JP2008031344A - Epoxy resin composition and its cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition which forms a cured product having a remarkably low linear expansion coefficient and being excellent in dimensional stability and durability as an insulating material for an electronic part. <P>SOLUTION: The epoxy resin composition contains, as essential ingredients, (A) a condensed polycyclic structure-containing compound having two epoxy groups in one molecule and typified by a 1,6-diglycidyloxynaphthalene-type epoxy resin and (B) a condensed polycyclic structure-containing compound having two phenolic hydroxy groups in one molecule and typified by 1,6-dihydroxynaphthalene. <P>COPYRIGHT: (C)2008,JPO&INPIT

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.

  That is, the present invention requires (A) a condensed polycyclic structure-containing compound having two epoxy groups in one molecule, and (B) a condensed polycyclic structure-containing compound having two phenolic hydroxyl groups in one molecule. It is related with the epoxy resin composition characterized by making it a component.

  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 excellent in the dimensional stability and durability of hardened | cured material as an insulating material of an electronic component.

  As described above, the epoxy resin composition used in the present invention has (A) a condensed polycyclic structure-containing compound having two epoxy groups in one molecule, and (B) two phenolic hydroxyl groups in one molecule. A condensed polycyclic structure-containing compound is an essential component.

  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 condensed polycyclic structure-containing compound (A) having two epoxy groups used in the present invention is a bifunctional epoxy having a condensed polycyclic structure such as a naphthalene ring or an anthracene ring in the molecular structure. A compound.

  Compounds having a naphthalene ring in the molecular structure include, for example, diglycidyloxynaphthalene, the following structural formula A-1

で表されるビナフチル型エポキシ樹脂、下記構造式Ａ−２

Binaphthyl type epoxy resin represented by the following structural formula A-2

で表されるビスグリシジルオキシナフチルメタン、及びポリオキシナフチレン構造を有する２官能性エポキシ化合物が挙げられる。

And a bifunctional epoxy compound having a polyoxynaphthylene structure.

  Here, as diglycidyloxynaphthalene, 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.

  Accordingly, the diglycidyloxynaphthalene has an average of 2,7-diglycidyloxynaphthalene, 1,6-diglycidyloxynaphthalene, 1,4-diglycidyloxynaphthalene, and repeating unit n of 0-2. These high molecular weight products are preferred.

Next, the bifunctional epoxy compound having a polyoxynaphthylene structure specifically includes:
The following general formula (2)

（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、ｏ及びｍはそれぞれ０〜２の整数であって、かつｏ又はｍの何れか一方は１以上である。）
で挙げられるエポキシ化合物が挙げられる。

(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 o and m each represent 0 to 2; It is an integer, and either o or m is 1 or more.)
And epoxy compounds mentioned in the above.

  Specific examples of the compound represented by the general formula (2) include those represented by the following A-3 to A-5.

  The bifunctional epoxy compound having a polyoxynaphthylene structure represented by the structure represented by A-3 to A-5 described above is obtained by, for example, reacting dihydroxynaphthalene in the presence of an acidic catalyst or a basic catalyst. It can be produced by obtaining a phenol resin and further glycidylating it.

  Examples of the dihydroxynaphthalene that can be used here include 1,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene. Among these, those having an orientation at the position adjacent to the phenolic hydroxyl group are particularly preferred in the aromatic nucleus to which the phenolic hydroxyl group is bonded, and in particular, the fluidity and flame retardancy of the epoxy resin from which 2,7-dihydroxynaphthalene can be obtained. From the point which is excellent in balance with property.

  Specific examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. And Lewis acid. Specific examples of the basic catalyst include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and phosphorus compounds such as triphenylphosphine. . Among these, it is particularly preferable to use a basic catalyst from the viewpoint of obtaining a bifunctional epoxy resin having a theoretical structure.

  Further, the amount of the basic catalyst used may be appropriately selected depending on the type of the basic catalyst and the target reaction rate. For example, in the case of using an alkali metal hydroxide as the basic catalyst, It is preferable to use it in a proportion of 0.01 to 0.5 mol, preferably 0.01 to 0.1, relative to 1 mol of the phenolic hydroxyl group of dihydroxynaphthalene.

