JP2015074718A - Phenolic resin, epoxy resin, production method of the same, curable composition, cured product of the same, semiconductor encapsulation material, and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phenolic resin and an epoxy resin, and production methods of these resins which have excellent fluidity and exhibit, in a cured product thereof, high flame retardancy, high adhesiveness to a substrate, and a low coefficient of linear expansion, and to provide a curable composition using the above resins, a cured product of the composition, a semiconductor encapsulation material, and a printed wiring board.SOLUTION: The phenolic resin has a resin structure obtained by reacting an alkylphenol, a β-naphthol compound, and formaldehyde in the absence of a catalyst. The phenolic resin comprises, as essential components, a phenolic hydroxyl group-containing compound (x1) and a phenolic hydroxyl group-containing compound (x2), in which a ratio [(x1)/(x2)] of contents of the above compounds calculated by liquid chromatography ranges from 3 to 100.

Description

  The present invention is excellent in fluidity, has high flame retardancy and substrate adhesion in a cured product, and has a low linear expansion coefficient, a phenol resin and an epoxy resin, a production method thereof, a curable composition using these, and its curing Product, semiconductor sealing material, and printed wiring board.

  Phenolic resins and epoxy resins are used in adhesives, molding materials, paints, photoresist materials, color developing materials, etc., as well as semiconductor encapsulants from the point that the resulting cured products have excellent heat resistance and moisture resistance. Widely used in the electrical and electronic fields such as insulating materials for printed wiring boards.

  Among these various applications, in the field of semiconductor encapsulation materials, technological innovations such as transition to surface mount packages such as BGA and CSP, compatibility with lead-free solder, elimination of halogenated flame retardants, etc. are being promoted. In addition to further improvements in heat resistance, low thermal expansion and moisture and solder resistance, there is a need for a resin material that has high flame resistance without using halogen flame retardants and has excellent adhesion to substrates. It has been. In particular, the semiconductor sealing material is used by filling a resin material with a filler such as silica, and the resin material needs to have a low viscosity and excellent fluidity in order to increase the filling rate of the filler.

  As an epoxy resin for a semiconductor encapsulant, for example, β-naphthol is reacted under alkaline conditions, and then the reaction product and orthocresol are reacted under acid catalyst conditions. The following structural formula (1)

で表される化合物を１７質量％、下記構造式（２）

17% by mass of the compound represented by the following structural formula (2)

で表される化合物を２１質量％、下記構造式（３）

21 mass% of the compound represented by the following structural formula (3)

で表される化合物を３６％含有するフェノール樹脂をポリグリシジルエーテル化して得られるエポキシ樹脂が知られている。このようなエポキシ樹脂はガラス転移温度で評価される耐熱性には優れるものの、硬化物における難燃性や基材密着性が低く、また、線膨張率も大きいものであった。

An epoxy resin obtained by polyglycidyl etherification of a phenol resin containing 36% of a compound represented by the formula is known. Although such an epoxy resin is excellent in heat resistance evaluated by the glass transition temperature, it has low flame retardancy and substrate adhesion in a cured product, and has a large linear expansion coefficient.

JP 2000-53739 A

  Therefore, the problem to be solved by the present invention is a phenol resin and an epoxy resin having excellent fluidity, high flame retardancy and cured substrate adhesion, low linear expansion coefficient, production methods thereof, and use of these. The present invention provides a curable composition and a cured product thereof, a semiconductor sealing material, and a printed wiring board.

  As a result of intensive studies to solve the above problems, the present inventors have found that the following structural formula (i)

（式中Ｒ^１は炭素原子数１〜６のアルキル基を、Ｒ^２は炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかを表す。また、ｎは０〜６の整数であり、ｎが２以上の場合複数のＲ^２はそれぞれ同一でも異なっていて良い。）
で表されるフェノール性水酸基含有化合物（ｘ１）と、下記構造式（ｉｉ）

(Wherein R ¹ represents an alkyl group having 1 to 6 carbon atoms, R ² represents any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom. Moreover, n is an integer of 0 to 6, and when n is 2 or more, a plurality of R ² may be the same or different.
A phenolic hydroxyl group-containing compound (x1) represented by the following structural formula (ii)

（式中Ｒ^２は炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかを表し、ｎは０〜６の整数である。ｎが２以上の場合複数のＲ^２はそれぞれ同一でも異なっていて良い。）
で表されるフェノール性水酸基含有化合物（ｘ２）とを含有し、化合物（ｘ２）の含有量に対する化合物（ｘ１）の含有量が３倍以上であるフェノール樹脂、或いは、これをポリグリシジルエーテル化して得られるエポキシ樹脂は流動性に優れること、従来難燃性向上や線膨張率の低減に優位と考えられていたナフタレン濃度の高い前記化合物（ｘ２）の含有量が少ないにも関わらず、硬化物における難燃性や低線膨張性が高く、かつ、銅箔等の基材への密着性にも優れることを見出し、本発明を完成するに至った。

(In the formula, R ² represents any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom, and n is an integer of 0 to 6. When n is 2 or more, the plurality of R ² may be the same or different.)
A phenolic hydroxyl group-containing compound (x2) represented by formula (1), wherein the content of the compound (x1) is at least three times the content of the compound (x2), or polyglycidyl ether The resulting epoxy resin is excellent in fluidity, and is a cured product despite the low content of the compound (x2) having a high naphthalene concentration, which has been considered to be superior in improving flame retardancy and reducing the linear expansion coefficient. It has been found that the flame retardancy and low linear expansion property of the resin are high, and the adhesiveness to a substrate such as a copper foil is excellent, and the present invention has been completed.

  That is, the present invention provides the following structural formula (i)

（式中Ｒ^１は炭素原子数１〜６のアルキル基を、Ｒ^２は炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかを表す。また、ｎは０〜６の整数であり、ｎが２以上の場合複数のＲ^２はそれぞれ同一でも異なっていて良い。）
で表されるフェノール性水酸基含有化合物（ｘ１）と、下記構造式（ｉｉ）

(Wherein R ¹ represents an alkyl group having 1 to 6 carbon atoms, R ² represents any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom. Moreover, n is an integer of 0 to 6, and when n is 2 or more, a plurality of R ² may be the same or different.
A phenolic hydroxyl group-containing compound (x1) represented by the following structural formula (ii)

（式中Ｒ^２は炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかを表し、ｎは０〜６の整数である。ｎが２以上の場合複数のＲ^２はそれぞれ同一でも異なっていて良い。）
で表されるフェノール性水酸基含有化合物（ｘ２）とを必須の成分として含有し、液体クロマトグラフから算出される両者の含有量の比［（ｘ１）／（ｘ２）］が３〜１００の範囲であることを特徴とするフェノール樹脂に関する。

(In the formula, R ² represents any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom, and n is an integer of 0 to 6. When n is 2 or more, the plurality of R ² may be the same or different.)
The phenolic hydroxyl group-containing compound represented by the formula (x2) is contained as an essential component, and the ratio [(x1) / (x2)] of both calculated from a liquid chromatograph is in the range of 3-100. The present invention relates to a phenol resin characterized by being.

  The present invention further relates to a curable composition containing the phenol resin and a curing agent.

  The present invention further relates to a cured product obtained by curing reaction of the curable composition.

  The present invention further relates to a semiconductor sealing material containing an inorganic filler in addition to the curable composition.

  The present invention further relates to a printed wiring board obtained by impregnating a reinforcing base material with a mixture of the curable composition and an organic solvent, and stacking a copper foil and thermocompression bonding.

  The present invention further relates to a method for producing a phenol resin, comprising reacting an alkylphenol, a β-naphthol compound, and formaldehyde under non-catalytic conditions.

  The present invention further includes the following structural formula (I):

（式中Ｒ^１は炭素原子数１〜６のアルキル基を、Ｒ^２は炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかを表す。また、ｎは０〜６の整数であり、ｎが２以上の場合複数のＲ^２はそれぞれ同一でも異なっていて良い。）
で表されるエポキシ化合物（ｙ１）と、下記構造式（ＩＩ）

(Wherein R ¹ represents an alkyl group having 1 to 6 carbon atoms, R ² represents any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom. Moreover, n is an integer of 0 to 6, and when n is 2 or more, a plurality of R ² may be the same or different.
An epoxy compound (y1) represented by the following structural formula (II)

（式中Ｒ^２は炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかを表し、ｎは０〜６の整数である。ｎが２以上の場合複数のＲ^２はそれぞれ同一でも異なっていて良い。）
で表されるエポキシ化合物（ｙ２）とを必須の成分として含有し、液体クロマトグラフから算出される両者の含有量の比［（ｙ１）／（ｙ２）］が３〜１００の範囲であることを特徴とするエポキシ樹脂に関する。

(In the formula, R ² represents any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom, and n is an integer of 0 to 6. When n is 2 or more, the plurality of R ² may be the same or different.)
And an epoxy compound (y2) represented by formula (2) as an essential component, and the content ratio [(y1) / (y2)] calculated from the liquid chromatograph is in the range of 3 to 100. It relates to a featured epoxy resin.

  The present invention further relates to a curable composition containing the epoxy resin and a curing agent.

  The present invention further relates to a cured product obtained by curing reaction of the curable composition.

  The present invention further relates to a semiconductor sealing material containing an inorganic filler in addition to the curable composition.

  The present invention further relates to a printed wiring board obtained by impregnating a reinforcing base material with a mixture of the curable composition and an organic solvent, and stacking a copper foil and thermocompression bonding.

  The present invention further provides an epoxy resin obtained by reacting an alkylphenol, a β-naphthol compound, and formaldehyde under non-catalytic conditions to obtain a phenol intermediate, and then reacting the obtained phenol intermediate with an epihalohydrin. It relates to the manufacturing method.

  According to the present invention, phenolic resin and epoxy resin having excellent fluidity, high flame retardance and substrate adhesion in a cured product, low linear expansion coefficient, production methods thereof, and a curable composition using them The cured product, semiconductor sealing material, and printed wiring board can be provided.

FIG. 1 is an HPLC chart of the phenol resin (A-1) obtained in Example 1. FIG. 2 is a GPC chart of the phenol resin (A-1) obtained in Example 1. FIG. 3 is a 13C-NMR chart of the phenol resin (A-1) obtained in Example 1. FIG. 4 is a GPC chart of the phenol resin (A-2) obtained in Example 2. FIG. 5 is a 13C-NMR chart of the phenol resin (A-2) obtained in Example 2. FIG. 6 is an HPLC chart of the epoxy resin (B-1) obtained in Example 3. FIG. 7 is a GPC chart of the epoxy resin (B-1) obtained in Example 3. FIG. 8 is a 13C-NMR chart of the epoxy resin (B-1) obtained in Example 3. FIG. 9 is a GPC chart of the epoxy resin (B-2) obtained in Example 4. FIG. 10 is a 13C-NMR chart of the epoxy resin (B-2) obtained in Example 4. FIG. 11 is a GPC chart of the phenol resin (A′-1) obtained in Comparative Synthesis Example 1. FIG. 12 is a GPC chart of the epoxy resin (B′-1) obtained in Comparative Synthesis Example 2.

