JP5008199B2 - Epoxy resin curing agent, epoxy resin composition, and electronic component device - Google Patents

Description

  The present invention relates to an epoxy resin curing agent, an epoxy resin composition, and an electronic component device including an element sealed by the epoxy resin composition.

Conventionally, curable resins such as epoxy resins have been widely used in the fields of molding materials, laminates and adhesives, various electronic and electrical parts, 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 viscosity tends to increase when the epoxy resin composition is made, and the handling property is poor, and the fluidity is low. There is.
An object of the present invention is to provide 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 a cured epoxy resin. Moreover, the 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 to solve the above-mentioned problems, the present inventors have used a calixarene derivative obtained by partially modifying the phenolic hydroxyl group of calixarene with an epoxy group as a curing agent for a resin. The inventors have found that the intended purpose can be achieved, and have completed the present invention.

（式中、ｎ’及びｎ”は０〜４、ｎ’＋ｎ”は１〜４、ｍは平均で３〜２０の数であり、ｍ×ｎ” ＞０であり、ｍ個の繰り返しのそれぞれに関して、Ｒ^１、Ｒ^２、Ｒ^３、ｎ’、ｎ”は同一でも異なっていてもよく、
Ｒ^１は、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く、
Ｒ^２は、それぞれ独立して、水素原子及び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、
Ｒ^３は、水素原子及び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。）
また、本発明は、（２）式（Ｉ−１）で示されるカリックスアレーン類（ｂ１）のフェノール性水酸基の５〜９０％にエポキシ化合物（ｂ２）のエポキシ基を反応させてなるカリックスアレーン誘導体であることを特徴とするエポキシ樹脂用硬化剤に関する。

（式（Ｉ−１）中、ｎは１〜４、ｍは平均で３〜２０の数であり、ｍ個の繰り返しのそれぞれに関して、Ｒ^１、Ｒ^２、ｎは同一でも異なっていてもよく、
Ｒ^１は、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く、
Ｒ^２は、それぞれ独立して、水素原子及び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い。）
また、本発明は、（３）前記カリックスアレーン類（ｂ１）が、式（Ｉ−２）で示される化合物であることを特徴とする前記（２）に記載のエポキシ樹脂用硬化剤に関する。

（式中、ｍは平均で３〜２０の数であり、ｍ個の繰り返しのそれぞれに関して、Ｒ^１、Ｒ^２は同一でも異なっていてもよく、
Ｒ^１は、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く、
Ｒ^２は、それぞれ独立して、水素原子及び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い。）
また、本発明は、（４）前記エポキシ化合物（ｂ２）が、分子内に１つ又は２つのエポキシ基を有することを特徴とする前記（２）又は（３）に記載のエポキシ樹脂用硬化剤に関する。
また、本発明は、（５）前記エポキシ化合物（ｂ２）が、分子内に１つのエポキシ基を有することを特徴とする前記（２）〜（４）のいずれか一項に記載のエポキシ樹脂用硬化剤に関する。
また、本発明は、（６）エポキシ樹脂及び前記（１）〜（５）のいずれか一項に記載のエポキシ樹脂用硬化剤を含有することを特徴とするエポキシ樹脂組成物に関する。
また、本発明は、（７）前記（６）に記載のエポキシ樹脂組成物によって封止された素子を備えることを特徴とする電子部品装置に関する。 The present invention relates to (1) a curing agent for epoxy resins, wherein a calixarene derivative represented by the formula (I-3) is used.

(Where n ′ and n ″ are 0 to 4, n ′ + n ″ is 1 to 4, m is an average number of 3 to 20, m × n ″> 0, and each of m repetitions. R ¹ , R ² , R ³ , n ′, n ″ may be the same or different,
R ¹ is selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, all of which may be the same or different;
R ² 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 may be the same or different,
R ³ 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. )
The present invention also relates to a calixarene derivative obtained by reacting the epoxy group of the epoxy compound (b2) with 5 to 90% of the phenolic hydroxyl group of the calixarene (b1) represented by (2) formula (I-1). It is related with the hardening | curing agent for epoxy resins characterized by these.

