KR102077867B1 - Thermosetting epoxy resin composition, adhesive film for forming insulating layer and multilayer printed wiring board - Google Patents

Abstract

(Problem) With a good balance of low dielectric loss tangent, it is possible to form a rough surface excellent in adhesion with the conductor layer, and to cope with further multilayering and high density of the buildup layer of the multilayer printed wiring board. An epoxy resin composition capable of forming an insulating layer is provided.
(Solution means) The active ester compound containing the said naphthalene structure when the nonvolatile component in the resin composition containing at least an epoxy resin (A) and the active ester compound (B) containing a naphthalene structure is 100 mass% ( The thermosetting epoxy resin composition whose content of B) is 0.1-30 mass%.

Description

Thermosetting epoxy resin composition, adhesive film for insulating layer formation and multilayer printed wiring board {THERMOSETTING EPOXY RESIN COMPOSITION, ADHESIVE FILM FOR FORMING INSULATING LAYER AND MULTILAYER PRINTED WIRING BOARD}

This invention is a thermosetting epoxy resin composition suitable for formation of the insulating layer which has a low dielectric constant tangent value, low roughness, and has a roughening surface which can raise a peeling strength, and its hardened | cured material. The present invention relates to a multilayer printed wiring board having a cured product layer having a roughened surface having low roughness and a high peel strength as an insulating layer.

According to the miniaturization and high performance of electronic devices, as a conductor formation method that can cope with additional multilayering and high density of the buildup layer of the multilayer printed wiring board used, the surface of the insulating layer is roughened, and the conductor is subjected to electroless plating. The additive method of forming a layer and the semiadditive method of forming a conductor layer by electroless plating and electrolytic plating are known. In these methods, the adhesion between the insulating layer surface and the plated conductor layer is mainly based on the surface of the insulating layer. It is ensured by making it the surface which has the fine unevenness | corrugation which exhibits an anchor effect by roughening process.

The anchor effect due to the irregularities formed on the surface of the insulating layer is larger as the roughness of the surface is larger, and the adhesion between the insulating layer and the plating conductor layer is higher as the roughness is larger. 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 so as to form a predetermined wiring pattern, the conductor layer enters into the recess at the portion to be removed in the surface of the insulating layer. Since the part is difficult to be removed, the etching process requires a long time, and as a result, there is a high risk of eroding even the wiring pattern portion to be left, resulting in damage or disconnection of the fine wiring. Therefore, in order to cope with miniaturization and densification of wiring, the surface state of the insulating layer is required to be a rough surface which is as fine as possible as possible and can secure sufficient adhesiveness with the thin film conductor layer formed by plating. .

The insulating layer is also required to have a low coefficient of thermal expansion so that a difference does not occur in the coefficient of thermal expansion between the conductor layer formed of the wiring pattern formed on the surface of the insulating layer. When the thermal expansion rate of an insulating layer is high, the difference with the linear thermal expansion rate of a conductor layer will become large, and it will become easy to produce a problem, such as a crack generate | occur | producing between an insulating layer and a conductor layer.

Conventionally, an "active ester compound" is known as a curing agent used in a thermosetting resin composition for forming an insulating layer of an inner layer circuit board of a multilayer printed wiring board as described above, and as such an "active ester compound", "dicyclopentadienyldi Active ester compounds containing a phenol structure ”are mainly used. However, the progress of further multilayering and densification of the buildup layer of the multilayered printed circuit board in recent years is remarkable, and many proposals have been made of epoxy resin compositions capable of forming an insulating layer that can cope with such a situation.

Patent Literature 1 provides a cured product that forms an insulating layer that exhibits low dielectric properties by using an active ester compound obtained by aryl esterifying a phenolic hydroxyl group in a phenol novolak resin as a curing agent of a thermosetting epoxy resin composition. It is described.

Although the roughness of the roughening surface which roughened the hardened | cured material surface is comparatively small in patent document 2, the said roughening surface shows high adhesiveness with respect to a plating conductor, and the epoxy resin which can form the insulating layer with a small coefficient of linear thermal expansion. As the composition, an epoxy resin composition containing (A) an epoxy resin, (B) an active ester compound, (C) a phenol resin having a triazine structure, (D) a maleimide compound, and (E) a phenoxy resin is described. have.

In addition, Patent Document 3, as a thermosetting epoxy resin composition which expresses a low dielectric constant and a low dielectric loss tangent and provides a cured product having excellent heat resistance and flame retardancy, has a polyaryleneoxy structure as a main skeleton, and has the above structure. The epoxy resin composition containing the active ester resin which has an arylcarbonyl group in the aromatic nucleus of is described.

As described above, many proposals have been made for an epoxy resin composition suitable for forming an insulating layer of an inner layer circuit board. However, it is possible to form a fine roughened surface excellent in adhesion with a conductor layer while being a low dielectric loss tangent. The demand for the epoxy resin composition which can form the insulating layer provided with the favorable balance with the characteristic which can respond to further multilayering and high density of the buildup layer of a printed wiring board is increasing further.

Patent Document 1: Japanese Patent Application Laid-Open No. 07-082348 Patent Document 2: Japanese Unexamined Patent Publication No. 2010-090238 Patent Document 3: Japanese Patent Laid-Open No. 2012-012534

The present invention provides low dielectric loss tangent, and can cope with further multilayering and high density of the build-up layer of a multilayer printed wiring board capable of forming a rough surface having fine irregularities excellent in adhesion to the conductor layer and etching property. An object of the present invention is to provide a printed wiring board having a thermosetting epoxy resin composition capable of forming an insulating layer provided with a good balance, an insulating layer formed of the cured product, and a multilayer printed wiring board constituted by the printed wiring board. It is.

The present invention also provides an insulating layer-forming adhesive film in which the resin composition layer made of the above-mentioned thermosetting epoxy resin composition is formed on a supporting film, and a prepreg for forming an insulating layer in which the thermosetting epoxy resin composition is impregnated into a sheet-like reinforcing substrate. The purpose is to provide.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining about the hardening | curing agent and compounding resins used for a thermosetting epoxy resin composition, among various resins known as a resin component mix | blended with an epoxy resin composition, "the active ester compound containing a naphthalene structure", When it mix | blends with a specific amount and resin composition, it discovers that it becomes a means which can solve the said subject, and achieves the following invention.

