KR20180134349A - Adhesive film for multilayer printed circuit boards - Google Patents

Abstract

Provided is an adhesive film for a multilayer printed circuit board which is excellent in the embedding property of unevenness even when the silica filler is roughened. Specifically, the adhesive film comprises (A) a novolak type phenolic resin having a weight average molecular weight (Mw) to number average molecular weight (Mn) dispersion ratio (Mw / Mn) of 1.05 to 1.8, and (B) (C) an inorganic filler having an average particle size of 0.1 (0.1 to 0.1) in the resin composition layer, wherein the resin composition layer comprises a resin composition comprising a resin composition comprising an epoxy resin represented by the following formula Mu m or more, and (C) the content of the inorganic filler in the resin solid content is 20 to 95% by mass.

Description

Adhesive film for multilayer printed circuit boards

The present invention relates to an adhesive film for a multilayer printed wiring board.

2. Description of the Related Art In recent years, a multilayered printed circuit board used in electronic devices, communication devices, and the like has become stronger not only in size, weight, and wiring density but also in speeding up the processing speed. Accordingly, as a manufacturing method of a multilayer printed wiring board, attention has been focused on a build-up manufacturing technique in which interlayer insulating layers are alternately stacked on a wiring layer of a circuit board.

In the build-up manufacturing technique, the interlayer insulating layer and the wiring layer can be produced by a method comprising the steps of: preparing a resin composition for forming an interlayer insulating layer (hereinafter also referred to as " resin composition for an interlayer insulating layer " Is pressed at a high temperature for a long time using a press apparatus to thermally cure the resin composition for an interlaminar insulating layer to obtain an interlaminar insulating layer having a copper foil, Conventionally, a method of forming wirings using a so-called " subtractive method " in which a via hole is formed and then a copper foil is removed by etching while leaving a necessary portion is conventionally used.

Further, with the demand for miniaturization and weight reduction of the multilayered printed circuit board as well as reduction in the wiring density, the resin composition for an interlayer dielectric layer and the copper foil are pressed at a high temperature for a short time using a vacuum laminator, Called additive method in which a resin composition for an interlaminar insulating layer is thermally cured under the conditions below and a via hole for interlayer connection is formed by a drill method or a laser method if necessary and a wiring layer is formed at a necessary portion by a plating method .

As a resin composition for an interlayer insulating layer used in a build-up method, there are a combination of an aromatic epoxy resin and a curing agent having active hydrogen for an epoxy resin (for example, a phenol curing agent, an amine curing agent, a carboxylic acid curing agent, Has been mainly used. A cured product obtained by curing using these curing agents is excellent in balance of physical properties. However, a hydroxyl group having a high polarity is generated by the reaction between an epoxy group and active hydrogen, so that the increase in the water absorption rate, the dielectric constant, There is a problem that it causes deterioration of the image quality. In addition, when these curing agents are used, there arises a problem that the storage stability of the resin composition is impaired.

On the other hand, it is known that a cyanate compound having a thermosetting cyanate group imparts a cured product excellent in electrical characteristics. However, the reaction in which a cyanate group forms a S-triazine ring by thermosetting requires a relatively long time of curing at a high temperature of, for example, 230 deg. C for 120 minutes or more. Therefore, It was not suitable as a resin composition for an interlayer insulating layer for a printed wiring board.

As a method of lowering the curing temperature of a cyanate compound, there is known a method in which a cyanate compound and an epoxy resin are used together and cured using a curing catalyst (see, for example, Patent Documents 1 and 2).

In addition, the buildup layer is required to have a low thermal expansion coefficient (low CTE) from the demand for dimensional stability and reduction of the amount of warpage after semiconductor mounting, and a countermeasure for lowering the CTE has been made (see, for example, 5). As the most mainstream method, a low CTE of the buildup layer is often achieved by making a silica filler (for example, 40% or more by mass of silica filler in the buildup layer).

Japanese Patent Application Laid-Open No. 2013-40298 Japanese Patent Application Laid-Open No. 2010-90237 Japanese Patent Publication No. 2006-527920 Japanese Patent Application Laid-Open No. 2007-87982 Japanese Patent Application Laid-Open No. 2009-280758

[a] When the silica filler is called up to make the buildup layer have a low CTE, it is difficult to embed unevenness of the wiring pattern of the inner layer circuit by the buildup material. Further, it is required to embed an inner layer circuit such as a through hole so that the unevenness is reduced by the build-up material. When the silica filler is called up in order to achieve low CTE of the buildup material, it tends to be difficult to satisfy these requirements.

The first invention has been made to solve such a problem, and it is an object of the present invention to provide an adhesive film for a multilayer printed circuit board which is excellent in the embeddability of unevenness even when the silica filler is thoroughly roughened.

[b] It is also difficult to make the resin composition for an interlaminar insulating layer for a multilayered printed circuit board superior in handleability when it is made into a film while improving heat resistance and insulation reliability.

A second aspect of the present invention is to solve the above problems and provides a resin film for an interlayer insulating layer formed by using a thermosetting resin composition having high heat resistance and high insulation reliability and excellent handling properties in the form of a film, A multilayer resin film having a resin film for a layer and a support, and a multilayer printed wiring board and a method of manufacturing the same.

[a] As a result of intensive research to solve the first problem, the present inventors have found that by using a resin composition comprising a specific novolac phenolic resin, a specific epoxy resin, and a specific inorganic filler, The inventors have found out that the problem can be solved, and accomplished the present invention. That is, the first invention provides the following adhesive film.

(A) a novolak type phenolic resin having a weight average molecular weight (Mw) and a number average molecular weight (Mn) in a dispersion ratio (Mw / Mn) of 1.05 to 1.8; and (B) (C) an inorganic filler, and (C) an inorganic filler, wherein the inorganic filler (C) in the resin composition layer has an average particle diameter of 0.1 탆 or more C) an adhesive film for a multilayer printed circuit board, wherein the content of the inorganic filler is 20 to 95% by mass in the resin solid content.

(Wherein p represents an integer of 1 to 5)

[b] The inventors of the present invention have conducted intensive studies to solve the second problem. As a result, the present inventors have found that in a thermosetting resin composition containing an epoxy resin, a curing agent, an inorganic filler and an antioxidant, a specific curing agent is combined with a specific antioxidant , The present inventors have found out that the above second problem can be solved and accomplished the present invention. It has also been found that the above second problem can be solved even when a specific curing agent and a specific compound are combined in a thermosetting resin composition containing an epoxy resin, a curing agent, an inorganic filler and a specific compound, and accomplished the present invention .

That is, the second invention provides the following [1] to [23].

[1] A resin film for an interlayer dielectric layer formed by using a thermosetting resin composition comprising (a) an epoxy resin, (b) a curing agent, (c) an inorganic filler, and (d)

Wherein the curing agent (b) comprises at least one member selected from the group consisting of (b1) an active ester type curing agent, (b2) a cyanate type curing agent, and (b3) a triazine ring containing phenol novolac type curing agent, (d) The resin film for an interlayer insulating layer, wherein the antioxidant is a hindered phenol-based antioxidant.

[2] The hindered phenol-based antioxidant according to [2], wherein the hindered phenol-based antioxidant comprises at least one member selected from the group consisting of a compound having a group represented by the following formula (dI) and a compound represented by the following formula (dII) 1]. ≪ / RTI >

(In the formula (dI), R ^d1 , R ^d2 and R ^d3 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, provided that at least one of R ^d1 and R ^d2 represents an alkyl group having 1 to 8 carbon atoms .

(In the formula (dII), R ^d4 and R ^d5 each independently represent an alkyl group having 1 to 8 carbon atoms, R ^d6 , R ^d7 and R ^d8 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms Provided that at least one of R ^d6 , R ^d7 and R ^d8 represents an alkyl group having 1 to 8 carbon atoms.

[3] The resin film for an interlayer insulating layer according to [2], wherein the compound having a group represented by the general formula (dI) is represented by any one of the following general formulas (dI-1) to (dI- .

(In the formulas (dI-1) and (dI-2), R ^d11 , R ^d12 , R ^d13 , R ^d21 , R ^d22 and R ^d23 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. at least one of R ^d11 and R ^d12, and R, at least one of the ^d21 and R ^d22 represents an alkyl group having 1 to 8. X ¹ and X ² are, each independently, represents an organic group of 1 to trivalent respectively. n ^1, and and n ² are each independently an integer of 1 to 3.)

(DI-3), R ^d31 and R ^d32 each independently represent an alkyl group having 1 to 8 carbon atoms, and Y represents -COOCH ₂ - or -COOCH ₂ CH ₂ -.

[4] The hindered phenol antioxidant according to any one of [1] to [4], wherein the hindered phenol antioxidant is at least one member selected from the group consisting of a compound represented by the formula (dI-1) Is 1,500 or less.

(5) A group comprising a compound represented by the following general formula (dII) and an epoxy resin, (b) a curing agent, (c) , Wherein the resin film for an interlaminar insulating layer contains at least one selected from the group consisting of

Wherein the curing agent (b) comprises at least one selected from the group consisting of (b1) an active ester curing agent, (b2) a cyanate curing agent, and (b3) Resin film for insulating layer.

(In the formula (dI), R ^d1 , R ^d2 and R ^d3 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, provided that at least one of R ^d1 and R ^d2 represents an alkyl group having 1 to 8 carbon atoms .

(In the formula (dII), R ^d4 and R ^d5 each independently represent an alkyl group having 1 to 8 carbon atoms, R ^d6 , R ^d7 and R ^d8 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms Provided that at least one of R ^d6 , R ^d7 and R ^d8 represents an alkyl group having 1 to 8 carbon atoms.

[6] The resin composition for an interlayer insulating layer according to [5], wherein the compound having a group represented by the general formula (dI) is represented by any one of the following general formulas (dI-1) to (dI- .

(In the formulas (dI-1) and (dI-2), R ^d11 , R ^d12 , R ^d13 , R ^d21 , R ^d22 and R ^d23 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. at least one of R ^d11 and R ^d12, and R, at least one of the ^d21 and R ^d22 represents an alkyl group having 1 to 8. X ¹ and X ² are, each independently, represents an organic group of 1 to trivalent respectively. n ^1, and and n ² are each independently an integer of 1 to 3.)

(DI-3), R ^d31 and R ^d32 each independently represent an alkyl group having 1 to 8 carbon atoms, and Y represents -COOCH ₂ - or -COOCH ₂ CH ₂ -.

[7] The organic electroluminescent device according to the above item [1], wherein the compound having a group represented by the general formula (dI) is at least one selected from the group consisting of a compound represented by the general formula (dI-1) The resin film for an interlayer insulating layer according to [6], wherein the resin film has a molecular weight of 1,500 or less.

(B) the total number of functional groups of the curing agent / (a) the total number of epoxy groups of the epoxy resin] based on the total number of the functional groups of the curing agent (b) relative to the total number of the epoxy groups of the epoxy resin (a) Resin film for an interlaminar insulating layer according to any one of [1] to [7], wherein the ratio is 0.2 to 2.

[9] The epoxy resin composition according to any one of [1] to [8], wherein the epoxy resin (a) is at least one selected from the group consisting of bisphenol A type epoxy resin, naphthalene type epoxy resin, aralkyl novolak type epoxy resin having biphenyl skeleton, and cresol novolak type epoxy resin The resin film for an interlayer insulating layer according to any one of [1] to [8] above,

[10] The resin film for an interlayer insulating layer according to any one of [1] to [9], wherein the curing agent (b) comprises a cyanate curing agent (b2).

[11] The curable resin composition according to any one of [1] to [6], wherein the curing agent (b) comprises at least one selected from the group consisting of (b1) an active ester curing agent and (b3) a phenol novolak curing agent containing a triazine ring. 9]. ≪ / RTI >

[12] The resin composition according to any one of [1] to [6], wherein the phenolic novolac curing agent containing (b3) triazine ring contains at least one of a phenol novolac resin containing a triazine ring and a cresol novolak resin containing a triazine ring. 9] and [11].

[13] The resin film for an interlayer insulating layer according to any one of [1] to [12], wherein the content of the inorganic filler (c) is 30 to 90 mass% with respect to the solid content of the thermosetting resin composition.

[14] The method according to any one of [1] to [13], wherein the inorganic filler (c) contains at least one kind selected from the group consisting of spherical silica and fused silica and has a volume average particle diameter of 0.01 to 5 μm A resin film for an interlaminar insulating layer.

[15] The resin film for an interlayer insulating layer according to any one of [1] to [14], wherein the thermosetting resin composition further comprises (e) a phenoxy resin.

[16] The resin film for an interlayer insulating layer according to [15], wherein the (e) phenoxy resin has an alicyclic structure.

[17] A resin film for an interlayer insulating layer according to any one of [1] to [16], which is used for a multilayer printed wiring board.

[18] The resin film for an interlayer insulating layer according to any one of [1] to [16], which is for forming a buildup layer of a multilayer printed wiring board.

[19] A multilayer resin film comprising the resin film for an interlayer insulating layer according to any one of [1] to [16], and a support.

[20] The multilayer resin film according to the above-mentioned [19], wherein the support is an organic resin film, the thickness of the organic resin film is 10 to 70 μm, and the thickness of the resin film for interlayer insulating layer is 1 to 80 μm.

[21] A multilayer resin film obtained by using at least one selected from the group consisting of the resin film for an interlayer insulating layer described in any one of [1] to [16] and the multilayer resin film described in [19] or [20] Printed wiring board.

[22] A semiconductor package in which a semiconductor element is mounted on the multilayered printed circuit board according to [21].

[23] A method for producing a multilayer printed wiring board using the resin film for an interlayer insulating layer according to any one of [1] to [16] and the multilayer resin film according to the above [19] or [20] A method for manufacturing a multilayer printed wiring board.

(1) A step of laminating the resin film for an interlaminar insulating layer and the multilayer resin film on one side or both sides of a circuit board.

(2) A step of thermally curing the resin film laminated in the step (1) to form an insulating layer.

(3) A step of punching the circuit board on which the insulating layer is formed in the step (2).

(4) Process of removing smear.

(5) A step of forming a conductive layer on the surface of the insulating layer obtained in the step (4) by plating.

(6) A step of forming a circuit on the conductor layer by the semiadditive method.

[a] According to the first invention, it is possible to provide an adhesive film for a multilayer printed wiring board which is excellent in the embedding property of unevenness even when the silica filler is roughened.

[b] According to the second invention, there is provided a resin film for an interlayer insulating layer formed by using a thermosetting resin composition having high heat resistance and insulation reliability and excellent handling property when formed into a film, and a resin film for the interlayer insulating layer and a support And a multilayer printed wiring board and a method of manufacturing the same.

[a] First invention

(A) a novolac-type phenolic resin having a weight average molecular weight (Mw) and a number average molecular weight (Mn) dispersion ratio (Mw / Mn) of 1.05 to 1.8 (B) an epoxy resin represented by the above general formula (1) (hereinafter also simply referred to as "(B) epoxy resin"), (C) an inorganic filler (Hereinafter also referred to as a " resin composition for an adhesive film ") on a support film, wherein the inorganic filler (C) in the resin composition layer has an average particle diameter of not less than 0.1 mu m , And the content of the inorganic filler (C) in the resin solid content is 20 to 95% by mass.

