JP2009242559A - Epoxy resin composition and cured product of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition and a cured product of the composition highly achieving both of high heat resistance/moisture resistance and a low dielectric loss tangent. <P>SOLUTION: The epoxy resin composition comprises, as essential components, an epoxy resin (I) expressed by general formula 1 and an active ester compound (II) having a structure obtained by the reaction of a phenol resin (ii-1) having a molecular structure in which phenols are connected through an aliphatic cyclic hydrocarbon group, an aromatic dicarboxylic acid or halides thereof (ii-2) and an aromatic monohydroxy compound (ii-3). In formula 1, X<SP>1</SP>represents a benzene skeleton or a naphthalene skeleton; Ar<SP>1</SP>represents a benzene skeleton, a biphenyl skeleton or a naphthalene skeleton; each R<SP>1</SP>independently represents a hydrogen atom, a 1-2C alkyl group or a phenyl group; l represents an average of repeating units and ranges from 0.01 to 5. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an epoxy resin composition that combines heat resistance, moisture resistance, and low dielectric loss tangent of a cured product, and particularly suitable for a multilayer printed board insulating material, and a cured product thereof.

  Epoxy resin compositions containing an epoxy resin and a curing agent as an essential component exhibit excellent heat resistance and insulation in the cured product, and are widely used in electronic component applications such as semiconductors and multilayer printed boards. .

  Among these electronic component applications, in the technical field of multilayer printed circuit board insulating materials, resin components are used from the viewpoint of improving workability in the prepreg manufacturing process, or improving coating properties during manufacturing in the use of adhesive film for buildup. There is a demand for a reduction in viscosity when dissolved in an organic solvent. On the other hand, insulation materials with excellent heat resistance and low dielectric loss tangent are required due to the trend toward higher frequency and smaller size in electronic components. In particular, reinforcing substrates such as glass cloth are used for adhesive film for build-up. Since the insulating film is used without any problems, various properties such as heat resistance and low dielectric loss tangent required for the resin material itself are more advanced.

  Conventionally, as an epoxy resin material having both heat resistance and low dielectric loss tangent in the technical field of insulating materials for electronic parts, an epoxy resin such as a cresol novolac type epoxy resin has been used as a main ingredient, and isophthalic acid chloride and α A technique is known in which an ester with naphthol, a polyhydric phenol such as dicyclopentadiene-type phenol resin, an ester of isophthalic acid chloride and α-naphthol is used in combination as a curing agent for an epoxy resin (the following patent document) 1).

  However, among the esters, the ester, which is a reaction product of isophthalic acid chloride and α-naphthol, is effective in reducing the dielectric loss tangent, but has almost no solvent solubility and is difficult to be varnished. It could not be applied to multilayer printed circuit board applications. On the other hand, when the ester obtained by reacting the dicyclopentadiene type phenol resin, isophthalic acid chloride and α-naphthol is used in combination with a cresol novolac type epoxy resin as described in Patent Document 1, a cured product is obtained. In addition to being inferior in moisture resistance, the effect of reducing the dielectric loss tangent is not sufficient, and has not reached the level required in recent years. As described above, there is no known insulating material suitable for a multilayer printed board insulating material having a low solution viscosity and a high combination of high heat resistance, moisture resistance, and low dielectric loss tangent.

JP 2004-155990 A

  Therefore, the problem to be solved by the present invention is to provide an epoxy resin composition having high heat resistance, high moisture resistance, and low dielectric loss tangent, and a cured product thereof.

  As a result of intensive studies to solve the above problems, the present inventors have used an epoxy resin having a specific aralkyl structure in the molecular structure as a main agent, and phenols are knotted via an aliphatic cyclic hydrocarbon group. By using, as a curing agent for an epoxy resin, an ester compound obtained by reacting a phenol resin having a molecular structure, an aromatic dicarboxylic acid or a halide thereof, and an aromatic monohydroxy compound in a predetermined ratio. The inventors found that the heat resistance and moisture resistance are increased and the dielectric loss tangent is decreased, and the present invention has been completed.

That is, the present invention is an epoxy resin composition containing the epoxy resin (I) and the active ester compound (II) as essential components,
The epoxy resin (I) has the following structural formula (1)

（構造式（１）中、Ｘ^１はベンゼン骨格、ナフタレン骨格であり、Ａｒ^１ベンゼン骨格、ビフェニル骨格、ナフタレン骨格であり、Ｒ^１はそれぞれ独立的に水素原子、炭素数１〜２のアルキル基、又はフェニル基である。ｌは繰り返し単位の平均で０．０１〜５である。）
で表されるものであり、かつ、
前記活性エステル化合物（II）が、脂肪族環状炭化水素基を介してフェノール類が結節された分子構造を有するフェノール樹脂（ii−１）、芳香族ジカルボン酸又はそのハライド（ii−２）、及び、芳香族モノヒドロキシ化合物（ii-３）を反応させて得られる構造を有するものであることを特徴とするエポキシ樹脂組成物に関する。

(In the structural formula (1), X ¹ is a benzene skeleton or a naphthalene skeleton, an Ar ¹ benzene skeleton, a biphenyl skeleton or a naphthalene skeleton, and each R ¹ is independently a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. Or a phenyl group. L is an average of 0.01 to 5 repeating units.)
And represented by
The active ester compound (II) is a phenol resin (ii-1) having a molecular structure in which phenols are knotted via an aliphatic cyclic hydrocarbon group, an aromatic dicarboxylic acid or a halide (ii-2) thereof, and And an epoxy resin composition having a structure obtained by reacting an aromatic monohydroxy compound (ii-3).

  The present invention further relates to a cured product obtained by curing the epoxy resin.

  ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin composition and its hardened | cured material which have high heat resistance, high moisture resistance, and low dielectric loss tangent highly can be provided.

