JP2013053239A - Calixarene compound, method for producing calixarene compound, curing agent for epoxy resin, epoxy resin composition and electronic component device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel calixarene compound which, when an epoxy resin composition is prepared, can be used as a curing agent for epoxy resin having good solubility and capable of imparting high heat resistance to an epoxy resin cured product.SOLUTION: The calixarene compound has a specific structure represented by formula (I-1). (In formula (I-1), n is a number of 2-20 on an average; in its unit structure, with respect to each of n repetitions, R, Rand Rmay be the same or different; Ris a hydrogen atom or a monovalent substituent represented by formula (I-2); at least one Rin one molecule is a hydrogen atom; Rin formula (I-2), with respect to each of n repetitions, may be the same or different and each independently represents a hydrogen atom or a 1-18C hydrocarbon group which may have a substituent). (In formula (I-2), Ris each independently selected from the group consisting of a hydrogen atom, a 1-18C hydrocarbon group which may have a substituent, a 1-18C hydrocarbonoxy group which may have a substituent, a 1-18C hydrocarbonthio group which may have a substituent, and a halogen atom, and all may be the same or different; Ris each independently selected from the group consisting of 0-18C divalent organic groups, and all may be the same or different).

Description

  The present invention relates to a calixarene compound, a method for producing the same, an epoxy resin curing agent, an epoxy resin composition, and an electronic component device including an element sealed thereby.

  Conventionally, curable resins such as epoxy resins have been widely used in the fields of molding materials, laminates and adhesives, various electronic and electrical components, paints and ink materials. In particular, epoxy resin compositions are widely used as sealing materials in the field related to sealing technology for electronic component elements such as transistors and ICs. This is because epoxy resins are balanced in various properties such as moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserts.

  On the other hand, in recent years, in the field of electronic components, speeding up and density increase have progressed, and accordingly, heat generation of electronic components has become remarkable. In addition, electronic components that operate at high temperatures are also increasing. For this reason, plastics used for electronic parts, particularly cured epoxy resins, are required to have high heat resistance and little change in physical properties compared to room temperature at high temperatures.

  In order to improve various properties of cured epoxy resins including heat resistance, methods using calixarenes as curing agents have been reported (see Patent Documents 1 to 5). According to these methods, it is possible to improve the glass transition temperature of the cured epoxy resin and to impart high heat resistance.

JP 2000-264953 A JP 2001-106868 A JP-A-2-123126 Japanese Patent Laid-Open No. 3-66724 JP-A-6-136341

  However, since the curing agent used in the above method has low solubility with the constituent components of the epoxy resin composition, the curing reaction does not proceed completely, and performance such as moisture resistance and electrical properties may be reduced. There is a problem that sufficient performance is not exhibited.

  The object of the present invention is a novel calixarene system that has good solubility when made into an epoxy resin composition and can be used as a curing agent for epoxy resins that can impart high heat resistance to cured epoxy resins. It is to provide a compound.

  Moreover, the other subject of this invention is providing the electronic component apparatus provided with the epoxy resin composition containing the said hardening | curing agent for epoxy resins, and the element sealed by it.

As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have obtained a novel calixarene compound obtained by β-alkenyl etherification of part or all of the phenolic hydroxyl group of the calixarene compound. It was useful as a curing agent for epoxy resins, and it was found that the intended problem could be achieved, and the present invention was completed.
The present invention relates to the following.

（上記式（Ｉ−１）中、ｎは平均で２〜２０の数であり、単位構造内、ｎ個の繰り返しのそれぞれに関して、Ｒ^１、Ｒ^２、Ｒ^３は同一でも異なっていてもよく、
Ｒ^１は、水素原子又は下記式（Ｉ−２）で示される１価の置換基であり、１分子中の少なくとも１つのＲ^１は水素原子であり、下記式（Ｉ−２）中のＲ^４は、ｎ個の繰り返しのそれぞれに関して、Ｒ^４は同一でも異なっていてもよく、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜１８の炭化水素基を示す。

Ｒ^２は、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜１８の炭化水素基、置換基を有していてもよい炭素数１〜１８の炭化水素オキシ基、置換基を有していてもよい炭素数１〜１８の炭化水素チオ基、及びハロゲン原子からなる群より選ばれ、全てが同一でも異なっていてもよく、
Ｒ^３は、それぞれ独立して、炭素数０〜１８の２価の有機基からなる群より選ばれ、全てが同一でも異なってもよい。） (1) A calixarene compound represented by the following formula (I-1).

(In the above formula (I-1), n is an average number of 2 to 20, and R ¹ , R ² , and R ³ may be the same or different with respect to each of n repetitions in the unit structure. ,
R ¹ is a hydrogen atom or a monovalent substituent represented by the following formula (I-2), at least one R ^{1 in} one molecule is a hydrogen atom, and R in the following formula (I-2) ⁴ represents each of n repetitions, R ⁴ may be the same or different, and each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent. .

R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , A hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom, all may be the same or different,
R ³ is independently selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, and all may be the same or different. )

（上記式（Ｉ−３）中、ｎは平均で２〜２０の数であり、単位構造内、ｎ個の繰り返しのそれぞれに関して、Ｒ^２、Ｒ^３は同一でも異なっていてもよく、
Ｒ^２は、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜１８の炭化水素基、置換基を有していてもよい炭素数１〜１８の炭化水素オキシ基、置換基を有していてもよい炭素数１〜１８の炭化水素チオ基、及びハロゲン原子からなる群より選ばれ、全てが同一でも異なっていてもよく、
Ｒ^３は、それぞれ独立して、炭素数０〜１８の２価の有機基からなる群より選ばれ、全てが同一でも異なってもよい。） (2) The calixarene compound according to (1) above, wherein 5 to 100% of the phenolic hydroxyl group of the calixarene compound (b1) represented by the following formula (I-3) is β-alkenyl etherified.

(In the above formula (I-3), n is an average number of 2 to 20, and R ² and R ³ may be the same or different for each of n repetitions in the unit structure,
R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , A hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom, all may be the same or different,
R ³ is independently selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, and all may be the same or different. )

(3) The calixarene compound as described in (1) or (2) above, wherein R ^{2 in the} formulas (I-1) and (I-3) is a hydrogen atom.
(4) The calixarene according to any one of the above (1) to (3), wherein R ^{3 in the} formulas (I-1) and (I-3) is (CH ₂ ) ₃ Compounds.

(5) reacting the calixarene compound (b1) represented by the formula (I-3) with at least one compound selected from the group of β-alkenyl halides represented by the formula (I-4). The method for producing a calixarene compound according to any one of (1) to (4) above,

（上記式（Ｉ−４）中、Ｒ^４は、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜１８の炭化水素基からなる群より選ばれ、全てが同一でも異なっていてもよく、Ｘは、ハロゲン原子から選ばれる。）

(In the above formula (I-4), each R ⁴ is independently selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, and all are the same. However, it may be different, and X is selected from halogen atoms.)

（上記式（Ｉ−５）中、Ｒ^１は、水素原子又は下記式（Ｉ−２）で示される１価の置換基であり、

１分子中の少なくとも１つのＲ^１は水素原子であり、前記式（Ｉ−２）中のＲ^４は、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜１８の炭化水素基を示す。
Ｒ^２は、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜１８の炭化水素基、置換基を有していてもよい炭素数１〜１８の炭化水素オキシ基、置換基を有していてもよい炭素数１〜１８の炭化水素チオ基、及びハロゲン原子からなる群より選ばれ、全てが同一でも異なっていてもよい。）

（上記式（Ｉ−５’）中、Ｒ^３は、それぞれ独立して、炭素数０〜１８の２価の有機基からなる群より選ばれ、全てが同一でも異なってもよい。） (6) Resorcinol derivative represented by the following formula (I-5) is reacted with at least one compound selected from the group of dialdehydes represented by the following formula (I-5 ′) (1) The manufacturing method of the calixarene compound as described in any one of (4).

(In the above formula (I-5), R ¹ is a hydrogen atom or a monovalent substituent represented by the following formula (I-2),

At least one R ¹ in one molecule is a hydrogen atom, the formula (I-2) R ⁴ in each independently represent a hydrogen atom, carbon atoms which may have a substituent 1 to 18 Represents a hydrocarbon group.
R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , A hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom, all of which may be the same or different. )

(In the above formula (I-5 ′), each R ³ is independently selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, and all may be the same or different.)

(7) A curing agent for epoxy resins, wherein the calixarene compound according to any one of (1) to (4) above is used.
(8) An epoxy resin composition comprising an epoxy resin and the epoxy resin curing agent according to (7) above.
(9) An electronic component device comprising an element sealed with the epoxy resin composition according to (8).

  According to the present invention, there is provided a novel calixarene compound as a curing agent for an epoxy resin that has good solubility when formed into an epoxy resin composition and can impart high heat resistance to the cured epoxy resin. be able to. Moreover, according to this invention, the electronic component apparatus provided with the epoxy resin composition containing the said hardening | curing agent for epoxy resins, and the element sealed by it can be provided.

It is a figure which shows the dynamic viscoelastic behavior of 175 degreeC and a 6-hour postcure in an Example and a comparative example. It is a figure which shows the dynamic viscoelastic behavior of 250 degreeC and the postcure after 6 hours in an Example and a comparative example.

Hereinafter, the present invention will be described in detail.
<Calixarene compounds>
The calixarene compound of the present invention is represented by the following formula (I-1).

Ｒ^２は、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜１８の炭化水素基、置換基を有していてもよい炭素数１〜１８の炭化水素オキシ基、置換基を有していてもよい炭素数１〜１８の炭化水素チオ基、及びハロゲン原子からなる群より選ばれ、全てが同一でも異なっていてもよく、
Ｒ^３は、それぞれ独立して、炭素数０〜１８の２価の有機基からなる群より選ばれ、全てが同一でも異なってもよい。） (In the above formula (I-1), n is an average number of 2 to 20, and R ¹ , R ² , and R ³ may be the same or different with respect to each of n repetitions in the unit structure. ,
R ¹ is a hydrogen atom or a monovalent substituent represented by the following formula (I-2), at least one R ^{1 in} one molecule is a hydrogen atom, and R in the following formula (I-2) ⁴ represents each of n repetitions, R ⁴ may be the same or different, and each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent. .

R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , A hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom, all may be the same or different,
R ³ is independently selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, and all may be the same or different. )

  Note that the “optionally substituted hydrocarbon group having 1 to 18 carbon atoms” here may be any hydrocarbon group having 1 to 18 carbon atoms in the main skeleton, and these hydrocarbons have. A part of hydrogen atoms may be substituted with other atoms (for example, halogen etc.) or substituents such as alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups and the like.

  Similarly, the “hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent” may be any hydrocarbon oxy group having 1 to 18 carbon atoms in the main skeleton. Some of the hydrogen atoms may be substituted with other atoms (for example, halogen etc.) or substituents such as alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, etc. The “hydrocarbon thio group having 1 to 18 carbon atoms that may be present” may be any hydrocarbon thio group having 1 to 18 carbon atoms in the main skeleton, and a part of the hydrogen atoms that these hydrocarbons have. It may be substituted by other atoms (for example, halogen etc.) or substituents such as alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups and the like.

  From the viewpoint of solubility, the calixarene compound has a structure in which 5 to 100% of the phenolic hydroxyl group of the calixarene compound (b1) represented by the following formula (I-3) is β-alkenyl etherified. Preferably, 10 to 50% has a structure formed by β-alkenyl etherification.

(In the above formula (I-3), n is an average number of 2 to 20, and R ² and R ³ may be the same or different for each of n repetitions in the unit structure,
R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , A hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom, all may be the same or different,
R ³ is independently selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, and all may be the same or different. )

In the above formulas (I-1) to (I-3), each R ² independently has a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, or a substituent. And a hydrocarbon oxy group having 1 to 18 carbon atoms which may be substituted, a hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom.

