JP7228104B2 - Epoxy (meth)acrylate resin composition, curable resin composition, cured product and article - Google Patents

Description

TECHNICAL FIELD The present invention relates to an epoxy (meth)acrylate resin composition having excellent heat resistance and dielectric properties, a curable resin composition containing the same, and a cured product and 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 used in inks, paints, coating agents, adhesives, optical It is widely used in the field of parts and the like. Among them, as the coating agent application, it is generally required to be able to impart designability to various substrate surfaces, have excellent curability, and be able to form a coating film that can prevent deterioration of the substrate surface. It is Moreover, in recent years, the industrial world has demanded a material capable of forming a cured coating film having not only curability but also adhesion to a substrate. Furthermore, when used as a solder resist curable composition for printed wiring boards, in addition to the above-mentioned required properties, it is also required to cure with a small amount of exposure, 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 reacting an intermediate obtained by reacting a cresol novolac type epoxy resin, acrylic acid and phthalic anhydride with tetrahydrophthalic anhydride A photosensitive resin composition containing an acrylate resin is known (see, for example, Patent Document 1). , there are problems such as deterioration of dielectric characteristics.

Therefore, materials having excellent dielectric properties in addition to heat resistance have been desired.

JP-A-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 same, a cured product of the curable resin composition, and the An object of the present invention is to provide an article having a coating film of a cured product.

As a result of intensive studies conducted by the present inventors to solve the above problems, the present inventors found that an epoxy (meth)acrylate resin composition containing a specific aromatic ester compound and a specific epoxy (meth)acrylate resin can be used. The inventors have found that the above problems can be solved by the method, and have completed the present invention.

That is, the present invention provides 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 monofunctional phenol compound (A1) having at least one vinylbenzyl group and an aromatic polybasic acid or a derivative thereof (A2) are essential reaction raw materials, and the epoxy (meth)acrylate resin (B) is , an epoxy (meth)acrylate resin composition comprising an epoxy resin (B1) and an unsaturated monobasic acid (B2) as essential reaction raw materials; a curable resin composition containing the same; The present invention relates to cured products and articles made from curable resin compositions.

Since the epoxy (meth)acrylate resin composition of the present invention has excellent heat resistance and excellent dielectric properties, 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 used particularly preferably for solder resist applications. The term "excellent dielectric properties" as used in the present invention means low dielectric constant and low dielectric loss tangent.

1 is a GPC chart of a monofunctional phenol compound obtained in Synthesis Example 1. FIG. 1 is a GPC chart of a monofunctional phenol compound obtained in Synthesis Example 2. FIG. 3 is a GPC chart of the aromatic ester compound obtained in Synthesis Example 3. FIG. 4 is a GPC chart of the aromatic ester compound obtained in Synthesis Example 4. FIG.

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 addition, in this invention, "(meth)acrylate" means an acrylate and/or a methacrylate. Moreover, "(meth)acryloyl" means acryloyl and/or methacryloyl. Furthermore, "(meth)acryl" means acryl and/or methacryl.

Examples of the aromatic ester compound (A) include a monofunctional phenol compound (A1) having at least one vinylbenzyl group, and an aromatic polybasic acid or derivative thereof (A2) (hereinafter referred to as "aromatic polybasic acid (A2 )” is used as an essential reaction raw material.

Examples of the monofunctional phenol compound (A1) include one or more selected from monocyclic or polycyclic aromatic compounds having one phenolic hydroxyl group. Examples of the monofunctional phenol compound (A1) include phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, 2,6-xylenol, o-phenylphenol, p-phenylphenol, 2 -benzylphenol, 4-benzylphenol, 4-(α-cumyl)phenol, α-naphthol, β-naphthol and other aromatic monohydroxy compounds. Among these, using one or more aromatic monohydroxy compounds selected from α-naphthol, β-naphthol, o-phenylphenol, and p-phenylphenol has excellent heat resistance and lower dielectric loss tangent curing. It is preferable because you can get things.

It is preferable that the vinylbenzyl group of the monofunctional phenol compound (A1) is directly substituted on the aromatic ring of the monofunctional phenol compound.

Examples of the vinylbenzyl group include an ethenylbenzyl group, an isopropenylbenzyl group, a normal propenylbenzyl group, and the like. Among these, an ethenylbenzyl group is preferred in terms of industrial availability and curability.

The monofunctional phenol compound (A1) may have one or more substituents such as an alkyl group and an aryl group in addition to the vinylbenzyl group. Examples of the alkyl group include alkyl groups having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, tertiary butyl group, pentyl group, normal hexyl group and cyclohexyl group. Examples of the aryl group include benzyl group, naphthyl group, methoxynaphthyl group and the like.

