TWI796478B - Acid group-containing (meth)acrylate resin composition, curable resin composition, cured product, insulating material, resin material for solder resist, and solder resist member - Google Patents

Abstract

The present invention provides an acid group-containing (meth)acrylate resin composition, a curable resin composition containing it, a cured product, an insulating material composed of the aforementioned curable resin composition, a solder resist resin material, and a solder resist member , characterized in that the acid group-containing (meth)acrylate resin composition contains an aromatic ester compound (A) containing a polymerizable unsaturated bond, and an acid group-containing (meth)acrylate resin (B). This acid group-containing (meth)acrylate resin composition can form a cured product with high light sensitivity, excellent heat resistance and dielectric properties.

Description

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

The present invention relates to an acid group-containing (meth)acrylate resin composition, a curable resin composition containing it, a cured product, an insulating material composed of the aforementioned curable resin composition, a solder resist resin material and a resist A welding member, wherein the acid group-containing (meth)acrylate resin composition has high photosensitivity, excellent heat resistance and dielectric properties.

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

As a conventional resin material for solder resist, there is known a photosensitive resin composition comprising an acid group-containing epoxy acrylate resin in which tetrahydrophthalic anhydride is further combined with It is obtained by reacting cresol novolac type epoxy resin, acrylic acid, and an intermediate obtained by reacting with phthalic anhydride (see for example: Patent Document 1.), but the heat resistance of the hardened product is not sufficient, and due to the formation of hydroxyl groups However, the dielectric constant and the dielectric dissipation factor are increased, so there are problems such as deterioration of the dielectric properties.

Therefore, materials having high photosensitivity, heat resistance of cured products, and substrate adhesion are desired.

[Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 8-259663

The problem to be solved by the present invention is to provide an acid group-containing (meth)acrylate resin composition, a curable resin composition containing it, a hardened product, an insulating material composed of the aforementioned photosensitive resin composition, and a solder resist A resin material and a solder resist member are used, wherein the acid group-containing (meth)acrylate resin composition has high photosensitivity, excellent heat resistance and dielectric properties.

As a result of intensive research by the present inventors to solve the above-mentioned problems, it was found that by using an acid group-containing (meth)acrylate resin containing a polymerizable unsaturated bond-containing aromatic ester compound and an acid group-containing (meth)acrylate resin, Base) acrylate resin composition can solve the above-mentioned problems, and further complete the present invention.

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

The acid group-containing (meth)acrylate resin composition of the present invention can form a hardened product with high photosensitivity, heat resistance and excellent dielectric properties, so it can be applied to insulating materials, resin materials for solder resist, and The aforementioned solder resist member made of resin for solder resist. In addition, the so-called "excellent dielectric properties" in the present invention refer to low dielectric constant and low dielectric loss factor.

[Mode for Carrying Out the Invention]

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

The aforementioned so-called polymerizable unsaturated bond-containing aromatic ester compound (A) refers to a compound having one or more polymerizable unsaturated bonds in the molecular structure and a structural site where aromatic rings are bonded to each other by ester bonds. Compounds Regardless of other specific structures, molecular weights, etc., a wide variety of compounds can be used.

As the aromatic ester compound (A) containing a polymerizable unsaturated bond, for example: an aromatic compound having a phenolic hydroxyl group, an aromatic compound having a carboxyl group, its acid halide and/or its esterified product (this In the specification, there are cases where an aromatic compound having a carboxyl group, its acid halide, and/or an esterified product thereof are collectively referred to as "aromatic compound having a carboxyl group, etc."), the reaction product of the aforementioned phenolic hydroxyl group Any one of the aromatic compound and the aforementioned aromatic compound having a carboxyl group has a substituent having a polymerizable unsaturated bond.

As an aromatic compound which has the said phenolic hydroxyl group, the 1st aromatic compound which has 2 or more phenolic hydroxyl groups, and the 2nd aromatic compound which has 1 phenolic hydroxyl group are mentioned, for example.

The aforementioned first aromatic compound is one having two or more phenolic hydroxyl groups. By having 2 or more phenolic hydroxyl groups, it can form an ester structure by reacting with the 3rd aromatic compound etc. or the 4th aromatic compound etc. mentioned later.

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

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

唑、異

唑、噻唑、異噻唑、吡啶、嘧啶、嗒

、吡

、三

等。 Examples of the monocyclic aromatic ring include benzene, furan, pyrrole, thiophene, imidazole, pyrazole,

azole, iso

Azole, Thiazole, Isothiazole, Pyridine, Pyrimidine, Pyridine

, pyri

,three

wait.

、喋啶、香豆素、吲哚、苯并咪唑、苯并呋喃、吖啶等。 Examples of the condensed aromatic ring include naphthalene, anthracene, anthracene, phenanthrene, quinoline, isoquinoline, quinazoline, and

, Pteridine, Coumarin, Indole, Benzimidazole, Benzofuran, Acridine, etc.

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

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 alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, halogen atoms, polymerizable unsaturated bond-containing Substituents etc.

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

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

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example.

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

Examples of the alkenyl group include vinyl, allyl, propenyl, isopropenyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-hexene Base, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-octenyl, 2-octenyl, 1-undecenyl, 1-pentadecenyl Carbenyl, 3-pentadecenyl, 7-pentadecenyl, 1-octadecenyl, 2-octadecenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl , 1,3-butadienyl, 1,4-butadienyl, hexa-1,3-dienyl, hexa-2,5-dienyl, pentadec-4,7-dienyl, Hexa-1,3,5-trienyl, pentadec-1,4,7-trienyl, etc.

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

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

The above-mentioned substituents of the first aromatic ring may be included alone or in combination of two or more kinds.

Furthermore, the above-mentioned first aromatic compound is one in which at least two of the hydrogen atoms constituting the above-mentioned substituted or unsubstituted first aromatic ring having 3 to 30 carbon atoms are substituted with hydroxyl groups.

Specific examples of the compound in which the aforementioned first aromatic ring is a monocyclic aromatic ring (hereinafter, may be simply referred to as "the first monocyclic aromatic ring compound") include, for example: catechol, resorcinol ( resorcinol), hydroquinone, 1,2,4-glucinol, phloroglucinol, gallicol, 2,3-dihydroxypyridine, 2,4-dihydroxypyridine, 4,6-dihydroxypyrimidine, 3- Methylcatechol, 4-methylcatechol, 4-allylpyrocatechol (4-allylpyrocatechol) and the like.

Specific examples of the compound in which the aforementioned first aromatic ring is a fused-ring aromatic ring (hereinafter, may be simply referred to as "the first condensed-ring 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-dihydroxy Anthracene, 1,4,9,10-tetrahydroxyanthracene, 2,4-dihydroxyquinoline, 2,6-dihydroxyquinoline, 5,6-dihydroxyindole, 2-methylnaphthalene-1,4 - Diols, etc.

Specific examples of the compound in which the aforementioned first aromatic ring is a ring-assembled aromatic ring (hereinafter, may be simply referred to as "the first ring-assembled aromatic ring compound") include, for example: 2,2'-dihydroxybis Benzene, 4,4'-dihydroxybiphenyl, 3,4,4'-trihydroxybiphenyl, 2,2',3-trihydroxybiphenyl, etc.

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

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

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

唑、異

唑、噻唑、異噻唑、吡啶、嘧啶、嗒

、吡

、三

等之單環芳香族化合物中移除1個氫原子而成者；從萘、蒽、萉、菲、喹啉、異喹啉、喹唑啉、呔

、喋啶、香豆素、吲哚、苯并咪唑、苯并呋喃、吖啶等之稠環芳香族化合物中移除1個氫原子而成者等之從芳香族化合物中移除1個氫原子而成者。此外，亦可為組合複數個此等的芳香族化合物而成者，可列舉例如：從聯苯、聯萘、聯吡啶、聯噻吩、苯基吡啶、苯基噻吩、聯三苯、二苯基噻吩、聯四苯等之環集合芳香族化合物中移除1個氫原子而成者。 Examples of the first aromatic ring group include: benzene, furan, pyrrole, thiophene, imidazole, pyrazole,

azole, iso

Azole, Thiazole, Isothiazole, Pyridine, Pyrimidine, Pyridine

, pyri

,three

Monocyclic aromatic compounds such as those obtained by removing one hydrogen atom; from naphthalene, anthracene, anthracene, phenanthrene, quinoline, isoquinoline, quinazoline, and

, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine and other condensed ring aromatic compounds by removing one hydrogen atom from aromatic compounds, etc. made of atoms. In addition, a plurality of these aromatic compounds may be combined, for example: biphenyl, binaphthyl, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenyl One hydrogen atom is removed from rings of thiophene, tetraphenyl, etc. aromatic compounds.

At this time, the first aromatic ring group may have a substituent. In this case, the so-called "substituent of the first aromatic ring group" refers to the hydrogen atom that constitutes the aromatic ring of the first aromatic ring group. At least one replacement. Examples of the "substituent of the first aromatic ring group" include an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, and a halogen atom.

Examples of the aforementioned alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, isopentyl, tertiary Pentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, cyclohexyl, etc.

As said alkoxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group etc. are mentioned, for example.

Examples of the aforementioned alkyloxycarbonyl group include methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, n-butyloxycarbonyl, Isobutyloxycarbonyl, secondary butyloxycarbonyl, tertiary butyloxycarbonyl and the like.

Examples of the aforementioned alkylcarbonyloxy group include methylcarbonyloxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, n-butylcarbonyloxy, Isobutylcarbonyloxy, secondary butylcarbonyloxy, tertiary butylcarbonyloxy and the like.

As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example.

Among these, Ar ¹ is preferably from benzene, naphthalene, anthracene, anthracene, phenanthrene, biphenyl, binaphthyl, tetraphenyl, allylbenzene, diallylbenzene, allylnaphthalene, diallyl Basenaphthalene, allylbiphenyl, diallylbiphenyl by removing one hydrogen atom, more preferably from benzene, naphthalene, biphenyl, allylbenzene, diallylnaphthalene, diallyl It is formed by removing one hydrogen atom from base biphenyl.

The aforementioned Ar ² systems are each independently a substituted or unsubstituted second aromatic ring group. It is also clear from the description of the above chemical formula (1) that two of the hydrogen atoms constituting the aromatic ring of the above-mentioned substituted or unsubstituted aromatic ring are bonded to "X".

唑、異

唑、噻唑、異噻唑、吡啶、嘧啶、嗒

、吡

、三

等之單環芳香族化合物中移除2個氫原子而成者；從萘、蒽、萉、菲、喹啉、異喹啉、喹唑啉、呔

、喋啶、香豆素、吲哚、苯并咪唑、苯并呋喃、吖啶等之稠環芳香族化合物中移除2個氫原子而成者等之從芳香族化合物中移除2個氫原子而成者。此外，亦可為組合複數個此等的芳香族化合物而成者，可列舉例如：從聯苯、聯萘、聯吡啶、聯噻吩、苯基吡啶、苯基噻吩、聯三苯、二苯基噻吩、聯四苯等之環集合芳香族化合物中移除2個氫原子而成者。 Examples of the above-mentioned second aromatic ring group include: benzene, furan, pyrrole, thiophene, imidazole, pyrazole,

azole, iso

Azole, Thiazole, Isothiazole, Pyridine, Pyrimidine, Pyridine

, pyri

,three

Monocyclic aromatic compounds such as those obtained by removing two hydrogen atoms; from naphthalene, anthracene, anthracene, phenanthrene, quinoline, isoquinoline, quinazoline, and

, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine and other condensed ring aromatic compounds by removing 2 hydrogen atoms from aromatic compounds made of atoms. In addition, a plurality of these aromatic compounds may be combined, for example: biphenyl, binaphthyl, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenyl It is formed by removing two hydrogen atoms from rings of thiophene, tetraphenyl, etc., in aromatic compounds.

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

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

As the aforementioned alkylene group, for example: methylene group, ethylidene group, propylidene group, 1-methylmethylene group, 1,1-dimethylmethylene group, 1-methylethylidene group, 1-methylidene group, ,1-Dimethylethylene, 1,2-Dimethylethylene, Propyl, Butyl, 1-Methylpropyl, 2-Methylpropyl, Pentyl, Hexyl etc.

As the aforementioned cycloalkylene group, for example: cyclopropylidene, cyclobutylene, cyclopentyl, cyclohexyl, cyclopentyl, cycloheptyl, and the following chemical formula (2-1) ~ A cycloalkylene group represented by (2-4), etc.

In addition, in the above-mentioned chemical formulas (2-1) to (2-4), "*" represents a bonding site with Ar ¹ or Ar ² .

As said aralkylene group, the aralkylene group represented by following chemical formula (3-1)-(3-8), etc. are mentioned, for example.

In addition, in the above-mentioned chemical formulas (3-1) to (3-8), "*" represents a bonded position with Ar ¹ or Ar ² .

The aforementioned alkylene group, the aforementioned cycloalkylene group, and the aforementioned aralkylene group may also have a substituent. In this case, examples of the "substituent of X" include the same ones as those described above for the "substituent of the first aromatic ring".

n in the above chemical formula (1) is an integer of 0-10, preferably an integer of 0-8, more preferably an integer of 0-5. In addition, when the compound represented by the said chemical formula (1) is an oligomer or a polymer, n means the average value.

Furthermore, at least two of the hydrogen atoms constituting the aforementioned Ar ¹ and the aforementioned Ar ² are substituted with hydroxyl groups.

Specific examples of the compound represented by the following chemical formula (1) are not particularly limited, but for example: various bisphenol compounds, compounds represented by the following chemical formulas (4-1) to (4-8), and These aromatic nuclei have one or more substituents containing polymerizable unsaturated bonds.

As said various bisphenol compound, bisphenol A, bisphenol AP, bisphenol B, bisphenol E, bisphenol F, bisphenol Z etc. are mentioned, for example.

In the above chemical formulas (4-1)~(4-8), n is an integer of 0~10, preferably an integer of 0~5. 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 a compound including 1 to 5 repeating units, and a "polymer" means a compound including 6 or more repeating units. In addition, the substitution position of the hydroxyl group of the substituent on the aromatic ring is arbitrary, and in the case of a naphthalene ring, it may be either a ring bonded to another structure or a ring not bonded to another structure.

In addition, in one embodiment, the above-mentioned first aromatic ring is represented by the above-mentioned chemical formula (1), which can be replaced by a hydroxyl group by at least one of the hydrogen atoms constituting the first aromatic ring, and the two Synthesized by the reaction of vinyl compound or dialkyloxymethyl compound.

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

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

The hydroxyl equivalent of the first aromatic compound is preferably 130~500g/equivalent, more preferably 130~400g/equivalent.

From the viewpoint of obtaining an acid group-containing (meth)acrylate resin composition capable of forming a cured product having high photosensitivity, heat resistance, and excellent dielectric properties, the aforementioned first aromatic compound is represented by the aforementioned chemical formula (1) , and n is an oligomer or a polymer, the weight average molecular weight is preferably 200~3000, more preferably 200~2000. In addition, in this specification, the value of "weight average molecular weight" shall be the value measured by the following method. That is, values obtained by measuring gel permeation chromatography (GPC) according to the following conditions are employed.

GPC measurement conditions

Measuring device: "HLC-8320 GPC" manufactured by Tosoh Co., Ltd.

Column: Guard column "HXL-L" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G4000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G3000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.

Detector: RI (Differential Refractometer)

Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Co., Ltd.

