JP5387872B2 - Epoxy resin composition and cured product thereof - Google Patents

Description

  The present invention relates to an epoxy resin composition having a very low linear expansion coefficient in a glass region of a cured product and excellent dimensional stability.

  An epoxy resin composition containing an epoxy resin and a curing agent as an essential component exhibits excellent heat resistance and insulation in the cured product, and is therefore widely used in electronic component applications such as semiconductors and printed wiring boards. .

  Among these electronic component applications, in the technical field of multilayer printed circuit board materials, in recent years, an adhesive film composed of an epoxy resin composition containing an epoxy resin and a curing agent as an essential component is used as an insulating layer of a build-up type multilayer board. The technology has attracted attention because it is extremely easy to cover the inner layer circuit pattern and fill the resin in the surface via holes and through holes, and is excellent in productivity of the multilayer substrate. However, the cured epoxy resin, which is an insulating layer constituting the film, usually has a poor coefficient of dimensional stability and cracks due to thermal shock because the coefficient of linear expansion is different from that of different materials such as copper wiring and solder. There has been a demand for an epoxy resin composition that has a problem that it is easy and has a low linear expansion coefficient of a cured product.

  Therefore, for example, as an insulating material constituting the adhesive film, an epoxy resin composition containing liquid bisphenol type epoxy resin, solid epoxy resin, epoxy resin curing agent, and inorganic filler as essential components is used, and the inorganic filling is performed. A technique is known in which a large amount of material is used to suppress the coefficient of linear expansion of the material itself (see Patent Document 1 below).

However, in recent years, there has been a demand for adhesive films having a lower coefficient of linear expansion, such as multi-layer vias being used for multilayer printed circuit boards as electronic components become more sophisticated. The cured epoxy resin itself did not reach the required level of linear expansion coefficient. Furthermore, the epoxy resin composition cannot avoid the use of a large amount of an inorganic filler, and the processability by laser at the time of forming an indispensable via hole for the build-up method and the adhesion with the plating layer are not sufficient. It was.

JP 2005-154727 A

  Therefore, the problem to be solved by the present invention is to provide an epoxy resin composition having an extremely low linear expansion coefficient of the cured epoxy resin itself and excellent in dimensional stability and durability of the cured product as an insulating material for electronic parts. There is.

  As a result of intensive studies to solve the above problems, the present inventors have used a bifunctional epoxy resin having a condensed polycyclic structure typified by a naphthalene skeleton as a main agent and a bifunctional typified by dihydroxynaphthalene. It has been found that these cured products themselves can achieve a very low linear expansion coefficient by using a phenolic hydroxyl group-containing compound containing a soluble condensed polycyclic structure as a curing agent, and the present invention has been completed.

（式中、Ｒ^１は水素原子又はメチル基を表し、Ｒ^２はそれぞれ独立的に水素原子、炭素原子数１〜４のアルキル基、又はアラルキル基を表し、ｎはそれぞれ０〜１０の整数である。）
で表されるジグリシジルオキシナフタレン化合物（Ａ）、並びに、１，４−ジヒドロキシナフタレン、１，５−ジヒドロキシナフタレン、１，６−ジヒドロキシナフタレン、２，６−ジヒドロキシナフタレン、２，７−ジヒドロキシナフタレン、及びこれらジヒドロキシナフタレンの芳香核上の水素基がメチル基又はエチル基で置換された化合物からなる群から選択される化合物（Ｂ）を必須成分とすることを特徴とするビルドアップフィルム用エポキシ樹脂組成物に関する。 That is, the present invention provides the following general formula (1)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aralkyl group, and n represents an integer of 0 to 10, respectively. is there.)
Diglycidyloxynaphthalene compound (A), and 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, And an epoxy resin composition for a build-up film comprising, as an essential component, a compound (B) selected from the group consisting of compounds in which a hydrogen group on the aromatic nucleus of dihydroxynaphthalene is substituted with a methyl group or an ethyl group Related to things.

ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin hardened | cured material itself has a remarkably low linear expansion coefficient, and can provide the epoxy resin composition for buildup films excellent in the dimensional stability and durability of hardened | cured material as an insulating material of an electronic component.

