JP2009001787A - Polyphenylene ether resin composition and electronic member - Google Patents

Abstract

Polyphenylene ether having good heat resistance and capable of realizing an adhesive sheet that satisfactorily reduces substrate warpage that occurs when a semi-cured adhesive sheet laminated on an inner circuit board is completely cured A resin composition is provided.
The following components (A) to (C), (A) a polyphenylene ether resin having an epoxy group, (B) a carboxyl group or an epoxy group, and having a weight average molecular weight of 10,000 or more. A polyphenylene ether resin composition comprising a thermoplastic elastomer resin and (C) a curing agent.
[Selection figure] None

Description

  The present invention relates to a polyphenylene ether resin composition and an electronic member that can realize an adhesive sheet suitable for, for example, a multilayer printed wiring board produced by a build-up method.

Epoxy resins having excellent cost performance are widely used as insulating materials for printed wiring boards, but in recent years, higher functionality has been demanded in order to cope with higher wiring density. For example, printed wiring boards used in high-frequency regions such as satellite communications are required to have an insulating material with excellent dielectric properties such as low dielectric constant and low dielectric loss tangent to prevent signal delay.
In recent years, with the miniaturization and high performance of electronic devices, the density of printed wiring boards has been increasing. For this reason, for example, in multilayer wiring boards, build-up multilayer printed wiring boards have been developed and made rapid progress by alternately laminating conductor circuit layers and insulating layers and conducting electrical continuity using blind holes only in areas where interlayer connections are required. ing. The insulating layer used in this build-up multilayer printed wiring board is usually a semi-cured (B-stage) adhesive sheet obtained by applying a resin solution on a support film and drying by heating. Is laminated on the inner layer circuit board by pressure heating lamination or heating press, and then the resin sheet is completely cured by heating to form an insulating layer. Next, a hole to be a via hole is drilled with a laser such as a carbon dioxide gas laser, the surface of the resin is roughened to improve adhesion with the plating, and the outer layer is selectively plated on the insulating layer. An additive system or the like that forms a circuit and simultaneously forms a conductor layer on the inner wall of the via hole is employed.

In addition to excellent dielectric properties, insulation, heat resistance and plating peel strength, such adhesive sheets require flexibility to prevent cracking of the sheet when winding or unwinding the sheet. At the same time, it is important that the solvent in the sheet is sufficiently removed.
Further, when laminating by pressure and heating on the inner layer circuit board, the adhesive sheet needs to be melted by heat to fill the space between the conductor circuits on the inner layer circuit board. Furthermore, after laminating the adhesive sheet to the substrate, the substrate is heated to completely cure the adhesive sheet. At this time, the adhesive sheet cures and shrinks, so that residual stress is generated in the cured sheet, thereby causing the inner layer to be cured. Since the circuit board is warped, it must be minimized.

In order to cope with these problems, several methods have been reported for resin compositions using polyphenylene ether having excellent dielectric properties. For example, Patent Document 1 reports a method for imparting flexibility to a sheet by using polybutadiene or a copolymer thereof.
Patent Document 2 reports a method in which the embedding property of the inner layer circuit is improved by using triallyl isocyanate and polybutadiene or a copolymer thereof.

JP-A-10-265552 JP 2000-104038 A

However, the resin compositions formed by the methods described in Patent Document 1 and Patent Document 2 still have room for improvement in terms of heat resistance, circuit embedding properties, warpage, and the like.
The present invention has been made in view of such circumstances, and has a good heat resistance and can realize an adhesive sheet that can satisfactorily reduce the warpage of a substrate that occurs when completely cured. It is an object to provide a resin composition.

As a result of intensive studies to solve the above problems, the present inventor has an epoxy group-containing polyphenylene ether resin, a carboxyl group or an epoxy group, and a thermoplastic elastomer resin having a weight average molecular weight of 10,000 or more, It has been found that a polyphenylene ether resin composition containing a curing agent can solve the above-mentioned problems, and has led to the present invention.
That is, the present invention provides the following polyphenylene ether resin composition.
[1]
Each of the following components (A) to (C),
(A) a polyphenylene ether resin having an epoxy group,
(B) a thermoplastic elastomer resin having a carboxyl group or an epoxy group and having a weight average molecular weight of 10,000 or more,
(C) a curing agent,
A polyphenylene ether resin composition comprising:
[2]
The polyphenylene ether resin composition according to the above [1], wherein the component (A) is a resin represented by the following general formula (1).

(In the formula, A is a hydrogen atom or the following general formula (2)

The structure represented by
m and n represent an integer of 1 or more,
R ₁ , R ₂ , R ₃ , R ₄ , Rx and Ry each independently represent a hydrogen atom or a monovalent functional group,
X ₁ , X ₂ and Z each independently represent a divalent functional group,
Y ₁ and Y ₂ each independently represent a divalent or higher functional group that may have an epoxy group. )
[3]
The polyphenylene ether resin composition according to the above [1] or [2], wherein the component (A) contains a polyphenylene ether skeleton in a proportion of 30 to 90% by mass.
[4]
The polyphenylene ether resin composition according to any one of the above [1] to [3], wherein the number average molecular weight of the polyphenylene ether skeleton of the component (A) is 1000 to 4000.
[5]
The polyphenylene ether resin composition according to any one of the above [1] to [4], wherein the component (A) has an average of 2.2 or more epoxy groups per molecule.
[6]
The polyphenylene ether resin composition according to any one of the above [1] to [5], wherein the component (B) is a copolymer of a diene compound and another compound.
[7]
(D) The polyphenylene ether resin composition according to any one of [1] to [6], further including an epoxy resin.
[8]
The polyphenylene ether resin composition according to the above [7], wherein the proportion of the component (A) in the total amount of the component (A), the component (B) and the component (D) is 30 to 85% by mass.
[9]
The polyphenylene ether resin composition according to the above [7] or [8], wherein the proportion of the component (B) in the total amount of the component (A), the component (B) and the component (D) is 1 to 20% by mass. object.
[10]
The polyphenylene ether resin composition according to any one of [1] to [9], wherein the component (C) is an acid anhydride curing agent.
[11]
The polyphenylene ether resin composition according to the above [10], wherein the acid anhydride curing agent is a curing agent having two or more acid anhydride groups in one molecule.
[12]
The polyphenylene ether resin composition according to any one of the above [1] to [11], wherein the component (C) includes a curing agent having a viscosity of 1000 mPa · s (25 ° C.) or less.
[13]
The electronic member formed using the polyphenylene ether resin composition in any one of said [1]-[12].
[14]
Semi-cured adhesive sheet, curable resin metal foil composite, epoxy prepreg,
1 type or 2 types or more selected from the group which consists of the laminated board which uses the said epoxy prepreg, or the said semi-hardened adhesive sheet, a curable resin metal foil composite, an epoxy prepreg, and an epoxy prepreg Printed wiring board, using
The electronic member according to [13], which is any one of the above.