As the hydrocarbon group having 1 to 18 carbon atoms which may have a substituent as R ² , an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, alicyclic Hydrocarbon group, aromatic hydrocarbon group, etc., for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group , Aliphatic hydrocarbon groups such as decyl group, dodecyl group, allyl group, vinyl group;
These aliphatic hydrocarbon groups include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, an epoxy group-containing group, a methacryloyl group, Substituted with mercapto group, imino group, ureido group, isocyanate group, etc .;
An alicyclic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group;
A group containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, or an epoxy group, a methacryloyl group , Mercapto group, imino group, ureido group, isocyanate group and the like substituted;
An aromatic hydrocarbon group such as phenyl group, tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group;
Further groups containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, and an epoxy group, a methacryloyl group, a mercapto group, and an imino group And the like substituted with a group, a ureido group or an isocyanate group.

Examples of the hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent as R ² include an aliphatic hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent, and an aliphatic group. Cyclic hydrocarbonoxy group, aromatic hydrocarbonoxy group, etc., for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group , Aliphatic hydrocarbon oxy groups such as hexyloxy group, octyloxy group, decyloxy group, dodecyloxy group, allyloxy group, vinyloxy group;
A group containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group or an epoxy group, a methacryloyl group , Mercapto group, imino group, ureido group, isocyanate group and the like substituted;
Cycloaliphatic hydrocarbon oxy groups such as cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclopentenyloxy group, cyclohexenyloxy group;
These alicyclic hydrocarbon oxy groups include an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, and an epoxy group, methacryloyl Substituted with a group, mercapto group, imino group, ureido group, isocyanate group, etc .;
Aromatic hydrocarbon oxy groups such as phenoxy group, tolyloxy group, dimethylphenoxy group, ethylphenoxy group, butylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, ethoxyphenoxy group, butoxyphenoxy group, tert-butoxyphenoxy group;
Further groups containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, and an epoxy group, a methacryloyl group, a mercapto group, and an imino group And the like substituted with a group, a ureido group or an isocyanate group.

Examples of the hydrocarbon thio group having 1 to 18 carbon atoms that may have a substituent as R ² include an aliphatic hydrocarbon thio group having 1 to 18 carbon atoms that may have a substituent, and an aliphatic group. Cyclic hydrocarbon thio group, aromatic hydrocarbon thio group, etc., for example, methylthio group, ethylthio group, propylthio group, isopropylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, pentylthio group, Aliphatic hydrocarbon thio groups such as hexylthio group, octylthio group, decylthio group, dodecylthio group, allylthio group, vinylthio group;
A group containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, or an epoxy group, a methacryloyl group , Mercapto group, imino group, ureido group, isocyanate group and the like substituted;
Cycloaliphatic hydrocarbon thio groups such as cyclopentylthio group, cyclohexylthio group, cycloheptylthio group, cyclopentenylthio group, cyclohexenylthio group;
These alicyclic hydrocarbon thio groups, groups containing an epoxy group such as an alkyl group, alkoxy group, aryl group, aryloxy group, hydroxyl group, amino group, halogen atom, glycidyloxy group, epoxycyclohexyl group, epoxy group, etc., methacryloyl Substituted with a group, mercapto group, imino group, ureido group, isocyanate group, etc .;
Phenylthio group, tolylthio group, dimethylphenylthio group, ethylphenylthio group, butylphenylthio group, tert-butylphenylthio group, methoxyphenylthio group, ethoxyphenylthio group, butoxyphenylthio group, tert-butoxyphenylthio group, etc. An aromatic hydrocarbon thio group of
Further groups containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, and an epoxy group, a methacryloyl group, a mercapto group, and an imino group And the like substituted with a group, a ureido group or an isocyanate group.

Examples of the halogen atom as R ² include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.
Among these, R ² is preferably a hydrogen atom from the viewpoint of high heat resistance.

In the above formulas (I-1) to (I-3), R ³ is selected from the group consisting of a divalent organic group having 0 to 18 carbon atoms, such as an oxygen atom, a sulfur atom, a sulfoxide group, Examples thereof include a sulfonyl group and a divalent hydrocarbon group having 1 to 18 carbon atoms which may have a substituent.

  In this case, the “divalent hydrocarbon group having 1 to 18 carbon atoms which may have a substituent” may be any hydrocarbon group having a main skeleton of 1 to 18 carbon atoms. A part of hydrogen atoms of the hydrocarbon may be substituted with other atoms (for example, halogen etc.) or substituents such as alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups.

Examples of the divalent hydrocarbon group having 1 to 18 carbon atoms that may have the above substituent as R ³ include aliphatic hydrocarbon groups such as a methylene group, an ethylene group, and a propylene group;
An alicyclic hydrocarbon group such as a cyclohexylene group and a cyclopentylene group;
Those substituted with an alkyl group, alkoxy group, aryl group, aryloxy group, amino group, halogen or the like on these aliphatic hydrocarbon group or alicyclic hydrocarbon group;
Aromatic hydrocarbon groups such as phenylene group, naphthylene group, anthracenylene group;
These aromatic hydrocarbon groups are substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen, and the like.

Among the divalent organic groups having 0 to 18 carbon atoms as R ³ , an aliphatic hydrocarbon group which may have a substituent is preferable from the viewpoint of ease of synthesis and synthesis yield. A propylene group which may have a substituent is more preferable, and a propylene group having no substituent is more preferable. Examples of the propylene group which may have a substituent include a methylpropylene group, an ethylpropylene group, an isopropylpropylene group, a phenylpropylene group, and a dimethylpropylene group.

R ¹ in the above formula (I-1) is a hydrogen atom or a monovalent substituent represented by the following formula (I-2), and at least one R ^{1 in} one molecule is a hydrogen atom. (I-2) R ⁴ in the for each of the n repeating, R ⁴ may be the same or different, each independently, a hydrogen atom, carbon atoms which may have a substituent 1 -18 hydrocarbon groups are shown.

上記式（Ｉ−２）において、Ｒ^４は水素原子、置換基を有していてもよい炭素数１〜１８の炭化水素基からなる群より選ばれるものである。

In the above formula (I-2), R ⁴ are those selected from the group consisting of a hydrogen atom, optionally substituted hydrocarbon group having 1 to 18 carbon atoms.

As the hydrocarbon group having 1 to 18 carbon atoms which may have a substituent as R ⁴ , an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, alicyclic Hydrocarbon group, aromatic hydrocarbon group, etc., for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group , Aliphatic hydrocarbon groups such as decyl group, dodecyl group, allyl group, vinyl group;
These aliphatic hydrocarbon groups include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, an epoxy group-containing group, a methacryloyl group, Substituted with mercapto group, imino group, ureido group, isocyanate group, etc .;
An alicyclic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group;
A group containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, or an epoxy group, a methacryloyl group , Mercapto group, imino group, ureido group, isocyanate group and the like substituted;
An aromatic hydrocarbon group such as phenyl group, tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group;
Further, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, an epoxy group-containing group, a methacryloyl group, a mercapto group, an imino group, And those substituted with an ureido group or an isocyanate group.

Among these, R ⁴ is preferably a hydrogen atom from the viewpoint of high heat resistance.

  In the above formulas (I-1) to (I-3), n is not particularly limited as long as it is an average of 2 to 20, but is 2 to 10 from the viewpoint of high heat resistance. Is more preferable, 2 to 5 is more preferable, and 3 is more preferable.

The calixarene compound of the present invention is a compound represented by the above formula (I-1), and 5 to 100% of the phenolic hydroxyl group of the calixarene compound (b1) represented by the above formula (I-3) A compound having a β-alkenyl etherified structure is preferable. Here, the phenolic hydroxyl group to be β-alkenyl etherified includes a phenolic hydroxyl group as R ² in addition to the hydroxyl group bonded to the benzene ring of the above formula (I-3). It is preferable that 5 to 100% of the total is β-alkenyl etherified.

  If the proportion of the β-alkenyl etherified phenolic hydroxyl group is less than 5%, the solubility with the constituent components of the epoxy resin composition may be inferior. The ratio of the β-alkenyl etherified phenolic hydroxyl group is more preferably 10 to 60%. From the viewpoint of solubility with the constituent components of the epoxy resin composition, it is more preferably 10% or more, and from the viewpoint of high heat resistance, it is more preferably 60% or less.

The confirmation method of what percentage of the phenolic hydroxyl group of the calixarene compound (b1) represented by the above formula (I-3) is β-alkenyl etherified can be confirmed, for example, by ¹ H-NMR. . Specifically, it can be confirmed how much the phenolic hydroxyl group disappeared when the calixarene compound represented by the above formula (I-1) is used as compared with the calixarene compound (b1).

<Method for producing calixarene compound>
The method for producing the calixarene compound of the present invention is not particularly limited, but the phenolic hydroxyl group of the calixarene compound (b1) represented by the above formula (I-3) is represented by the following formula (I- And a method of reacting at least one compound selected from the group of β-alkenyl halides represented by 4). To obtain a calixarene compound in which 5 to 100% of the phenolic hydroxyl group of the calixarene compound (b1) is β-alkenyl etherified, the amount of β-alkenyl halide used is controlled or the reaction is in progress. There is a method of stopping at.

(In the above formula (I-4), each R ⁴ is independently selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, and all are the same. However, it may be different, and X is selected from halogen atoms.)

In the above formula ^(I-4), R 4 are those selected from the group consisting of a hydrogen atom, optionally substituted hydrocarbon group having 1 to 18 carbon atoms. In addition, R ⁴ of the above formula (I- ⁴ ) may be the same as R ⁴ of the above formula (I-2). Specifically, it is as follows.

The hydrocarbon group having 1 to 18 carbon atoms which may have a substituent as R ^{4 in the} above formula (I-4) may be an aliphatic having 1 to 18 carbon atoms which may have a substituent. Group hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, etc., for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, An aliphatic hydrocarbon group such as a pentyl group, hexyl group, octyl group, decyl group, dodecyl group, allyl group, vinyl group;
These aliphatic hydrocarbon groups include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, an epoxy group-containing group, a methacryloyl group, Substituted with mercapto group, imino group, ureido group, isocyanate group, etc .;
An alicyclic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group;
A group containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, or an epoxy group, a methacryloyl group , Mercapto group, imino group, ureido group, isocyanate group and the like substituted;
An aromatic hydrocarbon group such as phenyl group, tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group;
Further, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, an epoxy group-containing group, a methacryloyl group, a mercapto group, an imino group, And those substituted with an ureido group or an isocyanate group.

Among these, R ^{4 in the} above formula (I-4) is preferably a hydrogen atom from the viewpoint of high heat resistance.
Moreover, as X of the said formula (I-4), a bromine atom is preferable from a reactive viewpoint.

  When the calixarene compound (b1) represented by the above formula (I-3) is reacted with at least one compound selected from the group of β-alkenyl halides represented by the above formula (I-4), A solvent can also be used. The solvent that can be used is not particularly limited, and examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide and the like. Can be mentioned.

  The reaction conditions and isolation method are not particularly limited as long as the reaction proceeds to obtain a product. For example, a calixarene compound represented by the above formula (I-3) ( b1) and at least one compound selected from the group of β-alkenyl halides represented by the above formula (I-4) are reacted at room temperature to 200 ° C., and if necessary after reaction, by-products, catalysts, etc. Examples include a method of removing the unnecessary components, a method of distilling off the solvent, a method of filtering the solid precipitated by cooling, a method of filtering the solid deposited by pouring into a poor solvent, and the like. Moreover, you may use the compound which accelerates | stimulates the reaction of the phenolic hydroxyl group of a calixarene type compound (b1) and the at least 1 compound chosen from the group of the compound shown by Formula (I-4) as needed. . The compound that accelerates the reaction that can be used is not particularly limited as long as the reaction is promoted, but is described below as an inorganic acid, organic acid, inorganic base, organic base, onium salt, and curing accelerator. And known compounds that promote the reaction between a hydroxyl group and a hydrocarbon halide. Among them, ammonium salts are preferable.