[1] A thermosetting epoxy resin composition containing at least an epoxy resin (A) and an active ester compound (B) containing a naphthalene structure,

The thermosetting epoxy resin composition whose content of the active ester compound (B) containing the said naphthalene structure when the non volatile component in the said thermosetting epoxy resin composition is 100 mass% is 0.1-30 mass%.

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

[3] The thermosetting epoxy resin composition according to [1] or [2], wherein the active ester compound (B) having a naphthalene structure is an active ester compound having an arylcarbonyloxy group bonded to a naphthalene nucleus of a polynaphthylene oxide structure. .

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

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

[6] The thermosetting epoxy resin composition according to any one of [1] to [5], further containing 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 on which a conductor layer is formed by plating.

[8] An adhesive film for insulating layer formation, wherein the resin composition layer made of the thermosetting epoxy resin composition according to any one of [1] to [7] is formed on a support film.

[9] A prepreg for forming an insulating layer, wherein the thermosetting epoxy resin composition according to any one of [1] to [7] is impregnated into the sheet-like fiber base material.

[10] An insulator for a printed wiring board, comprising the cured product of the resin composition layer of the adhesive film for forming an insulating layer according to [8].

[11] An insulator for a printed wiring board, comprising the cured product of the prepreg for forming an insulating layer according to [9].

[12] An insulator for a printed wiring board, wherein a conductor layer formed by patterning is formed on the insulating layer comprising the insulator for a printed wiring board according to [10] or [11].

[13] [10] to [12], wherein the surface roughness Ra of the insulating layer is 10 to 200 nm, Rq is 15 to 250 nm, and the peel strength of the insulating layer and the conductor layer is 0.35 kgf / cm or more. The insulator for printed wiring boards in any one of them.

[14] A multilayer printed wiring board, in which a plurality of insulators for a printed wiring board according to [12] or [13] are laminated.

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

The thermosetting epoxy resin composition has low dielectric loss tangent, can form a roughened surface excellent in adhesion with the conductor layer, and has good balance of properties that can cope with further multilayering and densification of the buildup layer of the multilayer printed wiring board. It is a thermosetting epoxy resin composition which can form the hardened | cured material layer used as a layer.

Moreover, even when the hardened | cured material formed by hardening | curing the said thermosetting epoxy resin composition forms fine unevenness | corrugation whose surface roughness Ra is 10-200 nm and Rq is 15-250 nm by the roughening process of the surface, Since it becomes the roughening surface excellent in adhesiveness with a conductor layer, it is especially useful as an insulation layer forming material in a multilayer printed wiring board.

Hereinafter, each of the thermosetting epoxy resin composition, the adhesive film for insulating layer formation, the prepreg for insulating layer formation, the insulator for a printed wiring board, and a multilayer printed wiring board of this invention is explained in full detail.

The thermosetting epoxy resin composition of this invention contains an epoxy resin (A) and the active ester compound (B) containing a naphthalene structure as an essential component, In addition, an inorganic filler, a thermoplastic resin, the hardening | curing agent for epoxy resins, and a hardening accelerator And the additive used for the resin composition which forms the insulating layer in a multilayer printed wiring board as needed.

<Epoxy Resin (A)>

The epoxy resin (A) used for the thermosetting epoxy resin composition of this invention is an epoxy resin normally used for the resin composition which forms the insulating layer in a multilayer printed wiring board, It can select suitably from the examples below, and can use it.

That is, as an epoxy resin (A), for example, bisphenol-A epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bisphenol AF-type epoxy resin, phenol novolak-type epoxy resin, tert- butyl- catechol type epoxy resin , Naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy Resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spirocyclic epoxy resins, cyclohexanedimethanol epoxy resins, trimethylol epoxy resins, halogenated epoxy resins, and the like. Can be.

Epoxy resin (A) may use 2 or more types together. When an epoxy resin (A) makes the non volatile component of an epoxy resin (A) 100 mass%, the aspect in which at least 50 mass% or more contains the epoxy resin which has two or more epoxy groups in 1 molecule is preferable. Moreover, the aspect in which an epoxy resin (A) has two or more epoxy groups in 1 molecule and contains a liquid aromatic epoxy resin (liquid epoxy resin) at the temperature of 20 degreeC is preferable, The said liquid epoxy resin and 1 molecule are preferable. The aspect which has three or more epoxy groups in the inside, and contains aromatic epoxy resin (solid epoxy resin) which is solid at the temperature of 20 degreeC is more preferable.

In addition, in this invention, an aromatic epoxy resin means the epoxy resin which has an aromatic ring frame | skeleton in the molecule | numerator. In addition, an epoxy equivalent (g / eq) means the molecular weight per 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, sufficient flexibility can be exhibited and a film excellent in handleability can be formed and the epoxy resin can be formed. The breaking strength of the cured product of the composition is improved, and the durability of the multilayer printed wiring board is improved.

In addition, when using a liquid epoxy resin and a solid epoxy resin together as an epoxy resin, it is preferable to make these compounding ratio (liquid epoxy resin: solid epoxy resin) into the range of 1: 0.1-1: 2 by mass ratio. By using a liquid epoxy resin within such a range, when using it in the form of an adhesive film, sufficient flexibility is obtained, handleability improves, and sufficient fluidity at the time of lamination can also be obtained. Moreover, by using a solid epoxy resin within such a range, when the adhesiveness of an epoxy resin composition is reduced and it uses in the form of an adhesive film, the degassing property at the time of vacuum lamination can be improved. Moreover, the peelability of a protective film and a support film can be made favorable at the time of vacuum lamination, and the heat resistance after hardening can also be improved.

In the epoxy resin composition of the present invention, when the nonvolatile component of the epoxy resin composition is 100% by mass, the content of the epoxy resin (A) is preferably 10 to 50% by mass, more preferably 20 to 40% by mass. %, More preferably, it is 20-35 mass%. There exists a tendency for the hardenability of an epoxy resin composition to improve by making content of an epoxy resin (A) into this range.