[Resin composition for adhesive film]

The resin composition for an adhesive film comprises (A) a novolak type phenolic resin, (B) an epoxy resin, and (C) an inorganic filler. Hereinafter, each of these components will be described.

≪ (A) Novolak type phenolic resin >

(A) The novolak type phenolic resin is used as a curing agent for an epoxy resin and has a dispersion ratio (Mw / Mn) of a weight average molecular weight (Mw) to a number average molecular weight (Mn) of 1.05 to 1.8.

Such a novolak type phenolic resin (A) can be produced, for example, by the production method described in Japanese Patent No. 4283773.

That is, a phenol compound and an aldehyde compound are used as a raw material, a phosphoric acid compound is used as an acid catalyst, and an unreactive oxygen-containing organic solvent is used as a reaction auxiliary solvent, and the two-layer separated state formed by these is used for example by mechanical stirring, And the mixture is stirred and mixed, and a condensation product (resin) can be synthesized by conducting a reaction between a phenol compound and an aldehyde compound as a whitish phase heterogeneous reaction system (phase separation reaction) in which two layers (organic phase and water phase) are mixed with each other.

Then, the condensate is dissolved by adding and mixing a non-water-soluble organic solvent (for example, methyl ethyl ketone, methyl isobutyl ketone or the like), and stirring and mixing are stopped and the organic phase (organic solvent phase) (A) a novolac phenol resin can be prepared by distilling water to remove water and recovering the organic phase while distilling water and / or neutralizing the organic phase and then distilling off the organic solvent have.

Since the above-mentioned novolak type phenol resin uses a phase separation reaction, the stirring efficiency is very important, and it is preferable from the viewpoint of the reaction efficiency that the surface area of the interface is increased as much as possible by miniaturizing the positive phase in the reaction system, Whereby the phenol compound is promoted to the resin.

Examples of the phenol compound to be used as a raw material include phenol, orthocresol, metacresol, para-cresol, xylenol, bisphenol compounds, ortho-substituted phenols having a hydrocarbon group having 3 or more carbon atoms, preferably 3 to 10 carbon atoms at the ortho position Compounds, parasubstituted phenol compounds having a hydrocarbon group having 3 or more carbon atoms, preferably 3 to 18 carbon atoms at the para position, and the like. These may be used singly or in combination of two or more.

Examples of the bisphenol compound include bisphenol A, bisphenol F, bis (2-methylphenol) A, bis (2-methylphenol) F, bisphenol S, bisphenol E and bisphenol Z.

Examples of the ortho-substituted phenol compound include 2-propylphenol, 2-isopropylphenol, 2-sec-butylphenol, 2-tert-butylphenol, 2-phenylphenol, 2-cyclohexylphenol, 2-naphthylphenol and the like.

Examples of the para substituted phenol compound include 4-propylphenol, 4-isopropylphenol, 4-sec-butylphenol, 4-tert-butylphenol, 4-phenylphenol, 4-cyclohexylphenol, 4-naphthylphenol, 4-dodecylphenol, 4-octadecylphenol and the like.

Examples of the aldehyde compound used as the raw material include formaldehyde, formalin, paraformaldehyde, trioxane, acetaldehyde, paraldehyde, propionaldehyde and the like. Of these, paraformaldehyde is preferable from the viewpoint of the reaction rate. These may be used singly or in combination of two or more.

The compounding molar ratio (F / P) of the aldehyde compound (F) and the phenol compound (P) is preferably 0.33 or more, more preferably 0.40 to 1.0, and still more preferably 0.50 to 0.90. By setting the compounding molar ratio (F / P) within the above range, an excellent yield can be obtained.

Phosphoric acid compounds used as acid catalysts play an important role in forming a site for a phase separation reaction with phenol compounds in the presence of water. As the phosphoric acid compound, for example, an aqueous solution type such as 89 mass% phosphoric acid and 75 mass% phosphoric acid can be used. If necessary, for example, polyphosphoric acid, phosphoric anhydride and the like may be used.

The content of the phosphoric acid compound is 5 parts by mass or more, preferably 25 parts by mass or more, and more preferably 50 to 100 parts by mass with respect to 100 parts by mass of the phenol compound, for example, from the viewpoint of controlling the phase separation effect. When the phosphoric acid compound is used in an amount of 70 parts by mass or more, it is preferable to suppress the generation of heat in the initial stage of the reaction by securing safety by dividing into the reaction system.

The non-reactive oxygen-containing organic solvent as a reaction auxiliary solvent plays a very important role in promoting the phase separation reaction. As the reaction auxiliary solvent, it is preferable to use at least one compound selected from the group consisting of an alcohol compound, a polyhydric alcohol ether, a cyclic ether compound, a polyhydric alcohol ester, a ketone compound and a sulfoxide compound.

Examples of the alcohol compound include monohydric alcohols such as methanol, ethanol and propanol, alcohols such as butanediol, pentanediol, hexanediol, ethylene glycol, propylene glycol, trimethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, Dihydric alcohols such as glycol and polyethylene glycol, and trihydric alcohols such as glycerin.

Examples of the polyhydric alcohol ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, Ethylene glycol glycol ether and the like.

Examples of the cyclic ether compound include 1,3-dioxane and 1,4-dioxane. Examples of the polyhydric alcohol ester include glycol ester compounds such as ethylene glycol acetate. Examples of the ketone compound include acetone, methyl ethyl ketone (hereinafter also referred to as " MEK ") and methyl isobutyl ketone, and examples of the sulfoxide compound include dimethyl sulfoxide, diethyl sulfoxide, .

Among these, ethylene glycol monomethyl ether, polyethylene glycol and 1,4-dioxane are preferable.

The reaction-assistant solvent is not limited to the above-mentioned examples, and may be solid or may be used alone or in combination of two or more as long as it has the above-mentioned characteristics and exhibits a liquid phase during the reaction.

The mixing amount of the reaction auxiliary solvent is not particularly limited and is, for example, 5 parts by mass or more, preferably 10 to 200 parts by mass, per 100 parts by mass of the phenol compound.

By using a surfactant in the non-uniform reaction process, the phase separation reaction can be promoted, the reaction time can be shortened, and the yield can be improved.

Examples of the surfactant include a soap, an alpha olefin sulfonic acid salt, an alkyl benzene sulfonic acid and a salt thereof, an alkyl sulfuric acid ester salt, an alkyl ether sulfuric acid ester salt, a phenyl ether ester salt, a polyoxyethylene alkyl ether sulfuric acid ester salt, An anionic surfactant such as an ether carboxylate; Polyoxyethylene alkylphenyl ethers, polyoxyalkylene alkyl ethers, polyoxyethylene styrenated phenol ethers, polyoxyethylene alkylamino ethers, polyethylene glycol aliphatic esters, aliphatic monoglycerides, sorbitan aliphatic esters, pentaerythritol aliphatic esters, poly Nonionic surfactants such as oxyethylene polypropylene glycol and aliphatic alkylolamide; Cationic surfactants such as monoalkylammonium chloride, dialkylammonium chloride, and amine acid salt compounds.

The blending amount of the surfactant is not particularly limited, but is 0.5 part by mass or more, preferably 1 to 10 parts by mass, per 100 parts by mass of the phenol compound.

The amount of water in the reaction system affects the phase separation effect and the production efficiency, but is generally 40 mass% or less on a mass basis. When the amount of water is 40 mass% or less, the production efficiency can be kept good.

The reaction temperature of the phenol compound and the aldehyde compound differs depending on the type of the phenol compound, reaction conditions, etc., and is not particularly limited, but is generally 40 ° C or higher, preferably 80 ° C to reflux temperature, more preferably reflux temperature . When the reaction temperature is 40 占 폚 or higher, a sufficient reaction rate is obtained. The reaction time varies depending on the reaction temperature, the amount of phosphoric acid, the water content in the reaction system, and the like, but is generally about 1 to 10 hours.

The reaction environment is normally atmospheric pressure, but from the viewpoint of maintaining the heterogeneous reaction characteristic of the present invention, the reaction may be carried out under pressure or under reduced pressure. For example, under a pressure of 0.03 to 1.5 MPa, the reaction rate can be increased, and a low boiling point solvent such as methanol can be used as a reaction auxiliary solvent.

The novolac phenol resin (A) can be produced by a process for producing a novolac phenolic resin having a weight average molecular weight (Mw) and a number average molecular weight (Mn) dispersion ratio (Mw / Mn) of 1.05 to 1.8 have.

Depending on the kind of the phenol compound, the novolac phenolic resin (A) shown below, for example, is obtained by the range of the molar ratio (F / P) of the aldehyde compound (F) to the phenol compound (P) .

The content of the monomer component of the phenol compound is, for example, not more than 3% by mass, preferably not more than 3% by mass, more preferably not more than 3% by mass, 1% by mass or less, and the content of the dimeric component of the phenolic compound is, for example, 5 to 95% by mass, preferably 10 to 95% by mass, and the weight average molecular weight (Mw) A novolak type phenolic resin having a dispersion ratio (Mw / Mn) of (Mn) of 1.05 to 1.8, preferably 1.1 to 1.7 can be produced with high yield.

As the novolak type phenolic resin (A), commercially available products can be used, and examples thereof include "PAPS-PN2" (trade name, manufactured by Asahi Yuki Kai Kogyo K.K.), "PAPS-PN3" (available from Asahi Yuki Kaisha Kogyo Co., Trade name, product name).

(A) an epoxy resin curing agent other than the novolak type phenol resin (hereinafter, simply referred to as " epoxy resin curing agent ") may be used in combination as long as the effect of the present invention is not impaired.

Examples of the epoxy resin curing agent include (A) various phenolic resin compounds, acid anhydride compounds, amine compounds and hydrazate compounds other than the novolak type phenol resin. Examples of the phenol resin compound include (A) a novolak type phenol resin other than the novolac type phenol resin, a resol type phenol resin, and the like, and examples of the acid anhydride compound include phthalic anhydride, benzophenone tetracarboxylate Acid dianhydride, and methyl anhydride. Examples of the amine compound include dicyandiamide, diaminodiphenylmethane and guanyl ether.

Among these epoxy resin curing agents, novolak type phenolic resins other than the novolak type phenolic resin (A) are preferable from the viewpoint of improving the reliability.

From the viewpoint of improving the peel strength of the metal foil and the peel strength of the electroless plating after chemical roughening (roughening), a triazine ring-containing novolak type phenolic resin and dicyandiamide are preferable.

(A) A novolac phenolic resin other than the novolac phenolic resin may be a commercially available product. Examples thereof include phenol novolak resins such as "TD2090" (trade name, manufactured by DIC Corporation), "KA-1165" And a cresol novolak resin such as a product of DIC Corporation). Examples of commercial products of triazine ring-containing novolac phenolic resins include phenolite LA-1356 (trade name, manufactured by DIC Corporation), phenolite LA7050 series (trade name, manufactured by DIC Corporation) Examples of commercially available products of triazine-containing cresol novolak resins include phenolite LA-3018 (trade name, manufactured by DIC Corporation) and the like.

≪ (B) Epoxy resin >

(B) The epoxy resin is an epoxy resin represented by the following general formula (1).

(Wherein p represents an integer of 1 to 5)

As the epoxy resin (B), a commercially available product may be used. Examples of commercially available epoxy resins (B) include "NC-3000" (an epoxy resin having a p value of 1.7 in the formula (1)), "NC-3000-H" 2.8 epoxy resin) (both manufactured by Nihon Kayaku Co., Ltd., trade name).

The resin composition for an adhesive film may contain (B) an epoxy resin other than an epoxy resin, a polymer type epoxy resin such as a phenoxy resin, or the like within a range that does not impair the effect of the present invention.

<Curing accelerator>

The resin composition for an adhesive film may contain a curing accelerator from the viewpoint of accelerating the reaction between (A) the novolak type phenolic resin and (B) the epoxy resin. As the curing accelerator, for example, imidazole compounds such as 2-phenylimidazole, 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-phenylimidazolium trimellitate; Organic phosphorus compounds such as triphenylphosphine; Onium salts such as phosphonium borate; Amines such as 1,8-diazabicyclo undecene; 3- (3,4-dichlorophenyl) -1,1-dimethylurea, and the like. These may be used singly or in combination of two or more kinds.

<(C) Inorganic filler>

The resin composition for an adhesive film includes (C) an inorganic filler having an average particle diameter of 0.1 mu m or more.

Examples of the inorganic filler (C) include inorganic fillers such as silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, Strontium titanate, calcium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. These may be used singly or in combination of two or more. Of these, silica is preferable from the viewpoint of lowering the thermal expansion coefficient of the interlayer insulating layer formed by curing the adhesive film.

The shape of the inorganic filler (C) is not particularly limited, but is preferably spherical in view of facilitating filling of the through hole formed in the inner layer circuit and the unevenness of the circuit pattern.

The average particle diameter of the inorganic filler (C) is 0.1 占 퐉 or more, preferably 0.2 占 퐉 or more, and more preferably 0.3 占 퐉 or more from the viewpoint of obtaining excellent filling property.

The content of the inorganic filler having an average particle diameter of less than 0.1 占 퐉 is preferably a solid content, preferably 3 vol% or less, more preferably 1 vol% or less, and further preferably no inorganic filler having an average particle diameter of less than 0.1 占 퐉 . The inorganic filler (C) may be used alone, or two or more kinds of inorganic fillers may be used in combination, or mixtures of different average particle diameters may be used.

As the inorganic filler (C), a commercially available product may be used. As the inorganic filler (C) in the marketed product, for example, spherical silica "SO-C1" (average particle diameter: 0.25 μm), "SO-C2" (average particle diameter: 0.5 μm), "SO- : SO-C5 (average particle diameter: 1.6 占 퐉) and SO-C6 (average particle diameter: 2.2 占 퐉) (all available from Admatechs Co., Ltd.).

The inorganic filler (C) may be subjected to a surface treatment. For example, when silica is used as the inorganic filler (C), a silane coupling agent treatment may be performed as a surface treatment. Examples of the silane coupling agent include an amino silane coupling agent, a vinyl silane coupling agent, and an epoxy silane coupling agent. Of these, silica treated with an aminosilane coupling agent is preferred.

The amount of inorganic filler (C) in the resin composition for an adhesive film is defined as follows. First, the resin composition forming the layer on the support film is dried at 200 占 폚 for 30 minutes, the solvent contained in the resin composition is removed, and the weight (solid content) after removal of the solvent is measured. The amount of the inorganic filler (C) contained in the solid content is defined as the amount of the inorganic filler (C) in the resin solid content.

When the amount of the solid content of the inorganic filler (C) previously mixed (C) is measured as the method of measuring the inorganic filler (C), the ratio in the solid content can be easily obtained. Examples of calculations in the case of using inorganic filler (C) (hereinafter also referred to as &quot; inorganic filler dispersion (C) &quot;) dispersed in a solvent are shown below.

The solid content of the inorganic filler (C) in the inorganic filler dispersion (C) was calculated by drying for 30 minutes at 200 占 폚 and found to be 70% by mass. When the resin composition was blended with 40 g of the inorganic filler dispersion (C), the total amount of the obtained resin composition was 100 g. 100 g of the resin composition was dried at 200 캜 for 30 minutes, and the weight of the solid after drying was measured to be 60 g. Since the amount of the inorganic filler (C) contained in the solid content is 40 g × 70 mass% = 28 g, the amount of the inorganic filler (C) in the resin solid content is determined as 28/60 = 47 mass% (46.6 mass%).

