JP2009209318A - Epoxy resin composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition which imparts excellent heat resistance and flame retardancy to a cured product thereof, and a cured product thereof. <P>SOLUTION: The epoxy resin composition includes as essential components an epoxy resin (I) represented by general formula 1 (wherein R<SP>1</SP>represents a hydrogen atom or a 1-4C alkyl group; and l represents an average number of repeating units and is 0.01-5), and a phenolic resin (II) having a chemical structure (b) in which a carboxy group bonds to a triazine ring through a divalent aromatic hydrocarbon group as a partial structure in its molecular structure. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an epoxy resin composition excellent in heat resistance and flame retardancy in a cured product, and suitable for semiconductor sealing materials, printed circuit board resin compositions and build-up adhesive films.

  A curable composition mainly composed of an epoxy resin gives a cured product excellent in heat resistance, adhesion, electrical insulation, etc., so that it is a semiconductor encapsulant, a printed wiring board, an adhesive film for build-up, paint, It is suitably used for mold material applications. Among these applications, in the technical fields of electrical parts and electronic parts such as semiconductor encapsulants, printed wiring boards, build-up adhesive films, and the like, flame resistance performance is required for resin materials. In order to impart properties, halogenated flame retardants such as brominated epoxy resins and antimony compounds such as trioxide, tetraoxide, and antimony pentoxide are blended as flame retardant aids. However, in recent years, as environmental and safety efforts have accelerated, halogen-based flame retardants that are likely to generate dioxins and antimony compounds that are suspected of causing carcinogenicity tend to be avoided. There is an increasing demand for the development of new flame retardant methods with low environmental impact.

  Furthermore, there is a need for a thermosetting resin composition having a high level of heat resistance, moisture resistance, flame retardancy, low dielectric constant, low dielectric loss tangent, low thermal expansion, etc. accompanying recent technological innovation. Phenolic resins used as resin curing agents are also required to have high value-added performance such as heat resistance, moisture resistance, flame resistance, and low dielectric constant. Development is strongly required.

Therefore, conventionally, as a thermosetting system that exhibits halogen-free and excellent flame retardancy, a technique using a novolac-type phenol resin containing a triazine ring in a molecular structure as a curing agent for an epoxy resin has been proposed (for example, (See the following Patent Documents 1 and 2.)
However, these novolak type phenol resins containing a triazine ring in their molecular structure exhibit high flame retardancy in the cured product, but the phenol resin decomposes the molecular structure during combustion and generates an inert gas. Therefore, it is difficult to obtain a cured product that is inherently weak against heat and excellent in heat resistance.
In particular, in the use of the adhesive film for buildup, since a glass cloth is not used, high heat resistance is required for the resin component itself constituting the adhesive film.

Japanese Patent No. 3502042 JP 2001-226464 A

  Therefore, the problem to be solved by the present invention is to provide an epoxy resin composition that gives excellent heat resistance and flame retardancy in a cured product, and a cured product thereof.

  As a result of diligent investigations to solve the above problems, the present inventors introduced a specific aralkyl structure into the epoxy resin structure, and as a phenol resin as a curing agent, a carboxyl group-containing aromatic hydrocarbon group and an amino group. By using a condensate obtained by reacting a triazine compound simultaneously with a triazine ring with aldehydes and phenols, the resulting cured product exhibits excellent flame retardancy and also has heat resistance. At the same time, it was found that they can be combined, and the present invention has been completed.

  That is, the present invention provides the following general formula 1

（一般式１中、Ｒ^１は水素原子、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である。）
で表されるエポキシ樹脂（Ｉ）、及び、カルボキシル基が二価の芳香族炭化水素基を介してトリアジン環に結合した化学構造（ｂ）を分子構造中に部分構造として有するフェノール樹脂（II）を必須成分とすることを特徴とするエポキシ樹脂組成物に関する。

(In General Formula 1, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and l is 0.01 to 5 in average of repeating units.)
And a phenol resin (II) having a chemical structure (b) in which the carboxyl group is bonded to the triazine ring via a divalent aromatic hydrocarbon group as a partial structure in the molecular structure. It is related with the epoxy resin composition characterized by using as an essential component.

