JP7228103B2 - Acid group-containing (meth)acrylate resin composition, curable resin composition, cured product, insulating material, resin material for solder resist, and resist member - Google Patents

Description

The present invention provides an acid group-containing (meth)acrylate resin composition having excellent alkali developability, heat resistance and dielectric properties, a curable resin composition containing the same, a cured product of the curable resin composition, and an insulating material. , a solder resist resin material and a resist member.

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 should be cured with a small amount of exposure, be excellent in alkali developability, heat resistance and strength in the cured product, dielectric properties, etc. It is also required to be excellent in

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 alkali developability and heat resistance have been desired.

JP-A-8-259663

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

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

That is, the present invention provides an acid group-containing (meth)acrylate resin composition containing an aromatic ester compound (A) and a resin (B) having an acid group and a polymerizable unsaturated bond, wherein the aromatic An acid characterized in that the ester compound (A) comprises a phenol compound (A1) having at least one vinylbenzyloxy group and an aromatic polybasic acid or a derivative thereof (A2) as essential reaction raw materials. The present invention relates to a group-containing (meth)acrylate resin composition, a curable resin composition containing the same, a cured product of the curable resin composition, an insulating material, a solder resist resin material, and a resist member.

Since the acid group-containing (meth)acrylate resin composition of the present invention has excellent alkali developability, heat resistance and dielectric properties, it contains the acid group-containing (meth)acrylate resin composition and a photopolymerization initiator. The resulting curable resin composition can be used as a coating agent or an adhesive, and as the coating agent, it can be suitably used particularly 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 product obtained in Synthesis Example 1. FIG. 2 is a diagram showing a GPC chart of the product obtained in Synthesis Example 2. FIG.

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

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.

As the aromatic ester compound (A), a phenol compound (A1) and an aromatic polybasic acid or its derivative (A2) are essential reaction raw materials.

The phenol compound (A1) has at least one vinylbenzyloxy group. The vinylbenzyloxy group is preferably bonded to the phenol compound through an ether bond.

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

In addition to the vinylbenzyloxy group, the phenol compound (A1) may have one or more substituents such as an alkyl group and an aryl group. to 20, preferably alkyl groups having 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.

As the phenol compound (A1), one or more compounds selected from monocyclic or polycyclic aromatic compounds having one or more phenolic hydroxyl groups can be used. compounds can be mentioned.

In the formula, _R1 is a hydrogen atom or a vinylbenzyl group, and at least one of the molecules is a vinylbenzyl group. R ₂ is a hydrogen atom, an alkyl group or an aryl group, n in formulas (1-1), (1-4), (1-5) and (1-6) is an integer of 0 to 4; n in formula (1-2) is an integer of 0 to 3, and n in formulas (1-3) and (1-7) is an integer of 0 to 6. Multiple R ₂ may be the same or different. R ₂ in formulas (1-3) and (1-7) indicates that it may be bonded to any 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, 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.

A compound represented by the following structural formula (2) can also be used as the phenol compound (A1).

〔式（２）中、ｍは０～２０の整数である。〕

[In formula (2), m is an integer of 0 to 20. ]

In the structural formula (2) above, each Ar ¹ independently represents a substituent containing a phenolic hydroxyl group or a vinylbenzyloxy group, and in the formula, at least one vinylbenzyloxy group and at least one phenolic hydroxyl group are present. , Z are each independently an oxygen atom, a sulfur atom, a ketone group, a sulfonyl group, a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, a 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 structural formulas (3-1) and (3-2).

In formulas (3-1) and (3-2), R ₁ is a hydrogen atom or a vinylbenzyl group, and in formula (2) at least one is a vinylbenzyl group and at least one is a hydrogen atom. R ₂ is a hydroxy group, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. n is an integer from 0 to 5; It indicates that the substituent in formula (3-2) may be bonded to any ring of 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, 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 in the structural formula (2) is not particularly limited, but examples thereof include methylene, ethylene, propylene, 1-methylmethylene, 1,1-dimethylmethylene and 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, and examples thereof include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclopentylene, cycloheptylene, or structural formula (4-1) below. and cycloalkylene represented by (4-4).

なお、上記構造式（４－１）～（４－４）において、「＊」はＡｒ^１と結合する部位を表す。

In the structural formulas (4-1) to (4-4) above, "*" 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 structural formula (5).

なお、上記構造式（５）において、「＊」はＡｒ^１と結合する部位を表す。

In the above structural formula (5), "*" represents the 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 structural formulas (6-1) to (6-5).

なお、式（６－１）～（６－５）において、「＊」はＡｒ^１と結合する部位を表す。

In formulas (6-1) to (6-5), "*" represents a site that binds to ^Ar1 .

Among the above, Z in formula (2) 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), (4-4), (5), and (6-1) to (6-5) are more preferable from the viewpoint of having excellent dielectric properties. m in formula (2) is preferably 0 or an integer of 1 to 10, more preferably 0 to 8, and from the viewpoint of having excellent alkali developability, heat resistance and dielectric properties, more preferably 0 ~5.

Further, the phenol compound (A1) may have a structure represented by the following structural formula (7).

〔式（７）中、Ｒ_１はビニルベンジル基であり、ｌは１以上の整数、Ｒ_２は水素原子、アルキル基、アリール基を示す。〕

[In formula (7), R ₁ is a vinylbenzyl group, 1 is an integer of 1 or more, and R ₂ is a hydrogen atom, an alkyl group, or an aryl group. ]

In formula (7), 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 the above, since an acid group-containing (meth)acrylate resin composition having excellent alkali developability, heat resistance and dielectric properties can be obtained, formulas (1-3), (1-7), (2), It is preferable to use a compound represented by (7), and further, in formulas (1-3), (1-7), and (2), Ar ¹ is phenol, ortho-cresol, dimethylphenol, phenylphenol, or α-naphthol and β-naphthol residues, and Z is formulas (4-3), (5), (6-1) to (6-5), and formula (7) is more preferred. Particularly preferred are those represented by the following structural formulas.