  ADVANTAGE OF THE INVENTION According to this invention, the polyphenylene ether resin composition which has a favorable heat resistance and can implement | achieve the adhesive sheet which reduces the curvature of the board | substrate which generate | occur | produces at the time of complete curing favorable can be provided.

  The best mode for carrying out the present invention (hereinafter, an embodiment of the present invention) will be described in detail below. In addition, this invention is not limited to the following embodiment, It can implement in various deformation | transformation within the range of the summary.

  The polyphenylene ether resin composition of the present embodiment includes (A) a polyphenylene ether resin having an epoxy group, (B) a thermoplastic elastomer resin having a carboxyl group or an epoxy group and having a weight average molecular weight of 10,000 or more, and (C) A curing agent is included.

The (A) component (A) component polyphenylene ether resin having an epoxy group (hereinafter also referred to as an epoxidized polyphenylene ether resin) is not particularly limited, and has, for example, a structure represented by the following general formula (1). Resin can be used.

（式中、Ａは、水素原子もしくは下記一般式（２）

で表される構造を示し、ｍ、ｎは１以上の整数を示し、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒｘ及びＲｙは、それぞれ独立に、水素原子又は１価の官能基を示し、Ｘ₁、Ｘ₂及びＺは、それぞれ独立に、２価の官能基を示し、Ｙ₁及びＹ₂は、それぞれ独立に、エポキシ基を有してもよい２価以上の官能基を示す。）

(In the formula, A is a hydrogen atom or the following general formula (2)

M, n represents an integer of 1 or more, and R ₁ , R ₂ , R ₃ , R ₄ , Rx and Ry each independently represent a hydrogen atom or a monovalent functional group. , X ₁ , X ₂ and Z each independently represent a divalent functional group, and Y ₁ and Y ₂ each independently represent a divalent or higher functional group which may have an epoxy group. )

In the general formula (1) or (2), as the monovalent functional group represented by R ₁ , R ₂ , R ₃ , R ₄ , Rx and Ry, for example, an optionally substituted alkyl group, substituted And an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, and an optionally substituted alkoxy group.

The “alkyl group” of the optionally substituted alkyl group represented by R ₁ , R ₂ , R ₃ , R ₄ , Rx and Ry is a straight chain having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Or a branched alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, etc. Preferably, they are a methyl group and an ethyl group, and more preferably a methyl group.

The “cycloalkyl group” of the optionally substituted cycloalkyl group represented by R ₁ , R ₂ , R ₃ , R ₄ , Rx and Ry represents a cycloalkyl group having 3 to 8 carbon atoms, for example, , A cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like, preferably a cyclopentyl group and a cyclohexyl group.

Examples of the “aryl group” of the optionally substituted aryl group represented by R ₁ , R ₂ , R ₃ , R ₄ , Rx and Ry include a phenyl group, a naphthyl group and the like, preferably a phenyl group It is.

As the “aralkyl group” of the optionally substituted aralkyl group represented by R ₁ , R ₂ , R ₃ , R ₄ , Rx and Ry, the alkyl moiety is the “alkyl group” defined above, and aryl Examples thereof include an aralkyl group in which the moiety is the “aryl group” defined above, and examples thereof include a benzyl group, a phenethyl group, a phenylpropyl group, and a 1-naphthylmethyl group, and a benzyl group is preferable.

The “alkoxy group” of the optionally substituted alkoxy group represented by R ₁ , R ₂ , R ₃ , R ₄ , Rx and Ry is a straight chain having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. A methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, etc. Preferably, it is a methoxy group or an ethoxy group.

The alkyl group, cycloalkyl group, aryl group, aralkyl group and alkoxy group represented by R ₁ , R ₂ , R ₃ , R ₄ , Rx and Ry are substituted with one or more substituents at substitutable positions. May be. Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group), aryl group (for example, phenyl group, naphthyl group), aralkyl group (for example, benzyl group, phenethyl group), alkoxy group (for example, methoxy group, ethoxy group) Group),
Etc.

R ₁ , R ₂ , R ₃ and R ₄ are preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, from the viewpoint of dielectric constant and solubility in a solvent, A methyl group is preferred.

  Rx and Ry are preferably hydrogen atoms from the viewpoint of adhesiveness.

  Moreover, in General formula (1), m represents the average repeating number of a polyphenylene ether frame | skeleton part, Preferably it is 1-30, More preferably, it shows an integer of 1-15. When m is 30 or less, solubility in a solvent tends to be exhibited.

Furthermore, in General formula (2), n represents the average repeating number of a polyphenylene ether skeleton part, Preferably it is 1-30, More preferably, it shows an integer of 1-15. By setting n to 30 or less, solubility in a solvent tends to develop.

In the general formula (1) or (2), examples of the divalent functional group represented by X ₁ , X ₂ and Z include a single bond, an optionally substituted alkylene group, and an optionally substituted arylene. Groups and the like.

The “alkylene group” of the optionally substituted alkylene group represented by X ₁ , X ₂ and Z is a divalent group derived from the above “alkyl group” by further removing one hydrogen atom at any position. Methylene group, ethylene group, methylethylene group, ethylethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, trimethylene group, 1-methyltrimethylene group, 2-methyltrimethyl group. Examples include a methylene group and a tetramethylene group, and a methylene group, an ethylene group, a methylethylene group, a 1,1-dimethylethylene group, a trimethylene group and the like are preferable.

