is independently an alkyl group having 1 to 4 carbon atoms, or a bonding point connecting the structural site represented by the structural formula (i-1) and a methylene group marked with *. is there. l is 0 or an integer of 1 to 3, and m is an integer of 1 or more. ]

Further, as the polyisocyanate compound, since an acid group-containing (meth)acrylate resin composition having high solvent solubility is obtained, an alicyclic diisocyanate compound or a modified product thereof, an aliphatic diisocyanate compound or a modified product thereof is Preferred are alicyclic diisocyanates or isocyanurate modified products thereof, and aliphatic diisocyanates or isocyanurate modified products thereof.

Further, in the total mass of the polyisocyanate compound, the ratio of the total mass of the alicyclic diisocyanate compound or its modified product and the aliphatic diisocyanate compound or its modified product is preferably 70% by mass or more, and 90% by mass. % Or more is preferable.

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

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

Examples of the polycarboxylic acid or an acid anhydride thereof include an aliphatic polycarboxylic acid compound or an acid anhydride thereof, an alicyclic polycarboxylic acid compound or an acid anhydride thereof, an aromatic polycarboxylic acid compound or an acid anhydride thereof. Etc.

In the aliphatic polycarboxylic acid compound or the acid anhydride thereof, the aliphatic hydrocarbon group may be linear or branched, and may have an unsaturated bond in the structure.

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

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

Examples of the aromatic polycarboxylic acid compound or an acid anhydride thereof include phthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl. Examples thereof include tetracarboxylic acid and benzophenonetetracarboxylic acid.

Among these, since the acid group-containing (meth)acrylate resin composition having high photosensitivity and capable of forming a cured product having excellent heat resistance and dielectric properties is obtained, the alicyclic polycarboxylic acid compound or The acid anhydride, the aromatic polycarboxylic acid compound or the acid anhydride is preferable. Further, since the amide imide resin (b3-1) can be efficiently produced, it is preferable to use a tricarboxylic acid anhydride having both a carboxyl group and an acid anhydride group in the molecular structure, and cyclohexanetricarboxylic acid anhydride or It is particularly preferable to use trimellitic anhydride. Further, the ratio of the total amount of the alicyclic tricarboxylic acid anhydride and the aromatic tricarboxylic acid anhydride to the total mass of the polycarboxylic acid or its acid anhydride is preferably 70% by mass or more, and 90% by mass or more. Is more preferable.

When the amide-imide resin (b3-1) is one in which the polyisocyanate compound and the polycarboxylic acid or an acid anhydride thereof are used as reaction raw materials, other reaction raw materials depending on desired resin performance and the like. You may use together. In this case, since the effect of the present invention is sufficiently exhibited, the ratio of the total mass of the polyisocyanate compound and the polycarboxylic acid or its acid anhydride to the total mass of the reaction raw material of the amide imide resin (b3-1). Is preferably 90% by mass or more, and more preferably 95% by mass or more.

When the amide-imide resin (b3-1) is one in which a polyisocyanate compound and a polycarboxylic acid or an acid anhydride thereof are used as reaction raw materials, the method is not particularly limited and may be produced by any method. For example, it can be produced by a method similar to that of a general amide-imide resin. Specifically, 0.5 to 2.0 mol of polycarboxylic acid or an acid anhydride thereof is used with 1 mol of the isocyanate group of the polyisocyanate compound, and stirred and mixed under a temperature condition of about 120 to 180°C. And a method of reacting.

The reaction between the polyisocyanate compound and the polycarboxylic acid or its acid anhydride can be carried out in the presence of a basic catalyst, if necessary. Further, the reaction can be carried out in an organic solvent if necessary.

As the basic catalyst, the same basic catalysts as described above can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

As the organic solvent, the same organic solvents as described above can be used, and the organic solvent can be used alone or in combination of two or more kinds.

The amount of the organic solvent used is preferably in the range of 10 to 500 parts by mass with respect to 100 parts by mass of the total amount of the reaction raw materials, because the reaction efficiency becomes good.

As the hydroxyl group-containing (meth)acrylate compound (b3-2), other specific structures are not particularly limited as long as it is a compound having a hydroxyl group and a (meth)acryloyl group in the molecular structure, and various compounds are used. be able to. For example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate. Hydroxy(meth)acrylate compounds such as; and (poly)oxy such as (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene chains in the molecular structures of the various hydroxy(meth)acrylate compounds. Examples include modified (poly)oxyalkylene compounds having an alkylene chain introduced therein; modified lactones having a (poly)lactone structure introduced into the molecular structure of each of the various hydroxy(meth)acrylate compounds. Among these, since the acid group-containing (meth)acrylate resin composition having high photosensitivity and capable of forming a cured product having excellent heat resistance and dielectric properties is obtained, one having a molecular weight of 1,000 or less is preferable. preferable. When the hydroxyl group-containing (meth)acrylate compound (b3-2) is the oxyalkylene modified product or the lactone modified product, the weight average molecular weight (Mw) is preferably 1,000 or less. These hydroxyl group-containing (meth)acrylate compounds may be used alone or in combination of two or more kinds.

Moreover, as the amide imide resin (B-3) having an acid group and a (meth)acryloyl group, the amide imide resin (b3-1) and a hydroxyl group-containing (meth)acrylate compound (b3-2) are used, if necessary. Besides, a (meth)acryloyl group-containing epoxy compound (b3-3) can be used together as a reaction raw material. Moreover, as the amide imide resin (B-3) having an acid group and a (meth)acryloyl group, the amide imide resin (b3-1) and a hydroxyl group-containing (meth)acrylate compound (b3-2) are used, if necessary. Besides, the (meth)acryloyl group-containing epoxy compound (b3-3) and the polycarboxylic acid anhydride (b3-4) can be used together as a reaction raw material.