In the formula, one R ₁ is a hydrogen atom, the other R ₁ is a vinylbenzyl group, each R ₂ is independently a hydrogen atom, an alkyl group or an aryl group, and n is an integer of 0 to 4 is. At this time, examples of the alkyl group and aryl group are the same as those described above.

The method for producing the phenol compound (A1) is not particularly limited, and a conventionally known Williamson ether synthesis method 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 aqueous sodium hydroxide solution is added thereto while heating. It can be manufactured by mixing. At this time, by setting the chemical equivalent ratio of the halide group of the vinylbenzyl halide compound to be used to less than 1.0 to the phenolic hydroxyl group of the phenolic compound, a compound containing both a phenolic hydroxyl group and a vinylbenzyloxy group can be synthesized. is.

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 acid group-containing (meth)acrylate resin composition having excellent alkali developability, heat resistance and dielectric properties can be obtained.

As the aromatic ester compound (A), in addition to the 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 basic acid or derivative thereof (A4) may be contained as a reaction raw material.

Examples of the compound (A3) having at least two phenolic hydroxyl groups include compounds represented by the following structural formulas (8-1) to (8-7).

In formulas (8-1) to (8-7), each R ₂ independently represents a hydrogen atom, an alkyl group or an aryl group, (8-1), (8-4), (8-5) , n in (8-6) is an integer of 1 to 4, n in (8-2) is an integer of 0 to 3, and n in (8-3) and (8-7) is An integer from 0 to 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 (8-7) 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 (9).

〔但し、式（９）中、ｍは０～２０の整数である。〕

[In formula (9), m is an integer of 0 to 20. ]

In the above formula (9), 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 (10-1) and (10-2).

In formulas (10-1) and (10-2), 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 (10-1) is an integer of 0 to 5, and n in formula (10-2) 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 (11-1) to (11) -4), and the like.

なお、上記式（１１－１）～（１１－４）において、「＊」はＡｒ^１と結合する部位を表す。

In the above formulas (11-1) to (11-4), "*" 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（１２）において、「＊」はＡｒ^１と結合する部位を表す。

In the above formula (12), "*" 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 (15-1) to (15-5).

なお、式（１３－１）～（１３－５）において、「＊」はＡｒ^１と結合する部位を表す。

In formulas (13-1) to (13-5), "*" represents a site that binds to ^Ar1 .

Among the above, Z in formula (9) 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), (11-4), (12), and (13-1) to (13-5) are more preferable from the viewpoint of adhesion and dielectric properties. In the formula (9), m is an integer of 0 or 1 to 10, preferably 0 to 8, and an acid group-containing (meth)acrylate resin composition having excellent alkali developability, heat resistance and dielectric properties. It is preferably 0 to 5 because it can be obtained.

Also, the compound (A3) having at least two phenolic hydroxyl groups may have a structure represented by the following formula (14).

但し式（１４）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 (14), l is an integer of 1 or more, and _R2 is a hydrogen atom, an alkyl group, or an aryl group. )

In formula (14), 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 the above-mentioned, an acid group-containing (meth)acrylate resin composition having excellent alkali developability, heat resistance and dielectric properties can be obtained. Further, in formula (9), Ar ¹ is a residue of phenol, orthocresol, dimethylphenol, phenylphenol, or α-naphthol, β-naphthol, and Z is a residue of formula (11-3 ), (12-1), (13-1) to (13-5) are preferred, and the compound represented by formula (16) is more preferred.

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

As the aromatic ester compound (A), an acid group-containing (meth)acrylate resin composition having excellent alkali developability, heat resistance and dielectric properties can be obtained. and more preferably have a structure represented by the following structural formula (I).

［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はビニルベンジルオキシ基を有するフェノール化合物の反応残基であり、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 a phenol compound having a vinylbenzyloxy group, Y is a reactive residue of a polyfunctional phenol compound. Also, n is an integer of 0-20. ]

As the aromatic ester compound (A), an acid group-containing (meth)acrylate resin composition having excellent alkali developability, heat resistance and dielectric properties can be obtained. is preferred.

［式（Ｉ－１）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る。］

[In formula (I-1), each ring A is independently a benzene ring or a naphthalene ring which may have a substituent. ]

The method for producing the aromatic ester compound (A) is not particularly limited, and any method may be used. For example, the phenol compound (A1) and the aromatic polybasic acid or its derivative (A2) may be produced by a method of reacting all reaction raw materials at once, or reacting the reaction raw materials sequentially. It may be manufactured by the method As a method of reacting all of the reaction raw materials at once, for example, the phenol compound (A1) and the aromatic polybasic acid or derivative thereof (A2) are mixed under basic or acidic conditions at 20 to 140 ° C. (Method 1), the phenol compound (A1), the aromatic polybasic acid or derivative thereof (A2), and the compound (A3) having at least two phenolic hydroxyl groups are basic A method obtained by reacting at 20 to 140 ° C. under acidic conditions (method 2), the phenol compound (A1), the aromatic polybasic acid or derivative thereof (A2), and the at least two phenolic A method (Method 3) obtained by reacting a compound (A3) having a hydroxyl group with the aromatic monobasic acid or derivative thereof (A4) under basic or acidic conditions at 20 to 140° C., and the like.