  The epoxy resin (I) used in the present invention has the following structural formula (1)

（一般式１中、Ｘ^１はベンゼン骨格、ナフタレン骨格であり、Ａｒ^１ベンゼン骨格、ビフェニル骨格、ナフタレン骨格であり、Ｒ^１はそれぞれ独立的に水素原子、炭素数１〜２のアルキル基、又はフェニル基であり、ｌは繰り返し単位の平均で０．０１〜５の範囲である）で表されるものである。本発明ではこのようなアラルキル構造をグリシジルオキシ基置換芳香族炭化水素を結節基とする分子構造を有することから硬化物において優れた難燃性と耐熱性とを発現させることができる。

(In General Formula 1, X ¹ is a benzene skeleton or a naphthalene skeleton, an Ar ¹ benzene skeleton, a biphenyl skeleton or a naphthalene skeleton, and each R ¹ is independently a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, or A phenyl group, and l is an average of repeating units in the range of 0.01 to 5. In the present invention, since such an aralkyl structure has a molecular structure having a glycidyloxy group-substituted aromatic hydrocarbon as a nodule group, excellent flame retardancy and heat resistance can be exhibited in the cured product.

  Examples of the epoxy resin (I) include the following formula Ia

（上記式Ｉ−ａ中、Ｘ^２はベンゼン骨格又はナフタレン骨格を現し、Ｒ^２は水素原子又は炭素原子数１〜４のアルキル基を表し、ｌは、繰り返し単位の平均で０．０１〜５の範囲である。）
で表されるビフェニル構造含有エポキシ樹脂、下記Ｉ−ｂ

(In the above formula Ia, X ² represents a benzene skeleton or a naphthalene skeleton, R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and l is an average of 0.01 to 5 repeating units. Range.)
The biphenyl structure-containing epoxy resin represented by the following Ib

（上記式Ｉ−ｂ中、Ｒ^３は水素原子又は炭素原子数１〜４のアルキル基を表し、ｌは、繰り返し単位の平均で０．０１〜５の範囲である。）
で表されるフェニレンジメチレン構造含有エポキシ樹脂、下記Ｉ−ｃ

(In the above formula Ib, R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and 1 is an average of 0.01 to 5 repeating units.)
A phenylenedimethylene structure-containing epoxy resin represented by the following Ic

（上記式Ｉ−ｃ中、Ｒ^４は水素原子又は炭素原子数１〜４のアルキル基を表し、ｌは、繰り返し単位の平均で０．０１〜５の範囲である。）
で表されるジビニルベンゼン型エポキシ樹脂、下記Ｉ−ｃ

(In the above formula Ic, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and l is an average of 0.01 to 5 repeating units.)
Divinylbenzene type epoxy resin represented by the following Ic

（上記式Ｉ−ｄ中、Ｒ^５は水素原子又は炭素原子数１〜４のアルキル基を表し、ｌは、繰り返し単位の平均で０．０１〜５の範囲である。）
で表されるナフタレン型エポキシ樹脂が挙げられる。

(In the above formula Id, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and l is in the range of 0.01 to 5 on the average of repeating units.)
The naphthalene type epoxy resin represented by these is mentioned.

As described above, R ^{2 to} R ⁵ in each structural formula are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, A propyl group, n-propyl group, t-butyl group is mentioned.

Among these, the epoxy resin represented by the structural formula Ia is particularly preferable from the viewpoint of excellent heat resistance of the cured product. Here, in the structural formula Ia, X ² is a benzene skeleton or a naphthalene skeleton as described above, but the following structural formula Ia-1

（上記式Ｉ−ａ−１中、Ｒ^２は水素原子又は炭素原子数１〜４のアルキル基を表し、ｌは、繰り返し単位の平均で０．０１〜５の範囲である。）
で表されるようにＸ^２のすべてがベンゼン骨格のものであってもよいし、下記構造式Ｉ−ａ−２

(In the above formula Ia-1, R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and l is in the range of 0.01 to 5 in average of repeating units.)
X ² may be all of benzene skeleton as represented by the following structural formula Ia-2

（上記式Ｉ−ａ−２中、Ｒ^２は水素原子又は炭素原子数１〜４のアルキル基を表し、ｌは、繰り返し単位の平均で０．０１〜５の範囲である。）
で表されるようにＸ^２のすべてがナフタレン骨格のものであってもよい。また、Ｘ^２としてベンゼン骨格とナフタレン骨格とが混在するものであってもよい。

(In the formula Ia-2, R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and l is in the range of 0.01 to 5 in average of repeating units.)
As shown, all of X ² may have a naphthalene skeleton. Further, X ² may be a mixture of a benzene skeleton and a naphthalene skeleton.

  In the present invention, in addition to the epoxy resin (I), other epoxy resin (I ′) may be used in combination.

  The epoxy resin (I ′) used here is, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, resorcin type epoxy resin, hydroquinone type epoxy resin, catechol type epoxy. Resin, dihydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, epoxy resin derived from divalent phenols such as tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy Resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol modified epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novo Epoxy resin derived from trivalent or higher valent phenols such as epoxy resin, naphthol-cresol co-condensed novolak epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin epoxy resin, biphenyl modified novolac epoxy resin, Examples thereof include an epoxy resin modified with an organic phosphorus compound.

  Next, as described above, the active ester compound (II) used in the present invention includes a phenol resin (ii-1) having a molecular structure in which phenols are knotted via an aliphatic cyclic hydrocarbon group, and an aromatic dicarboxylic acid. It has a structure obtained by reacting an acid or its halide (ii-2) and an aromatic monohydroxy compound (ii-3).

In the present invention, the active ester compound (II) is preferably the aromatic dicarboxylic acid or its halide (ii-) because the dielectric loss tangent of the cured product is particularly low and the viscosity when dissolved in an organic solvent is sufficiently low. 2) With respect to 1 mol of the carboxyl group or acid halide group in
0.05 to 0.75 mol of phenolic hydroxyl group in the phenol resin (ii-1),
The aromatic monohydroxy compound (ii-3) preferably has a structure obtained by reacting at a ratio of 0.25 to 0.95 mol.