  Hereinafter, the present invention will be described in detail. The phenolic resin of the present invention has the following structural formula (i)

（式中Ｒ^１は炭素原子数１〜６のアルキル基を、Ｒ^２は炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかを表す。また、ｎは０〜６の整数であり、ｎが２以上の場合複数のＲ^２はそれぞれ同一でも異なっていて良い。）
で表されるフェノール性水酸基含有化合物（ｘ１）と、下記構造式（ｉｉ）

(Wherein R ¹ represents an alkyl group having 1 to 6 carbon atoms, R ² represents any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom. Moreover, n is an integer of 0 to 6, and when n is 2 or more, a plurality of R ² may be the same or different.
A phenolic hydroxyl group-containing compound (x1) represented by the following structural formula (ii)

（式中Ｒ^２は炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかを表し、ｎは０〜６の整数である。ｎが２以上の場合複数のＲ^２はそれぞれ同一でも異なっていて良い。）
で表されるフェノール性水酸基含有化合物（ｘ２）とを必須の成分として含有し、液体クロマトグラフから算出される両者の含有量の比［（ｘ１）／（ｘ２）］が３〜１００の範囲であることを特徴とする。

(In the formula, R ² represents any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom, and n is an integer of 0 to 6. When n is 2 or more, the plurality of R ² may be the same or different.)
The phenolic hydroxyl group-containing compound represented by the formula (x2) is contained as an essential component, and the ratio [(x1) / (x2)] of both calculated from a liquid chromatograph is in the range of 3-100. It is characterized by being.

  More specifically, the phenol resin of the present invention is a phenol resin obtained by subjecting an alkylphenol, a β-naphthol compound, and formaldehyde as raw materials to a polycondensation reaction thereof, in which the phenolic hydroxyl group-containing compound ( x1) and (x2) are contained in a predetermined ratio.

  The phenolic hydroxyl group-containing compound (x1) represented by the structural formula (i) has a low molecular weight and excellent fluidity, and has a molecular structure with high thermal stability despite a low naphthalene concentration. Therefore, the cured product is excellent in flame retardancy and further has excellent base material adhesion. On the other hand, the phenolic hydroxyl group-containing compound (x2) represented by the structural formula (ii) has high molecular orientation and excellent low linear expansion, but is not sufficient in fluidity and poor in thermal stability. Although it has a molecular structure, it is inferior in flame retardancy despite the high naphthalene concentration.

  In the present invention, the ratio [(x1) / (x2)] of the phenolic hydroxyl group-containing compound (x1) and the phenolic hydroxyl group-containing compound (x2) is in the range of 3 to 100, The excellent characteristics of the compound are exhibited synergistically, and while containing the phenolic hydroxyl group-containing compound (x2), the fluidity is high, and any of flame retardancy, cured substrate adhesion, and low linear expansion in a cured product It has succeeded in realizing a phenol resin that is also excellent.

  Since the phenol resin of the present invention is further excellent in flame retardancy in a cured product, the ratio of the content of the phenolic hydroxyl group-containing compound (x1) and the phenolic hydroxyl group-containing compound (x2) [(x1 ) / (X2)] is preferably in the range of 4 to 60, more preferably in the range of 5 to 20.

  In the present invention, the ratio [(x1) / (x2)] of the phenolic hydroxyl group-containing compound (x1) and the phenolic hydroxyl group-containing compound (x2) is a liquid chromatograph measured under the following conditions. It is a value calculated by the ratio of the peak area derived from the phenolic hydroxyl group-containing compound (x1) and the peak area derived from the phenolic hydroxyl group-containing compound (x2).

<HPLC measurement conditions>
“Agilent 1220 Infinity LC” manufactured by Tosoh Corporation
Column: “TSK-GEL ODS-120T” manufactured by Tosoh Corporation
Detector: VWD 254nm
Data processing: “Agilent EZChrom Elite” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Acetonitrile
Flow rate 1.0ml / min

  The phenolic hydroxyl group-containing compound (x1), which is one of the essential components of the phenol resin of the present invention, has the following structural formula (i)

（式中Ｒ^１は炭素原子数１〜６のアルキル基を、Ｒ^２は炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかを表す。また、ｎは０〜６の整数であり、ｎが２以上の場合複数のＲ^２はそれぞれ同一でも異なっていて良い。）
で表される分子構造を有する。

(Wherein R ¹ represents an alkyl group having 1 to 6 carbon atoms, R ² represents any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom. Moreover, n is an integer of 0 to 6, and when n is 2 or more, a plurality of R ² may be the same or different.
It has a molecular structure represented by

R ¹ in the structural formula (i) is an alkyl group having 1 to 6 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, Examples thereof include an s-butyl group, a t-butyl group, a pentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group. Among these, a methyl group is preferable because a cured product having high flame retardancy and a low coefficient of linear expansion can be obtained.

In addition, the bonding position of R ^{1 in} the structural formula (i) may be on any carbon atom that forms an aromatic ring. It is preferably on the carbon atom located at the para-position or ortho-position of the carbon atom to be bonded, and since it becomes a phenol resin having further excellent fluidity, on the carbon atom positioned at the ortho-position of the carbon atom to which the phenolic hydroxyl group is bonded. It is more preferable that

R ² in the structural formula (i) is any one of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom. Specific examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, and pentyl. Group, neopentyl group, hexyl group, cyclohexyl group and the like. The alkoxy group having 1 to 6 carbon atoms is a methoxy group, an ethoxy group, an n-propyloxy group, an i-propyloxy group, an n-butyloxy group, an isobutyloxy group, an s-butyloxy group, or a t-butyloxy group. Pentyloxy group, neopentyloxy group, hexyloxy group, cyclohexyloxy group and the like. Examples of the aryl group include a phenyl group, a naphthyl group, or a structural site in which one or more alkyl groups or alkoxy groups are substituted on the aromatic nucleus. Examples of the aralkyl group include a phenylmethyl group, a naphthylmethyl group, or a structural site in which one or more alkyl groups or alkoxy groups are substituted on the aromatic nucleus. Examples of the halogen atom include a fluorine atom, a bromo atom, and a chlorine atom.

N in the structural formula (i) is a value representing the number of substitutions of R ² and is an integer of 0 to 6. Among them, n is preferably 0 because it is excellent in fluidity, and a cured product having high flame retardancy and low linear expansion coefficient can be obtained.

  That is, the phenolic hydroxyl group-containing compound (x1) represented by the structural formula (i) is more preferably the following structural formula (i-1)

で表される分子構造を有するものである。

It has the molecular structure represented by these.

In the structural formula (i), when the bonding position of R ¹ is on the carbon atom located at the ortho position of the carbon atom to which the phenolic hydroxyl group is bonded, the phenolic hydroxyl group represented by the structural formula (i) The containing compound (x1) has the following structural formula (io) or (ip)

で表されるものとなる。

It will be represented by

  The phenolic hydroxyl group-containing compound (x2), which is another essential component of the phenol resin of the present invention, has the following structural formula (ii)

（式中Ｒ^２は炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかを表し、ｎは０〜６の整数である。ｎが２以上の場合複数のＲ^２はそれぞれ同一でも異なっていて良い。）
で表される分子構造を有する。

(In the formula, R ² represents any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom, and n is an integer of 0 to 6. When n is 2 or more, the plurality of R ² may be the same or different.)
It has a molecular structure represented by

R ² and n in the structural formula (ii) are synonymous with R ² and n in the structural formula (i), and a cured product having excellent fluidity, high flame retardancy, and low linear expansion coefficient is obtained. Therefore, n is preferably 0.

  That is, the phenolic hydroxyl group-containing compound (x2) represented by the structural formula (ii) is more preferably the following structural formula (ii-1)

で表される分子構造を有するものである。

It has the molecular structure represented by these.

  The phenolic resin of the present invention may contain other phenolic hydroxyl group-containing compounds in addition to the phenolic hydroxyl group-containing compounds (x1) and (x2). In this case, the phenolic hydroxyl group-containing compound (x1) in the phenolic resin exhibits the effect of the present invention that a cured product having excellent fluidity and high flame retardancy and low linear expansion coefficient is obtained. The total content of (x2) and the value calculated from the GPC peak area ratio is preferably 30% or more, and more preferably 40% or more.

  The total content of the phenolic hydroxyl group-containing compounds (x1) and (x2) in the phenol resin is calculated from an analysis chart of GPC measured under the following conditions. Specifically, It is a value calculated from the ratio of the total peak area derived from the phenolic hydroxyl group-containing compounds (x1) and (x2) to the peak area of the entire phenol resin of the present invention.

<GPC measurement conditions>
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-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 refractometer)
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).

  In addition, the total content of the phenolic hydroxyl group-containing compounds (x1) and (x2) in the phenol resin is sufficient for the effect of the present invention that a cured product having high flame retardancy and low linear expansion coefficient can be obtained. Since it is exhibited, the content of the phenolic hydroxyl group-containing compound (x1) is in the range of 30 to 90%, and the content of the phenolic hydroxyl group-containing compound (x2) is in the range of 1 to 10%. Is preferred.

  The contents of the phenolic hydroxyl group-containing compounds (x1) and (x2) in the phenolic resin are calculated from the phenolic hydroxyl group-containing compounds (x1) and (x2) calculated from the GPC analysis chart by the above method. And the ratio [(x1) / (x2)] of the two contents calculated from the analysis chart diagram of the liquid chromatograph by the above method. That is, the total of both contents in the phenol resin calculated from the GPC analysis chart is α%, and the ratio [(x1) / (x2)] of both is expressed by [β / γ]. The content of the phenolic hydroxyl group-containing compound (x1) in the phenol resin is α × [β / (β + γ)] (%), and the content of the phenolic hydroxyl group-containing compound (x2) is α ×. [γ / (β + γ)] (%).