The calixarene compound (b1) can be produced by a known method. For example, the calixarene compound (b1) of the above formula (I-3) in which R ² = hydrogen, R ³ = propylene, and n = 3 is a resorcinol containing glutaraldehyde in a solvent in the presence of an acid catalyst such as concentrated hydrochloric acid. It can be obtained by reacting at 30 to 200 ° C.

  Although it does not specifically limit as a manufacturing method of the calixarene type compound of this invention, In addition to said manufacturing method, the resorcinol derivative shown by following formula (I-5), and following formula (I- The method of making it react with at least 1 compound chosen from the group of the dialdehyde shown by 5 ') is also mentioned.

(In the above formula (I-5), R ¹ is a hydrogen atom or a monovalent substituent represented by the above formula (I-2), and at least one R ^{1 in} one molecule is a hydrogen atom, R ⁴ in the above formula (I-2) independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent.

R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , A hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom, all of which may be the same or different. )

（上記式（Ｉ−５’）中、Ｒ^３は、それぞれ独立して、炭素数０〜１８の２価の有機基からなる群より選ばれ、全てが同一でも異なってもよい。）

(In the above formula (I-5 ′), each R ³ is independently selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, and all may be the same or different.)

  In order to obtain a calixarene compound in which 5 to 100% of the phenolic hydroxyl group of the calixarene compound (b1) is β-alkenyl etherified, a resorcinol derivative represented by the above formula (I-5) has a β- This is achieved by adjusting the alkenyl etherification rate. When obtaining the resorcinol derivative represented by the above formula (I-5), that is, when synthesizing the hydroxyl group of the raw resorcinol derivative hydroxyl group by β-alkenyl ether, the amount of β-alkenyl halide used is controlled. Alternatively, there are methods such as stopping the reaction on the way.

In the above formula (I-5), each R ² independently represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, or an optionally substituted carbon. It is selected from the group consisting of a hydrocarbon oxy group having 1 to 18 carbon atoms, a hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom.

R ² in the above formula (I-5) is a compound selected from the group consisting of a resorcinol derivative represented by the above formula (I-5) and a dialdehyde represented by the above formula (I-5 ′). Of the calixarene compound of the above formula (I-1) obtained by reacting R ² with R ² , and the same can be mentioned. Specifically, it is as follows.

The hydrocarbon group having 1 to 18 carbon atoms which may have a substituent as R ^{2 in the} above formula (I-5) may be an aliphatic having 1 to 18 carbon atoms which may have a substituent. Group hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, etc., for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, An aliphatic hydrocarbon group such as a pentyl group, hexyl group, octyl group, decyl group, dodecyl group, allyl group, vinyl group;
These aliphatic hydrocarbon groups include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, an epoxy group-containing group, a methacryloyl group, Substituted with mercapto group, imino group, ureido group, isocyanate group, etc .;
An alicyclic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group;
A group containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, or an epoxy group, a methacryloyl group , Mercapto group, imino group, ureido group, isocyanate group and the like substituted;
An aromatic hydrocarbon group such as phenyl group, tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group;
Further groups containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, and an epoxy group, a methacryloyl group, a mercapto group, and an imino group And the like substituted with a group, a ureido group or an isocyanate group.

As C1-C18 hydrocarbon oxy group which may have a substituent as R < ² > of said formula (I-5), it is C1-C18 which may have a substituent. An aliphatic hydrocarbonoxy group, an alicyclic hydrocarbonoxy group, an aromatic hydrocarbonoxy group, etc., for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, aliphatic hydrocarbon oxy groups such as tert-butoxy group, pentyloxy group, hexyloxy group, octyloxy group, decyloxy group, dodecyloxy group, allyloxy group, vinyloxy group;
A group containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group or an epoxy group, a methacryloyl group , Mercapto group, imino group, ureido group, isocyanate group and the like substituted;
Cycloaliphatic hydrocarbon oxy groups such as cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclopentenyloxy group, cyclohexenyloxy group;
These alicyclic hydrocarbon oxy groups include an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, and an epoxy group, methacryloyl Substituted with a group, mercapto group, imino group, ureido group, isocyanate group, etc .;
Aromatic hydrocarbon oxy groups such as phenoxy group, tolyloxy group, dimethylphenoxy group, ethylphenoxy group, butylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, ethoxyphenoxy group, butoxyphenoxy group, tert-butoxyphenoxy group;
Further groups containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, and an epoxy group, a methacryloyl group, a mercapto group, and an imino group And the like substituted with a group, a ureido group or an isocyanate group.

The hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent as R ^{2 in the} above formula (I-5) may have 1 to 18 carbon atoms which may have a substituent. Aliphatic hydrocarbon thio group, alicyclic hydrocarbon thio group, aromatic hydrocarbon thio group, etc., for example, methylthio group, ethylthio group, propylthio group, isopropylthio group, n-butylthio group, sec-butylthio group, an aliphatic hydrocarbon thio group such as a tert-butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, an allylthio group, a vinylthio group;
A group containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, or an epoxy group, a methacryloyl group , Mercapto group, imino group, ureido group, isocyanate group and the like substituted;
Cycloaliphatic hydrocarbon thio groups such as cyclopentylthio group, cyclohexylthio group, cycloheptylthio group, cyclopentenylthio group, cyclohexenylthio group;
These alicyclic hydrocarbon thio groups, groups containing an epoxy group such as an alkyl group, alkoxy group, aryl group, aryloxy group, hydroxyl group, amino group, halogen atom, glycidyloxy group, epoxycyclohexyl group, epoxy group, etc., methacryloyl Substituted with a group, mercapto group, imino group, ureido group, isocyanate group, etc .;
Phenylthio group, tolylthio group, dimethylphenylthio group, ethylphenylthio group, butylphenylthio group, tert-butylphenylthio group, methoxyphenylthio group, ethoxyphenylthio group, butoxyphenylthio group, tert-butoxyphenylthio group, etc. An aromatic hydrocarbon thio group of
Further groups containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, and an epoxy group, a methacryloyl group, a mercapto group, and an imino group And the like substituted with a group, a ureido group or an isocyanate group.

Examples of the halogen atom as R ^{2 in the} above formula (I-5) include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.
Among these, R ² is preferably a hydrogen atom from the viewpoint of high heat resistance.

In the above formula (I-5 ′), R ³ is selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, and examples thereof include an oxygen atom, a sulfur atom, a sulfoxide group, a sulfonyl group, and a substituent. C1-C18 bivalent hydrocarbon group etc. which may have are mentioned.

  In this case, the “divalent hydrocarbon group having 1 to 18 carbon atoms which may have a substituent” may be any hydrocarbon group having a main skeleton of 1 to 18 carbon atoms. A part of hydrogen atoms of the hydrocarbon may be substituted with other atoms (for example, halogen etc.) or substituents such as alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups.

R ³ in the above formula (I-5 ′) is one compound selected from the group consisting of a resorcinol derivative represented by the above formula (I-5) and a dialdehyde represented by the above formula (I-5 ′). DOO the calixarene compound of the formula obtained when reacted (I-1), and corresponds to R ^3, the same thing can be mentioned. Specifically, it is as follows.

Examples of the divalent hydrocarbon group having 1 to 18 carbon atoms that may have the substituent as R ^{3 in the} above formula (I-5 ′) include a methylene group, an ethylene group, and a propylene group. An alicyclic hydrocarbon group such as a cyclohexylene group and a cyclopentylene group;
Those substituted with an alkyl group, alkoxy group, aryl group, aryloxy group, amino group, halogen or the like on these aliphatic hydrocarbon group or alicyclic hydrocarbon group;
Aromatic hydrocarbon groups such as phenylene group, naphthylene group, anthracenylene group;
These aromatic hydrocarbon groups are substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen, and the like.

Among the divalent organic groups having 0 to 18 carbon atoms as R ^{3 in the} above formula (I-5 ′), they have a substituent from the viewpoint of ease of synthesis and synthesis yield. An aliphatic hydrocarbon group that may be substituted, a propylene group that may have a substituent is more preferable, and a propylene group that has no substituent is more preferable. Examples of the propylene group which may have a substituent include a methylpropylene group, an ethylpropylene group, an isopropylpropylene group, a phenylpropylene group, and a dimethylpropylene group.

R ¹ in the above formula (I-5) is a hydrogen atom or a monovalent substituent represented by the following formula (I-2), and at least one R ^{1 in} one molecule is a hydrogen atom. R ⁴ in (I-2) each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent. Incidentally, ^{R 1} in the formula (I-5) can be mentioned the same ones as ^{R 1} in the above formula (I-1). Specifically, it is as follows.

上記式（Ｉ−２）において、Ｒ^４は水素原子、置換基を有していてもよい炭素数１〜１８の炭化水素基からなる群より選ばれるものである。

In the above formula (I-2), R ⁴ are those selected from the group consisting of a hydrogen atom, optionally substituted hydrocarbon group having 1 to 18 carbon atoms.

The hydrocarbon group having 1 to 18 carbon atoms which may have a substituent as R ^{4 in the} above formula (I-2) may be a fatty acid having 1 to 18 carbon atoms which may have a substituent. Group hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, etc., for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, An aliphatic hydrocarbon group such as a pentyl group, hexyl group, octyl group, decyl group, dodecyl group, allyl group, vinyl group;
These aliphatic hydrocarbon groups include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, an epoxy group-containing group, a methacryloyl group, Substituted with mercapto group, imino group, ureido group, isocyanate group, etc .;
An alicyclic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group;
A group containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, or an epoxy group, a methacryloyl group , Mercapto group, imino group, ureido group, isocyanate group and the like substituted;
An aromatic hydrocarbon group such as phenyl group, tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group;
Further, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, an epoxy group-containing group, a methacryloyl group, a mercapto group, an imino group, And those substituted with an ureido group or an isocyanate group.

Among these, R ⁴ is preferably a hydrogen atom from the viewpoint of high heat resistance.

  In reacting the resorcinol derivative represented by the above formula (I-5) with at least one compound selected from the group of dialdehydes represented by the above formula (I-5 '), a solvent may be used. The solvent that can be used is not particularly limited. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, chloroform Etc.

  The reaction conditions are not particularly limited as long as the reaction proceeds to obtain a product. For example, the resorcinol derivative represented by the above formula (I-5) and the above formula (I-5) can be used. ') Is reacted with at least one compound selected from the group of dialdehydes shown at room temperature to 200 ° C, and after the reaction, unnecessary components such as by-products and catalysts are removed if necessary. The method of leaving, the method of filtering the solid which precipitated by cooling, the method of throwing into the poor solvent and filtering the solid which precipitated, etc. are mentioned.

  In addition, if necessary, a compound that promotes the reaction between the resorcinol derivative represented by the above formula (I-5) and at least one compound selected from the group of dialdehydes represented by the above formula (I-5 ′). You may use. The compound that accelerates the reaction that can be used is not particularly limited as long as the reaction is promoted, but is described below as an inorganic acid, organic acid, inorganic base, organic base, onium salt, and curing accelerator. And known compounds that promote the reaction between a hydroxyl group and a hydrocarbon halide. Among them, organic acids and inorganic acids are preferable.

The resorcinol derivative represented by the formula (I-5) can be produced by a known method. For example, in the above formula, one R ¹ = hydrogen, the other R ¹ = “substituents in which all R ⁴ ═hydrogen are represented by the formula (I-2)”, and R ² = benzoyl group The resorcinol derivative of (I-5) can be obtained by reacting the hydroxyl group of monobenzoyl resorcinol with allyl bromide to form allyl ether and then debenzoating with a base.