<Active ester compound (B) containing a naphthalene structure>

The "active ester compound (B) containing a naphthalene structure" (naphthalene type active ester compound) in the thermosetting epoxy resin composition of this invention has a function as a hardening | curing agent of an epoxy resin, and roughens a resin hardened | cured material surface. When it does, it is thought that it contributes also to the formation of the fine unevenness | corrugation which has favorable adhesiveness with a conductor layer.

The active ester compound (B) containing a naphthalene structure is not particularly limited as long as it has a naphthalene structure and an arylcarbonyloxy group, but an active ester compound having a polynaphthylene oxide structure and an arylcarbonyloxy group is preferable, and a polynap The active ester compound which the arylcarbonyloxy group couple | bonded with the naphthalene nucleus of a styrene oxide structure is more preferable. The polynaphthylene oxide structure may be a polynaphthylene oxide structure substituted with an alkyl group having 1 to 4 carbon atoms. The active ester compound as described above can be produced by a condensation reaction between a compound having a naphthalene structure having a nuclear substituted hydroxyl group and a carboxylic acid compound having a carboxyl group at the naphthalene nucleus or benzene nucleus. Such an active ester compound is a compound contained in "the active ester compound esterified by the arylcarboxylic acid, for example as a main frame | skeleton described in patent document 3".

Specifically as an active ester compound (B) containing a naphthalene structure, the compound represented by following General formula (1) is mentioned.

[In formula (1), R <_1> is a hydrogen atom or a C1-C4 alkyl group each independently, Preferably it is a hydrogen atom. R ₂ is each independently a hydrogen atom or a monovalent group represented by the following general formula (2). Each X is independently a hydrogen atom, a benzoyl group or a naphthylcarbonyl group, preferably a benzoyl 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 the above. X is the same as above. p is an integer of 1 or 2. And at least one of X in the formulas (1) and (2) is a benzoyl group or a naphthylcarbonyl group.]

In the thermosetting epoxy resin composition of this invention, when the non volatile component of a thermosetting epoxy resin composition is 100 mass%, content of the active ester compound (B) containing a naphthalene structure becomes 0.1-30 mass%. As a result, it is possible to form a roughened surface having fine unevenness which exhibits low dielectric tangent and is excellent in adhesion to the conductor layer and etching property. The range with more preferable content of the active ester compound (B) containing a naphthalene structure is 3-30 mass%, More preferably, it is 5-28 mass%.

<Inorganic filler>

By further containing an inorganic filler, the thermosetting epoxy resin composition of this invention can reduce a linear thermal expansion rate and can reduce dielectric loss tangent. Examples of the 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, and the like. Among them, silica, such as amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica, spherical silica, is preferable, and fused silica and spherical silica are more preferable in that the surface roughness of the insulating layer is reduced. , Spherical fused silica is more preferred. You may use these 1 type or in combination or 2 or more types. As an example of the commercially available spherical fused silica, "SOC2", "SOC1", etc. made by ADMATICS Co., Ltd. are mentioned.

Although the average particle diameter of an inorganic filler is not specifically limited, 5 micrometers or less are preferable, 3 micrometers or less are more preferable, and 2 micrometers or less are from a viewpoint that an insulating layer surface becomes low roughness and enables fine wiring formation. More preferably, 1 micrometer or less is still more preferable, 0.8 micrometer or less is especially preferable, 0.6 micrometer or less is especially preferable, and 0.4 micrometer or less is especially preferable. On the other hand, in the case where the resin composition is used as a resin varnish, from the viewpoint of preventing the viscosity of the varnish from rising and the handleability to be lowered, 0.01 µm or more is preferable, 0.03 µm or more is more preferable, and 0.05 µm or more Preferably, 0.07 micrometer or more is further more preferable, 0.1 micrometer or more is especially preferable. The average particle diameter of the said inorganic filler can be measured by the laser diffraction scattering method based on the Mie scattering theory. Specifically, it can measure by making a particle size distribution of an inorganic filler by volume basis with a laser diffraction scattering type particle size distribution measuring device, and making the median diameter into an average particle diameter. The measurement sample can use preferably what disperse | distributed the inorganic filler in water according to the ultrasonic wave. As a laser diffraction scattering type particle size distribution measuring apparatus, LA-950 etc. by Horiba Corporation can be used. Inorganic fillers include aminosilane coupling agents, ureidosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, vinylsilane coupling agents, styrylsilane coupling agents, and acrylates. It is preferable to surface-treat with surface treatment agents, such as a silane coupling agent, an isocyanate silane coupling agent, a sulfide silane coupling agent, an organosilazane compound, and a titanate coupling agent, and to improve the moisture resistance and dispersibility. You may use these 1 type or in combination or 2 or more types.

When mix | blending an inorganic filler, although it changes also with the characteristic calculated | required by a thermosetting epoxy resin composition, content of an inorganic filler is 30-90 mass%, when the non volatile component in a thermosetting epoxy resin composition is 100 mass%. It is preferable that it is 40-80 mass%, and it is still more preferable that it is 50-70 mass%. When there is too little content of an inorganic filler, there exists a tendency for the linear thermal expansion rate of hardened | cured material to become high, and when there is too much content, film formation becomes difficult and hardened | cured material tends to become weak when preparing an adhesive film.

<Thermoplastic>

By further containing a thermoplastic resin, the thermosetting epoxy resin composition of this invention can improve the mechanical strength of hardened | cured material, and can also improve the film forming ability at the time of using in the form of an adhesive film. Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyether sulfone resin, polyphenylene ether resin, polycarbonate resin, polyether ether Ketone resin and polyester resin are mentioned, A phenoxy resin and polyvinyl acetal resin are especially preferable. These thermoplastic resins may be used independently, respectively and may be used in combination of 2 or more type. It is preferable that it is the range of 8000-200000, and, as for the weight average molecular weight of a thermoplastic resin, it is more preferable that it is the range of 12000-100000. In addition, the weight average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). The weight average molecular weight by GPC method specifically, LC-9A / RID-6A by Shimadzu Corporation as a measuring apparatus, Shodex K-800P / K-804L by Showa Denko Co., Ltd. as a column. / K-804L can be calculated using a calibration curve of standard polystyrene by measuring at a column temperature of 40 ° C using chloroform or the like as a mobile phase.