Column temperature: 40°C

Developing solvent: tetrahydrofuran

Flow rate: 1.0ml/min

Standard: follow the aforementioned "GPC-8320 GPC" measurement manual, use the following monodisperse polystyrene with known molecular weight

use polystyrene

"A-500" manufactured by Tosoh Co., Ltd.

"A-1000" manufactured by Tosoh Co., Ltd.

"A-2500" manufactured by Tosoh Co., Ltd.

"A-5000" manufactured by Tosoh Co., Ltd.

"F-1" manufactured by Tosoh Co., Ltd.

"F-2" manufactured by Tosoh Co., Ltd.

"F-4" manufactured by Tosoh Co., Ltd.

"F-10" manufactured by Tosoh Co., Ltd.

"F-20" manufactured by Tosoh Co., Ltd.

"F-40" manufactured by Tosoh Co., Ltd.

"F-80" manufactured by Tosoh Co., Ltd.

"F-128" manufactured by Tosoh Co., Ltd.

Sample: what filtered the tetrahydrofuran solution of 1.0 mass % in terms of resin solid content with the microfilter (50 microliters).

As said 2nd aromatic compound, it is a thing which 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 on a substituted or unsubstituted second aromatic ring having 3 to 30 carbon atoms.

Examples of the second aromatic ring having 3 to 30 carbon atoms include monocyclic aromatic rings, condensed ring aromatic rings, ring-integrated aromatic rings, and aromatic rings linked by alkylene groups. Examples of the monocyclic aromatic ring, the fused-ring aromatic ring, and the aggregated ring aromatic ring include the same ones as those described above for the first aromatic ring.

Examples of the aforementioned aromatic ring linked by an alkylene group include: diphenylmethane, diphenylethane, 1,1-diphenylethane, 2,2-diphenylpropane, naphthylphenyl Methane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenylpyridylmethane, fennel, diphenylcyclopentane, etc.

The second aromatic ring having 3 to 30 carbon atoms of the second aromatic compound may have a substituent. In this case, examples of the "substituent of the second aromatic ring" include the same ones as those described above for the "substituent of the first aromatic ring".

Furthermore, as in the above-mentioned 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.

As said 2nd aromatic compound, the compound represented by following chemical formula (5-1)-(5-17) is mentioned, for example.

In the above chemical formulas (5-1) to (5-17), R ¹ is a substituent containing a polymerizable unsaturated bond. The aforementioned substituents containing a polymerizable unsaturated bond are the same as those described above. In addition, p is an integer of 0 or more, preferably 1 to 3, more preferably 1 or 2, further preferably 1. Furthermore, when p is more than 2, it means that the bonding position on the aromatic ring can be arbitrary, for example: in the naphthalene ring of chemical formula (5-6), in the heterocyclic ring of chemical formula (5-17), it can also be in any Substitution on one ring, in the case of chemical formula (5-9) etc., can also be substituted on any ring of the benzene ring present in one molecule, which means that the number of substituents in one molecule is p.

More specifically, examples of the second aromatic compound include phenol, cresol, xylenol, o-allylphenol, m-allylphenol, p-allylphenol, 2,4-diallyl 2,6-diallylphenol, 2-allyl-4-methylphenol, 2-allyl-6-methylphenol, 2-allyl-4-methoxy-6 The aromatic rings of -methylphenol, 2-propargylphenol, 3-propargylphenol, 4-propargylphenol, etc. are monocyclic aromatic rings (hereinafter referred to as "second monocyclic aromatic rings") Aromatic ring compound"); 1-naphthol, 2-naphthol, 2-allyl-1-naphthol, 3-allyl-1-naphthol, 1-allyl-2-naphthol Phenol, 3-allyl-2-naphthol, 5-allyl-1-naphthol, 6-allyl-1-naphthol, diallyl-naphthol, 2-allyl-4- Methoxy-1-naphthol, 2-propargyl-1-naphthol, 3-propargyl-1-naphthol, 1-propargyl-2-naphthol, 3-propargyl-2- Compounds in which the aromatic ring of naphthol, etc. is a condensed ring aromatic ring (hereinafter, may be simply referred to as "the second condensed ring aromatic ring compound"); allyl hydroxybiphenyl, hydroxypropargyl biphenyl, etc. The aromatic ring is a compound of ring-assembled aromatic rings (hereinafter, may be simply referred to as "second ring-assembled aromatic ring compound") and the like.

Among the above, the aforementioned second aromatic compound is preferably the second monocyclic aromatic ring compound, the second condensed ring aromatic ring compound, more preferably o-allyl phenol, m-allyl phenol, p-allyl phenol , 2-allyl-1-naphthol, 3-allyl-1-naphthol, 1-allyl-2-naphthol, 3-allyl-2-naphthol, 5-allyl -1-naphthol, 6-allyl-1-naphthol.

In addition, in another embodiment, the aforementioned second aromatic compound is preferably the second fused-ring aromatic ring compound (fused-ring aromatic ring compound), more preferably 2-allyl-1-naphthol, 3 -Allyl-1-naphthol, 1-allyl-2-naphthol, 3-allyl-2-naphthol, 5-allyl-1-naphthol, 6-allyl-1 - Naphthol. When the second aromatic compound is a fused-ring aromatic ring compound, molecular movement is suppressed by steric hindrance, and the dielectric loss factor can be reduced, which is preferable. In addition, from the viewpoint of high handleability and low viscosity of the polymerizable unsaturated bond-containing aromatic ester compound (A), 2-allylphenol having a benzene ring skeleton is preferable, and on the other hand, From the point of view that the obtained acid group-containing (meth)acrylate resin composition can form a cured product with high photosensitivity, heat resistance and excellent dielectric properties, it is preferably 2-allyl- 1-naphthol, 1-allyl-2-naphthol, etc.

In addition, the above-mentioned second aromatic compound having one phenolic hydroxyl group may be used alone or in combination of two or more.

Examples of the aromatic compound having a carboxyl group include a third aromatic compound having two or more carboxyl groups, a fourth aromatic compound having one carboxyl group, or their acid halides and esterified products.

The aforementioned third aromatic compound, its acid halide, and/or its esterified product are aromatic compounds having two or more carboxyl groups, or derivatives thereof, specifically, acid halides, esterified products (in this specification , the third aromatic compound, its acid halide, and/or its ester compound may be collectively referred to as "the third aromatic compound, etc."). The third aromatic compound or the like can form an ester structure by reacting with the above-mentioned first or second aromatic compound having two or more carboxyl groups or the like.

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

The above-mentioned "carboxyl group etc." include, for example: carboxyl group; halide acyl group such as fluoride acyl group, chloride acyl group, bromide acyl group; alkyloxy group such as methyloxycarbonyl group and ethyloxycarbonyl group; aryloxycarbonyl; aryloxycarbonyl such as phenyloxycarbonyl, naphthyloxycarbonyl, etc. In addition, when having an acyl halide group, the aforementioned third aromatic compound is an acid halide; when having an alkyloxycarbonyl group or an aryloxycarbonyl group, the aforementioned third aromatic compound may be an esterified compound. Among these, the aforementioned third aromatic compound preferably has a carboxyl group, an acyl halide group, or an aryloxycarbonyl group, more preferably has a carboxyl group or an acyl halide group, and still more preferably has a carboxyl group, an acyl chloride group, or an acyl chloride group. Acyl bromide.

Examples of the third aromatic ring having 3 to 30 carbon atoms include monocyclic aromatic rings, condensed ring aromatic rings, ring-integrated aromatic rings, and aromatic rings linked by alkylene groups. Examples of the aforementioned single-ring aromatic ring, the aforementioned condensed-ring aromatic ring, the aforementioned ring-set aromatic ring, and the aromatic ring connected via an alkylene group include the same ones as those described above for the first aromatic ring and the second aromatic ring. .

The third aromatic ring having 3 to 30 carbon atoms, such as the third aromatic compound, may have a substituent. In this case, examples of the "substituent of the third aromatic ring" include the same ones as those described above for the "substituent of the first aromatic ring".

As said 3rd aromatic compound etc., the compound represented by following chemical formula (6-1)-(6-15) is mentioned, for example.

In the above chemical formulas (6-1) to (6-15), R ¹ is a substituent containing a polymerizable unsaturated bond. In this case, the aforementioned polymerizable unsaturated bond-containing substituents are the same as those described above. In addition, R ² is a hydroxyl group, a halogen atom, an alkyloxy group, or an aryloxy group. Also, p is an integer of 0 or more, preferably 0 or 1 to 3, more preferably 0 or 1, further preferably 0. q is 2 or 3. Furthermore, when p and q are 2 or more, the bonding position on the aromatic ring can be arbitrary, which means, for example: in the naphthalene ring of chemical formula (6-5) and the heterocyclic ring of chemical formula (6-15) It can be substituted on any ring. For chemical formula (6-7) etc., it can also be substituted on any ring of the benzene ring present in one molecule, which means that the number of substituents in one molecule is p and q.

-2,4,6-三甲酸等之三

甲酸；此等之酸鹵化物、酯化物等。此等之中，較佳為苯二甲酸、苯三甲酸，更佳為異酞酸、對酞酸、異酞醯氯、對酞醯氯、1,3,5-苯三甲酸、1,3,5-苯三甲醯氯，進一步較佳為異酞醯氯、對酞醯氯、1,3,5-苯三甲醯氯。 As the above-mentioned third aromatic compound, etc., more specifically, phthalic acid such as isophthalic acid, terephthalic acid, 5-allyl isophthalic acid, and 2-allyl terephthalic acid; Tricarboxylic acid, benzenetricarboxylic acid such as 5-allyl trimellitic acid; naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7 Naphthalene dicarboxylic acid, 3-allylnaphthalene-1,4-dicarboxylic acid, 3,7-diallylnaphthalene-1,4-dicarboxylic acid, etc.; 2,4,5-pyridinetricarboxylic acid, etc. pyridinetricarboxylic acid; 1,3,5-tri

-2,4,6-tricarboxylic acid etc.

Formic acid; their acid halides, esters, etc. Among these, phthalic acid and benzenetricarboxylic acid are preferred, and isophthalic acid, terephthalic acid, isophthaloyl chloride, terephthaloyl chloride, 1,3,5-benzenetricarboxylic acid, 1,3 , 5-benzenetriformyl chloride, more preferably isophthaloyl chloride, terephthaloyl chloride, 1,3,5-benzenetriformyl chloride.

Among the above, the third aromatic compound whose aromatic ring is a monocyclic aromatic ring is preferred, and the third aromatic compound whose aromatic ring is a condensed aromatic ring is preferred, such as phthalic acid and benzenetricarboxylic acid , naphthalene dicarboxylic acid, acid halides of these, more preferably phthalic acid, naphthalene dicarboxylic acid, acid halides of these, further preferably isophthalic acid, terephthalic acid, naphthalene-1,5-dicarboxylic acid , naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, acid halides of these.

In addition, the above-mentioned third aromatic compound and the like may be used alone or in combination of two or more.

The above-mentioned 4th aromatic compound, its acid halide, and/or its esterification product are aromatic compounds having one carboxyl group, or its derivatives, specifically, acid halides and esterification products (in this specification, there are When the fourth aromatic compound, its acid halide, and/or its esterified product are collectively referred to as "the fourth aromatic compound, etc."). The fourth aromatic compound has a function of stopping the esterification reaction because it has one carboxyl group or the like.

As said 4th aromatic compound etc., the compound which has 1 carboxyl group etc. on the substituted or unsubstituted 4th aromatic ring with 3-30 carbon atoms is mentioned, for example.

The aforementioned "carboxyl group, etc." include the same ones as the above-mentioned "carboxyl group, etc.".

Examples of the fourth aromatic ring having 3 to 30 carbon atoms include monocyclic aromatic rings, condensed ring aromatic rings, ring-integrated aromatic rings, and aromatic rings linked by alkylene groups. Examples of the aforementioned single-ring aromatic ring, the aforementioned condensed-ring aromatic ring, the aforementioned ring-integrated aromatic ring, and the aromatic ring linked by an alkylene group include the first aromatic ring, the second aromatic ring, and the second aromatic ring described above. 3 with the same aromatic ring.

The fourth aromatic ring having 3 to 30 carbon atoms in the aforementioned fourth aromatic compound or the like may have a substituent. In this case, examples of the "substituent of the fourth aromatic ring" include the same ones as those described above for the "substituent of the first aromatic ring".

As said 4th aromatic compound etc., the compound represented by following chemical formula (7-1)-(7-15) is mentioned, for example.

In the above chemical formulas (7-1) to (7-15), R ¹ is a substituent containing a polymerizable unsaturated bond. In this case, the aforementioned polymerizable unsaturated bond-containing substituents are the same as those described above. In addition, R ² is a hydroxyl group, a halogen atom, an alkyloxy group, or an aryloxy group. In addition, p is an integer of 0 or 1 or more, preferably 0 or 1 to 3, more preferably 0 or 1, further preferably 0. q is 1. Furthermore, the position of the substituent on the aromatic ring in the above chemical formula is arbitrary, which means for example: in the naphthalene ring of chemical formula (7-5), in the heterocyclic ring of chemical formula (7-15) can also be in Substitution on any ring, in terms of chemical formula (7-7) etc., can also be substituted on any ring of the benzene ring present in one molecule, which means that the number of substituents in one molecule is p and q.

More specifically, examples of the fourth aromatic compound and the like include benzoic acid, chlorotoluene, naphthoic acid, naphthoyl chloride and the like.

[Structure of the aromatic ester compound (A) containing a polymerizable unsaturated bond]

At least one of the aforementioned aromatic compound having a phenolic hydroxyl group and the aforementioned aromatic compound having a carboxyl group has a substituent having a polymerizable unsaturated bond having 2 to 30 carbon atoms. That is, both the aforementioned aromatic compound having a phenolic hydroxyl group and the aforementioned aromatic compound having a carboxyl group may have a substituent containing a polymerizable unsaturated bond, or only the aforementioned aromatic compound having a phenolic hydroxyl group may have a substituent containing an unsaturated bond. As the substituent of a polymerizable unsaturated bond, only the aforementioned aromatic compound having a carboxyl group, etc. may have a substituent having a polymerizable unsaturated bond. Moreover, when using 2 or more types of aromatic compounds which have a phenolic hydroxyl group, 2 or more types of aromatic compounds which have a carboxyl group, etc., only a part may have the substituent which has a polymerizable unsaturated bond.

In one embodiment, it is preferable that at least the second aromatic compound has a substituent having a polymerizable unsaturated bond. As mentioned above, the structure derived from the said 2nd aromatic compound becomes the molecular terminal located in the aromatic ester compound (A) containing a polymerizable unsaturated bond. As a result, the polymerizable unsaturated bond-containing substituent of the second aromatic compound is also arranged at the molecular terminal of the aromatic ester compound (A). In this case, since the obtained acid group-containing (meth)acrylate resin composition can form a cured product having high photosensitivity, heat resistance and excellent dielectric properties, it is preferable.

The aforementioned aromatic ester compound (A) containing a polymerizable unsaturated bond is, as mentioned above, a reaction product of a compound having a phenolic hydroxyl group and an aromatic compound having a carboxyl group, although it may contain the aforementioned first to fourth aromatic compounds and other compounds, but because of the function of stopping the reaction of esterification, it is necessary to contain either one or both of the second aromatic compound and the fourth aromatic compound. Furthermore, the composition of the aforementioned polymerizable unsaturated bond-containing aromatic ester compound (A) can be controlled by appropriately changing the amount of the aforementioned 1st to 4th aromatic compounds used, reaction conditions, and the like.

