TWI756552B - Thermosetting epoxy resin composition, adhesive film for insulating layer formation, prepreg for insulating layer formation, insulator for printed wiring board, multilayer printed wiring board, and semiconductor device - Google Patents

Abstract

The present invention provides a thermosetting epoxy resin composition, which is characterized by comprising at least an epoxy resin (A), an active ester compound containing a naphthalene structure (B), a thermoplastic resin and an inorganic filler in the resin composition. The content of the naphthalene structure-containing active ester compound (B) is 0.1 to 30 mass % when the nonvolatile content is 100 mass %, and the average particle diameter of the inorganic filler is 0.01 μm or more and 5 μm or less.

Description

Thermosetting epoxy resin composition, adhesive film for insulating layer formation, prepreg for insulating layer formation, insulator for printed wiring board, multilayer printed wiring board, and semiconductor device

The present invention relates to a thermosetting epoxy resin composition having a low value of dielectric tangent and low roughness, suitable for forming an insulating layer having a roughened surface capable of improving peel strength, a thermosetting epoxy resin composition and a cured product thereof, and a thermosetting epoxy resin composition having a roughened surface A multilayer printed wiring board with a low degree of hardness and a roughened surface that can improve peel strength as an insulating layer.

With the miniaturization and high performance of electronic equipment, it is known that a method of forming conductors corresponding to the multi-layer and high-density in the build-up layer of the multi-layer printed wiring board used is to roughen the surface of the insulating layer, An additive method for forming a conductor layer by electroless plating, a semi-additive method for forming a conductor layer by electroless plating or electrolytic plating, and in the case of these methods, between the surface of the insulating layer and the plated conductor layer Adhesion is mainly ensured by roughening the surface of the insulating layer to have a fine unevenness that exerts a fixing effect.

The fixing effect of the unevenness formed on the surface of the insulating layer is greater when the surface roughness is greater, and the greater the roughness is, the better the adhesion between the insulating layer and the plated conductor layer is. However, when the roughness of the surface of the insulating layer is large, when the thin-film conductor layer formed on the roughened surface is partially removed by etching to form a specific wiring pattern, the conductors entering the recesses in the parts on the surface of the insulating layer that should be removed Since the layer portion is difficult to remove, it takes a long time for the etching process. At the same time, due to its influence, the portion of the wiring pattern that should be left is eroded to damage the fine wiring, and the risk of disconnection increases. Therefore, in order to correspond to the miniaturization and high density of wiring, the surface state of the insulating layer is required to be as fine as possible asperities and roughened surfaces that can sufficiently ensure adhesion with the thin-film conductor layer formed by plating.

Furthermore, the insulating layer is also required to have a low coefficient of linear thermal expansion so that there is no difference in the coefficient of linear thermal expansion between the insulating layer and the conductor layer formed by the wiring pattern formed on the surface of the insulating layer. When the coefficient of linear thermal expansion of the insulating layer is high, the difference between the coefficient of linear thermal expansion of the insulating layer and that of the conductor layer becomes large, and problems such as cracks easily occur between the insulating layer and the conductor layer.

In the past, "active ester compounds" have been known as curing agents used in thermosetting resin compositions for forming the insulating layers of inner-layer circuit boards of multilayer printed wiring boards. "Active ester compound containing dicyclopentadiene diphenol structure" was used. However, in recent years, there has been a remarkable progress in increasing the number of layers and increasing the density in the build-up of multilayer printed wiring boards, and there are also many proposals for epoxy resin compositions that can form insulating layers that can respond to these conditions.

Patent Document 1 describes that an insulating layer exhibiting low dielectric properties can be formed by using an active ester compound obtained by arylating a phenolic hydroxyl group in a novolak resin as a curing agent for a thermosetting epoxy resin composition of hardening.

In Patent Document 2, although the roughened surface of the hardened product surface roughened has a relatively small roughness, the roughened surface shows high adhesion to the plated conductor and has a small coefficient of linear thermal expansion. The epoxy resin composition of the insulating layer is described as containing (A) an epoxy resin, (B) an active ester compound, (C) a phenol resin having a triazine structure, (D) a maleimide compound, and (E) Epoxy resin composition of phenoxy resin.

In addition, in Patent Document 3, as a thermosetting epoxy resin composition capable of imparting a cured product exhibiting low dielectric constant and low dielectric tangent, and having both excellent heat resistance and flame retardancy, it is described that it contains a polymer An epoxy resin composition of an active ester resin having an aryloxy structure as the main skeleton and having an aryl carbonyl group on the aromatic nucleus of the structure.

As mentioned above, there have been many proposals for epoxy resin compositions suitable for forming the insulating layer of inner-layer circuit boards. There is a growing desire to form an epoxy resin composition having a well-balanced insulating layer that can respond to the characteristics of increasing the number of layers and increasing the density by building up layers of a multilayer printed wiring board.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 07-082348

[Patent Document 2] Japanese Patent Laid-Open No. 2010-090238

[Patent Document 3] Japanese Patent Laid-Open No. 2012-012534

An object of the present invention is to provide a roughened surface with fine unevenness that exhibits a low dielectric tangent, is excellent in adhesion to a conductor layer, and is excellent in etching properties, and is capable of forming a well-balanced increase in thickness that is compatible with a multilayer printed wiring board. Thermosetting epoxy resin composition of insulating layer with the characteristics of more layers and higher density in layers, printed wiring board having insulating layer formed by hardened material, and multilayer composed of the printed wiring board printed wiring board.

Furthermore, an object of the present invention is to provide an adhesive film for forming an insulating layer in which a resin composition layer composed of the above-mentioned thermosetting epoxy resin composition is formed on a support film, and to impregnate the above-mentioned thermosetting epoxy resin composition A prepreg for forming an insulating layer in a sheet-like reinforcing base material.

The inventors of the present invention, as a result of an active review of hardeners used in thermosetting epoxy resin compositions or compounded resins, found that among various resins known as resin components compounded in epoxy resin compositions, "naphthalene-containing" When the active ester compound of the structure" is blended in a resin composition in a specific amount, it becomes a means for solving the above-mentioned problems, and thus the following inventions have been completed.

[1] A thermosetting epoxy resin composition comprising at least an epoxy resin (A) and a naphthalene structure-containing active ester compound (B), wherein the thermosetting epoxy resin composition is Content of the said naphthalene structure containing active ester compound (B) is 0.1-30 mass % when the non-volatile matter in an epoxy resin composition is 100 mass %.