When mix | blending a thermoplastic resin, when the non-volatile component in a thermosetting epoxy resin composition is 100 mass%, the compounding quantity has preferable 0.1-10 mass%, and its 0.5-5 mass% is more preferable. If it is in this range, the effect of film forming ability and mechanical strength improvement will be exhibited, and also the raise of melt viscosity and the roughness of the insulating layer surface after a wet roughening process can be reduced.

<Hardener for epoxy resin>

The thermosetting epoxy resin composition of this invention can also use the hardening | curing agent for general epoxy resins further. As an example of the hardening | curing agent for epoxy resins which can be used, TD2090, TD2131 [DIC Corporation, brand name], MEH-7600, MEH-7851, MEH-8000H [Meiwa Chemical Co., Ltd., brand name], NHN, CBN, GPH -65, GPH-103 [Nihon Kayaku Co., Ltd.], SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 [Shin-Nitetsu Chemical Co., Ltd.], LA7052, LA7054, LA3018, LA1356 Phenolic hardening agents, such as [DIC Corporation, a brand name], Benzoxazine type hardening agents, such as Fa, Pd [Shikoku Chemical Co., Ltd., a brand name], HFB2006M [Showa Polymer Co., Ltd., a brand name], Methylhexahydro phthalic anhydride And acid anhydride curing agents such as methylnadic acid anhydride and hydrogenated methylnadic acid anhydride, and cyanate ester curing agents such as PT30, PT60, and BA230S75 (Lonza Japan Co., Ltd.).

<Hardening accelerator>

The thermosetting epoxy resin composition of this invention can adjust hardening time and hardening temperature efficiently by containing a hardening accelerator further. As a hardening accelerator, For example, organic phosphine compounds, such as TPP, TPP-K, TPP-S, TPTP-S [Hokkyo Chemical Industry Co., Ltd., brand name], Curazole 2MZ, 2E4MZ, Cl1Z, Cl1Z-CN, Cl1Z Imidazole compounds, such as -CNS, Cl1Z-A, 2MZ-OK, 2MA-OK, and 2PHZ [Shikoku Kasei Kogyo Co., Ltd., brand name], Novaca cua [Asahi Kasei Kogyo Co., Ltd.], Fujikyua [Fuji Kasei] Amine adduct compounds, such as an industry, a brand name, 1, 8- diazabicyclo [5, 4, 0] undecene-7, 4- dimethylamino pyridine, benzyl dimethylamine, 2, 4, 6-tris Amine compounds such as (dimethylaminomethyl) phenol and 4-dimethylaminopyridine, and organometallic complexes such as cobalt, copper, zinc, iron, nickel, manganese and tin or organometallic salts. A hardening accelerator may use 2 or more types together. When mix | blending a hardening accelerator, when making the total amount of the epoxy resin contained in an epoxy resin composition into 100 mass% (nonvolatile component), it is preferable to use in 0.05-1 mass%.

The thermosetting epoxy resin composition of this invention may arbitrarily contain various resin additives other than the above-mentioned in the range in which the effect of this invention is exhibited. Examples of the resin additive include organic fillers such as silicone powder, nylon powder, fluorine powder and rubber particles, thickeners such as oruben and benton, silicone, fluorine and polymer antifoaming agents or leveling agents, imidazole series, thiazole series and tria Adhesion-imparting agents, such as a sol type and a silane coupling agent, phthalocyanine blue, phthalocyanine green, iodine green, dispersing agents, such as disazo yellow and carbon black, flame retardants, such as a metal hydroxide and a phosphorus containing compound, etc. are mentioned.

The thermosetting epoxy resin composition of this invention mixes the said components suitably, and also stirrings, such as a kneading | mixing means, such as a three roll, a ball mill, a bead mill, and a sand mill, or a super mixer, a planetary mixer, as needed. It can prepare by kneading or mixing by a means. Moreover, it can also prepare as a resin varnish by adding the organic solvent further.

In the thermosetting epoxy resin composition of the present invention, since a rough surface having a low dielectric tangent and excellent adhesion to a conductor layer can be formed, a resin composition for forming a conductor layer by plating (a conductor layer is formed by plating). It can be used suitably as a resin composition for insulating layers of the multilayer printed wiring board used, and is suitable as a resin composition for buildup layers of a multilayer printed wiring board.

Although the thermosetting epoxy resin composition of this invention is a composition suitable especially as an insulation layer formation material of a multilayer printed wiring board, it is used for the use which needs resin compositions, such as a soldering resist, an underfill material, a die bonding material, a semiconductor sealing material, a supplementary resin, and a part embedding resin. It can be used extensively. Moreover, it is although it does not specifically limit as an aspect of the resin composition of this invention, It can apply to sheet-like laminated materials, such as an adhesive film and a prepreg, and a circuit board (laminate board use, multilayer printed wiring board use, etc.). Although the resin composition of this invention can be apply | coated to a circuit board in a varnish state, and can form an insulation layer, industrially, it is generally used for formation of an insulation layer as a form of sheet-like laminated materials, such as an adhesive film and a prepreg.

<Sheet type laminated material>

(Adhesive film for insulating layer formation)

The adhesive film for insulating layer formation of this invention is characterized by the resin composition layer which consists of a thermosetting epoxy resin composition formed on the support film. The adhesive film for insulating layer formation prepares the resin varnish which melt | dissolved the resin composition in the organic solvent, the method known to a person skilled in the art, for example, apply | coats this resin varnish to a support body using a die coater, etc., and heats it, or It can manufacture by drying an organic solvent by hot air spray etc., and forming 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, acetate esters such as propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl. Carbitols, such as carbitol, Aromatic hydrocarbons, such as toluene and xylene, Amide system solvents, such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, etc. are mentioned. You may use the organic solvent in combination of 2 or more type.

Although drying conditions are not specifically limited, It drys so that content of the organic solvent to a resin composition layer may be 10 mass% or less, Preferably it is 5 mass% or less. Although it changes also with the amount of the organic solvent in a varnish, and the boiling point of an organic solvent, a resin composition layer can be formed by drying the varnish containing 30-60 mass% of organic solvents at 50-150 degreeC for 3 to 10 minutes, for example. have.