Specific examples of the monofunctional phenol compound (A1) include compounds represented by the following structural formula (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１～５の整数、ｍは０～４の整数であり、ｎとｍの和は５である。式（２）中のｎは１～７の整数、ｍは０～６の整数であり、式（２）におけるｎとｍの和は７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. In formula (1), n is an integer of 1 to 5, m is an integer of 0 to 4, and the sum of n and m is 5. n in formula (2) is an integer of 1 to 7, m is an integer of 0 to 6, and the sum of n and m in formula (2) is 7. R ₁ and R ₂ in formulas (1) and (2) may be the same or different. ]

Incidentally, the hydroxyl group, R ₁ and R ₂ in formula (2) indicate that they may be bonded to any ring as substituents on the naphthalene ring.

Examples of the alkyl group include alkyl groups having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, tertiary butyl group, pentyl group, normal hexyl group and cyclohexyl group. 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 that

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

Examples of the aromatic polybasic acid or derivative thereof (A2) include aromatic compounds such as isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid. dicarboxylic acids; aromatic tricarboxylic acids such as trimesic acid and trimellitic acid; pyromellitic acid; and acid halides and esters thereof. These can be used alone or in combination of two or more. Among them, 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 aromatic ester compound (A), in addition to the monofunctional phenol compound (A1) and the aromatic polybasic acid or derivative thereof (A2), a compound (A3) having at least two phenolic hydroxyl groups, an aromatic A group monobasic acid or derivative thereof (A4) may be contained as a reactant.

Examples of the compound (A3) having at least two phenolic hydroxyl groups include compounds represented by the following structural formulas (3-1) to (3-7).

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

Moreover, the compound (A3) 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。〕

[In formula (4), m is an integer of 0 to 20. ]

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

Ar ¹ is not particularly limited, but 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), each R ₂ is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. n in formula (5-1) is an integer of 0 to 5, and n in formula (5-2) is an integer of 0 to 7. Examples of the alkyl group include alkyl groups having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, tertiary butyl group, pentyl group, normal hexyl group, cyclohexyl group and the like. . Examples of the aryl group include benzyl group, naphthyl group, methoxynaphthyl group and the like.

The alkylene having 1 to 20 carbon atoms in Z is not particularly limited, but 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) -4), and the like.

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 ^Ar1 .

Examples of the arylene having 6 to 20 carbon atoms include, but are not particularly limited to, 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 ^Ar1 .

Examples of the aralkylene having 8 to 20 carbon atoms include, but are not particularly limited to, 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 formulas (8-1) to (8-5), "*" represents a site that binds to ^Ar1 .

Among the above, Z in formula (4) is preferably cycloalkylene having 3 to 20 carbon atoms, arylene having 6 to 20 carbon atoms, or 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 formula (4) is an integer of 0 or 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.

Also, the compound (A3) having at least two phenolic hydroxyl groups may have a structure represented by 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 formula (9), l is an integer of 1 or more, and _R2 is a hydrogen atom, an alkyl group, or an aryl group. )

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

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

Examples of the aromatic monobasic acid or derivative thereof (A4) include benzoic acid and benzoyl chloride.

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

［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、Ｘは前記単官能フェノール化合物（ａ１）の反応残基であり、Ｙは多官能フェノール化合物の反応残基である。また、ｎは０～２０の整数である。］

[In formula (I), ring A is each independently a benzene ring or naphthalene ring which may have a substituent, X is a reaction residue of the monofunctional phenol compound (a1), Y is a reactive residue of a polyfunctional phenol compound. Also, n is an integer of 0-20. ]

Specific examples of compounds 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 example, the monofunctional phenol compound (A1) and all of the reaction raw materials containing the aromatic polybasic acid or derivative thereof (A2) may be reacted at once, or the reaction raw materials may be sequentially added. You may manufacture by the method to make it react. As a method of reacting all of the reaction raw materials at once, for example, the monofunctional phenol compound (A1) and the aromatic polybasic acid or derivative thereof (A2) under basic conditions or under acidic conditions, 20 to A method obtained by reacting at 140 ° C. (method 1), the monofunctional phenol compound (A1), the aromatic polybasic acid or derivative thereof (A2), and the compound having at least two phenolic hydroxyl groups (A3 ) under basic or acidic conditions at 20 to 140° C. (Method 2), the monofunctional phenol compound (A1), the aromatic polybasic acid or derivative thereof (A2), A method obtained by reacting the compound (A3) having at least two phenolic hydroxyl groups and the aromatic monobasic acid or derivative thereof (A4) under basic or acidic conditions at 20 to 140° C. (Method 3 ) and the like.