  Other phenolic hydroxyl group-containing compounds other than the phenolic hydroxyl group-containing compounds (x1) and (x2) include, for example, the following structural formula (iii)

（式中Ｒ^１は炭素原子数１〜６のアルキル基を、Ｒ^２は炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかを表す。また、ｎは０〜６の整数であり、ｎが２以上の場合複数のＲ^２はそれぞれ同一でも異なっていて良い。）
で表されるフェノール性水酸基含有化合物（ｘ３）や、下記構造式（ｉｖ）

(Wherein R ¹ represents an alkyl group having 1 to 6 carbon atoms, R ² represents any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom. Moreover, n is an integer of 0 to 6, and when n is 2 or more, a plurality of R ² may be the same or different.
A phenolic hydroxyl group-containing compound (x3) represented by the following structural formula (iv)

（式中Ｒ^１は炭素原子数１〜６のアルキル基を、Ｒ^２は炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかを表す。また、ｎは０〜６の整数であり、ｎが２以上の場合複数のＲ^２はそれぞれ同一でも異なっていて良い。ｍは２以上の整数である。）
で表されるフェノール性水酸基含有化合物（ｘ４）が挙げられる。

(Wherein R ¹ represents an alkyl group having 1 to 6 carbon atoms, R ² represents any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom. In addition, n is an integer of 0 to 6, and when n is 2 or more, a plurality of R ² may be the same or different, and m is an integer of 2 or more.)
And a phenolic hydroxyl group-containing compound (x4) represented by the formula:

^R 1, ^{R 2} and n in the structural formula (iii) or (iv) have the same meanings as ^R 1, ^{R 2} and n in the structural formula (i). R ¹ in the structural formula (iii) or (iv) is preferably a methyl group because a cured product having high flame retardancy and low coefficient of linear expansion is obtained. In addition, the bonding position of R ^{1 in} the structural formula (iii) or (iv) may be on any carbon atom that forms an aromatic ring. Carbon located at the ortho position of the carbon atom to which the phenolic hydroxyl group is bonded is preferable because it is on the carbon atom positioned at the para-position or ortho-position of the carbon atom to which the hydroxyl group is bonded, and the phenolic resin is further excellent in fluidity. More preferably, it is on an atom. Furthermore, n in the structural formula (iii) or (iv) is preferably 0 because a cured product having excellent fluidity and high flame retardancy and low coefficient of linear expansion is obtained.

  That is, the phenolic hydroxyl group-containing compound (x3) represented by the structural formula (iii) is more preferably the following structural formula (iii-1)

で表される分子構造を有するものであり、前記構造式（ｉｖ）で表されるフェノール性水酸基含有化合物（ｘ４）は、より好ましくは、下記構造式（ｉｖ−１）

The phenolic hydroxyl group-containing compound (x4) represented by the structural formula (iv) is more preferably the following structural formula (iv-1)

（式中ｍは２以上の整数である。）
で表される分子構造を有するものである。

(In the formula, m is an integer of 2 or more.)
It has the molecular structure represented by these.

  When the phenol resin of the present invention contains the phenolic hydroxyl group-containing compound (x3), the content of each component in the phenol resin is a value calculated from the peak area ratio of GPC, and the phenolic hydroxyl group-containing compound ( It is preferable that the total content of x1) and (x2) is in the range of 30 to 80%, and the content of the phenolic hydroxyl group-containing compound (x3) is in the range of 15 to 50%.

  The phenolic resin of the present invention contains the phenolic hydroxyl group-containing compound (x1) represented by the structural formula (io) or (ip), or the phenolic hydroxyl group-containing compound represented by the structural formula (iii-1). When the compound (x3) contains the phenolic hydroxyl group-containing compound (x4) represented by the structural formula (iv-1), that is, when ortho-cresol is used as the alkylphenol of the resin raw material, the fluidity is high, and the cured product Therefore, the abundance ratio of the methylene group (o) located at the ortho position of the phenolic hydroxyl group to the methylene group (p) located at the para position in the phenol resin [(o) / (P)] is a value calculated from a 13C-NMR chart and is preferably in the range of 40/60 to 80/20.

  In the present invention, the abundance ratio [(o) / (p)] of the methylene group (o) and the methylene group (p) is a value calculated from an analysis chart of 13C-NMR measured under the following conditions. Specifically, the peak area derived from the methylene group (o) located at the ortho position of the phenolic hydroxyl group detected at 22 to 27 ppm on the 13C-NMR analysis chart of the phenol resin, and detected at 28 to 33 ppm. It is a value calculated from the ratio to the peak area derived from the methylene group (p) located at the para position of the phenolic hydroxyl group.

<13C-NMR measurement conditions>
Equipment: “JNM-ECA500” manufactured by JEOL Ltd.
Measurement mode: NNE (1H complete decoupling method for NOE elimination)
Solvent: Heavy chloroform pulse angle: 45 ° Pulse sample concentration: 30 wt%
Integration count: 4000 times

  Since the phenol resin of the present invention is excellent in flame retardancy and a cured product having a low linear expansion coefficient is obtained, the hydroxyl group equivalent is preferably in the range of 130 to 150 g / eq. Moreover, it is preferable that the value measured on 150 degreeC conditions is the range whose melt viscosity is 0.1-4.0 dPa * s.

The phenol resin of the present invention can be produced, for example, by a method of reacting alkylphenol, β-naphthol compound, and formaldehyde under non-catalytic conditions. In addition, the non-catalytic condition in the present invention means a condition in which no catalyst is intentionally added.

  Examples of the alkylphenol used here include cresol, ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, isobutylphenol, s-butylphenol, t-butylphenol, pentylphenol, neopentylphenol, hexylphenol, and cyclohexyl. Phenol etc. are mentioned. Among them, cresol is preferable because a cured product having high flame retardancy and a low coefficient of linear expansion can be obtained.

  The substitution position of the alkyl group in the alkylphenol may be on any carbon atom of the aromatic ring. However, since the phenolic hydroxyl group-containing compound (x1) is easily formed, the paraffin of the carbon atom to which the phenolic hydroxyl group is bonded. It is preferably on the carbon atom located at the ortho or ortho position, and more preferably on the carbon atom located at the ortho position of the carbon atom to which the phenolic hydroxyl group is bonded, because a phenol resin with better fluidity is obtained. preferable.

  That is, the alkylphenol used in the production method is preferably paracresol or orthocresol, particularly preferably orthocresol.

  The β-naphthol compound used in the production method is, for example, the following structural formula (α)

（式中Ｒ^２は炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかを表し、ｎは０〜６の整数であり、ｎが２以上の場合複数のＲ^２はそれぞれ同一でも異なっていて良い。）
で表されるものが挙げられる。中でも、難燃性が高く線膨張率の低い硬化物が得られることから、置換基を有しないβ−ナフトールであることが好ましい。

(Wherein R ² represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, or a halogen atom, and n is an integer of 0 to 6; When n is 2 or more, the plurality of R ² may be the same or different.)
The thing represented by is mentioned. Among these, β-naphthol having no substituent is preferable because a cured product having high flame retardancy and a low coefficient of linear expansion can be obtained.

  The formaldehyde used in the production method may be either formalin in the form of an aqueous solution or paraformaldehyde in the solid state.

  In the said manufacturing method, since the reaction ratio of the said alkylphenol and (beta) -naphthol compound is easy to produce | generate the said phenolic hydroxyl group containing compound (x1), both molar ratio [(alkylphenol) / ((beta) -naphthol compound)] Is preferably in the range of [10.0 / 1.0] to [1.0 / 2.0], and in the range of [4.0 / 1.0] to [1.0 / 1.5]. More preferably.

  The reaction charge of formaldehyde is such that the phenolic hydroxyl group-containing compound (x1) is easily formed, so that formaldehyde is 0.2 to 1 on a molar basis with respect to the total number of moles of alkylphenol and β-naphthol compound. The ratio is preferably 5 times the amount, and more preferably 0.3 to 1.0 times the amount.

  The reaction of the alkylphenol, β-naphthol compound, and formaldehyde is performed under non-catalytic conditions. Thereby, the phenolic hydroxyl group-containing compound (x1) is easily generated, and the ratio of the content of the phenolic hydroxyl group-containing compound (x1) and the phenolic hydroxyl group-containing compound (x2) [(x1) / (x2 )] Is easily adjusted to a range of 3 to 100.

  The reaction of the alkylphenol, β-naphthol compound, and formaldehyde is performed, for example, by charging the reaction vessel with alkylphenol and β-naphthol compound, raising the temperature to about 120-200 ° C., adding formaldehyde, and then adding 120-200 It can be performed by a method of reacting for several hours under the temperature condition of ° C.

  At this time, the reaction may be carried out in an organic solvent as necessary, and examples of the organic solvent used here include methyl cellosolve, isopropyl alcohol, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. These organic solvents may be used alone or in combination of two or more. Moreover, it is preferable to use the usage-amount in the case of using these organic solvents in the range of 1-70 mass% with respect to the total mass of a reaction raw material, ie, the total mass of an alkylphenol, a beta-naphthol compound, and formaldehyde.

  After completion of the reaction, the phenolic resin of the present invention can be obtained by drying under heating and reduced pressure conditions.

  The epoxy resin of the present invention has the following structural formula (I)

（式中Ｒ^１は炭素原子数１〜６のアルキル基を、Ｒ^２は炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかを表す。また、ｎは０〜６の整数であり、ｎが２以上の場合複数のＲ^２はそれぞれ同一でも異なっていて良い。）
で表されるエポキシ化合物（ｙ１）と、下記構造式（ＩＩ）

(Wherein R ¹ represents an alkyl group having 1 to 6 carbon atoms, R ² represents any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom. Moreover, n is an integer of 0 to 6, and when n is 2 or more, a plurality of R ² may be the same or different.
An epoxy compound (y1) represented by the following structural formula (II)

（式中Ｒ^２は炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかを表し、ｎは０〜６の整数である。ｎが２以上の場合複数のＲ^２はそれぞれ同一でも異なっていて良い。）
で表されるエポキシ化合物（ｙ２）とを必須の成分として含有し、液体クロマトグラフから算出される両者の含有量の比［（ｙ１）／（ｙ２）］が３〜１００の範囲であることを特徴とする。

(In the formula, R ² represents any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom, and n is an integer of 0 to 6. When n is 2 or more, the plurality of R ² may be the same or different.)
And an epoxy compound (y2) represented by formula (2) as an essential component, and the content ratio [(y1) / (y2)] calculated from the liquid chromatograph is in the range of 3 to 100. Features.

  More specifically, the epoxy resin of the present invention is obtained by polyglycidyl ether of a phenol resin intermediate obtained by polycondensation reaction using alkylphenol, β-naphthol compound, and formaldehyde as raw materials. The epoxy compounds (y1) and (y2) are contained therein in a predetermined ratio.

  The epoxy compound (y1) represented by the structural formula (I) has a low molecular weight and excellent fluidity, and it has a high thermal stability despite its low naphthalene concentration. It has the characteristic that it is excellent in flame retardancy. On the other hand, the epoxy compound (y2) represented by the structural formula (II) has high molecular orientation and excellent low linear expansion, but has insufficient fluidity and a molecular structure with poor thermal stability. Therefore, it is inferior in flame retardancy despite the high naphthalene concentration.