In one embodiment, the aforementioned polymerizable unsaturated bond-containing aromatic ester compound (A) includes, for example, polymerizable unsaturated bond-containing Aromatic ester compounds; aromatic ester compounds containing polymerizable unsaturated bonds that are reaction products of the first aromatic compound, the second aromatic compound, and the third aromatic compound; the first aromatic compound, the third aromatic compound, etc. Aromatic compounds, polymerizable unsaturated bond-containing aromatic ester compounds of reaction products with fourth aromatic compounds, etc.; first aromatic compound, second aromatic compound, third aromatic compound, etc., and fourth aromatic compound Aromatic ester compound containing a polymerizable unsaturated bond that is a reaction product of an aromatic compound, etc.; a second aromatic compound, an aromatic compound that is a reaction product of a third aromatic compound; a second aromatic compound, and a third aromatic compound 4 Aromatic compounds containing polymerizable unsaturated bonds, etc., which are reaction products of aromatic compounds.

In addition, the polymerizable unsaturated bond-containing aromatic ester compound (A) of this aspect does not have a hydroxyl group in the molecule of the obtained resin in principle. However, a compound having a hydroxyl group as a by-product of the reaction product may be included within a range that does not inhibit the effects of the present invention.

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 a structure derived from the third aromatic compound. In addition, n is an integer of 0-10. In addition, when the polymerizable unsaturated bond-containing aromatic ester compound (A) is an oligomer or a polymer, n represents the average value.

That is, in the above-mentioned chemical formula (8), Ar ¹ is each independently, and can be exemplified by removing two or more hydrogen atoms from a substituted or unsubstituted first aromatic ring having 3 to 30 carbon atoms. , or one obtained by removing two or more hydrogen atoms from a structure having a first aromatic ring linked by a linking group.

In addition, in the above-mentioned chemical formula (8), Ar ² is each independently, and one hydrogen atom is removed from a substituted or unsubstituted second aromatic ring having 3 to 30 carbon atoms.

In the above chemical formula (8), Ar ³ may be one obtained by removing two or more hydrogen atoms from a substituted or unsubstituted third aromatic ring having 3 to 30 carbon atoms.

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

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

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

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

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

That is to say, in the above chemical formula (9), Ar ¹ are each independently, and can be exemplified by removing two or more hydrogen atoms from the substituted or unsubstituted first aromatic ring having 3 to 30 carbon atoms. , or one obtained by removing two or more hydrogen atoms from a structure having a first aromatic ring linked by a linking group.

In addition, in the above-mentioned chemical formula (9), Ar ² is each independently, and one hydrogen atom is removed from a substituted or unsubstituted second aromatic ring having 3 to 30 carbon atoms.

In the above chemical formula (9), Ar ³ may be one obtained by removing two or more hydrogen atoms from a substituted or unsubstituted third aromatic ring having 3 to 30 carbon atoms.

In the above chemical formula (9), Ar ⁴ may include one obtained by removing one hydrogen atom from a substituted or unsubstituted fourth aromatic ring having 3 to 30 carbon atoms.

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

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

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

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

In the above chemical formula (10), 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 a structure derived from the fourth aromatic compound. In addition, n is an integer of 0-10. In addition, when the polymerizable unsaturated bond-containing aromatic ester compound (A) is an oligomer or a polymer, n represents the average value.

That is, in the above-mentioned chemical formula (10), Ar ¹ is each independently, and can be exemplified by removing two or more hydrogen atoms from the substituted or unsubstituted first aromatic ring having 3 to 30 carbon atoms. , or one obtained by removing two or more hydrogen atoms from a structure having a first aromatic ring linked by a linking group.

In addition, in the above-mentioned chemical formula (10), Ar ³ may include one obtained by removing two or more hydrogen atoms from a substituted or unsubstituted third aromatic ring having 3 to 30 carbon atoms.

In the above chemical formula (10), Ar ⁴ may include one obtained by removing one hydrogen atom from a substituted or unsubstituted fourth aromatic ring having 3 to 30 carbon atoms.

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

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

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

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

In the above chemical formulas (11-1)~(11-10), s is an integer of 0~10, preferably an integer of 0~5, and 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. Furthermore, the wavy line in the chemical formula corresponds to the structure obtained by reacting compounds of Ar ³ and Ar ¹ and/or Ar ² .

In addition, the aforementioned polymerizable unsaturated bond-containing aromatic ester compound (A), in one embodiment, includes, for example: the polymerizable unsaturated bond-containing aromatic ester compound (A) represented by the following chemical formula (a1) -1) An aromatic ester compound (A-2) having a polymerizable unsaturated bond represented by the following chemical formula (a2).

[In the formula, Ar ⁵ is independently a substituted or unsubstituted aromatic ring group, Ar ⁶ is independently a substituted or unsubstituted second aromatic ring group, the aforementioned Ar ⁵ and the aforementioned Ar ⁶ are At least one of them has a substituent having a polymerizable unsaturated bond. n is an integer from 1 to 3. 〕

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

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

唑、異

唑、噻唑、異噻唑、吡啶、嘧啶、嗒

、吡

、三

等之單環芳香族化合物中移除2個或3個氫原子而成者；從萘、蒽、萉、菲、喹啉、異喹啉、喹唑啉、呔

、喋啶、香豆素、吲哚、苯并咪唑、苯并呋喃、吖啶等之稠環芳香族化合物中移除2個或3個氫原子而成者等之從芳香族化合物移除2個或3個氫原子而成者。此外，亦可為組合複數個此等的芳香族化合物而成者，可列舉例如：從聯苯、聯萘、聯吡啶、聯噻吩、苯基吡啶、苯基噻吩、聯三苯、二苯基噻吩、聯四苯等之環集合芳香族化合物中移除2個或3個氫原子而成者；從二苯基甲烷、二苯基乙烷、1,1-二苯基乙烷、2,2-二苯基丙烷、萘基苯基甲烷、三苯基甲烷、二萘基甲烷、二萘基丙烷、苯基吡啶基甲烷、茀、二苯基環戊烷等之藉由伸烷基鍵結之芳香族化合物中移除2個或3個氫原子而成者等。此等之中，從可得到可形成具有高光感度、耐熱性及介電特性優異的硬化物的含酸基之(甲基)丙烯酸酯樹脂組成物來看，Ar⁵較佳為經取代或未經取代的苯環結構或萘環結構，更佳為經取代或未經取代的苯環結構。 Examples of the first aromatic ring group include: benzene, furan, pyrrole, thiophene, imidazole, pyrazole,

azole, iso

Azole, Thiazole, Isothiazole, Pyridine, Pyrimidine, Pyridine

, pyri

,three

Monocyclic aromatic compounds such as those obtained by removing 2 or 3 hydrogen atoms; from naphthalene, anthracene, anthracene, phenanthrene, quinoline, isoquinoline, quinazoline,

, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine and other condensed ring aromatic compounds by removing 2 or 3 hydrogen atoms, etc., removed from aromatic compounds 2 One or three hydrogen atoms. In addition, a plurality of these aromatic compounds may be combined, for example: biphenyl, binaphthyl, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenyl The one obtained by removing 2 or 3 hydrogen atoms from the ring set aromatic compounds such as thiophene and tetraphenyl; from diphenylmethane, diphenylethane, 1,1-diphenylethane, 2, 2-diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenylpyridylmethane, fennel, diphenylcyclopentane, etc. Aromatic compounds obtained by removing 2 or 3 hydrogen atoms, etc. Among these, Ar ⁵ is preferably substituted or unsubstituted from the viewpoint of obtaining an acid group-containing (meth)acrylate resin composition capable of forming a cured product having high photosensitivity, heat resistance, and excellent dielectric properties. A substituted benzene ring structure or a naphthalene ring structure, more preferably a substituted or unsubstituted benzene ring structure.

The aforementioned first aromatic ring group of Ar ⁵ may also have a substituent. In this case, the so-called substituent of the first aromatic ring group is the hydrogen atom of the aromatic ring constituting the first aromatic ring group. At least one replacement. Examples of the "substituent of the first aromatic ring group" include an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, and a halogen atom.

Examples of the aforementioned alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, isopentyl, tertiary Pentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, cyclohexyl, etc.

As said alkoxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group etc. are mentioned, for example.

Examples of the aforementioned alkyloxycarbonyl group include methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, n-butyloxycarbonyl, Isobutyloxycarbonyl, secondary butyloxycarbonyl, tertiary butyloxycarbonyl and the like.

Examples of the aforementioned alkylcarbonyloxy group include methylcarbonyloxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, n-butylcarbonyloxy, Isobutylcarbonyloxy, secondary butylcarbonyloxy, tertiary butylcarbonyloxy and the like.

As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example.

In one embodiment of the present invention, the aforementioned Ar ⁵ may also have a substituent having a polymerizable unsaturated bond. Specific examples of the polymerizable unsaturated bond-containing substituent include alkenyl groups, alkynyl groups, and the like.

Examples of the alkenyl group include vinyl, allyl, propenyl, isopropenyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-hexene Base, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-octenyl, 2-octenyl, 1-undecenyl, 1-pentadecenyl Carbenyl, 3-pentadecenyl, 7-pentadecenyl, 1-octadecenyl, 2-octadecenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl , 1,3-butadienyl, 1,4-butadienyl, hexa-1,3-dienyl, hexa-2,5-dienyl, pentadec-4,7-dienyl, Hexa-1,3,5-trienyl, pentadec-1,4,7-trienyl, etc.

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

The aforementioned polymerizable unsaturated bond-containing substituent may further have a substituent. The aforementioned so-called substituents are those that are substituted with at least one of the hydrogen atoms constituting the aforementioned polymerizable unsaturated bond-containing substituents. As said substituent, an alkyloxycarbonyl group, an alkylcarbonyloxy group, a halogen atom, etc. are mentioned, for example. In this case, examples of the alkyloxycarbonyl group, the alkylcarbonyloxy group, and the halogen atom include those mentioned above.

Among them, as the substituent having a polymerizable unsaturated bond, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms is preferred, and a substituted or unsubstituted alkenyl group having 2 carbon atoms is more preferred. ~10 alkenyl groups, more preferably substituted or unsubstituted alkenyl groups with 2~5 carbon atoms, particularly preferably vinyl, allyl, propenyl, isopropenyl, 1-propenyl, 1-propenyl, -butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, most preferably allyl, propenyl, isopropenyl, 1-propenyl.

As a preferable structure of the said ^Ar5 , for example, following formula (12-1)-(12-17) etc. are mentioned.

In the above-mentioned formulas (12-1) to (12-17), "*" represents the position of bonding to "-C(O)OAr ⁶ ". Furthermore, "-*" can also be bonded to any position of the aromatic ring.

Among these, formulas (12-1)~(12-11) are preferred, and formulas (12-1), (12-2), (12-6), (12-7), ( 12-9), more preferably formula (12-1), (12-2), (12-6), (12-7). In addition, from the viewpoint of high handleability and low viscosity of the aromatic ester compound (A) containing a polymerizable unsaturated bond, formulas (12-1) and (12-2) are preferable, and on the other hand, From the point of view that the obtained acid group-containing (meth)acrylate resin composition can form a hardened product with high photosensitivity, heat resistance and excellent dielectric properties, the formula (12-6), (12-7 ).

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

Ar ⁶ in the aforementioned chemical formula (a1) is a substituted or unsubstituted second aromatic ring group. It is also clear from the description of the aforementioned chemical formula (10) that one of the hydrogen atoms of the aromatic ring constituting the second aromatic ring group is substituted with "-OC(O)Ar ⁵ ".

唑、異

唑、噻唑、異噻唑、吡啶、嘧啶、嗒

、吡

、三

等之單環芳香族化合物中移除1個氫原子而成者；從萘、蒽、萉、菲、喹啉、異喹啉、喹唑啉、呔

、喋啶、香豆素、吲哚、苯并咪唑、苯并呋喃、吖啶等之稠環芳香族化合物中移除1個氫原子而成者等之從芳香族化合物中移除1個氫原子而成者。此外，亦可為組合複數個此等的芳香族化合物而成者，可列舉例如：從聯苯、聯萘、聯吡啶、聯噻吩、苯基吡啶、苯基噻吩、聯三苯、二苯基噻吩、聯四苯等之環集合芳香族化合物中移除1個氫原子而成者；從二苯基甲烷、二苯基乙烷、1,1-二苯基乙烷、2,2-二苯基丙烷、萘基苯基甲烷、三苯基甲烷、二萘基甲烷、二萘基丙烷、苯基吡啶基甲烷、茀、二苯基環戊烷等之藉由伸烷基鍵結之芳香族化合物中移除1個氫原子而成者等。此等之中，從可得到可形成具有高光感度、耐熱性及介電特性優異的硬化物的含酸基之(甲基)丙烯酸酯樹脂組成物來看，Ar⁶較佳為經取代或未經取代的苯環結構或萘環結構。 Examples of the above-mentioned second aromatic ring group include: benzene, furan, pyrrole, thiophene, imidazole, pyrazole,

azole, iso

Azole, Thiazole, Isothiazole, Pyridine, Pyrimidine, Pyridine

, pyri

,three

Monocyclic aromatic compounds such as those obtained by removing one hydrogen atom; from naphthalene, anthracene, anthracene, phenanthrene, quinoline, isoquinoline, quinazoline, and

, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine and other condensed ring aromatic compounds by removing one hydrogen atom from aromatic compounds, etc. made of atoms. In addition, a plurality of these aromatic compounds may be combined, for example: biphenyl, binaphthyl, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenyl One hydrogen atom is removed from the ring collection aromatic compounds such as thiophene and tetraphenyl; from diphenylmethane, diphenylethane, 1,1-diphenylethane, 2,2-bis Aromatic compounds bonded by alkylene groups such as phenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenylpyridylmethane, fennel, diphenylcyclopentane, etc. A compound obtained by removing one hydrogen atom, etc. Among these, Ar ⁶ is preferably substituted or unsubstituted from the viewpoint of obtaining an acid group-containing (meth)acrylate resin composition capable of forming a cured product having high photosensitivity, heat resistance, and excellent dielectric properties. Substituted benzene ring structure or naphthalene ring structure.

The aforementioned second aromatic ring group of Ar ⁶ may also have a substituent. At this time, the substituent of the so-called second aromatic ring group is the hydrogen atom of the aromatic ring constituting the aforementioned second aromatic ring group. At least one replacement. Examples of the "substituent of the second aromatic ring group" include an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, and a halogen atom. 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, the above-mentioned Ar ⁶ may have a substituent containing a polymerizable unsaturated bond such as the above-mentioned alkenyl group and alkynyl group. The aforementioned polymerizable unsaturated bond-containing substituents may be present alone or in combination of two or more.

As preferable structures of the aforementioned Ar ⁶ , the following formulas (13-1) to (13-17) can be cited.

In the above-mentioned formulas (13-1) to (13-17), "*" indicates the position of bonding to "-OC(O)Ar ⁵ ". In addition, "-*" may be bonded to any position of the aromatic ring.

Among these, formula (13-1)~(13-11) is preferred, formula (13-1), (13-6) and (13-9) are more preferred, and formula (13-9) is more preferred -1), (13-6).

In addition, at least one of the hydrogen atoms of the aromatic rings of the formulas (13-1) to (13-17) may be substituted with a polymerizable unsaturated bond-containing group.

According to an embodiment, it is more preferable that Ar ⁵ is the above-mentioned formula (12-1), (12-2), (12-6), (12-7), (12-9), and Ar ⁶ is the above-mentioned formula ( 13-1), (13-6), (13-9); further preferably Ar ⁵ is the above formula (12-1), (12-2), (12-6), (12-7), Ar ⁶ is the above formula (13-1), (13-6); particularly preferably, Ar ⁵ is the above formula (12-1), Ar ⁶ is the above formula (13-1), (13-6).