In Method 1, the reaction between the phenolic compound (A1) and the aromatic polybasic acid or derivative thereof (A2) is performed based on 1 mol of the phenolic hydroxyl group of the phenolic compound (A1), the aromatic The number of moles of functional groups capable of reacting with the phenolic hydroxyl groups possessed by the polybasic acid or derivative thereof (A2) is preferably in the range of 0.9 to 1.1, more preferably in the range of 0.95 to 1.05. more preferred.

In Method 2, the reaction of the phenol compound (A1), the aromatic polybasic acid or derivative thereof (A2), and the compound (A3) having at least two phenolic hydroxyl groups is the phenol compound (A1) and moles of functional groups capable of reacting with the phenolic hydroxyl groups of the aromatic polybasic acid or derivative thereof (A2) per mol of the phenolic hydroxyl groups of the compound (A3) having at least two phenolic hydroxyl groups The number 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 phenolic 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 derivative thereof In the reaction (A4), the phenolic compound (A1) and the compound (A3) having at least two phenolic hydroxyl groups have 1 mol of the phenolic hydroxyl group, and the aromatic polybasic acid or derivative thereof (A2) And the number of moles of the functional group capable of reacting with the phenolic hydroxyl group possessed by the aromatic monobasic acid or its derivative (A4) is preferably in the range of 0.9 to 1.1, preferably 0.95 to 1.0. 05 range is more preferred.

As the resin (B) having an acid group and a polymerizable unsaturated bond, for example, an epoxy resin having an acid group and a polymerizable unsaturated bond, a urethane resin having an acid group and a polymerizable unsaturated bond, an acid group and a polymerizable acrylic resins having a polyunsaturated bond, amideimide resins having an acid group and a polymerizable unsaturated bond, acrylamide resins having an acid group and a polymerizable unsaturated bond, and the like.

Examples of the epoxy resin having an acid group and a polymerizable unsaturated bond include, for example, an acid group-containing epoxy (meth)acrylate resin containing an epoxy resin, an unsaturated monobasic acid, and a polybasic acid anhydride as essential reaction raw materials, , epoxy resins, unsaturated monobasic acids, polybasic acid anhydrides, polyisocyanate compounds, and acid group- and urethane group-containing epoxy (meth)acrylate resins using hydroxyl group-containing (meth)acrylate compounds as reaction raw materials.

Examples of the epoxy resin include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, Bisphenol novolak type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition Reactive epoxy resins, biphenylaralkyl-type epoxy resins, fluorene-type epoxy resins, xanthene-type epoxy resins, dihydroxybenzene-type epoxy resins, trihydroxybenzene-type epoxy resins, oxazolidone-type epoxy resins, and the like can be mentioned. These epoxy resins can be used alone or in combination of two or more.

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.

Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, β-furfurylacrylic acid and the like. Esterified products, acid halides, acid anhydrides, etc. of the unsaturated monobasic acids can also be used. Furthermore, compounds represented by the following structural formula (15) and the like can also be used.

［式（１５）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 (15), 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 (1) is preferably in the range of 100-500, more preferably in the range of 150-400.

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

Examples of the polybasic acid anhydrides include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, and aromatic polybasic acid anhydrides.

Examples of the aliphatic polybasic acid anhydrides include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, and itaconic acid. acids, glutaconic acid, acid anhydrides of 1,2,3,4-butanetetracarboxylic acid, and the like. The aliphatic polybasic acid anhydride may have an aliphatic hydrocarbon group of either a straight chain type or a branched type, and may have an unsaturated bond in its structure.

As the alicyclic polybasic acid anhydride, in the present invention, an alicyclic polybasic acid anhydride in which an acid anhydride group is bonded to an alicyclic structure, and an aromatic ring in other structural sites It does not matter whether or not Examples of the alicyclic polybasic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2, 3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene- Examples include acid anhydrides of 1,2-dicarboxylic acids.

Examples of the aromatic polybasic acid anhydride include phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, An acid anhydride of benzophenonetetracarboxylic acid and the like can be mentioned.

These polybasic acid anhydrides can be used alone or in combination of two or more.

Examples of the polyisocyanate compounds include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; norbornane diisocyanate, isophorone diisocyanate, Alicyclic diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate; ,3′-dimethylbiphenyl, o-tolidine diisocyanate and other aromatic diisocyanate compounds; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (15); these isocyanurate modified products, biuret modified products, allophanate modified products, and the like. In addition, these polyisocyanate compounds can be used alone or in combination of two or more.

［式中、Ｒ^１はそれぞれ独立に水素原子、炭素原子数１～６の炭化水素基の何れかである。Ｒ^２はそれぞれ独立に炭素原子数１～４のアルキル基、または構造式（１５）で表される構造部位と＊印が付されたメチレン基を介して連結する結合点の何れかである。ｌは０または１～３の整数であり、ｍは１～１５の整数である。］

[In the formula, each R ¹ is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Each R ² is independently either an alkyl group having 1 to 4 carbon atoms, or a bonding point connecting the structural site represented by the structural formula (15) via a methylene group marked with *. l is 0 or an integer of 1-3; m is an integer of 1-15; ]

Examples of the hydroxyl group-containing (meth)acrylate compounds include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol (meth)acrylate. , pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth) Acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane(meth)acrylate, ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate and the like. In addition, a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, (poly)oxypropylene chain, or (poly)oxytetramethylene chain is introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds ( Poly)oxyalkylene modified products and lactone modified products obtained by introducing a (poly)lactone structure into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds can also be used. These hydroxyl group-containing (meth)acrylate compounds can be used alone or in combination of two or more.