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

ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin composition which provides the heat resistance and flame retardance which were excellent in hardened | cured material, and its hardened | cured material can be provided.
For this reason, the epoxy resin composition of the present invention is particularly suitable for applications that require high flame retardancy and heat resistance, such as semiconductor sealing materials, printed wiring boards, build-up films, and IC-embedded boards.

  The epoxy resin (I) used in the epoxy resin composition of the present invention has the following general formula 1

（一般式１中、Ｒ^１は水素原子、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である。）
で表されるものである。本発明ではこのようなビフェニル骨格をエポキシ樹脂構造中に導入することにより、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。
上記各構造式におけるＲ^１は前記したとおり、それぞれ独立的に水素原子、また、炭素原子数１〜５のアルキル基であり、該アルキル基としては具体的には、メチル基、エチル基、プロピル基、ｎ−プロピル基、ｔ−ブチル基が挙げられる。
これらのなかでも特に全てのＲ^１がメチル基であるエポキシ樹脂であることが耐熱性の改善効果が顕著なものとなる点から好ましい。

(In General Formula 1, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and l is 0.01 to 5 in average of repeating units.)
It is represented by In the present invention, by introducing such a biphenyl skeleton into the epoxy resin structure, excellent flame retardancy and heat resistance can be expressed in the cured product.
As described above, R ¹ in each structural formula is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Group, n-propyl group and t-butyl group.
Among these, epoxy resins in which all R ¹ are methyl groups are particularly preferable from the viewpoint that the effect of improving heat resistance becomes remarkable.

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, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol modified epoxy resin, phenol aralkyl type epoxy resin, Biphenyl aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolak Type epoxy resin, naphthol-cresol co-condensed novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl modified novolak type epoxy resin, etc. Examples thereof include an epoxy resin modified with a compound.

  Next, the phenol resin (II) used in the present invention has a chemical structure (b) in which a carboxyl group is bonded to a triazine ring via a divalent aromatic hydrocarbon group as a partial structure in the molecular structure. . In the present invention, since the triazine skeleton is included in the molecular structure of the phenol resin (II), the cured product is decomposed when exposed to a high temperature environment near 300 ° C. that generally causes combustion, and the inert nitrogen gas Is released to form an inert gas layer on the surface of the molded product, thereby exhibiting excellent flame retardancy. On the other hand, when the phenol resin (II) is cured, the carboxyl group in the resin is bonded to the epoxy resin (I), thereby preventing the triazine skeleton from being excessively decomposed in a high temperature environment. As a result, the phenol resin (II) having the carboxyl group-containing triazine skeleton (A) in the molecular structure is a material having a good balance between heat resistance and flame retardancy.

  Here, the chemical structure (A) present in the phenol resin (II) in which the carboxyl group is bonded to the triazine ring via the divalent aromatic hydrocarbon group is such that the carboxyl group and the triazine ring are divalent. This is a partial chemical structure having a structure bonded through an aromatic hydrocarbon group. Here, examples of the divalent aromatic hydrocarbon group include a phenylene group, a naphthylene group, a biphenylene group, and a structure in which an alkyl group having 1 to 4 carbon atoms is bonded to these aromatic nuclei. Specifically, the chemical structure (A) is preferably represented by the following structural formula (1) in the present invention because the effect of improving the heat resistance of the cured product becomes remarkable.

ここで、Ｒは、水素原子；メチル基、エチル基、プロピル基、ｉ−プロピル基、ｔ−ブチル基等の炭素原子数１〜４の脂肪族炭化水素基；フェニル基、ナフチル基、ビフェニル基等の芳香族炭化水素基、臭素原子、又は塩素原子を表す。また、破線部は他の分子構造との結合手を表し、ｎ及びｍは１〜４の整数を表す。

Here, R is a hydrogen atom; an aliphatic hydrocarbon group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, i-propyl group, t-butyl group; phenyl group, naphthyl group, biphenyl group Represents an aromatic hydrocarbon group such as, a bromine atom, or a chlorine atom. Moreover, a broken-line part represents the bond with another molecular structure, and n and m represent the integer of 1-4.

  Among these structural formulas (1), a triazine structure having a benzoic acid structure represented by the following structural formula is particularly preferred because of its excellent effect of improving heat resistance.