(In formula (I-1), n is 1 to 4, m is an average number of 3 to 20, and R ¹ , R ² and n may be the same or different with respect to each of m repetitions. ,
R ¹ is selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, all of which may be the same or different;
R ² 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 may be the same or different. )
The present invention also relates to (3) the epoxy resin curing agent according to (2), wherein the calixarene (b1) is a compound represented by the formula (I-2).

(In the formula, m is an average number of 3 to 20, and for each of m repetitions, R ¹ and R ² may be the same or different,
R ¹ is selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, all of which may be the same or different;
R ² 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 may be the same or different. )
In addition, the present invention provides (4) the epoxy resin curing agent according to (2) or (3), wherein the epoxy compound (b2) has one or two epoxy groups in the molecule. About.
In addition, the present invention provides the epoxy resin according to any one of (2) to (4), wherein (5) the epoxy compound (b2) has one epoxy group in the molecule. It relates to a curing agent.
The present invention also relates to an epoxy resin composition comprising (6) an epoxy resin and the epoxy resin curing agent according to any one of (1) to (5).
The present invention also relates to (7) an electronic component device comprising an element sealed with the epoxy resin composition according to (6).

  According to the present invention, it is possible to provide an epoxy resin curing agent that has good solubility when formed into an epoxy resin composition and can impart high heat resistance to the cured epoxy resin. 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.

  Hereinafter, the present invention will be described in detail.

（式中、ｎ’及びｎ”は０〜４、ｎ’＋ｎ”は１〜４、ｍは平均で３〜２０の数であり、ｍ×ｎ” ＞０であり、ｍ個の繰り返しのそれぞれに関して、Ｒ^１、Ｒ^２、Ｒ^３、ｎ’、ｎ”は同一でも異なっていてもよく、
Ｒ^１は、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く、
Ｒ^２は、それぞれ独立して、水素原子及び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、
Ｒ^３は、水素原子及び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。）
また、本発明のエポキシ樹脂用硬化剤は、式（Ｉ−１）で示されるカリックスアレーン類（ｂ１）のフェノール性水酸基の５〜９０％にエポキシ化合物（ｂ２）のエポキシ基を反応させてなるカリックスアレーン誘導体であることを特徴とする。

（式（Ｉ−１）中、ｎは１〜４、ｍは平均で３〜２０の数であり、ｍ個の繰り返しのそれぞれに関して、Ｒ^１、Ｒ^２、ｎは同一でも異なっていてもよく、
Ｒ^１は、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く、
Ｒ^２は、それぞれ独立して、水素原子及び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い。）
前記カリックスアレーン類（ｂ１）としては、上記式（Ｉ−１）で示される化合物であれば特に限定されないが、高耐熱性の観点から下記式（Ｉ−２）で示される化合物であることが好ましい。

（式中、ｍは平均で３〜２０の数であり、ｍ個の繰り返しのそれぞれに関して、Ｒ^１、Ｒ^２は同一でも異なっていてもよく、
Ｒ^１は、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く、
Ｒ^２は、それぞれ独立して、水素原子及び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い。） Curing agent for epoxy resin The curing agent for epoxy resin of the present invention is characterized by using a calixarene derivative represented by the formula (I-3).

(Where n ′ and n ″ are 0 to 4, n ′ + n ″ is 1 to 4, m is an average number of 3 to 20, m × n ″> 0, and each of m repetitions. R ¹ , R ² , R ³ , n ′, n ″ may be the same or different,
R ¹ is selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, all of which may be the same or different;
R ² 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 may be the same or different,
R ³ 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. )
In addition, the epoxy resin curing agent of the present invention is obtained by reacting the epoxy group of the epoxy compound (b2) with 5-90% of the phenolic hydroxyl group of the calixarene (b1) represented by the formula (I-1). It is a calixarene derivative.