[2] The thermosetting epoxy resin composition according to [1], wherein the naphthalene structure-containing active ester compound (B) is an active ester compound having a polyoxynaphthalene structure and an arylcarbonyloxy group.

[3] The thermosetting epoxy resin composition according to [1] or [2], wherein the naphthalene structure-containing active ester compound (B) is an aryl group bonded to the naphthalene nucleus of the polyoxynaphthalene structure Active ester compound of carbonyloxy group.

[4] The thermosetting epoxy resin composition according to any one of [1] to [3], wherein the epoxy resin (A) contains a liquid epoxy resin.

[5] The thermosetting epoxy resin composition according to any one of [1] to [4], which further contains an inorganic filler.

[6] The thermosetting epoxy resin composition according to any one of [1] to [5], which further contains a thermoplastic resin.

[7] The thermosetting epoxy resin composition according to any one of [1] to [6], which is a resin composition for an insulating layer of a multilayer printed wiring board in which a conductor layer is formed by plating.

[8] An adhesive film for forming an insulating layer, wherein a resin composition comprising the thermosetting epoxy resin composition according to any one of [1] to [7] is provided on a support film layered.

[9] A prepreg for forming an insulating layer, obtained by impregnating a sheet-like fiber base material with the thermosetting epoxy resin composition according to any one of [1] to [7].

[10] An insulator for a printed wiring board comprising either the resin composition layer of the adhesive film for forming an insulating layer as described in [8] or the prepreg for forming an insulating layer as described in [9] of hardened matter.

[11] An insulator for a printed wiring board, wherein a patterned conductor layer is provided on an insulating layer made of the insulator for a printed wiring board as described in [10].

[12] The insulator for a printed wiring board according to [10] or [11], wherein the surface roughness Ra of the insulating layer is 10 to 200 nm, Rq is 15 to 250 nm, and the peel strength between the insulating layer and the conductor layer is Department of 0.35kgf/cm or more.

[13] A multilayer printed wiring board obtained by laminating a plurality of insulators for a printed wiring board as described in [11] or [12].

[14] A semiconductor device comprising the multilayer printed wiring board as described in [13].

The above-mentioned thermosetting epoxy resin composition has a low dielectric tangent, can form a roughened surface with excellent adhesion to the conductor layer, and can be formed to have a well-balanced structure that can correspond to the build-up of a multilayer printed wiring board. The thermosetting epoxy resin composition of the hardened layer of the insulating layer with the characteristics of more layers and high density.

In addition, when the cured product obtained by curing the thermosetting epoxy resin composition is subjected to surface roughening treatment to form fine irregularities with surface roughness Ra of 10 to 200 nm and Rq of 15 to 250 nm, due to It also becomes a roughened surface which is excellent in adhesion to the conductor layer, so it is particularly useful as a material for forming an insulating layer in a multilayer printed wiring board.

Hereinafter, the thermosetting epoxy resin composition, the adhesive film for insulating layer formation, the prepreg for insulating layer formation, the insulator for printed wiring boards, and the multilayer printed wiring board of the present invention will be described in detail.

The thermosetting epoxy resin composition of the present invention contains an epoxy resin (A) and a naphthalene structure-containing active ester compound (B) as essential components, and may also contain an inorganic filler, a thermoplastic resin, and an epoxy resin as necessary. Hardeners, hardening accelerators, and additives used in resin compositions for forming insulating layers in multilayer printed wiring boards.

<Epoxy resin (A)>

The epoxy resin (A) used in the thermosetting epoxy resin composition of the present invention is an epoxy resin commonly used in a resin composition for forming an insulating layer in a multilayer printed wiring board, and can be appropriately selected from the following examples use.

That is, the epoxy resin (A) is exemplified by, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, and novolak type epoxy resin. Resin, tertiary butyl-catechol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthyl ether type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin , cresol novolac epoxy resin, biphenyl epoxy resin, anthracene epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin Formula epoxy resin, epoxy resin containing spiro ring, cyclohexane dimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy resin, etc.

An epoxy resin (A) may use 2 or more types together. The epoxy resin (A) preferably contains at least 50 mass % or more of the epoxy resin having two or more epoxy groups in one molecule when the nonvolatile content of the epoxy resin (A) is 100 mass %. Furthermore, it is preferable that the epoxy resin (A) contains two or more epoxy groups in 1 molecule, and is a liquid aromatic epoxy resin (liquid epoxy resin) at a temperature of 20° C. , and more preferably, it contains the liquid epoxy resin and an aromatic epoxy resin (solid epoxy resin) which has three or more epoxy groups in one molecule and is solid at a temperature of 20°C.

Moreover, in this invention, an aromatic epoxy resin means the epoxy resin which has an aromatic ring skeleton in the molecule|numerator. In addition, the epoxy equivalent (g/eq) means the molecular weight per one epoxy group. By using a liquid epoxy resin and a solid epoxy resin as the epoxy resin, when the epoxy resin composition is used in the form of an adhesive film, a film showing sufficient flexibility and excellent workability can be formed, and the ring can be improved. The fracture strength of the cured product of the oxy-resin composition is improved, and the durability of the multilayer printed wiring board is improved.

In addition, when using together a liquid epoxy resin and a solid epoxy resin as the epoxy resin, the mixing ratio (liquid epoxy resin: solid epoxy resin) of the same is preferably 1:0.1~ by mass ratio. 1:2 range. By using the liquid epoxy resin within this range, sufficient flexibility can be obtained when used in the form of an adhesive film, workability can be improved, and sufficient fluidity at the time of lamination can also be obtained. In addition, by using a solid epoxy resin within this range, the adhesiveness of the epoxy resin composition can be reduced, and when it is used in the form of an adhesive film, the degassing property during vacuum lamination can be improved. In addition, the peelability of the protective film or the support film during vacuum lamination is good, and the heat resistance after curing can also be improved.

In the epoxy resin composition of the present invention, the content of the epoxy resin (A) is preferably 10 to 50 mass %, more preferably 20 to 40 mass %, when the nonvolatile content of the epoxy resin composition is taken as 100 mass %. %, and more preferably 20 to 35% by mass. By making content of an epoxy resin (A) into this range, there exists a tendency for the curability of an epoxy resin composition to improve.