  Specifically, the phenol resin (II) having the carboxyl group-containing triazine skeleton (A) in the molecular structure specifically includes phenols (x1), a carboxyl group-containing aromatic hydrocarbon group, and an amino group on the triazine ring. A molecular structure obtained by reacting the triazine compound (x2) having a substituent with the aldehyde (x3) is preferable from the viewpoint of improving the curability and flame retardancy of the cured product.

  The phenols (x1) used here are, for example, phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-isopropylphenol, m-propylphenol. , P-propylphenol, p-sec-butylphenol, p-tert-butylphenol, p-cyclohexylphenol, p-chlorophenol, o-bromophenol, m-bromophenol, phenols such as p-bromophenol, α-naphthol Monohydric phenols such as naphthols such as β-naphthol, xylenols such as 2,4-xylenol, 2,5-xylenol and 2,6-xylenol; resorcin, catechol, hydroquinone, 2,2-bis (4 '-Hydroxyfe Nyl) propane, 1,1′-bis (dihydroxyphenyl) methane, 1,1′-bis (dihydroxynaphthyl) methane, tetramethylbiphenol, biphenol, hexamethylbiphenol, 1,2-dihydroxynaphthalene, 1,3-dihydroxy Naphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene And dihydric phenols such as naphthalenediols such as 2,7-dihydroxynaphthalene; and trihydric phenols such as trishydroxyphenylmethane.

  Among these, phenol, o-cresol, m-cresol, naphthols, 2,2-bis (4′-hydroxyphenyl) propane, 2,6-xylenol, resorcin, hydroquinone, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene are preferred from the viewpoint of easy industrial production and excellent curability to obtain a phenol resin (II), and phenol and o-cresol are particularly preferred.

  The triazine compound (x2) having a carboxyl group-containing aromatic hydrocarbon group and an amino group as a substituent on the triazine ring is, for example, carboxyl naphthyl-1,3,5-triazine-2,4-diamine; carboxyl biphenyl-1 , 3,5-triazine-2,4-diamine; other structural formula (2)

（式中、Ｒは、水素原子、脂肪族炭化水素基、芳香族炭化水素基、ハロゲン原子のいずれかを表し、ｎ及びｍは１〜５の整数を表す）
で表わされる化合物が挙げられる。

(In the formula, R represents a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a halogen atom, and n and m represent an integer of 1 to 5)
The compound represented by these is mentioned.

  Among these, the compound represented by the structural formula (2) is particularly preferable from the viewpoint that the effect of improving the heat resistance of the cured product becomes remarkable.

Examples of the aldehydes (x3) include formaldehyde, paraformaldehyde,
Aliphatic aldehydes such as acetaldehyde and crotonaldehyde; aromatic aldehydes such as benzaldehyde, 4-methylbenzaldehyde, 3,4-dimethylbenzaldehyde, biphenylaldehyde, naphthylaldehyde, salicylaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2- Hydroxy-4-methylbenzaldehyde, 2-hydroxy-3,4-dimethylbenzaldehyde, 4-hydroxybiphenylaldehyde, 2-hydroxy-1-naphthaldehyde, 5-hydroxy-1-naphthaldehyde, 6-hydroxy-1-naphthaldehyde And hydroxyl group-substituted aromatic aldehydes such as 7-hydroxy-2-naphthaldehyde. Among these, formaldehyde, paraformaldehyde, benzaldehyde, and salicylaldehyde are particularly preferable, and formaldehyde and paraformaldehyde are particularly preferable from the viewpoints of industrial supply stability, heat resistance, flame retardancy, and dielectric properties of the obtained cured product.

  The above-mentioned phenol resin (II) includes phenols (x1), a compound (x2) having a carboxyl group, an amino group, and a triazine skeleton, and aldehydes (x3), in addition to the compound (x2). The compound may have a structure obtained by reacting the compound (x4) having an amino group-containing triazine skeleton. By using this compound (x4), it becomes easy to adjust the balance between flame retardancy and heat resistance of the cured product.

  The compound (x4) having a triazine ring is not particularly limited, but the following structural formula (3)

(In the formula, R ² , R ³ and R ⁴ are an amino group, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a hydroxy group, a hydroxyalkyl group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms. An alkoxy group having 1 to 6 carbon atoms, an alkyloxycarbonyl group having 1 to 6 carbon atoms, an acid group, a vinyl group, a cyano group, or a halogen atom)
The compound represented by these is mentioned.