The method for producing the epoxy resin having an acid group and a polymerizable unsaturated bond is not particularly limited, and any method may be used. The production of the epoxy resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent if necessary, and a basic catalyst may be used if necessary.

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.

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

Examples of the urethane resin having an acid group and a polymerizable unsaturated bond include, for example, a polyisocyanate compound, a hydroxyl group-containing (meth)acrylate compound, a carboxyl group-containing polyol compound, and optionally a polybasic acid anhydride, the carboxyl group Those obtained by reacting with a polyol compound other than the contained polyol compound, or reacting with a polyol compound other than a polyisocyanate compound, a hydroxyl group-containing (meth)acrylate compound, a polybasic acid anhydride, and a carboxyl group-containing polyol compound and the like.

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

As the hydroxyl group-containing (meth)acrylate compound, the same ones as those exemplified as the hydroxyl group-containing (meth)acrylate compound described above can be used, and the hydroxyl group-containing (meth)acrylate compound can be used alone. More than one species can be used in combination.

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

As the polybasic acid anhydride, the same ones as those exemplified as the polybasic acid anhydrides described above can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more. can also

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

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

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

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

As the acrylic resin having an acid group and a polymerizable unsaturated bond, for example, a (meth)acrylate compound (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or a glycidyl group is polymerized as an essential component. A reaction obtained by introducing a (meth)acryloyl group by further reacting the acrylic resin intermediate obtained by further reacting a (meth)acrylate compound (β) having a reactive functional group capable of reacting with these functional groups products, and those obtained by reacting a hydroxyl group in the reaction product with a polybasic acid anhydride.

The acrylic resin intermediate may be obtained by copolymerizing the (meth)acrylate compound (α) and, if necessary, other polymerizable unsaturated group-containing compounds. The other polymerizable unsaturated group-containing compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like (meth) Alkyl acrylic ester; Alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate; phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxy aromatic ring-containing (meth)acrylates such as ethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene; These can be used alone or in combination of two or more.

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

The polybasic acid anhydride can be the same as those exemplified as the polybasic acid anhydrides described above, and the polybasic acid anhydrides can be used alone or in combination of two or more. can.

The method for producing the acrylic resin having an acid group and a polymerizable unsaturated bond is not particularly limited, and any method may be used. The production of the acrylic resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent if necessary, and a basic catalyst may be used if necessary.

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

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

Examples of the amideimide resin having an acid group and a polymerizable unsaturated bond include, for example, an amideimide resin having an acid group and/or an acid anhydride group, a hydroxyl group-containing (meth)acrylate compound and/or an epoxy group-containing (meth)acrylate Those obtained by reacting a compound with, if necessary, a compound having one or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group. be done. The compound having a reactive functional group may or may not have a (meth)acryloyl group.

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

Examples of the amide-imide resin include those obtained by reacting a polyisocyanate compound and a polybasic acid anhydride as starting materials.

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

As the polybasic acid anhydride, the same ones as those exemplified as the polybasic acid anhydrides described above can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more. can also

Moreover, the amide-imide resin can also use polybasic acid together as a reaction raw material other than the said polyisocyanate compound and polybasic acid anhydride if needed.

Any compound having two or more carboxyl groups in one molecule can be used as the polybasic acid. For example, 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, terephthalic acid, tetrahydrophthalic acid, hexahydro phthalic 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-tetrahydro naphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and the like. be done. 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 hydroxyl group-containing (meth)acrylate compound, the same ones as those exemplified as the hydroxyl group-containing (meth)acrylate compound described above can be used, and the hydroxyl group-containing (meth)acrylate compound can be used alone. More than one species can be used in combination.

As the epoxy group-containing (meth)acrylate compound, a wide variety of compounds can be used without any particular limitation as long as they have a (meth)acryloyl group and an epoxy group in the molecular structure. . For example, glycidyl group-containing (meth)acrylate monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, epoxycyclohexylmethyl (meth)acrylate; dihydroxybenzene diglycidyl ether, dihydroxynaphthalenediglycidyl ether, Examples include mono(meth)acrylated diglycidyl ether compounds such as biphenol diglycidyl ether and bisphenol diglycidyl ether. These epoxy group-containing (meth)acrylate compounds can be used alone or in combination of two or more. Among these, a (meth)acrylate compound having one epoxy group is preferable because it facilitates control of the reaction, and contains an acid group capable of forming a cured product having excellent alkali developability, heat resistance and dielectric properties. A glycidyl group-containing (meth)acrylate monomer is preferred because a (meth)acrylate resin composition can be obtained. Moreover, the molecular weight of the glycidyl group-containing (meth)acrylate monomer is preferably 500 or less. Furthermore, the ratio of the glycidyl group-containing (meth)acrylate monomer to the total mass of the epoxy group-containing (meth)acrylate compound is preferably 70% by mass or more, more preferably 90% by mass or more.

The method for producing the amide-imide resin having an acid group and a polymerizable unsaturated bond is not particularly limited, and any method may be used. The production of the amide-imide resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent if necessary, and a basic catalyst may be used if necessary.

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

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

Examples of the acrylamide resin having an acid group and a polymerizable unsaturated bond include, for example, a phenolic hydroxyl group-containing compound, an alkylene oxide or an alkylene carbonate, an N-alkoxyalkyl (meth)acrylamide compound, a polybasic acid anhydride, Examples include those obtained by reacting with an unsaturated monobasic acid as necessary.

The phenolic hydroxyl group-containing compound is a compound having at least two phenolic hydroxyl groups in the molecule. Examples of the compound having at least two phenolic hydroxyl groups in the molecule include compounds represented by the following structural formulas (16-1) to (16-4).