<Activated ester compound (B) containing naphthalene structure>

The "naphthalene structure-containing active ester compound (B)" (naphthalene-type active ester compound) in the thermosetting epoxy resin composition of the present invention functions as a hardener for epoxy resins, and it is considered that in roughening the resin On the surface of the cured product, it also contributes to the formation of fine irregularities with good adhesion to the conductor layer.

The naphthalene structure-containing active ester compound (B) is not particularly limited as long as it has a naphthalene structure and an arylcarbonyloxy group, but is preferably an active ester compound having a polyoxynaphthalene structure and an arylcarbonyloxy group, more preferably a polyoxynaphthalene structure and an arylcarbonyloxy group. An active ester compound in which an arylcarbonyloxy group is bonded to the naphthalene nucleus of the naphthalene oxide structure. As for the polyoxynaphthalene structure, it can also be a polyoxynaphthalene structure substituted with an alkyl group having 1 to 4 carbon atoms. The above-mentioned active ester compound can be produced by the condensation reaction of a compound having a naphthalene structure having a nucleus-substituted hydroxyl group and a carboxylic acid compound having a carboxyl group on a naphthalene nucleus or a benzene nucleus. The active ester compound is, for example, a compound included in the "active ester compound esterified with an arylcarboxylic acid using a polyaryloxy group structure as a main skeleton" described in Patent Document 3.

Specific examples of the naphthalene structure-containing active ester compound (B) are compounds represented by the following general formula (1).

[式(1)中，R₁各獨立為氫原子或碳數1~4之烷基，較好為氫原子，R₂各獨立為氫原子或以下述通式(2)表示之1價基，X各獨立為氫原子、苯甲醯基或萘羰基，較好為苯甲醯基，n及m各獨立為0~5之整數，n或m之任一者為1以上之整數]。

[In formula (1), R ₁ is each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom, and R ₂ is each independently a hydrogen atom or a monovalent group represented by the following general formula (2) , X is each independently a hydrogen atom, a benzyl group or a naphthylcarbonyl group, preferably a benzyl group, n and m are each independently an integer of 0 to 5, and either n or m is an integer of 1 or more].

[式(2)中，R₁係與上述相同，X係與上述相同，p為1或2之整數，又，上述通式(1)及通式(2)中之X中之至少一者為苯甲醯基或萘羰基]。

[In formula (2), R ₁ is the same as above, X is the same as above, p is an integer of 1 or 2, and at least one of X in the above general formula (1) and general formula (2) be benzyl or naphthyl carbonyl].

In the thermosetting epoxy resin composition of the present invention, the content of the naphthalene structure-containing active ester compound (B) is 0.1 to 30 mass % when the nonvolatile content of the thermosetting epoxy resin composition is taken as 100 mass % %. According to this, a roughened surface can be formed that exhibits a low dielectric tangent and has fine irregularities excellent in adhesion to the conductor layer and etching properties. The more preferable range of content of the active ester compound (B) containing a naphthalene structure is 3-30 mass %, and it is still more preferable that it is 5-28 mass %.

<Inorganic filler>

By further containing an inorganic filler in the thermosetting epoxy resin composition of the present invention, the coefficient of linear thermal expansion and the dielectric tangent can be reduced. Examples of inorganic fillers include 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, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, etc. Among them, silicon dioxide such as amorphous silicon dioxide, pulverized silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, hollow silicon dioxide, spherical silicon dioxide, etc. is preferred, and the reduction is further reduced. The surface roughness of the insulating layer is more preferably fused silica, spherical silica, and more preferably spherical fused silica. These can be used alone or in combination of two or more. Examples of commercially available spherical fused silica include "SOC2" and "SOC1" manufactured by ADMATECHS Co., Ltd.

The average particle size of the inorganic filler is not particularly limited, but is preferably 5 μm or less, more preferably 3 μm or less, and more preferably 2 μm from the viewpoint of making the surface of the insulating layer low in roughness and enabling fine wiring formation Hereinafter, it is still more preferably 1 μm or less, still more preferably 0.8 μm or less, more preferably 0.6 μm or less, and still more preferably 0.4 μm or less. On the other hand, when the resin composition is used as a resin paint, from the viewpoint of preventing an increase in the viscosity of the paint and a decrease in workability, it is preferably 0.01 μm or more, more preferably 0.03 μm or more, and still more preferably 0.05 μm The above, more preferably 0.07 μm or more, and still more preferably 0.1 μm or more. The average particle size of the above-mentioned inorganic filler can be measured by the laser diffraction and scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be made on a volume basis by a laser diffraction scattering particle size distribution analyzer, and the median diameter can be used as the average particle size to measure. As a measurement sample, what disperse|distributed the inorganic filler in water by ultrasonic wave can be preferably used. As the laser diffraction scattering particle size distribution analyzer, LA-950 manufactured by Horiba, Ltd., etc. can be used. The inorganic filler is preferably an aminosilane-based coupling agent, a ureido-based alkane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, a vinylsilane-based coupling agent, and a styrene-based coupling agent. Surface treatment agents such as base silane coupling agents, acrylate silane coupling agents, isocyanate silane coupling agents, thioether silane coupling agents, organosilazane compounds, titanate coupling agents, etc. are surface-treated to improve their resistance. Wet and dispersive. These can be used alone or in combination of two or more.

When formulating inorganic fillers, the content of the inorganic fillers varies according to the required properties of the thermosetting epoxy resin composition, but the content of the inorganic fillers is 100% by mass of the nonvolatile components in the thermosetting epoxy resin composition. In this case, it is preferably 30 to 90 mass %, more preferably 40 to 80 mass %, and still more preferably 50 to 70 mass %. When the content of the inorganic filler is too small, the linear thermal expansion coefficient of the cured product tends to be high, and when the content is too large, it is difficult to form a thin film during preparation of the adhesive film, and the cured product tends to become brittle.