  In the present invention, by setting the content ratio [(y1) / (y2)] of the epoxy compound (y1) and the epoxy compound (y2) in the range of 3 to 100, the excellent characteristics of both compounds can be obtained. Successful realization of an epoxy resin that is synergistically effective and contains the epoxy compound (y2) but has high fluidity and is excellent in any of flame retardancy, base material adhesion, and low linear expansion in cured products. It is a thing.

  Since the epoxy resin of the present invention is more excellent in flame retardancy in a cured product, the ratio of the content of the epoxy compound (y1) and the epoxy compound (y2) [(y1) / (y2)] Is preferably in the range of 4 to 60, more preferably in the range of 5 to 20.

  In the present invention, the ratio [(y1) / (y2)] of the content of the epoxy compound (y1) and the epoxy compound (y2) in the analysis chart of the liquid chromatograph measured under the above-mentioned conditions. It is a value calculated by the ratio of the peak area derived from the epoxy compound (y1) and the peak area derived from the epoxy compound (y2).

  The epoxy compound (y1), which is one of the essential components of the epoxy resin of the present invention, has the following structural formula (I)

（式中Ｒ^１は炭素原子数１〜６のアルキル基を、Ｒ^２は炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかを表す。また、ｎは０〜６の整数であり、ｎが２以上の場合複数のＲ^２はそれぞれ同一でも異なっていて良い。）
で表される分子構造を有する。

(Wherein R ¹ represents an alkyl group having 1 to 6 carbon atoms, R ² represents any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom. Moreover, n is an integer of 0 to 6, and when n is 2 or more, a plurality of R ² may be the same or different.
It has a molecular structure represented by

R ¹ in the structural formula (I) is an alkyl group having 1 to 6 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, Examples thereof include an s-butyl group, a t-butyl group, a pentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group. Among these, a methyl group is preferable because a cured product having high flame retardancy and a low coefficient of linear expansion can be obtained.

In addition, the bonding position of R ^{1 in} the structural formula (I) may be on any carbon atom that forms an aromatic ring, but since it becomes a compound that is easy to produce industrially, the glycidyloxy group is It is preferably on the carbon atom located at the para-position or ortho-position of the carbon atom to be bonded, and since it becomes an epoxy resin with further excellent fluidity, on the carbon atom positioned at the ortho-position of the carbon atom to which the glycidyloxy group is bonded. It is more preferable that

R ² in the structural formula (I) is any one of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom. Specific examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, and pentyl. Group, neopentyl group, hexyl group, cyclohexyl group and the like. The alkoxy group having 1 to 6 carbon atoms is a methoxy group, an ethoxy group, an n-propyloxy group, an i-propyloxy group, an n-butyloxy group, an isobutyloxy group, an s-butyloxy group, or a t-butyloxy group. Pentyloxy group, neopentyloxy group, hexyloxy group, cyclohexyloxy group and the like. Examples of the aryl group include a phenyl group, a naphthyl group, or a structural site in which one or more alkyl groups or alkoxy groups are substituted on the aromatic nucleus. Examples of the aralkyl group include a phenylmethyl group, a naphthylmethyl group, or a structural site in which one or more alkyl groups or alkoxy groups are substituted on the aromatic nucleus. Examples of the halogen atom include a fluorine atom, a bromo atom, and a chlorine atom.

N in the structural formula (I) is a value representing the number of substitutions of R ² and is an integer of 0 to 6. Among them, n is preferably 0 because it is excellent in fluidity, and a cured product having high flame retardancy and low linear expansion coefficient can be obtained.

  That is, the epoxy compound (y1) represented by the structural formula (I) is more preferably the following structural formula (I-1)

で表される分子構造を有するものである。

It has the molecular structure represented by these.

In addition, when the bonding position of R ¹ in the structural formula (I) is on the carbon atom located at the ortho position of the carbon atom to which the glycidyloxy group is bonded, the epoxy compound represented by the structural formula (I) (Y1) represents the following structural formula (Io) or (Ip)

で表されるものとなる。

It will be represented by

  The epoxy compound (y2), which is another essential component of the epoxy resin of the present invention, has the following structural formula (II):

（式中Ｒ^２は炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかを表し、ｎは０〜６の整数である。ｎが２以上の場合複数のＲ^２はそれぞれ同一でも異なっていて良い。）
で表される分子構造を有する。

(In the formula, R ² represents any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom, and n is an integer of 0 to 6. When n is 2 or more, the plurality of R ² may be the same or different.)
It has a molecular structure represented by

R ² and n in the structural formula (II) are synonymous with R ² and n in the structural formula (I), and a cured product having excellent fluidity, high flame retardancy and low linear expansion coefficient is obtained. Therefore, n is preferably 0.

  That is, the epoxy compound (y2) represented by the structural formula (II) is more preferably the following structural formula (II-1)

で表される分子構造を有するものである。

It has the molecular structure represented by these.

  The epoxy resin of the present invention may contain other epoxy compounds in addition to the epoxy compounds (y1) and (y2). In this case, the content of the epoxy compound (y1) in the epoxy resin is sufficiently exerted since the effect of the present invention that a cured product having excellent fluidity and high flame retardancy and low linear expansion coefficient can be obtained. The value calculated from the peak area ratio of GPC is preferably 30% or more, and more preferably 40% or more.

  In addition, content of the said epoxy compounds (y1) and (y2) in an epoxy resin is specifically with respect to the peak area of the whole epoxy resin of this invention in the analysis chart figure of GPC measured on the above-mentioned conditions. It is a value calculated from the ratio of the total peak areas derived from the epoxy compounds (y1) and (y2).

  Further, the total content of the epoxy compounds (y1) and (y2) in the epoxy resin sufficiently exhibits the effect of the present invention that a cured product having high flame retardancy and low linear expansion coefficient can be obtained. Therefore, the content of the epoxy compound (y1) is in the range of 30 to 90%, the content of the epoxy compound (y2) is preferably in the range of 1 to 10%, and the epoxy compound (y1) Is more preferably in the range of 35 to 70%, and the content of the epoxy compound (y2) is more preferably in the range of 3 to 8%.

  The content of each of the epoxy compounds (y1) and (y2) in the epoxy resin is the total content of the epoxy compounds (y1) and (y2) calculated from the GPC analysis chart by the above method. And the value calculated from the ratio [(y1) / (y2)] of the two contents calculated from the analysis chart of the liquid chromatograph by the above method. That is, the total of both contents in the phenol resin calculated from the GPC analysis chart is α%, and the ratio [(y1) / (y2)] of both is expressed by [β / γ]. In this case, the content of the epoxy compound (y1) in the epoxy resin is α × [β / (β + γ)] (%), and the content of the epoxy compound (y2) is α × [γ / (β + γ) ] (%).

  Other epoxy compounds other than the epoxy compounds (y1) and (y2) include, for example, the following structural formula (III)

（式中Ｒ^１は炭素原子数１〜６のアルキル基を、Ｒ^２は炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかを表す。また、ｎは０〜６の整数であり、ｎが２以上の場合複数のＲ^２はそれぞれ同一でも異なっていて良い。）
で表されるエポキシ化合物（ｙ３）や、下記構造式（ＩＶ）

(Wherein R ¹ represents an alkyl group having 1 to 6 carbon atoms, R ² represents any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom. Moreover, n is an integer of 0 to 6, and when n is 2 or more, a plurality of R ² may be the same or different.
An epoxy compound (y3) represented by the following formula (IV)

（式中Ｒ^１は炭素原子数１〜６のアルキル基を、Ｒ^２は炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかを表す。また、ｎは０〜６の整数であり、ｎが２以上の場合複数のＲ^２はそれぞれ同一でも異なっていて良い。ｍは２以上の整数である。）
で表されるエポキシ化合物（ｙ４）が挙げられる。

(Wherein R ¹ represents an alkyl group having 1 to 6 carbon atoms, R ² represents any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom. In addition, n is an integer of 0 to 6, and when n is 2 or more, a plurality of R ² may be the same or different, and m is an integer of 2 or more.)
The epoxy compound (y4) represented by these is mentioned.

^R 1, ^{R 2} and n in the structural formula (III) or (IV) have the same meanings as ^R 1, ^{R 2} and n in the structural formula (I). R ¹ in the structural formula (III) or (IV) is preferably a methyl group because a cured product having high flame retardancy and low linear expansion coefficient can be obtained. In addition, the bonding position of R ^{1 in} the structural formula (III) or (IV) may be on any carbon atom that forms an aromatic ring, but since it becomes a compound that is easy to produce, a glycidyloxy group Is preferably a carbon atom located at the ortho position of the carbon atom to which the glycidyloxy group is bonded, since it is preferably an epoxy resin that is more excellent in fluidity. More preferably. N in the structural formula (III) or (IV) is preferably 0 because a cured product having excellent fluidity and high flame retardancy and low linear expansion coefficient is obtained.

  That is, the epoxy compound (y3) represented by the structural formula (III) is more preferably the following structural formula (III-1)

で表される分子構造を有するものであり、前記構造式（ＩＶ）で表されるエポキシ化合物（ｙ４）は、より好ましくは、下記構造式（ＩＶ−１）

More preferably, the epoxy compound (y4) represented by the structural formula (IV) has a molecular structure represented by the following structural formula (IV-1):

（式中ｍは２以上の整数である。）
で表される分子構造を有するものである。

(In the formula, m is an integer of 2 or more.)
It has the molecular structure represented by these.

  When the epoxy resin of the present invention contains the epoxy compound (y3), the content of each component in the epoxy resin is a value calculated from the peak area ratio of GPC, and the epoxy compounds (y1) and (y2) It is preferable that the total content of is in the range of 30 to 80%, and the content of the epoxy compound (y3) is in the range of 15 to 50%.

  The epoxy resin (y1) represented by the structural formula (Io) or (Ip), the epoxy compound (y3) represented by the structural formula (III-1), When the epoxy compound (y4) represented by the structural formula (IV-1) is contained, that is, when orthocresol is used as the alkylphenol of the resin raw material, an epoxy resin having high fluidity and low linear expansion coefficient in the cured product Therefore, in the epoxy resin, the abundance ratio [(o) / (p)] of the methylene group (o) located at the ortho position of the glycidyloxy group and the methylene group (p) located at the para position is 13C- A value calculated from the NMR chart is preferably in the range of 40/60 to 80/20.

  In the present invention, the abundance ratio [(o) / (p)] between the methylene group (o) and the methylene group (p) is a value calculated from an analysis chart of 13C-NMR measured under the above conditions. Specifically, the peak area derived from the methylene group (o) located at the ortho position of the glycidyloxy group detected at 22 to 27 ppm on the 13C-NMR analysis chart of the epoxy resin, and detected at 28 to 33 ppm It is a value calculated from the ratio to the peak area derived from the methylene group (p) located at the para position of the glycidyloxy group.