Further, when R ² in the general formula (2) is an aralkyl group, the aralkyl group may be represented by the following general formula X

［一般式Ｘ中、Ｒ^３及びＲ^４は各々独立して、メチル基又は水素原子であり、Ａｒは、フェニレン基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたフェニレン基、ナフチレン基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたナフチレン基、ｎは繰り返し数の平均値で０．１〜４である。］
で表される構造が挙げられる。

[In General Formula X, R ³ and R ⁴ are each independently a methyl group or a hydrogen atom, and Ar is nucleus-substituted by 1 to 3 of a phenylene group or an alkyl group having 1 to 4 carbon atoms. A naphthylene group nucleus-substituted with 1 to 3 of a phenylene group, a naphthylene group, or an alkyl group having 1 to 4 carbon atoms, and n is an average number of repetitions of 0.1 to 4. ]
The structure represented by is mentioned.

  Specific examples of the compound having an aralkyl group represented by the general formula X include compounds represented by the following structural formulas A-6 and A-7.

In the above general formula (2), the compound having an aralkyl group as R ² is obtained by, for example, reacting dihydroxynaphthalene and an aralkylating agent in the presence of an acid catalyst to obtain a phenol resin, and then the obtained phenol It can be produced by reacting a resin with epihalohydrins.

  Specific examples of the aralkylating agent used herein include benzyl chloride, benzyl bromide, benzyl iodide, o-methylbenzyl chloride, m-methylbenzyl chloride, p-methylbenzyl chloride, p-ethylbenzyl chloride, p-isopropyl. Benzyl chloride, p-tert-butylbenzyl chloride, p-phenylbenzyl chloride, 5-chloromethylacenaphthylene, 2-naphthylmethyl chloride, 1-chloromethyl-2-naphthalene and their nuclear substituted isomers, α-methyl Versyl chlorides such as benzyl chloride and α, α-dimethylbenzyl chloride; benzyl methyl ether, o-methylbenzyl methyl ether, m-methylbenzyl methyl ether, p-methylbenzyl methyl ether, Benzyl alkyl ethers such as ethyl benzyl methyl ether and nucleosubstituted isomers thereof, such as benzyl ethyl ether, benzyl propyl ether, benzyl isobutyl ether, benzyl n-butyl ether, p-methylbenzyl methyl ether and nucleosubstituted isomers thereof; Alcohol, o-methylbenzyl alcohol, m-methylbenzyl alcohol, p-methylbenzyl alcohol, p-ethylbenzyl alcohol, p-isopropylbenzyl alcohol, p-tert-butylbenzyl alcohol, p-phenylbenzyl alcohol, α-naphthylcarbyl Benzyl and their nuclei substituted isomers, α-methylbenzyl alcohol, and benzyl alcohols such as α, α-dimethylbenzyl alcohol; styrene, o-methylstyrene, Aromatic vinyl compounds such as m-methylstyrene, p-methylstyrene, α-methylstyrene, β-methylstyrene and the like can be mentioned.

  Among these, benzyl chloride, benzyl bromide, and benzyl alcohol are particularly preferable from the viewpoint of good flame retardancy of the cured product.

  Next, examples of the compound having an anthracene ring include epoxy resins obtained by reacting 9,10-bis (3,5-dimethyl-4-hydroxybenzyl) anthracene with epihalohydrins.

  Among these, those having a naphthalene ring are preferable from the viewpoints of particularly good moldability to a film, a low linear expansion coefficient, and excellent moisture resistance and toughness of a cured product, and in particular, low viscosity and a linear expansion coefficient. From the low point, the diglycidyloxynaphthalene, that is, the reaction product of dihydroxynaphthalene and epihalohydrin is preferable, and the reaction product of 1,6-dihydroxynaphthalene and epihalohydrin is particularly preferable. Moreover, the bifunctional epoxy compound which has the said polyoxy naphthylene structure from the point which is high in heat resistance and is more excellent in toughness is preferable.

  In addition, 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 condensed polycyclic structure-containing compound (B) having two phenolic hydroxyl groups in one molecule used in the present invention is a bifunctional compound having a condensed polycyclic structure such as a naphthalene ring or an anthracene ring in the molecular structure. It is a phenolic hydroxyl group-containing compound.

  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 A compound in which a methyl group or an ethyl group is substituted by a nucleus, the following structural formula B-1

で表されるビナフトール化合物、下記構造式Ａ−２

A binaphthol compound represented by the following structural formula A-2

で表されるビス（ヒドロキシナフチル）メタン、並びにポリオキシナフチレン構造を有する２官能性ナフトール化合物が挙げられる。

And a bifunctional naphthol compound having a polyoxynaphthylene structure.

Here, the bifunctional naphthol compound having a polyoxynaphthylene structure specifically includes:
The following general formula (4)

（式中、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及びｍはそれぞれ０〜２の整数であって、かつｎ又はｍの何れか一方は１以上である。）
で挙げられるナフトール化合物が挙げられる。

(In the formula, each R ² independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aralkyl group, and n and m are each an integer of 0 to 2, and One of them is 1 or more.)
And the naphthol compounds mentioned above.

