JP2021075627A - Epoxy (meth)acrylate resin composition, curable resin composition, cured product, and article - Google Patents

Abstract

To provide an epoxy (meth)acrylate resin composition having excellent heat resistance and dielectric characteristics, a curable resin composition containing the same, a cured product of the curable resin composition, and an article having a coating film of the cured product.SOLUTION: The epoxy (meth)acrylate resin composition is used which contains an aromatic ester compound and an epoxy (meth)acrylate resin. The aromatic ester compound uses a phenol compound having at least one vinylbenzyl group and at least two phenolic hydroxyl groups, an aromatic polybasic acid or its derivative, and a monofunctional phenol compound represented by one of structural formulae (a-1)-(a-4) as essential reaction raw materials. The epoxy (meth)acrylate resin uses an epoxy resin and an unsaturated monobasic acid as essential reaction raw materials.SELECTED DRAWING: None

Description

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

In recent years, curable compositions such as active energy ray-curable compositions that can be cured by active energy rays such as ultraviolet rays and thermosetting compositions that can be cured by heat have been introduced into inks, paints, coating agents, adhesives, and optics. It is widely used in the field of materials and the like. Among them, as the coating agent application, it is generally required that a coating film capable of imparting design to the surface of various base materials, having excellent curability, and preventing deterioration of the surface of the base material can be formed. Has been done. Further, in recent years, the industry has been demanding a material capable of forming a cured coating film having not only curability but also substrate adhesion. Further, when used as a curable composition for a solder resist for a printed wiring board, in addition to the above-mentioned required characteristics, it is also required to be cured with a small exposure amount and to have excellent heat resistance, strength, dielectric properties, etc. in the cured product. ing.

As a conventional curable composition for solder resist, an acid group-containing epoxy obtained by further reacting tetrahydrophthalic anhydride with an intermediate obtained by reacting a cresol novolac type epoxy resin with acrylic acid and phthalic anhydride. A photosensitive resin composition containing an acrylate resin is known (see, for example, Patent Document 1), but the heat resistance of the cured product is not sufficient, and the dielectric constant and dielectric loss tangent increase due to the formation of hydroxyl groups. , There was a problem that the dielectric property deteriorated.

Therefore, a material having excellent dielectric properties in addition to heat resistance has been required.

Japanese Unexamined Patent Publication No. 8-259663

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

As a result of diligent studies to solve the above problems, the present inventors use an epoxy (meth) acrylate resin composition containing a specific aromatic ester compound and a specific epoxy (meth) acrylate resin. The present invention was completed by finding that the above problems can be solved.

That is, the present invention is an epoxy (meth) acrylate resin composition containing an aromatic ester compound (A) and an epoxy (meth) acrylate resin (B), wherein the aromatic ester compound (A) is a compound. A phenol compound (A1) having at least one vinyl benzyl group and at least two phenolic hydroxyl groups, an aromatic polybasic acid or a derivative thereof (A2), and the following structural formulas (a-1) to (a-4). The monofunctional phenol compound (A3) represented by any of them is used as an essential reaction raw material, and the epoxy (meth) acrylate resin (B) is an epoxy resin (B1) and an unsaturated monobasic acid (B2). The present invention relates to an epoxy (meth) acrylate resin composition comprising the above as an essential reaction raw material, a curable resin composition containing the epoxy (meth) acrylate resin composition, a cured product composed of the curable resin composition, and an article. ..

［上記構造式（ａ−１）〜（ａ−４）中、Ｒ^１は、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のアルコキシ基、アリール基、またはハロゲン原子の何れかであり、Ｒ^２は、それぞれ独立して、水素原子またはメチル基である。また、ｐは、０または１以上の整数である。］

[In the structural formulas (a-1) to (a-4), R ¹ is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom. And R ² is an independent hydrogen atom or methyl group, respectively. Further, p is 0 or an integer of 1 or more. ]

Since the epoxy (meth) acrylate resin composition of the present invention has excellent heat resistance and excellent dielectric properties, it is a curable resin composition containing the epoxy (meth) acrylate resin composition and a photopolymerization initiator. Can be used as a coating agent or an adhesive, and as the coating agent, it can be particularly preferably used for solder resist applications. The "excellent dielectric property" in the present invention means a low dielectric constant and a low dielectric loss tangent.

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

In the present invention, "(meth) acrylate" means acrylate and / or methacrylate. Further, "(meth) acryloyl" means acryloyl and / or methacryloyl. Further, "(meth) acrylic" means acrylic and / or methacrylic.

Examples of the aromatic ester compound (A) include a phenol compound (A1) having at least one vinylbenzyl group and at least two phenolic hydroxyl groups (hereinafter, abbreviated as “phenolic compound (A1)”), and aromatics. It is represented by any of the following structural formulas (a-1) to (a-4), as well as a polybasic acid or a derivative thereof (A2) (hereinafter, abbreviated as "aromatic polybasic acid (A2)"). A monofunctional phenol compound (A3) (hereinafter, abbreviated as “monofunctional phenol compound (A3)”) is used as an essential reaction raw material.

［上記構造式（ａ−１）〜（ａ−４）中、Ｒ^１は、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のアルコキシ基、アリール基、またはハロゲン原子の何れかであり、Ｒ^２は、それぞれ独立して、水素原子またはメチル基である。また、ｐは、０または１以上の整数である。］

[In the structural formulas (a-1) to (a-4), R ¹ is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom. And R ² is an independent hydrogen atom or methyl group, respectively. Further, p is 0 or an integer of 1 or more. ]

The phenol compound (A1) has at least one vinylbenzyl group and at least two phenolic hydroxyl groups, and examples thereof include compounds represented by the following structural formulas (1) or (2). ..

［式（１）及び（２）中、Ｒ^１はビニルベンジル基であり、Ｒ^２は、水素原子、アルキル基、またはアリール基である。また、式（１）中のｎは１〜４の整数、ｍは０〜３の整数、ｐは２〜５の整数であり、ｎとｍとｐの和は６である。式（２）中のｎは１〜６の整数、ｍは０〜５の整数、ｐは２〜７の整数であり、式（２）におけるｎとｍとｐの和は８である。式（１）、（２）におけるＲ^１、Ｒ^２は同一のものからなるものであっても、異なるものからなるものであってもよい。］

[In formulas (1) and (2), R ¹ is a vinylbenzyl group and R ² is a hydrogen atom, an alkyl group, or an aryl group. Further, in the equation (1), n is an integer of 1 to 4, m is an integer of 0 to 3, p is an integer of 2 to 5, and the sum of n, m, and p is 6. In equation (2), n is an integer of 1 to 6, m is an integer of 0 to 5, p is an integer of 2 to 7, and the sum of n, m, and p in equation (2) is 8. ^{R 1} and R ² in the formulas (1) and (2) may be the same or different. ]

^{It should be noted that the hydroxyl groups, R 1} and R ² in the formula (2) may be bonded to any ring as a substituent on the naphthalene ring.

Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, a pentyl group, a normal hexyl group, a cyclohexyl group and the like. Examples of the aryl group include a phenyl group, a benzyl group, a naphthyl group, a methoxynaphthyl group and the like.

^{R 2} in the structural formulas (1) and (2) is selected from a hydrogen atom, a methyl group and an aryl group because an epoxy (meth) acrylate resin composition having excellent heat resistance and dielectric properties can be obtained. It is preferably a compound.

The method for producing the phenol compound (A1) is not particularly limited, and a synthesis method by a dehydrohalogenation reaction using a conventionally known alkaline compound or the like can be used. For example, a vinylbenzyl halide compound, a polyhydric phenol compound, and an interphase transfer catalyst such as an ammonium salt are dissolved in an organic solvent such as toluene, methyl isobutyl ketone, or methyl ethyl ketone, an alkaline compound is added thereto, and the mixture is mixed while heating. It can be manufactured by. Above all, since the yield of the compound containing both a phenol group and a vinylbenzyl group is high, it is preferable to use hydrotalcites as the alkaline compound.

Examples of the aromatic polybasic acid (A2) include aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid; Aromatic tricarboxylic acids such as trimesic acid and trimellitic acid; pyromellitic acid; and their acid halides and esterified products can be mentioned. These can be used alone or in combination of two or more. Of these, isophthalic acid or a mixture of isophthalic acid and terephthalic acid is preferable because an epoxy (meth) acrylate resin composition having excellent heat resistance and dielectric properties can be obtained.

As the monofunctional phenol compound (A3), a phenol compound represented by any of the following structural formulas (a-1) to (a-4) is used.

［上記構造式（ａ−１）〜（ａ−４）中、Ｒ^１は、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のアルコキシ基、アリール基、またはハロゲン原子の何れかであり、Ｒ^２は、それぞれ独立して、水素原子またはメチル基である。また、ｐは、０または１以上の整数である。］

[In the structural formulas (a-1) to (a-4), R ¹ is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom. And R ² is an independent hydrogen atom or methyl group, respectively. Further, p is 0 or an integer of 1 or more. ]

The aromatic ester compound (A) includes at least the phenol compound (A1), the aromatic polybasic acid (A2), and the monofunctional phenol compound (A3), as well as at least other than the phenol compound (A1). Compound (A4) having two phenolic hydroxyl groups (hereinafter, abbreviated as "compound having phenolic hydroxyl group (A4)"), aromatic monobasic acid or a derivative thereof (A5) (hereinafter, "aromatic monobase") Acid (A5) ”) may be contained as a reaction raw material.

Examples of the compound (A4) having a phenolic hydroxyl group include compounds represented by the following structural formulas (3-1) to (3-7).

In formulas (3-1) to (3-7), R ₂ independently represents a hydrogen atom, an alkyl group, or an aryl group, respectively, and represents (3-1), (3-4), (3-5). , (3-6) is an integer of 1 to 4, n in (3-2) is an integer of 0 to 3, and n in (3-3) and (3-7) is. It is an integer from 0 to 6. Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, a pentyl group, a normal hexyl group, a cyclohexyl group and the like. .. Examples of the aryl group include a benzyl group, a naphthyl group, a methoxynaphthyl group and the like. The hydroxyl in formula (3-7), R ₂ indicates that may be attached to either ring of the naphthalene ring.

Further, the compound (A4) having at least two phenolic hydroxyl groups may be a compound represented by the following formula (4).

〔但し、式（４）中、ｍは０〜２０の整数である。〕

[However, in equation (4), m is an integer from 0 to 20. ]

In the above formula (4), Ar ¹ independently represents a substituent containing a phenolic hydroxyl group, and Z independently represents an oxygen atom, a sulfur atom, a ketone group, a sulfonyl group, a substituted or unsubstituted group. It is an alkylene having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene having 3 to 20 carbon atoms, an arylene having 6 to 20 carbon atoms, or an aralkylene having 8 to 20 carbon atoms.

Ar ¹ is not particularly limited, and examples thereof include residues of aromatic hydroxy compounds represented by the following formulas (5-1) and (5-2).

In formulas (5-1) and (5-2), R ₂ is independently one of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. N in the formula (5-1) is an integer of 0 to 5, and n in the formula (5-2) is an integer of 0 to 7. Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, a pentyl group, a normal hexyl group, a cyclohexyl group and the like. .. Examples of the aryl group include a benzyl group, a naphthyl group, a methoxynaphthyl group and the like.

The alkylene having 1 to 20 carbon atoms in Z is not particularly limited, but is methylene, ethylene, propylene, 1-methylmethylene, 1,1-dimethylmethylene, 1-methylethylene, 1,1-dimethylethylene, 1 , 2-Dimethylethylene, propylene, butylene, 1-methylpropylene, 2-methylpropylene, pentylene, hexylene and the like.

The cycloalkylene having 3 to 20 carbon atoms is not particularly limited, but cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclopentylene, cycloheptylene, and the following formulas (6-1) to (6). Examples thereof include cycloalkylene represented by -4).

なお、上記式（６−１）〜（６−４）において、「＊」はＡｒ^１と結合する部位を表す。

In the above formulas (6-1) to (6-4), "*" represents a site that binds to ^{Ar 1.}

The arylene having 6 to 20 carbon atoms is not particularly limited, and examples thereof include an arylene represented by the following formula (12).

なお、上記式（７−１）において、「＊」はＡｒ^１と結合する部位を表す。

In the above formula (7-1), "*" represents a site that binds to ^{Ar 1.}

The aralkylene having 8 to 20 carbon atoms is not particularly limited, and examples thereof include aralkylene represented by the following formulas (8-1) to (8-5).

なお、式（８−１）〜（８−５）において、「＊」はＡｒ^１と結合する部位を表す。

In the formulas (8-1) to (8-5), "*" represents a site that binds to ^{Ar 1.}

Of the above, Z in the formula (4) is preferably a cycloalkylene having 3 to 20 carbon atoms, an arylene having 6 to 20 carbon atoms, and an aralkylene having 8 to 20 carbon atoms, and is preferably an aralkylene having 8 to 20 carbon atoms. 3), (6-4), (7-1), (8-1) to (8-5) are epoxy (meth) acrylates having excellent heat resistance and dielectric properties. It is more preferable because a resin composition can be obtained. M in the formula (4) is 0 or an integer of 1 to 10, preferably 0 to 8, and is preferable because an epoxy (meth) acrylate resin composition having excellent heat resistance and dielectric properties can be obtained. Is 0-5.