  Since the epoxy resin of this invention is excellent in a flame retardance and a hardened | cured material with a low coefficient of linear expansion is obtained, it is preferable that an epoxy equivalent is the range of 210-300 g / eq. Moreover, it is preferable that the value measured on 150 degreeC conditions is the range whose melt viscosity is 0.1-4.0 dPa * s.

In the epoxy resin of the present invention, for example, an alkylphenol, a β-naphthol compound, and formaldehyde are reacted under non-catalytic conditions to obtain a phenol resin intermediate (first step), and then the obtained phenol resin intermediate is converted to epihalohydrin. It can be produced by a method of reacting to glycidyl ether (second step). The phenol resin intermediate obtained in the first step of this production method corresponds to the phenol resin of the present invention described above.

  The alkylphenol used in the first step is, for example, cresol, ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, isobutylphenol, s-butylphenol, t-butylphenol, pentylphenol, neopentylphenol, hexylphenol, cyclo Examples include hexylphenol. Among them, cresol is preferable because a cured product having high flame retardancy and a low coefficient of linear expansion can be obtained.

  The substitution position of the alkyl group in the alkylphenol may be on any carbon atom of the aromatic ring, but since the epoxy compound (y1) is easily formed, the para-position or ortho of the carbon atom to which the glycidyloxy group is bonded. It is preferably on the carbon atom located at the position, and more preferably on the carbon atom located at the ortho position of the carbon atom to which the glycidyloxy group is bonded, since an epoxy resin having further excellent fluidity can be obtained.

  That is, the alkylphenol used in the production method is preferably paracresol or orthocresol, particularly preferably orthocresol.

  The β-naphthol compound used in the production method is, for example, the following structural formula (α)

（式中Ｒ^２は炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかを表し、ｎは０〜６の整数であり、ｎが２以上の場合複数のＲ^２はそれぞれ同一でも異なっていて良い。）
で表されるものが挙げられる。中でも、難燃性が高く線膨張率の低い硬化物が得られることから、置換基を有しないβ−ナフトールであることが好ましい。

(Wherein R ² represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, or a halogen atom, and n is an integer of 0 to 6; When n is 2 or more, the plurality of R ² may be the same or different.)
The thing represented by is mentioned. Among these, β-naphthol having no substituent is preferable because a cured product having high flame retardancy and a low coefficient of linear expansion can be obtained.

  The formaldehyde used in the production method may be either formalin in the form of an aqueous solution or paraformaldehyde in the solid state.

  In the first step of the production method, the reaction ratio between the alkylphenol and the β-naphthol compound is such that the phenolic hydroxyl group-containing compound (x1), which is a precursor of the epoxy compound (y1), is easily generated. The molar ratio [(alkylphenol) / (β-naphthol compound)] is preferably in the range of [10.0 / 1.0] to [1.0 / 2.0], and [4.0 / 1. More preferably, it is in the range of 0] to [1.0 / 1.5].

  Moreover, since the reaction charge of formaldehyde is easy to produce the phenolic hydroxyl group-containing compound (x1), which is a precursor of the epoxy compound (y1), it is based on the total number of moles of alkylphenol and β-naphthol compound. The proportion of formaldehyde is preferably 0.2 to 1.5 times the molar amount, more preferably 0.3 to 1.0 times the molar amount.

  The reaction of the alkylphenol, β-naphthol compound, and formaldehyde is performed under non-catalytic conditions. Thereby, it becomes easy to produce | generate the said phenolic hydroxyl group containing compound (x1) which is a precursor of the said epoxy compound (y1), Content of the said epoxy compound (y1) and the said epoxy compound (y2) in a final product. It is easy to adjust the ratio [(y1) / (y2)] to a range of 3 to 100.

  The reaction of the alkylphenol, β-naphthol compound, and formaldehyde is performed, for example, by charging the reaction vessel with alkylphenol and β-naphthol compound, raising the temperature to about 120-200 ° C., adding formaldehyde, and then adding 120-200 It can be performed by a method of reacting for several hours under the temperature condition of ° C.

  At this time, the reaction may be carried out in an organic solvent as necessary, and examples of the organic solvent used here include methyl cellosolve, isopropyl alcohol, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. These organic solvents may be used alone or in combination of two or more. Moreover, it is preferable to use the usage-amount in the case of using these organic solvents in the range of 1-70 mass% with respect to the total mass of a reaction raw material, ie, the total mass of an alkylphenol, a beta-naphthol compound, and formaldehyde.

  After completion of the first step, the phenol resin intermediate can be obtained by drying under heating and decompression conditions.

  The subsequent second step is a step of reacting the obtained phenolic resin intermediate with epihalohydrin. The reaction in the second step is performed using, for example, 0.9 mol to 2 mol of 1 mol of phenolic hydroxyl group using 1 mol of phenolic hydroxyl group in the phenol resin intermediate and 2 mol of epihalohydrin in a range of 2 to 10 mol. It can be carried out by a method of reacting at a temperature of 20 to 120 ° C. for 0.5 to 10 hours while adding 0 mol of a basic catalyst all at once or dividedly. The basic catalyst used here may be solid or an aqueous solution thereof. When an aqueous solution is used, water and epihalohydrin are continuously added from the reaction mixture under reduced pressure or atmospheric pressure. A method may be employed in which the water is removed by distilling and separating, and the epihalohydrin is continuously returned to the reaction mixture.

  In addition, in the first batch of epoxy resin production, all of the epihalohydrins used for charging are new when industrial production is performed, but after the next batch, the epihalohydrin recovered from the crude reaction product is consumed in the reaction. It is preferable to use in combination with a new epihalohydrin corresponding to the amount disappeared in minutes. At this time, the epihalohydrin used is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and the like. Of these, epichlorohydrin is preferred because it is easily available industrially.

  Specific examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. In particular, alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity of the epoxy resin synthesis reaction, and specific examples include sodium hydroxide and potassium hydroxide. These basic catalysts may be used in the form of an aqueous solution of about 10 to 55% by mass or in the form of a solid. In addition, the reaction between the phenol intermediate and epihalohydrin can increase the reaction rate by using an organic solvent in combination. Although it does not specifically limit as an organic solvent used here, For example, alcohol solvents, such as ketone solvents, such as acetone and methyl ethyl ketone, methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, and tertiary butanol, methyl Examples thereof include cellosolve solvents such as cellosolve and ethyl cellosolve, ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide and dimethylformamide. These organic solvents may be used alone or in combination of two or more kinds in order to adjust the polarity.

  After completion of the reaction, the reaction mixture is washed with water, and unreacted epihalohydrin and the organic solvent to be used in combination are distilled off by distillation under heating and reduced pressure. In addition, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is again dissolved in an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, and alkali metal water such as sodium hydroxide and potassium hydroxide. Further reaction can be carried out by adding an aqueous solution of oxide. At this time, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present for the purpose of improving the reaction rate. When the phase transfer catalyst is used, the amount used is preferably 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the epoxy resin. After completion of the reaction, the produced salt is removed by filtration, washing with water, and the like, and the target epoxy resin of the present invention can be obtained by distilling off a solvent such as toluene and methyl isobutyl ketone under heating and reduced pressure.

  One of the curable compositions of the present invention comprises the phenol resin of the present invention and a curing agent as essential components. As a hardening | curing agent used here, an epoxy resin is mentioned, for example.

  Specifically, the epoxy resin is a diglycidyloxynaphthalene compound such as 1,6-diglycidyloxynaphthalene or 2,7-diglycidyloxynaphthalene; a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, or a naphthol novolak type. Epoxy resins, bisphenol novolac type epoxy resins, novolak type epoxy resins such as mixed novolac type epoxy resins made from multiple types of phenolic hydroxyl group-containing compounds; aralkyl type epoxy resins such as phenol aralkyl type epoxy resins and naphthol aralkyl type epoxy resins A naphthalene skeleton-containing epoxy resin such as 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane; a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, etc. Sphenol type epoxy resin; biphenyl type epoxy resin such as biphenyl type epoxy resin and tetramethylbiphenyl type epoxy resin; triphenylmethane type epoxy resin; tetraphenylethane type epoxy resin; dicyclopentadiene-phenol addition reaction type epoxy resin; Examples thereof include phosphorus-modified epoxy resins in which phosphorus atoms are introduced into various epoxy resins. These may be used alone or in combination of two or more.

  When using an epoxy resin as the curing agent, the blending ratio of the phenol resin and the epoxy resin of the present invention is equivalent ratio of the phenolic hydroxyl group in the phenol resin to the epoxy group in the epoxy resin (phenolic hydroxyl group / epoxy group). Is preferably in the ratio of 1 / 0.5 to 1 / 1.5 because of excellent reactivity and low linear expansion in the cured product.

Moreover, when using an epoxy resin as a hardening | curing agent, you may use together with the hardening | curing agent for other epoxy resins together with the phenol resin of this invention. Examples of other curing agents for epoxy resins include various known curing agents such as amine compounds, amide compounds, acid anhydrides, and phenolic hydroxyl group-containing compounds. Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, and guanidine derivative. Examples of the amide compound include polyamide resin synthesized from dicyandiamide, a dimer of linolenic acid, and ethylenediamine. Sekiic acid anhydrides include, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydro And phthalic anhydride. Examples of the phenolic hydroxyl group-containing compound include dihydroxynaphthalene compounds such as 1,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene; Novolak resin such as mixed novolac as raw material; phenol aralkyl type resin such as phenol aralkyl resin and naphthol aralkyl resin; naphthalene skeleton-containing phenol resin such as 1,1-bis (2,7-dihydroxy-1-naphthyl) alkane; bisphenol Bisphenol compounds such as A and bisphenol F; Biphenyl compounds such as biphenyl and tetramethylbiphenyl; Triphenylol methane; Tetraphenylol ethane; Dicyclo Ntajien - phenol addition reaction type resins; phosphorus-modified phenol compound to introduce a phosphorus atom in these various phenolic hydroxyl group-containing compounds, and the like. These may be used alone or in combination of two or more.

When the other curing agent for epoxy resin is used, the blending ratio of the phenolic resin of the present invention and the curing agent for other epoxy resin is the effect of the present invention, that is, excellent fluidity, high flame retardancy and high linear expansion. If it is the range which does not impair the effect that the hardened | cured material with a low rate is obtained, it will not restrict | limit in particular, For example, the phenol resin of this invention is in the range of 5-95 mass parts in both total mass 100 mass parts. Preferably there is.