The “arylene group” of the optionally substituted arylene group represented by X ₁ , X ₂ and Z is a divalent derivative derived from the above “aryl group” by further removing one hydrogen atom at any position. Means the group of

The optionally substituted alkylene group and arylene group represented by X ₁ , X ₂ and Z may be substituted with one or more substituents at substitutable positions. Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group), aryl group (for example, phenyl group, naphthyl group), aralkyl group (for example, benzyl group, phenethyl group), alkoxy group (for example, methoxy group, ethoxy group) Group) and the like.

In the general formula (1) or (2), the “divalent or higher functional group” of the bivalent or higher functional group which may have an epoxy group represented by Y ₁ and Y ₂ includes the above X ₁ , It includes the same ones listed as the divalent functional groups X ₂ and Z. Y ₁ and Y ₂ may be a divalent or higher functional group having an epoxy group at the molecular end from the viewpoint of improving the heat resistance of the resin composition.

  The form of the molecule excluding the polyphenylene ether skeleton in the component (A) is not particularly limited. For example, it takes various forms such as bisphenol A type, bisphenol F type, biphenyl type, phenol novolak type, cresol novolak type and the like. be able to.

  (A) The ratio of the polyphenylene ether frame | skeleton part contained in the polyphenylene ether resin which has an epoxy group becomes like this. Preferably it is 30-90 mass%, More preferably, it is 40-80 mass%. If the proportion of the polyphenylene ether skeleton is 30% by mass or more, the effect of reducing the dielectric constant is increased, so that excellent dielectric properties tend to be exhibited, and if it is 90% by mass or less, the polyphenylene ether resin having an epoxy group The viscosity of the resin during production is moderately low and the production is easy, and the fluidity of the component (A) is improved, so that the embedding property of the adhesive sheet in the inner layer circuit tends to be good. Here, the embedding property of the adhesive sheet refers to the performance of embedding the step difference of the circuit pattern of the heat-melted semi-cured adhesive sheet at the time of heat lamination to the core substrate.

  (A) The polyphenylene ether resin having an epoxy group may be produced by any method, but is preferably produced by addition reaction of polyphenylene ether and an epoxy compound. The “polyphenylene ether skeleton” corresponds to such a polyphenylene ether as a raw material. In the present embodiment, when discussing the mass ratio of the polyphenylene ether skeleton and the number average molecular weight of the polyphenylene ether skeleton, the mass ratio of the polyphenylene ether as a raw material and the number average molecular weight of the polyphenylene ether may be read respectively. it can.

  It does not specifically limit as a raw material polyphenylene ether, For example, resin represented by following General formula (3) can be used.

(In the formula, a represents an integer of 1 or more, and R ₅ , R ₆ , R ₇ and R ₈ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms)

  Specifically, poly (2,6-dimethyl-1,4-phenylene oxide), poly (3,5-dimethyl-1,4-phenylene oxide), poly (2,3,6-trimethyl-1,4) -Phenylene oxide etc. are mentioned.

  The number average molecular weight of the polyphenylene ether is preferably 1000 to 4000, more preferably 1500 to 3000. When the number average molecular weight is 4000 or less, the melt viscosity of the resin composition tends to be moderately low and the processability tends to be good, and when it is 1000 or more, the effect of reducing the dielectric constant increases, so that excellent dielectric properties are obtained. It tends to develop.

  The method for producing polyphenylene ether is not particularly limited. For example, a method of adding 2,6-xylenol using a phenolic compound having two or more phenolic hydroxyl groups as a seed crystal, or a high molecular weight polyphenylene ether is used. Examples thereof include a method of subjecting to a redistribution reaction and adjusting the number average molecular weight within the above preferable range.

  As a method for subjecting the high molecular weight polyphenylene ether to the redistribution reaction, for example, as shown in the document “Journal of Organic Chemistry, 34, 297 to 303 (1968)”, the high molecular weight polyphenylene ether resin is used as a radical initiator. Use a method of reducing the molecular weight of a high molecular weight polyphenylene ether resin by reacting with a polyphenol compound such as bisphenol A, tetramethylbisphenol A, tetramethylbiphenyl, dihydroxydiphenyl ether, phenol novolak, cresol novolak, pyrogallol in the presence. Can do.

  The radical initiator is not particularly limited, and examples thereof include dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-tert-butyl cumi. Luperoxyhexyne-3,2,5-dimethyl-2,5-di-tert-butylperoxyhexane, α, α′-bis (tert-butylperoxy-m-isopropyl) benzene [1,4 (or 1,3) -bis (tert-butylperoxyisopropyl) benzene], diisopropylbenzene hydroperoxide, tert-butyl hydroperoxide, tert-butyl peroxyacetate, tert-butylperoxybenzene, benzoyl peroxide, etc. The peroxide can be used. At this time, cobalt naphthenate, a quaternary ammonium salt, an amine compound, or the like may be further used as a catalyst for the radical initiator.

  The epoxy compound to be reacted with the polyphenylene ether is not particularly limited, and for example, glycidyl halide such as epichlorohydrin, an epoxy resin having two or more epoxy groups in the molecule, and the like can be used. Examples of epoxy resins having two or more epoxy groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, hindered type epoxy resins, biphenyl type epoxy resins, and alicyclic epoxy resins. , Triphenylmethane type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin and epoxy resins halogenated from these; diglycidyl ether such as polyethylene glycol, polypropylene glycol, butanediol, hexanediol, cyclohexanedimethanol, etc. Can be used.

  As the epoxy compound, it is particularly preferable to use a polyfunctional epoxy resin having 3 or more epoxy groups in the molecule from the viewpoint of heat resistance. Examples of polyfunctional epoxy resins having 3 or more epoxy groups in the molecule include phenol novolac epoxy resins, cresol novolac epoxy resins, naphthol novolac epoxy resins, bis A novolac epoxy resins, dicyclopentadiene / phenol epoxy Examples thereof include resins, alicyclic amine epoxy resins, aliphatic amine epoxy resins, and the like. These may be used alone or in combination of two or more.

  In order to obtain a polyphenylene ether resin having an epoxy group, it can be obtained, for example, by reacting the polyphenylene ether and an epoxy compound at 100 to 200 ° C. for 1 to 20 hours in the presence of a catalyst. Examples of the catalyst include metal hydroxides such as sodium hydroxide and potassium hydroxide, alkylate salts such as sodium methylate and sodium butyrate, quaternary ammonium salts such as tetrabutylammonium chloride and tetramethylammonium bromide, tetra Phosphonium salts such as phenylphosphonium bromide and amyltriphenylphosphonium bromide, imidazoles such as 2-methylimidazole and 2-methyl-4-imidazole, amines such as N, N-diethylethanolamine, and metal halides such as potassium chloride One or more of tri-O-tolylphosphine and the like can be used.