In Method 1, the reaction between the monofunctional phenol compound (A1) and the aromatic polybasic acid or derivative thereof (A2) is carried out with respect to 1 mol of the phenolic hydroxyl group of the monofunctional phenol compound (A1). , The number of moles of functional groups capable of reacting with phenolic hydroxyl groups possessed by the aromatic polybasic acid or its derivative (A2) is preferably in the range of 0.9 to 1.1, preferably 0.95 to 1.1. 05 range is more preferred.

In Method 2, the reaction of the monofunctional phenol compound (A1), the aromatic polybasic acid or derivative thereof (A2), and the compound (A3) having at least two phenolic hydroxyl groups is the monofunctional phenol With respect to 1 mol of the phenolic hydroxyl group of the compound (A1) and the compound (A3) having at least two phenolic hydroxyl groups, it can react with the phenolic hydroxyl group of the aromatic polybasic acid or its derivative (A2). The number of moles of functional groups is preferably in the range of 0.9 to 1.1, more preferably in the range of 0.95 to 1.05.

In Method 3, the monofunctional phenol compound (A1), the aromatic polybasic acid or derivative thereof (A2), the compound (A3) having at least two phenolic hydroxyl groups and the aromatic monobasic acid or In the reaction of the derivative (A4), the aromatic polybasic acid or its The number of moles of the functional group capable of reacting with the phenolic hydroxyl group possessed by the derivative (A2) and the aromatic monobasic acid or its derivative (A4) is preferably in the range of 0.9 to 1.1. A range of 95 to 1.05 is more preferred.

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 resins, phenylene ether-type epoxy resins, naphthylene ether-type epoxy resins, biphenyl-type epoxy resins, triphenylmethane-type epoxy resins, phenol novolac-type epoxy resins, and cresol novolac-type epoxy resins. Epoxy resins, bisphenol novolak type epoxy resins, naphthol novolac type epoxy resins, naphthol-phenol co-condensation novolak type epoxy resins, naphthol-cresol co-condensation novolak type epoxy resins, phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, dicyclopentadiene -phenol addition reaction type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, oxazolidone type epoxy resin and the like. These epoxy resins (B1) can be used alone or in combination of two or more. Among these, since an epoxy (meth)acrylate resin composition having excellent heat resistance and dielectric properties can be obtained, bisphenol type epoxy resin, hydrogenated bisphenol type epoxy resin, biphenol type epoxy resin, hydrogenated biphenol type epoxy resin A resin, a dihydroxybenzene type epoxy resin is preferable, and a bisphenol type epoxy resin or a 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 resin. Resin etc. are mentioned.

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. Resin etc. are mentioned.

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, tetramethyl-2,2' - Biphenol-type epoxy resin and the like.

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. , hydrogenated tetramethyl-2,2'-biphenol type epoxy resin, and the like.

When the epoxy resin (B1) is any one 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, The epoxy equivalent of the epoxy resin (B1) is preferably in the range of 110 to 400 g/equivalent so that an epoxy (meth)acrylate resin composition having excellent heat resistance and dielectric properties can be obtained.

The unsaturated monobasic acid (B2) refers to a compound having an acid group and a polymerizable unsaturated bond in one molecule. In addition, in this invention, a "polymerizable unsaturated bond" means the unsaturated bond which can be radically polymerized.

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-furfurylacrylic acid and the like. Esterified products, acid halides, acid anhydrides, etc. of the unsaturated monobasic acids can also be used. Furthermore, compounds represented by the following structural formula (10) and the like 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 the 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. Y is a hydrogen atom or a methyl group. ]

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

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

Examples of the (poly)carbonate chain include (poly)carbonate chains 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 100-500, more preferably in the range of 150-400.

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 resulting epoxy (meth)acrylate resin has an epoxy group and a (meth)acryloyl group, and has excellent heat resistance and dielectric properties. It is preferably in the range of 0.25 to 0.75 mol per 1 mol of the epoxy resin (B1), since an acrylate resin composition can be obtained.

The method for producing the epoxy (meth)acrylate resin (B) is not particularly limited, and any method may be used. For example, it may be produced by a method of reacting all reaction raw materials containing the epoxy resin (B1) and the unsaturated monobasic acid (B2) at once, or by a method of sequentially reacting the reaction raw materials. You may Among them, 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 , an acidic compound is added and mixed at a temperature of 50 to 100°C to deactivate the basic catalyst.

Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene- 5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1 -methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-( 2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, amine compounds such as tetramethylammonium hydroxide; trioctylmethylammonium chloride, trioctylmethylammonium acetate, etc. ammonium salts; phosphines such as trimethylphosphine, tributylphosphine, and triphenylphosphine; Phosphonium salts such as chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; Organic tin compounds such as 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; Organometallic compounds such as zinc octylate and bismuth octylate; Inorganic tin compounds such as tin octoate; etc. These basic catalysts can be used alone or in combination of two or more.

Since an epoxy (meth)acrylate resin composition having excellent heat resistance and dielectric properties is obtained, the amount of the basic catalyst used is the total of the epoxy resin (B1) and the unsaturated monobasic acid (B2). It is preferably in the range of 0.01 to 0.5 parts by mass, more preferably in the range of 0.01 to 0.4 parts by mass, based on 100 parts by mass.

Moreover, 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 , 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, since the reaction efficiency is improved.

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 can 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 deactivating the basic catalyst with the acidic compound after the reaction, the above A method of separating and 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 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) compound having excellent heat resistance and dielectric properties. A range of 10/90 to 90/10 is preferable, and a range of 20/80 to 80/20 is more preferable, since an acrylate resin composition can be obtained.

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

As for the photopolymerization initiator, an appropriate one may be selected and used according to the type of active energy ray to be irradiated. 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 photopolymerization initiators include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino) -2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone and other alkylphenone photoinitiators; 2,4,6-trimethylbenzoyl-diphenyl- acylphosphine oxide-based photopolymerization initiators such as phosphine oxide; intramolecular hydrogen abstraction type photopolymerization initiators such as benzophenone compounds; 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, 1-[4-(2-hydroxyethoxy)phenyl]-2- Hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2′-dimethoxy-1,2-diphenylethan-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1- one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, and the like.

Commercially available products of the other photopolymerization initiators include, for example, "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-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 Stouffer Chemical), “Trigonal P1” (manufactured by Akzo), “Sunray 1000” ( Sands), "Deep" (Upjohn), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (Ward Blenkinsop), "Runtecure-1104" (Runtec 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, for example, preferably in the range of 0.05 to 15% by mass in the total of components other than the solvent of the curable resin composition, and in the range of 0.1 to 10% by mass. is more preferable.

The curable resin composition of the present invention may contain resin components other than the epoxy (meth)acrylate resin composition described above. Examples of the other resin components include epoxy resins; vinyl group-containing compounds such as styrene, acrylic acid, methacrylic acid and their esters; cyanate ester resins; bismaleimide resins; benzoxazine resins; Contained resin; polyphosphate and phosphate-carbonate copolymer; and various (meth)acrylate monomers.

As the epoxy resin, the same epoxy resin as exemplified as the 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. Examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, ) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate and other aliphatic mono (meth) acrylate compounds; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate , adamantyl mono (meth) acrylate and other alicyclic mono (meth) acrylate compounds; glycidyl (meth) acrylate, tetrahydrofurfuryl acrylate and other heterocyclic mono (meth) acrylate compounds; 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 , benzylbenzyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate, etc. Mono (meth) acrylate compounds such as aromatic mono (meth) acrylate compounds: In the molecular structure of the various mono (meth) acrylate monomers (poly ) (poly)oxyalkylene-modified mono(meth)acrylate compounds introduced with polyoxyalkylene chains such as oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains; Lactone-modified mono(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of; 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, norbornane di(meth)acrylate, norbornane dimethanol di(meth) Alicyclic di(meth)acrylates such as acrylates, dicyclopentanyl di(meth)acrylates, and tricyclodecanedimethanol di(meth)acrylates rate compounds; aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; ) A polyoxyalkylene-modified di(meth)acrylate compound into which a (poly)oxyalkylene chain such as an oxypropylene chain or (poly)oxytetramethylene chain is introduced; ) Lactone-modified di(meth)acrylate compounds having a lactone structure; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; the aliphatic tri(meth)acrylate compounds A (poly)oxyalkylene-modified tri(meth)acrylate compound in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, (poly)oxypropylene chain, or (poly)oxytetramethylene chain is introduced into the molecular structure of; Lactone-modified tri(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of the aliphatic tri(meth)acrylate compound; pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipenta A tetrafunctional or higher aliphatic poly(meth)acrylate compound such as erythritol hexa(meth)acrylate; (poly)oxyethylene chain, (poly)oxypropylene chain, ( Tetrafunctional or higher (poly)oxyalkylene-modified poly(meth)acrylate compound introduced with a (poly)oxyalkylene chain such as a poly(poly)oxytetramethylene chain; in the molecular structure of the aliphatic poly(meth)acrylate compound (poly ) Tetra- or higher-functional lactone-modified poly(meth)acrylate compounds into which a lactone structure is introduced; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(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 group-containing (meth)acrylate such as dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, etc. Acrylate compound; a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, (poly)oxypropylene chain, or (poly)oxytetramethylene chain introduced into the molecular structure of the hydroxyl group-containing (meth)acrylate compound (poly ) Oxyalkylene modified product; 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 (Acryloyloxymethyl) isocyanate group-containing (meth)acrylate compounds such as ethyl isocyanate; ) epoxy group-containing (meth)acrylate compounds such as acrylate monomers, mono(meth)acrylates of diglycidyl ether compounds of droxybenzene diglycidyl ether, dihydroxynaphthalenediglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether; is mentioned. These various (meth)acrylate monomers can be used alone or in combination of two or more.