The compound represented by the structural formula (3) specifically includes melamine, guanamine derivatives such as acetoguanamine and benzoguanamine, cyanuric acid, or cyanuric acid such as methyl cyanurate, ethyl cyanurate, acetyl cyanurate, and cyanuric chloride. Derivatives and the like. Among these, guanamine derivatives such as melamine, acetoguanamine, and benzoguanamine in which any two or three of R ² , R ³ , and R ⁴ are amino groups are more preferable because they are easily available industrially. .

The phenol resin (II) used in the present invention is obtained by reacting the components (x1) to (x3) or the components (x1) to (x4). Specifically, For example,
In the molecular structure of the phenol novolac resin, the following structure a or structure b

を有するものが挙げられる。なお、ここでＲ及びｎは前記構造式（１）におけるものと同義であり、Ｘは前記フェノールノボラック樹脂中の芳香核を表す。また、該フェノール樹脂（II）の分子構造中には、下記構造ｃに示すようにトリアジン構造が複数連結した構造を有していてもよい。

The thing which has is mentioned. Here, R and n are synonymous with those in the structural formula (1), and X represents an aromatic nucleus in the phenol novolac resin. Further, the molecular structure of the phenol resin (II) may have a structure in which a plurality of triazine structures are linked as shown in the following structure c.

ここで、構造ｃ中、Ｒ、ｎ、Ｘは前記構造ａ又は構造ｂにおけるものと同義であり、ｐは１〜５の整数である。

Here, in the structure c, R, n, and X are synonymous with those in the structure a or the structure b, and p is an integer of 1 to 5.

  Moreover, in this invention, it is preferable that the content rate of the remaining unreacted phenols (x1) is 3 mass% or less in the said phenol resin (II). When the content rate of unreacted phenol (x1) is 3 mass% or less, it becomes what was excellent in the heat resistance of the hardened | cured material obtained by hardening this, and moisture resistance.

  Next, the method for producing the phenol resin (II) by reacting the components (x1) to (x3) or the components (x1) to (x4) described above is specifically phenols. A method of reacting (x1), compound (x2), aldehydes (x3) and, if necessary, the compound (x4) in the absence of a catalyst or in the presence of a catalyst may be mentioned. At this time, the pH of the system is preferably in the range of 3.0 to 9.0. The reaction order of each raw material is not particularly limited, and the compound (x2) may be added after the phenols (x1) and aldehydes (x3) are reacted first, and if necessary, the compound (x4) may be added. The aldehydes (x3), the compound (x2), and the compound (x4), if necessary, may be reacted with the phenols (x1). Alternatively, all the raw materials may be added and reacted at the same time.

  At this time, the molar ratio of the aldehydes (x3) to the phenols (x1) is not particularly limited, but preferably the aldehydes (x3) / phenols (x1) = 0.1 to 1.1 (moles). Ratio), and more preferably 0.2 to 0.8 as the ratio.

  The molar ratio of the compound (x2) to the phenol (x1) is such that the reaction system is uniform and the reaction product is uniform, and the crosslink density of the resulting cured product is appropriate, and the cured product properties It is preferable that it is the range used as compound (x2) / phenol (x1) = 0.05-1.50 (molar ratio), and especially compound (x2) / phenol (x1) = 0. It is preferable that it is 05-0.50 (molar ratio).

  When using the compound (x4), the molar ratio of the compound (x2) and the total amount of the compound (x4) to the phenols (x1) is such that the reaction system is uniform and the reaction product is uniform. In addition, the crosslinking density of the obtained cured product is appropriate, and the total amount of the compound (x2) and the compound (x4) / phenols (x1) = 0.05 to be excellent in the balance between flame retardancy and heat resistance. The ratio is preferably 1.50 (molar ratio), particularly preferably in the range of 0.05 to 0.50 as the ratio, and compound (x2) / compound (x4) = 0.05 to 9 It is preferable that the range be 0.000 (molar ratio). Further, in the balance of physical properties, when importance is attached to heat resistance, it is preferably in the range of compound (x2) / compound (x4) = 0.5 to 7.0 (molar ratio). In the case where emphasis is placed on solubility, the range is preferably in the range of compound (x2) / compound (x4) = 0.1 to 3.0 (molar ratio). Therefore, the range of (x2) / compound (x4) = 0.5 to 3.0 where these ranges overlap is particularly preferred from the viewpoint of obtaining a phenol resin (II) having a good balance between heat resistance and solvent solubility. .