  Moreover, when using the other hardening agent for epoxy resins, the compounding ratio with the said epoxy resin is the sum total of the active hydrogen atom which the phenol resin of this invention and the hardening agent for other epoxy resins contain, and an epoxy resin contains It is preferable that the equivalent ratio (active hydrogen atom / epoxy group) to the epoxy group is 1 / 0.5 to 1 / 1.5 because it is excellent in reactivity and low linear expansion in the cured product. .

  Another curable composition of the present invention comprises the epoxy resin of the present invention and a curing agent as essential components.

Examples of the curing agent used here include various known curing agents such as an amine compound, an amide compound, an acid anhydride, and a phenolic hydroxyl group-containing compound. Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, and guanidine derivative. Examples of the amide compound include polyamide resin synthesized from dicyandiamide, a dimer of linolenic acid, and ethylenediamine. Sekiic acid anhydrides include, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydro And phthalic anhydride. Examples of the phenolic hydroxyl group-containing compound include dihydroxynaphthalene compounds such as 1,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene; Novolak resin such as mixed novolac as raw material; phenol aralkyl type resin such as phenol aralkyl resin and naphthol aralkyl resin; naphthalene skeleton-containing phenol resin such as 1,1-bis (2,7-dihydroxy-1-naphthyl) alkane; bisphenol Bisphenol compounds such as A and bisphenol F; Biphenyl compounds such as biphenyl and tetramethylbiphenyl; Triphenylol methane; Tetraphenylol ethane; Dicyclo Ntajien - phenol addition reaction type resins; phosphorus-modified phenol compound to introduce a phosphorus atom in these various phenolic hydroxyl group-containing compounds, and the like. These may be used alone or in combination of two or more.

  In the curable resin composition of the present invention, the mixing ratio of the epoxy resin and the curing agent is such that the equivalent ratio of the epoxy group in the epoxy resin to the active hydrogen atom in the curing agent (epoxy group / active hydrogen atom) is 1. A ratio of 0.5 / 1 / 1.5 is preferable because of excellent reactivity and low linear expansion in the cured product.

  The curable composition of the present invention may contain other epoxy resins in addition to the epoxy resin of the present invention.

  Specific examples of the other epoxy resin include diglycidyloxynaphthalene compounds such as 1,6-diglycidyloxynaphthalene and 2,7-diglycidyloxynaphthalene; phenol novolac epoxy resin, cresol novolac epoxy resin, naphthol Novolac type epoxy resins, bisphenol novolac type epoxy resins, novolak type epoxy resins such as mixed novolac type epoxy resins made from multiple types of phenolic hydroxyl group-containing compounds; aralkyl types such as phenol aralkyl type epoxy resins and naphthol aralkyl type epoxy resins Epoxy resin; naphthalene skeleton-containing epoxy resin such as 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane; bisphenol A type epoxy resin, bisphenol F type epoxy Bisphenol type epoxy resin such as oil; Biphenyl type epoxy resin such as biphenyl type epoxy resin and tetramethylbiphenyl type epoxy resin; Triphenylmethane type epoxy resin; Tetraphenylethane type epoxy resin; Dicyclopentadiene-phenol addition reaction type epoxy resin A phosphorus-modified epoxy resin obtained by introducing a phosphorus atom into these various epoxy resins. These may be used alone or in combination of two or more.

When the other epoxy resin is used, the blending ratio of the epoxy resin of the present invention and the other epoxy resin is the effect of the present invention, that is, a cured product having excellent fluidity, flame retardancy and low linear expansion coefficient. If it is the range which does not impair the effect of being obtained, it will not restrict | limit in particular, For example, it is preferable that the epoxy resin of this invention is the range of 5-95 mass parts in both total mass 100 mass parts.

  When other epoxy resins are used, the mixing ratio of the curable composition is such that the equivalent ratio (epoxy groups / active hydrogen atoms) of the epoxy groups in all epoxy components to the active hydrogen atoms in the curing agent is 1. A ratio of 0.5 / 1 / 1.5 is preferable because of excellent reactivity and low linear expansion in the cured product.

  In the curable composition of the present invention, a curing accelerator can be appropriately used as needed. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. Especially when used as a semiconductor sealing material, imidazole compounds are 2-ethyl-4-methylimidazole, and phosphorus compounds are triphenylphosphine because they are excellent in curability, heat resistance, electrical properties, moisture resistance reliability, and the like. As the tertiary amine, 1,8-diazabicyclo- [5.4.0] -undecene (DBU) is preferable.

  The curable composition of the present invention may further contain other additive components depending on the application and desired performance. Specifically, for the purpose of further improving the flame retardancy, a non-halogen flame retardant containing substantially no halogen atom may be blended.

  Examples of the non-halogen flame retardant include a phosphorus flame retardant, a nitrogen flame retardant, a silicone flame retardant, an inorganic flame retardant, and an organic metal salt flame retardant. These may be used alone or in combination.

  The phosphorus flame retardant can be either inorganic or organic. Examples of the inorganic compound include phosphorous such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate. Examples thereof include inorganic nitrogen-containing phosphorus compounds such as ammonium acids and phosphoric acid amides.

  The red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like, and the surface treatment method is, for example, (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, oxidation A method of coating with an inorganic compound such as bismuth, bismuth hydroxide, bismuth nitrate, or a mixture thereof; (ii) inorganic compounds such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, and phenol resins; (Iii) Double coating with a thermosetting resin such as a phenol resin on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide. And the like.

  The organic phosphorus compounds include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, and 9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7-dihydro And cyclic organic phosphorus compounds such as oxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

  The blending amount thereof is appropriately selected depending on the type of the phosphorus-based flame retardant, the other components of the curable composition, and the desired degree of flame retardancy. For example, in 100 parts by mass of the curable composition When red phosphorus is used as a non-halogen flame retardant, it is preferably blended in the range of 0.1 to 2.0 parts by mass. When an organic phosphorus compound is used, 0.1 to 10.0 parts by mass is similarly applied. It is preferable to mix | blend in the range of 0.5 part, and it is preferable to mix | blend especially in the range of 0.5-6.0 mass part.

  In addition, when using the phosphorous flame retardant, the phosphorous flame retardant may be used in combination with hydrotalcite, magnesium hydroxide, boric compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. Good.

  Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable.

  Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, (i) guanylmelamine sulfate, melem sulfate, melam sulfate (Ii) co-condensates of phenolic compounds such as phenol, cresol, xylenol, butylphenol, nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine, formguanamine and formaldehyde, (iii) (Ii) a mixture of a co-condensate of (ii) and a phenol resin such as a phenol formaldehyde condensate, (iv) a mixture of (ii) and (iii) further modified with paulownia oil, isomerized linseed oil, etc. .

  Examples of the cyanuric acid compound include cyanuric acid and cyanuric acid melamine.

  The compounding amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, the other components of the curable composition, and the desired degree of flame retardancy. For example, the curable composition 100 It is preferable to mix | blend in the range of 0.05-10 mass parts in a mass part, and it is preferable to mix | blend especially in the range of 0.1-5 mass parts.

  Moreover, when using the said nitrogen-type flame retardant, you may use together a metal hydroxide, a molybdenum compound, etc.

  The silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.

  The amount of the silicone-based flame retardant is appropriately selected depending on the type of the silicone-based flame retardant, the other components of the curable composition, and the desired degree of flame retardancy. For example, the curable composition 100 In a mass part, it is preferable to mix | blend in the range of 0.05-20 mass parts. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.

  Examples of the inorganic flame retardant include metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound, and low melting point glass.

  Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, and zirconium hydroxide.

  Examples of the metal oxide include zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, Examples thereof include chromium oxide, nickel oxide, copper oxide, and tungsten oxide.

  Examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.

  Examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.

  Examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

Examples of the low-melting-point glass include Shipley (Bokusui Brown), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, and P ₂ O _5. Glassy compounds such as —B ₂ O ₃ —PbO—MgO, P—Sn—O—F, PbO—V ₂ O ₅ —TeO ₂ , Al ₂ O ₃ —H ₂ O, and lead borosilicate Can be mentioned.

  The blending amount of the inorganic flame retardant is appropriately selected depending on the kind of the inorganic flame retardant, the other components of the curable composition, and the desired degree of flame retardancy. For example, the curable composition 100 It is preferable to mix | blend in the range of 0.5-50 mass parts in a mass part, and it is preferable to mix | blend especially in the range of 5-30 mass parts.

  The organometallic salt flame retardant, for example, ferrocene, acetylacetonate metal complex, organometallic carbonyl compound, organocobalt salt compound, organosulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound are ionically bonded or coordinated Examples include a bonded compound.

  The amount of the organic metal salt flame retardant is appropriately selected depending on the type of the organic metal salt flame retardant, the other components of the curable composition, and the desired degree of flame retardancy. In 100 parts by mass of the composition, it is preferable to blend in the range of 0.005 to 10 parts by mass.

  In addition, various compounding agents such as a silane coupling agent, a release agent, a pigment, and an emulsifier can be added to the curable composition of the present invention as necessary.

  An inorganic filler can be mix | blended with the curable composition of this invention as needed. The phenolic hydroxyl group-containing compound and phenol resin used in the present invention can be suitably used particularly for semiconductor sealing materials.

  Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Especially, since it becomes possible to mix | blend more inorganic fillers, the said fused silica is preferable. 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 an increase in the melt viscosity of the curable composition, a spherical one is mainly used. It is preferable. Furthermore, in order to increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably in the range of 0.5 to 95 parts by mass in 100 parts by mass of the curable composition.

  In addition, when using the curable composition of this invention for uses, such as an electrically conductive paste, electrically conductive fillers, such as silver powder and copper powder, can be used.

  When adjusting the curable composition of this invention to the varnish for printed wiring boards, it is preferable to mix | blend an organic solvent. Examples of the organic solvent that can be used here include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, and propylene glycol monomethyl ether acetate. The amount used can be appropriately selected depending on the application. For example, in printed wiring board applications, it is preferable to use a polar solvent having a boiling point of 160 ° C. or lower, such as methyl ethyl ketone, acetone, dimethylformamide, and the non-volatile content of 40 to 80% by mass. It is preferable to use in the ratio which becomes. On the other hand, in build-up adhesive film applications, as organic solvents, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, It is preferable to use carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like, and the nonvolatile content is 30 to 60% by mass. It is preferable to use in proportions.

  The curable composition of this invention is obtained by mixing each above-mentioned component uniformly. The curable composition of the present invention in which a phenol resin or an epoxy resin, a curing agent and, if necessary, a curing accelerator are blended can be easily made into a cured product by a method similar to a conventionally known method. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.