In addition, the curable resin composition of the present invention may optionally contain a curing agent, a curing accelerator, an organic solvent, an inorganic filler, polymer fine particles, a pigment, an antifoaming agent, a viscosity modifier, a leveling agent, and a flame retardant. , and various additives such as storage stabilizers.

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

Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic 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-dioxotetrahydrofuran-3-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, benzophenonetetracarboxylic acid and the like. 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 as those exemplified as the unsaturated monobasic acid (B2) described above can be used, and the unsaturated monobasic acid can be used alone or in combination of two or more. They can also be used in combination.

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

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

Examples of the azo compound include azobisisobutyronitrile.

Examples of the organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and alkylperoxycarbonates. 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, neopentyl glycol, 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, etc.; , hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,4-cyclohexanedicarboxylic acid and other dicarboxylic acids; , δ-valerolactone, 3-methyl-δ-valerolactone, lactone-type polyester polyol obtained by polycondensation reaction with various lactones such as 3-methyl-δ-valerolactone; Examples include polyether polyols obtained by ring-opening polymerization with cyclic ether compounds such as ethers. These polyol compounds can be used alone or in combination of two or more.

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

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

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

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

Examples of the flame retardant include red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate and ammonium polyphosphate; inorganic phosphorus compounds such as phosphate amide; acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxy Cyclic organic compounds such as phenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide Organic phosphorus compounds such as phosphorus compounds and derivatives obtained by reacting them with compounds such as epoxy resins and phenolic resins; triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, nitrogen-based flame retardants such as phenothiazine; silicone oils, silicone rubbers, silicone-based flame retardants such as silicone resins; inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass; These flame retardants can be used alone or in combination of two or more. Further, when using these flame retardants, 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 an active energy ray. Examples of the active energy rays 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, the irradiation may be performed in an atmosphere of an inert gas such as nitrogen gas or in an air atmosphere in order to efficiently perform the curing reaction using the ultraviolet rays.

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

The integrated amount of active energy rays is not particularly limited, but is preferably 10 to 5,000 mJ/cm ² , more preferably 50 to 1,000 mJ/cm ² . It is preferable that the integrated amount of light is within the above range because the generation of uncured portions can be prevented or suppressed.

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

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

EXAMPLES The present invention will be specifically described below 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 rate 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: 1.0% by mass of tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (50 μl)

(Synthesis Example 1: Synthesis of a monofunctional phenol compound (A1-1) having a vinylbenzyl group)
72.1 parts by mass of α-naphthol and 156 parts by mass of hydrotalcite (“Kyoward 500SH” manufactured by Kyowa Chemical Industry Co., Ltd.) were placed in a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer. , and 608 g of toluene were charged and heated to 70°C. Next, 76.3 parts by mass of a mixture of meta-chloromethylstyrene and para-chloromethylstyrene ("CMS-P" manufactured by AGC Seimikaru Cal Co., Ltd.) was added dropwise, and the mixture was heated to 110°C. After continuing the reaction for 5 hours, the reaction mixture was cooled and filtered to remove insolubles to obtain a reaction solution of a monofunctional phenol compound (A1-1) having a vinylbenzyl group. Analysis of the reaction solution revealed a solid hydroxyl equivalent of 347 g/eq and a non-volatile content of 15.6% by mass, confirming that a compound having the structure of the following formula (2-1) was obtained.