In the structural formulas (16-1) to (16-4) above, R ¹ is 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. , R ² are each independently a hydrogen atom or a methyl group. In addition, p is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, still more preferably 0. q is an integer of 2 or more, preferably 2 or 3; The position of the substituent on the aromatic ring in the above structural formula is arbitrary. For example, in the naphthalene ring of structural formula (16-2), any ring may be substituted. 16-3) may be substituted on any of the benzene rings present in the molecule, and in structural formula (16-4), on any of the benzene rings present in the molecule , and indicates that the number of substituents in one molecule is p and q.

Further, as the phenolic hydroxyl group-containing compound, for example, a compound having one phenolic hydroxyl group in the molecule and a compound represented by any of the following structural formulas (x-1) to (x-5) are essential. or a reaction product used as a reaction raw material, or a compound having at least two phenolic hydroxyl groups in the molecule and a compound represented by any of the following structural formulas (x-1) to (x-5): A reaction product used as a raw material can also be used. In addition, a novolac-type phenolic resin that uses one or more compounds having one phenolic hydroxyl group in the molecule as a reaction raw material, and one or more compounds having at least two phenolic hydroxyl groups in the molecule. A novolak-type phenol resin or the like used as a reaction raw material can also be used.

［式（ｘ－１）中、ｈは０または１である。式（ｘ－２）～（ｘ－５）中、Ｒ^３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、ハロゲン原子の何れかであり、ｉは、０または１～４の整数である。式（ｘ－２）、（ｘ－３）及び（ｘ－５）中、Ｚは、ビニル基、ハロメチル基、ヒドロキシメチル基、アルキルオキシメチル基の何れかである。式（ｘ－５）中、Ｙは、炭素原子数１～４のアルキレン基、酸素原子、硫黄原子、カルボニル基の何れかであり、ｊは１～４の整数である。］

[In formula (x−1), h is 0 or 1. In formulas (x-2) to (x-5), R ³ is 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, i is an integer of 0 or 1-4. In formulas (x-2), (x-3) and (x-5), Z is a vinyl group, a halomethyl group, a hydroxymethyl group or an alkyloxymethyl group. In formula (x-5), Y is an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom or a carbonyl group, and j is an integer of 1 to 4. ]

Examples of the compound having one phenolic hydroxyl group in the molecule include compounds represented by the following structural formulas (7-1) to (7-4).

In the structural formulas (17-1) to (17-4) above, R ⁴ is 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. , R ⁵ are each independently a hydrogen atom or a methyl group. In addition, p is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, still more preferably 0. The position of the substituent on the aromatic ring in the above structural formula is arbitrary. For example, the naphthalene ring of structural formula (17-2) may be substituted on any ring, and the structural formula ( 17-3) may be substituted on any of the benzene rings present in the molecule, and in structural formula (17-4), on any of the benzene rings present in the molecule indicates that it may be replaced with

As the compound having at least two phenolic hydroxyl groups in the molecule, the compounds represented by the above structural formulas (16-1) to (16-4) can be used.

These phenolic hydroxyl group-containing compounds can be used alone or in combination of two or more.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. Among these, ethylene oxide and propylene oxide are preferable because they yield an acid group-containing (meth)acrylate resin composition capable of forming a cured product having excellent alkali developability, heat resistance and dielectric properties. The alkylene oxides can be used alone or in combination of two or more.

Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate, and the like. Among these, ethylene carbonate and propylene carbonate are preferable because they yield an acid group-containing (meth)acrylate resin composition capable of forming a cured product having excellent alkali developability, heat resistance and dielectric properties. The alkylene carbonates can be used alone or in combination of two or more.

Examples of the N-alkoxyalkyl(meth)acrylamide compounds include N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, and N-methoxyethyl(meth)acrylamide. , N-ethoxyethyl (meth)acrylamide, N-butoxyethyl (meth)acrylamide and the like. The N-alkoxyalkyl(meth)acrylamide compounds can be used alone or in combination of two or more.

As the polybasic acid anhydride, the same ones as those exemplified as the polybasic acid anhydrides described above can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more. can also

As the unsaturated monobasic acid, the same unsaturated monobasic acid as exemplified above can be used, and the unsaturated monobasic acid can be used alone or in combination of two or more. .

The method for producing the acrylamide resin having an acid group and a polymerizable unsaturated bond is not particularly limited, and any method may be used. The production of the acrylamide resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent, if necessary, and if necessary, a basic catalyst and an acidic catalyst may be used.

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.

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

As the acidic catalyst, the same ones as those exemplified as the acidic catalysts described above can be used, and the acidic catalysts can be used alone or in combination of two or more.

The method for producing the acid group-containing (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 resin (B) having an acid group and a polymerizable unsaturated bond at 30 to 120°C.

The solid content mass ratio [(A)/(B)] of the aromatic ester compound (A) and the resin (B) having an acid group and a polymerizable unsaturated bond is excellent in heat resistance and dielectric properties. It is preferably in the range of 0.1 to 1, more preferably in the range of 0.25 to 0.7, since an acid group-containing (meth)acrylate resin composition can be obtained.

Since the acid group-containing (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 do.

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 acid group-containing (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 above 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 unsaturated monobasic acid as exemplified above can be used, and the unsaturated monobasic acid can be used alone or in combination of two or more. can also

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 above 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.

In addition, since the cured product of the present invention has excellent alkali developability, heat resistance and dielectric properties, it can be used, for example, in semiconductor device applications such as solder resists, interlayer insulating materials, packaging materials, underfill materials, circuit elements, etc. It can be suitably used as a package adhesive layer or an adhesive layer between an integrated circuit element and a circuit board. In addition, it can be suitably used for thin film transistor protective films, liquid crystal color filter protective films, color filter pigment resists, black matrix resists, spacers, and the like in thin display applications such as LCDs and OELDs. Among these, it can be preferably used for solder resist applications.