The (meth)acryloyl group-containing epoxy compound (b3-3) is not particularly limited as long as it has a (meth)acryloyl group and an epoxy group in its molecular structure, and other specific structures are not particularly limited. Can be used. For example, glycidyl group-containing (meth)acrylate monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, Examples thereof include mono(meth)acrylate compounds of diglycidyl ether compounds such as biphenol diglycidyl ether and bisphenol diglycidyl ether. Among these, since the acid group-containing (meth)acrylate resin composition having high photosensitivity and capable of forming a cured product excellent in heat resistance and dielectric properties is obtained, the glycidyl group-containing (meth)acrylate monomer is preferable. Further, its molecular weight is preferably 500 or less. Furthermore, the ratio of the glycidyl group-containing (meth)acrylate monomer in the total mass of the (meth)acryloyl group-containing epoxy compound (b3-3) is preferably 70% by mass or more, and 90% by mass or more. Is more preferable.

As the polycarboxylic acid anhydride (b3-4), those exemplified as the above-mentioned polycarboxylic acid anhydride (b1-3) can be used, and the polycarboxylic acid (b3-4) is used alone. It is also possible to use two or more types together.

The amide imide resin (B-3) having an acid group and a (meth)acryloyl group is an amide imide resin (b3-1) having an acid group or an acid anhydride group, and contains the hydroxyl group, depending on desired resin performance and the like. In addition to the (meth)acrylate compound (b3-2), the (meth)acryloyl group-containing epoxy compound (b3-3) and the polycarboxylic acid anhydride (b3-4), other reaction raw materials can be used in combination. In this case, the ratio of the total mass of the components (b3-1) to (b3-4) in the total mass of the reaction raw materials of the acid group-containing (meth)acrylate resin (B-3) may be 80% by mass or more. It is more preferably 90% by mass or more.

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

The reaction between the amide-imide resin (b3-1) and the hydroxyl group-containing (meth)acrylate compound (b3-2) is mainly carried out with the acid group and/or the acid anhydride group in the amide-imide resin (b3-1). It reacts with the hydroxyl group in the hydroxyl group-containing (meth)acrylate compound (b3-2). Since the hydroxyl group-containing (meth)acrylate compound (b3-2) is particularly excellent in reactivity with an acid anhydride group, the amide imide resin (b3-1) has an acid anhydride group as described above. Preferably. The content of the acid anhydride group in the amide imide resin (b3-1) is the difference between the above-mentioned two measured values of the acid value, that is, the acid value under the condition that the acid anhydride group is ring-opened. And the acid value under the condition that the acid anhydride group is not ring-opened.

When the amide imide resin (b3-1) has an acid group and an acid anhydride group, the reaction ratio of the amide imide resin (b3-1) and the hydroxyl group-containing (meth)acrylate compound (b3-2) is When the amide imide resin (b3-1) has an acid anhydride group, the hydroxyl group contained in the hydroxyl group-containing (meth)acrylate compound (b3-2) relative to 1 mole of the acid anhydride group contained in the amide imide resin (b3-1). It is preferable to use it in a range in which the number of moles of is from 0.9 to 1.1. Moreover, when the said amide imide resin (b3-1) has an acid group, of the hydroxyl group which the said hydroxyl group containing (meth)acrylate compound (b3-2) has with respect to 1 mol of acid groups which the said amide imide resin (b3-1) has. It is preferably used in a range where the number of moles is 0.01 to 1.0.

The reaction between the amide-imide resin (b3-1) and the hydroxyl group-containing (meth)acrylate compound (b3-2) may use a basic catalyst or an acidic catalyst, if necessary. Especially, when the said amide imide resin (b3-1) has an acid group and an acid anhydride group, and when the said amide imide resin (b3-1) has an acid anhydride group, it is preferable to use a basic catalyst. When the amide-imide resin (b3-1) has an acid group, it is preferable to use an acidic catalyst.

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

As the acidic catalyst, those exemplified as the above-mentioned acidic catalyst can be used, and the acidic catalyst can be used alone or in combination of two or more kinds.

The basic catalyst or the acidic catalyst is preferably added in an amount of 0.001 to 5 parts by mass with respect to 100 parts by mass as the total mass of the reaction raw materials.

The reaction between the amide imide resin (b3-1) and the hydroxyl group-containing (meth)acrylate compound (b3-2) is carried out by heating and stirring under a temperature condition of about 80 to 140°C in the presence of a suitable catalyst. It can be carried out.

The reaction may be carried out in an organic solvent as necessary, and the same organic solvent as the above-mentioned organic solvent can be used, and the organic solvent may be used alone or in combination of two or more kinds. It can also be used together. In the case where the amide imide resin (b3-1) is produced continuously, the reaction may be continued as it is in the organic solvent used in the production of the amide imide resin (b3-1).