The amount of the inorganic filler (C) in the resin composition for an adhesive film is preferably as large as possible from the viewpoint of lowering the coefficient of thermal expansion of the interlayer insulating layer after heat curing. However, From the point of view, there is an appropriate amount of inorganic filler. From such a viewpoint, the content of the inorganic filler (C) is preferably 20 to 95% by mass, more preferably 30 to 90% by mass, and more preferably 50 to 90% by mass in the resin solid fraction. When the content of the inorganic filler (C) is 20 mass% or more, the coefficient of thermal expansion can be lowered. When the content of the inorganic filler is 95 mass% or less, the filling property can be maintained satisfactorily.

<Flame Retardant>

The resin composition for an adhesive film may further contain a flame retardant.

The flame retardant is not particularly limited, and examples thereof include an inorganic flame retardant and a resin flame retardant.

Examples of the inorganic flame retardant include aluminum hydroxide, magnesium hydroxide and the like exemplified as (C) inorganic fillers.

As the resin flame retardant, a halogen-based resin or a non-halogen-based resin may be used, but it is preferable to use a non-halogen-based resin from consideration for an environmental load. The resin flame retardant may be blended as a filler or may have a functional group reactive with the thermosetting resin.

Commercially available resin flame retardants can be used. Examples of commercially available resin flame retardants to be blended as fillers include "PX-200" (trade name, product of Daihachi Kagaku Kogyo Kabushiki Kaisha) which is an aromatic phosphate ester flame retardant, "Exolit OP 930" (Trade name, manufactured by K.K.).

Examples of commercially available resin flame retardants having functional groups reactive with thermosetting resins include epoxy-based phosphorus-containing flame retardants and phenolic phosphorus-containing flame retardants. Examples of the epoxy-based phosphorus-containing flame retardant include, for example, "FX-305" (trade name, manufactured by Shinnitetsu Sumikin Kagaku Kogyo Co., Ltd.) (Trade name, available from Sanko K.K.), and &quot; XZ92741 &quot; (trade name, available from Dow Chemical Co., Ltd.). These may be used singly or in combination of two or more kinds.

<Solvent>

From the viewpoint of efficient layer formation, the resin composition for an adhesive film preferably contains a solvent. Examples of the solvent include ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Acetic acid ester compounds such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; Carbitol compounds such as cellosolve, methyl carbitol, and butyl carbitol; Aromatic hydrocarbon compounds such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, diethylene glycol dimethyl ether, propylene glycol monomethyl ether and the like. These may be used singly or in combination of two or more kinds.

&Lt; Amount of Residual Solvent >

The amount of the residual solvent in the adhesive film of the present invention is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, still more preferably 2 to 10% by mass, Do. When the amount of the residual solvent is 1% by mass or more, the handling property of the adhesive film is improved and occurrence of cracking, for example, of dropping of powder when cutting with a cutter can be suppressed. On the other hand, when it is 20 mass% or less, the tackiness is suppressed, and the film is easily wound and unwound. Further, in order to enable the unwinding, it is often the case that a protective film is provided on the varnish coated surface of the adhesive film after drying. However, if the amount of residual solvent is 20 mass% or less, peeling between the protective film and the adhesive film of the present invention is facilitated .

Since the residual solvent is removed by drying and thermosetting in the process of producing the multilayered printed circuit board, it is preferable that the residual solvent is small in view of the environmental load, and it is preferable to make the film thickness change before and after drying and thermosetting small It is preferable that the number is smaller.

Further, in the production of the adhesive film of the present invention, it is preferable to determine the drying conditions so as to be the target residual solvent amount. Since the drying conditions differ depending on the kind of the solvent contained in the resin composition, the amount of the solvent, and the like, it is preferable to determine the conditions after the conditions are presented in advance by the respective coaters.

Here, the amount of the residual solvent in the present invention means the ratio (mass%) of the solvent contained in the resin composition layer of the support film and can be defined as follows.

First, the weight (W _a ) of the support film is measured, and the weight (W _b ) after forming the resin composition layer thereon is measured. Thereafter, the support film and the resin composition layer formed thereon are left in a dryer at 200 캜 for 10 minutes, and the weight (W _c ) after drying is measured. Can be calculated by the following formula using the weights (W _a ) to (W _c ) obtained.

The ratio of solvent (mass%) = (1 - (( W c) - (W a)) / ((W b) - (W a))) × 100

&Lt; Other components >

The adhesive film of the present invention may contain other components as long as the effect of the present invention is not impaired. Examples of other components include thickeners such as orthobenzene and benzene; Ultraviolet absorbers such as thiazole series and triazole series; Adhesion-imparting agents such as silane coupling agents; Colorants such as phthalocyanine blue, phthalocyanine green, (iodine) iodine green, disazo yellow and carbon black; And any resin component other than the above.

[Support film]

The support film in the present invention means a support for the production of the adhesive film of the present invention and is usually finally peeled off or removed when a multilayer printed wiring board is produced.

The support film is not particularly limited, and examples thereof include an organic resin film, a metal foil, a release paper, and the like.

Examples of the material of the organic resin film include polyolefins such as polyethylene and polyvinyl chloride; Polyesters such as polyethylene terephthalate (hereinafter also referred to as &quot; PET &quot;) and polyethylene naphthalate; Polycarbonate, polyimide, and the like. Of these, PET is preferable from the viewpoints of price and handleability.

Examples of the metal foil include copper foil and aluminum foil. When a copper foil is used as a support, a copper foil can be used as a conductor layer to form a circuit. In this case, as the copper foil, rolled copper, electrolytic copper foil or the like can be used. The thickness of the copper foil is not particularly limited, and for example, a copper foil having a thickness of 2 to 36 mu m can be used. In the case of using a copper foil with a thin thickness, a copper foil with a carrier may be used from the viewpoint of improving workability.

These support films and protective films to be described later may be subjected to surface treatment such as release treatment, plasma treatment or corona treatment. Examples of mold release treatments include release treatments with a silicone resin-based release agent, an alkyd resin-based release agent, a fluororesin-based release agent, and the like.

The thickness of the support film is not particularly limited, but is preferably 10 to 120 탆, more preferably 15 to 80 탆, and further preferably 15 to 70 탆, from the viewpoint of handling.

The support film is not necessarily a single component as described above, but may be formed of a plurality of layers (two or more layers) of separate materials.

If the support film has a two-layer structure, for example, a support film exemplified above may be used as the first support film, and a layer formed of an epoxy resin, a curing agent of an epoxy resin, . As the material used for the second layer, materials exemplified in the material used for the adhesive film of the present invention may be used.

The layer formed on the first layer support film (which may be a plurality of layers of two or more layers from the second layer onward) is a layer which is intended to give a function, and for the purpose of, for example, improving adhesion with plated copper Can be used.

The method for forming the second layer is not particularly limited, and for example, there can be mentioned a method of coating a varnish obtained by dissolving and dispersing each material in a solvent onto a first layer support film and drying.

When the support film is formed of a plurality of layers, the thickness of the first support film is preferably 10 to 100 占 퐉, more preferably 10 to 60 占 퐉, and still more preferably 13 to 50 占 퐉.

The thickness of the layer formed on the first support film (which may be a plurality of layers of two or more layers after the second layer) is preferably 1 to 20 占 퐉. If it is 1 m or more, the intended function can be performed. If it is 20 m or less, the economical efficiency as a support film is excellent.

In the case where the support film is formed of a plurality of layers, when separating the support film, the layer (two or more layers) formed on the side of the multilayered printed circuit board together with the adhesive film of the present invention and the layer 2 Layer or more).

[Protection film]

The adhesive film of the present invention may have a protective film. The protective film is provided on the surface opposite to the surface on which the support of the adhesive film is provided, and is used for the purpose of preventing adherence of foreign matter to the adhesive film and occurrence of scratches. The protective film is peeled off before the adhesive film of the present invention is laminated on a circuit board or the like with a laminate, a thermal press, or the like.

The protective film is not particularly limited, but the same material as the support film can be used. The thickness of the protective film is not particularly limited. For example, a thickness of 1 to 40 mu m can be used.

[Method of producing adhesive film]

The adhesive film of the present invention can be produced by coating and drying a resin composition for an adhesive film on a support film. The obtained adhesive film can be wound into a roll, and can be stored and stored. More specifically, for example, a resin composition for an adhesive film is prepared by dissolving each of the resin components in the organic solvent, (C) an inorganic filler or the like is mixed, the varnish is coated on a support film, And then drying the organic solvent by spraying or the like to form a resin composition layer on the support film.

In the adhesive film of the present invention, the resin composition layer formed on the support film may be either uncured or semi-cured (B-staged) obtained by drying.

As a method for applying a varnish to a support film, there is no particular limitation, but a coating method using a known coating device such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater or a die coater is applied . The coating apparatus may be appropriately selected depending on the target film thickness.

[b] Second invention

Next, a resin film for an interlayer insulating layer, a multilayer resin film, a multilayer printed wiring board and a manufacturing method thereof according to the second invention will be described.

[Resin film for interlayer insulating layer]

As described above, the thermosetting resin composition (hereinafter referred to as the resin composition for an interlayer insulating layer) used for forming the resin film for an interlaminar insulating layer of the present invention is a resin composition which comprises (a) an epoxy resin (Hereinafter also referred to as "component (c)"), and (d) antioxidants (hereinafter sometimes referred to as "antioxidants" (Hereinafter also referred to as "component (d)") or (d ') the following specific compound (hereinafter also referred to as "component (d')").

The resin film for an interlayer insulating layer is also generally referred to as an interlayer insulating film.

&Lt; Resin composition for interlaminar insulating layer >

[(A) Epoxy resin]

(a) The epoxy resin is not particularly limited, and for example, an epoxy resin having two or more epoxy groups in one molecule is preferably used.

Examples of the epoxy resin (a) include a glycidyl ether type epoxy resin, a glycidylamine type epoxy resin, and a glycidyl ester type epoxy resin. Of these, glycidyl ether type epoxy resins are preferred.

(a) The epoxy resin is also classified by the difference in main skeleton. In each type of epoxy resin, a bisphenol A type epoxy resin (preferably a bisphenol A type liquid epoxy resin), a bisphenol F type epoxy resin, Bisphenol-type epoxy resins such as bisphenol S type epoxy resin; Phenol novolak type epoxy resin, alkylphenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthol alkyl phenol copolymer novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, aralkyl Novolak type epoxy resins such as novolak type epoxy resins; Stilbene type epoxy resin; Triazine skeleton-containing epoxy resin; Fluorene skeleton-containing epoxy resin; Naphthalene type epoxy resin; Triphenylmethane type epoxy resin; Biphenyl type epoxy resins; Xylylene-type epoxy resins; And alicyclic epoxy resins such as dicyclopentadiene type epoxy resins. The epoxy resin (a) may be used alone or in combination of two or more.

Examples of the aralkyl novolak type epoxy resin include an aralkyl cresol copolymer novolak type epoxy resin having a naphthol skeleton and an aralkyl novolak type epoxy resin having a biphenyl skeleton. Volatile epoxy resins are preferred.

Among them, at least one member selected from the group consisting of a bisphenol-type epoxy resin and a novolak-type epoxy resin is preferable from the viewpoints of heat resistance, insulation reliability, and handleability in the form of a film, and a bisphenol A type epoxy resin, More preferably at least one selected from the group consisting of an epoxy resin, an aralkyl novolak type epoxy resin and a bisphenol A novolak type epoxy resin. Further, as the aralkyl novolak type epoxy resin, an aralkyl novolak type epoxy resin having a biphenyl skeleton is more preferable.

(a) a combination of bisphenol A type epoxy resin and aralkyl novolak type epoxy resin (particularly, aralkyl novolak type epoxy resin having biphenyl skeleton), or a combination of cresol novolak type epoxy resin A combination of an epoxy resin and a bisphenol A novolak type epoxy resin is preferable.

When a combination of a bisphenol A type epoxy resin and an aralkyl novolak type epoxy resin (in particular, an aralkyl novolak type epoxy resin having a biphenyl skeleton) is used in combination, the content ratio (bisphenol A type epoxy resin / aralkyl novolac Type epoxy resin) is preferably 15/85 to 50/50, more preferably 15/85 to 45/55, and more preferably 20/80 to 40/60 from the viewpoint of heat resistance, insulation reliability, Is more preferable.

When the cresol novolak type epoxy resin and the bisphenol A novolac type epoxy resin are used in combination, the content ratio (cresol novolak type epoxy resin / bisphenol A novolac type epoxy resin) , It is preferably 50/50 to 85/15, more preferably 45/55 to 85/15, and further preferably 55/45 to 75/25.

Here, the aralkyl novolak type epoxy resin having a biphenyl skeleton refers to an aralkyl novolak type epoxy resin containing an aromatic ring of a biphenyl derivative in the molecule, and includes a structural unit represented by the following general formula (a1) Containing epoxy resin.

In the general formula (a1), R ^a1 represents a hydrogen atom or a methyl group.

The content of the structural unit represented by the general formula (a1) in the epoxy resin containing the structural unit represented by the general formula (a1) is preferably from 50 to 100 (in terms of heat resistance, insulation reliability, By mass, more preferably from 70 to 100% by mass, still more preferably from 80 to 100% by mass.

Examples of the epoxy resin containing the structural unit represented by the general formula (a1) include an epoxy resin represented by the following general formula (a1-1).

In the general formula (a1-1), R ^a1 is as defined above, and m ¹ represents an integer of 1 to 20. It may be the same or different each other and a plurality of R ^a1, but preferably the same.

The bisphenol A novolak type epoxy resin can be represented by the following general formula (a2).

In the general formula (a2), m2 represents an integer of 1 to 10.

The epoxy resin (a) may contain an epoxy resin which is in a liquid state at room temperature (hereinafter may be abbreviated as liquid epoxy resin in some cases) from the viewpoint of improving the handling property of the resin film for an interlayer insulating layer. Examples of the liquid epoxy resin include, but are not limited to, bifunctional liquid epoxy resins such as bisphenol A type liquid epoxy resin. When the epoxy resin (a) contains a liquid epoxy resin, the content thereof is preferably 10 to 60% by mass, more preferably 10 to 60% by mass, based on the epoxy resin (a) Is 10 to 50% by mass, and more preferably 10 to 40% by mass.

As the epoxy resin (a), a commercially available product may be used. As the epoxy resin (a) of the marketed product, "NC-3000-H", "NC-3000-L", "NC-3100" and "NC-3000" (manufactured by Nihon Kayaku Co., Quot; NC-7000-L &quot; (trade name, manufactured by Nippon Kayaku Co., Ltd., naphthol novolak type epoxy resin), &quot; jER828 &quot; (manufactured by Mitsubishi Chemical Corporation, (Trade name, bisphenol A type epoxy resin) and &quot; jER157S70 &quot; (trade name, bisphenol A novolak type epoxy resin, manufactured by Mitsubishi Chemical Corporation).