<Thermoplastic resin>

By further containing a thermoplastic resin, the thermosetting epoxy resin composition of the present invention can improve the mechanical strength of the cured product, and can also improve the film formability when used in the form of an adhesive film. The thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyimide resins, polyimide resins, polyetherimide resins, polysiloxane resins, polyethersiloxane resins, and polyphenylene ethers. Resin, polycarbonate resin, polyether ether ketone resin, polyester resin, preferably phenoxy resin and polyvinyl acetal resin. These thermoplastic resins may be used alone or in combination of two or more. The weight average molecular weight of the thermoplastic resin is preferably in the range of 8,000 to 200,000, more preferably in the range of 12,000 to 100,000. The weight average molecular weight in the present invention is measured by gel permeation chromatography (GPC) method (in terms of polystyrene). Specifically, LC-9A/RID-6A manufactured by Shimadzu Corporation can be used as the measuring device for the weight average molecular weight measured by the GPC method, and Shodex K-800P/K-804L/K- manufactured by Showa Denko Co., Ltd. 804L was used as a column, chloroform or the like was used as a mobile phase, the measurement was performed at a column temperature of 40°C, and the calibration line was calculated using standard polystyrene.

When blending a thermoplastic resin, when the blending amount is 100% by mass of the nonvolatile content in the thermosetting epoxy resin composition, it is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass. Within this range, the film forming ability or mechanical strength can be improved, and the increase in melt viscosity or the surface roughness of the insulating layer after the wet roughening step can be reduced.

<hardener for epoxy resin>

The thermosetting epoxy resin composition of the present invention may further use a general curing agent for epoxy resins. Examples of epoxy resin curing agents that can be used are TD2090, TD2131 [DIC (stock), trade name], MEH-7600, MEH-7851, MEH-8000H [Meiwa Chemicals (stock), trade name), NHN, CBN, GPH-65, GPH-103 [Nihon Kayaku Co., Ltd., trade name], SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 [Nippon Steel Chemical Co., Ltd., trade name], LA7052 , LA7054, LA3018, LA1356 [DIC (stock), trade name] and other phenolic hardeners, Fa, Pd [Shikoku Chemicals (stock), trade name], HFB2006M [Showa Polymer (stock), trade name] etc. Benzoxazine-based hardener, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride and other acid anhydride-based hardeners, PT30, PT60, BA230S75 [Japan LONZA (stock) ), trade name] and other cyanate ester-based hardeners.

<hardening accelerator>

By further containing a hardening accelerator, the thermosetting epoxy resin composition of this invention can adjust hardening time and hardening temperature effectively. Examples of hardening accelerators include organic phosphine compounds such as TPP, TPP-K, TPP-S, TPTP-S [Beixing Chemical Industry Co., Ltd., trade name], Curezol 2MZ, 2E4MZ, C11Z, C11Z-CN, C11Z-CNS, C11Z-A, 2MZ-OK, 2MA-OK, 2PHZ [Shikoku Chemical Industry (stock), trade name] and other imidazole compounds, Novacure [Asahi Kasei Industry (stock), trade name], Fujicure [Fuji Chemical Industry (stock), Amine adduct compounds such as trade names], 1,8-diazabicyclo[5,4,0]undecene-7,4-dimethylaminopyridine, benzyldimethylamine, 2, Amine compounds such as 4,6-paraffin (dimethylaminomethyl)phenol and 4-dimethylaminopyridine, organometallic complexes such as cobalt, copper, zinc, iron, nickel, manganese, and tin, or organometallic salts, etc. . A hardening accelerator may use 2 or more types together. When preparing a hardening accelerator, it is preferable to use it within the range of 0.05-1 mass %, when the total amount of the epoxy resin contained in an epoxy resin composition is 100 mass % (non-volatile matter).

The thermosetting epoxy resin composition of the present invention may optionally contain various resin additives other than those described above within the range in which the effects of the present invention are exhibited. Resin additives include, for example, organic fillers such as silicon powder, nylon powder, fluorine powder, and rubber particles, tackifiers such as Orben and Benton, polysiloxane-based, fluorine-based, and polymer-based defoaming agents or leveling agents, and imidazole. Adhesion imparting agents such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, carbon black, etc., metal hydroxides, phosphorus-containing compounds, etc. flame retardant, etc.

The thermosetting epoxy resin composition of the present invention can be appropriately mixed with the above-mentioned components, and can be kneaded by means of triaxial rollers, ball mills, bead mills, sand mills, etc., or super kneaders, planetary kneaders, etc. as necessary Stirring means kneading or mixing to prepare. And it prepares as a resin paint by further adding an organic solvent.

Since the thermosetting epoxy resin composition of the present invention has a low dielectric tangent and can form a roughened surface with excellent adhesion to the conductor layer, it can be preferably used as a resin composition for forming a conductor layer by plating (a resin composition for an insulating layer of a multilayer printed wiring board in which a conductor layer is formed by plating), and is further preferably used as a build-up resin composition for a multilayer printed wiring board.

The thermosetting epoxy resin composition of the present invention is particularly suitable as a material for forming an insulating layer of a multilayer printed wiring board, and can be used for solder resist, underfill material, die bonding material, semiconductor sealing material, buried hole resin, Parts are embedded in resin, etc., in a wide range of applications that require a resin composition. In addition, the form of the resin composition of the present invention is not particularly limited, but can be applied to sheet-like laminates such as adhesive films and prepregs, and circuit boards (for laminates, multilayer printed wiring boards, etc.). The resin composition of the present invention can also be coated on a circuit substrate in a lacquer state to form an insulating layer, but industrially, it is generally used in the formation of an insulating layer in the form of a laminated material such as an adhesive film and a prepreg.

<Laminated sheet material>

(Adhesive film for insulating layer formation)

The adhesive film for forming an insulating layer of the present invention is characterized in that a resin composition layer made of a thermosetting epoxy resin composition is provided on the support film. The adhesive film for forming the insulating layer can be formed by a method known in the art, such as dissolving the resin composition in an organic solvent to adjust the resin paint, using a die coater or the like to coat the resin paint on the support, and then It is manufactured by drying an organic solvent by heating, blowing hot air, etc. to form a resin composition layer.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. Acetate such as cellosolve, carbitol such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. amide-based solvents, etc. The organic solvent may be used in combination of two or more.

The drying conditions are not particularly limited, but the resin composition layer is preferably dried to an organic solvent content of 10% by mass or less, preferably 5% by mass or less. The amount of organic solvent in the paint also varies with the boiling point of the organic solvent. For example, by drying the paint containing 30 to 60% by mass of the organic solvent at 50 to 150°C for about 3 to 10 minutes, a resin composition can be formed. Floor.