The amide imide resin (B-3) having an acid group and a (meth)acryloyl group is used as a reaction raw material in addition to the amide imide resin (b3-1) and the hydroxyl group-containing (meth)acrylate compound (b3-2). When the (meth)acryloyl group-containing epoxy compound (b3-3) is used, the amide imide resin (b3-1), the hydroxyl group-containing (meth)acrylate compound (b3-2), and the (meth)acryloyl group-containing epoxy compound It may be produced by a method of reacting all the reaction raw materials including (b3-3) at once, or may be produced by a method of sequentially reacting the reaction raw materials. Among them, a product obtained by reacting the amide imide resin (b3-1) with the hydroxyl group-containing (meth)acrylate compound (b3-2) (hereinafter, referred to as “generation” because the reaction is easily controlled). It may be referred to as "product (1)".) is preferably produced by a method of reacting the (meth)acryloyl group-containing epoxy compound (b3-3).

The reaction between the product (1) and the (meth)acryloyl group-containing epoxy compound (b3-3) is mainly performed by the acid group in the product (1) and the (meth)acryloyl group-containing epoxy compound ( b3-3). The reaction ratio is such that the number of moles of the epoxy group contained in the (meth)acryloyl group-containing epoxy compound (b3-3) is 0.05 to 1.1 with respect to 1 mole of the acid group contained in the product (1). It is preferable to use it in the following range. The reaction can be carried out, for example, in the presence of a suitable basic catalyst with heating and stirring under temperature conditions of about 90 to 140°C. When the reaction is continuously performed with the amide-imide resin (b3-1) and the hydroxyl group-containing (meth)acrylate compound (b3-2), the basic catalyst may or may not be added. .. Further, the reaction may be carried out in an organic solvent if necessary. The basic catalyst and the organic solvent may be the same as the basic catalyst and the organic solvent, and they may be used alone or in combination of two or more kinds.

The amide imide resin (B-3) having an acid group and a (meth)acryloyl group is used as a reaction raw material in addition to the amide imide resin (b3-1) and the hydroxyl group-containing (meth)acrylate compound (b3-2). When using the (meth)acryloyl group-containing epoxy compound (b3-3) and the polycarboxylic acid anhydride (b3-4), the amide imide resin (b3-1) and the hydroxyl group-containing (meth)acrylate compound (b3-2). The reaction raw material containing the (meth)acryloyl group-containing epoxy compound (b3-3) and the polycarboxylic acid anhydride (b3-4) may be reacted in a batch, or the reaction raw material may be used. You may manufacture by the method of making it react sequentially. Among them, since the reaction can be easily controlled, the product (1) obtained by reacting the amide imide resin (b3-1) with the hydroxyl group-containing (meth)acrylate compound (b3-2), The product obtained by reacting the (meth)acryloyl group-containing epoxy compound (b3-3) (hereinafter, may be referred to as “product (2)”) with the polycarboxylic acid anhydride (b3). It is preferable to manufacture it by a method of reacting -4).

The reaction of the product (2) with the polycarboxylic acid anhydride (b3-4) is mainly to react the hydroxyl group in the product (2) with the polybasic acid anhydride. At this time, in the product (2), the reaction ratio between the product (1) and the (meth)acryloyl group-containing epoxy compound (b3-3) is 1 mol of acid groups contained in the product (1). The number of moles of epoxy groups contained in the (meth)acryloyl group-containing epoxy compound (b3-3) is preferably 0.1 to 1.2, and 0.2 to 1.1. More preferably. Here, in the product (2), for example, a hydroxyl group generated by ring opening of the epoxy group in the (meth)acryloyl group-containing epoxy compound (b3-3) is present. The reaction ratio of the polycarboxylic acid anhydride (b3-4) is adjusted so that the acid value of the amideimide resin (B-3) having an acid group and a (meth)acryloyl group produced is about 50 to 120 mgKOH/g. Preferably. The reaction can be carried out, for example, in the presence of a suitable basic catalyst with heating and stirring under a temperature condition of about 80 to 140°C. When the reaction is continuously performed with the product (1) and the (meth)acryloyl group-containing epoxy compound (b3-3), the basic catalyst may or may not be added. Further, the reaction may be carried out in an organic solvent if necessary. The basic catalyst and the organic solvent may be the same as the basic catalyst and the organic solvent, and they may be used alone or in combination of two or more kinds.

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

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

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

The acrylic resin intermediate may be a copolymer of the (meth)acrylate compound (α) and other polymerizable unsaturated group-containing compound, if necessary. Examples of the other polymerizable unsaturated group-containing compounds include (meth)acrylates such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, and 2-ethylhexyl(meth)acrylate. Acrylic acid alkyl ester; alicyclic structure-containing (meth)acrylate such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate; phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxy Examples thereof include aromatic ring-containing (meth)acrylates such as ethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. These may be used alone or in combination of two or more.

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

The polybasic acid anhydride is, for example, phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hexahydroanhydride. Examples thereof include phthalic acid, methylhexahydrophthalic anhydride, octenyl succinic anhydride, and tetrapropenyl succinic anhydride. These polybasic acid anhydrides can be used alone or in combination of two or more kinds.

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

As the organic solvent, the same organic solvents as described above can be used, and the organic solvent can be used alone or in combination of two or more kinds.

As the basic catalyst, the same basic catalysts as described above can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

The acid value of the acrylic resin (B-4) having an acid group and a (meth)acryloyl group has high photosensitivity and contains an acid group (meth) capable of forming a cured product having excellent heat resistance and dielectric properties. Since the acrylate resin composition is obtained, the range of 30 to 150 mgKOH/g is preferable, and the range of 40 to 120 mgKOH/g is more preferable. The acid value of the acrylic resin (B-4) having an acid group and a (meth)acryloyl group in the present invention is a value measured by the neutralization titration method of JIS K0070 (1992).