(Synthesis Example 2: Synthesis of a monofunctional phenol compound (A1-2) having a vinylbenzyl group)
72.1 parts by mass of β-naphthol and 156 parts by mass of hydrotalcite ("Kyoward 500SH" manufactured by Kyowa Chemical Industry Co., Ltd.) were placed in a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer. , and 608 parts by mass of toluene were charged and heated to 70°C. Next, 76.3 parts by mass of a mixture of meta-chloromethylstyrene and para-chloromethylstyrene ("CMS-P" manufactured by AGC Seimikaru Cal Co., Ltd.) was added dropwise, and the mixture was heated to 110°C. After continuing the reaction for 5 hours, the reaction mixture was cooled and filtered to remove insoluble matter to obtain a reaction solution of a monofunctional phenol compound (A1-2) having a vinylbenzyl group. When the reaction solution was analyzed in the same manner as above, the solid content hydroxyl equivalent was 352 g / eq and the non-volatile content was 14.4% by mass, so that a compound having the structure of the following formula (2-2) was obtained. was confirmed.

(Synthesis Example 3: Synthesis of a bifunctional phenol compound (A1-3) having a vinylbenzyl group)
A flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer was charged with 80.1 parts by mass of 1,6-dihydroxynaphthalene, 156 parts by mass of Kyoward 500SH, and 624 parts by mass of toluene, and heated to 70°C. bottom. Then, 76.3 parts by mass of CMS-P was added dropwise and heated to 110°C. After continuing the reaction for 5 hours, the reaction mixture was cooled and filtered to remove insoluble matter to obtain a reaction solution of a bifunctional phenol compound (A1-3) having a vinylbenzyl group. When the reaction solution was analyzed in the same manner as above, it was found to have a solid content hydroxyl equivalent of 177 g/eq and a non-volatile content of 16.0%. It was confirmed that a compound having the structure of the following formula was obtained.

(Synthesis Example 4: Synthesis of aromatic ester compound (A-1))
A flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer was charged with 445 parts by mass of the reaction solution of the monofunctional phenol compound (A1-1) having a vinylbenzyl group obtained in Synthesis Example 1 and isophthaloyl chloride. 20.2 parts by mass was charged, and the inside of the system was replaced with nitrogen under reduced pressure and dissolved. After that, 0.12 parts by mass of tetrabutylammonium bromide was dissolved, and while purging with nitrogen gas, the inside of the system was controlled at 60°C or less, and 41.2 parts by mass of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. . Stirring was then continued under these conditions for 1 hour. After completion of the reaction, the mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Further, water was added to the toluene layer in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes, and the mixture was allowed to stand still for liquid separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Then, it was dried under heat and reduced pressure to obtain an aromatic ester compound (A-1) having a structure of the following formula (Ia).

(Synthesis Example 5: Synthesis of aromatic ester compound (A-2))
A flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer was charged with 733 parts by mass of the reaction solution of the monofunctional phenol compound (A1-2) having a vinylbenzyl group obtained in Synthesis Example 2 and isophthaloyl chloride. 30.3 parts by mass was charged, and the inside of the system was replaced with nitrogen under reduced pressure for dissolution. After that, 0.19 parts by mass of tetrabutylammonium bromide was dissolved, and while purging with nitrogen gas, the inside of the system was controlled at 60°C or less, and 61.8 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. . Stirring was then continued under these conditions for 1 hour. After completion of the reaction, the mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Further, water was added to the toluene layer in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes, and the mixture was allowed to stand still for liquid separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Then, it was dried under heat and reduced pressure to obtain an aromatic ester compound (A-2) having a structure of the following formula (Ib).

(Synthesis Example 6: Synthesis of aromatic ester compound (A-3))
A thermometer, a dropping funnel, a condenser, a fractionating tube, and a flask equipped with a stirrer were charged with 222 parts by mass of the reaction solution of the monofunctional phenol compound (A1-1) having a vinylbenzyl group obtained in Synthesis Example 1, and Synthesis Example 3. 221 parts by mass of the reaction solution of the bifunctional phenol compound (A1-3) having a vinylbenzyl group obtained in 1. and 40.4 parts by mass of isophthaloyl chloride were charged, and the system was decompressed and replaced with nitrogen to dissolve. Thereafter, 0.17 parts by mass of tetrabutylammonium bromide was dissolved, and while purging with nitrogen gas, the inside of the system was controlled at 60° C. or lower, and 82 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued under these conditions for 1.0 hour. After completion of the reaction, the mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Further, water was added to the toluene layer in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes, and the mixture was allowed to stand still for liquid separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Then, it was dried under heat and reduced pressure to obtain the desired aromatic ester compound (A-3).