  Specifically, when the epoxy compound is epichlorohydrin, after dissolving polyphenylene ether in epichlorohydrin at least 1 time, preferably at least 5 times the phenolic hydroxyl group of polyphenylene ether, an alkali such as sodium hydroxide or potassium hydroxide is used. It can be produced by adding a metal hydroxide, heating and stirring. The addition amount of the alkali metal hydroxide is 1 equivalent or more with respect to the phenolic hydroxyl group, and the reaction condition is 50 to 100 ° C. for 1 to 10 hours. The resulting product is washed with water or filtered to remove the generated salt, and unreacted epichlorohydrin is volatilized and recovered, or a poor solvent such as methanol is added to precipitate the resin, and the (A) component epoxy A polyphenylene ether resin can be obtained.

  (A) The epoxidized polyphenylene ether resin has an epoxy group as a polar group in the molecule, and details are unknown, but (B) a carboxyl group or an epoxy group described later has a weight average molecular weight. Good compatibility with 10,000 or more thermoplastic elastomer resins and (D) epoxy resins. As a result, it is estimated that it is possible to significantly reduce the warpage of the substrate that occurs when the semi-cured adhesive sheet laminated on the inner circuit board is completely cured.

  In addition, (A) the epoxidized polyphenylene ether resin has an epoxy group in the molecule and is easily dissolved in a mixed solvent containing a polar solvent such as a ketone solvent. In particular, it is easy to dissolve in a mixed solvent containing methyl ethyl ketone (boiling point 79.6 ° C.) having a relatively low boiling point.

  Further, when (A) the epoxidized polyphenylene ether resin has two or more epoxy groups in the molecule, the heat resistance and adhesiveness of the obtained adhesive sheet and laminate can be further improved. In order to obtain an epoxidized polyphenylene ether resin having an average of 2 or more epoxy groups in the molecule, at least 5% by mass, preferably 10% by mass, more preferably 20% by mass of the epoxy compound used in the reaction is a polyfunctional epoxy. A resin may be used. By containing many polyfunctional epoxy resins, the average number of epoxy groups in the resulting epoxidized polyphenylene ether resin can be increased.

  Moreover, when making a polyphenylene ether and an epoxy compound react, it is preferable to use 2 or more types of epoxy compounds together. In particular, it is preferable to use one or more polyfunctional epoxy resins and bifunctional epoxy resins. The polyfunctional epoxy resin can be used from the viewpoint of increasing the number of epoxy groups in the resulting epoxidized polyphenylene ether resin, but it is difficult to dissolve the polyphenylene ether, and gelation may easily occur due to the reaction with the polyphenylene ether. is there. However, when a bifunctional epoxy resin is added during the reaction, the polyphenylene ether is easily dissolved, so that the reaction is likely to occur. Further, gelation can be reduced, and the reaction can be favorably progressed even in a system in which no solvent is added.

  (A) The content of the polyphenylene ether resin having an epoxy group is preferably 30 to 85% by mass with respect to the total of 100% by mass of the component (A), the component (B) and the component (D) described later, and more Preferably it is 50-85 mass%. When it is 30% by mass or more, it tends to develop excellent dielectric properties, and when it is 85% by mass or less, the viscosity when dissolved in a solvent and the melt viscosity of the resin are moderately low and the workability tends to be excellent. .

(B) Component (B) The thermoplastic elastomer resin having a carboxyl group or an epoxy group and a weight average molecular weight of 10,000 or more (hereinafter also referred to as a thermoplastic elastomer resin) is not particularly limited, For example, diene-based compounds and other compounds such as polybutadiene, acrylonitrile-butadiene copolymer, styrene-butadiene copolymer having a carboxyl group or an epoxy group in the molecule and having a weight average molecular weight of 10,000 or more. A copolymer etc. are mentioned.

  Since the thermoplastic elastomer resin has a carboxyl group or an epoxy group in the molecule, compatibility with (A) a polyphenylene ether resin having an epoxy group and (D) an epoxy resin to be described later is improved. In order to more effectively reduce the internal stress generated when the resin composition is cured, as a result, the warpage of the substrate that occurs when the semi-cured adhesive sheet laminated on the inner circuit board is completely cured is significantly reduced. It becomes possible. Moreover, since a glass transition temperature becomes high because a weight average molecular weight is 10,000 or more, the heat resistance of an adhesive sheet or a laminated board becomes favorable.

  The said thermoplastic elastomer resin may be used independently, or may use 2 or more types together. When two or more kinds of thermoplastic elastomers having different molecular weights are used, the average weight average molecular weight thereof is 10,000 or more, more preferably 100,000 or more. The upper limit of the weight average molecular weight is not particularly limited, but is preferably 1,000,000 or less.

  The thermoplastic elastomer resin must be dissolved in the same solvent as the solvent for dissolving the epoxidized polyphenylene ether resin as the component (A).

  The content of the (B) thermoplastic elastomer resin is preferably 1 to 20% by mass, more preferably 100% by mass, more preferably 100% by mass of the (A) component, the (B) component and the (D) component described later. 3 to 15% by mass. When the content is 1% by mass or more, the effect of reducing internal stress generated during the curing reaction of the polyphenylene ether resin composition is high, and the substrate generated when the semi-cured adhesive sheet laminated on the inner circuit board is completely cured. Warpage can be reduced. Moreover, the heat resistance of an adhesive sheet or a laminated board can be made favorable as it is 20 mass% or less.

The (C) component curing agent contained in the (C) component polyphenylene ether resin composition is not particularly limited as long as it is a curing agent that reacts with an epoxy resin. For example, amide-based curing agents such as dicyandiamide and aliphatic polyamide. Further, amine-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, imidazole-based curing agents and derivatives thereof, epoxy adducts, or microcapsules can be used. These curing agents may be used alone or in combination of two or more.