The epoxy equivalent of the epoxy resin (a) is preferably 150 to 500 g / eq, more preferably 150 to 400 g / eq, and even more preferably 170 to 350 g / eq from the viewpoints of heat resistance, insulation reliability, More preferably from 200 to 320 g / eq, further preferably from 170 to 230 g / eq, and from 250 to 320 g / eq.

Here, the epoxy equivalent is the mass (g / eq) of the resin per epoxy group and can be measured according to the method specified in JIS K 7236 (2001). Specifically, 2 g of an epoxy resin was weighed into a 200 ml beaker using an automatic titrator "GT-200 type" manufactured by Mitsubishi Chemical Analytec Co., Ltd., and 90 ml of methyl ethyl ketone was dropped. After dissolving in an ultrasonic cleaner, And 1.5 g of cetyltrimethylammonium bromide, and titrating with 0.1 mol / L perchloric acid / acetic acid solution.

The content of the epoxy resin (a) in the resin composition for an interlaminar insulating layer is not particularly limited so far as the solid content of the resin composition for an interlaminar insulating layer (here, (c) the inorganic filler is excluded) from the viewpoints of heat resistance, insulation reliability, , More preferably from 30 to 70 parts by mass, still more preferably from 35 to 60 parts by mass.

Herein, "solid content" in the present invention is a non-volatile component excluding volatile components such as an organic solvent, unless otherwise specified, and indicates components left without volatilization when the thermosetting resin composition is dried, Phase and wax. Here, in the present specification, the room temperature refers to 25 占 폚.

[(B) Curing agent]

In the present invention, the curing agent (b) includes at least one selected from the group consisting of (b1) an active ester type curing agent, (b2) a cyanate type curing agent, and (b3) a phenazine novolak type curing agent containing a triazine ring do. In the case of using two or more of (b1) to (b3), there is no particular limitation, but from the viewpoints of heat resistance, insulation reliability, and handleability in the form of a film, (b1) the active ester curing agent and (b2) (B1) a phenol novolac type curing agent containing an active ester type curing agent and (b3) a triazine ring is preferable.

The above-mentioned (b1) may be used in combination of two or more, the above-mentioned (b2) may be used in combination of two or more, and the above-mentioned (b3) may be used in combination of two or more.

<(b1) Active ester-based curing agent>

(b1) The active ester-based curing agent is not particularly limited as long as it (a) functions as a curing agent for the epoxy resin and has an active ester. (b1) When the active ester type curing agent is contained, dielectric tangent tends to be reduced.

(b1) Examples of the active ester curing agent include those having a highly reactive ester group such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxycarboxylic ester compounds, and the curing action of the epoxy resin And the like can be used.

As the active ester curing agent (b1), a compound having at least two active ester groups in one molecule is preferable, and two or more active ester groups in a molecule obtained from a compound having a polyvalent carboxylic acid and an aromatic compound having a phenolic hydroxyl group , More preferably an aromatic compound obtained from a compound having at least two or more carboxylic acids in one molecule and an aromatic compound having a phenolic hydroxyl group and an aromatic compound having two or more ester groups in the molecule of the aromatic compound Compound is more preferable. The active ester-based curing agent (b1) may also contain a linear or multi-branched polymer.

If the compound having at least two or more carboxylic acids in one molecule is a compound containing an aliphatic chain, compatibility with the epoxy resin (a) and the (b2) cyanate resin can be enhanced, If it is a compound, the heat resistance can be increased. From the viewpoint of heat resistance and the like, the active ester curing agent (b1) is preferably an active ester compound obtained from a carboxylic acid compound and a phenol compound or a naphthol compound.

Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid. Of these, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid and terephthalic acid are preferable, and isophthalic acid and terephthalic acid are more preferable from the viewpoint of heat resistance.

Examples of the thiocarboxylic acid compound include thioacetic acid and thiobenzoic acid.

Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenol phthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o- Cresol, catechol, alpha -naphthol, beta -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzo Phenol, tetrahydroxybenzophenone, fluoroglucine, benzenetriol, dicyclopentadienyldiphenol, phenol novolac, and the like. Among them, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxy Naphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzenetriol, dicyclopentadienyldiphenol and phenol novolac are preferable Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dihydroxybenzophenone, More preferred are fluoroglucine, benzenetriol, dicyclopentadienyldiphenol and phenol novolac, and more preferred are 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene , Dihydroxybenzophenone, trihydroxybenzophenone, tetrahydrofuran More preferred are dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyldiphenol, and phenol novolac are particularly preferable, and more preferred are dihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyldiphenol and phenol novolac , And dicyclopentadienyldiphenol and phenol novolak are very preferable, and dicyclopentadienyldiphenol is most preferable.

Examples of the thiol compound include benzenedithiol, trianedithiol, and the like.

As the active ester curing agent (b1), an active ester curing agent disclosed in Japanese Patent Laid-Open No. 2004-277460 may be used, or a commercially available product may be used.

Examples of commercially available active ester curing agents (b1) include compounds containing a dicyclopentadienyldiphenol structure, acetylated phenol novolak, and benzoylated phenol novolak. Of these, dicyclopentadienyldi Compounds containing a phenolic structure are preferred. Specifically, EXB9451 (active ester group equivalent: about 220 g / eq), EXB9460, EXB9460S-65T, HPC-8000-65T Quot; DC808 &quot; (manufactured by Mitsubishi Chemical Corporation, active ester group equivalent: about 149 g / eq) as an acetylated product of phenol novolac, an ester group equivalent: about 223 g / YLH1026 &quot; (manufactured by Mitsubishi Chemical Corporation, active ester group equivalent: about 200 g / eq) as a benzoyl compound of phenol novolac.

(b1) The production method of the active ester type curing agent is not particularly limited, and can be produced by a known method. Specifically, it can be obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound.

((b2) cyanate-based curing agent)

As the cyanate-based curing agent (b2), a known cyanate resin can be used. As the cyanate resin, for example, a cyanate resin having two or more cyanate groups in one molecule is preferably used.

Specific examples of the cyanate-based curing agent (b2) include 2,2-bis (4-cyanatophenyl) propane [bisphenol A cyanate resin], bis (4-cyanatophenyl) ethane [bisphenol E cyanate Bis (4-cyanatophenyl) methane [tetramethyl bisphenol F type cyanate resin], 2,2-bis (4-cyanatophenyl) Bisphenol-type cyanate resins such as 3,3-hexafluoropropane [hexafluorobisphenol A-type cyanate resin]; Dicyclopentadiene-type cyanate resins such as cyanate ester compounds of phenol-added dicyclopentadiene polymers; Novolak type cyanate resins such as phenol novolak type cyanate ester compounds and cresol novolak type cyanate ester compounds; ?,? '- bis (4-cyanatophenyl) -m-diisopropylbenzene; And prepolymers of these cyanate resins (hereinafter also referred to as &quot; cyanate prepolymer &quot;). These may be used singly or in combination of two or more kinds.

Among them, a cyanate resin represented by the following general formula (b2-I), a cyanate resin represented by the following general formula (b2-IV) and a cyanate resin represented by the following general formula (b2-I) are preferable from the viewpoints of heat resistance, insulation reliability, A prepolymer is preferable, and a cyanate resin represented by the following general formula (b2-I) and its prepolymer are more preferable.

In formula (b2-I), R ^b1 represents an alkylene group having 1 to 3 carbon atoms which may be substituted with a halogen atom, a sulfur atom, a group represented by the following general formula (b2-II) &Lt; / RTI &gt; R ^b2 and R ^b3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Two R ^b2 each other, or two R ^b3 each other may be the same or different, respectively. However, it is preferably the same.

In the general formula (b2-II), R ^b4 represents an alkylene group having 1 to 3 carbon atoms. The two R &lt; ^b4 &gt; may be the same or different, but are preferably the same.

In the general formula (b2-IV), R ^b5 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom. n represents an integer of 1 or more. It may be the same or different each other and a plurality of R ^b5, but preferably the same.

Examples of the alkylene group having 1 to 3 carbon atoms represented by R ^b1 in the general formula (b2-I) include a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, (-C (CH ₃ ) ₂ -). Of these, a methylene group or a 2,2-propylene group (-C (CH ₃ ) ₂ -) is preferable from the viewpoints of heat resistance, insulation reliability and handling property in the form of a film, and a 2,2- (CH ₃ ) ₂ -).

Examples of the halogen atom substituting the alkylene group having 1 to 3 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alkylene group having 1 to 3 carbon atoms represented by R ^b4 in the general formula (b2-II) include methylene, ethylene, 1,2-propylene, 1,3-propylene, 2,2- (-C (CH ₃ ) ₂ -).

Of these groups represented by R ^b1 , a methylene group or a 2,2-propylene group (-C (CH ₃ ) ₂ -) is preferable from the viewpoints of heat resistance, insulation reliability and handling property in a film, Propylene group (-C (CH ₃ ) ₂ -) is more preferable.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ^b2 or R ^b3 in the general formula (b2-I) include a methyl group, an ethyl group, a propyl group, and a butyl group.

In the general formula (b2-IV), examples of the alkyl group having 1 to 3 carbon atoms represented by ^Rb5 include a methyl group, an ethyl group and a propyl group.

Examples of the halogen atom for substituting the alkyl group having 1 to 3 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the general formula (b2-IV), n represents an integer of 1 or more and is preferably 1 to 7, more preferably 1 to 4, from the viewpoints of heat resistance, insulation reliability and handling property in the form of a film.

The cyanate prepolymer refers to a polymer in which a cyanate resin has formed a triazine ring by a cyclization reaction, and mainly includes 3, 5, 7, 9, and 11-mer of a cyanate ester compound. In the cyanate prepolymer, the conversion ratio of the cyanate group is not particularly limited, but is preferably 20 to 70 mass%, more preferably 30 to 65 mass% from the viewpoint of obtaining good solubility in an organic solvent.

Examples of the cyanate prepolymer include a prepolymer of a cyanate resin represented by the general formula (b2-I) and a prepolymer of a cyanate resin represented by the general formula (b2-IV). Among these, from the viewpoints of heat resistance, insulation reliability and handling properties in the form of a film, it is preferable to be a prepolymer of a dicyanate compound having two cyanate groups in one molecule, and a cyanate compound represented by the general formula (b2-I) (B2-V)), and more preferably a prepolymer having at least a part of 2,2-bis (4-cyanatophenyl) propane triarized to be a trimer.

The weight average molecular weight (Mw) of the cyanate prepolymer is not particularly limited, but is preferably 500 to 4,500, more preferably 600 to 4,000, and most preferably 1,000 to 4,000 from the viewpoint of solubility in an organic solvent and workability And particularly preferably from 1,500 to 4,000. If the weight average molecular weight (Mw) of the cyanate prepolymer is 500 or more, the crystallization of the cyanate prepolymer is inhibited and the solubility in an organic solvent tends to be good. When the weight average molecular weight is 4,500 or less, There is an excellent tendency.

In the present invention, the weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) (manufactured by Tosoh Corporation) using a calibration curve of standard polystyrene. Specifically, the weight average molecular weight .

The cyanate prepolymer may be a prepolymerized cyanate resin in the presence of a monofunctional phenol compound. When the cyanate prepolymer is prepared, the unreacted cyanate groups in the obtained cured product can be reduced by blending a monofunctional phenol compound, so that moisture resistance and electric characteristics tend to be excellent.

Examples of the monofunctional phenol compound include alkyl-substituted phenol compounds such as p-nonylphenol, p-tert-butylphenol, p-tert-amylphenol and p-tert-octylphenol; phenol compounds represented by the following general formula (b2-VI) such as p- (a-cumyl) phenol, mono-, di- or tri- (a-methylbenzyl) phenol. These may be used singly or in combination of two or more kinds.

In the general formula (b2-VI), R ^b6 and R ^b7 each independently represent a hydrogen atom or a methyl group, and m represents an integer of 1 to 3. When m is an integer of 2 or 3, a plurality of R ^{b6 s} or R ^{b7 s} may be the same or different, but are preferably the same.

The amount of the monofunctional phenol compound to be used is preferably such that the equivalent ratio (hydroxyl group / cyanate group) of the phenolic hydroxyl group of the monofunctional phenol compound to the cyanate group of the cyanate resin is 0.01 to 0.30, More preferably 0.01 to 0.20, and still more preferably 0.01 to 0.15. When the amount of the monofunctional phenol compound used is within the above range, there is a tendency that a dielectric loss tangent in a high frequency band is sufficiently low, and a good moisture resistance tends to be obtained.

The production method of the cyanate prepolymer is not particularly limited and a known production method can be applied.

The cyanate prepolymer can suitably be produced, for example, by reacting the dicyanate compound with the monofunctional phenol compound. The reaction between the dicyanate compound and the monofunctional phenol compound results in the formation of a compound having a group represented by -OC (= NH) -O- (i.e., iminocarbonate), and the iminocarbonate Or the iminocarbonate and the dicyanate compound react with each other, whereby the monofunctional phenol compound is eliminated and a cyanate prepolymer having a triazine ring is obtained. The reaction can be carried out by, for example, mixing and dissolving the dicyanate compound and the monofunctional phenol compound in the presence of a solvent such as toluene, and optionally adding a reaction accelerator such as zinc naphthenate Can be added.

As the cyanate resin, a commercially available product may be used. Commercially available cyanate resins include bisphenol-type cyanate resins, novolac-type cyanate resins, and prepolymers in which some or all of these cyanate resins are triazine-converted to trimers.

Examples of commercially available cyanate resins of bisphenol A type (2,2-bis (4-hydroxyphenyl) propane type) include Primaset BADCy (trade name, manufactured by Lonsai Co., Ltd.), Arocy B- 10 &quot; (manufactured by Huntsman, trade name) may be used. Examples of commercially available cyanate resins of bisphenol E type (1,1-bis (4-hydroxyphenyl) ethane type) include Arocy L10 (manufactured by Huntsman, product name), Primaset Quot; LECy &quot; (trade name, a product of Lonsai Co., Ltd.) may be used. As a commercially available product of 2,2'-bis (4-cyanate-3,5-methylphenyl) ethane type cyanate resin, &quot; Primaset METHYLCY (Manufactured by The Lion Corporation) may be used.

As a commercially available product of the novolak-type cyanate resin, a phenol novolac-type cyanate resin "Primaset PT30" (trade name, manufactured by Lonza Co., Ltd.) may be used.

As a commercially available product of the cyanate resin prepolymer, "Primaset BA200" (trade name, manufactured by Lonsai Co., Ltd.), "Primaset BA230S" (trade name, manufactured by Lonza Co., Ltd.), which is a prepolymerized bisphenol A type cyanate resin May be used, or &quot; Primaset BA3000 &quot; or the like may be used.

Arocy XP71787.02L "(trade name, product of Huntsman Co.), which is a cyanate resin containing a dicyclopentadiene structure," Arocy XU-371 "(product name, product of Huntsman) Primaset DT-4000 "(trade name, manufactured by The Lion Corporation, trade name)," Primaset DT-7000 "(trade name, product of Lonsa), or the like may be used.

((b3) phenol novolac type curing agent containing triazine ring)

As the phenol novolac type curing agent containing (b3) triazine ring, among the novolak type phenol resins used as the curing agent of the epoxy resin, those containing a triazine ring can be used. A novolak type phenolic resin containing triazine ring is a randomly bonded aminotriazine ring structure and a phenol structure through a methylene group. The phenol novolac type curing agent containing triazine ring is preferably at least one of a phenol novolac resin containing a triazine ring and a cresol novolak resin containing a triazine ring.