(Synthesis Example 7: Synthesis of aromatic ester compound (A'-1))
244 parts by mass of 2,5-xylenol and 1120 parts by mass of toluene were charged into a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube and stirrer, and the system was replaced with nitrogen under reduced pressure. Then, 203 parts by mass of isophthaloyl 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 is added, and while performing nitrogen gas purging, the inside of the system is controlled to 60 ° C. or less, and 410 parts by mass of a 20% sodium hydroxide aqueous solution is added dropwise over 3 hours, After completion of dropping, the mixture was stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by standing liquid separation. Water was further added to the obtained toluene layer, and the mixture was stirred for 15 minutes, and the aqueous layer was removed by standing 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'-1) represented by the following structural formula was obtained.

(Synthesis Example 8: Production of epoxy acrylate resin (B-1))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with a bisphenol A epoxy resin ("EPICLON 850CRP" manufactured by DIC Corporation, with an epoxy equivalent of 173 g/equivalent. Hereinafter referred to as "bisphenol A epoxy resin (1)"). 0.21 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.21 parts by mass of methoquinone as a thermal polymerization inhibitor, followed by 72 parts by mass of acrylic acid and 0.21 part of triphenylphosphine. Parts by mass were added, and an esterification reaction was carried out at 100° C. for 10 hours while blowing air. After confirming that the acid value was 1 mgKOH/g or less, 0.21 part by mass of oxalic acid was added and 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. Further, the number of moles of acid groups possessed by acrylic acid per 1 mole of epoxy groups possessed by the bisphenol A type epoxy resin (1) was 0.5.

(Synthesis Example 9: Production of epoxy acrylate resin (B-2))
A flask equipped with a thermometer, a stirrer, and a reflux condenser 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 part by mass of metoquinone as a thermal polymerization inhibitor. After adding 0.18 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. Next, after confirming that the acid value was 1 mgKOH/g or less, 0.18 parts by mass of oxalic acid was added and 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. Further, the number of moles of acid groups possessed by acrylic acid per 1 mole of epoxy groups possessed by the bisphenol A type epoxy resin (1) was 0.15.

(Synthesis Example 10: Production of epoxy acrylate resin (B-3))
A flask equipped with a thermometer, a stirrer, and a reflux condenser 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 part by mass of metoquinone as a thermal polymerization inhibitor. After adding 0.19 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 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. Further, the number of moles of acid groups possessed by acrylic acid per 1 mole of epoxy groups possessed by the bisphenol A type epoxy resin (1) was 0.3.

(Synthesis Example 11: Production of epoxy acrylate resin (B-4))
A flask equipped with a thermometer, a stirrer, and a reflux condenser 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 part by mass of metoquinone as a thermal polymerization inhibitor. After adding 0.22 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 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. Further, the number of moles of acid groups possessed by acrylic acid per 1 mole of epoxy groups possessed by the bisphenol A type epoxy resin (1) was 0.7.

(Synthesis Example 12: Production of epoxy acrylate resin (B-5))
A flask equipped with a thermometer, a stirrer, and a reflux condenser 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 part by mass of metoquinone as a thermal polymerization inhibitor. After adding 0.23 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 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. Further, the number of moles of acid groups possessed by acrylic acid per 1 mole of epoxy groups possessed by the bisphenol A type epoxy resin (1) was 0.85.

(Synthesis Example 13: Production of epoxy acrylate resin (B-6))
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with a naphthalene-type epoxy resin ("EPICLON 4032D" manufactured by DIC Corporation, with an epoxy equivalent of 141 g/equivalent. Hereinafter abbreviated as "naphthalene-type epoxy resin (1)" ), 0.18 parts by weight of dibutylhydroxytoluene as an antioxidant and 0.18 parts by weight of methoquinone as a thermal polymerization inhibitor were added, followed by 72 parts by weight of acrylic acid and 0.18 parts by weight of triphenylphosphine. was added, and an esterification reaction was carried out at 100°C for 10 hours while blowing air. Next, after confirming that the acid value was 1 mgKOH/g or less, 0.18 parts by mass of oxalic acid was added and 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. Further, the number of moles of acid groups possessed by acrylic acid per 1 mole of epoxy groups possessed by naphthalene-type epoxy resin (1) was 0.50.

(Example 1: Preparation of curable resin composition (1))
The aromatic ester compound (A-1) obtained in Synthesis Example 3 and the epoxy acrylate resin (B-1) obtained in Synthesis Example 8 were mixed to obtain an epoxy (meth)acrylate resin composition, and then an acrylate monomer. , a bisphenol A type epoxy resin ("EPICLON 850S" manufactured by DIC Corporation), a photopolymerization initiator ("Omnirad 184" manufactured by IGM), 2-ethyl-4-methylimidazole, and 4-dimethylaminopyridine. 1 were mixed to obtain a curable resin composition (1).