<Curing agent for epoxy resin>
The curing agent for epoxy resin of the present invention is characterized by using the calixarene compound of the present invention represented by the above formula (I-1).

<Epoxy resin composition>
The epoxy resin composition of the present invention contains the epoxy resin and the calixarene compound of the present invention as a curing agent for epoxy resin.

(Epoxy resin)
The epoxy resin usable in the present invention is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule. Examples of the epoxy resin include phenols such as phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, phenols such as cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and / or α-naphthol, β- Novolac obtained by epoxidizing a novolak resin obtained by condensation or cocondensation of naphthols such as naphthol and dihydroxynaphthalene and a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and hydroxybenzaldehyde under an acidic catalyst. Type epoxy resin;
Diglycidyl ethers (bisphenol type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin) such as bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or unsubstituted biphenol, and stilbene phenols;
Glycidyl ethers of alcohols such as butanediol, polyethylene glycol, polypropylene glycol;
Glycidyl ester type epoxy resins of carboxylic acids such as phthalic acid, isophthalic acid, tetrahydrophthalic acid;
Glycidyl-type or methylglycidyl-type epoxy resins such as those in which active hydrogen bonded to a nitrogen atom such as aniline or isocyanuric acid is substituted with a glycidyl group;
Vinylcyclohexene diepoxide obtained by epoxidizing an olefin bond in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro ( 3,4-epoxy) cycloaliphatic epoxy resins such as cyclohexane-m-dioxane;
Glycidyl ether of paraxylylene and / or metaxylylene modified phenolic resin;
Glycidyl ether of terpene-modified phenolic resin;
Glycidyl ether of dicyclopentadiene-modified phenolic resin;
Glycidyl ether of cyclopentadiene modified phenolic resin;
Glycidyl ether of polycyclic aromatic ring-modified phenolic resin;
Glycidyl ether of a naphthalene ring-containing phenolic resin;
Halogenated phenol novolac epoxy resin;
Hydroquinone type epoxy resin;
Trimethylolpropane type epoxy resin;
A linear aliphatic epoxy resin obtained by oxidizing an olefinic bond with a peracid such as peracetic acid;
Diphenylmethane type epoxy resin;
Epoxidized products of aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins;
Sulfur atom-containing epoxy resin;
Naphthalene type epoxy resin; and the like. These may be used alone or in combination of two or more.

  Among the above epoxy resins, biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom-containing type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin in terms of reflow crack resistance and fluidity, Preferred are hydroxybenzaldehyde type epoxy resins, epoxides of naphthols and phenols, epoxides of aralkyl type phenol resins such as phenol aralkyl resins, naphthol aralkyl resins, and naphthalene type epoxy resins. It may be used alone or in combination of two or more. However, in order to exhibit these performances, it is preferable to use 30% by mass or more, and more preferably 50% by mass or more, based on the total amount of the epoxy resin. Specific examples of preferable epoxy resins are shown below.

The biphenyl type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton, but an epoxy resin represented by the following formula (II) is preferable. Formula (II) with 3,3' oxygen atom of R ⁸ Among the epoxy resin when the 4 and 4 'position a position which is substituted as indicated, R ⁸ is a methyl group 5,5'-position in, YX-4000H (manufactured by Japan epoxy Resins Co., Ltd.) other ^{R 8} is a hydrogen atom, all the ^{R 8} are hydrogen atoms 4,4'-bis (2,3-epoxypropoxy) biphenyl, all When R ⁸ is a hydrogen atom, and R ⁸ in the 3, 3 ′, 5, 5 ′ positions when the oxygen atom substitution positions of R ⁸ are the 4 and 4 ′ positions are methyl groups, YL-6121H (manufactured by Japan Epoxy Resin Co., Ltd.), etc., which is a mixed product when R ⁸ other than is a hydrogen atom, is commercially available.

(In the above formula (II), R ⁸ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aryl group having 4 to 18 carbon atoms, all of which may be the same or different, and n is an average value. , Represents a number from 0 to 10.)

The stilbene type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton, but an epoxy resin represented by the following formula (III) is preferable. Among the epoxy resins represented by the following formula (III), 3,3' when the oxygen atom is the 4 and 4 'positions of the positions is substituted of R ^9, 5, 5' position of R ⁹ is methyl R ⁹ is a hydrogen atom and all of R ¹⁰ are hydrogen atoms, and three of the 3, 3 ′, 5, 5 ′ positions are methyl groups, and one is a tert-butyl group. ESLV-210 (manufactured by Sumitomo Chemical Co., Ltd.), which is a mixed product in the case where the other than is a hydrogen atom and all of R ¹⁰ are hydrogen atoms, is commercially available.

(In the formula (III), R ⁹ and R ¹⁰ represents a monovalent organic group having 1 to 18 carbon hydrogen atom or a carbon, may all respectively be the same or different, n is an average value from 0 Indicates a number of 10.)

The diphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton, but an epoxy resin represented by the following formula (IV) is preferable. Among the epoxy resins represented by the following formula (IV), 3, 3 ′, 5 when R ¹¹ is all hydrogen atoms and oxygen atoms are substituted in R ¹² at positions 4 and 4 ′. , YSLV-80XY (manufactured by Nippon Steel Chemical Co., Ltd.), in which R ^{12 at} the 5′-position is a methyl group and the other R ¹² is a hydrogen atom, is commercially available.

(In the formula (IV), R ¹¹ and R ¹² represents a monovalent organic group having 1 to 18 carbon hydrogen atom or a carbon, may all respectively be the same or different, n is an average value from 0 Indicates a number of 10.)

Although it will not specifically limit if it is an epoxy resin containing a sulfur atom as a sulfur atom containing type epoxy resin, For example, the epoxy resin shown by following formula (V) is mentioned. Among the epoxy resins represented by the following formula (V), R ¹³ in the 3 and 3 'positions when the positions where oxygen atoms are substituted in the R ¹³ are the 4 and 4' positions is a tert-butyl group, YSLV-120TE (manufactured by Nippon Steel Chemical Co., Ltd.), in which R ^{13 at the} 6,6′-position is a methyl group and the other is a hydrogen atom, is commercially available.

(In the above formula (V), R ¹³ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, n is an average value, and a number of 0 to 10 Is shown.)

The novolak type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolak type phenol resin, but a novolak type phenol resin such as phenol novolak, cresol novolak, naphthol novolak or the like is glycidyl etherified. An epoxy resin epoxidized using the above method is preferable, and for example, an epoxy resin represented by the following formula (VI) is more preferable. Among epoxy resins represented by the following formula (VI), ESCN-190, ESCN-195 (manufactured by Sumitomo Chemical Co., Ltd.), etc., in which all of R ¹⁴ are hydrogen atoms, R ¹⁵ is a methyl group and i = 1, are commercially available. It is available as a product.

(In the above formula (VI), R ¹⁴ and R ¹⁵ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, and i is an integer of 0 to 3, n Is an average value and represents a number from 0 to 10.)

  The dicyclopentadiene type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a compound having a dicyclopentadiene skeleton as a raw material, but an epoxy resin represented by the following formula (VII) is preferable. Among epoxy resins represented by the following formula (VII), HP-7200 (manufactured by Dainippon Ink & Chemicals, Inc.) in which i = 0 is available as a commercial product.

(In the formula (VII), R ¹⁶ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 0 to 3, and n is an average value. And represents a number from 0 to 10.)

  The hydroxybenzaldehyde type epoxy resin is not particularly limited as long as it is an epoxy resin made from a compound having a hydroxybenzaldehyde skeleton, but a novolak type phenol resin of a compound having a hydroxybenzaldehyde skeleton and a compound having a phenolic hydroxyl group, etc. A hydroxybenzaldehyde type epoxy resin such as an epoxy resin obtained by glycidyl etherification of a hydroxybenzaldehyde type phenol resin is preferable, and an epoxy resin represented by the following formula (VIII) is more preferable. Among the epoxy resins represented by the following formula (VIII), 1032H60 (manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-502H (Nippon Kayaku Co., Ltd., trade name) where i = 0 and k = 0 are commercially available products. Is available as

(In the above formula (VIII), R ¹⁷ and R ¹⁸ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different, i is an integer of 0 to 3, k Is an integer from 0 to 4, n is an average value, and represents a number from 0 to 10.)

The copolymer type epoxy resin of naphthols and phenols is not particularly limited as long as it is an epoxy resin made from a compound having a naphthol skeleton and a compound having a phenol skeleton, but a compound having a naphthol skeleton And a novolak-type phenol resin using a compound having a phenol skeleton, which is glycidyl etherified, and more preferably an epoxy resin represented by the following formula (IX). Among the epoxy resins represented by the following formula (IX), NC-7300 (manufactured by Nippon Kayaku Co., Ltd.) in which R ²¹ is a methyl group, i = 1, j = 0, and k = 0 is a commercially available product. It is available.

(In the above formula (IX), R ^{19 to} R ²¹ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 0 to 3, j Is an integer of 0 to 2, k is an integer of 0 to 4, p is an average value of 0 to 1, l and m are average values of 0 to 11 and (l + m) is 1 Indicates the number of ~ 11.)

  Examples of the epoxy resin represented by the above formula (IX) include random copolymers containing 1 constituent unit and m constituent units at random, alternating copolymers containing alternating units, copolymers containing regular units, and blocks. The block copolymer contained in a shape is mentioned, Any one of these may be used independently, or 2 or more types may be used in combination.

Epoxidized products of aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins include phenols such as phenol and cresol and / or naphthols such as naphthol and dimethylnaphthol, dimethoxyparaxylene, bis (methoxymethyl) biphenyl, and the like. The epoxy resin is not particularly limited as long as it is made of a phenol resin synthesized from the above derivatives. For example, a phenol resin synthesized from phenols such as phenol and cresol and / or naphthols such as naphthol and dimethylnaphthol and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, and derivatives thereof is preferably glycidyl ether, Epoxy resins represented by the following formulas (X) and (XI) are more preferable. Among epoxy resins represented by the following formula (X), i = 0, R- ³⁸ is a hydrogen atom NC-3000S (manufactured by Nippon Kayaku Co., Ltd.), i = 0, and R ³⁸ is a hydrogen atom epoxy resin the formula CER-3000 all R ⁸ is mixed with the epoxy resin is a hydrogen atom in a weight ratio of 80:20 (II) (manufactured by Nippon Kayaku Co., Ltd., trade name) are available as commercial products. Further, among epoxy resins represented by the following formula (XI), ESN-175 (Nippon Steel Chemical Co., Ltd.) where j = 0 and k = 0 are available as commercial products.

(In the above formulas (X) and (XI), R ^{37 to} R ^{41 each} represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, and i is 0 to 3). And j is an integer of 0 to 2, k is an integer of 0 to 4. n is an average value and represents a number of 0 to 10.)

The naphthalene type epoxy resin is not particularly limited as long as it is an epoxy compound containing a naphthalene ring. For example, a naphthol compound synthesized from a naphthol derivative such as naphthol, dihydroxynaphthalene, or dimethylnaphthol is preferably glycidyl etherified, and an epoxy resin represented by the following formula (XI-a) is more preferable. Among the epoxy resins represented by the following formula (XI-a), EXA-4700, EXA-4701 (n = 1, all of R ⁴² and R ⁴³ are hydrogen atoms, and all of R ⁴⁴ are glycidyloxy groups) manufactured by Dainippon ink and chemicals, Inc.), n = ^0, all ^{R 42} and ^{R 43} is a hydrogen ^atom, manufactured by HP-4032 (Dainippon ink and chemicals, Inc. ^{R 44} is glycidyloxy group), n = 1 EXA-4750 (manufactured by Dainippon Ink & Chemicals, Inc.), in which all of R ⁴² and R ⁴³ are hydrogen atoms, one of R ⁴⁴ is a hydrogen atom and the other is a glycidyloxy group, is available as a commercial product. It is.