  Examples of the compound represented by the general formula (4) include those represented by the following B-3 to B-5.

Further, when R ² in the general formula (4) is an aralkyl group, the aralkyl group may be represented by the following general formula X

［一般式Ｘ中、Ｒ^３及びＲ^４は各々独立して、メチル基又は水素原子であり、Ａｒは、フェニレン基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたフェニレン基、ナフチレン基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたナフチレン基、ｎは繰り返し数の平均値で０．１〜４である。］
で表される構造が挙げられる。

[In General Formula X, R ³ and R ⁴ are each independently a methyl group or a hydrogen atom, and Ar is nucleus-substituted by 1 to 3 of a phenylene group or an alkyl group having 1 to 4 carbon atoms. A naphthylene group nucleus-substituted with 1 to 3 of a phenylene group, a naphthylene group, or an alkyl group having 1 to 4 carbon atoms, and n is an average number of repetitions of 0.1 to 4. ]
The structure represented by is mentioned.

  Specific examples of the compound having an aralkyl group represented by the general formula X include compounds represented by the following structural formulas A-6 and A-7.

  Next, examples of the compound having an anthracene ring include 9,10-bis (3,5-dimethyl-4-hydroxybenzyl) anthracene.

  Among these, those having a naphthalene ring are preferable from the viewpoint of excellent moldability into a film, a low linear expansion coefficient, and excellent moisture resistance and toughness of the cured product, and 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and diglycidyloxynaphthalenes typified by compounds in which the methyl group or ethyl group is substituted with a nucleus Are preferable, and 1,6-dihydroxynaphthalene is particularly preferable.

  The epoxy resin composition of the present invention uses a condensed polycyclic structure-containing compound (A) having two epoxy groups in one molecule (hereinafter simply referred to as “epoxy resin (A)”) as a main agent. And a condensed polycyclic structure-containing compound (B) having two phenolic hydroxyl groups in one molecule (hereinafter simply referred to as “curing agent (B)”) as a curing agent, By using these at a blending ratio in which the ratio of the former epoxy group / the latter phenolic hydroxyl group is 0.95 to 1.05, a cured product having an extremely low linear expansion coefficient can be obtained. 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 of the present invention comprises the epoxy resin (A) and the curing agent (B) as essential components. In addition to these components, the epoxy resin component It is preferable to use a tri- or higher functional epoxy resin (A ′) from the viewpoint 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 35 wt% or more is highly filled, the inorganic filler is prevented from being exposed on the surface of the cured product after the roughening treatment, which is preferable from the viewpoint that high plating peel strength can be obtained stably.

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. It is preferable from the point which can prevent generation | occurrence | production of a void.

  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 of the present invention may be used in combination with another curing agent for epoxy resin 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 of the present invention may further contain a curing accelerator (C) in addition to the components described above.

  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 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.

  In addition to the above-described components, the epoxy resin composition of the present invention can further use an inorganic filler (E). 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 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.

  The epoxy resin composition of the present invention is obtained by uniformly mixing the above-described components, and various kinds of adhesives, paints, semiconductor sealing materials, circuit board materials, composite materials, build-up adhesive films, and the like. Applicable to usage.

  For example, in order to prepare an epoxy resin composition for solvent-free adhesives, paints, and sealing materials, components such as a curing agent and an inorganic filler as necessary are premixed. Thereafter, the mixture can be sufficiently mixed using a stirring mixer, an extruder, a kneader, a roll or the like until uniform. In these applications, the amount of the inorganic filler (E) used is usually in a range where the filling rate is 30 to 95% by mass.

  In addition, in order to adjust the epoxy resin composition for solvent-type adhesives, paints, copper-clad laminates, build-up substrates, fiber reinforced composite materials, the epoxy resin component, curing agent component, curing accelerator of the present invention, And if needed, a flame retardant etc. can be manufactured by dissolving in organic solvents (D), such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone. 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 of the present invention thus obtained, for example, in the case of a coating application, the coating material prepared as described above is applied to a substrate, and the coating is applied at 15 to 200 ° C. The desired cured film can be obtained by leaving it for 5 minutes to 1 week in this environment.
In the case of an adhesive, the substrate may be bonded using the adhesive and then cured in the same manner as the paint. The cured encapsulant is obtained by molding the composition using a casting, transfer molding machine, injection molding machine or the like, and further heating at 80 to 200 ° C. for 2 to 10 hours. Can do.
Moreover, the hardened | cured material of the varnish composition for circuit board materials and a composite material is a laminated body, As a method of obtaining this hardened | cured material, glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber is used for the varnish for circuit boards. It can be obtained by impregnating a base material such as paper and drying by heating to obtain a prepreg, which is then subjected to hot press molding.
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.