It is preferable that the thickness of the resin composition layer formed in the adhesive film for insulating layer formation is more than the thickness of a laminated body. The thickness of the conductor layer included in the circuit board is usually in the range of 5 to 70 µm, so the resin composition layer preferably has a thickness of 10 to 100 µm. From the viewpoint of thinning, it is more preferably 15 to 80 μm.

Examples of the support include films of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate Polyester film such as diester, polycarbonate film, polyimide film and other plastic films. Furthermore, release paper, metal foils, such as copper foil and aluminum foil, etc. can also be used. Among them, in terms of versatility, a plastic film is preferable, and a polyethylene terephthalate film is more preferable. Surface treatments such as surface modification (MAD) treatment and corona treatment may also be applied to the support and the protective film described later. In addition, film release treatment can also be applied by release agents such as silicone resin-based mold release agents, alkyd resin-based mold release agents, and fluororesin mold release agents.

The thickness of the support is not particularly limited, but is preferably 10 to 150 μm, more preferably 25 to 50 μm.

On the surface of the resin composition layer which is not adhered to the support, a protective film may be further laminated on the support. The thickness of the protective film is not particularly limited, but is, for example, 1 to 40 μm. By laminating the protective film, it is possible to prevent the adhesion of dirt and the like to the surface of the resin composition layer.

The adhesive film for insulating layer formation which has the said structure can also be wound up in a roll shape, and can be stored.

(Prepreg for forming insulating layer)

The prepreg for forming an insulating layer of the present invention is characterized in that a sheet-like fiber base material is impregnated with a thermosetting epoxy resin composition. That is, it can be produced by impregnating the thermosetting epoxy resin composition of the present invention in a sheet-like reinforcing base material by a hot melt method or a solvent method, and heating and semi-hardening. As the sheet-like reinforcing base material, fibers for prepregs made of common fibers such as glass cloth and aramid fibers can be used. Further, the prepreg for forming an insulating layer of the present invention is preferably configured to be provided on a support.

The hot-melt method does not dissolve the resin composition in the organic solvent, but temporarily coats it on the support, and laminates it on the sheet-like reinforcing substrate, or directly coats the resin composition with a die coater. A method of fabricating a prepreg on a sheet-like reinforcing substrate. The solvent method is the same as the above-mentioned manufacturing method of the adhesive film for forming an insulating layer. The resin is dissolved in an organic solvent to prepare a resin varnish, and the sheet-like reinforcing substrate is dipped in the varnish to impregnate the resin varnish into the sheet. in the form of a reinforced substrate, followed by drying. In addition, the prepreg for forming an insulating layer of the present invention may be prepared by continuously thermally laminating the adhesive film for forming an insulating layer from both sides of a sheet-like reinforcing base material under heating and pressurizing conditions. A support or a protective film can also be used similarly to the adhesive film for insulating layer formation mentioned above.

As described above, an insulator for a printed wiring board made of a cured product of the resin composition layer of the adhesive film for forming an insulating layer and an insulator for a printed wiring board made of a cured product of the prepreg for forming an insulating layer are suitable as Insulation layer for multilayer printed wiring boards. In addition, it is more preferable to provide a patterned conductor layer (circuit) on the insulating layer made of the printed wiring board insulator. Moreover, a multilayer printed wiring board in which a plurality of insulators for printed wiring boards provided with the conductor layers (circuits) are laminated is preferable.

<Multilayer Printed Wiring Board Using Laminated Sheets>

Next, an example of a method for producing a multilayer printed wiring board using the sheet-like laminate produced as described above will be described.

First, a sheet-like laminate is laminated on one side or both sides of a circuit substrate using a vacuum laminator. Examples of substrates used for the circuit substrate include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. In addition, the term "circuit board" here refers to a patterned conductor layer (circuit) formed on one side or both sides of the above-mentioned board. And in the multilayer printed wiring board formed by alternately laminating conductor layers and insulating layers, one or both sides of the outermost layer of the multilayer printed wiring board are patterned conductor layers (circuits) are also included here. It is called the circuit board. In addition, the surface of the conductor layer can also be subjected to pre-roughening treatment by blackening treatment, copper etching, or the like.

In the above lamination, when the sheet-like laminated material has a protective film, after removing the protective film, the sheet-like laminated material and the circuit substrate may be preheated as needed, and the sheet-like laminated material is laminated on the circuit substrate while pressing and heating the sheet-like laminated material. superior. In the sheet-like laminate of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum lamination method is preferable. The lamination conditions are not particularly limited, but, for example, the pressing temperature (lamination temperature) is preferably 70 to 140° C., and the pressing pressure (lamination pressure) is preferably 1 to 11 kgf/cm ² (9.8 ×10 ⁴ to 107.9 × 10 ⁴ N/m ² ), the pressing time (lamination time) is preferably 5 to 180 seconds, and the lamination is performed under a reduced pressure condition where the air pressure is 20 mmHg (26.7 hPa) or less. In addition, the lamination method may be a batch type or a continuous type using a roll. Vacuum lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum coater manufactured by Nichigo Morton Co., Ltd., a vacuum pressurized laminator manufactured by Meiji Co., Ltd., and a roll-type dry coater manufactured by Hitachi Kogyo Co., Ltd. Cloth machine, vacuum laminator manufactured by Hitachi AIC (stock), etc.

After laminating the sheet-like laminate material on the circuit board, after cooling to around room temperature, when peeling off the support body, the resin composition can be peeled off to thermally harden the resin composition to form a cured product, and an insulating layer can be formed on the circuit board. The thermal curing conditions can be appropriately selected according to the type and content of the resin components in the resin composition, but it is preferably 20 minutes to 180 minutes at 150°C to 220°C, and more preferably 30 minutes to 160°C to 210°C. Choose within 120 minutes. After the insulating layer is formed, when the support body is not peeled off before curing, it can be peeled off at this time as needed.