  When a catalyst is used, examples of the basic catalyst include hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide and barium hydroxide, and oxides thereof, ammonia, 1 to Tertiary amines, hexamethylenetetramine, sodium carbonate and the like can be mentioned. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, sulfonic acid and phosphoric acid, organic acids such as oxalic acid and acetic acid, Lewis acids, and zinc acetate. And divalent metal salts. Here, when the epoxy resin composition of the present invention is used as a resin for electrical and electronic materials, it is preferable that inorganic substances such as metals do not remain as catalyst residues. As an acidic catalyst, it is preferable to use an organic acid. From such a viewpoint, in the present invention, it is particularly preferable to carry out the above reaction without a catalyst.

  The above reaction may be performed in the presence of various solvents from the viewpoint of reaction control. If necessary, impurities such as salts may be removed by neutralization and washing with water, but impurities may not be removed when no catalyst is used or amines are used in the catalyst.

  After completion of the reaction, condensed water, unreacted aldehydes (x3), phenols (x1), solvent and the like are removed according to a conventional method such as atmospheric distillation or vacuum distillation. At this time, in order to obtain a phenol resin (II) substantially free of methylol groups, it is preferable to perform a heat treatment at 120 ° C. or higher. Further, if the temperature is 120 ° C. or higher, the methylol group can be extinguished by taking a sufficient time, but it is preferable to perform heat treatment at a higher temperature, preferably 150 ° C. or higher, for efficient elimination. At this time, it is preferable to distill together with heating according to a conventional method for obtaining a novolac resin at a high temperature.

  The phenol resin (II) thus obtained is particularly preferably a phenol resin having an ICI melt viscosity at 150 ° C. of 100 poise or less from the viewpoint of excellent balance between flame retardancy and heat resistance. In the molecular structure, the following structural formula (1)

（式中、Ｒは、水素原子、炭素原子数１〜４の脂肪族炭化水素基、芳香族炭化水素基、臭素原子、又は塩素原子を表し、破線部は他の分子構造との結合手を表し、ｎ及びｍは１〜４の整数を表す。）
で表される構造部位を有し、かつ、１５０℃でのＩＣＩ溶融粘度が１００ポイズ以下であるフェノール樹脂であることが特に好ましい。

(In the formula, R represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, an aromatic hydrocarbon group, a bromine atom, or a chlorine atom, and a broken line part represents a bond with another molecular structure. And n and m represent an integer of 1 to 4.)
And a phenol resin having an ICI melt viscosity at 150 ° C. of 100 poise or less.

  Moreover, it is preferable that the said phenol resin (II) contains a nitrogen atom in the molecular structure in the ratio used as 2-13 mass%. That is, as described above, since the triazine skeleton contained in the resin contributes to the flame retardant effect efficiently without waste, the phenol resin (II) exhibits an excellent flame retardant effect even if the amount of nitrogen atoms is reduced. To do. Therefore, it is noteworthy that an excellent flame retardant effect is exhibited even if the amount of nitrogen atoms is significantly reduced as compared with the amount of nitrogen atoms of about 20% by mass as in the case of a conventional ATN resin. As described above, the amount of nitrogen atoms in the phenolic resin (II) can be reduced. As a result, the phenolic resin (II) has a low melt viscosity and the fluidity at the time of melting is greatly improved. Workability is drastically improved by lowering the viscosity. In addition, content of the nitrogen atom in phenol resin (II) can be calculated | required by calculating from the total preparation mass of a raw material component, the preparation mass of a compound (x2) and a compound (x4), and the mass of a nitrogen atom. .

  The phenol resin (II) preferably further has a molecular weight distribution (Mw / Mn) in the range of 2 to 5. That is, when Mw / Mn is 2 or more, the solvent solubility is good, whereas when Mw / Mn is 5 or less, the flame retardancy is good.

  In addition, the amount of carboxyl groups in the phenolic resin (II) is adjusted to an appropriate range so that the phenolic resin (II) has mutually contradictory performances of heat resistance and flame retardancy. Specifically, it is preferable that the carboxyl group content is in a range that satisfies the condition of carboxyl group equivalent of 500 to 1500 g / equivalent. In addition, content of the carboxyl group in phenol resin (II) can be calculated | required by calculating from the total preparation mass of a raw material component, the preparation mass of a compound (x2), and the mass of a carboxyl group.