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

Examples of the urethane resin (B-5) having an acid group and a (meth)acryloyl group include a polyisocyanate compound, a hydroxyl group-containing (meth)acrylate compound, a carboxyl group-containing polyol compound, and, if necessary, a polybasic acid anhydride. , A product obtained by reacting a polyol compound other than the carboxyl group-containing polyol compound, a polyisocyanate compound, a hydroxyl group-containing (meth)acrylate compound, a polybasic acid anhydride, and a polyol other than the carboxyl group-containing polyol compound Those obtained by reacting with a compound, those obtained by reacting with an epoxy resin, an unsaturated monobasic acid, a polybasic acid anhydride, a polyisocyanate compound, and a hydroxyl group-containing (meth)acrylate compound, etc. Can be mentioned.

As the polyisocyanate compound, the same polyisocyanate compound as described above can be used, and the polyisocyanate compound can be used alone or in combination of two or more kinds.

As the hydroxyl group-containing (meth)acrylate compound, the same ones as the above-mentioned hydroxyl group-containing (meth)acrylate compound (b3-2) can be used, and the hydroxyl group-containing (meth)acrylate compound may be used alone. Two or more kinds can be used in combination.

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

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

Examples of the polyol compound other than the carboxyl group-containing polyol compound include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; Aromatic polyol compounds such as biphenols and bisphenols; (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains in the molecular structures of the various polyol compounds. Introduced (poly)oxyalkylene modified products; lactone modified products in which a (poly)lactone structure is introduced into the molecular structure of each of the various polyol compounds are included. The polyol compounds other than the carboxyl group-containing polyol compound may be used alone or in combination of two or more kinds.

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

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

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

As the organic solvent, the same organic solvents as described above can be used, and the organic solvent can be used alone or in combination of two or more kinds.

As the basic catalyst, the same basic catalysts as described above can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

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

The content of the polymerizable unsaturated bond-containing aromatic ester compound (A) in the acid group-containing (meth)acrylate resin composition of the present invention has high photosensitivity, and is excellent in heat resistance and dielectric properties. Since the acid group-containing (meth)acrylate resin composition capable of forming a product is obtained, the range of 10 to 90 mass% is preferable.

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

The mass ratio [(A)/(B)] of the solid content of the polymerizable unsaturated bond-containing aromatic ester compound (A) and the acid group-containing (meth)acrylate resin (B) has high photosensitivity. The range of 50/50 to 95/5 is preferable because an acid group-containing (meth)acrylate resin composition having a heat resistance and a dielectric property and capable of forming a cured product can be obtained.

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

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

Examples of commercial products of the other photopolymerization initiators include "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", and "Omnirad-379". , "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100", "Omnirad-2100". Omnirad-754", "Omnirad-784", "Omnirad-500", "Omnirad-81" (manufactured by IGM), "Kayacure-DETX", "Kayacure-MBP", "Kayacure-DMBI", "Kayacure-EPA". , "Kayacure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "Vicure-10", "Vicure-55" (manufactured by Stofa Chemical Co., Ltd.), "Trigonal P1" (manufactured by Akzo), "Sandray 1000" ( Sands), "Deep" (Apjon), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (Word Brenkinsop), "Runtecure-1104" (Runtec) Manufactured by the company) and the like.

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

The curable resin composition of the present invention may contain a resin component other than the acid group-containing (meth)acrylate resin (B). As the other resin component, for example, an epoxy resin such as a bisphenol type epoxy resin or a novolac type epoxy resin is reacted with (meth)acrylic acid, a dicarboxylic acid anhydride, or an unsaturated monocarboxylic acid anhydride, if necessary. Resins having a carboxyl group and a (meth)acryloyl group in the resin thus obtained, various (meth)acrylate monomers and the like can be mentioned.

Examples of the (meth)acrylate monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, and 2-ethylhexyl. Aliphatic mono(meth)acrylate compounds such as (meth)acrylate and octyl(meth)acrylate; alicyclic mono(meth)acrylate compounds such as cyclohexyl(meth)acrylate, isobornyl(meth)acrylate and adamantyl mono(meth)acrylate Heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl Aroma such as (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, benzylbenzyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate Mono(meth)acrylate compounds such as group mono(meth)acrylate compounds: (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene in the molecular structures of the various mono(meth)acrylate monomers. (Poly)oxyalkylene-modified mono(meth)acrylate compound in which a polyoxyalkylene chain such as a chain has been introduced; a lactone-modified mono(meth)in which a (poly)lactone structure is introduced into the molecular structure of each of the various mono(meth)acrylate compounds. ) Acrylate compounds; Aliphatic di(such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, etc. (Meth)acrylate compound; 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, tricyclodecane dimethanol di Alicyclic di(meth)acrylate compounds such as (meth)acrylate; biphenol di(meth)acrylate, bisphenol Aromatic di(meth)acrylate compounds such as di(meth)acrylate; (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene in the molecular structures of the various di(meth)acrylate compounds. A polyoxyalkylene-modified di(meth)acrylate compound having a (poly)oxyalkylene chain such as a chain introduced therein; a lactone-modified di(meth) having a (poly)lactone structure introduced into the molecular structure of each of the various di(meth)acrylate compounds ) Acrylate compound; Aliphatic tri(meth)acrylate compound such as trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate; (Poly)oxyethylene chain in the molecular structure of the aliphatic tri(meth)acrylate compound. A (poly)oxyalkylene-modified tri(meth)acrylate compound introduced with a (poly)oxyalkylene chain such as a (poly)oxypropylene chain or a (poly)oxytetramethylene chain; a molecule of the aliphatic tri(meth)acrylate compound Lactone-modified tri(meth)acrylate compounds having a (poly)lactone structure introduced therein; pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. An aliphatic poly(meth)acrylate compound of (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene chain or the like (poly) in the molecular structure of the aliphatic poly(meth)acrylate compound Tetra- or more-functional (poly)oxyalkylene-modified poly(meth)acrylate compound having an oxyalkylene chain introduced therein; tetra- or more-functional lactone having a (poly)lactone structure introduced into the molecular structure of the aliphatic poly(meth)acrylate compound Examples thereof include modified poly(meth)acrylate compounds. The various (meth)acrylate monomers may be used alone or in combination of two or more.