  In the present invention, the ratio of the raw materials constituting the active ester compound (II) is adjusted to the above range, specifically, the phenol resin with respect to the number of functional groups of the aromatic carboxylic acid or halide (ii-2) thereof. A cured product of the active ester compound obtained by adjusting the number of functional groups in (ii-1) to be small and the amount (number of moles) of the aromatic monohydroxy compound (ii-3) to be increased. Can significantly reduce the dielectric loss tangent. Specifically, even when the active ester compound (II) is used alone as a curing agent component without being used in combination with an ester which is a reaction product of the above-described isophthalic acid chloride and α-naphthol. An excellent low dielectric loss tangent can be realized. Furthermore, the softening point of the active ester compound (II) itself is lowered, and the solution viscosity when dissolved in an organic solvent is also lowered. In addition, the heat resistance of the cured product is extremely high. In this way, it should be noted that it exhibits high heat resistance while having low viscosity.

  Here, in the phenol resin (ii-1), the molecular structure in which phenols are knotted through an aliphatic cyclic hydrocarbon group is an unsaturated aliphatic cyclic hydrocarbon containing two double bonds in one molecule. Examples include a structure obtained by polyaddition reaction of a compound and phenols. Here, examples of the phenols include substituted phenols having one or more substituted phenols, alkyl groups, alkenyl groups, allyl groups, aryl groups, aralkyl groups, halogen groups, or the like. Specific examples include cresol, xylenol, ethylphenol, isopropylphenol, butylphenol, octylphenol, nonylphenol, vinylphenol, isopropenylphenol, allylphenol, phenylphenol, benzylphenol, chlorophenol, bromophenol, naphthol, and dihydroxynaphthalene. However, it is not limited to these. Moreover, you may use these mixtures. Among these, phenol is particularly preferable from the viewpoint of excellent fluidity and curability.

  Specific examples of unsaturated alicyclic hydrocarbon compounds include dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnorborna-2-ene, α-pinene, β-pinene, and limonene. Can be mentioned. Among these, dicyclopentadiene is preferred from the viewpoint of property balance, particularly heat resistance and hygroscopicity. In addition, since dicyclopentadiene is contained in petroleum fractions, industrial dicyclopentadiene may contain other aliphatic or aromatic dienes as impurities, but heat resistance, curability, In consideration of moldability and the like, a product having a purity of 90% by mass or more of dicyclopentadiene is desirable.

  Next, the aromatic dicarboxylic acid or its halide (ii-2) is an aromatic dicarboxylic acid such as isophthalic acid, terephthalic acid, 1,4-, 2,3-, or 2,6-naphthalenedicarboxylic acid, and These acid halides include acid fluorides, acid chlorides, acid bromides, acid iodides and the like. Among these, an acid chloride of an aromatic dicarboxylic acid is preferable from the viewpoint of good reactivity, and isophthalic acid dichloride and terephthalic acid dichloride are particularly preferable, and isophthalic acid dichloride is particularly preferable.

  Next, as the aromatic monohydroxy compound (ii-3), for example, phenol; alkylphenols such as o-cresol, m-cresol, p-cresol, 3,5-xylenol; o-phenylphenol, p-phenyl Examples thereof include aralkylphenols such as phenol, 2-benzylphenol, 4-benzylphenol and 4- (α-cumyl) phenol; and naphthols such as α-naphthol and β-naphthol. Among these, α-naphthol and β-naphthol are preferable from the viewpoint of lowering the dielectric loss tangent of the cured product.

  The active ester compound (II) described above is a structure obtained by reacting a phenol resin (ii-1), an aromatic dicarboxylic acid or its halide (ii-2), and an aromatic monohydroxy compound (ii-3). In particular, the following structural formula (2)

（式中、Ｘはベンゼン環又はナフタレン環であり、ｋは０又は１を表し、ｎは繰り返し単位の平均値で０．０５〜２．５である。）
で表される構造のものがとりわけ硬化物の誘電正接が低く、かつ、有機溶剤に溶解させた際の溶液粘度が低くなる点から好ましい。
特に、上記構造式（１）においてｎの値、即ち、繰り返し単位の平均値が０．２５〜１．５の範囲にあるものが、溶液粘度が低くビルドアップ用接着フィルムへの製造が容易となる点から好ましい。また、上記構造式（１）中、ｋの値は０であることが、本発明の効果が顕著なものとなる点から好ましい。

(In the formula, X represents a benzene ring or a naphthalene ring, k represents 0 or 1, and n represents an average value of repeating units of 0.05 to 2.5.)
In particular, the structure represented by the formula is preferred because the cured product has a low dielectric loss tangent and a low solution viscosity when dissolved in an organic solvent.
In particular, in the above structural formula (1), the value of n, that is, the average value of the repeating units is in the range of 0.25 to 1.5, the solution viscosity is low, and it is easy to produce a buildup adhesive film. This is preferable. In the structural formula (1), the value of k is preferably 0 from the viewpoint that the effect of the present invention becomes remarkable.

Here, n in the structural formula (1) can be determined as follows.
[How to find n in Structural Formula (1)]
According to GPC measurement performed under the following conditions, styrene equivalent molecular weights (α1, α2, α3, α4) corresponding to n = 1, n = 2, n = 3, and n = 4, and n = 1 and n = The ratios (β1 / α1, β2 / α2, β3 / α3, β4 / α4) to the respective theoretical molecular weights (β1, β2, β3, β4) of 2, n = 3, and n = 4 were determined, and these (β1 / The average value of α1 to β4 / α4) is obtained. A value obtained by multiplying the number average molecular weight (Mn) obtained by GPC by this average value is defined as an average molecular weight. Next, the value of n is calculated using the molecular weight of the structural formula a as the average molecular weight.