In the epoxy resin composition of the present invention, a maleimide compound or hexamine may be used in combination as a component for curing the phenol resin (II). As such maleimide compounds,
Aliphatic bismaleimide having a structure in which two maleimides are knotted by an alkylene group, polyoxyalkylene group, aromatic bismaleimide having a structure in which two maleimides are knotted by a phenylene group or a biphenylene group, aromatic nucleus of phenol novolac resin And a polyfunctional maleimide compound in which a maleimide group is bonded via an alkyl group.

  The blending ratio of the epoxy resin (I) and the phenol resin (II) is the molar ratio of the epoxy group in the epoxy resin (I) to the phenolic hydroxyl group in the phenol resin (II) (epoxy group). / Phenolic hydroxyl group) is preferably from 0.8 to 1.2 in terms of curability and heat resistance of the cured product.

  The epoxy resin composition of the present invention essentially comprises the epoxy resin (I) and the phenol resin (II). Further, depending on the use and required characteristics, a phenol novolac resin, a cresol novolac resin, Aromatic hydrocarbon formaldehyde resin-modified phenol resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl modified phenol resin, phenol trimethylol methane resin, tetraphenolol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin , Naphthol-cresol co-condensed novolak resin, biphenyl modified phenolic resin, aminotriazine modified phenolic resin, bisphenol A novolak resin, bisphenol F novolak resin, etc. Good.

  Moreover, in order to advance the hardening reaction of the said epoxy resin (I) and the said phenol resin (II) rapidly, a hardening accelerator can also be used suitably. Examples of the curing accelerator include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like.

  The epoxy resin composition of the present invention is an inorganic filler, a thermosetting and thermoplastic resin used as a modifier, a flame retardant, a pigment, a silane coupling agent, a mold release agent, if necessary depending on the use. Various compounding agents such as can be added.

  Examples of the inorganic filler 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 blending ratio of the inorganic filler varies in the desired range depending on the application and desired characteristics. For example, when used for a semiconductor encapsulant, the higher one 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 thing amount, 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 above-described epoxy resin (I), the phenol resin (II), and other compounding agents blended as necessary. At this time, the viscosity may be adjusted according to the purpose of improving workability, the use, and the heat curing conditions. Solvents usable at this time are not particularly limited, but alcoholic solvents such as methanol, ethanol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, aromatic hydrocarbon solvents such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, Examples include non-alcoholic polar solvents such as cyclohexanone and dimethylformamide, solvents having a boiling point of 160 ° C. or lower, N-methylpyrrolidone, and the like. Further, even if the solvent is added to the epoxy resin (I) and the phenol resin (II) in advance, the epoxy resin (I) and the phenol resin (II) are necessary. After mixing the various compounding agents blended according to the above, a method may be used in which a solvent is added to adjust the viscosity to make it uniform.

  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 resist ink resin composition include, for example, the epoxy resin (I) and the phenol resin (II), an organic solvent, a pigment, talc, and a filler. In addition, a method for forming a resist ink composition, applying the resist ink on a printed board by a screen printing method, and then forming a resist ink cured product can be mentioned. Examples of the organic solvent used here include methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, cyclohexanone, dimethyl sulfoxide, dimethylformamide, dioxolane, tetrahydrofuran, propylene glycol monomethyl ether acetate, ethyl lactate and the like. .

When the epoxy resin composition of the present invention is used as a binder for a friction material, in addition to the epoxy resin (I) and the phenol resin (II), it further generates formaldehyde by heating hexamethylenetetramine, paraformaldehyde or the like. In addition, it can be produced by blending a curing accelerator such as imidazole and its derivatives, carboxylic acid compounds, amines, and BF ₃ amine compounds using the substance. 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.

  When used as a binder for a friction material, there is a method in which a fiber base material and a curing agent are used in combination with the epoxy resin composition, followed by thermosetting. In this case, as the fiber base material, for example, inorganic fibers such as glass fiber, ceramic fiber, asbestos fiber, carbon fiber and stainless steel fiber, natural fibers such as cotton and hemp, synthetic organic fibers such as polyester and polyamide, etc. Examples of the shape of the fiber base include short fibers, long fibers, yarns, mats, and sheets.