Further, the compound (A4) having a phenolic hydroxyl group may have a structure described in the following formula (9).

但し式（９）中、ｌは１以上の整数、Ｒ_２は水素原子、アルキル基、又はアリール基を示す。）

However, in the formula (9), l is an integer of 1 or more, and R ₂ is a hydrogen atom, an alkyl group, or an aryl group. )

In formula (9), l is preferably an integer of 1 to 20, more preferably 1 to 15, and even more preferably 1 to 12. Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, a pentyl group, a normal hexyl group, a cyclohexyl group and the like. .. Examples of the aryl group include a benzyl group, a naphthyl group, a methoxynaphthyl group and the like.

Among the above, since an epoxy (meth) acrylate resin composition having excellent heat resistance and dielectric properties can be obtained, the compounds represented by the formulas (4) and (9) are preferable, and further, the compound of the formula (4) is preferable. Of these, Ar ¹ is a residue of phenol, orthocresol, dimethylphenol, phenylphenol, or α-naphthol or β-naphthol, and Z is a residue of the formulas (6-3), (7-1), (8-1). ) To (8-5), and the compound represented by the formula (9) is more preferable.

Examples of the aromatic monobasic acid (A5) include benzoic acid, methyl benzoic acid, benzoic acid chloride, methyl benzoic acid chloride and the like.

As the aromatic ester compound (A), an epoxy (meth) acrylate resin composition having excellent heat resistance and dielectric properties can be obtained, so that the aromatic ester compound (A) has a structure represented by the following structural formula (I). preferable.

［式（Ｉ）中、環Ａは、それぞれ独立して、置換基を有していてもよいベンゼン環またはナフタレン環であり、Ｙはそれぞれ独立して、前記フェノール化合物（Ａ１）の反応残基または前記フェノール化合物（Ａ１）以外の多官能フェノール化合物であり、Ｚは前記フェノール化合物（Ａ３）の反応残基である、ｎは１〜２０の整数である。なお、ｎが１の場合、Ｙは前記フェノール化合物（Ａ１）の反応残基であり、ｎが２〜２０の整数の場合、Ｙは少なくとも１つが前記フェノール化合物（Ａ１）の反応残基である。］

[In the formula (I), the ring A is a benzene ring or a naphthalene ring which may independently have a substituent, and Y is an independent reaction residue of the phenol compound (A1). Alternatively, it is a polyfunctional phenol compound other than the phenol compound (A1), Z is a reaction residue of the phenol compound (A3), and n is an integer of 1 to 20. When n is 1, Y is a reaction residue of the phenol compound (A1), and when n is an integer of 2 to 20, at least one of Y is a reaction residue of the phenol compound (A1). .. ]

Specific examples of the compound having the structure represented by the structural formula (I) include aromatic ester compounds represented by the following formulas (Ia) and (Ib).

The method for producing the aromatic ester compound (A) is not particularly limited, and any method may be used for producing the aromatic ester compound (A). For example, it may be produced by a method in which all of the reaction raw materials containing the phenol compound (A1), the aromatic polybasic acid (A2), and the monofunctional phenol compound (A3) are reacted at once. , The reaction raw material may be produced by a method of sequentially reacting.

As a method for reacting all of the reaction raw materials at once, for example, the phenol compound (A1), the aromatic polybasic acid (A2), and the monofunctional phenol compound (A3) are used, if necessary. Examples thereof include a method obtained by reacting a reaction raw material containing a compound having a phenolic hydroxyl group (A4) and the aromatic monobasic acid (A5) at 20 to 140 ° C. under basic or acidic conditions.

As the epoxy (meth) acrylate resin (B), an epoxy resin (B1) and an unsaturated monobasic acid (B2) are essential reaction raw materials.

The specific structure of the epoxy resin (B1) is not particularly limited as long as it has a plurality of epoxy groups in the resin and can react with the unsaturated monobasic acid (B2). Examples of the epoxy resin (B1) include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type. Epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-shrink novolak type epoxy resin, naphthol-cresol co-shrink novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene -Pharmon-added reaction type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, xantene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, oxazolidone type epoxy resin and the like can be mentioned. These epoxy resins (B1) can be used alone or in combination of two or more. Further, among these, since an epoxy (meth) acrylate resin composition having excellent heat resistance and dielectric properties can be obtained, a bisphenol type epoxy resin, a hydrogenated bisphenol type epoxy resin, a biphenol type epoxy resin, and a hydrogenated biphenol type epoxy can be obtained. The resin and dihydroxybenzene type epoxy resin are preferable, and the bisphenol type epoxy resin or the hydrogenated bisphenol type epoxy resin is more preferable.

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

Examples of the hydrogenated bisphenol type epoxy resin include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol B type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol F type epoxy resin, and hydrogenated bisphenol S type epoxy resin. Examples include resin.

Examples of the biphenol type epoxy resin include 4,4'-biphenol type epoxy resin, 2,2'-biphenol type epoxy resin, tetramethyl-4,4'-biphenol type epoxy resin, and tetramethyl-2,2'. -Biphenol type epoxy resin and the like can be mentioned.

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

When the epoxy resin (B1) is any of the bisphenol type epoxy resin, the hydrogenated bisphenol type epoxy resin, the biphenol type epoxy resin, the hydrogenated biphenol type epoxy resin, or the dihydroxybenzene type epoxy resin. Since an epoxy (meth) acrylate resin composition having excellent heat resistance and dielectric properties can be obtained, the epoxy equivalent of the epoxy resin (B1) is preferably in the range of 110 to 400 g / equivalent.

The unsaturated monobasic acid (B2) refers to a compound having an acid group and a polymerizable unsaturated bond in one molecule. In the present invention, the "polymerizable unsaturated bond" means an unsaturated bond capable of radical polymerization.

Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group.

Examples of the unsaturated monobasic acid (B2) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, β-fulfurylacrylic acid and the like. Further, an esterified product of the unsaturated monobasic acid, an acid halide, an acid anhydride and the like can also be used. Further, a compound represented by the following structural formula (10) can also be used.

［式（１０）中、Ｘは、炭素数１〜１０のアルキレン鎖、ポリオキシアルキレン鎖、（ポリ）エステル鎖、芳香族炭化水素鎖、または（ポリ）カーボネート鎖を表し、構造中にハロゲン原子やアルコキシ基等を有していても良い。Ｙは、水素原子またはメチル基である。］

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

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

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

［式（Ｘ−１）中、Ｒ_１は、炭素原子数１〜１０のアルキレン基であり、ｎは１〜５の整数である。］

[In the formula (X-1), R ₁ is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5. ]

Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, a binaphthylene chain and the like. Further, as a partial structure, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring can also be used.