(GPC measurement conditions)
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “H _XL -L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

Specifically, the method in which the phenol resin (ii-1), the aromatic dicarboxylic acid or its halide (ii-2), and the aromatic monohydroxy compound (ii-3) are reacted with each other is alkalinized. The reaction can be carried out in the presence of a catalyst.
Examples of the alkali catalyst that can be used here include sodium hydroxide, potassium hydroxide, triethylamine, and pyridine. Of these, sodium hydroxide and potassium hydroxide are particularly preferred because they can be used in the form of an aqueous solution and the productivity is good.

  Specifically, in the reaction, a phenol resin (ii-1), an aromatic dicarboxylic acid or its halide (ii-2), and an aromatic monohydroxy compound (ii-3) are mixed in the presence of an organic solvent. And a method of reacting the alkali catalyst or an aqueous solution thereof while dropping continuously or intermittently. At that time, the concentration of the aqueous solution of the alkali catalyst is preferably in the range of 3.0 to 30%. Examples of the organic solvent that can be used here include toluene and dichloromethane.

  After completion of the reaction, if an aqueous solution of an alkali catalyst is used, the reaction solution is allowed to stand for separation, the aqueous layer is removed, and the remaining organic layer is repeated until the aqueous layer after washing becomes almost neutral, The target resin can be obtained.

  Since the active ester compound (II) thus obtained is usually obtained as an organic solvent solution, when used as a laminate varnish or build-up adhesive film, it is mixed with other ingredients as it is, Furthermore, the target epoxy resin composition can be produced by appropriately adjusting the amount of the organic solvent. As described above, the present invention is characterized by low melt viscosity when the active ester compound (II) is dissolved in an organic solvent to form a resin solution. Specifically, toluene having a nonvolatile content of 65% is used. The solution viscosity in the case of using an active ester resin as a solution is 300 to 10,000 mPa · S (25 ° C.).

  In the epoxy resin composition of the present invention, in addition to the active ester compound (II) as an epoxy resin curing agent, an amine compound, an amide compound, an acid anhydride compound, a pheno-amine as long as the effects of the present invention are not impaired. Other epoxy resin curing agents (II ′) such as ruthenium compounds may be used in combination.

Examples of amine compounds that can be used here include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, and guanidine derivatives.
Examples of the amide compounds include polyamide resins synthesized from dimer of dicyandiamide and linolenic acid and ethylenediamine.

  Acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydroanhydride Examples include phthalic acid.

  Phenol compounds include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin, α-naphthol aralkyl resin, β-naphthol aralkyl resin, biphenyl aralkyl resin. , Trimethylolmethane resin, tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, aminotriazine-modified phenol resin, and the like. Specific examples of the aminotriazine-modified phenol resin include copolymers of formaldehyde and amino group-containing triazine compounds such as melamine and benzoguanamine, phenols such as phenol and cresol, and formaldehyde.

  Among these, polyhydric phenol compounds are particularly preferred because the linear expansion coefficient of the cured product is lower, and they are resistant to thermal and physical impacts and are excellent in toughness. Phenol novolac resins, cresol novolac resins, phenol aralkyl resins Α-naphthol aralkyl resin, β-naphthol aralkyl resin, biphenyl aralkyl resin, and aminotriazine-modified phenol resin are preferable.

  In the epoxy resin composition of the present invention, the compounding amount of the curing agent for epoxy resin (II ′) is such that the ratio of the epoxy group in the epoxy resin (I) to the active hydrogen in the curing agent (II ′) is as follows. In addition, the molar ratio of the former epoxy group / the latter active hydrogen is 0.05 to 0.95, and a tough cured product having a low coefficient of linear expansion and strong against thermal shock / physical impact is obtained. It is preferable because it can be obtained.

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

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

  The addition amount of the curing accelerator (III) can be appropriately adjusted depending on the target curing time, etc., but is based on the total mass of the epoxy resin component, the curing agent component and the curing accelerator (III). 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 (IV) in addition to the above-described components, depending on the intended use. 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 it is used as a build-up film, the coating property to the base material sheet is improved. The organic solvent (IV) that can be used here is, for example, an alcoholic solvent such as methanol, ethanol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether,
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, carbitols such as cellosolve, butyl carbitol, toluene And aromatic hydrocarbons such as xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.

  As described above, the active ester compound (II) used in the present invention is usually obtained as an organic solvent solution. Therefore, when the epoxy resin composition of the present invention is used as a laminate varnish or a build-up adhesive film. The organic solvent solution of the active ester compound (II) may be mixed with other ingredients as it is, and the organic solvent (IV) may be added as appropriate to adjust the amount of the organic solvent.

  The epoxy resin composition of the present invention may contain an inorganic filler, a modifier, a flame retardant, and the like as appropriate in addition to the components described above, depending on the intended use.

  Examples of the inorganic filler used here include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, and magnesium hydroxide. Among these, fused silica is particularly preferable from the viewpoint that the filling rate of the inorganic filler can be increased. Here, the fused silica can be used in either crushed or spherical shape, but in order to increase the blending amount of the fused silica and to suppress the increase in the melt viscosity of the molding material, it is preferable to mainly use the spherical one. preferable. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica.

  The desired range of the blending ratio of the inorganic filler varies depending on the application and desired characteristics. For example, when used for a semiconductor sealing material, a higher ratio is preferable in view of the linear expansion coefficient and flame retardancy, and the epoxy resin composition It is preferable that it is the range of 65-95 mass% with respect to the whole quantity, especially the range of 85-95 mass%. Moreover, when using for uses, such as an electrically conductive paste and an electrically conductive film, electroconductive fillers, such as silver powder and copper powder, can be used.