  The method for producing a resin composition for a copper clad laminate from the epoxy resin composition of the present invention is specifically varnished using the epoxy resin (I), the phenol resin (II), and an organic solvent. A method is mentioned.

  As the organic solvent used here, alcoholic solvents such as methanol, ethanol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, aromatic hydrocarbon solvents such as toluene, xylene, acetone, methyl ethyl ketone, methyl Examples of the solvent include non-alcoholic polar solvents such as isobutyl ketone, cyclohexanone, dimethylformamide, N-methylpyrrolidone, and dimethylacetamide.

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.
As described above, the composition varnished with the epoxy resin (I), the phenol resin (II) and an organic solvent is used as a paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass roving. A prepreg which is a cured product is obtained by impregnating various reinforcing substrates such as cloth and heating at a heating temperature according to the solvent type used, preferably 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. The interlayer insulation material of such a build-up printed circuit board is adjusted by a method of blending the epoxy resin (I), the phenol resin (II), the organic solvent, rubber, and filler, among the varnishing methods described above. can do. 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 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.

  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 encapsulating material, the epoxy resin (I), the phenol resin (II), other coupling agents blended as necessary, a mold release Examples thereof include a method in which an additive such as an agent or an inorganic filler is premixed and then sufficiently mixed until uniform using an extruder, a kneader, a 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 a resin for underfill is, for example, by previously applying the epoxy resin composition of the present invention on a substrate or a semiconductor element, then semi-curing it, 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 is composed of, for example, a curing accelerator and a silane coupling agent in addition to the epoxy resin (I) and the phenol resin (II). There is a method in which an object is prepared and applied onto a silicon substrate by spin coating or the like. 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 of adjusting the epoxy resin composition of the present invention to a resin composition for an adhesive is, for example, the epoxy resin (I), the phenol resin (II), if necessary, resins, a curing accelerator, a solvent, addition Examples include a method of uniformly mixing an agent, etc., at room temperature or under heating using a mixing mixer or the like. After applying to various base materials, the base material can be adhered by leaving it to stand at room temperature or under heating. .

  The method for preparing the composite material from the epoxy resin composition of the present invention is to varnish the epoxy resin (I) and the phenol resin (II) with an organic solvent in order to adjust the viscosity according to the application. Is impregnated into a reinforcing base material and heated to obtain a prepreg, then the fiber direction is changed little by little, the layers are laminated so as to be pseudo-isotropic, and then cured by heating. A method is mentioned. Examples of the organic solvent used here include alcoholic solvents such as methanol, ethanol, isopropyl alcohol, methyl cellosolve, and ethyl cellosolve, aromatic hydrocarbon solvents such as toluene and xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, Non-alcoholic polar solvents such as dimethylformamide and the like have a boiling point of 160 ° C. or lower. 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 is a copper-clad laminate because it is a halogen-free curing system with a low environmental load, and can have both excellent flame resistance and heat resistance. It is particularly useful as a resin composition for plates.

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, the curing agent (II) selection, other blending components, and the like may be suitably heat-cured under appropriate temperature conditions depending on the use, etc. It is preferable to cure at a temperature condition of 25 ° C to 200 ° C.

  Next, the present invention will be specifically described with reference to examples and comparative examples. In the following, “part” and “%” are based on mass.

Example 1
A reactor equipped with a condenser and an atmospheric pressure and vacuum distillation apparatus was charged with 940 parts of phenol, 185 parts of BAG, 434 parts of 41.5% formalin, and 3 parts of triethylamine, and the temperature was raised to 115 ° C. and reacted for 2 hours. . Next, the temperature was raised to 135 ° C. during atmospheric distillation and reacted for 2 hours as it was, and the temperature was raised to 180 ° C. again while performing atmospheric distillation, followed by distillation under reduced pressure at 180 ° C., and low boiling points such as unreacted monomers and water. The component was removed to obtain 780 parts of a phenol resin having a softening point of 106 ° C. The obtained phenol resin had a nitrogen atom content of 7.2% by mass, a carboxyl group equivalent of 975 g / equivalent, an ICI melt viscosity at 150 ° C. of 10 poise, and a molecular weight distribution (Mw / Mn) of 2. 46.
(Adjustment of epoxy resin composition and evaluation of physical properties)
The following structural formula