The novolac-type phenolic resin containing triazine ring can be produced by using the production method described in, for example, Japanese Patent Application Laid-Open No. 2002-226556. That is, the phenol compound, the aminotriazine compound, and the aldehyde compound can be produced by co-condensation reaction in the presence of a weakly alkaline catalyst such as an alkylamine or in the absence of a catalyst in the vicinity of neutral.

Examples of the phenol compound to be used as the raw material include phenol, orthocresol, metacresol, para-cresol, xylenol, bisphenol compounds, ortho-substituted phenol compounds having 3 or more carbon atoms and preferably 3 to 10 carbon atoms in the ortho position, para And para-substituted phenol compounds having a hydrocarbon group having 3 or more carbon atoms, preferably 3 to 18 carbon atoms at the position. These may be used singly or in combination of two or more kinds.

Examples of the bisphenol compound include bisphenol A, bisphenol F, bis (2-methylphenol) A, bis (2-methylphenol) F, bisphenol S, bisphenol E and bisphenol Z.

Examples of the ortho-substituted phenol compound include 2-propylphenol, 2-isopropylphenol, 2-sec-butylphenol, 2-tert-butylphenol, 2-phenylphenol, 2-cyclohexylphenol, Butylphenol and the like.

Examples of the para substituted phenol compound include 4-propylphenol, 4-isopropylphenol, 4-sec-butylphenol, 4-tert- butylphenol, 4-phenylphenol, 4-cyclohexylphenol, 4-dodecylphenol, 4-octadecylphenol, and the like.

Examples of the aminotriazine compound used as a raw material include melamine, benzoguanamine, and acetoguanamine.

Examples of the aldehyde compound used as a raw material include formaldehyde, formalin, paraformaldehyde, trioxane, acetaldehyde, paraldehyde, and propionaldehyde. Of these, paraformaldehyde is preferable from the viewpoint of the reaction rate. These may be used singly or in combination of two or more kinds.

The compounding molar ratio (F / P) of the aldehyde compound (F) and the phenol compound (P) is preferably 0.33 or more, more preferably 0.40 to 1.0, and still more preferably 0.50 to 0.90. By setting the compounding molar ratio (F / P) within the above range, an excellent yield can be obtained.

The content of nitrogen atoms in the phenol novolak type curing agent containing (b3) triazine ring is preferably 8 to 30%, more preferably 8 to 20%.

As the phenol novolac type curing agent containing (b3) triazine ring, commercially available products can be used, and "PAPS-PN2" (trade name, manufactured by Asahi Yuki Kai Kogyo K.K.), "PAPS-PN3" Phenolite LA-7054 &quot; (trade name, triazine-containing phenol novolak resin, manufactured by DIC Corporation), &quot; Phenolite LA-3018 &quot; (triazine-containing cresol novolak resin, manufactured by DIC Corporation).

The curing agent (b) of the resin composition for an interlaminar insulating layer used in the present invention may contain an epoxy resin curing agent other than the curing agents (b1) to (b3) Resin curing agent &quot;).

Examples of the epoxy resin curing agent include a phenol resin containing no triazine ring, a phosphorus-containing phenol compound, an acid anhydride compound, an amine compound, and a hydrazate compound.

Examples of the phenolic resin not containing triazine ring include novolak type phenol resin, resol type phenol resin and the like. The phosphorus-containing phenol compound is a compound having two or more phenolic hydroxyl groups and further containing phosphorus atoms and is a compound having 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa- Phosphaphenanthrene-10-oxide [HCA-HQ or HCA-HQ-HS (manufactured by Sanko Chemical Co., Ltd.)]. Examples of the acid anhydride compound include phthalic anhydride, benzophenonetetracarboxylic acid dianhydride, and methyl hymeic acid. Examples of the amine compound include dicyandiamide, diaminodiphenylmethane and guanyl ether.

Of these epoxy resin curing agents, phenol resins and phosphorus-containing phenol compounds that do not contain triazine rings are preferable from the standpoint of improving reliability, and phosphorus-containing phenol compounds are more preferable from the viewpoint of flame retardancy.

In the present invention, those having a function as a curing agent as well as other functions are given priority over those having a function as a curing agent and classified as &quot; curing agent &quot;. For example, the phosphorus-containing phenol compound has a function as a curing agent and also has a function as a flame retardant, but is classified as a curing agent.

(b2) a cyanate-based curing agent, and (b1) at least one selected from the group consisting of an active ester-based curing agent and (b3) a phenol novolak-based curing agent containing a triazine ring May be included. In particular, when at least one selected from the group consisting of (b1) an active ester-based curing agent and (b3) a phenanopyrrole-based curing agent containing a triazine ring is contained, the ease of gelation by the phosphorus- It is preferable because the effect is large. That is, when it is desired to use a phosphorus-containing phenol compound having an effect as a curing agent and a flame retardant effect, it is preferable to use a phenol novolak type curing agent containing at least (b1) an active ester type curing agent and (b3) By using a combination of these two types, gelation can be suppressed, and handling properties in the form of a film can be maintained satisfactorily. From the same viewpoint, it is preferable that (b) the curing agent comprises a phenol novolac-based curing agent containing (b3) triazine ring.

The content of each of the active ester-based curing agent, (b2) cyanate-based curing agent and (b3) triazine ring-containing phenol novolak-based curing agent in the curing agent (b) is not particularly limited, When the component (b2) or the component (b3) is used in combination, the content of the component (b1) is preferably 40 to 70% by mass based on the total amount of the components (b1) to (b3) , More preferably from 50 to 65 mass%.

The mass ratio of the total amount of the components (b1) to (b3) in the curing agent (b) is preferably 20% by mass or more, more preferably 20% by mass or more from the viewpoints of heat resistance, insulation reliability, 40 mass% or more, and more preferably 50 mass% or more. The upper limit is not particularly limited and may be 100% by mass, 90% by mass or 80% by mass.

The content ratio of the epoxy resin (a) and the curing agent (b) in the resin composition for an interlaminar insulating layer is preferably from (a) the total number of epoxy groups of the epoxy resin, It is preferable to adjust the ratio of the total number of functional groups of the above-mentioned (b) curing agent [(b) the total number of functional groups of the curing agent / (a) the total number of epoxy groups of the epoxy resin] When the ratio is not less than 0.2, the amount of unreacted epoxy groups in the obtained interlayer insulating layer tends to be reduced. When the ratio is not more than 2, the amount of the curing agent (b) is not excessively increased, There is a tendency to be able to do. From the same viewpoint, the ratio is more preferably 0.4 to 1.5.

[(C) inorganic filler]

The resin composition for an interlayer insulating layer used in the present invention further contains (c) an inorganic filler. (c) The inorganic filler is important from the viewpoint of making it possible to prevent the resin from scattering and to shape the laser machining when the interlayer insulating layer formed by thermosetting the resin composition for the interlayer insulating layer is laser-processed. In addition, when the surface of the interlayer insulating layer is harmonized with an oxidizing agent, it is important from the viewpoint of forming a suitable roughened surface and enabling formation of a conductor layer having excellent bonding strength by plating, and it is preferable to select from such a viewpoint Do.

(c) As the inorganic filler, inorganic fillers such as silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, strontium titanate, Calcium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. Of these, silica, particularly spherical silica and fused silica are preferable from the viewpoints of thermal expansion coefficient, handling property of varnish and reliability of insulation. The inorganic fillers may be used singly or in combination of two or more kinds.

The inorganic filler (c) is preferably small in particle diameter from the viewpoint of forming a fine wiring. From the same viewpoint, the inorganic filler (c) preferably has a specific surface area of 3 m 2 / g or more, may be 3 to 200 m 2 / g, may be 3 to 130 m 2 / g, may be 3 to 50 m 2 / g, To 20 m &lt; 2 &gt; / g. The specific surface area can be obtained by the BET method by the low temperature and low humidity physical adsorption of an inert gas. Specifically, a specific surface area of a powder particle can be determined from the adsorption amount of a molecule having a known occupation area of adsorption of nitrogen or the like on the surface of the powder particle at a liquid nitrogen temperature.

The volume average particle diameter of the inorganic filler (c) is preferably 0.01 to 5 占 퐉, more preferably 0.1 to 2 占 퐉, and most preferably 0.2 to 1 占 퐉, from the viewpoint of obtaining a good circuit board fillability and insulating reliability More preferable. The volume average particle diameter refers to a particle diameter at a point corresponding to 50% of the volume when the cumulative frequency distribution curve by the particle diameter is taken as 100% of the total volume of the particles, and can be measured by a particle size distribution measuring apparatus using a laser diffraction scattering method have.

(trade name, manufactured by Nippon Aerosil Co., Ltd., specific surface area: 110 ± 20 m 2 / g), which is fumed silica, and "AEROSIL (registered trademark) PL-1 &quot; manufactured by Fuso Kagaku Kogyo K.K. under the trade name of AEROSIL (registered trademark) R202 (trade name, manufactured by Nippon Aerosil Co., Ltd., specific surface area 100 ± 20 m 2 / g) , A product name, a specific surface area of 181 m &lt; 2 &gt; / g, and PL-7 (trade name, trade name, specific surface area 36 m2 / g, manufactured by FUSO KAGAKU KOGYO KABUSHIKI KAISHA).

As the inorganic filler (c), an inorganic filler surface-treated with a surface treatment agent such as a silane coupling agent may be used from the viewpoint of improving the moisture resistance of the obtained interlayer insulating layer.

As the inorganic filler surface-treated with the surface treatment agent, a commercially available product may be used, or a silica filler "SO-C2" (trade name, manufactured by Admatechs Co., Ltd.) treated with an amino silane coupling agent and treated with a phenyl silane coupling agent "Sciqas series" (manufactured by Sakai Kagaku Kogyo K.K., trade name, 0.1 μm grade), which is a silica filler treated with an epoxy silane coupling agent, and the like, "YC100C" (trade name, manufactured by Admatechs Co., .

The content of the inorganic filler (c) in the resin composition for an interlaminar insulating layer is preferably such that the solid content of the resin composition for an interlaminar insulating layer ((c) the inorganic filler itself By mass, more preferably 30 to 70% by mass, and further preferably 40 to 60% by mass, based on the total mass of the resin composition. When the content of the inorganic filler (c) is 30 mass% or more based on the solid content of the resin composition for an interlaminar insulating layer, good laser processability tends to be obtained. When the content is 90 mass% or less, the adhesion strength with the conductor layer formed by the plating method is There is an excellent tendency.

[(D) Antioxidant]

The antioxidant (d) contained in the resin composition for an interlaminar insulating layer is a hindered phenol-based antioxidant. The hindered phenol-based antioxidant has a substituent at the ortho position of the phenolic hydroxyl group, and tends to refer to a compound having a substituent having a large steric hindrance such as a t-butyl group and a trimethylsilyl group.

The resin composition for an interlaminar insulating layer should not contain a non-hindered phenol-based antioxidant, but if it contains a non-hindered phenol-based antioxidant, the content of the non-hindered phenol- By mass or less, more preferably 15% by mass or less, further preferably 5% by mass or less, and even more preferably 0% by mass.

(d) Since the antioxidant is a hindered phenol-based antioxidant, handling properties in the form of a film are improved.

Examples of the hindered phenol antioxidant include 2,6-di-t-butyl-p-cresol (trade name: Yoshinox BHT), 4,4'-butylidenebis- (6-t- (Trade name: Yoshinox BB), 2,2'-methylenebis- (4-ethyl- Butyl-4-ethylphenol (trade name: Yoshinox 250), 1,1,3-tris (2-methyl-4 (3,5-di-t-butyl-4-hydroxyphenyl) propionate (trade name: (Trade name: Tominox TT; IRGANOX1010, IRGANOX1010FD), pentaerythrityl tetrakis [3- (3,5-di-t- butyl-4-hydroxyphenyl) propionate] (trade name: Tominox SS, IRGANOX1076, IRGANOX1076FD) ), Triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate] (trade name: Tominox 917; IRGANOX245, IRGANOX245FF) -Butyl-4-hydroxybenzyl) (Trade name: IRGANOX 319), 1,6-hexanediol-bis [3- (3,5-di-t-butyl- (Trade name: IRGANOX565, IRGANOX565DD), 2,4-bis- (n-octylthio) -6- (4-hydroxy- (Trade name: IRGANOX1035FF), N, N'-hexamethylenebis [3 (3,5-di-t- butylphenyl) (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid amide] (trade name: IRGANOX1098), 1,3,5-trimethyl- (Trade name: IRGANOX1330), calcium bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate) calcium (trade name: IRGANOX1425WL), 2,4- (Trade name: IRGANOX1520L), isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate have.

The hindered phenol-based antioxidant preferably contains at least one member selected from the group consisting of a compound having a group represented by the following formula (dI) and a compound represented by the following formula (dII). The compound having a group represented by the following formula (dI) may also include a compound represented by the following formula (dII).

(In the formula (dI), R ^d1 , R ^d2 and R ^d3 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, provided that at least one of R ^d1 and R ^d2 represents an alkyl group having 1 to 8 carbon atoms .

(In the formula (dII), R ^d4 and R ^d5 each independently represent an alkyl group having 1 to 8 carbon atoms, R ^d6 , R ^d7 and R ^d8 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms Provided that at least one of R ^d6 , R ^d7 and R d8 represents an alkyl group having 1 to 8 carbon atoms.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ^d1 , R ^d2 and R ^{d3 in the} formula (dI) include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, , n-hexyl group, n-octyl group and the like. Among them, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, a methyl group, an ethyl group, an n-propyl group and a t-butyl group is more preferable, and a methyl group, desirable.

And at least one of R ^d1 and R ^d2 represents an alkyl group having 1 to 8 carbon atoms. R ^d1 This may be a combination of an alkyl group having 1 to 8 carbon atoms, R ^d2 is a hydrogen atom, R ^d1 is a hydrogen atom, R ^d2 that may be a combination of an alkyl group having 1 to 8 carbon atoms, both of the R ^d1 and R ^d2 having 1 Lt; / RTI &gt; to 8 carbon atoms.

The alkyl group having 1 to 8 carbon atoms represented by R ^d4 , R ^d5 , R ^d6 , R ^d7 and R ^{d8 in the} formula (dII) is explained as in the case of R ^d1 , R ^d2 and R ^d3 , .

At least one of R ^d6 , R ^d7 and R ^d8 represents an alkyl group having 1 to 8 carbon atoms, preferably two alkyl groups having 1 to 8 carbon atoms. R ^d6 is a hydrogen atom, R ^d7 is a hydrogen atom and R ^d8 is a combination of alkyl groups having 1 to 8 carbon atoms, R ^d6 is a hydrogen atom, R ^d7 is an alkyl group having 1 to 8 carbon atoms, and R ^d8 is a hydrogen atom R ^d6 may be an alkyl group having 1 to 8 carbon atoms, R ^d7 may be a combination of a hydrogen atom and R ^d8 may be a hydrogen atom, R ^d6 is an alkyl group having 1 to 8 carbon atoms, R ^d7 is a hydrogen atom and R ^d8 is a hydrogen atom may be a combination, R ^d6 is an alkyl group, R ^d7 having 1 to 8 may be a combination of an alkyl group and R ^d8 are hydrogen atoms having 1 to 8 carbon atoms, R ^d6 alkyl group, R ^d7 of a carbon number of 1 to 8 and a hydrogen atom, R ^d8 may be a combination of alkyl groups having 1 to 8 carbon atoms, R ^d6 may be a hydrogen atom, R ^d7 may be an alkyl group having 1 to 8 carbon atoms, and R ^d8 may be a combination of alkyl groups having 1 to 8 carbon atoms. R ^d6 , R ^d7 and R ^d8 may all be an alkyl group having 1 to 8 carbon atoms.