In addition, the sheet-like laminate material may be laminated on one side or both sides of the circuit board using a vacuum press. The lamination step of heating and pressurizing under reduced pressure can be performed using a general vacuum heat press. For example, it can be performed by pressing a metal plate such as a heated SUS plate from the support layer side. The pressure condition is a reduced pressure condition in which the degree of reduced pressure is usually 1×10 ^-2 MPa or less, preferably 1×10 ^-3 MPa or less. Heating and pressurization may be performed in one stage, but from the viewpoint of controlling resin exudation, it is preferable to perform the conditions in two or more stages. For example, it is preferable to set the temperature to 70~150°C and the pressure to 1~15kgf/cm ² in the pressurizing system of the first stage, and set the temperature to 150~200°C and the pressure to set the pressure of the second stage to 150~200°C. It is carried out in the range of 1~40kgf/cm ² . The time for each stage is preferably 30 to 120 minutes. An insulating layer can be formed on the circuit board by thermally curing the resin composition layer. Commercially available vacuum heat presses include, for example, MNPC-V-750-5-200 (manufactured by Meiki Seiki Co., Ltd.), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.).

The dielectric tangent of the insulating layer is preferably at most 0.009, more preferably at most 0.006. The lower the dielectric tangent, the better. In particular, although there is no lower limit, it is set to 0.001 or more, 0.003 or more, or the like.

Next, the insulating layer formed on the circuit board is subjected to drilling processing to form through holes and through holes. The perforation process can be performed by conventional methods such as drilling machine, laser, plasma, etc., and these methods can be combined as needed, but the most commonly used method is to use carbon dioxide laser, YAG laser and other lasers for perforation processing . When the support body is not peeled off before the punching process, it is peeled off at this time.

Next, the surface of the insulating layer is roughened. In the case of the dry roughening treatment, plasma treatment and the like are mentioned, and in the case of the wet roughening treatment, a method of sequentially performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid. The wet roughening treatment is preferable in terms of removing the smear in the through holes while forming the uneven anchor on the surface of the insulating layer. The swelling treatment with the swelling liquid is performed by immersing the insulating layer in the swelling liquid at 50 to 80° C. for 5 to 20 minutes (preferably at 55 to 70° C. for 8 to 15 minutes). Examples of the swelling liquid include an alkaline solution, a surfactant solution, and the like, preferably an alkaline solution, and the alkaline solution includes, for example, a sodium hydroxide solution, a potassium hydroxide solution, and the like. Commercially available swelling agents include, for example, Swelling Dip Securiganth P, Swelling Dip Securiganth SBU, and the like by Japan ATOTECH Co., Ltd. The roughening treatment by the oxidizing agent is performed by immersing the insulating layer in the oxidizing agent solution at 60 to 80° C. for 10 to 30 minutes (preferably at 70 to 80° C. for 15 to 25 minutes). Examples of the oxidizing agent include an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide/sulfuric acid, and nitric acid. Furthermore, the permanganate concentration in the alkaline permanganic acid solution is preferably 5 to 10% by weight. Commercially available oxidants are listed as, for example, Concentrate manufactured by ATOTECH (stock) in Japan. Alkaline permanganic acid solutions such as Compact CP and Dozing Solution Securiganth P. The neutralization treatment by the neutralization solution is performed by immersing in the neutralization solution at 30 to 50°C for 3 to 10 minutes (preferably at 35 to 45°C for 3 to 8 minutes). The neutralizing solution is preferably an acidic aqueous solution, and a commercially available product is, for example, Reduction Solution Securiganth P manufactured by ATOTECH Co., Ltd., Japan.

The roughness of the roughened surface of the insulating layer surface roughened is preferably 200 nm or less, more preferably 150 nm or less, and still more preferably 100 nm or less, from the viewpoint of forming fine wiring. In addition, in order to ensure the anchoring effect of the roughened surface, the thickness is preferably 10 nm or more. In addition, the so-called Ra value is a kind of numerical value representing the surface roughness, and it is called the arithmetic mean roughness. Specifically, the absolute value of the change height of the surface from the mean line is measured in the measurement area and the arithmetic mean is obtained. . For example, WYKONT 3300 manufactured by Veeco Instruments can be used to obtain the value obtained by using a VSI contact mode with a 50-fold lens and a measurement range of 121 μm×92 μm.

In addition, since the root mean square roughness (Rq value) reflects the local state of the surface of the insulating layer, it was found that the surface of the insulating layer can be confirmed to be dense and smooth by grasping the Rq value, thereby stabilizing the peel strength. In order to obtain a dense and smooth surface of the insulating layer, the Rq value is preferably 250 nm or less, more preferably 200 nm or less, still more preferably 150 nm or less, still more preferably 100 nm or less. In addition, from the viewpoint of stabilizing the peel strength, it is preferably at least 15 nm, more preferably at least 30 nm. In addition, the Rq value is a kind of numerical value representing the surface roughness, which is called the root mean square roughness. Specifically, the absolute value of the change height of the surface from the mean line is measured in the measurement area and used as the mean square. root to represent.

Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. For dry plating, conventional methods such as vapor deposition, sputtering, and ion plating can be used. Examples of wet plating include a method of forming a conductor layer by combining electroless plating and electrolytic plating, a method of forming a plating resist of a pattern opposite to that of the conductor layer, and a method of forming the conductor layer only by electroless plating. As for the subsequent pattern formation method, for example, a subtractive method, a semi-additive method, etc. known to those skilled in the art can be used, and a multi-layer printed wiring board can be manufactured by repeating the above-mentioned series of steps several times, and laminating layers in multiple stages. .

The peel strength between the insulating layer and the conductor layer is preferably at least 0.35 kgf/cm, more preferably at least 0.4 kgf/cm, in order to sufficiently adhere the insulating layer and the conductor layer. The upper limit of peel strength is preferably as high as possible, and although it is not particularly limited, it is generally 1.5 kgf/cm or less, 1.2 kgf/cm or less, 1.0 kgf/cm or less, 0.8 kgf/cm or less, and the like. Since the insulating layer of the insulator for a printed wiring board of the present invention has low roughness and high peel strength between the insulating layer and the conductor layer, it can be preferably used as a build-up layer of a multilayer printed wiring board.

<Semiconductor device>

A semiconductor device can be manufactured by using the multilayer printed wiring board of the present invention. That is, the semiconductor device of the present invention includes the multilayer printed wiring board of the present invention. A semiconductor device can be manufactured by mounting a semiconductor chip on the conductive portion of the multilayer printed wiring board of the present invention. The so-called "conducting part" refers to "the part that conducts electrical signals in the multilayer printed wiring board", and its position may be the surface or the embedded position. In addition, the semiconductor wafer is not particularly limited as long as it is an electrical circuit element using a semiconductor as a material.