It is preferable that the thickness of the resin composition layer formed in the adhesive film for insulating layer formation shall be more than the thickness of a conductor layer. Since the thickness of the conductor layer which a circuit board has is normally 5-70 micrometers, it is preferable that a resin composition layer has a thickness of 10-100 micrometers. From a viewpoint of thinning, 15-80 micrometers is more preferable.

Examples of the support include a film of polyolefin such as polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), a film of polyester such as polyethylene naphthalate, polycarbonate film, poly Various plastic films, such as a mid film, are mentioned. Moreover, you may use metal foil, such as a release paper, copper foil, and aluminum foil. Especially, a plastic film is preferable and a polyethylene terephthalate film is more preferable from a versatility viewpoint. Surface treatments, such as a mad process and a corona treatment, may be given to the support body and the protective film mentioned later. Moreover, the mold release process may be performed with mold release agents, such as a silicone resin mold release agent, an alkyd resin mold release agent, and a fluororesin mold release agent.

Although the thickness of a support body is not specifically limited, 10-150 micrometers is preferable and 25-50 micrometers is more preferable.

The protective film based on a support body can be further laminated | stacked on the surface in which the support body of a resin composition layer is not in close contact. Although the thickness of a protective film is not specifically limited, For example, it is 1-40 micrometers. By laminating | stacking a protective film, adhesion | attachment of a dust etc. to a surface of a resin composition layer, and a damage can be prevented.

The adhesive film for insulating layer formation which has the above-mentioned structure can also be wound up and stored in roll shape.

(Prepreg for insulation layer formation)

The prepreg for insulating layer formation of this invention is characterized by the thermosetting epoxy resin composition being impregnated into the sheet-like fiber base material. That is, the thermosetting epoxy resin composition of this invention can be manufactured by impregnating a sheet-like reinforcement base material by the hot-melt method or the solvent method, and heating and semi-hardening. As a sheet-like reinforcement base material, the fiber for prepreg which consists of commonly used fibers, such as glass cloth and aramid fiber, can be used. And the structure formed on the support body is suitable for the prepreg for insulating layer formation of this invention.

In the hot-melt method, the resin composition is coated on the support body without dissolving the resin composition in an organic solvent and then laminated on the sheet-like reinforcing substrate, or the resin composition is directly coated on the sheet-like reinforcing substrate by a die coater, thereby prepreg It is a method of manufacturing. In the solvent method, the resin is dissolved in an organic solvent to prepare a resin varnish in the same manner as in the above-described method for producing an insulating film for forming an insulating layer. Impregnation is followed by drying. Moreover, the prepreg for insulating layer formation of this invention can also be prepared by thermally laminating the adhesive film for insulating layer formation on both sides of a sheet-shaped reinforcement base material under heating and pressurization conditions. A support body, a protective film, etc. can also be used similarly to the adhesive film for insulating layer formation mentioned above.

As mentioned above, the insulator for printed wiring boards which consists of hardened | cured material of the resin composition layer of the said adhesive film for insulating layer formation, and the hardened | cured material of the said prepreg for insulating layer formation is insulation for multilayer printed wiring boards. It is suitable as a layer. Moreover, it is more preferable that the patterned conductor layer (circuit) is formed on the insulating layer which consists of the said insulator for printed wiring boards. Moreover, the multilayer printed wiring board in which the insulator for printed wiring boards in which the said conductor layer (circuit) is formed is laminated | stacked is suitable.

<Multilayer printed wiring board using sheet type laminated material>

Next, an example of the method of manufacturing a multilayer printed wiring board using the sheet-like laminated material manufactured as mentioned above is demonstrated.

First, a sheet-like laminated material is laminated (laminated) on one side or both sides of a circuit board using a vacuum laminator. As a board | substrate used for a circuit board, a glass epoxy board, a metal board | substrate, a polyester board | substrate, a polyimide board | substrate, a BT resin board | substrate, a thermosetting polyphenylene ether board | substrate, etc. are mentioned, for example. In addition, a circuit board means here that the conductor layer (circuit) pattern-processed was formed in the single side | surface or both surfaces of the above board | substrates. In the multilayer printed wiring board formed by alternately stacking the conductor layer and the insulating layer, the one or both sides of the outermost layer of the multilayer printed wiring board are also used as patterned conductor layers (circuits) in the circuit board referred to herein. . Moreover, the roughening process may be previously performed to the conductor layer surface by blackening process, copper etching, etc.

In the laminate, in the case where the sheet-like laminated material has a protective film, after removing the protective film, the sheet-like laminated material and the circuit board are preheated as needed, and the sheet-like laminated material is laminated on the circuit board while pressing and heating. . In the sheet-like laminated material of this invention, the method of laminating to a circuit board under reduced pressure by the vacuum lamination method is used suitably. The conditions of the laminate are not particularly limited, but for example, the crimping temperature (lamination temperature) is preferably 70 to 140 ° C, and the crimping pressure (lamination pressure) is preferably 1 to 11 kgf / cm ² (9.8 × 10). ⁴ ~107.9 × 10 ⁴ N / m ^2), and to the compression time (the time the laminate) is preferably 5-180 seconds, it is preferred to laminate under reduced pressure to a pressure less than 20 mmHg (26.7 hPa) . In addition, the laminating method may be batch type or continuous type using a roll. Vacuum lamination can be performed using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, Nichigo Morton Co., Ltd. Vacuum Applicator, the Meiki Co., Ltd. vacuum press type laminator, Hitachi Industries, Ltd. roll type dry coater, Hitachi AIC ( Note) The vacuum laminator of manufacture etc. are mentioned.

After laminating a sheet-like laminated material on a circuit board and cooling to around room temperature, when peeling a support body, it can peel, heat-cure a resin composition, and can form a hardened | cured material, and an insulating layer can be formed on a circuit board. . Although the conditions of thermosetting may be suitably selected according to the kind, content, etc. of the resin component in a resin composition, Preferably it is 20 minutes-180 minutes at 150 degreeC-220 degreeC, More preferably, it is 30 minutes at 160 degreeC-210 degreeC It is selected in the range of-120 minutes. After forming an insulating layer, when a support body is not peeled off before hardening, you may peel here as needed.