The compound having a group represented by the general formula (dI) is preferably a compound represented by any one of the following general formulas (dI-1) to (dI-3).

(In the formulas (dI-1) and (dI-2), R ^d11 , R ^d12 , R ^d13 , R ^d21 , R ^d22 and R ^d23 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. at least one of R ^d11 and R ^d12, and R, at least one of the ^d21 and R ^d22 represents an alkyl group having 1 to 8. X ¹ and X ² are, each independently, represents an organic group of 1 to trivalent respectively. n ^1, and and n ² are each independently an integer of 1 to 3.)

The alkyl group having 1 to 8 carbon atoms is described in the same manner as in the case of R ^d1 , R ^d2 and R ^d3 , and preferable examples are also the same.

At least one of R ^d11 and R ^d12 represents an alkyl group having 1 to 8 carbon atoms. R ^d11 is be a combination of an alkyl group having 1 to 8 carbon atoms, R ^d12 is a hydrogen atom, R ^d11 are each a hydrogen atom, R ^d12 is be a combination of an alkyl group having 1 to 8 carbon atoms, both of the R ^d11 and R ^d12 having 1 Lt; / RTI &gt; to 8 carbon atoms. It is preferable that both of R ^d11 and R ^d12 are t-butyl groups, and R ^d13 is a combination of hydrogen atoms.

In addition, R ^d11 is a t- butyl group, R ^d13 hydrogen atom, R ^d12 is an alkyl group having 1 to 8, R ^d13 is a combination of an alkyl group having 1 to 8 also preferred, and R ^d11 are each a hydrogen atom, R ^d12 is The combination of methyl groups is also more preferable.

At least one of R ^d21 and R ^d22 represents an alkyl group having 1 to 8 carbon atoms. R ^d21 is be a combination of an alkyl group, R ^d22 is a hydrogen atom with 1 to 8 carbon atoms, R ^d21 are each a hydrogen atom, R ^d22 is be a combination of an alkyl group having 1 to 8 carbon atoms, both of the R ^d21 and R ^d22 having 1 Lt; / RTI &gt; to 8 carbon atoms. R ^d21 is a t-butyl group, R ^d22 is an ethyl group, and R ^d23 is a combination of hydrogen atoms.

In addition, when R ^d13 is a hydrogen atom, it has the same meaning as it does not have a substituent R ^d13 . R ^d23 is a hydrogen atom means the same as when R ^d23 does not have a substituent R ^d23 .

The 1 to 3-valent organic groups represented by X ¹ and X ² are not particularly limited and include groups containing an aliphatic hydrocarbon group, an amide bond-containing group, an aromatic hydrocarbon group, a heteroaromatic hydrocarbon group, and a combination thereof.

The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group of 1 to 10 carbon atoms, more preferably an aliphatic hydrocarbon group of 1 to 6 carbon atoms, and more preferably an aliphatic hydrocarbon group of 1 to 4 carbon atoms. The aliphatic hydrocarbon group may be straight-chain or branched.

Examples of the amide bond-containing group include - (CH ₂ ) ₂ -C (═O) -NH- (CH ₂ ) ₆ -NH-C (═O) - (CH ₂ ) ₂ -.

As the aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 10 carbon atoms is preferable, and an aromatic hydrocarbon group having 6 carbon atoms is more preferable.

Examples of the heteroaromatic hydrocarbon group include an isocyanurate skeleton-containing group and the like.

Specific examples of the group containing a combination of these groups include an aliphatic hydrocarbon group-aromatic hydrocarbon group and the like.

n ¹ and n ² are each independently an integer of 1 to 3, and may be all 1, 2 or 3.

(DI-3), R ^d31 and R ^d32 each independently represent an alkyl group having 1 to 8 carbon atoms, and Y represents -COOCH ₂ - or -COOCH ₂ CH ₂ -.

The alkyl group having 1 to 8 carbon atoms represented by R ^d31 and R ^d32 is described as in the case of R ^d1 , R ^d2 and R ^d3 , and preferable examples are also the same. Among them, t-butyl group is particularly preferable.

The compound having a group represented by the general formula (dI) is at least one member selected from the group consisting of a compound represented by the general formula (dI-1) and a compound represented by the general formula (dI-2) It is also preferable that the molecular weight is 1,500 or less. At least one member selected from the group consisting of the compound represented by the general formula (dI-1) and the compound represented by the general formula (dI-2) is more preferable and the molecular weight is more preferably 1,000 or less, And still more preferably 400 or less.

[(D ') the following specific compound]

The resin composition for an interlayer insulating layer may contain the component (d ') instead of the component (d). (d ') is at least one member selected from the group consisting of a compound having a group represented by the formula (dI) and a compound represented by the formula (dII). Each of the groups in the formulas (dI) and (dII) is the same as defined above, and preferable ones are the same.

Particularly, the compound having a group represented by formula (dI) is preferably a compound represented by any one of the above-mentioned formulas (dI-1) to (dI-3). The compound having a group represented by formula (dI) is at least one member selected from the group consisting of the compound represented by formula (dI-1) and the compound represented by formula (dI-2) It is also preferable that the molecular weight is 1,500 or less. At least one member selected from the group consisting of the compound represented by the general formula (dI-1) and the compound represented by the general formula (dI-2) is more preferable and the molecular weight is more preferably 1,000 or less, And still more preferably 400 or less.

The content of the component (d) or the component (d ') in the resin composition for an interlaminar insulating layer is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 10 parts by mass, from the viewpoint of heat resistance, insulation reliability, By mass, more preferably 0.05 to 5% by mass, still more preferably 0.05 to 2% by mass, particularly preferably 0.05 to 1% by mass.

[(E) Phenoxy resin]

The resin composition for an interlayer insulating layer preferably contains (e) a phenoxy resin.

Here, the "phenoxy resin" is a generic name of a polymer having a central structure of an aromatic diol and an aromatic diglycidyl ether in the main chain, and in this specification indicates a weight average molecular weight of 10,000 or more. When the polymer in which the main chain has a middle structure of an aromatic diol and an aromatic diglycidyl ether has an epoxy group, those having a weight average molecular weight of 10,000 or more are classified as (e) phenoxy resins, and those having a weight average molecular weight of less than 10,000 a) Classify with epoxy resin.

(e) The phenoxy resin preferably contains an alicyclic structure from the viewpoint of improving handling properties when the film is formed into a film. Here, the &quot; alicyclic structure &quot; means &quot; an organic compound having a structure in which carbon atoms are bonded in a cyclic form except an aromatic compound. &Quot; Among them, at least one selected from cyclic saturated hydrocarbons (cycloalkanes) and cyclic unsaturated hydrocarbons containing one double bond in the ring (cycloalkene) is preferable.

Examples of the phenoxy resin (e) include a phenoxy resin containing a cyclohexane structure, a phenoxy resin containing a trimethylcyclohexane structure, and a phenoxy resin containing a terpene structure. Among them, a phenoxy resin containing at least one selected from a terpene structure and a trimethylcyclohexane structure is preferable, and a phenoxy resin containing a trimethylcyclohexane structure is preferable from the viewpoint of improving handling properties in the form of a film. More preferable.

As the phenoxy resin containing a trimethylcyclohexane structure, bisphenol TMC (bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane) disclosed in Japanese Patent Laid-Open Publication No. 2006-176658 can be used as a raw material , And the like.

As the phenoxy resin containing a terpene structure, for example, in the phenoxy resin disclosed in Japanese Patent Laid-Open Publication No. 2006-176658, bis (4-hydroxyphenyl) -3 , Phenoxy resins synthesized using terfendi phenol instead of 3,5-trimethylcyclohexane, and the like.

(e) The phenoxy resin may be used alone or in combination of two or more.

The weight average molecular weight of the phenoxy resin (e) is preferably 10,000 to 60,000, more preferably 12,000 to 50,000, further preferably 15,000 to 45,000, particularly preferably 17,000 to 40,000, and particularly preferably 20,000 to 37,000. If the weight average molecular weight of the phenoxy resin (e) is not less than the above lower limit value, a peel strength with an excellent conductor layer tends to be obtained, and if it is not more than the upper limit value, increase in roughness and increase in thermal expansion coefficient can be prevented.

The weight average molecular weight is a value measured by a gel permeation chromatography (GPC) method (in terms of polystyrene) and can be measured by the method described in the examples.

(e) As a method for producing a phenoxy resin, for example, there can be used a bisphenol compound containing a trimethylcyclohexane structure or a bisphenol compound containing a terpene structure and a bifunctional epoxy resin as raw materials, (Phenolic hydroxyl group / epoxy group) of the phenolic hydroxyl group and the epoxy group in the range of 1 / 0.9 to 1 / 1.1, for example.

(e) Phenoxy resins can be commercially available. As the phenoxy resin (e) in the marketed product, a bisphenol compound (1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane) containing a biphenyl type epoxy resin and a trimethylcyclohexane structure YX7200B35 &quot; (trade name, a product of Mitsubishi Chemical Corporation) containing a skeleton derived from the above-mentioned compound is preferable.

When the resin composition for an interlaminar insulating layer contains (e) a phenoxy resin, its content is preferably from 0.2 to 30 mass parts per 100 mass parts of the solid content of the resin composition for an interlaminar insulating layer (here, (c) inorganic filler excluded) More preferably from 1 to 20 parts by mass, still more preferably from 3 to 20 parts by mass. When the content of the phenoxy resin (e) is 0.2 parts by mass or more, the flexibility and handleability are excellent, and the peel strength of the conductor layer tends to be excellent. When the content is 20 parts by mass or less, , And an appropriate roughness tends to be obtained.

[(F) Curing accelerator]

The resin composition for an interlayer insulating layer may contain a curing accelerator (f) from the viewpoint of enabling short-time curing at a low temperature.

Examples of the curing accelerator (f) include a metal-based curing accelerator and an organic-based curing accelerator.

(Metal-based hardening accelerator)

As the metal-based curing accelerator, for example, an organometallic curing accelerator can be used. The organometallic curing accelerator has (b2) a promoting action of the self-polymerization reaction of the cyanate-based curing agent and a promoting action of (a) the epoxy resin and (b) the curing agent.

Examples of the organometallic curing accelerator include transition metals, Group 12 metal organic salts and organometallic complexes. Examples of the metal include copper, cobalt, manganese, iron, nickel, zinc, and tin.

Examples of the organometallic salt include carboxylic acid salts. Specific examples thereof include naphthenic acid salts such as cobalt naphthenate and zinc naphthenate, 2-ethylhexanoate salts such as cobalt 2-ethylhexanoate and zinc 2-ethylhexanoate, Zinc octylate, tin octylate, tin stearate, and zinc stearate.

Examples of the organometallic complexes include chelate complexes such as acetylacetone complexes. Specific examples thereof include organic cobalt complexes such as cobalt (II) acetylacetonato and cobalt (III) acetylacetonato; Organic copper complexes such as copper (II) acetylacetonato; Organic zinc complexes such as zinc (II) acetylacetonato; An organic iron complex such as iron (III) acetylacetonato, an organic nickel complex such as nickel (II) acetylacetonato; And organic manganese complexes such as manganese (II) acetylacetonato. Among them, cobalt (II) acetylacetonato, cobalt (III) acetylacetonato, zinc (II) acetylacetonato, iron (III) acetylacetonato, zinc naphthenate and cobalt naphthenate are preferable from the viewpoints of curability and solubility And zinc naphthenate is more preferable. These may be used singly or in combination of two or more kinds.

When the resin composition for an interlaminar insulating layer contains a metal-based curing accelerator, the content thereof is preferably 1 to 500 mass ppm, more preferably 10 to 500 mass ppm, relative to the cyanate curing agent (b2) from the viewpoints of reactivity and storage stability More preferably from 50 to 400 ppm by mass, and particularly preferably from 150 to 300 ppm by mass. The metal-based curing accelerator may be compounded at one time or divided into a plurality of circuits.

(Organic curing accelerator)

Examples of the organic curing accelerator (which does not include the organometallic curing accelerator) include amine compounds such as organic phosphorus compounds, imidazole compounds, secondary amines and tertiary amines; Quaternary ammonium salts and the like. These may be used singly or in combination of two or more kinds. Of these, organic phosphorus compounds, imidazole compounds and amine compounds are preferable from the viewpoint of smear removal in via holes, and organic phosphorus compounds are more preferable. The organic curing accelerator may be compounded at one time or divided into a plurality of circuits.

Examples of the organophosphorus compound include organic phosphine compounds such as ethylphosphine, propylphosphine, butylphosphine, phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, tricyclohexylphosphine , Triphenylphosphine / triphenylborane complex, tetraphenylphosphonium tetraphenylborate, and the like. Of these, triphenylphosphine is preferable.

Examples of the imidazole compound include 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, and the like.

When the resin composition for an interlaminar insulating layer contains an organic curing accelerator, the content thereof is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, per 100 parts by mass of the epoxy resin (a) from the viewpoints of reactivity and storage stability And more preferably 0.01 to 2 parts by mass.

&Lt; Other components >

The resin composition for an interlaminar insulating layer may contain components other than the above components within a range that does not impair the effect of the present invention. Examples of the other components include resin components other than the above components (hereinafter, also referred to as &quot; other resin components &quot;), additives, and flame retardants.

(Other resin component)

Examples of other resin components include a polymer of a bismaleimide compound and a diamine compound, a bismaleimide compound, a bisaryl naphthamide resin, and a benzoxazine compound.

(additive)

Examples of additives include thickeners such as benzene, benzene and the like; Adhesion-imparting agents such as imidazole-based, thiazole-based, triazole-based and silane coupling agents; Rubber particles; Coloring agents and the like.

(Flame retardant)

Examples of the flame retardant include an inorganic flame retardant and a resin flame retardant. Examples of the inorganic flame retardant include aluminum hydroxide, magnesium hydroxide and the like. The resin flame retardant may be a halogen-based resin or a non-halogen-based resin, but from the viewpoint of environmental load, a halogen-free resin is preferable.

The resin composition for an interlaminar insulating layer can be produced by mixing the components (a) to (d), and optionally (e), (f) and other components. As the mixing method, a known method can be applied, and for example, be mixed using a bead mill or the like.

&Lt; Thickness of Resin Film for Interlayer Insulating Layer >

The thickness of the resin film for an interlayer insulating layer can be determined according to the thickness of a conductor layer formed on a printed wiring board, for example. Since the thickness of the conductor layer is usually 5 to 70 占 퐉, the thickness of the resin film for interlayer insulating layer is preferably 1 to 100 占 퐉, and from the viewpoint of enabling the thickness of the multilayer printed wiring board to be thin, More preferably from 1 to 70 mu m, even more preferably from 15 to 70 mu m, and still more preferably from 20 to 50 mu m.