Further, the curable resin composition of the present invention, if necessary, a curing agent, a curing accelerator, an organic solvent, inorganic fine particles or polymer fine particles, a pigment, a defoaming agent, a viscosity modifier, a leveling agent, a flame retardant, It is also possible to contain various additives such as a storage stabilizer.

The curing agent is not particularly limited as long as it has a functional group capable of reacting with the carboxy group in the acid group-containing (meth)acrylate resin, and examples thereof include an epoxy resin. Examples of the epoxy resin include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, Bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-contracting novolac type epoxy resin, naphthol-cresol co-contracting novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition Examples thereof include reactive epoxy resins, biphenylaralkyl epoxy resins, fluorene epoxy resins, xanthene epoxy resins, dihydroxybenzene epoxy resins, trihydroxybenzene epoxy resins and the like. These epoxy resins can be used alone or in combination of two or more kinds. Further, among these, a curable resin composition having excellent alkali developability and high photosensitivity and capable of forming a cured product having excellent elongation can be obtained, and therefore, a phenol novolac type epoxy resin, cresol novolac Type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-contracted novolac type epoxy resin and the like are preferable, and the softening point is 20 to 120. Those in the range of °C are particularly preferred.

The curing accelerator is for promoting a curing reaction of the curing agent, and when an epoxy resin is used as the curing agent, a phosphorus compound, an amine compound, an imidazole, an organic acid metal salt, a Lewis acid, Examples thereof include amine complex salts. These curing accelerators can be used alone or in combination of two or more kinds. Further, the addition amount of the curing accelerator is preferably, for example, in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the curing agent.

As the organic solvent, the same organic solvents as described above can be used, and the organic solvent can be used alone or in combination of two or more kinds.

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

As a source of ultraviolet rays, ultraviolet lamps are generally used in terms of practicality and economy. Specific examples thereof include a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, and an LED.

Integrated light quantity of the active energy ray is not particularly limited, it is preferably from 10~5,000mJ / cm ^2, more preferably 50~1,000mJ / cm ^2. When the integrated light amount is within the above range, it is possible to prevent or suppress the generation of an uncured portion, which is preferable.

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

Further, the cured product obtained by curing the curable resin composition of the present invention is excellent in heat resistance and dielectric properties, and therefore, for example, in a semiconductor device application, a solder resist, an interlayer insulating material, a package material, an underfill. It can be preferably used as a package adhesive layer for materials and circuit elements, or as an adhesive layer for an integrated circuit element and a circuit board. Further, it can be suitably used as a thin film transistor protective film, a liquid crystal color filter protective film, a color filter pigment resist, a black matrix resist, a spacer and the like in thin display applications represented by LCD and OELD.

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

The resist member of the present invention is, for example, a photomask on which a desired pattern is formed after applying the solder resist resin material on a substrate and evaporating and drying an organic solvent in a temperature range of about 60 to 100°C. Through exposure with an active energy ray, the unexposed area is developed with an alkaline aqueous solution, and further heat-cured in a temperature range of about 140 to 180°C.

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

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

In the examples of the present application, the acid value of the acid group-containing (meth)acrylate resin was measured by the neutralization titration method of JIS K 0070 (1992).

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

Measuring device: Tosoh Corporation "HLC-8320 GPC"
Column: Tosoh Co., Ltd. guard column "HXL-L"
+ Tosoh Corporation “TSK-GEL G4000HXL”
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: "GPC workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation
Column temperature: 40°C
Developing solvent: Tetrahydrofuran Flow rate: 1.0 ml/min Standard: The following monodisperse polystyrene having a known molecular weight was used according to the measurement manual of "GPC-8320 GPC" Polystyrene used "A-500" manufactured by Tosoh Corporation. "
Tosoh Corporation "A-1000"
Tosoh Corporation "A-2500"
Tosoh Corporation "A-5000"
Tosoh Corporation "F-1"
Tosoh Corporation "F-2"
Tosoh Corporation "F-4"
Tosoh Corporation “F-10”
Tosoh Corporation "F-20"
Tosoh Corporation "F-40"
Tosoh Corporation “F-80”
Tosoh Corporation "F-128"
Sample: a tetrahydrofuran solution of 1.0% by mass in terms of resin solid content, filtered through a microfilter (50 μl).