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

［式（Ｘ−２）中、Ｒ_２は、炭素原子数１〜１０のアルキレン基であり、ｎは１〜５の整数である。］

[In the formula (X-2), R ₂ is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5. ]

The molecular weight of the compound represented by the structural formula (15) is preferably in the range of 100 to 500, more preferably in the range of 150 to 400.

These unsaturated monobasic acids (B2) can be used alone or in combination of two or more.

The amount of the unsaturated monobasic acid (B2) used is such that the obtained epoxy (meth) acrylate resin has an epoxy group and a (meth) acryloyl group, and the epoxy (meth) has excellent heat resistance and dielectric properties. Since an acrylate resin composition can be obtained, the range of 0.25 to 0.75 mol is preferable with respect to 1 mol of the epoxy resin (B1).

The method for producing the epoxy (meth) acrylate resin (B) is not particularly limited, and any method may be used for producing the epoxy (meth) acrylate resin (B). For example, it may be produced by a method in which all of the reaction raw materials containing the epoxy resin (B1) and the unsaturated monobasic acid (B2) are reacted at once, or by a method in which the reaction raw materials are sequentially reacted. You may. In particular, since the reaction is easy to control, the epoxy resin (B1) and the unsaturated monobasic acid (B2) are reacted in the presence of a basic catalyst in a temperature range of 80 to 140 ° C., and then , The method of inactivating the basic catalyst by adding an acidic compound and mixing in a temperature range of 50 to 100 ° C. is preferable.

Examples of the basic catalyst include N-methylmorpholin, pyridine, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), and 1,5-diazabicyclo [4.3.0] nonen-. 5 (DBN), 1,4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1 -Methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (N-phenyl) aminopropyltrimethoxysilane, 3-( Amine compounds such as 2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane and tetramethylammonium hydroxide; and four such as trioctylmethylammonium chloride and trioctylmethylammonium acetate. Class ammonium salts; phosphines such as trimethylphosphine, tributylphosphine, triphenylphosphine; tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl (2-hydroxypropyl) phosphonium Phosphonium salts such as chloride, triphenylphosphonium chloride, benzylphosphonium chloride; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, Organic tin compounds such as 1,1,3,3-tetrabutyl-1,3-dodecanoyl distanoxane; organic metal compounds such as zinc octylate and bismuth octylate; inorganic tin compounds such as tin octanate; inorganic metal compounds And so on. These basic catalysts can be used alone or in combination of two or more.

The amount of the basic catalyst used is the total of the epoxy resin (B1) and the unsaturated monobasic acid (B2) because an epoxy (meth) acrylate resin composition having excellent heat resistance and dielectric properties can be obtained. The range of 0.01 to 0.5 parts by mass is preferable, and the range of 0.01 to 0.4 is more preferable with respect to 100 parts by mass.

Further, the reaction between the epoxy resin (B1) and the unsaturated monobasic acid (B2) can be carried out in an organic solvent, if necessary.

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

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

In the reaction between the epoxy resin (B1) and the unsaturated monobasic acid (B2) under the basic catalyst, in addition to the method of inactivating the basic catalyst with the acidic compound after the reaction, the above. A method of separating / removing the basic catalyst may be used.

The method for producing the epoxy (meth) acrylate resin composition of the present invention is not particularly limited, and any method may be used for producing the epoxy (meth) acrylate resin composition. For example, it can be obtained by mixing the aromatic ester compound (A) and the epoxy (meth) acrylate resin (B) at 30 to 120 ° C.

The mass ratio [(A) / (B)] of the solid content of the aromatic ester compound (A) and the epoxy (meth) acrylate resin (B) is an epoxy (meth) having excellent heat resistance and dielectric properties. Since an acrylate resin composition can be obtained, the range of 10/90 to 90/10 is preferable, and the range of 20/80 to 80/20 is more preferable.

Since the epoxy (meth) acrylate resin composition of the present invention has a polymerizable (meth) acryloyl group in the molecular structure, it can be used as a curable resin composition by adding, for example, a photopolymerization initiator. Can be done.

As the photopolymerization initiator, an appropriate one may be selected and used depending on the type of active energy ray to be irradiated and the like. Further, it may be used in combination with a photosensitizer such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound, and a nitrile compound. Specific examples of the photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino). Alkylphenone-based photopolymerization initiators such as -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; 2,4,6-trimethylbenzoyl-diphenyl- Acylphosphine oxide-based photopolymerization initiators such as phosphenyl oxide; intramolecular hydrogen abstraction type photopolymerization initiators such as benzophenone compounds and the like can be mentioned. These photopolymerization initiators can be used alone or in combination of two or more.

Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2-. Hydroxy-2-methyl-1-propane-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethane-1-one, diphenyl (2,4,6-trimethoxybenzoyl) phosphenyl Oxide, 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphenyl oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- On, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone and the like can be mentioned.

Examples of commercially available products of the other photopolymerization initiator include "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", and "Omnirad-379". , "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100", "Omnirad-2100" Omnirad-754 "," Omnirad-784 "," Omnirad-500 "," Omnirad-81 "(manufactured by IGM)," KayaCure-DETX "," KayaCure-MBP "," KayaCure-DMBI "," KayaCure-EPA " , "Kayacure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "Vicure-10", "Vicure-55" (manufactured by Stofa Chemical Co., Ltd.), "Trigonal P1" (manufactured by Akzo), "Sandray 1000" (manufactured by Akzo) Sands), "Deep" (Apjon), "QuantaCure-PDO", "QuantaCure-ITX", "QuantaCure-EPD" (Wordbrenkinsop), "Runtecure-1104" (Runtec) (Manufactured by the company) and the like. These photopolymerization initiators can be used alone or in combination of two or more.

The amount of the photopolymerization initiator added is preferably in the range of 0.05 to 15% by mass, preferably in the range of 0.1 to 10% by mass, in the total of the components other than the solvent of the curable resin composition, for example. Is more preferable.

The curable resin composition of the present invention may contain other resin components other than the epoxy (meth) acrylate resin composition described above. The other resin components include epoxy resin; vinyl group-containing compounds such as styrene, acrylic acid, methacrylic acid and esterified products thereof; cyanate ester resin; bismaleimide resin; benzoxazine resin; allyl group such as triallyl isocyanurate. Containing resin; polyphosphate ester, phosphoric acid ester-carbonate copolymer; various (meth) acrylate monomers and the like can be mentioned.