In the above chemical formulas (a1) and (a2), at least one of the aforementioned Ar ⁵ and the aforementioned Ar ⁶ has a substituent having a polymerizable unsaturated bond. In this case, only Ar ⁵ may have a substituent containing a polymerizable unsaturated bond, only Ar ⁶ may have a substituent containing a polymerizable unsaturated bond, or both Ar ⁵ and Ar ⁶ may have a substituent containing a polymerizable unsaturated bond. the substituent.

According to one embodiment, in the above chemical formula (a1), preferably at least one of Ar ⁶ has a substituent containing a polymerizable unsaturated bond, more preferably all Ar ⁶ have a substituent containing a polymerizable unsaturated bond , it is further preferred that Ar ⁵ has no substituents containing polymerizable unsaturated bonds, and all Ar ⁶ have substituents containing polymerizable unsaturated bonds. If a substituent containing a polymerizable unsaturated bond is present in Ar ⁶ , an acid group-containing (meth)acrylate resin composition capable of forming a hardened product with high photosensitivity, heat resistance, and a good balance between dielectric properties can be obtained. , so it is better.

In addition, according to an embodiment, in the above chemical formula (a2), preferably at least one of Ar ⁵ has a substituent containing a polymerizable unsaturated bond, more preferably all Ar ⁵ have a substituent containing a polymerizable unsaturated bond As for the substituent, it is more preferable that Ar ⁶ has no substituent containing a polymerizable unsaturated bond, and all of Ar ⁵ have a substituent containing a polymerizable unsaturated bond. If a substituent containing a polymerizable unsaturated bond exists in Ar ⁵ , an acid group-containing (meth)acrylate resin composition can be obtained that can form a cured product with high photosensitivity, heat resistance, and a good balance between dielectric properties. , so it is better.

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

In view of the above, as a better aspect of the polymerizable unsaturated bond-containing aromatic ester compound (A-1) represented by the aforementioned chemical formula (a1), the following chemical formula (a1-1) or (a1- 2) Compounds shown.

[where R ¹ is a substituent containing a polymerizable unsaturated bond. R ² are independently any one of alkyl, alkoxy, alkyloxycarbonyl, alkylcarbonyloxy and halogen atoms. h is an integer of 1 to 3, i is an integer of 1 or more independently, j is an integer of 0 or 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, the plural R ¹ or R ² may be the same as or different from each other. In formula (a1-2), R ¹ and R ² can also be substituted on any carbon atom on the naphthalene ring. 〕

In the aforementioned formula (a1-1), particularly preferred examples of R ¹ include the aforementioned allyl group, propenyl group, isopropenyl group, and 1-propenyl group. i is preferably 1 or 2, more preferably 1.

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

The specific structure of the aromatic ester compound (A-1) containing a polymerizable unsaturated bond shown in the above chemical formula (a1) is not particularly limited, but for example: the following chemical formula (14-1) ~ ( 14-44) and the like.

In above-mentioned chemical formula (14-1)～(14-44), be preferably chemical formula (14-1)～(14-39), be more preferably chemical formula (14-1)～(14-3), (14- 10)~(14-13), (14-18)~(14-39), more preferably chemical formula (14-1)~(14-3), (14-12), (14-13), (14-19)~(14-21), (14-23)~(14-26), (14-29), (14-30), (14-32)~(14-39), especially good It is chemical formula (14-1), (14-2), (14-12), (14-13), (14-26), (14-32), (14-37).

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

As a manufacturing method of the said polymerizable unsaturated bond containing aromatic ester compound (A-1), the method of making the said 2nd aromatic compound, the said 3rd aromatic compound etc. react, for example is mentioned.

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

Ar ⁵ in the aforementioned chemical formula (a2) is a substituted or unsubstituted first aromatic ring group. As described later, since n in the aforementioned chemical formula (a2) is an integer of 1 to 3, one of the hydrogen atoms constituting the aromatic ring of the first aromatic ring group becomes replaced by "-C(O)OAr ⁶ " instead.

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

Ar ⁶ in the aforementioned chemical formula (a2) is a substituted or unsubstituted second aromatic ring group. It is also clear from the description of the aforementioned chemical formula (11) that 1 to 3 of the hydrogen atoms constituting the aromatic ring of the second aromatic ring group are replaced by "-OC(O)Ar ⁵ ".

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

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

In view of the above, as a better aspect of the polymerizable unsaturated bond-containing aromatic ester compound (A-2) represented by the aforementioned chemical formula (a2), the following chemical formula (a2-1) or (a2- 2) Compounds shown.

[where R ¹ is a substituent containing a polymerizable unsaturated bond. R ² are independently any one of alkyl, alkoxy, alkyloxycarbonyl, alkylcarbonyloxy and halogen atoms. h is an integer of 1 to 3, i is an integer of 1 or more independently, j is an integer of 0 or 1 or more independently, and i+j is an integer of 5 or less. When i and j are integers of 2 or more, the plural R ¹ or R ² may be the same as or different from each other. 〕

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

In the aforementioned formula (a2-2), particularly preferred examples of R ¹ include the aforementioned allyl, propenyl, isopropenyl, and 1-propenyl groups. l is preferably 1 or 2, more preferably 1.

The specific structure of the aromatic ester compound (A-2) containing a polymerizable unsaturated bond shown in the above chemical formula (a2) is not particularly limited, but for example: the following chemical formula (15-1) ~ ( The compound shown in 15-3), etc.

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

Examples of the method for 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 aforementioned polymerizable unsaturated bond-containing aromatic ester compound (A) is not particularly limited, and can be produced by an appropriate known method.

For example, the ratio of the molar number of the carboxyl group of the aromatic compound having a carboxyl group to the molar number of the hydroxyl group of the aromatic compound having a phenolic hydroxyl group (carboxyl group etc./hydroxyl group) can be obtained from forming a product having high photosensitivity, From the viewpoint of the acid group-containing (meth)acrylate resin composition of a hardened product having excellent heat resistance and dielectric properties, 0.3 to 3 is preferable.

In addition, in the production of the aforementioned polymerizable unsaturated bond-containing aromatic ester compound (A), the reaction between the aforementioned aromatic compound having a phenolic hydroxyl group and the aromatic compound having a carboxyl group is not particularly specific in terms of reaction conditions. Appropriate and well-known methods can be used for restrictions.

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

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

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

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

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

As the acid group-containing (meth)acrylate resin (B), as long as it has an acid group and a (meth)acryl group, various resins can be used regardless of other specific structures, molecular weights, etc. .

As an acid group contained in the said acid group containing (meth)acrylate resin (B), a carboxyl group, a sulfonic acid group, a phosphoric acid group etc. are mentioned, for example. Among these, a carboxyl group is preferable from the viewpoint of expressing excellent alkali developability.

Examples of the acid group-containing (meth)acrylate resin (B) include: (1) an epoxy resin (B-1) having an acid group and a (meth)acryl group; Acrylamide resin (B-2) having acid group and (meth)acryl group, [3] Amidoimide resin (B-3) having acid group and (meth)acryl group, [4] Acrylic resin (B-4) having acid group and (meth)acryl group, [5] urethane resin (B-5) having acid group and (meth)acryl group, etc.

[1] The epoxy resin (B-1) which has an acid group and a (meth)acryl group is demonstrated.

Examples of the epoxy resin (B-1) having an acid group and a (meth)acryl group include epoxy resin (b1-1), unsaturated monocarboxylic acid (b1-2), and poly Carboxylic anhydride (b1-3) obtained as an essential reaction raw material, etc.

As said epoxy resin (b1-1), as long as it has a some epoxy group in resin, its specific structure will not be specifically limited.

Examples of the aforementioned epoxy resin (b1-1) include bisphenol-type epoxy resins, hydrogenated bisphenol-type epoxy resins, phenylene ether-type epoxy resins, naphthyl ether-type epoxy resins, and biphenyl-type epoxy resins. Oxygen resin, hydrogenated biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, bisphenol novolak type epoxy resin, naphthol novolak type epoxy resin Naphthol-phenol novolak type epoxy resin, naphthol-cresol novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin , dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl aralkyl type epoxy resin, fennel type epoxy resin, dibenzopyran type epoxy resin, dihydroxybenzene type epoxy resin, three Hydroxybenzene type epoxy resin, etc.

The above-mentioned unsaturated monocarboxylic acid (b1-2) refers to a compound having a (meth)acryl group and a carboxyl group in one molecule, and examples thereof include acrylic acid, methacrylic acid, and the like. Furthermore, esterified products, acid halides, acid anhydrides, etc. of the aforementioned unsaturated monocarboxylic acid (b1-2) can also be used. These unsaturated monocarboxylic acids (b1-2) may be used individually or in combination of 2 or more types.

啉酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸環己酯等之其他的(甲基)丙烯酸酯化合物等。 Examples of esterified products of the unsaturated monocarboxylic acid (b1-2) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and (meth)acrylic acid. Isopropyl ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-ethyl (meth)acrylate Alkyl (meth)acrylate compounds such as hexyl (meth)acrylate; hydroxyl-containing (meth)acrylic acid such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate Ester compounds; nitrogen-containing (meth)acrylate compounds such as dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate; glycidyl (meth)acrylate , Tetrahydrofuryl (meth)acrylate, (meth)acrylic acid

Other (meth)acrylate compounds such as phenyl ester, isocamphoryl (meth)acrylate, and cyclohexyl (meth)acrylate.

As an acid halide of the said unsaturated monocarboxylic acid (b1-2), (meth)acryloyl chloride etc. are mentioned, for example.

As an acid anhydride of the said unsaturated monocarboxylic acid (b1-2), (meth)acrylic anhydride etc. are mentioned, for example.

As long as the above-mentioned polycarboxylic acid anhydride (b1-3) is an acid anhydride of a compound having two or more carboxyl groups in one molecule, any one can be used. Examples of the polycarboxylic acid anhydride include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, and fumaric acid. , citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butane tetracarboxylic 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-dioxo Tetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, phthalic acid, trimellitic acid, pyromelite acid, naphthalene dicarboxylic acid, naphthalenetricarboxylic acid, naphthalene tetracarboxylic acid , biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ketone tetracarboxylic acid, etc., anhydrides of dicarboxylic acid compounds, etc.

The method for producing the aforementioned epoxy resin (B-1) having an acid group and a (meth)acryl group, as long as the aforementioned epoxy resin (b1-1), the aforementioned unsaturated monocarboxylic acid (b1-2), And said polycarboxylic acid anhydride (b1-3) which is an essential reaction raw material is not specifically limited, It can manufacture by any method. For example, it may be produced by a method of reacting all the reaction raw materials together, or may be produced by a method of sequentially reacting the reaction raw materials. Among them, it is preferable to react the epoxy resin (b1-1) with the unsaturated monocarboxylic acid (b1-2) first, and then react the polycarboxylic acid anhydride (b1-3) in order to control the reaction easily. method of response. This reaction can be carried out by the following method, for example: in the presence of an esterification reaction catalyst, make epoxy resin (b1-1) and unsaturated monocarboxylic acid (b1-2) in the temperature range of 100 ~ 150 ℃ After the lower reaction, the method of adding polycarboxylic anhydride (b1-3) to the reaction system and reacting it at a temperature range of 80 to 120°C, etc.

The reaction ratio of the aforementioned epoxy resin (b1-1) and unsaturated monocarboxylic acid (b1-2) is preferably: relative to 1 mole of epoxy groups in the epoxy resin (b1-1), with 0.9~ Use the unsaturated monocarboxylic acid (b1-2) in the range of 1.1 mol. In addition, the reaction ratio of the aforementioned polycarboxylic acid anhydride (b1-3) is preferably used in a range of 0.2 to 1.0 moles relative to 1 mole of epoxy groups in the epoxy resin (b1-1).

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

It is preferable that the addition amount of the said reaction catalyst is the range of 0.001-5 mass parts with respect to the total 100 mass parts of reaction raw materials.

The reaction of the aforementioned epoxy resin (b1-1), the aforementioned unsaturated monocarboxylic acid (b1-2), and the aforementioned polycarboxylic acid anhydride (b1-3) can be performed in an organic solvent as needed.

Examples of the aforementioned organic solvents 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 esters, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; carbitol , Cellusu, methanol, isopropanol, butanol, propylene glycol monomethyl ether and other alcohol solvents; Glycol ether solvents such as acid esters; methoxy propanol, cyclohexanone, methyl celuso, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, etc. These organic solvents may be used alone or in combination of two or more. In addition, from the standpoint of good reaction efficiency, the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials.

The acid value of the aforementioned epoxy resin (B-1) with acid groups and (meth)acryl groups can be obtained from the acid group-containing ( In view of the meth)acrylate resin composition, it is preferably in the range of 30-150 mgKOH/g, more preferably in the range of 40-120 mgKOH/g. Furthermore, the acid value of the epoxy resin (B-1) having an acid group and a (meth)acryl group in the present invention is a value measured by the neutralization titration method of JIS K 0070 (1992).

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

Examples of the acrylamide resin (B-2) having an acid group and a (meth)acryl group include: a resin (b2-1) containing a phenolic hydroxyl group, a cyclic carbonate compound (b2-2a ) or 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) Those obtained as necessary reaction raw materials, etc.

The aforementioned so-called phenolic hydroxyl-containing resin (b2-1) refers to a resin having two or more phenolic hydroxyl groups in the molecule, such as: aromatic polyhydroxy compounds, one or more than two kinds of resins in the molecule A novolak-type phenolic resin with a compound having a phenolic hydroxyl group as a reaction raw material, represented by any one of the compound having a phenolic hydroxyl group and the following structural formulas (x-1) to (x-5) The compound (x) is a reaction product and the like as an essential reaction raw material.

(h in the formula is 0 or 1. ^R1 is any one of aliphatic hydrocarbon group, alkoxyl group, halogen atom, aryl group, aryloxyl group and aralkyl group independently, i is 0 or 1~4 Integer. Z is any one of vinyl group, halomethyl group, hydroxymethyl group, and alkyloxymethyl group. Y is any one of alkylene group with 1 to 4 carbon atoms, oxygen atom, sulfur atom, or carbonyl group .j is an integer from 1 to 4.)

Examples of the above-mentioned aromatic polyhydroxy compound include dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxyanthracene, trihydroxyanthracene, tetrahydroxyanthracene, In addition to phenol, tetrahydroxybiphenyl, bisphenol, etc., there are also compounds having one or more substituents on their aromatic nucleus. In addition, examples of substituents on the aromatic nucleus include aliphatic hydrocarbon groups such as methyl, ethyl, vinyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, and nonyl. ; alkoxy groups such as methoxy, ethoxy, propyloxy, butoxy, etc.; halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, etc.; phenyl, naphthyl, anthracenyl, and others Aryl groups substituted by the aforementioned aliphatic hydrocarbon group, the aforementioned alkoxy group, the aforementioned halogen atom, etc. on the aromatic nucleus; phenyloxy group, naphthyloxy group, and the aforementioned aliphatic hydrocarbon group, the aforementioned alkoxy group aryloxy group substituted by the above-mentioned halogen atom, etc.; phenylmethyl, phenylethyl, naphthylmethyl, naphthylethyl, and the above-mentioned aliphatic hydrocarbon group, the above-mentioned alkoxy group, an aralkyl group substituted with the aforementioned halogen atom, etc. These aromatic polyhydroxy compounds may be used alone or in combination of two or more. Among them, halogen-free compounds are preferable from the viewpoint that an acid group-containing (meth)acrylate resin having high insulation reliability can be obtained.