  Among these, it is preferable to use an acid anhydride curing agent because the excellent dielectric properties of the (A) epoxidized polyphenylene ether resin can be maintained when the polyphenylene ether resin composition is cured. Among acid anhydride curing agents, when an acid anhydride curing agent having two or more acid anhydride groups in one molecule (so-called polyfunctional acid anhydride) is used, a polyphenylene ether resin composition having excellent heat resistance This is preferable because a cured product tends to be obtained. Examples of such polyfunctional acid anhydrides include styrene-maleic anhydride copolymer, ethylene glycol bisanhydro trimellitate, glycerin bis (anhydro trimellitate) monoacetate, and the like.

  Further, when the component (C) contains a curing agent having a viscosity at 25 ° C. of 1000 mPa · s or less as measured with a B-type viscometer, the inner layer circuit of the semi-cured adhesive sheet (that is, the B stage adhesive sheet) This is preferable because the embedding property tends to be good. Examples of such a curing agent include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnamedic acid anhydride, hydrogenated methylnamedic acid anhydride, and the like. It is preferable to use a polyfunctional acid anhydride and an acid anhydride that is liquid at room temperature because both excellent heat resistance and embedding can be achieved. The amount of these acid anhydride curing agents used is preferably 0.8 to 1.5 with respect to the number of epoxy groups contained in the resin composition to be cured. More preferably, the amount used is 0.8 to 1.3. In addition, as a ratio for which (C) component accounts in a polyphenylene ether resin composition, Preferably it is 0.1-20 mass%.

(D) Component The polyphenylene ether resin composition of the present embodiment includes the essential component (A
) To (C), (D) an epoxy resin may be further contained. (D) The epoxy resin is not particularly limited as long as it is a resin having one or more epoxy groups in the molecule, and is preferably a resin having two or more epoxy groups in the molecule. (D) Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hindered-in type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, and triphenylmethane type epoxy resin. And epoxy resins halogenated from these. Also, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolac type epoxy resin, bis A novolac type epoxy resin, dicyclopentadiene / phenol epoxy resin, alicyclic amine epoxy resin, aliphatic amine epoxy resin, etc. A functional epoxy resin may be used. The (D) component epoxy resin does not include the (A) component epoxidized polyphenylene ether resin.

  The (D) epoxy resin preferably contains an epoxy resin that is liquid at room temperature from the viewpoint of the flexibility of the adhesive sheet and the embedding property of the inner layer circuit of the semi-cured adhesive sheet.

  Further, the (D) epoxy resin preferably contains a flame retardant epoxy resin such as a brominated epoxy resin or an epoxy group-containing phosphazene compound from the viewpoint of flame retardancy. (D) Content of an epoxy resin is 3-60 mass% with respect to a total of 100 mass% of (A) component, (B) component, and (D) component, Preferably it is 5-50 mass%. When the amount of the component (D) is 3% by mass or more, handleability and flame retardancy tend to be imparted, and when it is 60% by mass or less, an excellent dielectric constant tends to be developed.

  Moreover, the polyphenylene ether resin composition of the present embodiment may contain various additives such as inorganic fillers and organic fillers in addition to the components (A) to (D) as necessary. . Examples of the inorganic filler include silica, alumina, aluminum hydroxide, calcium carbonate, clay, and titanium oxide. Examples of the organic filler include silicone powder and nylon powder.

Adhesive sheet (semi-cured adhesive sheet)

  As a method for producing an adhesive sheet, first, the resin of component (A), component (B) and, if necessary, component (D) are dissolved in a solvent, and then a curing agent and component (C) are added. The agent is dissolved or uniformly dispersed to obtain a varnish of the polyphenylene ether resin composition. Although the solid content density | concentration in a varnish is not specifically limited, Preferably it is 30-80 mass%.

  As the solvent, in addition to halogen-based solvents such as dichloromethane and chloroform and aromatic solvents such as benzene, toluene, xylene and mesitylene, which are well-known solvents used for the preparation of varnish, it is possible to use ketone solvents. it can. Examples of the ketone solvent include aliphatic ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, and cyclohexanone, and aromatic ketones such as acetophenone. A solvent such as dimethylformamide, methyl cellosolve, propylene glycol monomethyl ether can also be used.

  Among the above solvents, it is preferable to use methyl ethyl ketone (MEK) as the ketone from the viewpoint of the solubility and boiling point of the polyphenylene ether resin composition. As a solvent to be combined with methyl ethyl ketone, it is preferable to use an aromatic solvent having a boiling point of 120 ° C. or lower such as toluene.

  The polyphenylene ether resin composition of the present embodiment is preferably dissolved in a mixed solvent containing ketones at room temperature. The term “dissolving at room temperature” as used herein means that when a 10% by mass solution is obtained, a transparent solution state is obtained at room temperature, and a state in which substantially no solid content is present is 1 day or more, preferably A state that is maintained for 30 days or more. The content of ketones in the mixed solvent is preferably 10 to 80% by mass.

  The adhesive sheet (semi-cured adhesive sheet) of the present embodiment is formed by coating the varnish of the polyphenylene ether resin composition on a support film and removing the solvent by heating and drying (film formation) ) Can be manufactured. The thickness of the dried film is preferably 15 to 120 μm, more preferably 15 to 70 μm.

  As drying conditions at this time, the heating temperature is 80 to 150 ° C., preferably 90 to 120 ° C., and the heating time is 1 to 20 minutes, preferably 2 to 10 minutes. When the drying conditions are within this range, the solvent remaining in the obtained adhesive sheet is sufficiently removed, and the volatile content in the sheet can be reduced to 1% by mass or less. In addition, curing of the adhesive sheet due to film formation can be suppressed, and embeddability between wirings when stacked on the inner circuit board can be ensured.

  Examples of the method for applying the varnish to the support film include a bar coater, a lip coater, a die coater, a roll coater, and a doctor blade coater. Examples of the support film include polyethylene terephthalate, polyethylene, polycarbonate, and the like, and the thickness thereof is preferably 10 to 150 μm. The support film may be appropriately subjected to release treatment, mat treatment, and the like.