As the epoxy resin, the same ones as those exemplified as the above-mentioned epoxy resin (B1) can be used, and the epoxy resin can be used alone or in combination of two or more.

The various (meth) acrylate monomers are not particularly limited as long as they have a (meth) acryloyl group, and are, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth). ) Acrylate mono (meth) acrylate compounds such as acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate. , Alicyclic mono (meth) acrylate compounds such as adamantyl mono (meth) acrylate; heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; benzyl (meth) acrylate, phenyl (meth) ) Acrylate, phenylbenzyl (meth) acrylate, phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxybenzyl (meth) acrylate Mono (meth) acrylate compounds such as aromatic mono (meth) acrylate compounds such as benzylbenzyl (meth) acrylate and phenylphenoxyethyl (meth) acrylate: (poly) in the molecular structure of the various mono (meth) acrylate monomers. ) A (poly) oxyalkylene modified mono (meth) acrylate compound introduced with a polyoxyalkylene chain such as an oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain; the various mono (meth) acrylate compounds described above. A lactone-modified mono (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the above; ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di ( Aliphalic di (meth) acrylate compounds such as meta) acrylate and neopentyl glycol di (meth) acrylate; 1,4-cyclohexanedimethanol di (meth) acrylate, norbornandi (meth) acrylate, norbornan dimethanol di (meth). Alicyclic di (meth) acrylics such as acrylate, dicyclopentanyldi (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate Rate compounds; aromatic di (meth) acrylate compounds such as biphenol di (meth) acrylate and bisphenol di (meth) acrylate; (poly) oxyethylene chains, (poly) in the molecular structure of the various di (meth) acrylate compounds. ) Polyoxyalkylene-modified di (meth) acrylate compounds introduced with (poly) oxyalkylene chains such as oxypropylene chains and (poly) oxytetramethylene chains; (poly) in the molecular structure of the various di (meth) acrylate compounds. ) A lactone-modified di (meth) acrylate compound having a lactone structure introduced; an aliphatic tri (meth) acrylate compound such as trimethylpropantri (meth) acrylate and glycerin tri (meth) acrylate; A (poly) oxyalkylene-modified tri (meth) acrylate compound in which a (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain is introduced into the molecular structure of the compound; A lactone-modified tri (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the aliphatic tri (meth) acrylate compound; pentaerythritol tetra (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, dipenta. A tetrafunctional or higher functional aliphatic poly (meth) acrylate compound such as erythritol hexa (meth) acrylate; in the molecular structure of the aliphatic poly (meth) acrylate compound, a (poly) oxyethylene chain, a (poly) oxypropylene chain, ( A tetrafunctional or higher functional (poly) oxyalkylene-modified poly (meth) acrylate compound into which a (poly) oxyalkylene chain such as a poly) oxytetramethylene chain has been introduced; ) A tetrafunctional or higher functional lactone-modified poly (meth) acrylate compound having a lactone structure introduced; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylpropandi (meth) acrylate, Pentaerythritol (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, Hydroxyl-containing (meth) such as dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane (meth) acrylate, ditrimethylolpropane di (meth) acrylate, and ditrimethylolpropanetri (meth) acrylate. Acrylate compound: A (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain is introduced into the molecular structure of the hydroxyl group-containing (meth) acrylate compound (poly). ) Oxyalkylene modified product; A lactone modified product in which a (poly) lactone structure is introduced into the molecular structure of the hydroxyl group-containing (meth) acrylate compound; 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis. Isocyanate group-containing (meth) acrylate compounds such as (acryloyloxymethyl) ethyl isocyanate; glycidyl group-containing (meth) groups such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and epoxycyclohexylmethyl (meth) acrylate. ) Acrylate monomer, epoxy group-containing (meth) acrylate compound such as mono (meth) acrylate of diglycidyl ether compound of droxybenzene diglycidyl ether, dihydroxynaphthalenediglycidyl ether, biphenol diglycidyl ether, bisphenol diglycidyl ether, etc. Can be mentioned. These various (meth) acrylate monomers can be used alone or in combination of two or more.

Further, the curable resin composition of the present invention contains, if necessary, a curing agent, a curing accelerator, an organic solvent, an inorganic filler or polymer fine particles, a pigment, a defoaming agent, a viscosity modifier, a leveling agent, and a flame retardant. , Various additives such as a storage stabilizer can also be contained.

Examples of the curing agent include polybasic acids, unsaturated monobasic acids, amine compounds, amide compounds, azo compounds, organic peroxides, polyol compounds, epoxy resins and the like.

Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid. , Tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic 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-dioxotetrax-yl) -1, 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, Examples thereof include benzophenone tetracarboxylic acid. Further, as the polybasic acid, for example, a copolymer of a conjugated diene-based vinyl monomer and acrylonitrile, which has a carboxyl group in its molecule, can also be used. These polybasic acids can be used alone or in combination of two or more.

As the unsaturated monobasic acid, the same one as exemplified as the unsaturated monobasic acid (B2) described above can be used, and the unsaturated monobasic acid may be used alone or in combination of two or more. It can also be used together.

Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, guanidine derivative and the like. These amine compounds may be used alone or in combination of two or more.

Examples of the amide compound include a polyamide resin synthesized from a dimer of dicyandiamide and linolenic acid and ethylenediamine. These amide compounds may be used alone or in combination of two or more.

Examples of the azo compound include azobisisobutyronitrile.

Examples of the organic peroxide include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, alkylperoxycarbonates and the like. These organic peroxides can be used alone or in combination of two or more.

Examples of the polyol compound include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1, 5-Pentanediol, neopentylglycol, 1,6-hexanediol, glycerin, glycerin mono (meth) acrylate, trimethylolethane, trimethylolmethane mono (meth) acrylate, trimethylolpropane, trimethylolpropane mono (meth) acrylate , Pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate and other polyol monomers; , Hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, polyester polyol obtained by cocondensation with a dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid; A lactone-type polyester polyol obtained by a polycondensation reaction with various lactones such as δ-valerolactone and 3-methyl-δ-valerolactone; the polyol monomer and ethylene oxide, propylene oxide, tetrahydrofuran, ethylglycidyl ether, propylglycidyl. Examples thereof include a polyether polyol obtained by ring-opening polymerization with a cyclic ether compound such as ether. These polyol compounds can be used alone or in combination of two or more.

As the epoxy resin, the same ones as those exemplified as the above-mentioned epoxy resin (B1) can be used, and the epoxy resin can be used alone or in combination of two or more.

Examples of the curing accelerator include phosphorus-based compounds, amine-based compounds, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like, which promote the curing reaction. These curing accelerators can be used alone or in combination of two or more. The amount of the curing accelerator added is preferably in the range of 0.01 to 10% by mass in the solid content of the curable resin composition, for example.