(Synthesis Example 1: Synthesis of polymerizable unsaturated bond-containing aromatic ester compound (A-1))
A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer was charged with 268 parts by mass of orthoallylphenol (2.0 mol) and 1200 parts by mass of toluene, and the system was replaced with nitrogen under reduced pressure. Next, 203 parts by mass (1.0 mol) of isophthaloyl chloride was charged, and the pressure in the system was replaced with nitrogen under reduced pressure. Next, 0.6 part by mass of tetrabutylammonium bromide was added, and while performing a nitrogen gas purging process, the temperature inside the system was controlled to 60° C. or lower, and 412 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours, After completion of dropping, the mixture was stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by stationary separation. Water was further added to the obtained toluene layer, the mixture was stirred for 15 minutes, and the aqueous layer was removed by static separation. This operation was repeated until the pH of the aqueous layer reached 7. Then, by heating and drying under reduced pressure, a polymerizable unsaturated bond-containing aromatic ester compound (A-1) represented by the following chemical formula was obtained. The ester group equivalent of the polymerizable unsaturated bond-containing aromatic ester compound (A-1) was 199 g/equivalent. The ester group equivalent is a calculated value calculated from the charging ratio.

(Synthesis Example 2: Synthesis of polymerizable unsaturated bond-containing aromatic ester compound (A-2))
A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer was charged with 134 parts by mass (1.0 mol) of orthoallylphenol and 711 parts by mass of toluene, and the system was replaced with nitrogen under reduced pressure. Next, 140 parts by mass (1.0 mol) of benzyl chloride was charged, and the system was replaced with nitrogen under reduced pressure. Next, 0.4 part by mass of tetrabutylammonium bromide was added, while the system was controlled at 60° C. or lower while performing a nitrogen gas purging process, 205 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours, After completion of dropping, the mixture was stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by stationary separation. Water was further added to the obtained toluene layer, the mixture was stirred for 15 minutes, and the aqueous layer was removed by static separation. This operation was repeated until the pH of the aqueous layer reached 7. Then, an aromatic ester compound (A-2) represented by the following chemical formula was obtained by heating and drying under reduced pressure. The ester group equivalent of this aromatic ester compound (A-2) was 119 g/equivalent. The ester group equivalent is a calculated value calculated from the charging ratio.

(Synthesis Example 3: Synthesis of aromatic ester compound (A-3))
A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer was charged with 216 parts by mass (2.0 mol) of orthocresol and 1200 parts by mass of toluene, and the system was replaced with nitrogen under reduced pressure. Next, 203 parts by mass (1.0 mol) of isophthaloyl chloride was charged, and the pressure in the system was replaced with nitrogen under reduced pressure. Next, while adding 0.5 parts by mass of tetrabutylammonium bromide and performing a nitrogen gas purging process, controlling the system temperature to 60° C. or lower, and dropping 412 parts by mass of a 20% aqueous sodium hydroxide solution over 3 hours, After completion of dropping, the mixture was stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by stationary separation. Water was further added to the obtained toluene layer, the mixture was stirred for 15 minutes, and the aqueous layer was removed by static separation. This operation was repeated until the pH of the aqueous layer reached 7. Then, an aromatic ester compound (A-3) represented by the following chemical formula was obtained by heating and drying under reduced pressure. The ester group equivalent of this aromatic ester compound (A-3) was 173 g/equivalent. The ester group equivalent is a calculated value calculated from the charging ratio.

(Synthesis Example 4: Synthesis of acid group-containing (meth)acrylate resin (B-1))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 101 parts by mass of diethylene glycol monomethyl ether acetate, and orthocresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation, epoxy equivalent: 214) 428 After dissolving 4 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of methquinone as a thermal polymerization inhibitor, 144 parts by mass of acrylic acid and 1.6 parts by mass of triphenylphosphine were added, The esterification reaction was carried out at 120° C. for 10 hours while blowing air. Thereafter, 311 parts by mass of diethylene glycol monomethyl ether acetate and 160 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110° C. for 2.5 hours to give an acid group-containing (meth)acrylate resin having a solid content of 64.0% by mass (B- 1) was obtained. The acid value of the solid content of the acid group-containing (meth)acrylate resin (B-1) was 85 mgKOH/g, and the weight average molecular weight was 8850.

(Synthesis Example 5: Synthesis of acid group-containing (meth)acrylate resin (B-2))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 392 parts by mass of diethylene glycol monomethyl ether acetate, an isocyanurate modified product of isophorone diisocyanate (“VESTANAT T-1890/100” manufactured by EVONIK, isocyanate group content 17. 2% by mass) (hereinafter abbreviated as "T-1890") 244 parts by mass, trimellitic anhydride 192 parts by mass, and dibutylhydroxytoluene 1.0 part by mass were added and dissolved. The reaction was carried out at 160° C. for 5 hours in a nitrogen atmosphere, and it was confirmed that the isocyanate group content was 0.1% by mass or less. The acid value of the solid content measured under the condition where the acid anhydride group was not ring-opened was 160 mgKOH/g. 0.3 parts by weight of methquinone, pentaerythritol polyacrylate mixture ("Aronix M-306" manufactured by Toagosei Co., Ltd., pentaerythritol triacrylate content of about 67%, hydroxyl value of 159.7 mg KOH/g) (hereinafter, "M-306" 172 parts by mass and 3.6 parts by mass of triphenylphosphine were added and reacted at 110° C. for 5 hours while blowing air. Then, 163 parts by mass of glycidyl methacrylate was added and reacted at 110° C. for 5 hours. Further, 112 parts by mass of succinic anhydride and 122 parts by mass of diethylene glycol monomethyl ether acetate were added and reacted at 110° C. for 5 hours to obtain an acid group-containing (meth)acrylate resin (B-2) having a solid content of 62.1% by mass. Obtained. The acid value of the solid content of the acid group-containing (meth)acrylate resin (B-2) was 79 mgKOH/g, and the weight average molecular weight was 3,790.