（式中、Ｒ^１は水素原子又はメチル基を表し、Ｒ^２はそれぞれ独立的に水素原子、炭素原子数１〜４のアルキル基、又はアラルキル基を表し、ｎはそれぞれ０〜１０の整数である。）
で表されるジグリシジルオキシナフタレン化合物（Ａ）、並びに、１，４−ジヒドロキシナフタレン、１，５−ジヒドロキシナフタレン、１，６−ジヒドロキシナフタレン、２，６−ジヒドロキシナフタレン、２，７−ジヒドロキシナフタレン、及びこれらジヒドロキシナフタレンの芳香核上の水素基がメチル基又はエチル基で置換された化合物からなる群から選択される化合物（Ｂ）を必須成分とするものである。 As described above, the epoxy resin composition for buildup film used in the present invention has the following general formula (1).

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aralkyl group, and n represents an integer of 0 to 10, respectively. is there.)
Diglycidyloxynaphthalene compound (A), and 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, And a compound (B) selected from the group consisting of compounds in which the hydrogen group on the aromatic nucleus of the dihydroxynaphthalene is substituted with a methyl group or an ethyl group .

  When such a bifunctional epoxy resin and a bifunctional phenolic curing agent are combined, a three-dimensionally crosslinked structure is adopted because the reaction between the epoxy group and the phenolic hydroxyl group is an addition reaction. It was thought that it was not cured because it was difficult to cure, but good curability despite the fact that the present invention is a combination of a bifunctional epoxy resin and a bifunctional phenolic curing agent. However, it is notable that the cured product exhibits the surprising performance of achieving an excellent low linear expansion coefficient.

Here, the dioxynaphthalene compound (A) used in the present invention is a bifunctional epoxy compound having a naphthalene ring in the molecular structure.

Here, as the diglycidyloxynaphthalene compound (A) , for example, the following general formula (1)

（式中、Ｒ^１は水素原子又はメチル基を表し、Ｒ^２はそれぞれ独立的に水素原子、炭素原子数１〜４のアルキル基、又はアラルキル基を表し、ｎはそれぞれ０〜１０の整数である。）で表されるものが挙げられる。

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aralkyl group, and n represents an integer of 0 to 10, respectively. There is one represented by.

  Here, the compound represented by the general formula (1) is an epoxy resin obtained by reacting dihydroxynaphthalenes with epihalohydrin and β-alkylepihalohydrin as essential monomer components. Examples of the dihydroxynaphthalene used here include 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and methyl groups thereof. Or the compound which the nucleus substituted the ethyl group is mentioned. Among these, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene and 1,4-dihydroxynaphthalene are particularly preferred from the viewpoint of the fluidity of the condensed polycyclic structure-containing compound (A).

  Moreover, in said general formula (1), n is an integer of 0-10 as above-mentioned, but the average of n is 0-2 especially from the point of condensed polycyclic structure containing compound (A) in this invention. It is preferable.

Therefore, the diglycidyloxynaphthalene compound (A) has an average of 2,7-diglycidyloxynaphthalene, 1,6-diglycidyloxynaphthalene, 1,4-diglycidyloxynaphthalene, and repeating unit n of 0 to 0. These high molecular weight compounds in 2 are preferred.

Among these, 1,6-reaction products of dihydroxynaphthalene with an epihalohydrin are preferable.

  Further, from the viewpoint of good curability, the epoxy equivalent of these epoxy resins is preferably 136 g / eq to 400 g / eq, and the hydrolyzable chlorine content is preferably 1000 ppm or less, and the resulting cured product has moisture resistance and insulation. From the viewpoint of improving the properties, the total chlorine content is preferably in the range of 2000 ppm or less.

Next, the compound (B) used in the present invention is a bifunctional phenolic hydroxy group-containing compound having a naphthalene ring in the molecular structure.

Examples of the compound having a naphthalene ring in the molecular structure include 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and these Examples include compounds in which the hydrogen group on the aromatic nucleus of dihydroxynaphthalene is substituted with a methyl group or an ethyl group .

Among these, particularly good formability of the film, and a low linear expansion coefficient, further, from the viewpoint of excellent cured product field moisture resistance and toughness, especially the 1,6-dihydroxynaphthalene are preferred.