<Support>

The resin film for an interlayer insulating layer of the present invention may be formed on a support.

Examples of the support include an organic resin film, a metal foil, a release paper, and the like. Although not particularly limited, an organic resin film is preferable as a support.

Examples of the material of the organic resin film include polyolefins such as polyethylene and polyvinyl chloride; Polyesters such as polyethylene terephthalate (hereinafter also referred to as &quot; PET &quot;) and polyethylene naphthalate; Polycarbonate, polyimide, and the like. Of these, PET is preferable from the viewpoints of price and handleability.

Examples of the metal foil include copper foil and aluminum foil. When a copper foil is used for the support, a copper foil may be used as a conductor layer to form a circuit. In this case, as the copper foil, rolled copper, electrolytic copper foil or the like can be used. The thickness of the copper foil may be, for example, 2 to 36 mu m. In the case of using a copper foil with a thin thickness, a copper foil with a carrier may be used from the viewpoint of improving workability.

As one embodiment of the present invention, there can be mentioned the resin film for the interlaminar insulating layer and the multilayer resin film having the support. The multilayer resin film is preferably a multilayer resin film in which the support is an organic resin film, the thickness of the organic resin film is 10 to 70 mu m, and the thickness of the resin film for interlaminar insulating layer is 1 to 80 mu m.

The multilayer resin film may have an adhesion-assisting layer together with a layer including a resin film for interlaminar insulating layer (a resin composition layer for an interlaminar insulating layer).

These supports and protective films to be described later may be subjected to surface treatment such as mold release treatment, plasma treatment, and corona treatment. Examples of the release treatment include release treatment with a silicone resin-based release agent, an alkyd resin-based release agent, a fluororesin-based release agent, and the like.

The thickness of the support is preferably 10 to 120 占 퐉, more preferably 10 to 70 占 퐉, even more preferably 15 to 70 占 퐉, and still more preferably 25 to 60 占 퐉, from the viewpoints of handleability and economical efficiency.

The support is usually finally peeled off or removed when producing the multilayered printed circuit board.

<Protection film>

A protective film may be disposed on the surface of the resin film for an interlayer insulating layer of the present invention opposite to the support. The protective film is provided on a surface opposite to the surface on which the support of the resin film for an interlayer insulating layer is provided. The protective film is used for the purpose of preventing adherence and scratches on the resin film for the interlayer insulating layer. The protective film is peeled off before a resin film for an interlayer insulating layer is laminated on a circuit board or the like by using a laminate, a thermal press, or the like.

As the protective film, the same material as the support can be used. The thickness of the protective film may be, for example, 1 to 40 占 퐉.

&Lt; Manufacturing Method of Resin Film for Interlayer Insulating Layer >

The resin film for an interlayer insulating layer of the present invention can be produced, for example, by coating a resin composition for an interlayer insulating layer on a support and then drying the resin composition. At this time, the resin composition for an interlaminar insulating layer is preferably dissolved and / or dispersed in an organic solvent to be in a varnish state.

(Organic solvent)

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone (hereinafter also referred to as &quot; MEK &quot;), methyl isobutyl ketone, and cyclohexanone; Acetic acid ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; Carbitol solvents such as cellosolve and butyl carbitol; Aromatic hydrocarbon solvents such as toluene and xylene; And amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. These may be used singly or in combination of two or more. Of these, ketone solvents are preferable from the viewpoint of solubility, and MEK and methyl isobutyl ketone are more preferable.

As a method of coating the resin composition for an interlaminar insulating layer, a known coating method such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, a die coater or the like may be used. The coating apparatus may be appropriately selected depending on the target film thickness.

As the drying conditions after coating the resin composition for an interlaminar insulating layer, it is preferable to dry the resin film for the interlaminar insulating layer so that the content of the organic solvent in the obtained resin film is 10 mass% or less, more preferably 5 mass% or less .

The drying conditions vary depending on the amount and type of the organic solvent in the varnish. For example, if the varnish contains 20 to 80% by mass of the organic solvent, it may be dried at 50 to 150 ° C for 1 to 10 minutes.

[Multilayer Printed Circuit Board]

The multilayer printed wiring board of the present invention is obtained by using at least one kind selected from the group consisting of a resin film for an interlayer insulating layer and a multilayer resin film of the present invention. That is, the resin film for an interlayer insulating layer of the present invention is useful as a multilayer printed wiring board. Further, the resin film for an interlayer insulating layer of the present invention is also useful for forming a build-up layer of a multilayer printed wiring board, particularly a build-up wiring board.

The multilayered printed circuit board of the present invention can be produced by a manufacturing method including, for example, the following steps (1) to (6) (the step (3) is optional) 2) or (3), the support may be peeled off or removed.

Hereinafter, the term "resin film" is simply referred to as "resin film for interlayer insulating layer" and "multilayer resin film".

(1) A step of laminating the resin film of the present invention on one side or both sides of a circuit board (hereinafter referred to as lamination step (1)).

(2) a step of thermally curing the laminated resin film in the step (1) to form an insulating layer (hereinafter referred to as an insulating layer forming step (2)).

(3) A step of punching the circuit board on which the insulating layer is formed in the step (2) (hereinafter referred to as punching step (3)).

(4) Step of removing smear [hereinafter referred to as desmearing step (4)].

(5) A step of forming a conductor layer on the surface of the insulating layer by plating after the desmearing step (4) (hereinafter referred to as a conductor layer forming step (5)).

(6) A step of forming a circuit on the conductor layer by a semi-additive method (hereinafter referred to as a circuit forming step (6)).

The lamination step (1) is a step of laminating the resin film of the present invention on one side or both sides of a circuit board by using a vacuum laminator. Examples of the vacuum laminator include a vacuum applicator made by Nichigo Morton Co., Ltd., a vacuum pressurized laminator made by Meikoshi Sakusho Co., Ltd., a roll dry coater made by Hitachi Seisakusho Co., Ltd., a vacuum type vacuum cleaner manufactured by Hitachi Kasei Electronics Co., A laminator, and the like.

When the protective film is provided on the resin film, the resin film for an interlayer insulating layer of the present invention or the resin composition layer for an interlayer insulating layer of the multilayer resin film of the present invention is brought into contact with the circuit board after peeling or removing the protective film, And laminated by pressing on a circuit board while heating.

The laminate can be obtained, for example, by preliminarily heating a resin film and a circuit board as necessary, and then subjecting the laminate to a pressing temperature of 60 to 140 캜, a pressing pressure of 0.1 to 1.1 MPa (9.8 x 10 ⁴ to 107.9 x 10 ⁴ N / It can be carried out under a reduced pressure of 20 mmHg (26.7 hPa) or less. The lamination method may be a batch method or a roll type continuous method.

In the insulating layer forming step (2), first, the resin film laminated on the circuit board in the lamination step (1) is cooled to the vicinity of room temperature.

When the support is peeled off, the resin film laminated on the circuit board is heat-cured after peeling, thereby forming an insulating layer, that is, an insulating layer to be an &quot; interlayer insulating layer &quot;. When a multilayer resin film containing an adhesion-assisting layer is used, the insulating layer formed here becomes a layer composed of a cured product of the resin composition layer for interlaminar insulating layer and a cured product of the adhesion-assisting layer.

The heating and curing may be carried out in two stages. For example, the first stage is at 100 to 200 ° C for 5 to 30 minutes, and the second stage is at 140 to 220 ° C for 20 to 80 minutes. In the case of using the support subjected to the releasing treatment, the support may be peeled off after thermosetting.

After the formation of the insulating layer by the above-described method, the punching step (3) may be carried out if necessary. The punching step (3) is a step of forming via holes, through holes, and the like by punching the circuit board and the formed insulating layer by a method such as drilling, laser, plasma, or a combination thereof. As the laser, a carbon dioxide gas laser, a YAG laser, a UV laser, an excimer laser, or the like is used.

In the desmearing step (4), so-called &quot; smear &quot; which occurs when a via hole, a through hole or the like is formed in the insulating layer and the circuit board is removed by an oxidizing agent. At this time, the surface of the insulating layer may be roughened with an oxidizing agent. That is, the harmonic processing and the removal of the smear can be performed at the same time.

Examples of the oxidizing agent include permanganates (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide, sulfuric acid, nitric acid and the like. Of these, alkaline permanganic acid solutions (for example, potassium permanganate and sodium hydroxide aqueous solution of sodium permanganate), which are commonly used for harmonization of the insulating layer in the production of a multilayer printed wiring board by a build-up method, can be used.

The roughening treatment forms an unevenness anchor on the surface of the insulating layer.

In the conductor layer forming step (5), the conductor layer is formed by plating on the surface of the insulating layer on which the uneven anchors are formed by the harmonic treatment performed simultaneously in the desmearing step (4).

Examples of the plating method include an electroless plating method and an electrolytic plating method. The metal for plating is not particularly limited as long as it is a metal usable for plating. The metal for plating may be selected from copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing at least one of these metal elements. , And copper is more preferable.

It is also possible to employ a method in which a plating resist having a pattern reverse to that of the conductor layer (wiring pattern) is first formed, and then a conductor layer (wiring pattern) is formed only by electroless plating.

After the conductor layer is formed, annealing may be performed at 150 to 200 DEG C for 20 to 120 minutes. By performing the annealing treatment, the bonding strength between the interlayer insulating layer and the conductor layer tends to be further improved and stabilized. The curing of the interlayer insulating layer may be advanced by this annealing treatment.

In the circuit forming step (6), a semi- additive process (SAP: Semi Additive Process) is used as a method of patterning the conductor layer and forming a circuit. A pattern of a plating resist is formed on the conductor layer (seed layer) formed in the conductor layer forming step (5), and plating is performed by electrolytic copper plating or the like to grow a circuit. Thereafter, the plating resist is removed, and then the seed layer between the circuits is etched to complete the wiring board.

The surface of the conductor layer (circuit) thus produced may be harmonized (blackened). By coarsening the surface of the conductor layer, the adhesion with the resin in contact with the conductor layer tends to be improved. CZ-8100 "," CZ-8101 ", and" CZ-5480 "(trade names, all manufactured by Mack &amp; Chemical Co., Ltd.), which are organic acid-based microetching agents, can be used.

Examples of the circuit board used in the multilayered printed circuit board of the present invention include a substrate made of a patterned conductor such as a glass epoxy, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, Layer (circuit) is formed.

In addition, a multilayer printed wiring board having conductor layers (circuits) formed by alternately layering conductor layers and insulating layers and patterned on one or both sides, a multilayered printed circuit board having interlayer insulation formed by resin films of the present invention on one side or both sides of the circuit board Having a conductor layer (circuit) patterned on one side or both sides thereof, a conductor layer (circuit) patterned on one side or both sides of a cured product formed by curing the resin film of the present invention and the like Are included in the circuit board of the present invention.

From the viewpoint of the adhesion of the interlayer insulating layer to the circuit board, the surface of the conductor layer of the circuit board may be previously subjected to the roughening treatment by blackening treatment or the like as described above.

[Semiconductor package]

The semiconductor package of the present invention comprises a semiconductor element mounted on the multilayered printed circuit board of the present invention. The semiconductor package of the present invention can be manufactured by mounting a semiconductor element such as a semiconductor chip or a memory at a predetermined position of the multilayered printed circuit board of the present invention. Further, the semiconductor element may be sealed with a sealing resin or the like.

Example

[a] Next, the first invention will be described in more detail by way of examples, but the first invention is not limited at all by these examples.

Example 1

25.8 parts by mass of "NC-3000-H" (trade name, trade name, solid concentration 100% by mass, manufactured by Nippon Kayaku Co., Ltd.) as a biphenyl novolak type epoxy resin,

, 6.3 parts by mass of &quot; PAPS-PN2 &quot; (trade name, a solid content concentration of 100% by mass, Mw / Mn = 1.17, manufactured by Asahi Yuki Kai Kogyo K.K.) as a novolac-

4.9 parts by mass of "LA-1356-60M" (trade name, solvent: MEK, solid content concentration of 60% by mass), which is a triazine-modified phenol novolak resin, as an epoxy resin curing agent,

(Solid content concentration: 70% by mass) dispersed in MEK was treated with an aminosilane coupling agent as the inorganic filler, the surface of "SO-C2" (trade name, manufactured by Admatechs Co., , 92.9 parts by mass,

0.026 parts by mass of &quot; 2E4MZ &quot; (product name, solid content concentration 100% by mass, manufactured by Shikoku Kasei Kogyo K.K.) as 2-ethyl-4-methylimidazole as a curing accelerator,

And 13.1 parts by mass of MEK as an additional solvent were mixed and mixed and subjected to a bead mill dispersion treatment to prepare a resin composition varnish 1 for an adhesive film.

The resin composition varnish 1 for the adhesive film obtained above was coated on PET (product name: G2, film thickness: 50 탆, manufactured by Dainippon DuPont Films Japan Limited) as a support film and dried to form a resin composition layer . The coating thickness was 40 占 퐉, and the drying was performed so that the residual solvent in the resin composition layer became 8.0% by mass. After drying, a polyethylene film (trade name: NF-13, thickness: 25 占 퐉) was laminated as a protective film on the resin composition layer side. Thereafter, the obtained film was wound up in a roll to obtain an adhesive film 1.

Examples 2 to 6, 8, Comparative Examples 1 to 4

Adhesive films 2 to 6 and 8 to 12 were obtained in the same manner as in Example 1 except that the raw material composition and the production conditions were changed as shown in Table 1 in Example 1.

Example 7

(Manufactured by Daikin DuPont Film Co., Ltd., trade name: G2, film thickness: 50 m) having a thickness of 10 mu m was coated with a resin varnish A prepared in the following procedure and dried. Thick support film 2 was prepared.

The resin varnish A used above was produced in the following procedure.

63.9 parts by mass of "NC-3000-H" (trade name, trade name, solid concentration 100% by mass, manufactured by Nippon Kayaku Co., Ltd.) as a biphenyl novolak type epoxy resin,

18.0 parts by mass of "LA-1356-60M" (trade name, solvent, solvent: MEK, solid content concentration of 60% by mass) which is a triazine-modified phenol novolac resin as an epoxy resin curing agent,

15.2 parts by mass of "EXL-2655" (trade name, manufactured by Rohm and Haas Electronic Materials, Ltd.) as core shell rubber particles,

As an inorganic filler, 8.8 parts by mass of "Aerosil R972" (trade name, average particle diameter: 0.02 μm, solid concentration of 100% by mass, manufactured by Nippon Aerosil Co., Ltd.)

1.28 parts by mass of &quot; 2E4MZ &quot; (product name, solid content concentration of 100% by mass, manufactured by Shikoku Chemical Industry Co., Ltd.) as 2-ethyl-4-methylimidazole as a curing accelerator,

As an additional solvent, 226.1 parts by mass of cyclohexanone was blended, followed by mixing and a bead mill dispersion treatment to prepare a resin varnish A.

The resin varnish A obtained above was coated on a support film PET (trade name: G2, film thickness: 50 mu m, manufactured by Dainippon DuPont Films Japan Ltd.) so as to have a film thickness of 10 mu m, Was obtained.