The mounting method of the semiconductor chip in the manufacture of the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip can effectively function, but specifically include a wire bonding mounting method, a flip-chip mounting method, and a build-up layer (BBUL) using a bump. ) installation method, installation method using anisotropic conductive film (ACF), installation method using non-conductive film (NCF), etc.

[Example]

Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples, but the present invention is not limited by these Examples and the like. In addition, in the following description, "part" and "%" mean "mass part" and "mass %".

test methods. Evaluation method

<Determination of peel strength (peel strength) of laminate, measurement of arithmetic mean roughness (Ra), and root mean square roughness (Rq)>

(1) Bottom layer treatment of laminates

Immerse both sides of the glass cloth substrate epoxy resin double-sided copper-clad laminate with the inner layer circuit formed (copper foil thickness 18μm, residual copper rate 60%, substrate thickness 0.3mm, R5715ES manufactured by Matsushita Electric Co., Ltd.) in Merck. In the CZ8100 manufactured by (stock), the roughening treatment of the copper foil surface was performed.

(2) Lamination of the next film

Using a batch vacuum pressure laminator MVLP-500 [Miki Seisakusho Co., Ltd., trade name], the adhesive films prepared in the following Examples and Comparative Examples were laminated on both sides of the above-mentioned laminate. The lamination was performed by reducing the pressure for 30 seconds to make the air pressure 13 hPa or less, and then pressing at 100° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Hardening of resin composition

The PET film was peeled off from the laminated adhesive film, and the resin composition was cured under curing conditions of 170° C. and 30 minutes to form an insulating layer.

(4) Coarsening treatment

The above-mentioned laminate with the insulating layer formed thereon was immersed in Swelling Dip Securiganth P containing diethylene glycol monobutyl ether of Japan ATOTECH Co., Ltd. of a swelling solution at 60°C for 10 minutes, and then immersed at 80°C as a roughening solution. Liquid Concentrate made by ATOTECH (stock) in Japan. Compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) for 20 minutes, and finally immersed in Reduction Solution Securiganth P manufactured by Japan ATOTECH Co., Ltd. as a neutralizing solution at 40° C. for 5 minutes. This roughened laminate was designated as sample A.

(5) Formation of conductor layer by semi-additive process

In order to form a circuit on the surface of the insulating layer, the laminate of Sample A was dipped in a solution for electroless plating containing PdCl ₂ , and then dipped in an electroless copper plating solution. After heating and annealing at 150° C. for 30 minutes, an etching resist pattern was formed, and after the pattern was formed by etching, copper sulfate electroplating was performed to form a conductor layer with a thickness of 30 μm. Next, annealing treatment was performed at 180° C. for 60 minutes. This laminate was designated as sample B.

(6) Determination of arithmetic mean roughness (Ra value) and root mean square roughness (Rq value)

For sample A, the Ra and Rq values were obtained from the values obtained by using a non-contact surface roughness meter (WYKONT3300 manufactured by Veeco Instruments) in the VSI contact mode with a 50x lens and a measurement range of 121 μm×92 μm. Next, the numerical value obtained by calculating the average value of each 10 points was used as a measurement value.

(7) Determination of the peel strength of the conductor layer

Make an incision with a width of 10mm and a length of 100mm on a part of the conductor layer of sample B, and clamp one end of the short strip conductor layer with a stripping jig (TSI Co., Ltd., AUTOCOM type testing machine AC-50C-SL). , at room temperature, measure the load (kgf/cm) when peeling off 35mm in the vertical direction at a speed of 50mm/min.

<Determination of Dielectric Tangent>

The adhesive films obtained in the following Examples and Comparative Examples were thermally cured at 190° C. for 90 minutes, and the PET film was peeled off to obtain a sheet-like cured product. The cured product was cut into test pieces with a width of 2 mm and a length of 80 mm, and a cavity resonator perturbation method permittivity measuring device CP521 manufactured by Kanto Applied Electronics Development Co., Ltd. and a network analyzer manufactured by Agilent Technology Co., Ltd. were used. (network analyzer) E8362B, the dielectric tangent (tan δ) was measured by the cavity resonance method at a measurement frequency of 5.8 GHz. The measurement was performed on two test pieces, and the average value was calculated.

Example 1

Liquid bisphenol A epoxy resin (epoxy equivalent 180, "828US" manufactured by Mitsubishi Chemical Corporation) was stirred in 15 parts of methyl ethyl ketone (hereinafter abbreviated as "MEK") and 15 parts of cyclohexanone. ) 15 parts, and 15 parts of biphenyl epoxy resin (epoxy equivalent 291, "NC3000H" manufactured by Nippon Kayaku Co., Ltd.), which were dissolved by heating. Subsequently, 43 parts of a naphthalene-type active ester compound [“EXB9411-65BK” manufactured by DIC Corporation, active ester equivalent 272, toluene solution with a solid content of 65%], and a hardening accelerator (manufactured by Koei Chemical Industry Co., Ltd.) were mixed. "4-Dimethylaminopyridine"] 0.15 part, spherical silica [average particle size 0.5μm, "SO-C2" treated with phenylaminosilane, manufactured by ADMATECHS Co., Ltd., carbon content per unit mass 0.18%] 100 parts, 15 parts of phenoxy resin (YL6954BH30, MEK solution with solid content of 30% by mass, weight average molecular weight 40,000), uniformly dispersed with a high-speed rotary kneader to make resin paint. Next, the resin paint was coated on a polyethylene terephthalate (thickness 38 μm, hereinafter abbreviated as “PET”) film with a die coater so that the thickness of the resin after drying was 40 μm. 80-120 degreeC (average 100 degreeC) was dried for 6 minutes, and the sheet-like adhesive film was obtained.

Example 2

Except for changing the naphthalene-type active ester compound of Example 1 [“EXB9411-65BK” manufactured by DIC Corporation, active ester equivalent 272, toluene solution of 65% solid content] from 43 parts to 80 parts, the rest is the same as that of Example 1. Exactly the same, making resin paint. Next, in the same manner as in Example 1, an adhesive film was obtained.