The epoxy resin composition of the present invention, the dioxy naphthalene compounds (A) (hereinafter, abbreviated as "epoxy resin (A)".) Was used as the main agent, and said compound (B) (hereafter, referred to This is simply abbreviated as “curing agent (B)”) as a curing agent, and these are blending ratios in which the ratio of the former epoxy group / the latter phenolic hydroxyl group is 0.95 to 1.05. Can be used to obtain a cured product having a very low linear expansion coefficient. As described above, usually, when a bifunctional epoxy resin and a bifunctional phenolic curing agent are reacted, the reaction product is a cured product having a crosslinked structure simply by increasing the molecular weight in a straight line. Things cannot be obtained. On the other hand, in the present invention, a crosslinked structure is formed even if the blending ratio is close to the equivalent ratio in which the ratio of epoxy group / phenolic hydroxyl group is 0.95 to 1.05 as described above, and Since the cured product obtained has a very low linear expansion coefficient in the glass region, it has excellent dimensional stability, heat resistance and toughness.

As described above, the epoxy resin composition for a build-up film of the present invention contains the epoxy resin (A) and the curing agent (B) as essential components. In addition to these components, As the epoxy resin component, it is preferable to use a tri- or higher functional epoxy resin (A ′) from the viewpoints of excellent curability and good moisture resistance and heat resistance of the cured product. In particular, when used as an adhesive film for build-up as described above, using a trifunctional or higher functional epoxy resin improves the breaking strength of the cured product and improves the cross-linking density of the cured product, thereby providing an inorganic filler. Even if it is highly filled to 35 wt% or more , it is preferable from the viewpoint that the inorganic filler can be prevented from being exposed on the surface of the cured product after the roughening treatment, and high plating peel strength can be stably obtained.

The trifunctional or higher functional epoxy resin (A ′) used here is, for example, an epoxidized product of a condensation product of a phenol and an aromatic aldehyde having a phenolic hydroxyl group, and
The following structural formula

で表される４官能ナフタレン型エポキシ樹脂が挙げられる。

The tetrafunctional naphthalene type epoxy resin represented by these is mentioned.

  The compounding ratio of the component (A) and the component (A ′) in the epoxy resin composition of the present invention is a mass ratio of the component (A) / component (A ′) and ranges from 1 / 0.3 to 1/2. In particular, the range of 1 / 0.5 to 1/1 is to moderately suppress the tackiness of the composition particularly in the case of producing an adhesive film for build-up, and the deaeration at the time of vacuum lamination is good. This is preferable from the viewpoint of preventing generation of voids.

  Moreover, when using the said component (A ') together as an epoxy resin component, with respect to the mole number of the phenolic hydroxyl group in the said hardening | curing agent (B), the epoxy group in a component (A) and a component (A'). The ratio of the total number of moles (epoxy group / phenolic hydroxyl group) is preferably in the range of 0.95 to 1.05.

Moreover, in addition to the above-mentioned curing agent (B), the epoxy resin composition for build-up films of the present invention may be used in combination with another curing agent for epoxy resins as long as the effects of the present invention are not impaired. Examples of the curing agent that can be used here include curing agents for epoxy resins such as amine compounds, acid anhydride compounds, amide compounds, and phenol compounds. Specifically, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, polyalkylene glycol polyamine, diaminodiphenyl sulfone, isophorone diamine, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylene diamine, phthalic anhydride, triethylene anhydride Mellitic acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenol novolac resin, cresol novolac resin, aromatic Hydrocarbon formaldehyde resin modified phenolic resin, dicyclopentadiene modified phenolic resin, phenol aralkyl resin, cresol aralkyl resin, naphtho Ruaralkyl resin, biphenyl modified phenol aralkyl resin, phenol trimethylol methane resin, tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl modified phenol resin, aminotriazine modified phenol Examples thereof include polyhydric phenol compounds including resins and the like, modified products thereof, imidazoles, BF ₃ -amine complexes, guanidine derivatives, and the like.

  In order not to impair the effect of the present invention that the above-mentioned curing agent expresses an extremely low linear expansion coefficient, the above-described curing agent (B) is in a range of 70% by mass or more in all components of the curing agent. It is preferable that

The epoxy resin composition for buildup films of the present invention may further contain a curing accelerator (C) in addition to the above-described components.

  Examples of the curing accelerator (C) that can be used here include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like. Among these, imidazoles are preferable because the effect of reducing the linear expansion coefficient of the cured product becomes remarkable.

  Moreover, although the addition amount of a hardening accelerator (C) can be suitably adjusted with the target hardening time etc., with respect to the total mass of an above-described epoxy resin component, a hardening | curing agent component, and the said hardening accelerator (C). Is preferably in the range of 0.1 to 7% by mass.