（上記式（XI−ａ）中、Ｒ^４２及びＲ^４３は水素原子又は炭素数１〜１８の１価の有機基を示し、Ｒ^４４は水素原子又はグリシジルオキシ基を示し、それぞれ全てが同一でも異なってもよく、ｎは平均値であり、０〜１０の数を示す。）

(In the above formula (XI-a), R ⁴² and R ⁴³ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, R ⁴⁴ represents a hydrogen atom or a glycidyloxy group, and they are all the same. May be different, n is an average value and represents a number from 0 to 10.)

Regarding R ^{8 to} R ²¹ and R ^{37 to} R ^{44 in the} above formulas (II) to (XI) and (XI-a), “all may be the same or different” means, for example, the above formula ( It means that all ^{8 to} 88 R ^{8 in} II) may be the same or different. It means that all of R ^{9 to} R ²¹ and R ^{37 to} R ⁴⁴ may be the same or different with respect to the respective numbers included in the formula. R ^{8 to} R ²¹ and R ^{37 to} R ⁴⁴ may be the same as or different from each other. For example, all of R ⁹ and R ¹⁰ may be the same or different.

  “N” in the above formulas (II) to (XI) and (XI-a) needs to be in the range of 0 to 10, and when it exceeds 10, the melt viscosity of the epoxy resin component becomes high. The viscosity at the time of melt molding of the epoxy resin composition also increases, which tends to cause unfilled defects and deformation of the bonding wire (gold wire connecting the element and the lead). The average n in one molecule of the epoxy resin is preferably set in the range of 0-4.

  In the epoxy resin composition of the present invention, the blending ratio of the epoxy resin and the calixarene compound of the present invention is the sum of the total number of epoxy groups of the epoxy resin, the total number of phenolic hydroxyl groups and the total number of allyl ether groups of the calixarene compound Ratio, that is, the total number of epoxy groups of the epoxy resin / (total number of phenolic hydroxyl groups of the calixarene compound + total number of allyl ether groups) is preferably 0.5 to 2.0, and preferably 0.7 to 1 0.5 is more preferable, and 0.8 to 1.3 is particularly preferable. When the blending ratio exceeds 2.0, the epoxy resin is insufficiently cured, and the heat resistance, moisture resistance, and electrical characteristics of the cured product tend to be lowered. On the other hand, if the blending ratio is less than 0.5, the curing agent component becomes excessive and not only the curing efficiency is lowered, but also a large amount of phenolic hydroxyl group remains in the cured resin, so that the electrical characteristics and moisture resistance of the package are lowered. Tend to.

(Other curing agents)
The epoxy resin composition of the present invention can be used in combination with another curing agent other than the calixarene compound of the present invention shown above as a curing agent. The compound that can be used in combination as the other curing agent is not particularly limited as long as it is a compound that can cure the epoxy resin.

  For example, phenol compounds such as phenol resin; amine compounds such as diamine and polyamine; organic anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride; carboxylic acid compounds such as dicarboxylic acid and polycarboxylic acid; These may be used in combination of one or more. Among these, it is preferable to use a compound having two or more phenolic hydroxyl groups in one molecule. Specific examples of other preferable curing agents are shown below.

  The phenol compound is not particularly limited as long as it is a phenol compound having two or more phenolic hydroxyl groups in one molecule generally used as a curing agent.

Specific examples of the phenol compound include compounds having two phenolic hydroxyl groups in one molecule such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol;
Phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and other phenols and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde, acetaldehyde, propionaldehyde, A novolak-type phenol resin obtained by condensation or cocondensation with aldehydes such as benzaldehyde and hydroxybenzaldehyde under an acidic catalyst;
Aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl;
Paraxylylene and / or metaxylylene-modified phenolic resin;
Melamine-modified phenolic resin;
Terpene-modified phenolic resin;
Dicyclopentadiene type phenol resin, dicyclopentadiene type naphthol resin synthesized by copolymerization from phenols and / or naphthols and dicyclopentadiene;
Cyclopentadiene modified phenolic resin;
Polycyclic aromatic ring-modified phenolic resin;
Biphenyl type phenolic resin;
Triphenylmethane phenol resin;
Examples thereof include phenol resins obtained by copolymerizing two or more of these resins; these may be used alone or in combination of two or more.

  Among the above phenol compounds, from the viewpoint of reflow crack resistance, aralkyl type phenol resins, dicyclopentadiene type phenol resins, hydroxybenzaldehyde type phenol resins, benzaldehyde type and aralkyl type copolymer type phenol resins, and novolak type phenol resins are used. preferable. These aralkyl-type phenol resins, dicyclopentadiene-type phenol resins, hydroxybenzaldehyde-type phenol resins, benzaldehyde-type and aralkyl-type copolymer phenol resins, and novolak-type phenol resins can be used alone or in combination. A combination of the above may also be used. However, in order to exert the effect of the calixarene compound of the present invention, these phenol resins are preferably 70% by mass or less in total with respect to the total amount of the calixarene compound of the present invention and the other curing agent. More preferably, it is used in combination so that it is 50% by mass or less, and more preferably 30% by mass or less.

  The aralkyl type phenolic resin is not particularly limited as long as it is a phenolic resin synthesized from phenols and / or naphthols and dimethoxyparaxylene, bis (methoxymethyl) biphenyl or a derivative thereof. Phenol resins represented by XII) to (XIV) are preferred.

(In the above formulas (XII) to (XIV), R ^{22 to} R ²⁸ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, and i is 0 to 3 , K is an integer of 0 to 4, j is an integer of 0 to 2, n is an average value, and represents a number of 0 to 10.)

Among the phenol resins represented by the formula (XII), MEH-7851 (Maywa Kasei Co., Ltd.) and the like in which i = 0 and R ²³ are all hydrogen atoms are commercially available.

  Among the phenol resins represented by the above formula (XIII), XL-225, XLC (manufactured by Mitsui Chemicals, Inc.), MEH-7800 (Maywa Kasei Co., Ltd.), etc., where i = 0 and k = 0 are obtained as commercial products. Is possible.

Among the phenol resins represented by the above formula (XIV), SN-170 (Nippon Steel Chemical Co., Ltd.) where j = 0, R ²⁷ k = 0, and R ²⁸ k = 0 are available as commercial products. It is.

  The dicyclopentadiene type phenol resin is not particularly limited as long as it is a phenol resin using a compound having a dicyclopentadiene skeleton as a raw material, but a phenol resin represented by the following formula (XV) is preferable. Among the phenolic resins represented by the following formula (XV), DPP (manufactured by Nippon Petrochemical Co., Ltd.) where i = 0 is available as a commercial product.

(In the formula (XV), R ²⁹ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 0 to 3, and n is an average value. And represents a number from 0 to 10.)

The hydroxybenzaldehyde type phenol resin is not particularly limited as long as it is a phenol resin using a compound having a hydroxybenzaldehyde skeleton as a raw material, but a phenol resin represented by the following formula (XVI) is preferable.
Among the phenol resins represented by the following formula (XVI), MEH-7500 (manufactured by Meiwa Kasei Co., Ltd.) where i = 0 and k = 0 is available as a commercial product.

(In the above formula (XVI), R ³⁰ and R ³¹ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different, i is an integer of 0 to 3, k Is an integer from 0 to 4, n is an average value, and represents a number from 0 to 10.)

  The copolymer type phenol resin of benzaldehyde type and aralkyl type is not particularly limited as long as it is a copolymer type phenol resin of a phenol resin and an aralkyl type phenol resin using a compound having a benzaldehyde skeleton as a raw material. A phenol resin represented by the following formula (XVII) is preferable.

  Among the phenol resins represented by the following formula (XVII), HE-510 (manufactured by Air Water Chemical Co., Ltd.) having i = 0, k = 0, q = 0 is available as a commercial product.

（上記式（XVII）中、Ｒ^３２〜Ｒ^３４は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なってもよく、ｉは０〜３の整数、ｋは０〜４の整数、ｑは０〜５の整数、ｌ、ｍはそれぞれ平均値で０〜１１の数であり、（ｌ＋ｍ）は１〜１１の数を示す。）

(In the above formula (XVII), R ^{32 to} R ³⁴ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, and i is an integer of 0 to 3, k Is an integer of 0 to 4, q is an integer of 0 to 5, l and m are average numbers of 0 to 11, and (l + m) is a number of 1 to 11.)

  The novolak type phenol resin is not particularly limited as long as it is a phenol resin obtained by condensation or cocondensation of phenols and / or naphthols and aldehydes in the presence of an acidic catalyst, but the following formula (XVIII) A phenol resin represented by is preferable.

I = 0 Among phenolic resins represented by the following formula ^{(XVIII), k = 0,} R 35 are all hydrogen atoms TAMANOL 758, 759 (manufactured by Arakawa Chemical Industries, Ltd.), HP-850N (Hitachi Chemical Co., Ltd. ) Etc. are available as commercial products.

(In the above formula (XVIII), R ³⁵ and R ^{36 each} represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different, i is an integer of 0 to 3, k Is an integer from 0 to 4, n is an average value, and represents a number from 0 to 10.)

“All may be the same or different” described for R ^{22 to} R ³⁶ in the above formulas (XII) to (XVIII) is, for example, that all i R ^{22s in} the above formula (XII) are the same. But it means they can be different from each other. For the other R ^{23 to} R ³⁶ , it means that all the numbers contained in the formula may be the same or different from each other. R ^{22 to} R ³⁶ may be the same as or different from each other. For example, all of R ²² and R ²³ may be the same or different, and all of R ³⁰ and R ³¹ may be the same or different.

  In the above formulas (XII) to (XVIII), “n” needs to be in the range of 0 to 10, and when it exceeds 10, the curing agent component containing the calixarene compound of the present invention and other curing agents. Since the melt viscosity of the epoxy resin composition becomes high, the viscosity at the time of melt molding of the epoxy resin composition also increases, which tends to cause unfilling failure and deformation of the bonding wire (gold wire connecting the element and the lead). The average n per molecule is preferably set in the range of 0-4.

  In the epoxy resin composition of the present invention, when another curing agent is used in combination with the calixarene compound of the present invention, the calixarene compound of the calixarene compound with respect to the total amount of the calixarene compound and the other curing agent. The blending amount is preferably 30% by mass or more, and more preferably 50% by mass or more. When the blending amount of the calixarene compound is less than 30% by mass, the heat resistance property of the cured product may be lowered, and the effect achievable by the present invention tends to be reduced.

  In the epoxy resin composition of the present invention, in addition to the calixarene compound of the present invention, when a phenol compound is used in combination as another curing agent, the calixarene compound is used with respect to the total amount of the calixarene compound and the phenolic compound. The compounding amount of the compound is preferably 30% by mass or more, and more preferably 50% by mass or more. When the blending amount of the calixarene compound is less than 30% by mass, the heat resistance property of the cured product may be lowered, and the effect achievable by the present invention tends to be reduced.

  Furthermore, in the epoxy resin composition of the present invention, when a compound having two or more phenolic hydroxyl groups in one molecule is used as another curing agent in addition to the calixarene compound of the present invention, the total epoxy of the epoxy resin The ratio of the total number of phenolic hydroxyl groups, the total number of phenolic hydroxyl groups of the calixarene compound and the total number of alkenyl ether groups of the calixarene compound and the number of phenolic hydroxyl groups of other curing agents, that is, the total number of alkenyl ether groups, The total number of epoxy groups of the epoxy resin / (total number of phenolic hydroxyl groups of calixarene compound + total number of allyl ether groups + number of phenolic hydroxyl groups of other curing agents) is preferably 0.5 to 2.0, 0.7 to 1.5 is more preferable, and 0.8 to 1.3 is particularly preferable. There. When the blending ratio exceeds 2.0, the epoxy resin is insufficiently cured, and the heat resistance, moisture resistance, and electrical characteristics of the cured product tend to be lowered. On the other hand, if the blending ratio is less than 0.5, the curing agent component becomes excessive and not only the curing efficiency is lowered, but also a large amount of phenolic hydroxyl group remains in the cured resin, so that the electrical characteristics and moisture resistance of the package are lowered. Tend to.