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

The resist member of the present invention is, for example, a photomask in which the desired pattern is formed after applying the solder resist resin material on a substrate and volatilizing and drying the organic solvent at a temperature range of about 60 to 100 ° C. It can be obtained by exposing to active energy rays through a ray, developing an unexposed portion with an alkaline aqueous solution, and further curing by heating at a temperature in the range of about 140 to 200°C.

Examples of the substrate include metal foil such as copper foil and aluminum foil.

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 phenolic compound (A1-1) having vinylbenzyloxy group)
A flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer was charged with 200 parts by mass of a polyadduct of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g/equivalent), metachloromethylstyrene, and parachloromethylstyrene. 98 parts by mass of a mixture (“CMS-P” manufactured by AGC Seimikaru Cal Co., Ltd.), 298 parts by mass of methyl isobutyl ketone, 12 parts by mass of tetrabutylammonium bromide, and 0.3 parts by mass of 2,4-dinitrophenol are added and stirred. while heating to 60°C. Then, 105 parts by mass of a 49% sodium hydroxide aqueous solution was added dropwise over 30 minutes. After holding at 60° C. for 1 hour, the temperature was raised to 80° C. and held for 2 hours. After diluting with 275 parts by mass of methyl isobutyl ketone and neutralizing with phosphoric acid until the pH of the lower layer reached 7, the organic layer was washed with water to remove salts from the organic layer. The reaction solution was concentrated by heating under reduced pressure to obtain a phenol compound (A1-1) having a vinylbenzyloxy group (brown solid with a hydroxyl equivalent weight of 406 g/equivalent). From this result, it was confirmed that the following structure was included. FIG. 1 shows the GPC data of the product.

(Synthesis Example 2: Synthesis of phenolic compound (R-1))
488.7 parts by mass of 2,6-xylenol, 281.7 parts by mass of paraxylene glycol dimethyl ether, and 7.7 parts by mass of paratoluenesulfonic acid were placed in a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer. was added, and the inside of the system was replaced with nitrogen under reduced pressure and dissolved. Then, the inside of the system was heated to 180° C. over 3 hours while purging with nitrogen gas. At this time, the generated volatile matter was appropriately removed. 3.3 parts by mass of a 49% sodium hydroxide aqueous solution was added and washed with water to remove the catalyst salt. After heating to 190° C. and reducing the pressure, residual monomers were removed by steam distillation to obtain a 2,6-xylenol aralkyl resin (hereinafter sometimes referred to as “phenol compound (R-1)”). The hydroxyl equivalent weight of this phenol compound (R-1) was 199 g/equivalent.

(Synthesis Example 3: Synthesis of phenolic compound (R-2))
433 parts by mass of α-naphthol, 315 parts by mass of paraxylene dichloride, and 703 parts by mass of toluene are added to a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer, and the system is decompressed and replaced with nitrogen to dissolve. let me Then, the inside of the system was heated to 90° C. while purging with nitrogen gas. 294 parts by mass of a 49% sodium hydroxide aqueous solution was added dropwise over 1 hour, and the mixture was kept as it was for 8 hours. 430 parts by mass of water was added, and the liquid was separated by standing to remove the lower layer. 15 parts by mass of p-toluenesulfonic acid was added, and the temperature was raised to 150° C. while removing volatile matter. After holding for 1 hour, the catalyst was removed by washing with water. After that, by drying under reduced pressure at 180° C., an α-naphthol aralkyl resin (hereinafter sometimes referred to as “phenol compound (R-2)”) was obtained. The hydroxyl equivalent weight of this phenol compound (R-2) was 217 g/equivalent.

(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 65 parts by mass of the phenol compound (A1-1) having a vinylbenzyloxy group obtained in Synthesis Example 1 and 16.2 parts by mass of isophthaloyl chloride. 322 parts by mass of toluene and 0.2 parts by mass of tetrabutylammonium bromide were added and dissolved. The inside of the system was controlled at 60° C. or lower, and 33 parts by mass of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. It was then stirred 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 the following structure. In addition, the GPC data of the product are shown in FIG.

(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 406 parts by mass of the phenol compound (A1-1) having a vinylbenzyloxy group obtained in Synthesis Example 1, dicyclopentadiene and phenol. 82.5 parts by mass of the adduct (hydroxyl equivalent: 165 g/equivalent), 202 parts by mass of isophthaloyl chloride, 1782 parts by mass of toluene, and 1.0 part by mass of tetrabutylammonium bromide were added and dissolved. The inside of the system was controlled at 60° C. or lower, and 440 parts by mass of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. It was then stirred 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 the following structure.

(Synthesis Example 6: 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 7: Synthesis of aromatic compound (A'-2))
A thermometer, a dropping funnel, a condenser, a fractionating tube, a flask equipped with a stirrer, 130 parts by mass of the phenol compound (R-1) obtained in Synthesis Example 2, a mixture of metachloromethylstyrene and parachloromethylstyrene (AGC "CMS-P" manufactured by Seimi Kelkal Co., Ltd.) 105 parts by mass, 235 parts by mass of methyl isobutyl ketone, 9.4 parts by mass of tetrabutylammonium bromide, and 0.1 part by mass of 2,4-dinitrophenol. °C. Then, 107 parts by mass of a 49% sodium hydroxide aqueous solution was added dropwise over 1 hour. The internal temperature rose to 70°C due to heat generation. After that, it was held at 70 to 75°C for 5 hours. The lower layer was neutralized with phosphoric acid until the pH of the lower layer reached 7, and then washed with water by a liquid separation operation. The catalyst was removed from the organic layer by extracting the emulsified lower layer. The reaction solution was concentrated by heating under reduced pressure to obtain a xylenol aralkyl resin having a vinylbenzyloxy group (hereinafter sometimes referred to as "aromatic compound (A'-2)"). From the results of GPC analysis, residual chloromethylstyrene, which is the starting material, was not confirmed.