Multilayer printed wiring board When manufacturing a multilayer printed wiring board using the adhesive sheet of the present embodiment, the adhesive sheet manufactured by the above method is bonded to the patterned inner layer circuit board and pressed from the support film side. Laminate while heating. The inner layer circuit surface may be roughened in advance. Lamination is carried out at normal pressure or under reduced pressure, batchwise or continuously with a roll, but it is preferable to laminate on both sides simultaneously. The lamination conditions at this time are preferably a pressure bonding temperature of 70 ° C. to 150 ° C. and a pressure bonding pressure of 0.1 to 1 MPa. Moreover, it is preferable to laminate under a reduced pressure of 2 KPa or less. After lamination, the support film is peeled off after cooling to room temperature, and then the adhesive film laminated on the inner circuit board is heated and cured. As curing conditions, it is preferable that the curing temperature is 130 to 200 ° C. and the curing time is within a range of 30 to 120 minutes.

  Next, after making holes in the via holes with a laser such as a carbon dioxide laser, roughen with an oxidizing agent such as permanganate, dichromate, or ozone for the purpose of removing smear and improving the adhesion between plating. Perform surface treatment. Thereafter, a conductor circuit is selectively formed on the edge layer resin by electroless plating or electrolytic plating, and at the same time, a conductor is formed on the inner wall of the via hole to form an outer layer circuit. Then, the adhesiveness of a conductor layer and a resin layer can be improved by annealing-processing for 30 minutes-60 minutes at 150-200 degreeC. A multilayer printed wiring board can be manufactured by forming a multi-stage buildup layer by repeating the above manufacturing method using an adhesive sheet on the conductive circuit layer thus obtained.

Prepreg The varnish for producing the prepreg of this embodiment mainly uses a mixed solvent of ketones such as ketylethylketone and toluene, and comparison of dimethylformamide, propylene glycol monomethyl ether, mesitylene, etc. as an auxiliary solvent A solvent having a high target boiling point can be used. In these solvents, (A) epoxy-based polyphenylene ether resin, (B) thermoplastic elastomer, and (D) epoxy resin of the present invention are dissolved, and (C) curing agent and other additives are dissolved or uniformly dissolved. Disperse to obtain a varnish of a polyphenylene ether resin composition for producing the prepreg of the present embodiment. Although the solid content density | concentration in a varnish is not specifically limited, Preferably it is 30-80 mass%.

  The prepreg of the present embodiment can be produced by impregnating the above varnish into a base material and then semi-curing it by drying and heating the solvent. Examples of the substrate include glass cloth, aramid cloth, polyester cloth, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper, linter paper and the like. The amount of resin impregnated into the substrate is not particularly limited, but it is preferable to impregnate the resin content after drying so as to be 30 to 70% by mass relative to the mass of the prepreg.

Curable resin metal foil composite The curable resin metal foil composite is composed of a film made of the polyphenylene ether resin composition of the present embodiment and a metal foil. Although the thickness of a film is not specifically limited, Usually, it is 15-150 micrometers. The metal foil used here is preferably conductive, and for example, a copper foil, an aluminum foil, or the like can be used.

  As a method for producing the curable resin metal foil composite, for example, a method for producing the varnish of the polyphenylene ether resin composition of the present embodiment by applying the varnish on the metal foil, a pre-made polyphenylene ether resin composition The method of heat-pressing metal foil on the film which forms, or the method of laminating | stacking metals, such as copper and aluminum, by means, such as sputtering, vapor deposition, and plating, etc. on the film which consists of a polyphenylene ether resin composition, etc. are mentioned.

Laminate The laminate of the present embodiment can be produced by laminating a prepreg, a curable resin / metal foil composite, a film and a copper foil in a layer configuration according to the purpose, and heating under pressure. As a method of manufacturing a laminated board, for example, a method of stacking a plurality of prepregs and curable resin metal foil composites on a substrate and bonding each layer under heat and pressure and simultaneously curing the resin, A laminate having a desired thickness can be obtained by, for example, a method in which a plurality of curable resin metal foil composites are superposed and each layer is bonded under heat and pressure, and at the same time, thermosetting is performed. The metal foil can be used as a surface layer or an intermediate layer. In addition, it is possible to successively make a multilayer by repeating lamination and curing a plurality of times.

  Hereinafter, the present embodiment will be described in more detail with reference to examples. In addition, this invention is not limited by the Example described below. In the following, “%” means mass%.

[Measuring method]
The measuring method of the physical property etc. in this specification is as follows.
(1) Number average molecular weight and weight average molecular weight Gel permeation chromatography analysis using shodex A-804, A-803, A-802, A802 manufactured by Showa Denko KK as a column and elution time of polystyrene with known molecular weight The number average molecular weight and the weight average molecular weight were determined by comparison.
(2) Epoxy equivalent It measured according to JISK7236.
(3) Number of epoxy groups (A) The number of epoxy groups in the polyphenylene ether resin having an epoxy group was calculated by dividing the molecular weight of the polyphenylene ether resin having an (A) epoxy group by the epoxy equivalent.
(4) Dielectric constant, dielectric loss tangent The adhesive film is peeled off from the support film, 16 sheets of the obtained resin film are laminated, and 18 μm thick copper foil is placed on the top and bottom, and the pressure is applied at 190 ° C. and 1 MPa for 90 minutes. By heating, a cured resin sheet with a double-sided copper foil having a resin layer thickness of about 0.5 mm was produced. This was measured based on JIS C 6481 using an LCR meter 4284A manufactured by Agilent Technologies.
(5) Glass transition temperature A sample obtained by etching a resin-cured sheet with a double-sided copper foil or a copper foil of a double-sided copper-clad laminate similar to that prepared for the above-described dielectric constant and dielectric loss tangent measurement was used. These samples were measured using a Seiko Instruments DCS6200 under measurement conditions of a temperature increase rate of 20 ° C./min, and the glass transition temperature was determined from the inflection point of the obtained DSC curve.
(6) Circuit embedding property Using a roll type laminator on an FR-4 substrate (17 cm × 34 cm, thickness 0.4 mm) having a wiring line / space of 150 μm / 100 μm and a wiring thickness of 18 μm. The adhesive sheet was laminated on one side of the substrate under the conditions of a pressure bonding temperature of 90 to 120 ° C., a pressure bonding pressure of 0.3 to 0.5 MPa, and a lamination speed of 0.2 to 0.5 m / min. The presence of bubbles between the wirings was visually checked, and when there was no bubble, “◯” was indicated, and when it was present, “X” was assigned.
(7) Size of substrate warpage and substrate warpage The FR-4 substrate laminated with the adhesive sheet obtained in the circuit embedding test was heated at 185 ° C for 1 hour and then cooled to room temperature. Thereafter, a test piece having a length of 17 cm and a width of 5 mm was cut out from the substrate, and when one end was fixed to a horizontal base, the height at which the other end was lifted from the base was measured. As for the substrate warpage, a case where warpage greater than 1.0 cm was observed was evaluated as x.
(8) Copper foil adhesive strength The support film is peeled off from the adhesive sheet, 16 sheets of the obtained resin film are laminated, and 18 μm thick copper foil is further placed on the top and bottom thereof, and pressure is applied at 190 ° C. and 1 MPa for 90 minutes. By heating, a cured resin sheet with a double-sided copper foil having a resin layer thickness of about 0.5 mm was produced. This was measured using an autograph AGS-H manufactured by Shimadzu Corporation according to JIS-c6481.