The epoxy resin composition for build-up films of the present invention can further use an organic solvent (D) in addition to the above-described components depending on the application. For example, when the epoxy resin composition is used as a varnish for a laminated board, the impregnation property to the base material is improved, and when used as an adhesive film for buildup, the coating property to the base material sheet is good. Become. Examples of the organic solvent (D) that can be used here include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. , Carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.

The epoxy resin composition for buildup films of the present invention can further use an inorganic filler (E) in addition to the above-described components. Specific examples of the inorganic filler (E) include fused silica, crystalline silica, alumina, silicon nitride, and aluminum nitride. When particularly increasing the blending amount of the inorganic filler, it is preferable to use fused silica. The fused silica can be used in either a crushed shape or a spherical shape, but in order to increase the blending amount of the fused silica and to suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. Furthermore, in order to increase the compounding amount of the spherical silica, it is preferable to prepare so that the particle size distribution of the spherical silica becomes wider. Here, the amount of the inorganic filler (E) used can be appropriately selected according to the application. For example, when used for the above-described adhesive film for buildup, the amount of the inorganic filler (E) used is increased. In such a case, the linear expansion coefficient of the cured product is lowered, but the adhesion with the plating layer tends to be lowered. The epoxy resin composition of the present invention can keep the amount of the inorganic filler (E) used low because the cured product exhibits a significantly low linear expansion coefficient. From this viewpoint, the amount of the inorganic filler (E) used is preferably 20 to 80% by mass in the epoxy resin composition.

Moreover, the epoxy resin composition for buildup films of this invention can add various compounding agents, such as a flame retardant, a silane coupling agent, a mold release agent, and a pigment, as needed.

  Here, examples of the flame retardant include a halogen compound, a phosphorus atom-containing compound, a nitrogen atom-containing compound, and an inorganic flame retardant compound. Specifically, halogen compounds such as tetrabromobisphenol A type epoxy resin, phosphorus atom-containing compounds such as red phosphorus and phosphate ester compounds, nitrogen atom-containing compounds such as melamine, aluminum hydroxide, magnesium hydroxide, zinc borate, boric acid Examples include inorganic flame retardant compounds such as calcium.

Build-up film for the epoxy resin composition of the present invention is obtained by uniformly mixing the respective components described above can be applied to the application of the adhesive film for build-up.

To prepare an epoxy resin composition for a build-up substrate, the epoxy resin component, the curing agent component, the curing accelerator, and, if necessary, a flame retardant, such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. It can manufacture by dissolving in the organic solvent (D). The amount of the solvent used in this case is preferably in the range of 10 to 70% by mass in the composition varnish.

In order to cure the epoxy resin composition for a build-up film of the present invention thus obtained, for example, in the case of a paint application, the paint prepared as described above is applied to a substrate, By leaving it to stand for 5 minutes to 1 week in an environment of 15 to 200 ° C., the desired cured film can be obtained .
The product form may be tablet, varnish, paste, powder, prepreg, film or tape (with / without base material, with / without release material), and one-component or two-component system.

The method for producing an adhesive film for buildup from the epoxy resin composition for buildup film according to the present invention includes, for example, multilayer printing by applying the epoxy resin composition of the present invention on a support film to form a resin composition layer. The method of setting it as the adhesive film for wiring boards is mentioned.

When the epoxy resin composition for build-up film of the present invention is used for an adhesive film for build-up, the adhesive film is softened under the lamination temperature condition (usually 70 ° C. to 140 ° C.) in the vacuum laminating method to laminate the circuit board. At the same time, it is important to show fluidity (resin flow) capable of filling the resin in the via hole or through hole existing in the circuit board, and it is preferable to blend the above-described components so as to exhibit such characteristics. .

  Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. It is usually preferable to allow resin filling in this range. When laminating both surfaces of the circuit board, it is desirable to fill about 1/2 of the through hole.

  From this point of view, the epoxy resin composition used in the present invention is a temperature-melting point derived by measuring dynamic viscoelasticity under the conditions of a measurement start temperature of 60 ° C., a heating rate of 5 ° C./min, and a frequency of 1 Hz / deg. From the viscosity (η), the melt viscosity is 4,000 to 50,000 poise at 90 ° C., 2,000 to 21,000 poise at 100 ° C., 900 to 12,000 poise at 110 ° C., and 500 to 9 at 120 ° C. It is preferable to use a material having a viscosity of 300 to 15,000 at 130 ° C.