Examples of the above-mentioned novolak-type phenolic resins include those obtained by reacting one or two or more compounds having one phenolic hydroxyl group in the molecule with an aldehyde compound under an acidic catalyst.

As the aforementioned compound having one phenolic hydroxyl group in the molecule, any compound may be used as long as it is an aromatic compound having one hydroxyl group on the aromatic nucleus. Phenol compounds with three substituents, naphthol or naphthol compounds with one or more substituents on the aromatic nucleus of naphthol, anthracenol or anthracenol compounds with one or more substituents on the aromatic nucleus of anthracenol wait. Also, examples of substituents on the aromatic nucleus include aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, aryl groups, aryloxy groups, aralkyl groups, and the specific examples of each are as described above. These compounds having one phenolic hydroxyl group may be used alone or in combination of two or more.

Examples of the aforementioned aldehyde compound include formaldehyde; alkyl aldehydes such as acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, and hexanal; salixaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2-hydroxy-4-methylbenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde and other hydroxybenzaldehyde; 2-hydroxy-3-methoxybenzaldehyde, 3-hydroxy- 4-methoxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde, etc. Benzaldehyde with alkoxy; alkoxybenzaldehyde such as methoxybenzaldehyde and ethoxybenzaldehyde; 1-hydroxy-2-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 6-hydroxy -Hydroxynaphthaldehyde such as 2-naphthaldehyde; halogenated benzaldehyde such as bromobenzaldehyde, etc.

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

As the reaction product of the above-mentioned compound having one phenolic hydroxyl group and the above-mentioned compound (x) as the necessary reaction raw materials, for example: under the condition of temperature of about 80~200℃ under the condition of acidic catalyst, It can be obtained by heating and stirring the compound having one phenolic hydroxyl group in the molecule and the compound (x). The reaction ratio between the aforementioned compound having one phenolic hydroxyl group in the molecule and the aforementioned compound (x) is preferably such that the aforementioned compound having one phenolic hydroxyl group in the molecule becomes The ratio of 0.5~5 moles.

The above-mentioned acid catalyst system is the same as that described above.

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

As said cyclic ether compound (b2-2b), ethylene oxide, propylene oxide, tetrahydrofuran, etc. are mentioned, for example. These cyclic ether compounds may be used alone or in combination of two or more. In addition, among these, ethylene oxide is preferable in terms of obtaining an acid group-containing (meth)acrylate resin composition capable of forming a cured product having high photosensitivity, heat resistance, and excellent dielectric properties. , or propylene oxide.

As said unsaturated monocarboxylic acid (b2-3a), the thing similar to the said unsaturated monocarboxylic acid (b1-2) 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-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide Amines, N-butoxyethyl(meth)acrylamide, etc. Among them, N-methoxymethyl (meth)acrylate resin composition is preferable in terms of obtaining an acid group-containing (meth)acrylate resin composition capable of forming a hardened product having high light sensitivity and excellent heat resistance. ) acrylamide. In addition, these N-alkoxyalkyl (meth)acrylamide compounds may be used alone or in combination of two or more.

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

In the case of using the above-mentioned N-alkoxyalkyl (meth)acrylamide compound (b2-3b), one of the acid group-containing compounds that can form a hardened product having high photosensitivity, heat resistance, and dielectric properties can be obtained. In view of the (meth)acrylate resin composition, the equivalent ratio [(b2-3b)/(b2-4))] to the aforementioned polycarboxylic acid anhydride (b2-4) is preferably in the range of 0.2 to 7, more preferably It is in the range of 0.25~6.7.

The production method of the aforementioned acrylamide resin (B-2) having an acid group and a (meth)acryl group is not particularly limited, and can be produced by any method. For example, it may be produced by a method of reacting all the reaction raw materials together, or may be produced by a method of sequentially reacting the reaction raw materials. Among them, from the viewpoint of easy control of the reaction, it is preferable to make the phenolic hydroxyl group-containing resin (b2-1), cyclic carbonate compound (b2-2a) or cyclic ether compound (b2-2b) Reaction, then, after making unsaturated monocarboxylic acid (b2-3a) and/or N-alkoxyalkyl (meth)acrylamide compound (b2-3b) react, make polycarboxylic acid anhydride (b2-4) method of response. The reaction system can be obtained by, for example: in the presence of an alkaline catalyst, in the temperature range of 100 to 200 ° C, the aforementioned phenolic hydroxyl-containing resin (b2-1) and the aforementioned cyclic carbonate compound (b2-2a ) or the aforementioned cyclic ether compound (b2-2b) reacted, in the presence of an acidic catalyst, in the temperature range of 80 ~ 140 ° C, the unsaturated monocarboxylic acid (b2-3a) and / or N-alkoxy Alkyl (meth)acrylamide compound (b2-3b) is reacted, and then polycarboxylic acid anhydride (b2-4) is added, and the method of making it react in the temperature range of 80-140 degreeC etc. is performed.

啉、吡啶、1,8-二吖雙環[5.4.0]十一烯-7(DBU)、1,5-二吖雙環[4.3.0]壬烯-5(DBN)、1,4-二吖雙環[2.2.2]辛烷(DABCO)、三正丁胺或者二甲基苄基胺、丁胺、辛胺、單乙醇胺、二乙醇胺、三乙醇胺、咪唑、1-甲基咪唑、2,4-二甲基咪唑、1,4-二乙基咪唑、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-(N-苯基) 胺基丙基三甲氧基矽烷、3-(2-胺基乙基)胺基丙基三甲氧基矽烷、3-(2-胺基乙基)胺基丙基甲基二甲氧基矽烷、四甲基氫氧化銨等之胺化合物類；三辛基甲基氯化銨、三辛基甲基乙酸銨等之四級銨鹽類；三甲基膦、三丁基膦、三苯基膦等之膦類；四甲基氯化鏻、四乙基氯化鏻、四丙基氯化鏻、四丁基氯化鏻、四丁基溴化鏻、三甲基(2-羥丙基)氯化鏻、三苯基氯化鏻、苄基氯化鏻等之鏻鹽類；二月桂酸二丁基錫、三月桂酸辛基錫、二乙酸辛基錫、二乙酸二辛基錫、二新癸酸二新辛基錫、二乙酸二丁基錫、辛酸錫、1,1,3,3-四丁基-1,3-十二醯基二錫氧烷(1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane)等之有機錫化合物；辛酸鋅、辛酸鉍等之有機金屬化合物；辛酸錫等之無機錫化合物；無機金屬化合物等。此等之鹼性觸媒，可單獨使用，亦可併用2種以上。 As the above-mentioned basic catalyst, for example, N-methyl

Pyridine, 1,8-diacribicyclo[5.4.0]undecene-7(DBU), 1,5-diacribicyclo[4.3.0]nonene-5(DBN), 1,4-di Acrylbicyclo[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)aminopropyl Trimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, tetramethyl Amine compounds such as ammonium hydroxide; quaternary ammonium salts such as trioctylmethylammonium chloride and trioctylmethylammonium acetate; phosphines such as trimethylphosphine, tributylphosphine, and triphenylphosphine Class; tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxypropyl)phosphonium chloride , triphenylphosphonium chloride, benzylphosphonium chloride and other phosphonium salts; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dineodecanoate Octyltin, dibutyltin diacetate, tin octoate, 1,1,3,3-tetrabutyl-1,3-dodecyldistannoxane (1,1,3,3-tetrabutyl-1,3 Organotin compounds such as -dodecanoyldistannoxane); organometallic compounds such as zinc octoate and bismuth octoate; inorganic tin compounds such as tin octoate; inorganic metal compounds, etc. These alkaline catalysts may be used alone or in combination of two or more.

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

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

As the above-mentioned organic solvent, the same ones as those mentioned above can be used, and the above-mentioned organic solvents may be used alone or in combination of two or more kinds.

From the standpoint of good reaction efficiency, the amount of the organic solvent used is preferably in the range of 10 to 500 parts by mass relative to the total of 100 parts by mass of the reaction raw materials.

The specific structure of the aforementioned acrylamide resin (B-2) having an acid group and a (meth)acryl group is not particularly limited, as long as the resin (b2-1) containing a phenolic hydroxyl group, a cyclic carbonate Compound (b2-2a) or 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 the necessary raw materials for the reaction, and those that have acid groups and (meth)acryl groups in the resin are sufficient, but as the above-mentioned obtained acid groups and (meth)acryl groups The acrylamide resin (B-2) of the acyl group includes, for example: a structural part (I) represented by the following structural formula (a-1) and a structural part represented by the following structural formula (a-2) (II) Those having a resin structure as a repeating structural unit have a structural part (III) represented by the following structural formula (a-3) and a structural part (IV) represented by the following structural formula (a-4) as repeating The resin structure of the structural unit.

[wherein ^R2 is each independently a hydrogen atom or a hydrocarbon group with 1 to 4 carbon atoms. R ³ are each independently a hydrogen atom, a hydrocarbon group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, or a halogen atom, and n is 1 or 2 independently. R ⁴ are each independently a methylene group or a structural site represented by any one 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 with 1 to 20 carbon atoms. In addition, R ⁵ and R ⁶ may also link 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 part shown in the aforementioned ^R3 , or the structural part (I) shown in the structural formula (a-1) or the structural part (II) shown in the structural formula (a-2) through the mark * The joint point of the ^R4 link. ]

[wherein ^R2 is each independently a hydrogen atom or a hydrocarbon group with 1 to 4 carbon atoms. R ³ are each independently a hydrogen atom, a hydrocarbon group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, or a halogen atom, and n is 1 or 2 independently. R ⁴ are each independently a methylene group or a structural site represented by any one 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 with 1 to 20 carbon atoms. In addition, R ⁵ and R ⁶ may also link 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 part shown in the aforementioned ^R3 , or the structural part (III) shown in the structural formula (a-3) or the structural part (IV) shown in the structural formula (a-4) through the marked * sign The joint point of the ^R4 link. ]

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

(In the formula, R ¹¹ is each independently a hydrogen atom or a hydrocarbon group with 1 to 4 carbon atoms. R ¹² and R ¹³ are each independently a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms. In addition, R ¹² and R ¹³ are also Can be connected to form a saturated or unsaturated ring. R ¹⁴ is a hydrocarbon group with 1 to 12 carbon atoms. R ¹⁵ is a hydrogen atom or a methyl group.)

The acid value of the aforementioned acrylamide resin (B-2) having an acid group and a (meth)acryl group can be obtained from an acid group-containing resin that can form a hardened product with high photosensitivity, heat resistance, and excellent dielectric properties. In view of the (meth)acrylate resin composition, it is preferably in the range of 30 to 150 mgKOH/g, more preferably in the range of 40 to 120 mgKOH/g. Furthermore, in the present invention, the acid value of the above-mentioned acid group-containing (meth)acrylate resin is a value measured based on JIS K 0070 (1992) neutralization titration method.

Next, [3] the amidoimide resin (B-3) which has an acid group and a (meth)acryloyl group is demonstrated.

Examples of the amidoimide resin (B-3) having an acid group and a (meth)acryl group include, for example, an amidoimide resin (b3-1) having an acid group or an acid anhydride group, Those obtained with a hydroxyl-containing (meth)acrylate compound (b3-2) as an essential reaction raw material, etc.

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

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

Examples of the polyisocyanate compound include butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene Aliphatic diisocyanate compounds such as diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate; toluene diisocyanate Isocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanate-3,3'-diisocyanate Aromatic diisocyanate compounds such as methyl biphenyl and di-o-toluidine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (i-1); these isocyanates Modified uric acid, modified biuret, modified allophanate, etc. In addition, these polyisocyanate compounds may be used individually, and may use 2 or more types together.

[In the formula, R ¹ is each independently a hydrogen atom or any one of a hydrocarbon group with 1 to 6 carbon atoms. R ² is any one of the binding points independently connected to an alkyl group with 1 to 4 carbon atoms or to the structural site represented by the structural formula (i-1) via a methylene group marked with an asterisk. l is 0 or an integer of 1 to 3, m is an integer of 1 or more. ]

In addition, as the aforementioned polyisocyanate compound, an alicyclic diisocyanate compound or a modified product thereof, an aliphatic diisocyanate compound, or an aliphatic The diisocyanate compound or its modified form is more preferably an alicyclic diisocyanate or its isocyanuric acid modified form, an aliphatic diisocyanate or its isocyanuric acid modified form.

In addition, in the total mass of the aforementioned polyisocyanate compounds, 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, more preferably More than 90% by mass.

Furthermore, when using an alicyclic diisocyanate compound or a modified product thereof, and an aliphatic diisocyanate compound or a modified product thereof, the mass ratio between the two is preferably in the range of 30/70 to 70/30.

As said polycarboxylic acid or its anhydride, what is necessary is just a compound or its anhydride which has plural carboxyl groups in a molecular structure, and various compounds can be used regardless of a specific structure. Furthermore, since the aforementioned amidoimide resin (b3-1) has both amido groups and amido groups, it is necessary to have both carboxyl groups and acid anhydride groups in the system, but in the present invention, molecular Among the compounds having both a carboxyl group and an acid anhydride group, a compound having a carboxyl group and a compound having an acid anhydride group may be used in combination.

As said polycarboxylic acid or its anhydride, an aliphatic polycarboxylic compound or its anhydride, an alicyclic polycarboxylic compound or its anhydride, an aromatic polycarboxylic compound or its anhydride etc. are mentioned, for example.

As the said aliphatic polycarboxylic acid compound or its anhydride, an aliphatic hydrocarbon group may be any of a linear type and a branched type, and may have an unsaturated bond in a structure.

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

As the aforementioned alicyclic polycarboxylic acid compound or its anhydride, the present invention refers to the carboxyl group or acid anhydride group bonded to the alicyclic structure as the alicyclic polycarboxylic acid compound or its anhydride, regardless of whether there are aromatic compounds in other structural parts. ring. Examples of the alicyclic polycarboxylic acid compound or its anhydride include: tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2. 1] Heptane-2,3-dicarboxylic acid, Methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2 , 3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, and their anhydrides.

Examples of the above-mentioned aromatic polycarboxylic acid compound or its anhydride include phthalic acid, trimellitic acid, pyromelite, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid , biphenyl tetracarboxylic acid, diphenyl ketone tetracarboxylic acid, etc.

Among them, the above-mentioned alicyclic polycarboxylate resin composition is preferable in terms of obtaining an acid group-containing (meth)acrylate resin composition capable of forming a hardened product having high photosensitivity, heat resistance, and dielectric properties. an acid compound or an acid anhydride thereof, or the aforementioned aromatic polycarboxylic acid compound or an acid anhydride thereof. In addition, from the viewpoint of efficient production of the aforementioned amidoimide resin (b3-1), it is preferable to use triformic anhydride having both carboxyl and acid anhydride groups in its molecular structure, and it is particularly preferable to use cyclohexanetrimethanoic anhydride. anhydride or trimellitic anhydride. Furthermore, the ratio of the total amount of alicyclic triformic anhydride to aromatic triformic anhydride is preferably at least 70% by mass, more preferably at least 90% by mass, based on the total mass of the polycarboxylic acid or its anhydride.