(Examples 2 to 12: Preparation of curable resin compositions (2) to (12))
Curable resin compositions (2) to (12) 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 performed using the curable resin compositions obtained in the above Examples and Comparative Examples.

[Heat resistance evaluation method]
The curable resin composition obtained in each example and comparative example is applied to a copper foil (manufactured by Furukawa Sangyo Co., Ltd., electrolytic copper foil "F2-WS" 18 μm) using an applicator so that the film thickness is 50 μm. and dried at 80° C. for 30 minutes. Then, after irradiating with ultraviolet rays 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. Then, the cured coating film was peeled off from the copper foil to obtain a cured product. A test piece of 6 mm × 35 mm was cut out from the cured product, and a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device "RSA II" manufactured by Rheometric Co., tensile method: frequency 1 Hz, temperature increase rate 3 ° C./min) was used. , the temperature at which the change in elastic modulus becomes maximum was evaluated as the glass transition temperature. In addition, it shows that it is excellent in heat resistance, so that a glass transition temperature is high.

[Method of measuring permittivity]
The curable resin composition obtained in each example and comparative example was 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 ultraviolet rays 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. Then, the cured coating film was peeled off from the glass substrate to obtain a cured product. Next, a test piece was stored in a room at a temperature of 23 ° C. and a humidity of 50% for 24 hours, and the dielectric constant of the test piece at 1 GHz was measured by the cavity resonance method using "Network Analyzer E8362C" manufactured by Agilent Technologies. It was measured.

[Method of measuring dielectric loss tangent]
The curable resin composition obtained in each example and comparative example was 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 ultraviolet rays 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. Then, the cured coating film was peeled off from the glass substrate to obtain a cured product. Next, a test piece was stored in a room at a temperature of 23 ° C. and a humidity of 50% for 24 hours, and the dielectric loss tangent of the test piece at 1 GHz was measured by the cavity resonance method using "Network Analyzer E8362C" manufactured by Agilent Technologies. It was measured.

Table 1 shows the evaluation results of the curable resin compositions (1) to (12) prepared in Examples 1 to 12 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 12 shown in Table 1 are examples of curable resin compositions 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 a 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 (11)

An epoxy (meth)acrylate resin composition containing an aromatic ester compound (A) and an epoxy (meth)acrylate resin (B),
The aromatic ester compound (A) contains a monofunctional phenol compound (A1) having at least one vinylbenzyl group and an aromatic polybasic acid or derivative thereof (A2) as essential reaction raw materials,
The monofunctional phenol compound (A1) is represented by the following structural formula (1) or (2),
The epoxy (meth)acrylate resin (B) contains an epoxy resin (B1) and an unsaturated monobasic acid (B2) as essential reaction raw materials, and has an epoxy group and a (meth)acryloyl group. An epoxy (meth)acrylate resin composition characterized by :

[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. In formula (1), n is an integer of 1 to 5, m is an integer of 0 to 4, and the sum of n and m is 5. n in formula (2) is an integer of 1 to 7, m is an integer of 0 to 6, and the sum of n and m in formula (2) is 7. R ₁ and R ₂ in formulas (1) and (2) may be the same or different. ] 2. The epoxy (meth)acrylate resin composition according to claim 1, wherein the aromatic ester compound (A) has a vinylbenzyl structure derived from the monofunctional phenol compound (A1) at the end of the molecular chain. 2. The epoxy (meth)acrylate resin composition according to claim 1, wherein the aromatic ester compound (A) has vinylbenzyl groups at both ends of the main chain. 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 formula (I), ring A is each independently a benzene ring or naphthalene ring which may have a substituent, X is a reaction residue of the monofunctional phenol compound (A1), Y is a reactive residue of a polyfunctional phenol compound. Also, n is an integer of 0-20. ] The epoxy according to claim 1, wherein the number of moles of acid groups possessed by the unsaturated monobasic acid (B2) is in the range of 0.25 to 0.75 per mol of the epoxy groups possessed by the epoxy resin (B1). meth)acrylate resin compositions. 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 1. The epoxy (meth)acrylate resin composition according to item 1. A curable resin composition comprising the epoxy (meth)acrylate resin composition according to any one of claims 1 to 6 and a photopolymerization initiator. 8. The curable resin composition according to claim 7 , further comprising a (meth)acrylate monomer. 8. The curable resin composition according to claim 7 , further comprising a curing agent. A cured product, which is a cured reaction product of the curable resin composition according to any one of claims 7 to 9 . An article comprising a coating film comprising the cured product according to claim 10 .

Images