  Various types of thermosetting resins and thermoplastic resins can be used as the modifier. For example, phenoxy resin, polyamide resin, polyimide resin, polyetherimide resin, polyethersulfone resin, polyphenylene ether Examples thereof include resins, polyphenylene sulfide resins, polyester resins, polystyrene resins, and polyethylene terephthalate resins.

Examples of the flame retardant imparting agent include halogen compounds, phosphorus atom-containing compounds, nitrogen atom-containing compounds, and inorganic flame retardant compounds. Specifically, halogen compounds such as tetrabromobisphenol A type epoxy resin and brominated phenol novolak type epoxy resin, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, Phosphate esters such as tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tris (2,6 dimethylphenyl) phosphate, resorcin diphenyl phosphate, ammonium polyphosphate, Condensation of polyphosphate amide, red phosphorus, guanidine phosphate, dialkylhydroxymethylphosphonate, etc. Phosphorus atom-containing compounds such as phosphate ester compounds, nitrogen-containing compounds such as melamine, aluminum hydroxide, magnesium hydroxide, zinc borate, and inorganic flame retardant compounds such as calcium borate.
However, the epoxy resin composition of the present invention is characterized by exhibiting an excellent flame retardant effect without using a halogen-based flame retardant having a high environmental load. It is preferable to use a phosphorus atom-containing compound, a nitrogen atom-containing compound, or an inorganic flame retardant compound.

  The epoxy resin composition of the present invention can be obtained by uniformly mixing the aforementioned epoxy resin (I), the active ester compound (II), and other compounding agents blended as necessary. Under the present circumstances, as above-mentioned, according to the objective of improving workability | operativity, a use, and heat-curing conditions, you may mix | blend organic solvent (IV) suitably and may adjust a viscosity.

  The conditions for thermosetting the epoxy resin composition of the present invention are not particularly limited, and can be cured under conditions for curing a normal phenol resin. Usually, it can be performed at a temperature of 120 ° C. or higher and 200 ° C. or lower. In particular, a temperature range of 130 to 180 ° C. is preferable from the viewpoint of good moldability. Moreover, in order to obtain the friction material excellent in heat resistance, it is preferable to fire after molding.

  The epoxy resin composition of the present invention described in detail above is a resin composition for resist ink, a binder for friction material, a resin composition for copper-clad laminate, an interlayer insulating material for a build-up printed board, an adhesive film for build-up, It can be used for a resin composition for a sealing material of an electronic component, a conductive paste, a resin casting material, an adhesive, a coating material such as an insulating paint, and the like.

  Examples of the method of using the epoxy resin composition of the present invention as a resin composition for resist ink include, for example, the epoxy resin (I) and the active ester compound (II), an organic solvent (IV ′), a pigment, A method for preparing a resist ink composition by adding talc and a filler, and then applying the resist ink composition on a printed circuit board by a screen printing method is described. Examples of the organic solvent (IV ′) used here include methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, cyclohexanone, dimethylsulfoxide, dimethylformamide, dioxolane, tetrahydrofuran, propylene glycol monomethyl ether acetate, ethyl lactate Etc.

  When the epoxy resin composition of the present invention is used as a binder for friction materials, in addition to the epoxy resin (I) and the active ester compound (II), formaldehyde is generated by heating hexamethylenetetramine, paraformaldehyde, etc. In addition, a binder for a friction material can be produced by blending the curing accelerator (III) with the substance to be used. In order to adjust the friction material using such a binder for friction material, a method of adding a filler, an additive and the like to each of the above components and thermally curing, a method of impregnating each of the above components into a fiber substrate and thermosetting it Is mentioned. Fillers and additives used here are, for example, silica, barium sulfate, calcium carbonate, silicon carbide, cashew oil polymer, molybdenum disulfide, aluminum hydroxide, talc, clay, graphite, graphite, rubber particles, aluminum powder, copper Examples thereof include powder and brass powder.

  Specifically, the method for producing a resin composition for copper clad laminates from the epoxy resin composition of the present invention includes the epoxy resin (I), the active ester compound (II), an organic solvent (IV), and if necessary. Examples of the method include blending the above-described other curing agent for epoxy resin (II ′) and curing accelerator (III) into a varnish.

  Next, specific examples of the method for producing a copper clad laminate from the above resin composition for copper clad laminate include the following methods.

  The varnish obtained by the above method is impregnated into various reinforcing substrates such as paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, and the heating temperature according to the solvent type used, preferably A prepreg which is a cured product is obtained by heating at 50 to 170 ° C. Under the present circumstances, it is preferable to adjust normally the compounding ratio of the epoxy resin composition to be used and a reinforcement base material so that the resin content in a prepreg may be 20-60 mass%.

  By laminating the obtained prepreg, further stacking copper foil, and heat-pressing at 170 to 250 ° C. for 10 minutes to 3 hours under a pressure of 1 to 10 MPa, an intended copper clad laminate can be obtained. it can.

Moreover, the resin composition for copper clad laminates of the present invention is extremely useful as an interlayer insulating material for build-up printed boards.
Among the above-mentioned varnishing methods, the interlayer insulating material for such a build-up printed circuit board is, in particular, the epoxy resin (I), the active ester compound (II), the organic solvent (IV), and the others described above as necessary. The curing agent for epoxy resin (II ′), the curing accelerator (III), and the inorganic filler can be adjusted by a method of blending. Specific examples of the method for producing a build-up substrate from the interlayer insulation material for a build-up substrate thus obtained include the following methods.