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

Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide and the like.

Examples of the flame retardant include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphate such as ammonium polyphosphate, and inorganic phosphorus compounds such as phosphoric acid amide; phosphoric acid ester compounds and phosphorus compounds. Acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphoran compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxy) Cyclic organics such as phenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide Organophosphorus compounds such as phosphorus compounds and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds and phenothiazine; silicone oils, silicone rubbers, Silicone-based flame retardants such as silicone resins; examples thereof include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and inorganic flame retardants such as low melting point glass. These flame retardants may be used alone or in combination of two or more. When these flame retardants are used, it is preferably in the range of 0.1 to 20% by mass in the total resin composition.

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

As the ultraviolet source, an ultraviolet lamp is generally used from the viewpoint of practicality and economy. Specific examples thereof include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and LEDs.

Integrated light quantity of the active energy ray is not particularly limited, it is preferably from 10~5,000mJ / cm ^2, more preferably 50~1,000mJ / cm ^2. When the integrated light amount is in the above range, it is preferable because the generation of the uncured portion can be prevented or suppressed.

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

The article of the present invention has a coating film made of the cured product. Examples of the article include plastic molded products such as mobile phones, home appliances, automobile interior / exterior materials, and OA equipment, semiconductor devices, display devices, imaging devices, and the like.

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

In the examples of the present application, the weight average molecular weight of the aromatic ester compound was measured by GPC under the following conditions.

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation,
Column: Guard column "HXL-L" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation
Detector: RI (Differential Refractometer)
Data processing: "GPC-8020 Model II Version 4.10" manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent tetrahydrofuran
Flow velocity 1.0 ml / min Standard: The following monodisperse polystyrene with a known molecular weight was used in accordance with the measurement manual of "GPC-8020 Model II Version 4.10".
(Polystyrene used)
"A-500" manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation
"F-40" manufactured by Tosoh Corporation
"F-80" manufactured by Tosoh Corporation
"F-128" manufactured by Tosoh Corporation
Sample: A solution obtained by filtering 1.0% by mass of a tetrahydrofuran solution in terms of resin solid content with a microfilter (50 μl).

(Synthesis Example 1: Synthesis of bifunctional phenol compound (A1-1) having a vinylbenzyl group)
80.1 parts by mass of 1,6-dihydroxynaphthalene and hydrotalcite ("Kyoward 500SH" manufactured by Kyowa Chemical Industry Co., Ltd.) in a flask equipped with a thermometer, dropping funnel, cooling tube, fractional tube, and stirrer. 156 parts by mass and 624 parts by mass of toluene were charged and heated to 70 ° C. Then, 76.3 parts by mass of a mixture of metachloromethylstyrene and parachloromethylstyrene (“CMS-P” manufactured by AGC Seimicelcal Co., Ltd.) was added dropwise, and then the mixture was heated to 110 ° C. After continuing the reaction for 5 hours, the mixture was cooled and filtered to remove insoluble matter, and a reaction solution of a polyfunctional phenol compound (A1-1) having a vinylbenzyl group was obtained. When the reaction solution was analyzed in the same manner as above, it was found that the solid content hydroxyl group equivalent was 177 g / eq and the non-volatile content was 16.0%. It was also confirmed that a compound having the structure of the following formula was obtained.

(Synthesis Example 2: Synthesis of Aromatic Ester Compound (A-1))
442 parts by mass of the reaction solution (B-1) obtained in Synthesis Example 1, 57.6 parts by mass of α-naphthol, and isophthalate chloride 80 in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractional tube, and a stirrer. 8.8 parts by mass was charged, and the inside of the system was replaced with reduced pressure nitrogen to dissolve it. Then, 0.27 parts by mass of tetrabutylammonium bromide was dissolved, and while purging with nitrogen gas, the temperature inside the system was controlled to 60 ° C. or lower, and 164.8 parts by mass of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. .. Then, stirring was continued for 1 hour under this condition. After completion of the reaction, the liquid was separated by standing and the aqueous layer was removed. Further, water was further added to the toluene layer in which the reaction product was dissolved, and the mixture was stirred for 15 minutes, and the aqueous layer was removed by a static separation solution. This operation was repeated until the pH of the aqueous layer reached 7. Then, it was dried under hot and reduced pressure to obtain an aromatic ester compound (A-1) having the following structure.

(Synthesis Example 3: Synthesis of Aromatic Ester Compound (A'-1))
A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractional tube, and a stirrer was charged with 244 parts by mass of 2,5-xylenol and 1120 parts by mass of toluene, and the inside of the system was replaced with nitrogen under reduced pressure. Next, 203 parts by mass of isophthalic acid chloride was charged, and the inside of the system was replaced with nitrogen under reduced pressure. Next, 0.6 parts by mass of tetrabutylammonium bromide was added, and while performing nitrogen gas purging treatment, the inside of the system was controlled to 60 ° C. or lower, and 410 parts by mass of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. After completion of the dropping, the mixture was stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by a static liquid separation. Water was further added to the obtained toluene layer, the mixture was stirred for 15 minutes, and the aqueous layer was removed by a static separation solution. This operation was repeated until the pH of the aqueous layer reached 7. Then, it was heated and dried under reduced pressure to obtain an aromatic ester compound (A'-1) represented by the following structural formula.

(Synthesis Example 4: Production of Epoxy Acrylate Resin (B-1))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, a bisphenol A type epoxy resin (“EPICLON 850CRP” manufactured by DIC Corporation, epoxy equivalent 173 g / equivalent. Hereinafter, “bisphenol A type epoxy resin (1)” (Omitted) 346 parts by mass was charged, 0.21 part by mass of dibutylhydroxytoluene was added as an antioxidant, 0.21 part by mass of methquinone was added as a thermal polymerization inhibitor, and then 72 parts by mass of acrylic acid and 0.21 parts by triphenylphosphine were added. A part by mass was added, and the esterification reaction was carried out at 100 ° C. for 10 hours while blowing air. Then, after confirming that the acid value was 1 mgKOH / g or less, 0.21 parts by mass of oxalic acid was added, and the mixture was stirred at 70 ° C. for 3 hours to obtain an epoxy acrylate resin (B-1). The epoxy equivalent of this epoxy acrylate resin (B-1) was 450 g / equivalent. The number of moles of acid groups contained in acrylic acid was 0.5 with respect to 1 mole of epoxy groups contained in the bisphenol A type epoxy resin (1).