[Polyphenylene ether: Production Example 1]
100 g of high molecular weight polyphenylene ether (manufactured by Asahi Kasei Chemicals Corporation) having a number average molecular weight of 17,000 and 8 g of bisphenol A were dissolved in 150 g of toluene by heating. Further, 0.1 g of cobalt naphthenate was added and the temperature of the solution was heated to 90 ° C. To this, 12.5 g of xylene 40% solution (manufactured by NOF Corporation: Nyper BMT-K40) of a mixture of benzoyl peroxide and its methyl substitution product (corresponding to 5 g of the mixture of benzoyl peroxide and its methyl substitution product) and toluene 37 0.5 g mixed solution was added over 2 hours. After completion of the dropwise addition, the temperature of the reaction solution was kept at 90 ° C., and stirred for 120 minutes for redistribution reaction. Thereafter, the temperature of the reaction solution was lowered to 70 ° C., and a solution prepared by mixing 75 g of toluene with 25 g of Niper BMT-K40 (corresponding to 10 g of benzoyl peroxide and its methyl substitution product) was added over 2 hours. After completion of the dropwise addition, the temperature of the reaction solution was kept at 70 ° C., and further stirred for 180 minutes to perform a redistribution reaction, thereby reducing the molecular weight of polyphenylene ether. After adding 100 g of 1N sodium hydroxide solution to the obtained reaction solution and stirring at 90 ° C. for 1 hour, the solution was allowed to stand to separate the reaction solution layer and the aqueous layer, and the aqueous layer was removed. As a result of measuring the reaction solution by gel permeation chromatography, the number average molecular weight of the obtained polyphenylene ether was 1,900.

[(A) Polyphenylene ether resin having epoxy group: Production Example 2]
25 g of cresol novolac type epoxy resin (Asahi Kasei Epoxy Co., Ltd .: ECN1299) and 25 g of bisphenol A type epoxy resin (Asahi Kasei Chemicals Co., Ltd .: AER250) were heated to 100 ° C. and mixed with stirring. After thoroughly mixing, 0.005 g of NaOCH ₃ was added as a catalyst and stirred for about 15 minutes. Thereafter, the mixture was heated to 165 ° C., and 204 g of the polyphenylene ether solution obtained in Production Example 1 (50 g in terms of polyphenylene ether) was added over 90 minutes. At this time, the solvent toluene was removed from the reaction system under normal pressure or reduced pressure by flowing nitrogen into the reaction vessel. Then, it stirred at 165 degreeC for 2 hours, and obtained the polyphenylene ether resin (epoxidized polyphenylene ether resin I) which has an epoxy group.
Next, 10 g of the epoxidized polyphenylene ether resin I was dissolved in 100 g of toluene, and a large excess of methanol was added to precipitate and precipitate the epoxidized polyphenylene ether resin I. The number average molecular weight of the obtained epoxidized polyphenylene ether resin I was 3060, and the epoxy equivalent was 550. The proportion of the polyphenylene ether skeleton was 62% by mass, and the number of epoxy groups per molecule was 5.5.

[(A) Polyphenylene ether resin having epoxy group: Production Example 3]
10 g of cresol novolac type epoxy resin (ECN1273) and 30 g of bisphenol A type epoxy resin (AER250) were heated to 100 ° C. and mixed with stirring. After thoroughly mixing, 0.005 g of NaOCH ₃ was added as a catalyst and stirred for about 15 minutes. Thereafter, the mixture was heated to 165 ° C., and 245 g of polyphenylene ether solution obtained in Production Example 1 (60 g in terms of polyphenylene ether) was added over 90 minutes. At this time, the solvent toluene was removed from the reaction system under normal pressure or reduced pressure by flowing nitrogen into the reaction vessel. Then, it stirred at 165 degreeC for 2 hours, and obtained the polyphenylene ether resin (epoxidized polyphenylene ether resin II) which has an epoxy group.
10 g of the epoxidized polyphenylene ether resin II was dissolved in 100 g of toluene, and a large excess of methanol was added to precipitate the epoxidized polyphenylene ether resin II. The resulting epoxidized polyphenylene ether resin II had a number average molecular weight of 2550 and an epoxy equivalent of 1020. The proportion of the polyphenylene ether skeleton was 69% by mass, and the number of epoxy groups per molecule was 2.5.

[(A) Polyphenylene ether resin having epoxy group: Production Example 4]
After dissolving 204 g of the polyphenylene ether solution obtained in Production Example 1 (50 g in terms of polyphenylene ether) in 250 g of epichlorohydrin, 10 g of a 50% by mass aqueous sodium hydroxide solution was added at 60 ° C. over 60 minutes, and then 60 Stir at 60 ° C. for 60 minutes. 50 g of water was added to this reaction solution, and after stirring, the product was removed by allowing the aqueous layer to separate. Then, epichlorohydrin and toluene were removed by distillation under reduced pressure, and a polyphenylene ether resin having an epoxy group (epoxidized polyphenylene). Ether resin III) was obtained. The resulting epoxidized polyphenylene ether resin III had a number average molecular weight of 2010 and an epoxy equivalent of 1570. The proportion of the skeleton of polyphenylene ether was 95% by mass, and the number of epoxy groups in one molecule was 1.7.