(Example 1: Preparation of acid group-containing (meth)acrylate resin composition (1))
Polymerizable unsaturated bond-containing aromatic ester compound (A-1) obtained in Synthesis Example 1, acid group-containing (meth)acrylate resin (B-1) obtained in Synthesis Example 4, and orthocresol novolak as a curing agent. -Type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation), dipentaerythritol hexaacrylate, diethylene glycol monoethyl ether acetate, a photopolymerization initiator (“Omnirad 907” manufactured by IGM), and 2-ethyl- 4-Methylimidazole and phthalocyanine green were mixed in the amount shown in Table 1 and kneaded by a roll mill to obtain an acid group-containing (meth)acrylate resin composition (1).

(Examples 2 to 7: Preparation of acid group-containing (meth)acrylate resin compositions (2) to (7))
The acid group-containing (meth)acrylate resin compositions (2) to (7) were obtained in the same manner as in Example 1 with the compositions and formulations shown in Table 1.

(Comparative Example 1: Preparation of acid group-containing (meth)acrylate resin composition (C1))
Aromatic ester compound (A-3) obtained in Synthesis Example 3, acid group-containing (meth)acrylate resin (B-1) obtained in Synthesis Example 4, and orthocresol novolac type epoxy resin (DIC stock) as a curing agent. "EPICLON N-680" manufactured by the company), dipentaerythritol hexaacrylate, diethylene glycol monoethyl ether acetate, a photopolymerization initiator ("OMNIRAD 907" manufactured by IGM), and 2-ethyl-4-methylimidazole, Phthalocyanine green was blended in the amount shown in Table 1 and kneaded by a roll mill to obtain an acid group-containing (meth)acrylate resin composition (C1).

(Comparative Example 2: Preparation of acid group-containing (meth)acrylate resin composition (C2))
Comparative Example except that the acid group-containing (meth)acrylate resin (B-2) obtained in Synthesis Example 4 was used in place of the acid group-containing (meth)acrylate resin (B-1) used in Comparative Example 1. An acid group-containing (meth)acrylate resin composition (C2) was obtained in the same manner as in 1.

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

[Evaluation method of light sensitivity]
The acid group-containing (meth)acrylate resin composition obtained in each Example and Comparative Example was applied on a glass substrate using an applicator so as to have a film thickness of 50 μm, and dried at 80° C. for 30 minutes. Next, "Step Tablet No. 2" manufactured by Kodak Co. was placed on the dried coating film and irradiated with ultraviolet rays of 1000 mJ/cm ² using a metal halide lamp. This was developed with a 1% sodium carbonate aqueous solution at 30° C. for 180 seconds, and the number of remaining steps of the step tablet was evaluated based on the step tablet method. It should be noted that the larger the number of remaining stages, the higher the photosensitivity.

Acid group-containing (meth)acrylate resin compositions (1) to (7) prepared in Examples 1 to 7 and acid group-containing (meth)acrylate resin compositions (C1) and (prepared in Comparative Examples 1 and 2). Table 1 shows the composition of C2) and the evaluation results.

"-" in the evaluation of Comparative Example 2 in Table 1 indicates that the evaluation is not possible. This was not evaluated because the aromatic ester compound and the acid group-containing (meth)acrylate resin were not compatible with each other and became cloudy when mixed.

(Example 8: Preparation of acid group-containing (meth)acrylate resin composition (8))
Polymerizable unsaturated bond-containing aromatic ester compound (A-1) obtained in Synthesis Example 1, acid group-containing (meth)acrylate resin (B-1) obtained in Synthesis Example 4, and orthocresol novolak as a curing agent. Type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation), dimethylaminopyridine as a curing accelerator, a photopolymerization initiator (“Omnirad 907” manufactured by IGM), and diethylene glycol monomethyl ether acetate as an organic solvent. The components were mixed in the amount shown in Table 2 and kneaded with a roll mill to obtain an acid group-containing (meth)acrylate resin composition (8).

(Examples 9 to 14: Preparation of acid group-containing (meth)acrylate resin compositions (9) to (14))
Acid group-containing (meth)acrylate resin compositions (9) to (14) were obtained in the same manner as in Example 8 with the compositions and formulations shown in Table 2.

(Comparative Example 3: Preparation of acid group-containing (meth)acrylate resin composition (C3))
Aromatic ester compound (A-3) obtained in Synthesis Example 3, acid group-containing (meth)acrylate resin (B-1) obtained in Synthesis Example 4, and orthocresol novolac type epoxy resin (DIC stock) as a curing agent. In a mass part shown in Table 2, "EPICLON N-680" manufactured by the company, dimethylaminopyridine as a curing accelerator, a photopolymerization initiator ("Omnirad 907" manufactured by IGM), and diethylene glycol monomethyl ether acetate as an organic solvent are used. The ingredients were blended and kneaded by a roll mill to obtain an acid group-containing (meth)acrylate resin composition (C3).

(Comparative Example 4: Preparation of acid group-containing (meth)acrylate resin composition (C4))
Comparative Example except that the acid group-containing (meth)acrylate resin (B-2) obtained in Synthesis Example 5 was used instead of the acid group-containing (meth)acrylate resin (B-1) used in Comparative Example 3. An acid group-containing (meth)acrylate resin composition (C4) was obtained in the same manner as in 3.