  The phenol resin and epoxy resin of the present invention are excellent in fluidity, have high flame retardancy in a cured product, and have a low coefficient of linear expansion, and thus can be used for various electronic material applications. Especially, it can use suitably for a semiconductor sealing material application taking advantage of the high fluidity.

  The semiconductor sealing material is, for example, a method of sufficiently mixing other compounds such as the phenolic resin or epoxy resin of the present invention, a curing agent, and a filler until uniform using an extruder, kneader, roll, or the like. Can be adjusted. Examples of the filler used here include the inorganic filler described above. As described above, the filler is preferably used in the range of 0.5 to 95 parts by mass in 100 parts by mass of the curable composition. Of these, flame retardancy, moisture resistance, and solder crack resistance are improved, and the linear expansion coefficient can be reduced. Therefore, it is preferably used in the range of 70 to 95 parts by mass, particularly in the range of 80 to 95 parts by mass. preferable.

  A method for molding a semiconductor package using the obtained semiconductor sealing material is, for example, molding the semiconductor sealing material using a casting or transfer molding machine, an injection molding machine, etc., and a temperature of 50 to 200 ° C. The method of heating for 2 to 10 hours under conditions is mentioned, By such a method, the semiconductor device which is a molding can be obtained.

  Moreover, in order to manufacture a printed circuit board using the phenol resin or epoxy resin of this invention, the varnish-like curable composition containing the phenol resin or epoxy resin of this invention, a hardening | curing agent, an organic solvent, other additives, etc. Can be impregnated into a reinforcing base material, and a copper foil is laminated and heat-pressed. Examples of the reinforcing substrate that can be used here include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. More specifically, the varnish-like curable composition described above is first heated at a heating temperature corresponding to the solvent type used, preferably 50 to 170 ° C., so that a prepreg as a cured product is obtained. obtain. Although it does not specifically limit as a mass ratio of the curable composition used at this time and a reinforcement base material, Usually, it is preferable to prepare so that the resin part in a prepreg may be 20-60 mass%. Next, the prepreg obtained as described above is laminated by a conventional method, and a copper foil is appropriately stacked, and then subjected to thermocompression bonding at a pressure of 1 to 10 MPa at 170 to 250 ° C. for 10 minutes to 3 hours, A desired printed circuit board can be obtained.

  Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “parts” and “%” are based on mass unless otherwise specified. The melt viscosity and liquid chromatograph (HPLC) were measured under the following conditions.

Melt viscosity measurement method: Measured with an ICI viscometer in accordance with ASTM D4287.

Liquid chromatograph (HPLC): Measurement conditions are as follows.
“Agilent 1220 Infinity LC” manufactured by Tosoh Corporation
Column: “TSK-GEL ODS-120T” manufactured by Tosoh Corporation
Detector: VWD 254nm
Data processing: “Agilent EZChrom Elite” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Acetonitrile
Flow rate 1.0ml / min

13C-NMR: Measurement conditions are as follows.
Equipment: “JNM-ECA500” manufactured by JEOL Ltd.
Measurement mode: NNE (1H complete decoupling method for NOE elimination)
Solvent: Heavy chloroform pulse angle: 45 ° Pulse sample concentration: 30 wt%
Integration count: 4000 times

GPC: Measurement conditions are as follows.
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-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 refractometer)
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).

Example 1 Production of Phenol Resin (A-1) A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube and a stirrer was equipped with 288 parts by mass of β-naphthol (2.0 mol) and 216 parts by mass of orthocresol. Parts (2.0 mol) were charged and the temperature was raised from room temperature to 180 ° C. with stirring. Subsequently, 145 parts by mass (2.0 mol) of 41.5% formalin aqueous solution was added over 2 hours. After completion of the addition, the mixture was further stirred at 180 ° C. for 1 hour. After completion of the reaction, the reaction product was dried under heating and reduced pressure to obtain 420 parts by mass of a phenol resin (A-1). The obtained phenol resin (A-1) had a hydroxyl group equivalent of 147 grams / equivalent. A liquid chromatograph (HPLC) chart of the phenol resin (A-1) is shown in FIG. 1, a GPC chart is shown in FIG. 2, and a 13C-NMR chart is shown in FIG.

  The ratio [(x1) / (x2)] of the phenolic hydroxyl group-containing compound (x1) and the phenolic hydroxyl group-containing compound (x2) calculated from the HPLC chart is 9.6, calculated from the GPC chart. The total content of the phenolic hydroxyl group-containing compounds (x1) and (x2) is 55.3%, and the phenolic hydroxyl group-containing compound in the phenol resin (A-1) calculated by the above formula The content of (x1) was 50.1%, the content of the phenolic hydroxyl group-containing compound (x2) was 5.2%, and the content of the phenolic hydroxyl group-containing compound (x3) was 35.5%. . The abundance ratio [(o) / (p)] of the methylene group (o) located at the ortho position of the phenolic hydroxyl group and the methylene group (p) located at the para position calculated from the 13C-NMR chart is 63/37.

Example 2 Production of Phenol Resin (A-2) A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer was equipped with 288 parts by mass of β-naphthol (2.0 mol) and 433 parts by mass of orthocresol. Part (4.0 mol) was charged and the temperature was raised from room temperature to 180 ° C. with stirring. Subsequently, 145 parts by mass (2.00 mol) of a 41.5% formalin aqueous solution was added over 2 hours. After completion of the addition, the mixture was further stirred at 180 ° C. for 1 hour. After completion of the reaction, the reaction product was dried under heating and reduced pressure to obtain 435 parts by mass of a phenol resin (A-2). The obtained phenol resin (A-2) had a hydroxyl group equivalent of 139 grams / equivalent. A GPC chart of the phenol resin (A-2) is shown in FIG. 4, and a 13C-NMR chart is shown in FIG.

  The ratio [(x1) / (x2)] of the phenolic hydroxyl group-containing compound (x1) and the phenolic hydroxyl group-containing compound (x2) calculated from the HPLC chart is 13.0, calculated from the GPC chart. The total content of the phenolic hydroxyl group-containing compounds (x1) and (x2) is 76.8%, and the phenolic hydroxyl group-containing compound in the phenol resin (A-2) calculated by the above formula The content of (x1) was 71.3%, the content of the phenolic hydroxyl group-containing compound (x2) was 5.5%, and the content of the phenolic hydroxyl group-containing compound (x3) was 19.2%. . The abundance ratio [(o) / (p)] of the methylene group (o) located at the ortho position of the phenolic hydroxyl group and the methylene group (p) located at the para position calculated from the 13C-NMR chart is 76/24.

Example 3 Production of Epoxy Resin (B-1) 147 parts by mass of phenol resin (A-1) obtained in Example 1 (hydroxyl group 1. 0 equivalents), 463 parts by mass of epichlorohydrin (5.0 mol) and 53 parts by mass of n-butanol were charged and dissolved while stirring. After the temperature was raised to 50 ° C., 220 parts by mass of a 20% aqueous sodium hydroxide solution (1.10 mol) was added over 3 hours, and the reaction was further continued at 50 ° C. for 1 hour. After completion of the reaction, stirring was stopped, the aqueous layer accumulated in the lower layer was removed, stirring was resumed, and unreacted epichlorohydrin was distilled off under reduced pressure at 150 ° C. Then, 300 parts by mass of methyl isobutyl ketone and 50 parts by mass of n-butanol were added to the resulting crude epoxy resin and dissolved. Further, 15 parts by mass of a 10% by mass sodium hydroxide aqueous solution was added to this solution and reacted at 80 ° C. for 2 hours. Next, the system was dehydrated by azeotropic distillation, and after microfiltration, the solvent was distilled off under reduced pressure to obtain 180 parts by mass of the desired epoxy resin (B-1). The epoxy equivalent of the obtained epoxy resin (B-1) was 227 grams / equivalent. A liquid chromatograph (HPLC) chart of the epoxy resin (B-1) is shown in FIG. 6, a GPC chart is shown in FIG. 7, and a 13C-NMR chart is shown in FIG.

The ratio [(y1) / (y2)] of the epoxy compound (y1) and the epoxy compound (y2) calculated from the HPLC chart is 7.4, and the epoxy compound (y1 calculated from the GPC chart) ) And (y2), the total content is 46.2%, the content of the epoxy compound (y1) in the epoxy resin (B-1) calculated by the above formula is 40.7%, The content of the epoxy compound (y2) was 5.5%, and the content of the epoxy compound (y3) was 34.2%. The abundance ratio [(o) / (p)] of the methylene group (o) located at the ortho position of the glycidyloxy group and the methylene group (p) located at the para position calculated from the 13C-NMR chart is 63/37.

Example 4 Production of Epoxy Resin (B-2) 139 parts by mass of phenol resin (A-2) obtained in Example 1 (hydroxyl group 1. 0 equivalents), 463 parts by mass of epichlorohydrin (5.0 mol) and 53 parts by mass of n-butanol were charged and dissolved while stirring. After the temperature was raised to 50 ° C., 220 parts by mass of a 20% aqueous sodium hydroxide solution (1.10 mol) was added over 3 hours, and the reaction was further continued at 50 ° C. for 1 hour. After completion of the reaction, stirring was stopped, the aqueous layer accumulated in the lower layer was removed, stirring was resumed, and unreacted epichlorohydrin was distilled off under reduced pressure at 150 ° C. Then, 300 parts by mass of methyl isobutyl ketone and 50 parts by mass of n-butanol were added to the resulting crude epoxy resin and dissolved. Further, 15 parts by mass of a 10% by mass sodium hydroxide aqueous solution was added to this solution and reacted at 80 ° C. for 2 hours. Next, the system was dehydrated by azeotropic distillation, and after microfiltration, the solvent was distilled off under reduced pressure to obtain 175 parts by mass of the desired epoxy resin (B-1). The epoxy equivalent of the obtained epoxy resin (B-2) was 226 grams / equivalent. A GPC chart of the epoxy resin (B-2) is shown in FIG. 9, and a 13C-NMR chart is shown in FIG.

The content ratio [(y1) / (y2)] of the epoxy compound (y1) and the epoxy compound (y2) calculated from the HPLC chart is 10.2, and the epoxy compound (y1 calculated from the GPC chart) ) And (y2), the total content is 64.0%, the content of the epoxy compound (y1) in the epoxy resin (B-2) calculated by the above formula is 58.3%, The content of the epoxy compound (y2) was 5.7%, and the content of the epoxy compound (y3) was 19.3%. The abundance ratio [(o) / (p)] of the methylene group (o) located at the ortho position of the glycidyloxy group and the methylene group (p) located at the para position calculated from the 13C-NMR chart is 76/24.