（上記式中ｌは繰り返し単位の平均値で０．０６である。）
で表されるビフェニル型エポキシ樹脂１００質量部と前記フェノール樹脂４２質量部とＭＥＫとを、最終的な組成物の不揮発分（Ｎ．Ｖ．）が５５質量％となるように配合してエポキシ樹脂組成物を得た。次いで、下記の如き条件で硬化させて両面銅張積層板を試作し、各種の評価を行った。結果を表１に示す。

(In the above formula, l is the average value of the repeating units and is 0.06.)
100 parts by mass of the biphenyl type epoxy resin represented by the formula, 42 parts by mass of the phenol resin and MEK are blended so that the non-volatile content (NV) of the final composition is 55% by mass. A composition was obtained. 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.

Comparative Example 1
A reactor equipped with a condenser and an atmospheric pressure and vacuum distillation apparatus was charged with 940 parts of phenol, 151 parts of melamine, and 434 parts of 41.5% by mass formalin, heated to 100 ° C., and reacted for 2 hours. . Next, the temperature was raised to 135 ° C. during atmospheric distillation, and the reflux reaction was continued for 2 hours, and the temperature was raised to 180 ° C. again under atmospheric distillation, followed by distillation under reduced pressure at 180 ° C. to remove unreacted monomers, water, etc. Low boiling components were removed to obtain 740 parts of a resin having a softening point of 136 ° C.
41 parts by mass of the resin thus obtained and an epoxy equivalent of 215 g / eq. An epoxy resin composition was obtained by blending 100 parts by mass of cresol novolac type epoxy resin and MEK so that the nonvolatile content (NV) of the final composition was 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.
[Heat-resistant decomposition test]
Cut the double-sided copper-clad laminate into a 6.35 mm x 6.35 mm size, set the test piece on a thermal mechanical analyzer (TMA), raise the temperature at 10 ° C / min, hold at 288 ° C, The time until lamination occurred was measured.
[Flame retardance test]
After removing the copper foil by performing etching treatment, a varnish was prepared by dispersing and adding 30% by mass of aluminum hydroxide to the solid content in the epoxy resin composition for the combustion test. Made. The test method was based on the UL-94 vertical test.

Claims (8)

The following general formula 1

(In General Formula 1, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and l is 0.01 to 5 in average of repeating units.)
And a phenol resin (II) having a chemical structure (b) in which the carboxyl group is bonded to the triazine ring via a divalent aromatic hydrocarbon group as a partial structure in the molecular structure. An epoxy resin composition characterized by comprising an essential component. The chemical structure (b) in the phenol resin (II) is represented by the following structural formula (1)

(In the formula, R represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, an aromatic hydrocarbon group, a bromine atom, or a chlorine atom, and a broken line part represents a bond with another molecular structure. And n and m represent an integer of 1 to 4.)
The epoxy resin composition according to claim 1, which is represented by: A phenol resin (II) reacts a phenol (x1), a triazine compound (x2) having a carboxyl group-containing aromatic hydrocarbon group and an amino group as a substituent on the triazine ring, and an aldehyde (x3). The epoxy resin composition according to claim 1 or 2, wherein the epoxy resin composition has a molecular structure obtained as described above. The triazine compound (x2) having a carboxyl group-containing aromatic hydrocarbon group and an amino group as a substituent on the triazine ring is represented by the following structural formula (2)

(In formula, R represents a hydrogen atom, a C1-C4 aliphatic hydrocarbon group, an aromatic hydrocarbon group, a bromine atom, or a chlorine atom, and n and m represent the integer of 1-4. )
The epoxy resin composition of Claim 3 which is a compound shown by these. In addition to the phenols (x1), the compound (x2), and the aldehydes (x3), the phenol resin (II) further reacts with another amino group-containing triazine compound (x4) of the compound (x2). The phenol resin composition according to claim 3 or 4, wherein the phenol resin composition is obtained. The epoxy resin composition according to claim 5, wherein the amino group-containing triazine-containing compound (x4) is one or more compounds selected from the group consisting of melamine, acetoguanamine and benzoguanamine. The epoxy resin composition according to any one of claims 1 to 6, wherein the phenol resin (II) has an ICI melt viscosity at 150 ° C of 100 poise or less. Hardened | cured material formed by thermosetting the epoxy resin composition as described in any one of Claims 1-7.