  That is, the interlayer insulating material for a build-up substrate is applied to a wiring board on which a circuit is formed using a spray coating method, a curtain coating method, etc., and then cured, and then, if necessary, a predetermined through-hole portion or the like After drilling, the surface is treated with a roughening agent, and the surface is washed with hot water to form irregularities, and a metal such as copper is plated. The plating method is preferably electroless plating or electrolytic plating, and examples of the roughening agent include oxidizing agents, alkalis, and organic solvents. Such operations are sequentially repeated as desired, and a build-up substrate can be obtained by alternately building up and forming a resin insulating layer and a conductor layer having a predetermined circuit pattern. However, it is preferable to drill the through-hole portion after the outermost resin insulation layer is formed, and a wiring board on which a circuit is formed from a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil. Further, it is possible to produce a build-up substrate by forming a roughened surface and omitting the plating process by thermocompression bonding at 170 to 250 ° C.

  Further, the interlayer insulating material of the build-up printed board can be used as an adhesive film for build-up as well as the paint-like material described above. The epoxy resin composition of the present invention is particularly useful as an adhesive film for buildup because the resin component itself exhibits excellent heat resistance.

  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 using 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.

  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 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 the range of 10-150 micrometers, Preferably it is used in the range of 25-50 micrometers. Moreover, it is preferable that the thickness of a protective film is the range of 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 preferably a pressure bonding temperature (laminating temperature) of 70 to 140 ° C. and a pressure bonding pressure of preferably 1 to 11 kgf / cm 2 (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m ² ), Lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less.

  In addition, in the above-described interlayer insulation material for build-up printed circuit boards and adhesive film for build-up, active components such as capacitors and passive components such as capacitors and active components such as IC chips are obtained due to the characteristic of exhibiting excellent heat resistance in the present invention. It is particularly useful as an insulating material in a so-called electronic component built-in substrate in which is embedded in a substrate.

  Specific uses when the epoxy resin composition of the present invention is used as a resin composition for encapsulants of electronic components include semiconductor encapsulants, semiconductor tape encapsulants, potting liquid encapsulants, and underfill Examples thereof include resins and semiconductor interlayer insulating films.

  In order to prepare the epoxy resin composition of the present invention for a semiconductor sealing material, the epoxy resin (I), the active ester compound (II), other coupling agents blended as necessary, a release agent. An example is a method in which additives such as molds and inorganic fillers are premixed and then sufficiently mixed until uniform using an extruder, kneader, roll or the like. When used as a semiconductor tape-like sealant, the resin composition obtained by the above-mentioned method is heated to prepare a semi-cured sheet, which is used as a sealant tape, and then this sealant tape is used as a semiconductor. A method of placing on a chip, heating to 100 to 150 ° C., softening and molding, and completely curing at 170 to 250 ° C. can be mentioned.

  Further, when used as a potting type liquid sealant, the resin composition obtained by the above-mentioned method is dissolved in a solvent as necessary, and then applied onto a semiconductor chip or an electronic component and directly cured. That's fine.

  The method of using the epoxy resin composition of the present invention as an underfill resin is, for example, by previously applying a varnish-like epoxy resin composition on a substrate or a semiconductor element, then semi-curing it, and then heating the semiconductor element. For example, a compression flow method in which the substrate is brought into close contact and completely cured can be used.

  The method of using the epoxy resin composition of the present invention as a semiconductor interlayer insulating material includes, for example, a curing accelerator and a silane coupling agent in addition to the epoxy resin (I) and the active ester compound (II). A method of preparing the composition and applying it on a silicon substrate by spin coating or the like can be mentioned. In this case, since the cured coating film is in direct contact with the semiconductor, it is preferable that the linear expansion coefficient of the insulating material be close to the linear expansion coefficient of the semiconductor so that cracks due to the difference in linear expansion coefficient do not occur in a high temperature environment.

  Next, a method for preparing a conductive paste from the epoxy resin composition of the present invention is, for example, a method in which fine conductive particles are dispersed in the epoxy resin composition to form a composition for an anisotropic conductive film, which is liquid at room temperature. And a paste resin composition for circuit connection and an anisotropic conductive adhesive.

  The method for adjusting the epoxy resin composition of the present invention to a resin composition for an adhesive is, for example, the epoxy resin (I), the active ester compound (II), if necessary, resins, a curing accelerator, a solvent, Examples include a method of uniformly mixing an additive or the like using a mixing mixer or the like at room temperature or under heating. After applying to various base materials, the base material can be adhered by leaving it to stand at room temperature or under heating. it can.

  A method for preparing a composite material from the epoxy resin composition of the present invention is a method of preparing a varnish using an organic solvent (IV) in order to prepare the epoxy resin (I) and the active ester compound (II) to have a viscosity according to the use. After impregnating the varnish into a reinforcing base material and heating to obtain a prepreg, the fiber direction is changed little by little, and the layers are laminated so as to have pseudo-isotropic properties, and then heated. And a method of curing and molding. The heating temperature can be appropriately selected depending on the type of solvent used, but is preferably in the range of 50 to 150 ° C. Examples of the reinforcing substrate include carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. The ratio of the resin component and the reinforcing substrate is not particularly limited, but it is usually preferable to adjust the resin component in the prepreg to 20 to 60% by mass.

  Among the various uses described above, the epoxy resin composition of the present invention has a low heat resistance and dielectric loss tangent of the cured product and a low solution viscosity. It is particularly useful as a film application.

  The cured product of the present invention is obtained by molding and curing the epoxy resin composition of the present invention described in detail above, and is used as a laminate, cast product, adhesive, coating film, film, etc. depending on the application. it can. As described above, it is particularly useful as a copper clad laminate for printed circuit boards.

  In order to cure the epoxy resin composition of the present invention, it may be cured by heating under an appropriate temperature condition as appropriate depending on the compounding component, application, etc., specifically, it is cured at a temperature condition of 25 ° C. to 200 ° C. It is preferable to make it.