  By using a resin composition having such a melt viscosity characteristic, the lamination of the resin composition on the circuit board surface and the filling of the resin composition into the via hole and the through hole are simultaneously performed by vacuum lamination using a vacuum laminator. Can be done in a lump.

  Specifically, the method for producing the adhesive film described above is, after preparing the varnish-like epoxy resin composition of the present invention, coating the varnish-like composition on the surface of the support film (Y), and further It can be produced by drying the organic solvent by heating or blowing hot air to form the layer (X) of the epoxy resin composition.

  The drying conditions are preferably such that the content of the organic solvent (D) in the layer (X) is 10% by mass or less, preferably 5% by mass or less. Although the drying conditions vary depending on the amount of organic solvent in the varnish, for example, a varnish containing 30 to 60% by mass of an organic solvent can be dried at 50 to 150 ° C. for about 3 to 10 minutes.

  The thickness of the formed layer (X) is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

  In addition, the layer (X) in this invention may be protected with the protective film mentioned later. By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches.

  The above-mentioned support film and protective film are made of polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples thereof include metal foil such as pattern paper, copper foil, and aluminum foil. In addition, the support film and the protective film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.

  Although the thickness of a support film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in 25-50 micrometers. Moreover, it is preferable that the thickness of a protective film shall be 1-40 micrometers.

  The support film (Y) described above is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled after the adhesive film is heat-cured, adhesion of dust and the like in the curing process can be prevented. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance.

  Next, the method for producing a multilayer printed wiring board using the adhesive film obtained as described above is, for example, when the layer (X) is protected by a protective film, after peeling these layers ( X) is laminated on one side or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum laminating method. The laminating method may be a batch method or a continuous method using a roll. Further, the adhesive film and the circuit board may be heated (preheated) as necessary before lamination.

  The lamination conditions are such that the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., the pressure bonding pressure is preferably 1 to 11 kgf / cm 2 (9.8 × 10 4 to 107.9 × 104 N / m 2), and the air pressure is 20 mmHg (26 It is preferable to laminate under a reduced pressure of 0.7 hPa or less.

  Here, the circuit board has a conductive layer (circuit) patterned on one or both sides of a substrate such as a glass epoxy, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermosetting polyphenylene ether substrate or the like. Can be mentioned.

  After laminating the adhesive film on the circuit board in this way, when the support film (Y) is peeled off, the insulating film is formed on the circuit board by peeling and thermosetting. The conditions of heat curing are selected in the range of 20 to 180 minutes at 150 to 220 ° C, more preferably 30 to 120 minutes at 160 to 200 ° C.

  If the support film (Y) is not peeled off after the insulating layer is formed, it is peeled off here. Next, holes are formed in the insulating layer formed on the circuit board by a method such as drilling, laser, or plasma to form via holes and through holes.

  Next, the surface of the insulating layer is roughened with an oxidizing agent. Examples of the oxidizing agent include permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like.

  Next, a conductor layer is formed on the surface of the resin composition layer on which uneven anchors are formed by the roughening treatment by a method combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. After forming the conductor layer, the peel strength of the conductor layer can be further improved and stabilized by annealing at 150 to 200 ° C. for 20 to 90 minutes. In this invention, as above-mentioned, the outstanding peel strength can be expressed from the point which can suppress the usage-amount of an inorganic filler (E) low.

  Moreover, as a method of patterning the conductor layer to form a circuit, for example, a subtractive method, a semi-additive method, or the like can be used.

Examples 1-4 and Comparative Examples 1-6
The epoxy resin composition was adjusted according to the compounding ratio shown in Table 1 and Table 2 for each component shown in Table 1 and Table 2.
This epoxy resin composition was press molded at 175 ° C. for 5 hours to obtain a cured product test piece. Its heat resistance was evaluated by measuring the glass transition temperature using a dynamic viscoelasticity measuring device (DMA). Moreover, the linear expansion coefficient in a glass area | region (50 degreeC) was measured and evaluated using the thermomechanical analyzer (TMA). The moisture absorption was compared and evaluated by measuring the rate of mass change after standing at 85 ° C. and 85% RH for 300 hours. The results are shown in Tables 1-2.