Comparative Synthesis Example 1 Production of Phenolic Resin (A′-1) 288 parts by mass of β-naphthol (2.0 moles), isopropyl alcohol in a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer 250 parts by mass, 122% by mass of a 37% formalin aqueous solution (1.50 mol) and 31 parts by mass of 49% sodium hydroxide (0.38 mol) were added, and the temperature was raised from room temperature to 75 ° C. with stirring. Stir for 1 hour. Subsequently, 54 parts by mass (0.5 mol) of orthocresol was charged, and the mixture was further stirred at 75 ° C. for 8 hours. After completion of the reaction, the reaction mixture was neutralized by adding 45 parts by mass of first sodium phosphate, added with 630 parts by mass of methyl isobutyl ketone, washed with 158 parts by mass of water three times, and then dried under heating under reduced pressure to obtain a phenol resin. (A'-1) 340 mass parts was obtained. The GPC chart of the obtained phenol resin (A′-1) is shown in FIG. The hydroxyl equivalent of the phenolic resin (A′-1) is 144 g / equivalent, and no peak corresponding to the phenolic hydroxyl group-containing compound (x1) is detected from the HPLC chart. The phenolic hydroxyl group-containing compound (x1) and The content ratio [(x1) / (x2)] to the phenolic hydroxyl group-containing compound (x2) is 0, and the phenolic hydroxyl group-containing compound (x1) and (x2) calculated from the GPC chart The total content was 45.2%, and the content of the phenolic hydroxyl group-containing compound (x3) was 42.5%.

Comparative Synthesis Example 2 Production of Epoxy Resin (B′-1) 180 parts by mass of the epoxy resin (B′-1) was changed in the same manner as in Example 1 except that the phenol resin (A′-1) was changed to 144 parts by mass. Obtained. The epoxy equivalent of the obtained epoxy resin (B′-1) was 229 g / equivalent. A GPC chart of the epoxy resin (B′-1) is shown in FIG. The ratio [(y1) / (y2)] of the content of the epoxy compound (y1) and the epoxy compound (y2) calculated from the HPLC chart is 0, and the epoxy compound (y1 calculated from the GPC chart) ) And (y2) was 38.9%, and the content of the epoxy compound (y3) was 36.3%.

Comparative Synthesis Example 3 Production of Epoxy Resin (B′-2) 180 parts by mass of epoxy resin (B′-2) was obtained in the same manner as Example 7 described in JP-A-2000-53739. The epoxy equivalent of the obtained epoxy resin (B′-2) was 219 grams / equivalent. The content ratio [(y1) / (y2)] of the epoxy compound (y1) and the epoxy compound (y2) calculated from the HPLC chart is 2.2, and the epoxy compound calculated from the GPC chart The total content of (y1) and (y2) was 28.0%, and the content of the epoxy compound (y3) was 41.2%. The abundance ratio [(o) / (p)] of the methylene group (o) located at the ortho position of the glycidyloxy group and the methylene group (p) located at the para position calculated from the 13C-NMR chart is 37/63.

Examples 5-12 and Comparative Examples 1-6
Phenol resins (A-1), (A-2), (A′-1) obtained above, epoxy resins (B-1), (B-2), (B′-1), (B′- For 2), various evaluation tests were performed in the following manner.

<Measurement of melt viscosity>
The phenol resins (A-1), (A-2), (A′-1), epoxy resins (B-1), (B-2), (B′-1), (B′-2), respectively. The melt viscosity at 150 ° C. was measured according to ASTM D4287. The results are shown in Table 1.

<Measurement of linear expansion coefficient>
1) Preparation of evaluation sample The phenol resins (A-1), (A-2), (A′-1), epoxy resins (B-1), (B-2), (B′-1), ( One of B′-2), a curing agent, and triphenylphosphine (hereinafter abbreviated as “TPP”) as a curing accelerator were blended in the compositions shown in Table 2 to obtain a curable composition. The obtained curable composition was molded for 90 seconds at a temperature of 175 ° C. using a transfer molding machine, and then post-cured at a temperature of 175 ° C. for 5 hours to prepare a resin plate. The resin plate was cut into a size of 5 mm × 5 mm × 0.8 mm, and a thermomechanical analysis was performed in a compression mode using a thermomechanical analyzer (TMA: Seiko Instruments SS-6100) as a test piece. .
Measurement conditions Measurement weight: 88.8mN
Temperature increase rate: 2 times at 3 ° C / min Measurement temperature range: -50 ° C to 270 ° C
The measurement under the above conditions was performed twice for the same sample, and the average linear expansion coefficient in the temperature range of 40 ° C. to 60 ° C. in the second measurement was evaluated.

<Measurement of adhesion>
1) Preparation of evaluation sample The phenol resins (A-1), (A-2), (A′-1), epoxy resins (B-1), (B-2), (B′-1), ( One of B′-2), a curing agent, and triphenylphosphine (hereinafter abbreviated as “TPP”) as a curing accelerator were blended in the compositions shown in Table 2 to obtain a curable composition. The obtained curable composition was press-molded with a glossy surface of 18 μm rolled copper foil for 90 seconds at a temperature of 175 ° C., and then post-cured at a temperature of 175 ° C. for 5 hours. Then, it cut out to the size of 100 mm x 100 mm x 10 mm, and it evaluated by the peel strength when peeling a rolled copper foil in a 90 degreeC direction using this as a test piece.

Curing agent curing agent used (1): Biphenyl aralkyl type epoxy resin (“NC-3000” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 274 g / equivalent)
Curing agent (2): Phenol aralkyl resin (“XLC-3L” manufactured by Mitsui Chemicals, hydroxyl equivalent: 176 g / equivalent)

<Evaluation of flame retardancy>
1) Preparation of evaluation sample The phenol resins (A-1), (A-2), (A′-1), epoxy resins (B-1), (B-2), (B′-1), ( B′-2), a curing agent, triphenylphosphine (hereinafter abbreviated as “TPP”) as a curing accelerator, spherical silica (“FB-560” manufactured by Electrochemical Co., Ltd.) as an inorganic filler, silane cup As a ring agent, a coupling agent (“KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.), carnauba wax (“PEARL WAX No. 1-P” manufactured by Celalica Noda Co., Ltd.), and carbon black are used in the composition shown in Table 3 below. It mix | blended and melt-kneaded for 5 minutes at the temperature of 85 degreeC using 2 rolls, and obtained the curable composition. Using the obtained curable composition, a sample having a width of 12.7 mm, a length of 127 mm, and a thickness of 1.6 mm was molded by a transfer molding machine at a temperature of 175 ° C. for 90 seconds, and then at a temperature of 175 ° C. for 5 hours. After curing, an evaluation sample was obtained.
2) Evaluation of flame retardance Using the five samples for evaluation having a thickness of 1.6 mm obtained in advance, a combustion test was conducted in accordance with the UL-94 test method. The results are shown in Table 3.
Flame retardant test class * 1: Maximum burning time in one flame contact (seconds)
* 2: Total burning time of 5 test pieces (seconds)

Claims (18)

The following structural formula (i)

(Wherein R ¹ represents an alkyl group having 1 to 6 carbon atoms, R ² represents any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom. Moreover, n is an integer of 0 to 6, and when n is 2 or more, the plurality of R ² may be the same or different.
A phenolic hydroxyl group-containing compound (x1) represented by the following structural formula (ii)

(In the formula, R ² represents any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom, and n is an integer of 0 to 6. When n is 2 or more, the plurality of R ² may be the same or different.)
The phenolic hydroxyl group-containing compound represented by the formula (x2) is contained as an essential component, and the ratio [(x1) / (x2)] of both calculated from a liquid chromatograph is in the range of 3-100. A phenolic resin characterized by being. In addition to the phenolic hydroxyl group-containing compounds (x1) and (x2), the following structural formula (iii)

(Wherein R ¹ represents an alkyl group having 1 to 6 carbon atoms, R ² represents any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom. In addition, n is an integer of 0 to 6, and when n is 2 or more, the plurality of R ² may be the same or different.
The phenol resin of Claim 1 containing the phenolic hydroxyl group containing compound (x3) represented by these. The phenol resin according to claim 1, which is obtained by a method in which an alkylphenol, a β-naphthol compound, and formaldehyde are reacted under non-catalytic conditions. The phenol resin according to claim 1, wherein the hydroxyl equivalent is in the range of 130 to 150 g / eq. A curable composition containing the phenol resin according to any one of claims 1 to 4 and a curing agent. A cured product obtained by curing reaction of the curable composition according to claim 5. The semiconductor sealing material which contains an inorganic filler in addition to the curable composition of Claim 5. A printed wiring board obtained by impregnating a reinforcing base material with a mixture of the curable composition according to claim 5 and an organic solvent, and stacking a copper foil and heat-pressing it. A method for producing a phenol resin, comprising reacting an alkylphenol, a β-naphthol compound, and formaldehyde under non-catalytic conditions. The following structural formula (I)

(Wherein R ¹ represents an alkyl group having 1 to 6 carbon atoms, R ² represents any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom. Moreover, n is an integer of 0 to 6, and when n is 2 or more, a plurality of R ² may be the same or different.
An epoxy compound (y1) represented by the following structural formula (II)

(In the formula, R ² represents any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom, and n is an integer of 0 to 6. When n is 2 or more, the plurality of R ² may be the same or different.)
And an epoxy compound (y2) represented by formula (2) as an essential component, and the content ratio [(y1) / (y2)] calculated from the liquid chromatograph is in the range of 3 to 100. Characteristic epoxy resin. In addition to the epoxy compounds (y1) and (y2), the following structural formula (III)

(Wherein R ¹ represents an alkyl group having 1 to 6 carbon atoms, R ² represents any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, and a halogen atom. Moreover, n is an integer of 0 to 6, and when n is 2 or more, a plurality of R ² may be the same or different.
The epoxy resin of Claim 10 containing the epoxy compound (y3) represented by these. The epoxy resin according to claim 10, which is obtained by a method in which an alkylphenol, a β-naphthol compound, and formaldehyde are reacted under non-catalytic conditions to obtain a phenol intermediate, and then the obtained phenol intermediate is reacted with an epihalohydrin. The epoxy resin according to claim 10, wherein the epoxy group equivalent is in the range of 210 to 300 g / eq. A curable composition comprising the epoxy resin according to any one of claims 10 to 13 and a curing agent. A cured product obtained by curing reaction of the curable composition according to claim 14. The semiconductor sealing material which contains an inorganic filler in addition to the curable composition of Claim 14. A printed wiring board obtained by impregnating a reinforcing base material with a mixture of the curable composition according to claim 14 and an organic solvent, and stacking copper foils and heat-pressing them. A method for producing an epoxy resin, comprising reacting an alkylphenol, a β-naphthol compound, and formaldehyde under a non-catalytic condition to obtain a phenol intermediate, and then reacting the obtained phenol intermediate with an epihalohydrin.

Images