Hereinafter, the present invention will be described in detail by way of examples. The measurement methods for various properties are as follows.
[Softening point]
Measurement was performed in accordance with “JIS K7234”.
[How to find n in the following structural formula a]

Here, n in the structural formula (1) can be determined as follows.
[How to find n in Structural Formula a]
According to GPC measurement performed under the following conditions, styrene equivalent molecular weights (α1, α2, α3, α4) corresponding to n = 1, n = 2, n = 3, and n = 4, and n = 1 and n = The ratios (β1 / α1, β2 / α2, β3 / α3, β4 / α4) to the respective theoretical molecular weights (β1, β2, β3, β4) of 2, n = 3, and n = 4 were determined, and these (β1 / The average value of α1 to β4 / α4) is obtained. A value obtained by multiplying the number average molecular weight (Mn) obtained by GPC by this average value is defined as an average molecular weight. Next, the value of n is calculated using the molecular weight of the structural formula a as the average molecular weight.

(GPC measurement conditions)
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “H _XL -L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

Synthesis example 1
A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with 203.0 g of isophthalic acid chloride (number of moles of acid chloride group: 2.0 mol) and 1338 g of toluene, and the system was purged with nitrogen under reduced pressure. And dissolved. Next, 96.0 g (0.67 mol) of α-naphthol and 220 g of dicyclopentadiene phenol resin (the number of moles of phenolic hydroxyl group: 1.33 mol) were charged, and the inside of the system was purged with nitrogen under reduced pressure and dissolved. Thereafter, 1.12 g of tetrabutylammonium bromide was dissolved, and the inside of the system was controlled to 60 ° C. or lower while applying a nitrogen gas purge, and 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued for 1.0 hour under these conditions. After completion of the reaction, the solution was allowed to stand for separation, and the aqueous layer was removed. Further, water was added to the toluene phase in which the reaction product was dissolved, and the mixture was stirred and mixed for about 15 minutes. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water was removed by decanter dehydration to obtain an active ester resin (II-1) in a toluene solution state having a nonvolatile content of 65%. The solution viscosity of the toluene solution having a nonvolatile content of 65% by mass was 3160 mPa · S (25 ° C.). The obtained active ester resin (II-a) has the following structural formula a

においてｎが１．１０の構造を有するものであり、乾燥後の軟化点は１４０℃であった。

N had a structure of 1.10, and the softening point after drying was 140 ° C.

Synthesis example 2
A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with 203.0 g of isophthalic acid chloride (number of moles of acid chloride group: 2.0 mol) and 1317 g of toluene, and the system was purged with nitrogen under reduced pressure. And dissolved. Next, 144.0 g (1.0 mol) of α-naphthol and 165 g of dicyclopentadiene phenol resin (mole number of phenolic hydroxyl group: 1 mol) were charged, and the inside of the system was purged with nitrogen under reduced pressure and dissolved. Thereafter, 1.10 g of tetrabutylammonium bromide was dissolved, and the inside of the system was controlled to 60 ° C. or lower while applying a nitrogen gas purge, and 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued for 1.0 hour under these conditions. After completion of the reaction, the solution was allowed to stand for separation, and the aqueous layer was removed. Further, water was added to the toluene phase in which the reaction product was dissolved, and the mixture was stirred and mixed for about 15 minutes. This operation was repeated until the pH of the water tank reached 7. Thereafter, water was removed by decanter dehydration to obtain an active ester resin (II-b) in a toluene solution state having a nonvolatile content of 65% by mass. The viscosity of this resin (II-b) was 830 mPa · S (25 ° C.). The obtained active ester resin (II-b) has a structure in which n is 0.24 in the structural formula a, and the softening point after drying was 119 ° C.

Synthesis example 3
A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with 203.0 g of isophthalic acid chloride (number of moles of acid chloride group: 2.0 mol) and 1800 g of toluene, and the system was purged with nitrogen under reduced pressure. And dissolved. Next, 57.6 g (0.4 mol) of α-naphthol and 412.5 g of dicyclopentadiene phenol resin (mole number of phenolic hydroxyl group: 2.5 mol) were charged, and the inside of the system was purged with nitrogen under reduced pressure and dissolved. Thereafter, 1.10 g of tetrabutylammonium bromide was dissolved, and the inside of the system was controlled to 60 ° C. or lower while applying a nitrogen gas purge, and 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued for 1.0 hour under these conditions. After completion of the reaction, the solution was allowed to stand for separation, and the aqueous layer was removed. Further, water was added to the toluene phase in which the reaction product was dissolved, and the mixture was stirred and mixed for about 15 minutes. This operation was repeated until the pH of the water tank reached 7. Thereafter, water was removed by decanter dehydration to obtain an active ester resin (II-c) in a toluene solution state having a nonvolatile content of 65% by mass. The softening point after drying of the obtained active ester resin (II-c) was 184 ° C.

Comparative Synthesis Example 1
A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with isophthalic acid chloride (203.0 g (1.0 mol) and dimethylformamide 1254 g), and the system was purged with nitrogen under reduced pressure and dissolved. Next, 288.0 g (2.0 mol) of α-naphthol was charged, the inside of the system was purged with nitrogen under reduced pressure, and then 1.05 g of tetrabutylammonium bromide was dissolved and purged with nitrogen gas, Was added dropwise over a period of 3 hours, and stirring was continued for 1.0 hour under these conditions. Furthermore, water was added to the toluene phase in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes, and the mixture was allowed to stand for separation to remove the aqueous layer until the pH of the water tank reached 7. The operation was repeated. Then, to remove water in the decanter dehydrated to synthesize a non-volatile content of 65% dimethyl formamide solution of the active ester resin (II-d).
However, such an active ester resin (II-d) was hardly dissolved in toluene and could not be varnished by blending with an epoxy resin.

Examples 1 and 2 and Comparative Examples 1 and 2 (Adjustment of epoxy resin composition and evaluation of physical properties)
In accordance with the formulation shown in Table 1 below, an epoxy resin and an ester compound were blended, and toluene was blended and adjusted so that the nonvolatile content (NV) of each composition was finally 55% by mass.