[Raw materials used]
(1) (A) Polyphenylene ether resin having epoxy group Epoxidized polyphenylene ether resins I to III produced in the above Production Examples 2 to 4

(2) (B) Thermoplastic elastomer resin (2-1) Carboxylic acid-modified acrylonitrile butadiene rubber JSR: PNR-1H Weight average molecular weight 300,000 (2-2) Carboxylic acid-modified acrylonitrile butadiene rubber Ube Industries, Ltd .: CTBN13 Weight average molecular weight 3500
(2-3) Epoxidized thermoplastic elastomer, manufactured by Daicel Chemical Industries, Ltd .: Epofriend AT501, weight average molecular weight, 8-100,000 (2-4) terminal epoxidized polybutadiene rubber, manufactured by Nagase Chemtuck, Inc .: Denarex R45, weight average molecular weight, 3000

(3) (C) Hardener (3-1) Styrene-maleic anhydride copolymer Kawa Crude Chemical Co., Ltd .: SMA-EF40
(3-2) Methylhexahydrophthalic anhydride New Nippon Rika Co., Ltd .: MH-700
MH-700
(3-3) Imidazole-based curing agent Shikoku Kasei Co., Ltd .: Curesol 2MA-OK

(4) (D) Epoxy resin (4-1) Liquid bisphenol A type epoxy resin Asahi Kasei Epoxy Co., Ltd .: AER250
(4-2) Tetrabromobisphenol A type epoxy resin manufactured by Asahi Kasei Epoxy Corporation: AER8018

[Examples 1-7, Comparative Examples 1-3, Reference Example 1]
After applying the varnish blended at the ratio (parts by mass) shown in Table 1 on a polyethylene terephthalate (hereinafter referred to as PET) film having a thickness of 38 μm using a doctor blade coater so that the thickness after drying becomes 35 μm, Dried at 110 ° C. for 10 minutes. The obtained adhesive sheet was measured for dielectric constant, dielectric loss tangent, glass transition temperature, circuit embedding property, substrate warpage, and copper foil adhesive strength, and the results are shown in Table 1.

As is clear from the results shown in Table 1, the adhesive sheets of Examples 1 to 7 have good electrical characteristics and heat resistance, and the warpage of the substrate that occurs during complete curing is greatly reduced. It was.
On the other hand, since the adhesive sheet of Comparative Example 1 shown in Table 2 does not contain the thermoplastic elastomer corresponding to the component (B) in the resin composition, it suppresses the warpage of the substrate that occurs during complete curing. I couldn't.
Moreover, since the adhesive sheet of Comparative Example 2 and Comparative Example 3 uses a low molecular weight resin (weight average molecular weight 3500 and weight average molecular weight 3000) as the thermoplastic elastomer corresponding to the component (B), the glass transition temperature. Was low and inferior in heat resistance.
In addition, as one of the reasons that the adhesive sheet of this example was able to reduce the warpage of the substrate, the thermoplastic elastomer resin of the component (B) was modified with a carboxyl group or an epoxy group. Therefore, the compatibility of the component (A) with the epoxidized polyphenylene ether resin is improved, and it is considered that the elastomer component is uniformly incorporated into the skeleton of the epoxidized polyphenylene ether resin or epoxy resin at the time of curing. It is presumed that the internal stress generated during the curing of the object can be effectively reduced.

  The polyphenylene ether resin composition of the present invention is excellent in dielectric properties and processability to build-up printed wiring boards, and is suitable as an adhesive sheet for build-up printed wiring boards.

Claims (14)

Each of the following components (A) to (C),
(A) a polyphenylene ether resin having an epoxy group,
(B) a thermoplastic elastomer resin having a carboxyl group or an epoxy group and having a weight average molecular weight of 10,000 or more,
(C) a curing agent,
A polyphenylene ether resin composition comprising: The polyphenylene ether resin composition according to claim 1, wherein the component (A) is a resin represented by the following general formula (1).

(In the formula, A is a hydrogen atom or the following general formula (2)

The structure represented by
m and n represent an integer of 1 or more,
R ₁ , R ₂ , R ₃ , R ₄ , Rx and Ry each independently represent a hydrogen atom or a monovalent functional group,
X ₁ , X ₂ and Z each independently represent a divalent functional group,
Y ₁ and Y ₂ each independently represent a divalent or higher functional group that may have an epoxy group. )   The polyphenylene ether resin composition according to claim 1 or 2, wherein the component (A) contains a polyphenylene ether skeleton at a ratio of 30 to 90% by mass.   The polyphenylene ether resin composition according to any one of claims 1 to 3, wherein the number average molecular weight of the polyphenylene ether skeleton of the component (A) is 1000 to 4000.   The polyphenylene ether resin composition according to any one of claims 1 to 4, wherein the component (A) has an average of 2.2 or more epoxy groups per molecule.   The polyphenylene ether resin composition according to any one of claims 1 to 5, wherein the component (B) is a copolymer of a diene compound and another compound.   (D) The polyphenylene ether resin composition according to any one of claims 1 to 6, further comprising an epoxy resin.   The polyphenylene ether resin composition according to claim 7, wherein a proportion of the component (A) in the total amount of the component (A), the component (B), and the component (D) is 30 to 85% by mass.   The polyphenylene ether resin composition according to claim 7 or 8, wherein a ratio of the component (B) in the total amount of the component (A), the component (B), and the component (D) is 1 to 20% by mass.   The polyphenylene ether resin composition according to any one of claims 1 to 9, wherein the component (C) is an acid anhydride curing agent.   The polyphenylene ether resin composition according to claim 10, wherein the acid anhydride curing agent is a curing agent having two or more acid anhydride groups in one molecule.   The polyphenylene ether resin composition according to any one of claims 1 to 11, wherein the component (C) includes a curing agent having a viscosity of 1000 mPa · s (25 ° C) or less.   The electronic member formed using the polyphenylene ether resin composition of any one of Claims 1-12. Semi-cured adhesive sheet, curable resin metal foil composite, epoxy prepreg,
1 type or 2 types or more selected from the group which consists of the laminated board which uses the said epoxy prepreg, or the said semi-hardened adhesive sheet, a curable resin metal foil composite, an epoxy prepreg, and an epoxy prepreg Printed wiring board, using
The electronic member according to claim 13, which is any one of the above.