When the above-mentioned amidoimide resin (b3-1) is a reaction raw material of the above-mentioned polyisocyanate compound and the above-mentioned polycarboxylic acid or its anhydride, depending on the desired resin performance, etc., it may be used in combination with other materials. Reaction raw material. In this case, from the point of view that the effects achieved by the present invention can be brought into full play, with respect to the total mass of reaction raw materials of the amidoimide resin (b3-1), the ratio of the aforementioned polyisocyanate compound to the aforementioned polycarboxylic acid or its anhydride The ratio of the total mass is preferably at least 90% by mass, more preferably at least 95% by mass.

The amidoimide resin (b3-1) is not particularly limited when a polyisocyanate compound, a polycarboxylic acid, or an acid anhydride thereof is used as a reaction raw material, and can be produced by any method. For example, it can be produced by the same method as general amidoimide resins. Specifically, 0.5 to 2.0 moles of polycarboxylic acid or its anhydride are used with respect to 1 mole of isocyanate groups in the polyisocyanate compound, and the reaction is carried out by stirring and mixing at a temperature of about 120 to 180°C. Methods.

The reaction of the aforementioned polyisocyanate compound and polycarboxylic acid or its anhydride can be performed in the presence of a basic catalyst as needed. In addition, this reaction can be carried out in an organic solvent as needed.

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

As the above-mentioned organic solvent, the same ones as those mentioned above can be used, and the above-mentioned organic solvents may be used alone or in combination of two or more kinds.

It is preferable that the usage-amount of the said organic solvent is the range of 10-500 mass parts with respect to the total 100 mass parts of reaction raw materials from a viewpoint that reaction efficiency becomes favorable.

As the hydroxyl group-containing (meth)acrylate compound (b3-2), other specific structures are not particularly limited as long as it has a hydroxyl group and a (meth)acryl group in the molecular structure, and various compounds can be used. various compounds. Examples include: hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane di(meth)acrylate, neopentylthritol tri(meth)acrylate, di-tri Hydroxy (meth)acrylate compounds such as methylolpropane tri(meth)acrylate and dipentylitol penta(meth)acrylate; in the molecular structure of the aforementioned various hydroxy(meth)acrylate compounds Modified (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene chains, etc. ; Introducing (poly)lactone structure lactone modifiers into the molecular structure of the above-mentioned various hydroxyl (meth)acrylate compounds. Among these, the molecular weight is preferably 1,000 or less in view of obtaining an acid group-containing (meth)acrylate resin composition capable of forming a cured product having high photosensitivity, heat resistance, and excellent dielectric properties. Furthermore, when the hydroxyl group-containing (meth)acrylate compound (b3-2) is the aforementioned oxyalkylene-modified body or lactone-modified body, 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.

In addition, as the aforementioned amidoimide resin (B-3) having an acid group and a (meth)acryloyl group, in addition to the aforementioned amidoimide resin (b3-1) and hydroxyl-containing ( In addition to the meth)acrylate compound (b3-2), a (meth)acryl group-containing epoxy compound (b3-3) can also be used together as a reaction raw material. Also, as the aforementioned amidoimide resin (B-3) having an acid group and a (meth)acryloyl group, in addition to the aforementioned amidoimide resin (b3-1) and hydroxyl-containing ( In addition to the meth)acrylate compound (b3-2), a (meth)acryl group-containing epoxy compound (b3-3) and polycarboxylic acid anhydride (b3-4) can also be used together as a reaction raw material.

The above-mentioned (meth)acryl group-containing epoxy compound (b3-3), as long as it has a (meth)acryl group and an epoxy group in the molecular structure, other specific structures are not particularly limited, and can be used A wide variety of compounds. Examples include glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidylether, epoxy ring (meth)acrylate Glycidyl group-containing (meth)acrylate monomers such as hexyl methyl ester; dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, Mono(meth)acrylates of diglycidyl ether compounds such as phenol diglycidyl ether, etc. Among them, the acid group-containing (meth)acrylate resin composition that can form a hardened product having high photosensitivity, heat resistance, and dielectric properties is preferably a glycidyl group-containing one. (meth)acrylate monomer. Furthermore, its molecular weight is preferably 500 or less. In addition, the proportion of the aforementioned glycidyl group-containing (meth)acrylate monomer in the total mass of the aforementioned (meth)acryl group-containing epoxy compound (b3-3) is preferably 70% by mass or more, More preferably, it is 90 mass % or more.

As said polycarboxylic acid anhydride (b3-4), what was exemplified as said polycarboxylic acid anhydride (b1-3) can be used, and said polycarboxylic acid (b3-4) may be used individually or in combination of 2 or more types.

The aforementioned amidoimide resins (B-3) with acid groups and (meth)acryl groups, depending on the desired resin properties, etc., except for the aforementioned amidoimide resins (b3) with acid groups or acid anhydride groups -1), in addition to the aforementioned hydroxyl group-containing (meth)acrylate compound (b3-2), (meth)acryl group-containing epoxy compound (b3-3) and polycarboxylic acid anhydride (b3-4), Other reaction raw materials may be used in combination. In this case, the ratio of the total mass of the aforementioned (b3-1) to (b3-4) components in the total mass of the reaction raw materials of the acid group-containing (meth)acrylate resin (B-3) is preferably 80% Mass % or more, more preferably 90 mass % or more.

The method for producing the amidoimide resin (B-3) having an acid group and a (meth)acryloyl group is not particularly limited, and may be produced by any method. For example: it can be produced by reacting all the reaction raw materials including the aforementioned amidoimide resin (b3-1) and the aforementioned hydroxyl group-containing (meth)acrylate compound (b3-2), or by reacting The raw materials are produced by reacting sequentially.

The reaction of the aforementioned amidoimide resin (b3-1) and the aforementioned hydroxyl-containing (meth)acrylate compound (b3-2) is mainly to make the acid in the aforementioned amidoimide resin (b3-1) group and/or acid anhydride group 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) has particularly excellent reactivity with an acid anhydride group, the amidoimide resin (b3-1) preferably has an acid anhydride group as described above. Furthermore, the content of the acid anhydride group in the aforementioned amidoimide resin (b3-1) is the difference between the two aforementioned acid value measurements, which can be obtained from the acid value under the condition of ring-opening the acid anhydride group and the condition without using the acid anhydride group. Calculate the difference in acid value under the conditions of ring opening of the acid anhydride group.

The ratio of the reaction between the aforementioned amidoimide resin (b3-1) and the aforementioned hydroxyl group-containing (meth)acrylate compound (b3-2), the aforementioned amidoimide resin (b3-1) has an acid group and In the case of an acid anhydride group, and when the amidoimide resin (b3-1) has an acid anhydride group, the above-mentioned It is preferable to use it in the range of 0.9-1.1 as the number of moles of the hydroxyl group which the hydroxyl group-containing (meth)acrylate compound (b3-2) has. In addition, when the aforementioned amidoimide resin (b3-1) has an acid group, the aforementioned hydroxyl group-containing (formyl The number of moles of the hydroxyl groups which the acrylate compound (b3-2) has is preferably used in the range of 0.01 to 1.0.

For the reaction of the aforementioned amidoimide resin (b3-1) and the aforementioned hydroxyl group-containing (meth)acrylate compound (b3-2), an alkaline catalyst or an acidic catalyst may be used as needed. Among them, when the aforementioned amidoimide resin (b3-1) has an acid group and an acid anhydride group, and when the aforementioned amidoimide resin (b3-1) has an acid anhydride group, it is preferable to use a basic As a catalyst, when the said amide imide resin (b3-1) has an acid group, it is preferable to use an acidic catalyst.

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

As the said acidic catalyst, what was illustrated as the said acidic catalyst can be used, and the said acidic catalyst may be used individually, and may use 2 or more types together.

The addition amount of the said basic catalyst or the said acidic catalyst is preferably used in the range of 0.001-5 mass parts with respect to 100 mass parts of total mass of reaction raw materials.

In addition, the reaction between the aforementioned amidoimide resin (b3-1) and the aforementioned hydroxyl-containing (meth)acrylate compound (b3-2) can be carried out at about 80~140°C in the presence of an appropriate catalyst. Heating and stirring under temperature conditions are carried out.

This reaction can also be performed in an organic solvent as needed, and as the above-mentioned organic solvent, the same ones as the above-mentioned organic solvents can be used, and the above-mentioned organic solvents can be used alone or in combination of two or more. Furthermore, when the manufacture of the aforementioned amidoimide resin (b3-1) is carried out continuously, the organic solvent used in the manufacture of the aforementioned amidoimide resin (b3-1) can also be directly continued reaction.

The aforementioned amidoimide resins (B-3) having acid groups and (meth)acryloyl groups, except the aforementioned amidoimide resins (b3-1) and the aforementioned hydroxyl-containing (meth)acrylates In addition to compound (b3-2), also use (meth)acryl group-containing epoxy compound (b3-3) under the situation of reaction raw material, also can make the above-mentioned amidoimide resin (b3-1) , the aforementioned hydroxyl-containing (meth)acrylate compound (b3-2) and the aforementioned (meth)acryl-containing epoxy compound (b3-3) are produced by reacting all the reaction raw materials together. It is produced by reacting the reaction raw materials sequentially. Among them, it is preferable to use the aforementioned (meth)acryl group-containing epoxy compound (b3-3) and the aforementioned amidoimide resin (b3-1) from the viewpoint of easy reaction control. It is produced by a method of reacting the product obtained by reacting the above-mentioned hydroxyl group-containing (meth)acrylate compound (b3-2) (hereinafter, sometimes referred to as "product (1)").

The reaction between the aforementioned product (1) and the aforementioned (meth)acryl-containing epoxy compound (b3-3) is mainly to make the acid group in the aforementioned product (1) and the aforementioned (meth)acryl-containing The base epoxy compound (b3-3) reacts. With respect to 1 mole of acid groups that the aforementioned product (1) has, its reaction ratio, the number of moles of epoxy groups that the aforementioned (meth)acryl-containing epoxy compound (b3-3) has is relatively It is better to use it in the range of 0.05~1.1. This reaction can be carried out, for example, in the presence of an appropriate alkaline catalyst, under heating and stirring at a temperature of about 90 to 140°C. In the case where the reaction between the aforementioned amidoimide resin (b3-1) and the aforementioned hydroxyl-containing (meth)acrylate compound (b3-2) proceeds continuously, the alkaline catalyst may not be added, but may be appropriately added . In addition, this reaction can also be performed in an organic solvent as needed. Furthermore, the above-mentioned basic catalyst and the above-mentioned organic solvent can use the same ones as the above-mentioned basic catalyst and organic solvent, and they can be used alone or in combination of two or more.

The aforementioned amidoimide resins (B-3) having acid groups and (meth)acryloyl groups, except the aforementioned amidoimide resins (b3-1) and the aforementioned hydroxyl-containing (meth)acrylates In addition to compound (b3-2), also use (meth)acryl group-containing epoxy compound (b3-3) and polycarboxylic acid anhydride (b3-4) as the situation of reaction raw material, also can make the above-mentioned amide Imide resin (b3-1), the aforementioned hydroxyl group-containing (meth)acrylate compound (b3-2), the aforementioned (meth)acryl group-containing epoxy compound (b3-3), and polycarboxylic acid anhydride (b3-4) can be produced by reacting all the reaction raw materials together, or by reacting the reaction raw materials sequentially. Among these, it is preferable to obtain by reacting the above-mentioned amidoimide resin (b3-1) and the above-mentioned hydroxyl group-containing (meth)acrylate compound (b3-2) from the viewpoint that the reaction control is easy. The product (1) is a product obtained by reacting the aforementioned (meth)acryl group-containing epoxy compound (b3-3) (hereinafter, sometimes referred to as "product (2)"), It can be produced by reacting with the aforementioned polycarboxylic acid anhydride (b3-4).

The reaction between the aforementioned product (2) and the aforementioned polycarboxylic acid anhydride (b3-4) is mainly to make the hydroxyl group in the aforementioned product (2) react with the aforementioned polybasic acid anhydride. At this time, in the aforementioned product (2), the reaction ratio between the aforementioned product (1) and the aforementioned (meth)acryl group-containing epoxy compound (b3-3) is greater than that of the aforementioned product (1). 1 mole of acid groups, the number of moles of epoxy groups contained in the (meth)acryl group-containing epoxy compound (b3-3) is preferably used in the range of 0.1 to 1.2, more preferably Become 0.2~1.1. Here, in the said product (2), for example, the hydroxyl group etc. which generate|occur|produce by ring-opening of the epoxy group in the said (meth)acryl group containing epoxy compound (b3-3) exist. The reaction ratio of the aforementioned polycarboxylic acid anhydride (b3-4) is preferably adjusted to 50-120 mgKOH by adjusting the acid value of the produced imide resin (B-3) with acid groups and (meth)acryl groups. /g or so. This reaction can be carried out, for example, in the presence of an appropriate alkaline catalyst, under heating and stirring at a temperature of about 80 to 140°C. When the reaction between the aforementioned product (1) and the aforementioned (meth)acryl group-containing epoxy compound (b3-3) proceeds continuously, the basic catalyst may not be added, but may be appropriately added. In addition, this reaction can also be performed in an organic solvent as needed. Furthermore, the above-mentioned basic catalyst and the above-mentioned organic solvent can use the same ones as the above-mentioned basic catalyst and organic solvent, and they can be used alone or in combination of two or more.

The acid value of the aforementioned amidoimide resin (B-3) having an acid group and a (meth)acryl group can be obtained from an acid-containing resin that can form a hardened product with high photosensitivity, heat resistance, and excellent dielectric properties. Based on the (meth)acrylate resin composition, it is preferably in the range of 30-150 mgKOH/g, more preferably in the range of 40-120 mgKOH/g. Furthermore, the acid value of the amidoimide resin (B-3) having acid groups and (meth)acryloyl groups in the present invention is the value measured by the neutralization titration method of JIS K 0070 (1992).

Next, [4] the acrylic resin (B-4) which has an acid group and a (meth)acryl group is demonstrated.

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

The aforementioned acrylic resin intermediate, in addition to the aforementioned (meth)acrylate compound (α), may also be copolymerized with a compound containing other polymerizable unsaturated groups as needed. The aforementioned compounds containing other polymerizable unsaturated groups include, for example: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylate ) Alkyl (meth)acrylate such as 2-ethylhexyl acrylate; cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate ((Meth) (meth)acrylic acid esters containing alicyclic structure such as )acrylate dicyclopentanyl); ) acrylates; silicon-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene wait. These may be used individually, and may use 2 or more types together.

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 , preferably a combination of the following. That is, when using a hydroxyl group-containing (meth)acrylate as the aforementioned (meth)acrylate compound (α), it is preferable to use an isocyanate group-containing (meth)acrylate as the (meth)acrylate compound. (β). In the case of using a carboxyl group-containing (meth)acrylate as the (meth)acrylate compound (α), it is preferable to use a glycidyl group-containing (meth)acrylate as the (meth)acrylate compound. (β). In the case of using an isocyanate group-containing (meth)acrylate as the aforementioned (meth)acrylate compound (α), it is preferable to use a hydroxyl-containing (meth)acrylate as the (meth)acrylate compound (β ). In the case of using a glycidyl group-containing (meth)acrylate as the (meth)acrylate compound (α), it is preferable to use a carboxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). The said (meth)acrylate compound ((beta)) may be used individually or in combination of 2 or more types.

The aforementioned polybasic acid anhydrides include, for example, phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride , methylhexahydrophthalic anhydride, octenyl succinic anhydride, dodecenyl succinic anhydride (dodeceny succinicanhydride) and the like. These polybasic acid anhydrides may be used alone or in combination of two or more.