  Among the various uses described above, particularly in the present invention, a buildup adhesive film and a laminate prepreg are particularly useful.

  The method for producing an adhesive film for buildup from the epoxy resin composition of the present invention is, for example, applied to the support film by forming the epoxy resin composition of the present invention on a support film to form a resin composition layer. The method of setting it as an adhesive film is mentioned.

  When the epoxy resin composition of the present invention is used for a build-up adhesive film, the adhesive film is softened under the lamination temperature condition (usually 70 ° C. to 140 ° C.) in the vacuum laminating method, and at the same time as laminating the circuit board, It is important to show fluidity (resin flow) capable of filling the via hole or through hole in the substrate, 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.

  Next, a method for producing a prepreg for an interlayer insulating layer of a multilayer printed wiring board by impregnating a sheet-like reinforcing substrate made of fibers with the epoxy resin composition of the present invention includes, for example, the epoxy resin composition of the present invention. There is a method in which a sheet-like reinforcing substrate made of fiber is impregnated by a hot melt method or a solvent method and semi-cured by heating. Examples of the sheet-like reinforcing substrate made of fibers that can be used here include glass cloth and aramid fibers.

  Next, a method for producing a multilayer printed wiring board using the above prepreg includes, for example, one or several prepregs of the present invention on a circuit board, and a metal plate sandwiched between release films and pressurizing / heating conditions. The method of carrying out press lamination below is mentioned. Specifically, the pressure condition is preferably 5 to 40 kgf / cm 2, and the temperature is preferably 120 to 200 ° C. for 20 to 100 minutes. Moreover, it can also be manufactured by laminating on a circuit board by a vacuum laminating method as in the case of an adhesive film, and then curing by heating. Thereafter, similar to the method described above, the surface of the prepreg cured with an oxidizing agent is roughened, and then a conductor layer is formed by plating to produce a multilayer printed wiring board.

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 (11)

(A) A condensed polycyclic structure-containing compound having two epoxy groups in one molecule and (B) a condensed polycyclic structure-containing compound having two phenolic hydroxyl groups in one molecule are essential components. An epoxy resin composition. The epoxy resin composition according to claim 1, wherein the condensed polycyclic structure-containing compound (A) having two epoxy groups in one molecule is diglycidyloxynaphthalene. The epoxy resin composition according to claim 1, wherein the condensed polycyclic structure-containing compound (A) having two epoxy groups in one molecule is a bifunctional epoxy compound having a polynaphthyleneoxy structure. The condensed polycyclic structure-containing compound (A) having two epoxy groups in one molecule is a bifunctional epoxy compound having a polynaphthyleneoxy structure in which the total number of naphthalene structures per molecule is 2 to 8. The epoxy resin composition according to claim 3. The condensed polycyclic structure-containing compound (A) having two epoxy groups in one molecule has a polynaphthyleneoxy structure as a main skeleton, and a (methyl) glycidyloxy group and Formula X

[In General Formula X, R ¹ and R ² are each independently a methyl group or a hydrogen atom, and Ar is substituted with 1 to 3 of a phenylene group or an alkyl group having 1 to 4 carbon atoms. A phenylene group, a naphthylene group, a naphthylene group nucleus-substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms, and p is an average number of repetitions of 0.1 to 4. ]
The epoxy resin composition according to claim 1, which has a molecular structure in which structural parts represented by 2. The epoxy resin composition according to claim 1, wherein the epoxy resin (A) has a melt viscosity of 0.1 to 30 dPa · s at 150 ° C. measured in accordance with “ASTM D4287”. The blending ratio of the bifunctional epoxy resin (A) having the condensed polycyclic structure and the dihydroxy compound (B) having the condensed polycyclic structure is such that the ratio of the former epoxy group / the latter phenolic hydroxyl group is 0. The epoxy resin composition according to any one of claims 1 to 6, which has a ratio of 95 to 1.05. The epoxy resin composition according to any one of claims 1 to 6, further comprising a curing accelerator (C) in addition to the components (A) and (B). The epoxy resin composition according to any one of claims 1 to 6, further comprising an inorganic filler (E) in addition to the component (A) and the component (B). A resin composition for buildup films, comprising the epoxy resin composition according to any one of claims 1 to 9. Hardened | cured material formed by hardening | curing the epoxy resin composition as described in any one of Claims 1-10.