表１及び表２中の各成分は、以下の通りである。
エポキシ樹脂（Ｅ−１）（1、6-ジヒドロキシナフタレン型エポキシ樹脂〔大日本インキ化学工業株式会社製「エピクロンHP-4032」エポキシ当量150g/eq.〕）
エポキシ樹脂（Ｅ−２）（ビスフェノールＡ型液状エポキシ樹脂〔大日本インキ化学工業株式会社製「EPICLON 850S」、エポキシ当量188g/eq.〕）
エポキシ樹脂（Ｅ−３）（テトラメチルビフェノール型エポキシ樹脂〔ジャパンエポキシレジン株式会社製「エピコートYX-4000H」、エポキシ当量195g/eq. 融点 105℃〕）
エポキシ樹脂（Ｅ−４）（クレゾールノボラック型エポキシ樹脂〔大日本インキ化学工業株式会社製「エピクロンN-665-EXP」、エポキシ当量203g/eq. 軟化点 68℃〕
エポキシ樹脂（Ｅ−５）（ナフタレン型４官能エポキシ樹脂〔大日本インキ化学工業株式会社製「エピクロンHP-4700」、エポキシ当量166g/eq. 軟化点 91℃〕
硬化剤（Ｈ−１）（フェノールノボラック樹脂〔大日本インキ化学工業株式会社製「フェノライトTD-2131」、軟化点80℃、水酸基当量104g/eq.〕）
ＴＰＰ（トリフェニルホスフィン（硬化促進剤））
２Ｅ４ＭＺ（２−エチル−４−メチルイミダゾール）

Each component in Table 1 and Table 2 is as follows.
Epoxy resin (E-1) (1,6-dihydroxynaphthalene type epoxy resin [Epicron HP-4032, epoxy equivalent 150 g / eq. Manufactured by Dainippon Ink & Chemicals, Inc.])
Epoxy resin (E-2) (Bisphenol A type liquid epoxy resin [Dainippon Ink Chemical Co., Ltd. “EPICLON 850S”, epoxy equivalent 188 g / eq.])
Epoxy resin (E-3) (tetramethylbiphenol type epoxy resin [Epicoat YX-4000H, manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 195 g / eq. Melting point 105 ° C.)]
Epoxy resin (E-4) (Cresol novolak type epoxy resin [Dainippon Ink Chemical Co., Ltd. “Epicron N-665-EXP”, epoxy equivalent 203 g / eq. Softening point 68 ° C.]
Epoxy resin (E-5) (Naphthalene-type tetrafunctional epoxy resin [Dainippon Ink Chemical Co., Ltd. “Epicron HP-4700”, epoxy equivalent 166 g / eq. Softening point 91 ° C.]
Curing agent (H-1) (Phenol novolac resin [Dainippon Ink Chemical Co., Ltd. “Phenolite TD-2131”, softening point 80 ° C., hydroxyl group equivalent 104 g / eq.])
TPP (Triphenylphosphine (curing accelerator))
2E4MZ (2-ethyl-4-methylimidazole)

Claims (6)

The following general formula (1)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aralkyl group, and n represents an integer of 0 to 10, respectively. is there.)
Diglycidyloxynaphthalene compound (A), and 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, And an epoxy resin composition for a build-up film comprising, as an essential component, a compound (B) selected from the group consisting of compounds in which a hydrogen group on the aromatic nucleus of dihydroxynaphthalene is substituted with a methyl group or an ethyl group object. The epoxy resin composition for buildup films according to claim 1, wherein the epoxy resin (A) has a melt viscosity at 150 ° C of 0.1 to 30 dPa · s as measured in accordance with “ASTM D4287”. The diglycidyl sulfopropyl compound (A), the mixing ratio of said compound (B), claim 1 ratio of the former epoxy groups / the latter of a phenolic hydroxyl group is a ratio to form 0.95 to 1.05 Or the epoxy resin composition for buildup films of 2. The epoxy resin composition for buildup films according to claim 1 or 2, further comprising a curing accelerator (C) in addition to the components (A) and (B). The epoxy resin composition for buildup films according to claim 1 or 2, further comprising an inorganic filler (E) in addition to the components (A) and (B). The buildup film formed by hardening | curing the epoxy resin composition for buildup films as described in any one of Claims 1-5 .