It does not specifically limit as a manufacturing method of the said acrylic resin (B-4) which has an acid group and a (meth)acryl group, It can manufacture by arbitrary methods. In the production of the aforementioned acrylic resin (B-4) having an acid group and a (meth)acryl group, it can also be carried out in an organic solvent if necessary, and an alkaline catalyst can also be used if necessary.

As the above-mentioned organic solvent, the same ones as those mentioned above can be used, and the above-mentioned organic solvents may be used alone or in combination of two or more kinds.

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

The acid value of the aforementioned acrylic resin (B-4) having an acid group and a (meth)acryl group can be obtained from an acid group-containing (meth)acrylic resin (formaldehyde) that can form a cured product with high photosensitivity, heat resistance, and excellent dielectric properties. Based on the acrylate resin composition, it is preferably in the range of 30-150 mgKOH/g, more preferably in the range of 40-120 mgKOH/g. Furthermore, the acid value of the acrylic resin (B-4) having an acid group and a (meth)acryl group in the present invention is a value measured by the neutralization titration method of JIS K 0070 (1992).

Next, [5] the urethane resin (B-5) which has an acid group and a (meth)acryl group is demonstrated.

Examples of the above-mentioned urethane resin (B-5) having acid groups and (meth)acryl groups include: polyisocyanate compounds, hydroxyl-containing (meth)acrylate compounds, carboxyl-containing polyvalent Alcohol compounds, polybasic acid anhydrides as needed, and polyol compounds other than the aforementioned carboxyl-containing polyol compounds; polyisocyanate compounds, hydroxyl-containing (meth)acrylate compounds, polybasic acid anhydrides, and carboxyl-containing Those obtained by reacting polyol compounds other than polyol compounds; those obtained by reacting epoxy resins, unsaturated monobasic acids, polybasic acid anhydrides, polyisocyanate compounds, and hydroxyl-containing (meth)acrylate compounds, etc.

As said polyisocyanate compound, the thing similar to the said polyisocyanate compound can be used, and said polyisocyanate compound may be used individually or in combination of 2 or more types.

As the above-mentioned hydroxyl-containing (meth)acrylate compound, the same thing as the above-mentioned hydroxyl-containing (meth)acrylate compound (b3-2) can be used, and the above-mentioned hydroxyl-containing (meth)acrylate compound can be independently It can be used, and 2 or more types can also be used together.

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

As the said polybasic acid anhydride, what was illustrated as the said polybasic acid anhydride can be used, and the said polybasic acid anhydride may be used individually or in combination of 2 or more types.

Examples of polyol compounds other than the aforementioned carboxyl group-containing polyol compounds include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerin, trimethylolpropane, di-trimethylolpropane, neopentyl Aliphatic polyol compounds such as tetraol and diperythritol; aromatic polyol compounds such as biphenol and bisphenol; introducing (poly)oxyethylene chains, (poly)oxyethylene chains, (poly (poly)oxyalkylene modified body of (poly)oxyalkylene chain such as (poly)oxypropylene chain, (poly)oxytetramethylene chain, etc.; ) Lactone modified body of lactone structure, etc. Polyol compounds other than the aforementioned carboxyl group-containing polyol compounds may be used alone or in combination of two or more.

As said epoxy resin, what was exemplified as said epoxy resin (b1-1) can be used, and said epoxy resin may be used individually or in combination of 2 or more types.

Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, and the like. Furthermore, esterified products, acid halides, acid anhydrides, etc. of the aforementioned unsaturated monobasic acids can also be used. These unsaturated monobasic acids may be used alone or in combination of two or more.

It does not specifically limit as a manufacturing method of the said urethane resin (B-5) which has an acid group and a (meth)acryl group, It can manufacture by arbitrary methods. The production of the aforementioned urethane resin having an acid group and a polymerizable unsaturated bond can also be carried out in an organic solvent if necessary, and an alkaline catalyst can also be used if necessary.

As the above-mentioned organic solvent, the same ones as those mentioned above can be used, and the above-mentioned organic solvents may be used alone or in combination of two or more kinds.

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

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

The content of the aforementioned aromatic ester compound (A) containing polymerizable unsaturated bonds in the acid group-containing (meth)acrylate resin composition of the present invention can be obtained to form a In view of the acid group-containing (meth)acrylate resin composition of the cured product having excellent properties, the range of 10 to 90% by mass is preferable.

In addition, 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 aforementioned aromatic ester compound (A) containing polymerizable unsaturated bonds to the solid content of the aforementioned acid group-containing (meth)acrylate resin (B) can be obtained from In view of obtaining an acid group-containing (meth)acrylate resin composition capable of forming a hardened product having high photosensitivity, heat resistance, and excellent dielectric properties, the range of 50/50 to 95/5 is preferable.

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.

(thioxanthone)及9-氧硫

衍生物、2,2'-二甲氧基-1,2-二苯基乙烷-1-酮、二苯基(2,4,6-三甲氧基苯甲醯)氧化膦、 2,4,6-三甲基苯甲醯二苯基氧化膦、雙(2,4,6-三甲基苯甲醯)苯基氧化膦、2-甲基-1-(4-甲硫基苯基)-2-

啉基丙烷-1-酮、2-苄基-2-二甲胺-1-(4-

啉基苯基)-1-丁酮等。 Examples of the aforementioned photopolymerization initiator include: 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethyl Oxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 9-oxosulfur

(thioxanthone) and 9-oxosulfur

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-

Linyl propan-1-one, 2-benzyl-2-dimethylamine-1-(4-

Linylphenyl)-1-butanone, etc.

As commercially available products of the aforementioned other photopolymerization initiators, for example: "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", "Omnirad -379", "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100 ", "Omnirad-754", "Omnirad-784", "Omnirad-500", "Omnirad-81" (manufactured by IGM Corporation), "KAYACURE-DETX", "KAYACURE-MBP", "KAYACURE-DMBI", " KAYACURE-EPA", "KAYACURE-OA" (manufactured by Nippon Kayaku Co., Ltd.), "VICURE-10", "VICURE-55" (manufactured by Stauffer Chemical), "TRIGONALP1" (manufactured by AKZO), "SANDORAY 1000 "(SANDOZ), "DEAP" (APJOHN), "QUANTACURE-PDO", "QUANTACURE-ITX", "QUANTACURE-EPD" (WARD BLEKINSOP), "Runtecure-1104" (Runtec) wait.

The addition amount of the said photoinitiator, for example: It is preferable to use it in the range of 1-20 mass % in the said curable resin composition.

The curable resin composition of the present invention may contain other resin components other than the aforementioned acid group-containing (meth)acrylate resin (B). As the aforementioned other resin components, for example: resins having carboxyl groups and (meth)acryl groups in the resin, various (meth)acrylate monomers, etc., wherein the resin is bisphenol-type epoxy resin , Epoxy resins such as novolac epoxy resins, etc., react with (meth)acrylic acid, dimethyl anhydride, and unsaturated monocarboxylic acid anhydrides as needed.

Examples of the aforementioned (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylate ) aliphatic mono(meth)acrylate compounds such as pentyl acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, etc.; (meth) Alicyclic mono(meth)acrylate compounds such as cyclohexyl acrylate, isocamphoryl (meth)acrylate, adamantyl mono(meth)acrylate, etc.; glycidyl (meth)acrylate, tetrahydroacrylate Heterocyclic mono(meth)acrylate compounds such as furfuryl esters; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate ester, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, (meth)acrylic acid Mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds such as phenoxybenzyl ester, benzylbenzyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate, etc. ; The poly(poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene chain, etc. introduced into the molecular structure of the aforementioned various mono(meth)acrylate monomers A mono(meth)acrylate compound modified by a (poly)oxyalkylene chain of an oxyalkylene chain; a (poly)lactone structure introduced into the molecular structure of the aforementioned various mono(meth)acrylate compounds Lactone-modified mono(meth)acrylate compounds; ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di( Aliphatic di(meth)acrylate compounds such as meth)acrylate and neopentyl glycol di(meth)acrylate; 1,4-cyclohexanedimethanol di(meth)acrylate, di(meth)acrylate alicyclic type such as norbornyl acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentyl (meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, etc. Di(meth)acrylate compounds; aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene chain, etc. into the molecular structure of the acrylate compound Alkyl-modified di(meth)acrylate compound; lactone-modified di(meth)acrylic acid by introducing (poly)lactone structure into the molecular structure of the above-mentioned various di(meth)acrylate compounds Ester compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerol tri(meth)acrylate; (poly)oxyalkylene chains of (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene chains, etc. Modified tri(meth)acrylate compound; lactone-modified tri(meth)acrylate compound by introducing (poly)lactone structure into the molecular structure of the aforementioned aliphatic tri(meth)acrylate compound aliphatic poly( Meth)acrylate compound; introduced (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene into the molecular structure of the aforementioned aliphatic poly(meth)acrylate compound Poly(meth)acrylate compounds modified by (poly)oxyalkylene groups with more than 4 functions in (poly)oxyalkylene chains, etc.; Poly(meth)acrylate compounds modified by lactones with four or more functions introduced into the molecular structure (poly)lactone structure, etc. The aforementioned various (meth)acrylate monomers may be used alone or in combination of two or more.

In addition, the curable resin composition of the present invention may contain hardeners, hardening accelerators, organic solvents, inorganic particles, polymer particles, pigments, defoamers, viscosity regulators, leveling agents (or even dyes), flame retardants, storage stabilizers and other additives.

The curing agent is not particularly limited as long as it has a functional group capable of reacting with the carboxyl group in the acid group-containing (meth)acrylate resin, and examples thereof include epoxy resins. Examples of the epoxy resin include bisphenol-type epoxy resins, phenylene ether-type epoxy resins, naphthyl ether-type epoxy resins, biphenyl-type epoxy resins, and triphenylmethane-type epoxy resins. , phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol novolak epoxy resin, naphthol novolak epoxy resin, naphthol-phenol co-condensed novolak epoxy resin, naphthalene Phenol-cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenylaralkyl Base type epoxy resin, fennel type epoxy resin, dibenzopyran type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, etc. These epoxy resins may be used alone or in combination of two or more. In addition, among these, phenol novolac type epoxy resin, cresol Novolac epoxy resin, bisphenol novolac epoxy resin, naphthol novolak epoxy resin, naphthol-phenol novolac epoxy resin, naphthol-cresol novolac epoxy Novolac type epoxy resins such as resins are particularly preferably those with a softening point in the range of 20 to 120°C.

The hardening accelerator is one that accelerates the hardening reaction of the hardening agent. When an epoxy resin is used as the hardening agent, phosphorus-based compounds, amine-based compounds, imidazoles, organic acid metal salts, Lewis acids, amines, etc. Wrong salt etc. These hardening accelerators may be used alone or in combination of two or more. In addition, the addition amount of the said hardening accelerator is preferably used in the range of 1-10 mass parts with respect to 100 mass parts of said hardening agents, for example.

As the aforementioned organic solvent, the same ones as those mentioned above can be used, and the aforementioned organic solvents may be used alone or in combination of two or more.

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

As a source of ultraviolet rays, ultraviolet lamps are generally used in terms of practicality and economy. Specifically, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, LEDs, and the like are exemplified.

The accumulated light quantity of the aforementioned active energy rays is not particularly limited, but is preferably 10-5,000 mJ/cm ² , more preferably 50-1,000 mJ/cm ² . When the integrated light quantity is within the above range, it is preferable because generation of unhardened portions can be prevented or suppressed.

Furthermore, the aforementioned irradiation of active energy rays may be performed in one step, or may be performed in two or more steps.

In addition, the cured product obtained by curing the curable resin composition of the present invention has excellent heat resistance and dielectric properties, so it is suitable as, for example, solder resist, interlayer insulating material, packaging material, and underfill in semiconductor devices. Materials (underfill material), package bonding layer of circuit components, etc., bonding layer of integrated circuit components and circuit substrates. In addition, it can be applied to thin film transistor protective film, liquid crystal color filter protective film, pigment photoresist for color filter, photoresist for black matrix, spacer, etc. in thin display applications represented by LCD and OELD.

The resin material for soldering resist of the present invention is composed of the aforementioned curable resin composition.

The solder resist member of the present invention can be, for example: coating the above-mentioned resin material for solder resist on the substrate, drying the organic solvent at a temperature range of about 60-100°C, and then forming a photomask with a desired pattern to activate Energy ray exposure is obtained by developing the unexposed part with an aqueous alkali solution, and further heating and hardening at a temperature range of 140~180°C.

As said base material, metal foils, such as a copper foil and an aluminum foil, etc. are mentioned, for example.

[Example]

Hereinafter, the present invention will be specifically described with examples and comparative examples.

The acid value of the acid group-containing (meth)acrylate resin in the examples of this case is determined by the neutralization titration method of JIS K 0070 (1992).

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

Measuring device: "HLC-8320 GPC" manufactured by Tosoh Co., Ltd.

Column: Guard column "HXL-L" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G4000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G3000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.

Detector: RI (Differential Refractometer)

Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Co., Ltd.

Column temperature: 40°C

Developing solvent: tetrahydrofuran

Flow rate: 1.0ml/min

Standard: follow the aforementioned "GPC-8320 GPC" measurement manual, use the following monodisperse polystyrene with known molecular weight

use polystyrene

"A-500" manufactured by Tosoh Co., Ltd.

"A-1000" manufactured by Tosoh Co., Ltd.

"A-2500" manufactured by Tosoh Co., Ltd.

"A-5000" manufactured by Tosoh Co., Ltd.

"F-1" manufactured by Tosoh Co., Ltd.

"F-2" manufactured by Tosoh Co., Ltd.

"F-4" manufactured by Tosoh Co., Ltd.

"F-10" manufactured by Tosoh Co., Ltd.

"F-20" manufactured by Tosoh Co., Ltd.

"F-40" manufactured by Tosoh Co., Ltd.

"F-80" manufactured by Tosoh Co., Ltd.

"F-128" manufactured by Tosoh Co., Ltd.

Sample: what filtered the tetrahydrofuran solution of 1.0 mass % in terms of resin solid content with the microfilter (50 microliters).

(Synthesis Example 1: Synthesis of Polymerizable Unsaturated Bond-Containing Aromatic Ester Compound (A-1))

In a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer, feed 268 parts by mass (2.0 mol) of o-allylphenol and 1200 parts by mass of toluene, and replace the system with nitrogen under reduced pressure. Next, 203 parts by mass (1.0 mol) of isophthaloyl chloride was fed, and nitrogen substitution was carried out in the system under reduced pressure. Next, 0.6 parts by mass of tetrabutylammonium bromide was added, the system was controlled to be below 60°C while performing nitrogen flushing, and 412 parts by mass of 20% sodium hydroxide aqueous solution was dripped over 3 hours. After the dropping was completed, it was stirred for 1 hour. After the reaction was completed, the water layer was removed by static liquid separation. Further, water was poured into the obtained toluene layer, stirred for 15 minutes, and the water layer was removed by static liquid separation. This operation was repeated until the pH of the aqueous layer became 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 this polymerizable unsaturated bond-containing aromatic ester compound (A-1) was 199 g/equivalent. Furthermore, the aforementioned ester group equivalent is a calculated value calculated from the feed ratio.