(Curing accelerator)
The epoxy resin composition of this invention can contain a hardening accelerator as needed. Examples of usable curing accelerators include diazabicycloalkenes such as 1,5-diazabicyclo [4.3.0] nonene-5, 1,8-diazabicyclo [5.4.0] undecene-7, and the like. Cycloamidine compounds, derivatives thereof, phenol novolac salts thereof;
And these compounds include maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5 Intramolecular polarization formed by adding a quinone compound such as methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, and a compound having a π bond such as diazophenylmethane. A compound having:
Tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and derivatives thereof;
Imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole;
Tetrasubstituted boron salts such as tetraphenylphosphonium and tetraphenylborate, tetraphenylboron salts such as 2-ethyl-4-methylimidazole and tetraphenylborate, N-methylmorpholine and tetraphenylborate;
Triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, Organic phosphines such as tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, or Complexes of these organic phosphines and organic borons;
These organic phosphines, maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5 Intramolecular polarization formed by adding a quinone compound such as methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, and a compound having a π bond such as diazophenylmethane. A compound having:
These organic phosphines, 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2- Iodinated phenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2, Reaction with halogenated phenol compounds such as 6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl And a compound having intramolecular polarization obtained by dehydrohalogenation (Japanese Patent Laid-Open No. 2004-15 See JP 036); and the like.

  When these curing accelerators are used in combination, from the viewpoint of fluidity, a compound having an intramolecular polarization formed by adding a compound having an organic phosphines and a π bond, an organic phosphine and a halogenated phenol compound are reacted. After that, a compound having intramolecular polarization obtained through a dehydrohalogenation step is preferable. From the viewpoint of curability, after reacting an organic phosphine with a halogenated phenol compound, a dehydrohalogenation step is performed. The resulting compound having intramolecular polarization is preferred. In particular, it is preferable to use a phosphonium compound represented by the following formula (I-6) or an intermolecular salt thereof.

(In the formula (I-6), each R ⁴ is independently selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, and all are the same. Or two or more R ⁴ may be bonded to each other to form a cyclic structure,
R ^{5 s} are each independently selected from the group consisting of a hydrogen atom, a hydroxyl group and an organic group having 1 to 18 carbon atoms which may have a substituent, all of which may be the same or different. R ⁵ may be bonded to each other to form a cyclic structure;
Y ⁻ is an organic group in which one proton is eliminated from an organic group having 0 to 18 carbon atoms having one or more releasable protons (H ⁺ ), and is bonded to one or more R ⁵ to form a cyclic structure. May be formed. )

In the above formula (I-6), R ⁴ is selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, and has a hydrogen atom and a substituent. An optionally substituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, etc., such as a hydrogen atom; a methyl group, an ethyl group, a propyl group, an isopropyl group, an aliphatic hydrocarbon group such as n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, allyl group, vinyl group;
Those aliphatic hydrocarbon groups substituted by alkyl groups, alkoxy groups, aryl groups, hydroxyl groups, amino groups, halogen atoms, etc .;
An alicyclic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group;
These alicyclic hydrocarbon groups substituted by alkyl groups, alkoxy groups, aryl groups, aryloxy groups, hydroxyl groups, amino groups, halogen atoms, etc .;
Aromatic hydrocarbon groups such as phenyl group and tolyl group; alkyl group-substituted aryl groups such as dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, alkoxy group-substituted aryl groups such as tert-butoxyphenyl group, those further substituted with an alkyl group, alkoxy group, aryl group, aryloxy group, amino group, halogen atom and the like;

R ^{4 in the} above formula (I-6) may be a ring structure in which two or more R ⁴ are bonded to each other, and two or three R ⁴ are bonded to each other, and are each divalent or trivalent as a whole. It becomes a hydrocarbon group. For example, an alkylene group such as ethylene, propylene, butylene, pentylene, hexylene, etc., an alkenyl group such as ethenyl, propenyl, butenyl group, an aralkylene group such as methylenephenylene group, phenylene, naphthylene, etc. And arylene groups such as anthracenylene, which may be substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen atom, or the like.

R ^{4 in the} above formula (I-6) is preferably a monovalent substituent selected from the group consisting of an alkyl group and an aryl group. Among these, from the viewpoint of easy availability of raw materials, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, p -Hydroxyphenyl group, m-hydroxyphenyl group, o-hydroxyphenyl group, 2,5-dihydroxyphenyl group, 4- (4-hydroxyphenyl) phenyl group, 1-naphthyl group, 2-naphthyl group, 1- (2 -Hydroxynaphthyl) group, 1- (4-hydroxynaphthyl) group, etc., unsubstituted or alkyl group or / and alkoxy group or / and hydroxyl-substituted aryl group, methyl group, ethyl group, propyl group, isopropyl group, n- Selected from chain or cyclic alkyl groups such as butyl, sec-butyl, tert-butyl, octyl and cyclohexyl Substituent is more preferable. Phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, p-hydroxyphenyl group, m-hydroxyphenyl group, o- Hydroxyphenyl group, 2,5-dihydroxyphenyl group, 4- (4-hydroxyphenyl) phenyl group, 1-naphthyl group, 2-naphthyl group, 1- (2-hydroxynaphthyl) group, 1- (4-hydroxynaphthyl) It is more preferable that it is an unsubstituted or alkyl group and / or an alkoxy group and / or a hydroxyl group-substituted aryl group.

In the above formula (I-6), R ⁵ is selected from the group consisting of a hydrogen atom, a hydroxyl group and an organic group having 1 to 18 carbon atoms which may have a substituent. C1-C18 aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, aliphatic hydrocarbon oxy group, alicyclic hydrocarbon oxy group, aromatic which may have a substituent Aromatic hydrocarbon oxy group, aliphatic hydrocarbon carbonyl group, alicyclic hydrocarbon carbonyl group, aromatic hydrocarbon carbonyl group, aliphatic hydrocarbon oxycarbonyl group, alicyclic hydrocarbon oxycarbonyl group, aromatic hydrocarbon oxy A carbonyl group, an aliphatic hydrocarbon carbonyloxy group, an alicyclic hydrocarbon carbonyloxy group, an aromatic hydrocarbon carbonyloxy group, and the like.

Specific examples of the optionally substituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, alicyclic hydrocarbon group, and aromatic hydrocarbon group as R ^{5 in the} above formula (I-6) are as follows. The same as those mentioned for R ⁴ in the above formula (I-6) can be used.

R ^{5 in the} above formula (I-6) is an optionally substituted aliphatic hydrocarbon oxy group having 1 to 18 carbon atoms, an alicyclic hydrocarbon oxy group, an aromatic hydrocarbon oxy group. Specific examples include aliphatic hydrocarbon oxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, allyloxy group and vinyloxy group;
Alicyclic hydrocarbon oxy groups such as cyclopropyloxy group, cyclohexyloxy group, cyclopentyloxy group;
Aromatic hydrocarbon oxy groups such as phenoxy group, methylphenoxy group, ethylphenoxy group, methoxyphenoxy group, butoxyphenoxy group, phenoxyphenoxy group;
These hydrocarbon oxy groups are substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, and the like.

R ^{5 in the} above formula (I-6) is an optionally substituted aliphatic hydrocarbon carbonyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon carbonyl group, an aromatic hydrocarbon carbonyl group. Specific examples include aliphatic hydrocarbon carbonyl groups such as formyl group, acetyl group, ethylcarbonyl group, butyryl group, allylcarbonyl;
An alicyclic hydrocarbon carbonyl group such as a cyclohexylcarbonyl group;
An aromatic hydrocarbon carbonyl group such as a phenylcarbonyl group or a methylphenylcarbonyl group;
These hydrocarbon carbonyl groups are substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, and the like.

R ^{5 in the} above formula (I-6), which may have a substituent, an aliphatic hydrocarbon oxycarbonyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon oxycarbonyl group, an aromatic hydrocarbon oxy Specific examples of the carbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, an aliphatic hydrocarbon oxycarbonyl group such as an allyloxycarbonyl group;
An alicyclic hydrocarbon oxycarbonyl group such as a cyclohexyloxycarbonyl group;
Aromatic hydrocarbon oxycarbonyl groups such as phenoxycarbonyl group and methylphenoxycarbonyl group;
These hydrocarbon oxycarbonyl groups substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, or a halogen atom;

R ^{5 in the} above formula (I-6), which may have a substituent, an aliphatic hydrocarbon carbonyloxy group having 1 to 18 carbon atoms, an alicyclic hydrocarbon carbonyloxy group, an aromatic hydrocarbon carbonyl Specific examples of the oxy group include an aliphatic hydrocarbon carbonyloxy group such as a methylcarbonyloxy group, an ethylcarbonyloxy group, a butylcarbonyloxy group, and an allylcarbonyloxy group;
An alicyclic hydrocarbon carbonyloxy group such as a cyclohexylcarbonyloxy group;
Aromatic hydrocarbon carbonyloxy groups such as phenylcarbonyloxy group and methylphenylcarbonyloxy group;
These hydrocarbon carbonyloxy groups are substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, and the like.

In the above R ⁵ , two or more R ⁵ may be bonded to each other to form a cyclic structure, and two to four R ⁵ may be bonded to form a divalent to tetravalent organic group as a whole. For example, an alkylene group such as ethylene, propylene, butylene, pentylene, and hexylene that can form a cyclic structure; an alkenyl group such as an ethenyl, propenyl, and butenyl group; an aralkylene group such as a methylenephenylene group; and an arylene group such as phenylene, naphthylene, and anthracenylene A group in which an oxy group or a dioxy group is bonded to an alkylene group, an alkenyl group, an aralkylene group or an arylene group; and the like. These include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, and a halogen. It may be substituted with an atom or the like.

R ^{5 in the} above formula (I-6) is preferably a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group. Among these, from the viewpoint of easy availability of raw materials, an unsubstituted or alkyl group such as hydrogen atom, hydroxyl group, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, or / And an aryl group substituted with an alkoxy group or / and a hydroxyl group, and a chain or cyclic group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an octyl group, and a cyclohexyl group A substituent selected from an alkyl group is more preferable. When two or more R ⁵ are bonded to each other to form a cyclic structure, a 1-(-2-hydroxynaphthyl) group, 1-(-4-hydroxynaphthyl) group is combined with a benzene ring to which R ⁵ is bonded. An organic group forming a polycyclic aromatic group such as a group is preferred.

In the above formula (I-6), Y ⁻ is an organic group in which one proton is eliminated from an organic group having 0 to 18 carbon atoms and having one or more releasable protons (H ⁺ ). R ⁵ may be bonded to each other to form a cyclic structure. For example, Y ^- represents a hydroxyl group, a mercapto group, a monovalent group proton is eliminated from the organic group having a hydrogen atom bonded to the Group 16 atoms such as hydro seleno group, a carboxyl group, a carboxymethyl group, a carboxyethyl group, carboxyphenyl A group in which a proton of a carboxylic acid is eliminated from a monovalent organic group having 1 to 18 carbon atoms having a carboxyl group such as a carboxynaphthyl group, a hydroxyphenyl group, a hydroxyphenylmethyl group, a hydroxynaphthyl group, a hydroxyfuryl group, Examples include a group in which a phenolic proton is eliminated from a monovalent organic group having 1 to 18 carbon atoms having a phenolic hydroxyl group such as a hydroxythienyl group and a hydroxypyridyl group.

Y ⁻ may be bonded to one or more R ⁵ to form a cyclic structure. For example, Y ⁻ is a 2-(-6-hydroxynaphthyl) in combination with a benzene ring to which it is bonded. And a divalent organic group that forms a group in which a proton is eliminated from a hydroxyl group of a hydroxy polycyclic aromatic group such as a group.