(Synthesis Example 5: Production of Epoxy Acrylate Resin (B-2))
A flask equipped with a thermometer, a stirrer, and a reflux cooler was charged with 346 parts by mass of bisphenol A type epoxy resin (1), 0.18 parts by mass of dibutylhydroxytoluene as an antioxidant, and 0 methquinone as a thermal polymerization inhibitor. After adding .18 parts by mass, 22 parts by mass of acrylic acid and 0.18 parts by mass of triphenylphosphine were added, and an esterification reaction was carried out at 100 ° C. for 5 hours while blowing air. Then, after confirming that the acid value was 1 mgKOH / g or less, 0.18 parts by mass of oxalic acid was added, and the mixture was stirred at 70 ° C. for 3 hours to obtain an epoxy acrylate resin (B-2). The epoxy equivalent of this epoxy acrylate resin (B-2) was 241 g / equivalent. The number of moles of acid groups contained in acrylic acid was 0.15 with respect to 1 mole of epoxy groups contained in the bisphenol A type epoxy resin (1).

(Synthesis Example 6: Production of Epoxy Acrylate Resin (B-3))
A flask equipped with a thermometer, a stirrer, and a reflux cooler was charged with 346 parts by mass of bisphenol A type epoxy resin (1), 0.19 parts by mass of dibutylhydroxytoluene as an antioxidant, and 0 methquinone as a thermal polymerization inhibitor. After adding .19 parts by mass, 43 parts by mass of acrylic acid and 0.19 parts by mass of triphenylphosphine were added, and an esterification reaction was carried out at 100 ° C. for 8 hours while blowing air. Then, after confirming that the acid value was 1 mgKOH / g or less, 0.19 parts by mass of oxalic acid was added, and the mixture was stirred at 70 ° C. for 3 hours to obtain an epoxy acrylate resin (B-3). The epoxy equivalent of this epoxy acrylate resin (B-3) was 301 g / equivalent. The number of moles of acid groups contained in acrylic acid was 0.3 with respect to 1 mole of epoxy groups contained in the bisphenol A type epoxy resin (1).

(Synthesis Example 7: Production of Epoxy Acrylate Resin (B-4))
A flask equipped with a thermometer, a stirrer, and a reflux cooler was charged with 346 parts by mass of bisphenol A type epoxy resin (1), 0.22 parts by mass of dibutylhydroxytoluene as an antioxidant, and 0 methquinone as a thermal polymerization inhibitor. After adding .22 parts by mass, 101 parts by mass of acrylic acid and 0.44 parts by mass of triphenylphosphine were added, and an esterification reaction was carried out at 100 ° C. for 10 hours while blowing air. Then, after confirming that the acid value was 1 mgKOH / g or less, 0.22 parts by mass of oxalic acid was added, and the mixture was stirred at 70 ° C. for 3 hours to obtain an epoxy acrylate resin (B-4). The epoxy equivalent of this epoxy acrylate resin (B-4) was 785 g / equivalent. The number of moles of acid groups contained in acrylic acid was 0.7 with respect to 1 mole of epoxy groups contained in the bisphenol A type epoxy resin (1).

(Synthesis Example 8: Production of Epoxy Acrylate Resin (B-5))
A flask equipped with a thermometer, a stirrer, and a reflux cooler was charged with 346 parts by mass of bisphenol A type epoxy resin (1), 0.23 parts by mass of dibutylhydroxytoluene as an antioxidant, and 0 methquinone as a thermal polymerization inhibitor. After adding .23 parts by mass, 122 parts by mass of acrylic acid and 0.46 parts by mass of triphenylphosphine were added, and an esterification reaction was carried out at 100 ° C. for 20 hours while blowing air. Then, after confirming that the acid value was 1 mgKOH / g or less, 0.23 parts by mass of oxalic acid was added, and the mixture was stirred at 70 ° C. for 3 hours to obtain an epoxy acrylate resin (B-5). The epoxy equivalent of this epoxy acrylate resin (B-5) was 1603 g / equivalent. The number of moles of acid groups contained in acrylic acid was 0.85 with respect to 1 mole of epoxy groups contained in the bisphenol A type epoxy resin (1).

(Synthesis Example 9: Production of Epoxy Acrylate Resin (B-6))
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, a naphthalene-type epoxy resin (“EPICLON 4032D” manufactured by DIC Corporation, epoxy equivalent 141 g / equivalent. Hereinafter, it is abbreviated as “naphthalene-type epoxy resin (1)”. ) 282 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.18 parts by mass of methquinone as a thermal polymerization inhibitor were added, followed by 72 parts by mass of acrylic acid and 0.18 parts by mass of triphenylphosphine. Was added, and the esterification reaction was carried out at 100 ° C. for 10 hours while blowing air. Then, after confirming that the acid value was 1 mgKOH / g or less, 0.18 parts by mass of oxalic acid was added, and the mixture was stirred at 70 ° C. for 3 hours to obtain an epoxy acrylate resin (B-6). The epoxy equivalent of this epoxy acrylate resin (B-6) was 388 g / equivalent. The number of moles of acid groups contained in acrylic acid was 0.50 with respect to 1 mole of epoxy groups contained in the naphthalene type epoxy resin (1).

(Example 1: Preparation of curable resin composition (1))
The aromatic ester compound (A-1) obtained in Synthesis Example 2 and the epoxy acrylate resin (B-1) obtained in Synthesis Example 4 are mixed to obtain an epoxy (meth) acrylate resin composition, and then an acrylate monomer is obtained. , Bisphenol A type epoxy resin (“EPICLON 850S” manufactured by DIC Co., Ltd.), a photopolymerization initiator (“Omnirad 184” manufactured by IGM Co., Ltd.), 2-ethyl-4-methylimidazole, and 4-dimethylaminopyridine. The mixture was mixed in the blending amount shown in 1 to obtain a curable resin composition (1).

(Examples 2 to 9: Preparation of curable resin compositions (2) to (9))
Curable resin compositions (2) to (9) were obtained in the same manner as in Example 1 with the compositions and formulations shown in Table 1.

(Comparative Examples 1 and 2: Preparation of curable resin compositions (C1) and (C2))
Curable resin compositions (C1) and (C2) were obtained in the same manner as in Example 1 with the compositions and formulations shown in Table 1.

The following evaluations were carried out using the curable resin compositions obtained in the above Examples and Comparative Examples.