(Synthesis Example 8: Synthesis of aromatic compound (A'-3))
A thermometer, a dropping funnel, a condenser, a fractionating tube, a flask equipped with a stirrer, 130 parts by mass of the phenol compound (R-2) obtained in Synthesis Example 3, a mixture of metachloromethylstyrene and parachloromethylstyrene (AGC "CMS-P" manufactured by Seimi Kelkal Co., Ltd.) 96 parts by mass, 226 parts by mass of methyl isobutyl ketone, 9 parts by mass of tetrabutylammonium bromide, and 0.2 parts by mass of 2,4-dinitrophenol were added and heated to 45°C while stirring. heated. Then, 98 parts by mass of a 49% sodium hydroxide aqueous solution was added dropwise over 1 hour. The internal temperature rose to 60°C due to heat generation. After that, it was kept at 55 to 65°C for 8 hours. After neutralizing with phosphoric acid until the pH of the lower layer reached 7, the organic layer was washed with water to remove salts from the organic layer. The reaction solution was concentrated by heating under reduced pressure to obtain a naphthol aralkyl resin having a vinylbenzyloxy group (hereinafter sometimes referred to as "aromatic compound (A'-3)"). From the results of GPC analysis, residual chloromethylstyrene, which is the starting material, was not confirmed.

(Synthesis Example 9: Synthesis of Resin (B-1) Having Acid Group and Polymerizable Unsaturated Bond)
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 101 parts by mass of diethylene glycol monomethyl ether acetate, and 428 of ortho-cresol novolak type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation, epoxy equivalent: 214). After dissolving parts by mass, adding 4 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of methoquinone as a thermal polymerization inhibitor, 144 parts by mass of acrylic acid and 1.6 parts by mass of triphenylphosphine are added, An esterification reaction was carried out at 120° C. for 10 hours while blowing air. Then, 311 parts by mass of diethylene glycol monomethyl ether acetate and 160 parts by mass of tetrahydrophthalic anhydride are added and reacted at 110° C. for 2.5 hours to obtain a resin having an acid group and a polymerizable unsaturated bond with a solid content of 64.0% by mass. (B-1) was obtained. The resin (B-1) having an acid group and a polymerizable unsaturated bond had a solid content acid value of 85 mgKOH/g and a weight average molecular weight of 8,850.

(Synthesis Example 10: Synthesis of Resin (B-2) Having Acid Group and Polymerizable Unsaturated Bond)
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 392 parts by mass of diethylene glycol monomethyl ether acetate, an isocyanurate modified form of isophorone diisocyanate ("VESTANAT T-1890/100" manufactured by EVONIK, isocyanate group content 17. 2% by mass), 192 parts by mass of trimellitic anhydride, and 1.0 part by mass of dibutylhydroxytoluene were added and dissolved. After reacting at 160° C. for 5 hours in a nitrogen atmosphere, it was confirmed that the isocyanate group content was 0.1% by mass or less. The solid content acid value was 160 mgKOH/g as measured under conditions where the acid anhydride group was not ring-opened. Metoquinone 0.3 parts by mass, pentaerythritol polyacrylate mixture ("Aronix M-306" manufactured by Toagosei Co., Ltd., pentaerythritol triacrylate content of about 67%, hydroxyl value 159.7 mg KOH / g) 172 parts by mass and triphenylphosphine 3.6 parts by mass was added and reacted at 110° C. for 5 hours while blowing air. Then, 163 parts by mass of glycidyl methacrylate was added and reacted at 110° C. for 5 hours. Furthermore, 112 parts by mass of succinic anhydride and 122 parts by mass of diethylene glycol monomethyl ether acetate are added and reacted at 110° C. for 5 hours to obtain a resin (B- 2) was obtained. The resin (B-2) having an acid group and a polymerizable unsaturated bond had a solid content acid value of 79 mgKOH/g and a weight average molecular weight of 3,790.

(Example 1: Preparation of curable resin composition (1))
The aromatic ester compound (A-1) obtained in Synthesis Example 4 and the resin (B-1) having an acid group and a polymerizable unsaturated bond obtained in Synthesis Example 9 are mixed to produce an acid group-containing (meth)acrylate. A resin composition was obtained, and then an ortho-cresol novolac type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation) as a curing agent, diethylene glycol monoethyl ether acetate, and a photopolymerization initiator ("Omnirad 907" manufactured by IGM). ), 2-ethyl-4-methylimidazole, dipentaerythritol hexaacrylate, and phthalocyanine green in the parts by mass shown in Table 1, and kneaded by a roll mill to obtain a curable resin composition (1). rice field. In addition, description of the mass part of resin which has an acid group and a polymerizable unsaturated bond in Table 1 is a solid content value.

(Examples 2 to 7: Preparation of curable resin compositions (2) to (7))
Curable resin compositions (2) to (7) were obtained in the same manner as in Example 1 with the compositions and formulations shown in Table 1.

(Comparative Examples 1 to 4: Preparation of curable resin compositions (C1) to (C4))
Curable resin compositions (C1) to (C4) 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.