Subsequently, it was cured under the following conditions to produce a double-sided copper-clad laminate, and various evaluations were performed. The results are shown in Table 1.
[Laminate production conditions]
Base material: 100 μm; glass cloth “WEA 2116” manufactured by Nitto Boseki Co., Ltd.
Number of plies: 6
Prepregation conditions: 160 ° C / 2 minutes
Copper foil: 18 μm; made by Nikko Metal Co., Ltd. Curing conditions: 170 ° C., 2.9 MPa for 1 hour
Thickness after molding: 0.8mm Resin content: 40%
[Oven heat resistance test]
A test piece (50 mm × 50 mm) was treated for 1 hour under the conditions of 220 ° C., 240 ° C., and 260 ° C. using a thermostatic chamber with an air circulation device. This was repeated two more times for a total of three evaluations.

[Dielectric properties]
A test piece was cut out to a size of 50 × 25 × 2 mm, and a dielectric loss tangent and a dielectric constant at a frequency of 1 GHz were obtained at 23 ° C. using an impedance analyzer 4291B (manufactured by Agilent Technologies) and a fixture.
[Water absorption rate]
Cut out a test piece to a size of 50 x 25 x 2 mm, use a pressure cooker tester, hold the test piece for 2 hours at 121 ° C, 2.1 atm, and 100% RH, and measure the weight change before and after that. did.
Water absorption (%) = (mass after test−mass before test) / mass before test × 100

[Solvent solubility]
The organic solvent solution of the curing agent used in each Example and Comparative Example was dried at 150 ° C. for 12 hours under vacuum and reduced pressure, and then the solid content obtained by dissolving the dried solid content in toluene at 25 ° C. The dissolution amount (g) of was evaluated.

なお、表１中の略号は以下の通りである。
「エポキシ樹脂Ｉ−ａ」：下記構造式

In addition, the symbol in Table 1 is as follows.
“Epoxy resin Ia”: Structural formula shown below

（式中のｌは繰り返し単位の平均を表し、１．６である）
で表されるエポキシ当量２９１ｇ／ｅｑ．、軟化点７０℃のビフェニルザイロック型エポキシ樹脂。
「エポキシ樹脂（Ｉ−ｂ）」：クレゾールノボラック型エポキシ樹脂（ＩＣＩ粘度：２３ｄＰａ・ｓ（１５０℃）、軟化点８４℃）
なお、表１中「１ｅｑ」は、エポキシ樹脂中のエポキシ基と、硬化剤中のエステル結合又はフェノール性水酸基とが当量となる割合であることを示すものであり、「ジメチルアミノピリジン 質量％／樹脂成分」とは、エポキシ樹脂と硬化剤との合計質量に対するジメチルアミノピリジンの質量基準の使用量である。

(In the formula, l represents the average of repeating units and is 1.6)
The epoxy equivalent represented by 291 g / eq. Biphenyl zylock type epoxy resin having a softening point of 70 ° C.
“Epoxy resin (Ib)”: Cresol novolac type epoxy resin (ICI viscosity: 23 dPa · s (150 ° C.), softening point 84 ° C.)
In Table 1, “1 eq” indicates that the epoxy group in the epoxy resin and the ester bond or the phenolic hydroxyl group in the curing agent are equivalent ratios, and “dimethylaminopyridine mass% / The “resin component” is the amount of dimethylaminopyridine based on the mass based on the total mass of the epoxy resin and the curing agent.

Claims (8)

An epoxy resin composition comprising an epoxy resin (I) and an active ester compound (II) as essential components,
The epoxy resin (I) has the following structural formula (1)

(In the structural formula (1), X ¹ is a benzene skeleton or a naphthalene skeleton, an Ar ¹ benzene skeleton, a biphenyl skeleton or a naphthalene skeleton, and each R ¹ is independently a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. Or a phenyl group. L is an average of 0.01 to 5 repeating units.)
And represented by
The active ester compound (II) is a phenol resin (ii-1) having a molecular structure in which phenols are knotted via an aliphatic cyclic hydrocarbon group, an aromatic dicarboxylic acid or a halide (ii-2) thereof, and An epoxy resin composition having a structure obtained by reacting an aromatic monohydroxy compound (II-3). Phenol resin (ii-1) having a molecular structure in which phenols are knotted via an aliphatic cyclic hydrocarbon group, aromatic dicarboxylic acid or its halide (ii-2), and aromatic monohydroxy compound (ii- 3)
With respect to 1 mol of the carboxyl group or acid halide group in the aromatic dicarboxylic acid or its halide (ii-2),
0.05 to 0.75 mol of phenolic hydroxyl group in the phenol resin (ii-1),
The epoxy resin composition according to claim 1, which has a structure obtained by reacting the aromatic monohydroxy compound (ii-3) at a ratio of 0.25 to 0.95 mol. The active ester compound (II) is represented by the following structural formula (2)

(In the formula, X is a benzene ring or a naphthalene ring, k represents 0 or 1, and n is an average of repeating units of 0.25 to 1.5.)
The epoxy resin composition according to claim 2, which has a structure represented by: The epoxy resin composition according to claim 1, 2, or 3, wherein the active ester compound (II) has a viscosity at 25 ° C of 300 to 10,000 mPa when a toluene solution having a nonvolatile content of 65% is used. The epoxy resin (I) has the following structural formula Ia

(In the formula, each R ′ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and 1 is an average of 0.01 to 5 repeating units.)
It is represented by these. The epoxy resin composition as described in any one of Claims 1-4. The epoxy resin composition according to any one of claims 1 to 5, further comprising a curing accelerator (III) in addition to the components (I) and (II). The epoxy resin composition according to any one of claims 1 to 6, further comprising an inorganic filler (IV) in addition to the components (I) and (II). Hardened | cured material formed by hardening the composition as described in any one of Claims 1-7.