[Evaluation method of heat resistance]
The curable resin composition obtained in each Example and Comparative Example was applied onto a copper foil (manufactured by Furukawa Sangyo Co., Ltd., electrolytic copper foil "F2-WS" 18 μm) so as to have a film thickness of 50 μm using an applicator. Then, it was dried at 80 ° C. for 30 minutes. ^{Then, after irradiating with an ultraviolet ray of 1000 mJ / cm 2} using a metal halide lamp, it was heated at 160 ° C. for 1 hour to obtain a cured coating film. Next, the cured coating film was peeled off from the copper foil to obtain a cured product. A 6 mm × 35 mm test piece was cut out from the cured product, and a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device “RSAII” manufactured by Leometric Co., Ltd., tensile method: frequency 1 Hz, heating rate 3 ° C./min) was used. The temperature at which the change in viscoelasticity was maximized was evaluated as the glass transition temperature. The higher the glass transition temperature, the better the heat resistance.

[Measurement method of permittivity]
The curable resin compositions obtained in each Example and Comparative Example were applied onto a glass substrate using an applicator so as to have a film thickness of 50 μm, and dried at 80 ° C. for 30 minutes. ^{Then, after irradiating with an ultraviolet ray of 1000 mJ / cm 2} using a metal halide lamp, it was heated at 160 ° C. for 1 hour to obtain a cured coating film. Next, the cured coating film was peeled off from the glass substrate to obtain a cured product. Next, a test piece stored in a room at a temperature of 23 ° C. and a humidity of 50% for 24 hours was used as a test piece, and the dielectric constant of the test piece at 1 GHz was determined by a cavity resonance method using a “network analyzer E8632C” manufactured by Agilent Technologies. It was measured.

[Measurement method of dielectric loss tangent]
The curable resin compositions obtained in each Example and Comparative Example were applied onto a glass substrate using an applicator so as to have a film thickness of 50 μm, and dried at 80 ° C. for 30 minutes. ^{Then, after irradiating with an ultraviolet ray of 1000 mJ / cm 2} using a metal halide lamp, it was heated at 160 ° C. for 1 hour to obtain a cured coating film. Next, the cured coating film was peeled off from the glass substrate to obtain a cured product. Next, a test piece stored in a room at a temperature of 23 ° C. and a humidity of 50% for 24 hours was used as a test piece, and a dielectric loss tangent of the test piece at 1 GHz was performed by a cavity resonance method using a “network analyzer E8632C” manufactured by Agilent Technologies. It was measured.

Table 1 shows the evaluation results of the curable resin compositions (1) to (9) prepared in Examples 1 to 9 and the curable resin compositions (C1) and (C2) prepared in Comparative Examples 1 and 2. ..

“Acrylate monomer” in Table 1 indicates a bisphenol A EO modified diacrylate (“Miramer M240” manufactured by MIWON).

Examples 1 to 9 shown in Table 1 are examples of a curable resin composition using the epoxy (meth) acrylate resin composition of the present invention. It was confirmed that this curable resin composition has excellent heat resistance and dielectric properties in the cured product, and has both heat resistance and dielectric properties in a well-balanced manner.

On the other hand, Comparative Example 1 is an example of a curable resin composition containing an aromatic ester compound made from a phenol compound having no vinylbenzyl group. It was confirmed that this curable resin composition had insufficient heat resistance.

Comparative Example 2 is an example of a curable resin composition that does not use the epoxy (meth) acrylate resin (B) specified in the present invention. It was confirmed that this curable resin composition had insufficient heat resistance and dielectric properties.

Claims (13)

An epoxy (meth) acrylate resin composition containing an aromatic ester compound (A) and an epoxy (meth) acrylate resin (B).
The aromatic ester compound (A) has a phenol compound (A1) having at least one vinylbenzyl group and at least two phenolic hydroxyl groups, an aromatic polybasic acid or a derivative thereof (A2), and the following structural formula (a). -1) The monofunctional phenol compound (A3) represented by any of (a-4) is used as an essential reaction raw material.
An epoxy (meth) acrylate resin composition, wherein the epoxy (meth) acrylate resin (B) contains an epoxy resin (B1) and an unsaturated monobasic acid (B2) as essential reaction raw materials.

[In the structural formulas (a-1) to (a-4), R ¹ is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom. And R ² is an independent hydrogen atom or methyl group, respectively. Further, p is 0 or an integer of 1 or more. ] The epoxy (meth) acrylate resin composition according to claim 1, wherein the phenol compound (A1) is represented by the following structural formula (1) or (2).

[In formulas (1) and (2), R ¹ is a vinylbenzyl group and R ² is a hydrogen atom, an alkyl group, or an aryl group. Further, in the equation (1), n is an integer of 1 to 4, m is an integer of 0 to 3, p is an integer of 2 to 5, and the sum of n, m, and p is 6. In equation (2), n is an integer of 1 to 6, m is an integer of 0 to 5, p is an integer of 2 to 7, and the sum of n, m, and p in equation (2) is 8. ^{R 1} and R ² in the formulas (1) and (2) may be the same or different. ] The epoxy (meth) acrylate resin composition according to claim 1, wherein the aromatic ester compound (A) has a vinylbenzyl structure derived from the phenol compound (A1). The epoxy (meth) acrylate resin composition according to claim 3, wherein the vinylbenzyl structure is composed of a vinylbenzyl-modified aryloxycarbonyl group. The epoxy (meth) acrylate resin composition according to claim 1, wherein the aromatic ester compound (A) has a structure represented by the following structural formula (I).

[In the formula (I), the ring A is a benzene ring or a naphthalene ring which may independently have a substituent, and Y is an independent reaction residue of the phenol compound (A1). Alternatively, it is a polyfunctional phenol compound other than the phenol compound (A1), Z is a reaction residue of the phenol compound (A3), and n is an integer of 1 to 20. When n is 1, Y is a reaction residue of the phenol compound (A1), and when n is an integer of 2 to 20, at least one of Y is a reaction residue of the phenol compound (A1). .. ] The epoxy (meth) acrylate resin composition according to claim 1, wherein the epoxy (meth) acrylate resin (B) has an epoxy group and a (meth) acryloyl group. The epoxy according to claim 1, wherein the number of moles of the acid group of the unsaturated monobasic acid (B2) is in the range of 0.25 to 0.75 with respect to 1 mol of the epoxy group of the epoxy resin (B1). Meta) Acrylate resin composition. Claimed that the mass ratio [(A) / (B)] of the solid content of the aromatic ester compound (A) and the epoxy (meth) acrylate resin (B) is in the range of 10/90 to 90/10. Item 2. The epoxy (meth) acrylate resin composition according to Item 1. A curable resin composition containing the epoxy (meth) acrylate resin composition according to any one of claims 1 to 8 and a photopolymerization initiator. The curable resin composition according to claim 9, further comprising a (meth) acrylate monomer. The curable resin composition according to claim 9, further comprising a curing agent. A cured product according to any one of claims 9 to 11, which is a cured reaction product of the curable resin composition. An article characterized by having a coating film made of the cured product according to claim 12.