In addition, the sheet-like lamination material may be laminated on one side or both sides of the circuit board using a vacuum press. The lamination process of heating and pressurizing under reduced pressure can be performed using a general vacuum hot press. For example, it can carry out by pressing metal plates, such as a heated SUS board, at the support body layer side. Press conditions are made into the pressure reduction conditions of 1 * 10 <^-2> MPa or less normally, Preferably it is 1 * 10 <^-3> MPa or less. Although heating and pressurization may be performed in one step, it is preferable to divide conditions into two or more steps from a viewpoint of controlling the exudation of resin. For example, the press of the first stage is set at a temperature of 70 to 150 캜, the pressure is in the range of 1 to 15 kgf / cm ² , and the press of the second stage is made a temperature of 150 to 200 캜, and the pressure is It is preferable to carry out in the range of 1-40 kgf / cm <^2> . It is preferable to perform time of each step for 30 to 120 minutes. Thus, an insulating layer can be formed on a circuit board by thermosetting a resin composition layer. Commercially available vacuum hot presses include, for example, MNPC-V-750-5-200 (manufactured by Meiki Corporation), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.

0.009 or less are preferable and, as for the dielectric tangent of an insulating layer, 0.006 or less are more preferable. The lower the dielectric loss tangent is, the better there is, and there is no particular lower limit, but it is 0.001 or more, 0.003 or more.

Subsequently, a perforation process is performed to the insulating layer formed on a circuit board, and a via hole and a through hole are formed. Although the drilling process can be performed by well-known methods, such as a drill, a laser, and a plasma, for example, combining these methods as needed, drilling by a laser, such as a carbon dioxide laser and a YAG laser, is the most common method. . When a support body is not peeled off before a punching process, it peels here.

Then, a roughening process is performed to the insulating layer surface. In the case of a dry roughening process, a plasma process etc. are mentioned, In the case of a wet roughening process, the swelling process with a swelling liquid, the roughening process with an oxidizing agent, and the neutralization process with a neutralizing liquid are mentioned in this order. A wet roughening process is preferable at the point which can remove the smear in a via hole, forming an uneven | corrugated anchor on the surface of an insulating layer. The swelling treatment by the swelling liquid is performed by immersing the insulating layer in the swelling liquid for 5 to 20 minutes (preferably 8 to 15 minutes at 55 to 70 ° C) at 50 to 80 ° C. Examples of the swelling liquid include an alkali solution, a surfactant solution, and the like, and preferably an alkaline solution. Examples of the alkali solution include sodium hydroxide solution and potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Securiganth P (Swelling Dip Securiganth P) manufactured by Atotech Japan Co., Ltd., and Swelling Dip Securiganth SBU (SBU). Can be mentioned. The roughening treatment by the oxidizing agent is performed by immersing the insulating layer in the oxidizing agent solution for 10 to 30 minutes (preferably 15 to 25 minutes at 70 to 80 ° C) at 60 to 80 ° C. Examples of the oxidizing agent include alkaline permanganate solutions in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, and nitric acid. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by weight. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as Concentrate Compact CP manufactured by Atotech Japan Co., Ltd. and Dosing Solution Securigans P. Neutralization treatment by neutralizing liquid is performed by immersing in neutralizing liquid for 3 to 10 minutes (preferably 3 to 8 minutes at 35-45 degreeC) at 30-50 degreeC. As a neutralization liquid, an acidic aqueous solution is preferable, and as a commercial item, reduction solution Securigans P of Atotech Japan Co., Ltd. product is mentioned.

The roughness of the roughened surface obtained by roughening the surface of the insulating layer is preferably 200 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less from the viewpoint of forming fine wirings. Moreover, in order to ensure the anchor effect of a roughening surface, it is preferable that it is 10 nm or more. On the other hand, Ra value is a kind of numerical value which shows surface roughness, and is called arithmetic mean roughness, and is specifically an arithmetic mean which measured the absolute value of the height which changes in a measurement area from the surface which is an average line. For example, it can obtain | require by the numerical value obtained by making the measurement range into 121 micrometer x 92 micrometers with a VSI contact mode and a 50x lens using WYKONT3300 by a Vico Instruments company.

In addition, since the root mean square roughness (Rq value) reflects the local state of the insulating layer surface, it can be confirmed that the grasp of the Rq value is a dense and smooth insulating layer surface, and the peel strength is stabilized. found. In order to make the Rq value a dense and smooth insulating layer surface, 250 nm or less is preferable, 200 nm or less is more preferable, 150 nm or less is more preferable, and 100 nm or less is still more preferable. Moreover, from a viewpoint of stabilizing peeling strength, 15 nm or more is preferable and 30 nm or more is more preferable. In addition, Rq value is a kind of numerical value which shows surface roughness, and is called a square average square root roughness, and specifically, it represents as a square average square root by measuring the absolute value of the height which changes in a measurement area from the surface which is an average line.

Subsequently, a conductor layer is formed on an insulating layer by dry plating or wet plating. As dry plating, well-known 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 having a pattern opposite to the conductor layer, and a method of forming a conductor layer only by electroless plating. As a method of subsequent pattern formation, for example, a subtractive method, a semiadditive method, and the like known to those skilled in the art can be used, and by repeating the above-described series of steps a plurality of times, a multilayer printed wiring board in which a buildup layer is laminated in multiple stages. Can be prepared.

The peel strength of the insulating layer and the conductor layer is preferably 0.35 kgf / cm or more, and more preferably 0.4 kgf / cm or more, in order to keep the insulating layer and the conductor layer in close contact. Although the upper limit of peeling strength is so good that there is no restriction | limiting in particular, 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. Since the insulation layer of the insulator for printed wiring boards of this invention has low roughness, and the peeling strength of an insulation layer and a conductor layer is high, it can be used suitably as a buildup layer of a multilayer printed wiring board.