Example 3

Except for changing the naphthalene-type active ester compound of Example 1 [“EXB9411-65BK” manufactured by DIC Corporation, active ester equivalent 272, toluene solution of 65% solid content] from 43 parts to 20 parts, the rest is the same as that of Example 1. Exactly the same, making resin paint. Next, in the same manner as in Example 1, an adhesive film was obtained.

Example 4

Except that 15 parts of biphenyl type epoxy resin [epoxy equivalent 291, "NC3000H" manufactured by Nippon Kayaku Co., Ltd.] of Example 1 were changed to naphthol type epoxy resin [epoxy equivalent 332, Nippon Steel Chemicals] (stock) "ESN475V"] 15 parts, and add cyanate resin (LONZA company "BA230S75", solid content of 75% methyl ethyl ketone solution) 15 parts and hardening catalyst [zinc naphthenate Except for 0.03 part of 3% cyclohexanone diluent of olein solution (metal content 8%), the rest was exactly the same as in Example 3, and resin paint was produced. Next, in the same manner as in Example 1, an adhesive film was obtained.

Comparative Example 1

Except that the naphthalene-type active ester compound of Example 1 ["EXB9411-65BK" manufactured by DIC Corporation, active ester equivalent 272, toluene solution with solid content of 65%] was changed to an active ester compound [manufactured by DIC Corporation] 43 parts "HPC8000-65T", active ester equivalent 223, toluene solution of 65% solid content] 35 parts, and spherical silica [average particle size 0.5μm, "SO-C2" treated with phenylamino silane, ADMATECHS Co., Ltd., carbon content per unit mass: 0.18%] was changed from 100 parts to 90 parts, and hardening accelerator [Koei Chemical Industry Co., Ltd., "4-dimethylaminopyridine"] 0.15 parts was changed to Except for 0.1 part, it was exactly the same as in Example 1, and a resin paint was produced. Next, in the same manner as in Example 1, an adhesive film was obtained.

Comparative Example 2

Except for changing the naphthalene-type active ester compound of Example 1 [“EXB9411-65BK” manufactured by DIC Corporation, active ester equivalent 272, toluene solution of 65% solid content] from 43 parts to 95 parts, the rest is the same as that of Example 1. Exactly the same, making resin paint. Next, in the same manner as in Example 1, an adhesive film was obtained.

The peel strength of the conductor layer, the surface roughness (Ra value) and (Rq value) after roughening treatment, and the dielectric tangent of the evaluation samples of the evaluation samples using the adhesive films produced in the Examples and Comparative Examples are shown in the respective measurement results. in Table 1.

As shown in Table 1, the hardened product of the epoxy resin composition of Comparative Example 1 was obtained by changing the active ester compound containing a naphthalene structure in the epoxy resin composition of Example 1 to an active ester compound outside the scope of the present invention. Although the values of Ra and Rq after the roughening treatment are far larger than the values of Ra and Rq of the roughened surface formed on the surface of the hardened product of the epoxy resin composition of Example 1, they are not close to the conductor layer. The adhesion (peel strength) was smaller than that of Example 1, and the value of the dielectric tangent became larger.

In addition, the epoxy resin composition of Comparative Example 2 had a lower adhesiveness (peel strength) with the conductor layer than that of Example 1 because the amount of the active ester compound containing a naphthalene structure was larger than the scope of the present invention.

From the results of the above examples and comparative examples, it can be understood that the epoxy resin composition of the present invention can be formed to have the characteristics of more layers and high density corresponding to the build-up of multilayer printed wiring boards in a well-balanced manner. The epoxy resin composition of the insulating layer formed by the hardened material.

Claims (12)

A thermosetting epoxy resin composition, which is characterized by a thermosetting epoxy resin composition comprising at least an epoxy resin (A), an active ester compound containing a naphthalene structure (B), a thermoplastic resin and an inorganic filler, Wherein, when the non-volatile matter in the resin composition is 100% by mass, the content of the active ester compound (B) containing a naphthalene structure is 0.1 to 30% by mass, and the active ester compound (B) containing a naphthalene structure is a Contains a compound represented by the following general formula (1), wherein the average particle size of the inorganic filler is 0.01 μm or more and 5 μm or less,

[In formula (1), each of R ₁ is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, each of R ₂ is independently a hydrogen atom or a monovalent group represented by the following general formula (2), and each of X is independently a hydrogen Atom, benzyl group or naphthylcarbonyl group, n and m are each independently an integer of 0 to 5, and either n or m is an integer of 1 or more]

[In formula (2), R ₁ is the same as above, X is the same as above, p is an integer of 1 or 2, and at least one of X in the above general formula (1) and general formula (2) be benzyl or naphthyl carbonyl]. The thermosetting epoxy resin composition according to claim 1, wherein the epoxy resin (A) contains a liquid epoxy resin at a temperature of 20°C. The thermosetting epoxy resin composition according to claim 1, wherein the content of the inorganic filler is 30 to 90 mass % when the nonvolatile content in the resin composition is 100 mass %. The thermosetting epoxy resin composition according to claim 1, wherein the content of the epoxy resin (A) is 10 to 50 mass % when the nonvolatile content in the resin composition is 100 mass %. The thermosetting epoxy resin composition of claim 1, which is a resin composition for an insulating layer of a multilayer printed wiring board in which a conductor layer is formed by plating. An adhesive film for forming an insulating layer, characterized by having a resin composition layer made of the thermosetting epoxy resin composition according to any one of claims 1 to 5 on a support film. A prepreg for forming an insulating layer, characterized by impregnating a sheet-like fiber base material with the thermosetting epoxy resin composition according to any one of claims 1 to 5. An insulator for a printed wiring board, characterized by being formed of a resin composition layer of a bonding film for forming an insulating layer as claimed in claim 6 or a cured product of either a prepreg for forming an insulating layer as claimed in claim 7 . An insulator for a printed wiring board, characterized by having a patterned conductor layer circuit on an insulating layer formed of the insulator for a printed wiring board as claimed in claim 8. The insulator for a printed wiring board according to claim 8 or 9, wherein the surface roughness Ra of the insulating layer is 10 to 200 nm, Rq is 15 to 250 nm, and the peel strength between the insulating layer and the conductor layer is 0.35kgf/cm or more. A multilayer printed wiring board, which is characterized by laminating a plurality of layers such as the insulator for a printed wiring board of claim 9 or 10. A semiconductor device characterized by using the multilayer printed wiring board as claimed in claim 11.