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

[Heat resistance evaluation method]
The acid group-containing (meth)acrylate resin composition obtained in each Example and Comparative Example was applied on a glass substrate using an applicator so as to have a film thickness of 50 μm, and dried at 80° C. for 30 minutes. Next, after irradiating with 1000 mJ/cm< ² > ultraviolet rays using a metal halide lamp, it heated at 160 degreeC for 1 hour, peeled the hardened material from the glass base material, and obtained the hardened material. A 6 mm×35 mm test piece was cut out from the cured product, and a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device “RSAII” manufactured by Rheometric Co., tension method: frequency 1 Hz, temperature rising rate 3° C./min) was used. The temperature at which the change in elastic modulus is maximum was evaluated as the glass transition temperature. The higher the glass transition temperature, the better the heat resistance.

[Measurement method of dielectric constant]
The acid group-containing (meth)acrylate resin composition obtained in each Example and Comparative Example was applied on a glass substrate using an applicator so as to have a film thickness of 50 μm, and dried at 80° C. for 30 minutes. Next, after irradiating with 1000 mJ/cm< ² > ultraviolet rays using a metal halide lamp, it heated at 160 degreeC for 1 hour, peeled the hardened material from the glass base material, and obtained the hardened material. Then, a test piece was stored in a room at a temperature of 23° C. and a humidity of 50% for 24 hours, and the permittivity of the test piece at 1 GHz was measured by the cavity resonance method using “Network Analyzer E8362C” manufactured by Agilent Technologies, Inc. It was measured.

[Measurement method of dielectric loss tangent]
The acid group-containing (meth)acrylate resin composition obtained in each Example and Comparative Example was applied on a glass substrate using an applicator so as to have a film thickness of 50 μm, and dried at 80° C. for 30 minutes. Next, after irradiating with 1000 mJ/cm< ² > ultraviolet rays using a metal halide lamp, it heated at 160 degreeC for 1 hour, peeled the hardened material from the glass base material, and obtained the hardened material. Then, a test piece was stored in a room at a temperature of 23° C. and a humidity of 50% for 24 hours, and the dielectric loss tangent at 1 GHz of the test piece was measured by the cavity resonance method using “Network Analyzer E8362C” manufactured by Agilent Technologies, Inc. It was measured.

Acid group-containing (meth)acrylate resin compositions (8) to (14) prepared in Examples 8 to 14, and acid group-containing (meth)acrylate resin compositions (C3) and (prepared in Comparative Examples 3 and 4). Table 2 shows the composition of C4) and the evaluation results.

In addition, the compounding amount of the acid group-containing (meth)acrylate resins (B-1) and (B-2) in Tables 1 and 2 is a solid content value.

"-" in the evaluation of Comparative Example 4 in Table 2 indicates that the evaluation is not possible. This was not evaluated because the aromatic ester compound and the acid group-containing (meth)acrylate resin were not compatible with each other and became cloudy when mixed.

The "curing agent" in Tables 1 and 2 is an orthocresol novolac type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation, epoxy equivalent: 214).

"Curing accelerator" in Table 2 indicates dimethylaminopyridine.

"Organic solvent" in Tables 1 and 2 indicates diethylene glycol monomethyl ether acetate.

"Photopolymerization initiator" in Tables 1 and 2 indicates "Omnirad-907" manufactured by IGM.

Examples 1 to 14 shown in Tables 1 and 2 are examples of the acid group-containing (meth)acrylate resin composition of the present invention, but the acid group-containing (meth)acrylate resin composition of the present invention is excellent in light. The cured product of the acid group-containing (meth)acrylate resin composition of the present invention has high heat resistance, and also has a low dielectric constant and a low dielectric loss tangent. It was confirmed that it was also excellent.

On the other hand, Comparative Examples 1 to 4 are examples of the acid group-containing (meth)acrylate resin composition using an aromatic ester compound having no polymerizable unsaturated bond. It was confirmed that the cured product had both a high dielectric constant and a high dielectric loss tangent and remarkably insufficient dielectric properties.

Claims (5)

An acid group-containing (meth)acrylate resin composition containing a polymerizable unsaturated bond-containing aromatic ester compound (A) and an acid group-containing (meth)acrylate resin (B);
A resin material for a solder resist comprising a curable resin composition containing a photopolymerization initiator ,
The resin material for a solder resist, wherein the polymerizable unsaturated bond-containing aromatic ester compound (A) is represented by the following chemical formula (a1) or the following chemical formula (a2) .

[In the formula, Ar ⁵ is independently a substituted or unsubstituted first aromatic ring group, and Ar ⁶ is independently a substituted or unsubstituted second aromatic ring group. And at least one of Ar ⁵ and Ar ⁶ has a polymerizable unsaturated bond-containing substituent. n is an integer of 1 to 3. ] The polymerizable unsaturated bond-containing aromatic ester compound (A) is
An aromatic compound having a phenolic hydroxyl group,
An aromatic compound having a carboxyl group, an acid halide thereof and/or an ester compound thereof,
At least one of the aromatic compound having a phenolic hydroxyl group, the aromatic compound having a carboxyl group, an acid halide thereof and/or an ester compound thereof is a polymerizable unsaturated bond-containing substituent. The resin material for a solder resist according to claim 1, which comprises: The mass ratio [(A)/(B)] of the solid content of the polymerizable unsaturated bond-containing aromatic ester compound (A) and the acid group-containing (meth)acrylate resin (B) is from 50/50. The resin material for a solder resist according to claim 1, which is in a range of 95/5. The resin material for a solder resist according to claim 1, wherein the curable resin composition further contains an organic solvent and a curing agent. A resist member comprising the resin material for solder resist according to claim 1.