<Semiconductor Device>

A semiconductor device can be manufactured by using the multilayer printed wiring board of this invention. That is, the semiconductor device of this invention contains the multilayer printed wiring board of this invention. A semiconductor device can be manufactured by mounting a semiconductor chip in the conduction part of the multilayer printed wiring board of this invention. A "conduction point" is a "point which transmits an electric signal in a multilayer printed wiring board", and the place may be a surface, a buried point, or any place. In addition, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method for mounting a semiconductor chip in manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding method, a flip chip mounting method, a bump press build-up layer The mounting method by (BBUL), the mounting method by an anisotropic conductive film (ACF), the mounting method by a nonelectroconductive film (NCF), etc. are mentioned.

Example

Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is not restrict | limited by these Examples. In addition, in the following description, "part" and "%" mean a "mass part" and the "mass%."

Measurement method, evaluation method

<Measurement of Peel Strength (Peel Strength) of Conductor Layer, Measurement of Arithmetic Average Roughness Ra, Square Average Square Root Roughness Rq>

(1) base treatment of laminate

Both sides of glass cloth base material epoxy resin double-sided copper clad laminated board (18 micrometers of copper foil, 60% of residual ratios, substrate thickness 0.3mm, Matsushita Electric Co., Ltd. product R5715ES) in which inner-layer circuit was formed were immersed in CZ8100 of Mech Corporation make And the roughening process of the copper foil surface was performed.

(2) Lamination of Adhesive Film

The adhesive film manufactured by each of the following Examples and each comparative example was laminated on both surfaces of the said laminated board using the batch type vacuum pressurizing laminator MVLP-500 (manufactured by Meiki Co., Ltd., brand name). Lamination was performed by depressurizing for 30 second, making atmospheric pressure 13 hPa or less, and crimping at 100 degreeC and pressure 0.74 MPa for 30 second after that.

(3) curing of the resin composition

The PET film was peeled from the laminated adhesive film, the resin composition was cured under curing conditions at 170 ° C. for 30 minutes to obtain an insulating layer.

(4) coordination treatment

Said laminated board with an insulating layer was immersed in 60 degreeC for 10 minutes in swelling dip securigans P containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd. which is swelling liquid, and then roughened As a liquid, it was immersed in Atotech Japan Co., Ltd. concentrate compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) for 20 minutes at 80 degreeC, Finally, as a neutralizing liquid, Atotech Japan It was immersed in reduction solution Securigans P of the company for 5 minutes at 40 degreeC. The laminated sheet after this roughening process was made into sample A.

(5) Conductor layer formation by semi additive method

To form a circuit on an insulating layer surface, immersing the laminate in Sample A, the electroless plating solution comprising a PdCl _2, followed by immersion in an electroless copper plating solution to the next. After heating at 150 degreeC for 30 minutes and performing an annealing process, the etching resist pattern was formed, After the pattern formation by etching, copper sulfate electroplating was performed and the conductor layer was formed in the thickness of 30 micrometers. Next, annealing treatment was performed at 180 degreeC for 60 minutes. This laminated sheet was referred to as Sample B.

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

Regarding Sample A, using a non-contact surface roughness machine (WYKONT3300, manufactured by Vico Instruments, Inc.), the Ra and Rq values were determined by numerical values obtained by setting the measurement range to 121 µm x 92 µm using a VSI contact mode and a 50x lens. Saved. And the numerical value obtained by obtaining the average value of ten points, respectively was made into the measured value.

(7) Measurement of Peel Strength (Peel Strength) of Conductor Layer

A cut line surrounding a range of 10 mm in width and 100 mm in length was placed in a portion of the conductor layer of Sample B, and one end of the single-layered conductor layer was peeled off and a grip tool (T.S.E., Autocom Type) The test machine AC-50C-SL) was hold | maintained and the load (kgf / cm) at the time of peeling 35 mm in the vertical direction at the speed | rate of 50 mm / min was measured at room temperature.

Measurement of Dielectric Junction

The adhesive film obtained by each following example and each comparative example was thermosetted at 190 degreeC for 90 minutes, the PET film was peeled off, and the sheet-like hardened | cured material was obtained. The cured product was cut into a test piece having a width of 2 mm and a length of 80 mm, using a cavity resonator perturbation dielectric constant measuring device CP521 manufactured by Kanto Application Electronics Development Co., Ltd. and a network analyzer E8362B manufactured by Agilent Technologies Co., Ltd. The dielectric tangent tantan was measured at a measurement frequency of 5.8 GHz by the cavity resonance method. The two test pieces were measured and the average value was computed.

Example 1

15 parts of liquid bisphenol A type epoxy resins (epoxy equivalent 180, "828US" of Mitsubishi Chemical Corporation) and 15 parts of biphenyl-type epoxy resins (epoxy equivalent 291, "NC3000H" of Nippon Kayaku Co., Ltd.) 15 parts of methyl ethyl ketone (hereinafter abbreviated as "MEK") and 15 parts of cyclohexanone were heated and dissolved while stirring. Here, 43 parts of naphthalene type active ester compounds ["EXB9411-65BK" of DIC Corporation make, active ester equivalent weight 272, toluene solution of 65% of solid content], hardening accelerator ["4 of Koe Chemical Industry Co., Ltd. product) -Dimethylaminopyridine "] 0.15 parts, spherical silica [average particle diameter: 0.5 micrometer, phenylaminosilane-treated" SO-C2 ", manufactured by Admateks Co., Ltd., 0.18% of carbon per unit mass] 100 parts, phenoxy 15 parts of resin (YL6954BH30, MEK solution of 30 mass% of solid content, the weight average molecular weight 40000) were mixed, it was disperse | distributed uniformly by the high speed rotary mixer, and the resin varnish was produced. Next, this resin varnish is applied onto a polyethylene terephthalate (thickness 38 mu m, hereinafter referred to as "PET") film with a die coater so that the resin thickness after drying is 40 mu m, and 80 to 120 deg. ), And dried for 6 minutes to obtain a sheet-shaped adhesive film.

Example 2

Except for changing 43 parts of the naphthalene type active ester compound ("EXB9411-65BK" made by DIC Corporation, active ester equivalent weight 272, 65% of solid content 65%) to 80 parts, it is completely the same as Example 1. The resin varnish was produced. Next, it carried out similarly to Example 1, and obtained the adhesive film.