Then, a resin composition varnish for an adhesive film coated on the support film 2 obtained above was produced in the same manner as in Example 1, under the raw material composition and manufacturing conditions shown in Table 1. [

Using the support film 2 and the resin composition varnish for an adhesive film, an adhesive film 7 was obtained in the same manner as in Example 1.

[Assessment Methods]

The obtained adhesive films 1 to 12 were evaluated by the following methods.

(Preparation and Test Method of Samples for Handling Test of Adhesive Film)

The resulting adhesive films 1 to 12 were cut into a size of 500 mm x 500 mm to prepare samples 1 to 12 for handling test of adhesive films.

The handling properties of the produced adhesive films were evaluated by the following methods (1) to (3) using Samples 1 to 12 for handling test, and those which were defective in any of the tests were evaluated as " It was called "good handling property" that there was not defect in examination.

(1) Handling property of adhesive films Samples 1 to 12 were first peeled from a protective film. When the protective film was peeled off, it was called poor handling that the coated and dried resin partially adhered to the side of the protective film, or that the powder fell off.

(2) Cracking occurred in the coated and dried resin having the center two points (500 mm x 250 mm, two points at the end) of the film.

MCL-E-679FG (R) &quot; (made by Hitachi Kasei Kabushiki Kaisha, copper foil thickness 12 占 퐉, plate thickness 0.41 mm) which is a copper clad laminate subjected to blackening and reduction treatment on the copper foil on the surface Using a vacuum pressurized laminator &quot; MVL-500 &quot; (trade name, available from Meiji Seisakusho Co., Ltd.). The vacuum degree at this time was 30 mmHg or less, the temperature was set at 90 DEG C, and the pressure was set at 0.5 MPa. After cooling to room temperature, the support film was peeled off (the adhesive film 7 was peeled off between the PET and the resin layer formed thereon in the support film 2). At this time, it was said that the material which fell off the powder or the PET was broken in the middle was poor handling property.

(Preparation and Test Method of Sample for Measurement of Thermal Expansion Coefficient)

Each of the resulting adhesive films 1 to 12 was cut into a size of 200 mm x 200 mm, the protective film was peeled off, and a vacuum press type laminator MVL-500 (available from Kabushiki Kaisha, Manufactured by Seisakusho Co., Ltd., trade name). The vacuum degree at this time was 30 mmHg or less, the temperature was set at 90 DEG C, and the pressure was set at 0.5 MPa.

After cooling to room temperature, the support film was peeled off (in the case of the adhesive film 7, the support film 2 was peeled off between the PET and the resin layer formed thereon) and cured in a dryer at 180 ° C for 120 minutes. Thereafter, the copper foil was removed with a ferric chloride solution and cut to a width of 3 mm and a length of 8 mm to obtain samples 1 to 12 for measuring thermal expansion coefficient.

Using the manufactured samples 1 to 12 for measuring the thermal expansion coefficient, the thermal expansion coefficient was measured by the following method.

Samples 1 to 12 for measuring the obtained thermal expansion coefficient were heated to 240 ° C at a temperature raising rate of 10 ° C / min using a thermomechanical analyzer manufactured by Seiko Instruments Inc., cooled to -10 ° C, Min to 300 캜, and the average thermal expansion coefficient of the change curve of the expansion amount at 0 to 150 캜 was obtained.

(Fabrication and Test Method of Filling Evaluation Board)

The inner layer circuit used for the evaluation of the embedding property is as follows. MCL-E-679FG (R) &quot; (trade name, manufactured by Hitachi Kasei Kabushiki Kaisha) as a copper clad laminate having a copper foil thickness of 12 탆 and a plate thickness of 0.15 mm (including copper foil thickness) Through holes were formed by drill punching so as to be 25 x 25 groups at intervals of 5 mm. Then, desmear and electroless plating were performed, and electrolytic plating was performed in the through hole using electrolytic plating.

As a result, a circuit board having a through-hole of 25 x 25 mm in thickness with a copper thickness of 0.2 mm, a diameter of 0.1 mm, and an interval of 5 mm was obtained.

Subsequently, the adhesive films 1 to 12 from which the protective film was peeled were arranged so that the resin composition layer was opposed to the circuit surface side of the circuit board, and then the vacuum laminator "MVL-500" (manufactured by Take- Trade name). The vacuum degree at this time was 30 mmHg, the temperature was set at 90 占 폚, and the pressure was set at 0.5 MPa.

After cooling to room temperature, a circuit board having a through-hole with an adhesive film on both surfaces thereof was sandwiched between two aluminum plates each having a thickness of 1 mm, and lamination was carried out using the above vacuum laminator. The vacuum degree at this time was 30 mmHg, the temperature was set at 90 占 폚, and the pressure was set at 0.7 MPa.

After cooling to room temperature, the support film was peeled off (in the case of the adhesive film 7, the support film 2 was peeled off between the PET and the resin layer formed thereon) and cured in a dryer at 180 ° C for 120 minutes. Thus, the evaluation boards 1 to 12 were obtained.

Using the produced embedding ability evaluation substrates 1 to 12, the embedding property was evaluated by the following method.

The step difference of the surface of the through hole portions of the landing evaluation substrates 1 to 12 was measured using a contact type surface roughness meter "SV2100" (trade name) manufactured by Mitsutoyo Corporation. The step difference was measured so that the central portion of the surface of the through hole was 10 pieces, and the average value of the ten recesses was calculated.

The components in Table 1 are shown below.

[Epoxy resin]

NC-3000-H: biphenyl novolak type epoxy resin (trade name, solid concentration 100% by mass, manufactured by Nihon Kayaku Co., Ltd.)

N-673-80M: cresol novolak type epoxy resin (trade name, solvent: MEK, solid concentration 80% by mass, manufactured by DIC Corporation)

[Novolac type phenolic resin]

PAPS-PN2: novolac phenolic resin (trade name, solid content concentration 100% by mass, Mw / Mn = 1.17, manufactured by Asahi Yuki Kai Kogyo Co., Ltd.)

PAPS-PN3: novolak type phenol resin (trade name, solid content concentration 100% by mass, Mw / Mn = 1.50, manufactured by Asahi Yuki Kai Kogyo Co., Ltd.)

HP-850: A novolac phenolic resin (trade name, solid content concentration 100% by mass, manufactured by Hitachi Kasei Kabushiki Kaisha) prepared by using hydrochloric acid instead of phosphoric acid

[Triazine-modified phenol novolak resin]

LA-1356-60M: triazine-modified phenol novolac resin (trade name, solvent: MEK, solid concentration 60% by mass, manufactured by DIC Corporation)

[Inorganic filler]

SO-C2: silica treated with an aminosilane coupling agent on the surface of silica "SO-C2" (trade name, average particle size: 0.5 μm) manufactured by Admatechs Co., Ltd. and dispersed in MEK solvent mass%)

· SO-C6: silica surface treated with aminosilane coupling agent and dispersed in MEK solvent (solid content concentration: 70%) was treated with the surface of silica "SO-C6" (trade name, mass%)

Aerosil R972: Fumed silica (trade name, solid content concentration 100% by mass, specific surface area: 100 m 2 / g, manufactured by Nippon Aerosil Co., Ltd.)

[Curing accelerator]

2E4MZ: 2-ethyl-4-methylimidazole (trade name, solid content concentration 100% by mass, manufactured by Shikoku Chemical Industry Co., Ltd.)

It can be seen from Table 1 that the adhesive film of the present invention has good handling properties and that the adhesive film of the present invention can provide an interlayer insulating layer having a low thermal expansion coefficient and excellent filling property.

On the other hand, when the adhesive film of the present invention was not used, the handling property, the thermal expansion coefficient, and the filling property were inferior.

That is, according to the first aspect of the invention, it is possible to provide an adhesive film having a low coefficient of thermal expansion, an excellent filling property and an excellent handling property, and an interlayer insulating layer having a low thermal expansion coefficient after curing can be provided.

[b] Next, the second invention will be described in more detail, but the second invention is not limited at all by these examples.

[Production of resin film for interlaminar insulating layer]

Examples 1 to 9 and Comparative Examples 1 to 4

The ingredients shown in Tables 2 to 4 (the values in the table are parts by mass of solid matter, and the solutions (except organic solvent) or the dispersion were solid content-converted amounts] were mixed and stirred. Thereafter, the resin composition was dispersed by a bead mill treatment to obtain a resin composition for an interlayer insulating layer on a varnish.

The resin composition for an interlaminar insulating layer obtained above was coated on a 38 탆 thick PET film using a die coater and dried at 100 캜 for 1.5 minutes to obtain a multilayer resin having a resin film for an interlaminar insulating layer having a thickness of 40 탆 A film was obtained, and each evaluation was carried out according to the following method. The results are shown in Tables 2 to 4.

[(1) Evaluation of insulation reliability]

Insulation reliability was evaluated by high temperature and high humidity bias test. Layered resin film having a thickness of 40 占 퐉 obtained in each example on a comb-shaped copper electrode of an evaluation device TEG (trade name: WALTS-KIT EM0101JY, manufactured by WALTS, L / S = 10 mu m / 10 mu m) The insulating layer was placed in the direction in which it was positioned on the side of the comb-shaped copper electrode and was attached at 110 DEG C using a laminator. Thereafter, the support PET film was peeled off, heated in an oven at 190 캜 for 2 hours, and cooled to room temperature to obtain a sample for measurement.

A lead wire was attached to the electrode portion of the TEG of the obtained measurement sample with solder, and a high temperature and high humidity bias test was performed (voltage; 5V (DC), test time; 200 hours, 130 캜, 85% RH (using high temperature and high humidity (manufactured by ESPEC)).

If the resistance value is maintained at 1.0 x 10 &lt; ⁷ &gt; OMEGA or more at a test time of 200 hours, it can be said that the insulation reliability is excellent.

[(2) Evaluation of handling property]

The multilayer resin film obtained in each example was allowed to stand at room temperature (25 占 폚) for 5 days. Then, with the resin film for interlayer insulating layer adhered to the support, the resin film side for the interlayer insulating layer was set outside And bent to 180 DEG, and the presence or absence of cracks was visually confirmed. Likewise, 20 multilayer resin films were identified and expressed as &quot; the number of multilayer resin films having cracks / 20 &quot;.

[(3) Measurement of glass transition temperature (Tg) (evaluation of heat resistance)]

The glass transition temperature (Tg) was determined by peeling the support from the multilayer resin film obtained in each of the examples and using only the resin film for the interlaminar insulating layer. The laminate obtained by laminating the five resin films was thermally cured at 190 DEG C for 120 minutes, .

The cured product was cut out in a length of 40 mm (X direction), 4 mm width (Y direction) and 200 m thickness (Z direction), and the evaluation board was evaluated by a thermomechanical analyzer , Q400) were subjected to thermomechanical analysis by the compression method. Specifically, the evaluation board was mounted on the apparatus in the tensile direction (xy direction) and then measured twice continuously under the measurement conditions of a load of 5 mg and a temperature raising rate of 10 캜 / minute. In the second measurement, The Tg appearing at the intersection of the different tangent lines of the curve was obtained and used as an index of heat resistance.

The components described in Tables 2 to 4 are shown below.

[(a) Epoxy resin]

N-673: cresol novolak type epoxy resin ("EPICLON (registered trademark) N-673", solid content concentration: 100% by mass, epoxy equivalent: 210 g / eq, manufactured by DIC Corporation)

· JER157S70: bisphenol A novolak type epoxy resin (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 210 g / eq, solids concentration: 100% by mass)

NC-3000-H: aralkyl novolak type epoxy resin having a biphenyl skeleton (solid content concentration: 100 mass%, epoxy equivalent: 289 g / eq, manufactured by Nihon Kayaku K.K.)

JER 828: liquid epoxy resin of bisphenol A type (solid content concentration: 100 mass%, epoxy equivalent: 185 g / eq, manufactured by Mitsubishi Chemical Corporation)

[(b) Curing agent]

BA230S: prepolymer of bisphenol A type cyanate resin (Prima Set BA230S manufactured by Lonza), component (b2)

HPC-8000-65T: active ester resin ("EPICLON (registered trademark) HPC-8000-65T" manufactured by DIC Corporation, solid content concentration of 65% by mass, toluene cut product)

(Phenolite (registered trademark) LA-7054, manufactured by DIC Corporation), (b3) phenol novolak resin containing triazine

PAPS-PN2: phenazine novolac resin containing triazine (manufactured by Asahi Yuki Kai Kogyo Co., Ltd., solid content concentration: 100% by mass, Mw / Mn = 1.17)

LA3018-50P: triazine-containing cresol novolak resin ("phenolite (registered trademark) LA3018-50P" manufactured by DIC Corporation), (b3)

(Other curing agent)

HCA-HQ-HS: phosphorus-containing phenol compound (manufactured by Sankyo Co.), 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide

[(c) inorganic filler]

· SO-C2: spherical silica treated with aminosilane coupling agent (manufactured by Admatechs Co., Ltd., volume average particle diameter: 0.5 μm, solid concentration: 100% by mass)

[(d) (d ') hindered phenol compound]

Yodinox BB: 4,4'-butylidenebis- (6-t-butyl-3-methylphenol) (Mitsubishi Chemical Corporation)

BHT: 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Kasei Kogyo K.K.)

Yosinox 425: 2,2'-methylenebis- (4-ethyl-6-t-butylphenol) (manufactured by Mitsubishi Chemical Corporation)

(Non-hindered phenol compound)

Bisphenol A: manufactured by Tokyo Kasei Kogyo Co., Ltd.

[(e) Phenoxy resin]

(JER (registered trademark) YX7200B35, epoxy equivalent weight: 3,000 to 16,000 g / eq, solid content concentration: 35 mass%, MEK cut) manufactured by Mitsubishi Chemical Co., Ltd. YX7200B35: phenoxy resin

[(f) Curing accelerator]

TPP: Triphenylphosphine (manufactured by Kanto Kagaku K.K.), organic curing accelerator

Zinc naphthenate: (manufactured by Wako Pure Chemical Industries, Ltd., solid content concentration: 8% by mass, Mineral Spirit solution), metal curing accelerator

2PZ-CNS-PW: 1-cyanoethyl-2-phenylimidazolium trimellitate (manufactured by Shikoku Kasei Kogyo K.K.)

[Additional Organic Solvents]

· Cyclohexanone: a high-grade product

From Tables 2 to 4, it can be seen that the resin films for interlaminar insulating layers of Examples 1 to 9 are excellent in heat resistance and insulation reliability as well as handling property.

On the other hand, the resin films for interlaminar insulating layers obtained in Comparative Examples 1 to 4 were inferior in both insulation reliability and handleability, and thus were incompatible with each other.

Claims (1)

(A) a novolak type phenolic resin having a weight average molecular weight (Mw) to number average molecular weight (Mn) dispersion ratio (Mw / Mn) of 1.05 to 1.8,
(B) an epoxy resin represented by the following general formula (1)
(C) inorganic filler
A resin composition layer formed by layering a resin film on a support film,
Wherein the inorganic filler (C) in the resin composition layer has an average particle diameter of 0.1 탆 or more,
(C) the content of the inorganic filler is 20 to 95% by mass in the resin solid content.

(Wherein p represents an integer of 1 to 5)