Previously illustrated Y ^- Among the oxygen anions proton from the hydroxyl group is eliminated, or hydroxyphenyl group, hydroxyphenyl methyl group, hydroxynaphthyl group, hydroxy furyl group, hydroxy thienyl group, a phenolic hydroxyl group such as hydroxy pyridyl group It is preferably a monovalent organic group having an oxygen anion formed by elimination of protons from.

When Y ⁻ is bonded to one or more R ⁵ to form a cyclic structure, for example, Y ⁻ is a 2-(-6-hydroxynaphthyl) group together with the benzene ring to which it is bonded. A group in which a proton is eliminated from a hydroxyl group of a hydroxy polycyclic aromatic group such as

  Further, the intermolecular salt of the phosphonium compound represented by the above formula (I-6) is not limited, but the phosphonium compound represented by the above formula (I-6), phenol, naphthol, Compounds having phenolic hydroxyl groups such as the compounds exemplified above as phenol compounds having two or more phenolic hydroxyl groups, compounds having silanol groups such as triphenylsilanol, diphenylsilanediol, trimethylsilanol, oxalic acid, acetic acid, benzoic acid And intermolecular salt compounds with organic acids such as hydrochloric acid, hydrogen bromide, sulfuric acid, nitric acid and the like.

  The compounding amount of the curing accelerator in the epoxy resin composition of the present invention is not particularly limited as long as a curing acceleration effect is achieved. However, from the viewpoint of improvement in curability and fluidity at the time of moisture absorption of the epoxy resin composition, it is preferable to add a total of 0.1 to 10 parts by mass of a curing accelerator with respect to a total of 100 parts by mass of the epoxy resin. 1 to 7.0 parts by mass is more preferable. When the blending amount of the curing accelerator is less than 0.1 parts by mass, it is difficult to cure the epoxy resin composition in a short time, and when it exceeds 10 parts by mass, the curing rate is too fast and a good molded product may not be obtained. .

(Inorganic filler)
The epoxy resin composition of this invention can contain an inorganic filler as needed. In particular, when an epoxy resin composition is used as a molding material for sealing, it is preferable to blend an inorganic filler.

  The inorganic filler used in the present invention is not particularly limited as long as it is generally used for a sealing molding material. Specific examples of inorganic fillers include fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, Examples include spinel, mullite, titania, talc, clay, mica, and the like, or beads formed by spheroidizing these. Examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, a composite metal hydroxide such as a composite hydroxide of magnesium and zinc, and zinc borate. Among these inorganic fillers, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. These inorganic fillers may be used alone or in combination of two or more.

  The blending amount of the inorganic filler is not particularly limited as long as the effect of the present invention is obtained, but is preferably in the range of 55 to 90% by volume with respect to the epoxy resin composition. These inorganic fillers are blended for the purpose of improving the thermal expansion coefficient, thermal conductivity, elastic modulus, etc. of the cured product. If the blending amount is less than 55% by volume, these properties tend to be insufficiently improved. If it exceeds 90% by volume, the viscosity of the epoxy resin composition is increased, the fluidity is lowered, and molding tends to be difficult.

  Moreover, 1-50 micrometers is preferable and, as for the average particle diameter (D50) of an inorganic filler, 10-30 micrometers is more preferable. When the average particle size is less than 1 μm, the viscosity of the epoxy resin composition tends to increase, and when it exceeds 50 μm, the resin component and the inorganic filler are easily separated, resulting in unevenness of the cured product and variations in the properties of the cured product. Or, there is a tendency that the filling property into a narrow gap is lowered.

  From the viewpoint of fluidity, the particle shape of the inorganic filler is preferably spherical rather than square, and the particle size distribution of the inorganic filler is preferably distributed over a wide range. For example, when the inorganic filler is blended in an amount of 75% by volume or more with respect to the epoxy resin composition, 70% by weight or more of the inorganic filler is a spherical particle, and the particle size distribution of the inorganic filler is distributed over a wide range of 0.1 to 80 μm. It is preferable that Since such an inorganic filler tends to have a close-packed structure, even if the blending amount is increased, an increase in the viscosity of the epoxy resin composition is small, and an epoxy resin composition excellent in fluidity can be obtained.

(Various additives)
The epoxy resin composition of the present invention includes the above-mentioned epoxy resin, epoxy resin curing agent, other curing agent, curing accelerator, inorganic filler, coupling agent exemplified below, ion exchanger, mold release Various additives such as an agent, a stress relaxation agent, a flame retardant, and a colorant can be contained as necessary. However, the epoxy resin composition of the present invention is not limited to the following additives, and various additives known in the art may be added as necessary.

(Coupling agent)
The epoxy resin composition of the present invention includes various silanes such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, and vinyl silane as necessary in order to enhance the adhesion between the resin component and the inorganic filler. Known coupling agents such as compounds, titanium compounds, aluminum chelates, and aluminum / zirconium compounds can be added.

  The blending amount of the coupling agent is preferably 0.05 to 5% by mass and more preferably 0.1 to 2.5% by mass with respect to the inorganic filler. If the blending amount is less than 0.05% by mass, the adhesion to the frame tends to decrease, and if it exceeds 5% by mass, the moldability of the package tends to decrease.

Examples of the coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloylpropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) ) Aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzyl) Silane coupling agents such as (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane;
Isopropyltriisostearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-aminoethyl-aminoethyl) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1 -Butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, Isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctylfo Feto) titanate, isopropyl tricumylphenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate coupling agents such as titanate; and the like, may be used in combination of two or more even with these alone. Among these, a coupling agent having a secondary amino group is preferable from the viewpoint of fluidity and wire flow.

(Ion exchanger)
The epoxy resin composition of the present invention can contain an anion exchanger as required. In particular, when an epoxy resin composition is used as a molding material for sealing, it is preferable to contain an anion exchanger from the viewpoint of improving moisture resistance and high-temperature storage characteristics of an electronic component device including an element to be sealed. . The anion exchanger used in the present invention is not particularly limited, and conventionally known anion exchangers can be used. For example, hydrotalcite, and hydrous hydroxide of an element selected from magnesium, aluminum, titanium, zirconium, and bismuth The thing is mentioned, These can be used individually or in combination of 2 or more types. Of these, hydrotalcite represented by the following formula (XIX) is preferable.
Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (XIX)
(In the above formula (XIX), 0 <X ≦ 0.5, m is a positive number.)

  The amount of these anion exchangers is not particularly limited as long as it is a sufficient amount capable of capturing anions such as halogen ions, but is preferably in the range of 0.1 to 30% by mass with respect to the epoxy resin. The range of ˜5% by mass is more preferable.

(Release agent)
In the epoxy resin composition of the present invention, a mold release agent may be blended in order to give good mold releasability from the mold during molding. There is no restriction | limiting in particular as a mold release agent used in this invention, A conventionally well-known thing can be used. Examples thereof include higher fatty acids such as carnauba wax, montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. It may be used in combination of two or more.

  Among these, an oxidized or non-oxidized polyolefin wax is preferable, and the blending amount of the polyolefin wax is preferably 0.01 to 10% by mass with respect to the epoxy resin, and 0.1 to 5% by mass. % Is more preferable. If the blending amount of the polyolefin wax is less than 0.01% by mass, the releasability tends to be insufficient, and if it exceeds 10% by mass, the adhesion may be inhibited. Examples of the polyolefin-based wax include low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000 such as H4, PE, and PED series manufactured by Hoechst.

  Moreover, when using another mold release agent together with polyolefin-type wax, it is preferable that the compounding quantity is 0.1-10 mass% with respect to an epoxy resin, and it is more preferable that it is 0.5-3 mass%. preferable.

(Stress relaxation agent)
The epoxy resin composition of the present invention may contain a stress relaxation agent such as silicone oil or silicone rubber powder as required. By blending a stress relaxation agent, the amount of warp deformation and package cracking of the package can be reduced. The stress relaxation agent that can be used is not particularly limited as long as it is a known flexible agent (stress relaxation agent) that is generally used.

  Commonly used flexible agents include, for example, silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, polybutadiene-based thermoplastic elastomers, NR (natural rubber), NBR, and the like. (Acrylonitrile-butadiene rubber), rubber particles such as acrylic rubber, urethane rubber, silicone powder, methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate Examples thereof include rubber particles having a core-shell structure such as a copolymer, and these may be used alone or in combination of two or more. Among these, a silicone-based flexible agent is preferable, and examples of the silicone-based flexible agent include those having an epoxy group, those having an amino group, and those obtained by modifying these with a polyether.

(Flame retardants)
In the epoxy resin composition of the present invention, a flame retardant can be blended as necessary to impart flame retardancy. There is no restriction | limiting in particular as a flame retardant used in this invention, For example, the well-known organic or inorganic compound and metal hydroxide containing a halogen atom, an antimony atom, a nitrogen atom, or a phosphorus atom are mentioned, These 1 type is mentioned. It may be used alone or in combination of two or more. The blending amount of the flame retardant is not particularly limited as long as the flame retardant effect is achieved, but is preferably 1 to 30% by mass and more preferably 2 to 15% by mass with respect to the epoxy resin.

(Coloring agent)
The epoxy resin composition of the present invention may contain known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, bengara and the like.

  The epoxy resin composition of the present invention can be prepared by any method as long as various components can be uniformly dispersed and mixed. As a general technique, there can be mentioned a method in which components of a predetermined blending amount are sufficiently mixed by a mixer or the like, then melt kneaded by a mixing roll, an extruder or the like, and then cooled and pulverized. More specifically, for example, a method in which predetermined amounts of the above-described components are uniformly stirred and mixed, kneaded with a kneader, roll, extruder, or the like that has been heated to 70 to 140 ° C., cooled, and pulverized. Can be obtained at The epoxy resin composition is easy to handle if it is tableted with dimensions and mass that match the molding conditions of the package.

<Electronic component device>
An electronic component device according to the present invention includes an element sealed with the above-described epoxy resin composition of the present invention. Such electronic component devices include, for example, lead frames, wired tape carriers, wiring boards, glass, silicon wafers and other supporting members, active elements such as semiconductor chips, transistors, diodes, thyristors, capacitors, resistors, coils Examples include those equipped with elements such as passive elements such as those in which these element portions are sealed with the epoxy resin composition of the present invention.

  More specifically, for example, after fixing a semiconductor element on a lead frame and connecting the terminal part of the element such as a bonding pad and the lead part by wire bonding or bump, the transfer is performed using the epoxy resin composition of the present invention. Sealed by molding or the like, DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-Tap) General resin-sealed ICs such as Outline Package (Tline) and TQFP (Thin Quad Flat Package), bumps on tape carriers TCP (Tape Carrier Package) encapsulated with the epoxy resin composition of the present invention, a semiconductor chip connected to a wiring formed on a wiring board or glass by wire bonding, flip chip bonding, solder, etc. COB (Chip On Board) module, hybrid IC, multichip module, in which active elements such as transistors, diodes, thyristors and / or passive elements such as capacitors, resistors, coils, etc. are sealed with the epoxy resin composition of the present invention The element is mounted on the surface of the organic substrate on which the terminals for connecting the wiring board are formed on the back surface, and after connecting the element and the wiring formed on the organic substrate by bump or wire bonding, the element is formed with the epoxy resin composition of the present invention. Sealed BGA (Ball Grid Ar ay), CSP (Chip Size Package), and the like.

  Especially, since the epoxy resin composition of this invention has few elastic modulus fall at high temperature, it can be used conveniently for the use as which heat resistance, high temperature operation guarantee, etc. are requested | required. Specifically, a power module package, an in-vehicle package, a semiconductor package that operates even at high temperatures, such as SiC, and the like can be given. Moreover, the epoxy resin composition of this invention can be used effectively also in a printed circuit board.