Example 3

Except for changing 43 parts of the naphthalene type active ester compound ("EXB9411-65BK" made by DIC Corporation, active ester equivalent weight 272, 65% of solid content 65%) to 20 parts, it is completely the same as Example 1. A resin varnish was produced. Next, it carried out similarly to Example 1, and obtained the adhesive film.

Example 4

Biphenyl type epoxy resin [Epoxy equivalent 291, "NC3000H" of Nippon Kayaku Co., Ltd. product) 15 parts naphthol type epoxy resin [Epoxy equivalent 332, "ESN475V" by Shin-Nitetsu Chemical Co., Ltd.] 15 parts of 3% cyclohexanone of cyanate ester resin ("BA230S75" by Lonza company, methyl ethyl ketone solution of 75% of solid content), and hardening catalyst [zinc naphthenate mineral spirit solution (8% of metal content)] Non-dilution liquid] The resin varnish was produced like Example 3 except having added 0.03 part. Next, it carried out similarly to Example 1, and obtained the adhesive film.

Comparative Example 1

43 parts of naphthalene type active ester compound ["EXB9411-65BK" by DIC Corporation, active ester equivalent weight 272, toluene solution of 65% of solid content] 43 parts of active ester compound [HPC8000-65T by DIC Corporation] To 35 parts of active ester equivalent 223 and a toluene solution of 65% solids content, and spherical silica (average particle diameter: 0.5 µm, phenylaminosilane-treated "SO-C2", manufactured by ADMATICS Co., Ltd., per unit mass) 0.18% of carbon amount] 100 parts were changed to 90 parts, and 0.15 parts of curing accelerators ("4-dimethylaminopyridine" manufactured by Koe Chemical Co., Ltd.) were changed to 0.1 parts, except that the resin was completely the same as in Example 1. Made a varnish. Next, it carried out similarly to Example 1, and obtained the adhesive film.

Comparative Example 2

Except for changing 43 parts of naphthalene type active ester compound ("EXB9411-65BK" made by DIC Corporation, active ester equivalent weight 272, 65% of solid content 65%) to 95 parts, it is exactly the same as Example 1. The resin varnish was produced. Next, it carried out similarly to Example 1, and obtained the adhesive film.

Table 1 shows the peel strength of the conductor layer of the evaluation sample using the adhesive films prepared in Examples and Comparative Examples, the surface roughness (Ra value) and (Rq value) after the roughening treatment, and the dielectric tangent of the evaluation sample. .

As shown in Table 1, the hardened | cured material of the epoxy resin composition of the comparative example 1 which changed the active ester compound containing the naphthalene structure in the epoxy resin composition of Example 1 into the active ester compound outside the range of this invention is roughened. Although the numerical values of Ra and Rq after the treatment showed much larger values than the values of Ra and Rq of the roughened surface formed on the surface of the cured product of the epoxy resin composition of Example 1, the adhesiveness (peel strength) with the conductor layer was It is smaller than that of Example 1, and the numerical value of dielectric loss tangent is large.

In addition, since the compounding quantity of the active ester compound containing the naphthalene structure of the epoxy resin composition of the comparative example 2 increases more than the range of this invention, adhesiveness (fill strength) with a conductor layer is compared with the thing of Example 1 It is small.

As is clear from the results of the above examples and comparative examples, the epoxy resin composition of the present invention forms an insulating layer made of a cured product having a good balance of properties capable of coping with further multilayering and densification of the buildup layer of the multilayer printed wiring board. It is an epoxy resin composition which can be done.

Claims (15)

As a thermosetting epoxy resin composition containing at least an epoxy resin (A), an active ester compound (B) containing a naphthalene structure, an inorganic filler, and a phenoxy resin,
Content of the active ester compound (B) containing the said naphthalene structure when the non volatile component in the said resin composition is 100 mass% is 0.1-30 mass%,
When the nonvolatile component in the resin composition is 100% by mass, the content of the inorganic filler is 30 to 80% by mass,
When the nonvolatile component in the resin composition is 100 mass%, the content of the phenoxy resin is 0.1 to 10 mass%,
The thermosetting epoxy resin composition whose content of an epoxy resin (A) is 10-50 mass%, when the non volatile component in the said resin composition is 100 mass%. The thermosetting epoxy resin composition according to claim 1, wherein the active ester compound (B) containing the naphthalene structure is an active ester compound having a polynaphthylene oxide structure and an arylcarbonyloxy group. The thermosetting epoxy resin composition according to claim 1, wherein the active ester compound (B) having a naphthalene structure is an active ester compound having an arylcarbonyloxy group bonded to a naphthalene nucleus of a polynaphthylene oxide structure. The thermosetting epoxy resin composition according to claim 1, wherein the epoxy resin (A) contains a liquid epoxy resin. delete delete The thermosetting epoxy resin composition of Claim 1 which is a resin composition for insulating layers of a multilayer printed wiring board in which a conductor layer is formed by plating. The adhesive film for insulating layer formation in which the resin composition layer which consists of a thermosetting epoxy resin composition in any one of Claims 1-4 and 7 is formed on a support film. The prepreg for insulating layer formation in which the thermosetting epoxy resin composition in any one of Claims 1-4 and 7 is impregnated in the sheet-like fiber base material. The insulator for printed wiring boards which consists of hardened | cured material of the resin composition layer of the adhesive film for insulating layer formation of Claim 8. The insulator for printed wiring boards which consists of hardened | cured material of the prepreg for insulating layer formation of Claim 9. The insulator for printed wiring boards with which the conductor layer patterned was formed on the insulation layer which consists of the insulator for printed wiring boards of Claim 10. The insulator for a printed wiring board according to claim 12, wherein the surface roughness Ra of the insulating layer is 10 to 200 nm, Rq is 15 to 250 nm, and the peel strength of the insulating layer and the conductor layer is 0.35 kgf / cm or more. . The multilayer printed wiring board in which the insulator for printed wiring boards of Claim 12 is laminated | stacked. The semiconductor device containing the multilayer printed wiring board of Claim 14.