(Synthesis Example 2: Synthesis of Polymerizable Unsaturated Bond-Containing Aromatic Ester Compound (A-2))

In a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer, feed 134 parts by mass (1.0 mol) of o-allylphenol and 711 parts by mass of toluene, and replace the system with nitrogen under reduced pressure. Next, 140 parts by mass (1.0 mol) of chlorotoluene was fed, and nitrogen substitution was performed in the system under reduced pressure. Next, 0.4 parts by mass of tetrabutylammonium bromide was added, the system was controlled to be below 60° C. while performing nitrogen flushing, and 205 parts by mass of a 20% aqueous sodium hydroxide solution was dropped over 3 hours. After the dropping was completed, it was stirred for 1 hour. After the reaction was completed, the water layer was removed by static liquid separation. Further, water was poured into the obtained toluene layer, stirred for 15 minutes, and the water layer was removed by static liquid separation. This operation was repeated until the pH of the aqueous layer became 7. Then, by heating and drying under reduced pressure, an aromatic ester compound (A-2) represented by the following chemical formula was obtained. The ester group equivalent of this aromatic ester compound (A-2) was 119 g/equivalent. Furthermore, the aforementioned ester group equivalent is a calculated value calculated from the feed ratio.

(Synthesis Example 3: Synthesis of Aromatic Ester Compound (A-3))

In a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer, feed 216 parts by mass (2.0 mol) of o-cresol and 1200 parts by mass of toluene, and replace the system with nitrogen under reduced pressure. Next, 203 parts by mass (1.0 mol) of isophthaloyl chloride was fed, and nitrogen substitution was carried out in the system under reduced pressure. Next, 0.5 parts by mass of tetrabutylammonium bromide was added, the system was controlled to be below 60° C. while performing nitrogen flushing, and 412 parts by mass of a 20% aqueous sodium hydroxide solution was dropped over 3 hours, and stirred for 1 hour after the dropping was completed. After the reaction was completed, the water layer was removed by static liquid separation. Further, water was poured into the obtained toluene layer, stirred for 15 minutes, and the water layer was removed by static liquid separation. This operation was repeated until the pH of the aqueous layer became 7. Then, by heating and drying under reduced pressure, an aromatic ester compound (A-3) represented by the following chemical formula was obtained. The ester group equivalent of this aromatic ester compound (A-3) was 173 g/equivalent. Furthermore, the aforementioned ester group equivalent is a calculated value calculated from the feed ratio.

(Synthesis Example 4: Synthesis of (meth)acrylate resin (B-1) containing acid groups)

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 101 parts by mass of diethylene glycol monomethyl ether acetate was charged, and an o-cresol novolak type epoxy resin (manufactured by DIC Co., Ltd. "EPICLON N -680", epoxy equivalent: 214) 428 parts by mass, add 4 parts by mass of dibutyl hydroxytoluene as an antioxidant, 0.4 parts by mass of p-hydroxyanisole (methoquinone) as a thermal polymerization inhibitor, add acrylic acid 144 Parts by mass and 1.6 parts by mass of triphenylphosphine were subjected to an esterification reaction at 120° C. for 10 hours while blowing in 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 obtain acid group-containing (meth)acrylic acid having a solid content of 64.0 mass % Ester resin (B-1). The solid content acid value of this 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 (meth)acrylate resin (B-2) containing acid groups)

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 392 parts by mass of diethylene glycol monomethyl ether acetate and an isocyanuric acid modified body of isophorone diisocyanate (manufactured by EVONIK "VESTANAT T- 1890/100", an isocyanate group content of 17.2% by mass) (hereinafter, abbreviated as "T-1890") 244 parts by mass, 192 parts by mass of trimellitic anhydride, and 1.0 part by mass of dibutylhydroxytoluene were dissolved. Under a nitrogen atmosphere, the reaction was carried out at 160° C. for 5 hours, 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 of non-ring opening of the acid anhydride group is 160 mgKOH/g. Add 0.3 parts by mass of p-hydroxyanisole, neopentylthritol polyacrylate mixture ("ARONIX M-306" manufactured by Toa Gosei Co., Ltd., the content of neopentylthritol triacrylate is about 67%, and the hydroxyl value is 159.7mgKOH/g ) (hereinafter, abbreviated as "M-306".) 172 parts by mass and 3.6 parts by mass of triphenylphosphine were reacted at 110° C. for 5 hours while blowing air. Next, 163 parts by mass of glycidyl methacrylate was added, and it was made to react at 110 degreeC 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). The solid content acid value of this acid group-containing (meth)acrylate resin (B-2) was 79 mgKOH/g, and the weight average molecular weight was 3790.

(Example 1: Preparation of (meth)acrylate resin composition (1) containing acid groups)

The polymerizable unsaturated bond-containing aromatic ester compound (A-1) obtained in Synthesis Example 1 and the acid group-containing (meth)acrylate resin obtained in Synthesis Example 4 were blended in parts by mass shown in Table 1 (B-1), ortho-cresol novolak-type epoxy resin ("EPICLON N-680" manufactured by DIC Co., Ltd.), diperythritol hexaacrylate, diethylene glycol monoethyl ether as a hardener Acetate, photopolymerization initiator ("Omnirad 907" manufactured by IGM Corporation), 2-ethyl-4-methylimidazole, and phthalocyanine green are kneaded by a roller mill to obtain acid group-containing (methyl) Acrylate resin composition (1).

(Example 2~7: preparation of acid group-containing (meth)acrylate resin composition (2)~(7))

The acid group-containing (meth)acrylate resin compositions (2)-(7) were obtained by the same method as in Example 1 with the composition and formulation shown in Table 1.

(Comparative Example 1: Preparation of acid group-containing (meth)acrylate resin composition (C1))

Blend the aromatic ester compound (A-3) obtained in Synthesis Example 3, the acid group-containing (meth)acrylate resin (B-1) obtained in Synthesis Example 4 in parts by mass shown in Table 1, as Hardener o-cresol novolak type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation), diperythritol hexaacrylate, diethylene glycol monoethyl ether acetate, photopolymerizer Starter ("Omnirad 907" manufactured by IGM Corporation), 2-ethyl-4-methylimidazole, and phthalocyanine green were kneaded by a roller mill to obtain an acid group-containing (meth)acrylate resin composition (C1 ).

(Comparative Example 2: Preparation of (meth)acrylate resin composition (C2) containing acid groups)

Use the (meth)acrylate resin (B-2) containing the acid group obtained in Synthesis Example 4 to replace the (meth)acrylate resin (B-1) containing the acid group used in Comparative Example 1, and Comparative Example 1 was carried out in the same manner to obtain an acid group-containing (meth)acrylate resin composition (C2).

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

[Evaluation method of light sensitivity]

The acid group-containing (meth)acrylate resin compositions obtained in Examples and Comparative Examples were coated on glass substrates using an applicator to a film thickness of 50 μm, and dried at 80° C. for 30 minutes. Next, "Step Tablet No. 2" manufactured by Kodak Co., Ltd. was placed on the dried coating film, and 1000 mJ/cm ² of ultraviolet rays was irradiated with a metal halide lamp. It was developed with a 1% aqueous solution of sodium carbonate at 30°C for 180 seconds, and evaluated based on the number of steps remaining on the Step Tablet based on the Step Tablet method. Furthermore, the more remaining segments, the higher the light sensitivity.

The acid-group-containing (meth)acrylate resin compositions (1)-(7) prepared in Examples 1-7, and the acid-group-containing (meth)acrylate resins prepared in Comparative Examples 1 and 2 The compositions and evaluation results of the compositions (C1) and (C2) are shown in Table 1.

In the evaluation of Comparative Example 2 in Table 1, "-" indicates that evaluation was not possible. This is because the aromatic ester compound is incompatible with the acid group-containing (meth)acrylate resin, and it becomes cloudy when mixed, so it cannot be evaluated.

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

The polymerizable unsaturated bond-containing aromatic ester compound (A-1) obtained in Synthesis Example 1 and the acid group-containing (meth)acrylate resin obtained in Synthesis Example 4 were blended in parts by mass shown in Table 2 (B-1), o-cresol novolak type epoxy resin ("EPICLON N-680" manufactured by DIC Co., Ltd.) as a hardening agent, dimethylaminopyridine as a hardening accelerator, and a photopolymerization initiator (IGM "Omnirad 907" manufactured by the company) and diethylene glycol monomethyl ether acetate as an organic solvent were kneaded by a roll mill to obtain an acid group-containing (meth)acrylate resin composition (8).

(Example 9~14: preparation of (meth)acrylate resin composition (9)~(14) containing acid groups)

The acid group-containing (meth)acrylate resin compositions (9)-(14) were obtained by the same method as in Example 8 with the composition and formulation shown in Table 2.

(Comparative Example 3: Preparation of (meth)acrylate resin composition (C3) containing acid groups)

Blend the aromatic ester compound (A-3) obtained in Synthesis Example 3, the (meth)acrylate resin (B-1) containing acid groups obtained in Synthesis Example 4 in parts by mass shown in Table 2, as O-cresol novolak-type epoxy resin as a hardener ("EPICLON N-680" manufactured by DIC Corporation, dimethylaminopyridine as a hardening accelerator, a photopolymerization initiator ("Omnirad 907" manufactured by IGM Corporation), Diethylene glycol monomethyl ether acetate as an organic solvent was kneaded by a roll mill to obtain an acid group-containing (meth)acrylate resin composition (C3).

(Comparative Example 4: Preparation of (meth)acrylate resin composition (C4) containing acid groups)

The (meth)acrylate resin (B-2) containing the acid group obtained in Synthesis Example 5 is used to replace the (meth)acrylate resin (B-1) containing the acid group used in Comparative Example 3, and Comparative Example 3 was carried out in the same manner to obtain an acid group-containing (meth)acrylate resin composition (C4).

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

[Evaluation method of heat resistance]

The acid group-containing (meth)acrylate resin compositions obtained in Examples and Comparative Examples were coated on glass substrates using an applicator to a film thickness of 50 μm, and dried at 80° C. for 30 minutes. Next, after irradiating 1000 mJ/cm ² of ultraviolet rays using a metal halide lamp, it was heated at 160° C. for 1 hour to peel off the cured product from the glass substrate to obtain a cured product. Cut out a test piece of 6mm x 35mm from the aforementioned cured product, and use a viscoelasticity measuring device (DMA: Rheometric Solid Viscoelasticity Measuring Device "RSAII", tensile method: frequency 1Hz, heating rate 3°C/min) to evaluate elasticity The temperature at which the rate change becomes maximum is taken as the glass transition temperature. In addition, the higher the glass transition temperature, the better the heat resistance.

[Measurement method of dielectric coefficient]

The acid group-containing (meth)acrylate resin compositions obtained in Examples and Comparative Examples were coated on glass substrates using an applicator to a film thickness of 50 μm, and dried at 80° C. for 30 minutes. Next, after irradiating 1000 mJ/cm ² of ultraviolet rays using a metal halide lamp, it was heated at 160° C. for 1 hour to peel off the cured product from the glass substrate to obtain a cured product. Next, the test piece was stored in a room with a temperature of 23°C and a humidity of 50% for 24 hours, and the dielectric coefficient of the test piece at 1 GHz was measured by the cavity resonance method using "Network Analyzer E8362C" manufactured by Agilent Technologies Co., Ltd.

[Measurement method of dielectric loss factor]

The acid group-containing (meth)acrylate resin compositions obtained in Examples and Comparative Examples were coated on glass substrates using an applicator to a film thickness of 50 μm, and dried at 80° C. for 30 minutes. Next, after irradiating 1000 mJ/cm ² of ultraviolet rays using a metal halide lamp, it was heated at 160° C. for 1 hour to peel off the cured product from the glass substrate to obtain a cured product. Next, the specimens stored in a room with a temperature of 23°C and a humidity of 50% for 24 hours were used as test pieces, and the dielectric dissipation factor of the test pieces at 1 GHz was measured by the cavity resonance method using "Network Analyzer E8362C" manufactured by Agilent Technologies Co., Ltd.

The acid group-containing (meth)acrylate resin compositions (8)~(14) prepared in Examples 8~14, and the acid group-containing (meth)acrylate resins prepared in Comparative Examples 3 and 4 The compositions and evaluation results of the compositions (C3) and (C4) are shown in Table 2.

Furthermore, the blending amounts of the acid group-containing (meth)acrylate resins (B-1) and (B-2) in Tables 1 and 2 are solid content values.

In the evaluation of Comparative Example 4 in Table 2, "-" indicates that evaluation was not possible. This is because the aromatic ester compound is incompatible with the acid group-containing (meth)acrylate resin, and it becomes cloudy when mixed, so it cannot be evaluated.

In addition, "curing agent" in Tables 1 and 2 represents an ortho-cresol novolak type epoxy resin ("Epiclon N-680" manufactured by DIC Corporation, epoxy equivalent: 214).

"Hardening accelerator" in Table 2 means dimethylaminopyridine.

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

The "photopolymerization initiator" in Tables 1 and 2 represents "Omnirad-907" manufactured by IGM Corporation.

Examples 1 to 14 shown in Tables 1 and 2 are examples of the acid group-containing (meth)acrylate resin composition of the present invention, and it can be confirmed that the acid group-containing (meth)acrylate resin of the present invention The composition has excellent light sensitivity. Moreover, the hardened product of the acid group-containing (meth)acrylate resin composition of the present invention has excellent heat resistance. In addition, the dielectric coefficient and dielectric loss factor are low, and the dielectric The properties are also excellent.

On the other hand, Comparative Examples 1 to 4 are examples of acid group-containing (meth)acrylate resin compositions using aromatic ester compounds not having a polymerizable unsaturated bond, and it can be confirmed that the acid group-containing (meth)acrylate resin composition Base) The cured product of the acrylate resin composition has a high dielectric coefficient and a high dielectric loss factor, and the dielectric properties are obviously insufficient.

Claims (9)

An acid group-containing (meth)acrylate resin composition, characterized in that it contains an aromatic ester compound (A) containing a polymerizable unsaturated bond, and an acid group-containing (meth)acrylate resin (B), The aforementioned 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 are each independently substituted or unsubstituted first aromatic ring group, Ar ⁶ are each independently substituted or unsubstituted second aromatic ring group, the aforementioned Ar ⁵ and the aforementioned Ar At least one of ⁶ has a substituent containing a polymerizable unsaturated bond, n is an integer of 1 to 3]. The acid group-containing (meth)acrylate resin composition according to claim 1, wherein the aforementioned aromatic ester compound (A) containing polymerizable unsaturated bonds is an aromatic compound having a phenolic hydroxyl group, and an aromatic compound having a carboxyl group. Reaction products of aromatic compounds, their acid halides and/or their esters, at least one of the aforementioned aromatic compounds with phenolic hydroxyl groups, and aromatic compounds with carboxyl groups, their acid halides and/or their esters Those having substituents containing polymerizable unsaturated bonds. The acid group-containing (meth)acrylate resin composition according to claim 1, wherein the aforementioned aromatic ester compound (A) containing polymerizable unsaturated bonds and the aforementioned acid group-containing (meth)acrylate resin ( The mass ratio [(A)/(B)] of the solid content of B) is in the range of 50/50~95/5. A curable resin composition, characterized in that it contains the acid group-containing (meth)acrylate resin composition according to claim 1 or 2, and a photopolymerization initiator. Such as the curable resin composition of claim 4, which further contains Machine solvents and hardeners. A hardened product characterized in that it is a hardened reaction product of the curable resin composition according to claim 4 or 5. An insulating material characterized in that it is made of the curable resin composition as claimed in claim 4 or 5. A resin material for solder resist, characterized in that it is composed of the curable resin composition as claimed in claim 4 or 5. A solder resist member characterized in that it is made of the resin material for solder resist according to claim 8.