  As a method for sealing an electronic component device using the epoxy resin composition of the present invention, a low pressure transfer molding method is the most general method, but a method such as an injection molding method or a compression molding method may be used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the scope of the present invention is not limited to these Examples.

<Synthesis 1 of calixarene compound 1>
(Synthesis Example 1): Synthesis of calixarene compound 1 Using a 500 ml four-necked flask, 88.0 g (0.8 mol) of resorcinol was dissolved in 90 ml of ethanol, and 30 ml of concentrated hydrochloric acid was added under ice cooling to about 5 ° C. For 30 minutes. To this was added dropwise 20.2 g (0.1 mol) of a 50% glutaraldehyde aqueous solution, followed by reaction at about 80 ° C. for 48 hours. The reaction mixture was cooled to room temperature, diluted with 300 ml of methanol, stirred for 30 minutes, and then a solid produced by heating was obtained. The obtained solid was washed 3 times with methanol and vacuum dried at 60 ° C. for 24 hours to obtain 22.2 g of a brown solid.

As a result of measuring ¹ H-NMR spectrum, measuring IR spectrum, and measuring mass spectrum of the obtained white solid, it was confirmed to be a calixarene compound having a structure represented by the following formula. The yield was 78%. Since the calixarene compound having the structure represented by the following formula (I-3a) is a known compound, measurement results of various spectra are omitted.

<Synthesis of calixarene compound 2>
(Example 1): Synthesis of calixarene compound 2 The calixarene compound 1 having the structure represented by the above formula (I-3a) obtained in Synthesis Example 1 and allyl bromide were reacted by the method described above, and A calixarene compound 2 having a structure represented by the formula (I-1a) was obtained.

As a result of measurement of ¹ H-NMR spectrum and IR spectrum, it was confirmed to be a calixarene compound having a structure represented by the following formula (I-1a). The calixarene compound 2 had a β-alkenyl etherification rate of 53% (the ratio of R ¹ hydrogen atom / β-alkenyl ether group was 47/53).

<Synthesis of resorcinol derivative>
(Synthesis Example 2): Synthesis of Resorcinol Derivative According to the above-described method, allyl bromide is reacted with the hydroxyl group of resorcinol to form allyl ether, and then converted to debenzoic acid using a base, the following formula (I-5a The resorcinol derivative represented by this was obtained.

As a result of measurement of ¹ H-NMR spectrum, it was confirmed that the compound was represented by the following formula (I-5a). Since it is a known compound, the spectrum chart is omitted.

<Synthesis of calixarene compound 3>
(Example 2): Synthesis of calixarene compound 3 The resorcinol derivative having the structure represented by the above formula (I-5a) obtained in Synthesis Example 2 and glutaraldehyde were reacted by the method described above, and the following formula (I- The calixarene compound 3 having the structure represented by 1b) was obtained.

¹ H-NMR spectrum, IR spectrum, mass spectrum and GPC measurement results, with the compound represented by the following formula (I-1b) as the main component, the oligomer component represented by the following formula (I-1c) as a by-product It was confirmed that the compound contained as a product. Of the two R ¹ on the same benzene ring of the following formulas (I-1b) and (I-1c), one was a hydrogen atom and the other was a β-alkenyl ether group.

Details of the measurement method of ¹ H-NMR spectrum and IR spectrum in Synthesis Examples and Examples are as follows.
(1) Measurement of ¹ H-NMR spectrum A sample was dissolved in deuterated dimethyl sulfoxide to form a solution, and placed in a φ5 mm sample tube for measurement. Measurement was performed using a 500 MHz nuclear magnetic resonance apparatus “JEOL ECA-500” manufactured by JEOL Ltd.

(2) Measurement of IR spectrum It measured by the film method using "Nicolet 380FT-IR" by Thermo ELECTRON Corporation.

[Preparation of epoxy resin composition and evaluation of its properties]
Each of the following components was blended in parts by mass shown in Table 1, and roll kneading was carried out under conditions of a kneading temperature of 80 ° C. and a kneading time of 15 minutes, whereby the epoxy resin compositions of Examples 3 to 4 and Comparative Examples 1 to 3, respectively. I got a thing.
In addition, the compounding quantity of the inorganic filler in each epoxy resin composition was 85% on a mass basis and 75% on a volume basis.

(Epoxy resin)
Epoxy resin: Hydroxybenzaldehyde type epoxy resin having an epoxy equivalent of 170 and a softening point of 67 ° C. (trade name “EPPN-502H” manufactured by Nippon Kayaku Co., Ltd.)

(Curing agent)
Curing agent 1: calixarene compound 2 obtained in Example 1
Curing agent 2: calixarene compound 3 obtained in Example 2
Curing agent 3: calixarene compound 1 obtained in Synthesis Example 1
Curing agent 4: calixarene compound represented by the following formula

硬化剤５：水酸基当量１０３のヒドロキシベンズアルデヒド型フェノール樹脂（明和化成株式会社製、商品名「ＭＥＨ−７５００」）

Curing agent 5: Hydroxybenzaldehyde type phenolic resin having a hydroxyl equivalent weight of 103 (Madewa Kasei Co., Ltd., trade name “MEH-7500”)

(Curing accelerator)
Curing accelerator: addition reaction product of triphenylphosphine and 1,4-benzoquinone

(Inorganic filler)
Inorganic filler: spherical fused silica having an average particle size (D50) of 17.5 μm and a specific surface area of 3.8 m ² / g

(Various additives)
Coupling agent: Epoxy silane (γ-glycidoxypropyltrimethoxysilane)
Colorant: Carbon black (Mitsubishi Chemical Corporation, trade name “MA-100”)
Mold release agent: Carnauba wax (manufactured by Celerica NODA)

  Each epoxy resin composition obtained in Examples 3 to 4 and Comparative Examples 1 to 3 was evaluated by each test shown below. The evaluation results are shown in Table 1 and FIGS.

  The epoxy resin composition was molded using a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Further, post-curing was performed at 175 ° C. for 6 hours or at 250 ° C. for 6 hours.

(1) Spiral flow (fluidity index)
Each epoxy resin composition was molded under the above conditions using a spiral flow measurement mold according to EMMI-1-66, and the flow distance (cm) was measured. The results are shown in Table 1.

(2) Hardness during heating Each epoxy resin composition obtained in Examples 3 to 4 and Comparative Examples 1 to 3 was molded into a disk having a diameter of 50 mm and a thickness of 3 mm under the above conditions, and immediately after molding, Shore D type hardness It measured using the meter (the Uejima Seisakusho make, HD-1120 (type D)). The results are shown in Table 1.

(3) Dynamic viscoelastic behavior (index of heat resistance)
Each epoxy resin composition obtained in Examples 3 to 4 and Comparative Examples 1 to 3 was molded into a size of length 80 mm × width 10 mm × thickness 3 mm under the above conditions, and at 175 ° C. for 6 hours or at 250 ° C. Post-cured for 6 hours. Next, it is cut into 5 mm in width and 55 mm in length with a diamond cutter, and measured using a viscoelasticity measuring device RSA3 (manufactured by TA Instruments) at a temperature rising rate of 5 ° C. and a frequency of 6.28 rad / s in a three-point bending mode. did. FIG. 1 shows the results of measurement using a cured product post-cured at 175 ° C. for 6 hours as a sample, and FIG. 2 shows the results of measurement using a cured product post-cured at 250 ° C. for 6 hours as a sample.

(4) Solubility of curing agent in epoxy resin (index of uniformity)
For 100 parts by mass of epoxy resin (Nippon Kayaku Co., Ltd., trade name “EPPN-502H”), the total number of epoxy groups of epoxy resin / (total number of phenolic hydroxyl groups of curing agent + total number of allyl ether groups of curing agent) Each curing agent was mixed so as to be 1, and heated at 120 ° C. for 3 minutes using a hot plate, and the appearance of the mixture was visually observed. Table 2 shows the transparent ones as ○ and those that remain cloudy as ×.
When the curing agent is uniformly dissolved in the epoxy resin, the mixture becomes transparent, and when the curing is insufficient, the mixture becomes cloudy.

  The calixarene compounds 2 and 3 of the present invention have excellent solubility in an epoxy resin, and Examples 3 and 4 using them as curing agents 1 and 2 have no problem in fluidity and heat hardness. It can be seen from FIG. 2 that it has excellent high temperature elastic modulus and high heat resistance. In particular, excellent performance is exhibited by post-curing at 250 ° C.

  On the other hand, the calixarene compound 1 used in Comparative Example 1 was extremely poor in solubility in the epoxy resin, and Comparative Example 1 using it as the curing agent 3 did not cure. Moreover, it turns out that the hardening | curing agent 4 (calixarene type compound) used in the comparative example 2 is inferior in the solubility to an epoxy resin, and the comparative example 2 using it is inferior in fluidity | liquidity. Moreover, it turns out that the comparative example 3 which used the hydroxybenzaldehyde type phenol resin as the hardening | curing agent 5 is inferior in the point of a high temperature elastic modulus by FIG.1 and FIG.2.

  According to the present invention, there is provided a novel calixarene compound as a curing agent for an epoxy resin that has good solubility when formed into an epoxy resin composition and can impart high heat resistance to the cured epoxy resin. be able to. Moreover, according to this invention, the electronic component apparatus provided with the epoxy resin composition containing the said hardening | curing agent for epoxy resins, and the element sealed by it can be provided.

Claims (9)

A calixarene compound represented by the following formula (I-1).

(In the formula (I-1), n is an average number of 2 to 20, and R ¹ , R ² , and R ³ may be the same or different with respect to each of n repetitions in the unit structure. ,
R ¹ is a hydrogen atom or a monovalent substituent represented by the following formula (I-2), at least one R ^{1 in} one molecule is a hydrogen atom, and R in the following formula (I-2) ⁴ represents each of n repetitions, R ⁴ may be the same or different, and each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent. .

R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , A hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom, all may be the same or different,
R ³ is independently selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, and all may be the same or different. ) The calixarene compound according to claim 1, wherein 5 to 100% of the phenolic hydroxyl group of the calixarene compound (b1) represented by the following formula (I-3) is β-alkenyl etherified.

(In the formula (I-3), n is an average number of 2 to 20, and R ² and R ³ may be the same or different with respect to each of n repetitions in the unit structure,
R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , A hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom, all may be the same or different,
R ³ is independently selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, and all may be the same or different. ) The calixarene compound according to claim 1 or 2, wherein R ^{2 in the} formulas (I-1) and (I-3) is a hydrogen atom. The calixarene compound according to any one of claims 1 to ₃ , wherein R ^{3 in the} formulas (I-1) and (I-3) is (CH ₂ ) ₃ . Wherein the calixarene compound (b1) represented by the formula (I-3) is reacted with at least one compound selected from the group of β-alkenyl halides represented by the formula (I-4). The manufacturing method of the calixarene compound as described in any one of Claims 1-4.

(In the formula (I-4), each R ⁴ is independently selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, and all are the same. However, it may be different, and X is selected from halogen atoms.) The resorcinol derivative represented by the following formula (I-5) is reacted with at least one compound selected from the group of dialdehydes represented by the following formula (I-5 ′). 5. The method for producing a calixarene compound according to any one of 4 above.

(In the formula (I-5), R ¹ is a hydrogen atom or a monovalent substituent represented by the following formula (I-2);

At least one R ¹ in one molecule is a hydrogen atom, the formula (I-2) R ⁴ in each independently represent a hydrogen atom, carbon atoms which may have a substituent 1 to 18 Represents a hydrocarbon group.
R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , A hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom, all of which may be the same or different. )

(In the formula (I-5 ′), each R ³ is independently selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, and all may be the same or different.)   A curing agent for epoxy resins, wherein the calixarene compound according to any one of claims 1 to 4 is used.   An epoxy resin composition comprising an epoxy resin and the epoxy resin curing agent according to claim 7.   An electronic component device comprising an element sealed with the epoxy resin composition according to claim 8.

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