[Evaluation method for alkali developability]
After applying the curable resin composition obtained in each example and comparative example to a glass substrate using an applicator so as to have a film thickness of 50 μm, the coating was performed at 80° C. for 30 minutes, 40 minutes, and 50 minutes, respectively. Samples with different drying times were prepared by drying for 60 minutes, 70 minutes, 80 minutes, and 90 minutes. These samples were developed with a 1% sodium carbonate aqueous solution at 30° C. for 180 seconds, and the drying time at 80° C. for samples that left no residue on the substrate was evaluated as the drying control range. It should be noted that the longer the drying control width, the better the alkali developability.

The compositions and evaluation results of the curable resin compositions (1) to (7) prepared in Examples 1 to 7 and the curable resin compositions (C1) to (C4) prepared in Comparative Examples 1 to 4 are shown in Table 1. shown.

(Example 8: Preparation of curable resin composition (8))
The aromatic ester compound (A-1) obtained in Synthesis Example 4 and the resin (B-1) having an acid group and a polymerizable unsaturated bond obtained in Synthesis Example 9 are mixed to produce an acid group-containing (meth)acrylate. A resin composition is obtained, and then an ortho-cresol novolac type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation) as a curing agent, a photopolymerization initiator (“Omnirad 184” manufactured by IGM), and 4-dimethylaminopyridine. were mixed in the amounts shown in Table 2 to obtain a curable resin composition (8).

(Examples 9 to 14: Preparation of curable resin compositions (9) to (14))
Curable resin compositions (9) to (14) were obtained in the same manner as in Example 8 with the compositions and formulations shown in Table 2.

(Comparative Examples 5 to 8: Preparation of curable resin compositions (C5) to (C8))
Curable resin compositions (C5) to (C8) were obtained in the same manner as in Example 8 with the compositions and formulations shown in Table 2.

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 2 shows the evaluation results of the curable resin compositions (8) to (14) prepared in Examples 8 to 14 and the curable resin compositions (C5) to (C8) prepared in Comparative Examples 5 to 8. .

"Hardener" in Tables 1 and 2 indicates an ortho-cresol novolac type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation).

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

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

"(A)/(B)" in Tables 1 and 2 represents an aromatic ester compound (A-1) for a resin (B-1) or (B-2) having an acid group and a polymerizable unsaturated bond, Mass ratio of (A-2), (A'-1), aromatic compound (A'-2) or (A'-3) is shown.

Examples 1 to 14 shown in Tables 1 and 2 are examples of curable resin compositions using the acid group-containing (meth)acrylate resin composition of the present invention. It was confirmed that this curable resin composition has excellent alkali developability, heat resistance and dielectric properties.

On the other hand, Comparative Examples 1 and 5 are examples of curable resin compositions containing aromatic ester compounds made from phenolic compounds having no vinylbenzyloxy group. It was confirmed that this curable resin composition had insufficient heat resistance.

Comparative Examples 2, 3, 6 and 7, like Comparative Examples 1 and 5, are examples of curable resin compositions containing an aromatic ester compound made from a phenolic compound having no vinylbenzyloxy group. It was confirmed that this curable resin composition was excellent in alkali developability, but had high dielectric constant and dielectric loss tangent, and had insufficient dielectric properties.

Comparative Examples 4 and 8 are examples of curable resin compositions that do not use the A component specified in the present invention. It was confirmed that this curable resin composition was significantly inadequate in heat resistance and dielectric properties.

Claims (10)

An acid group-containing (meth)acrylate resin composition containing an aromatic ester compound (A) and a resin (B) having an acid group and a polymerizable unsaturated bond,
The aromatic ester compound (A) contains a phenol compound (A1) having at least one vinylbenzyloxy group and an aromatic polybasic acid or derivative thereof (A2) as essential reaction raw materials ,
an acid group-containing (meth)acrylate resin composition in which the phenol compound (A1) is represented by any one of the following structural formulas (1-1) to (1-8) ;
A curable resin composition comprising a photopolymerization initiator and an epoxy resin as a curing agent .

[In formulas (1-1) to (1-8), each R ₁ is independently a hydrogen atom or a vinylbenzyl group, and at least one in each molecule is a vinylbenzyl group. _Each R2 is independently a hydrogen atom, an alkyl group, or an aryl group. R ₂ in formulas (1-3) and (1-7) may be bonded to any naphthalene ring. Further, n in formulas (1-1), (1-4), (1-5), (1-6), and (1-8) is an integer of 0 to 4, and formula (1-2) n is an integer of 0 to 3, and n in formulas (1-3) and (1-7) is an integer of 0 to 6. R ₁ and R ₂ may be the same or different. ] 2. The curable resin composition according to claim 1, wherein the aromatic ester compound (A) has vinylbenzyloxy groups at both ends. 3. The curable resin composition according to claim 2 , 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 a phenol compound having a vinylbenzyloxy group, Y is a reactive residue of a polyfunctional phenol compound. Also, n is an integer of 0-20. ] 4. The curable resin composition according to claim 3 , wherein the aromatic ester compound (A) is represented by the following structural formula (I-1).

[In formula (I-1), each ring A is independently a benzene ring or a naphthalene ring which may have a substituent. ] The solid content mass ratio [(A)/(B)] between the aromatic ester compound (A) and the resin (B) having an acid group and a polymerizable unsaturated bond is in the range of 0.1 to 1. The curable resin composition according to claim 1. 2. The curable resin composition according to claim 1 , further comprising an organic solvent and a curing agent other than an epoxy resin curing agent . A cured product, which is a cured reaction product of the curable resin composition according to any one of claims 1 to 6 . An insulating material comprising the curable resin composition according to any one of claims 1 to 6 . A resin material for a solder resist, comprising the curable resin composition according to any one of claims 1 to 6 . A resist member comprising the solder resist resin material according to claim 9 .

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