(In formula (I-1), n is 1 to 4, m is an average number of 3 to 20, and R ¹ , R ² and n may be the same or different with respect to each of m repetitions. ,
R ¹ is selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, all of which may be the same or different;
R ² 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 may be the same or different. )
The calixarene (b1) is not particularly limited as long as it is a compound represented by the above formula (I-1), but it is a compound represented by the following formula (I-2) from the viewpoint of high heat resistance. preferable.

(In the formula, m is an average number of 3 to 20, and for each of m repetitions, R ¹ and R ² may be the same or different,
R ¹ is selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, all of which may be the same or different;
R ² 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 may be the same or different. )

  Examples of the epoxy compound (b2) include phenyl glycidyl ether, methyl glycidyl ether, tert-butyl glycidyl ether, styrene oxide, ethylene oxide and the like in addition to the epoxy resin exemplified as the epoxy resin component described later. The epoxy compound (b2) is not particularly limited as long as it is a compound having one or more epoxy groups in the molecule, but from the viewpoint of solubility, a smaller number of epoxy groups in the molecule is preferable. The number is more preferably one or two, and particularly preferably one. These epoxy compounds (b2) may be used individually by 1 type, or may use 2 or more types together.

  The curing agent for epoxy resin of the present invention is a calixarene derivative obtained by reacting an epoxy group of the epoxy compound (b2) with a part of the phenolic hydroxyl group of the calixarene (b1) represented by the formula (I-1). Yes, 5 to 90% of the phenolic hydroxyl group is reacted with the epoxy group of the epoxy compound (b2). When the proportion of the phenolic hydroxyl group reacted with the epoxy group is less than 5%, the solubility with the constituent components of the epoxy resin composition is poor, and conversely, when it exceeds 90%, heat resistance is imparted to the cured epoxy resin. I can't. The proportion of the phenolic hydroxyl group reacted with the epoxy group is preferably 10 to 70% from the viewpoint of achieving both solubility with the constituent components of the epoxy resin composition and heat resistance of the cured epoxy resin. More preferably, it is -50%.

In the above formulas (I-1) to (I-3), R ¹ is selected from the group consisting of divalent organic groups 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. Examples of the divalent hydrocarbon group having 1 to 18 carbon atoms that may have a substituent include aliphatic hydrocarbon groups such as a methylene group, an ethylene group and a propylene group; a cyclohexylene group and a cyclopentyl group. An alicyclic hydrocarbon group such as a len group; an aliphatic group or an alicyclic hydrocarbon group substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen, or the like; a phenylene group And aromatic hydrocarbon groups such as naphthylene group and anthracenylene group; those obtained by substituting alkyl group, alkoxy group, aryl group, aryloxy group, amino group, halogen and the like on these aromatic hydrocarbon groups;
Among the divalent organic groups having 0 to 18 carbon atoms, an aliphatic hydrocarbon group which may have a sulfur atom and a substituent is preferable from the viewpoint of ease of synthesis and synthesis yield. A methylene group which may have a group is more preferable. Examples of the methylene group which may have a substituent include, for example, a methylene group, a methylmethylene group, an ethylmethylene group, an isopropylmethylene group, a phenylmethylene group, a hydroxyphenylmethylene group, a cyclohexylmethylene group, a dimethylmethylene group, and a methyldimethyl group. Examples thereof include an isopropylmethylene group, a methylphenylmethylene group, a cyclohexylmethylene group, a cyclopentylmethylene group, and among these, a methylmethylene group is preferable.
In the above formulas (I-1) to (I-3), R ² 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. An atom, an optionally substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, etc., for example, a hydrogen atom; a methyl group, an ethyl group, Aliphatic hydrocarbon groups such as propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, allyl group and vinyl group; A group containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, an epoxy group, a methacryloyl group, a Substituted with a lucapto group, imino group, ureido group, isocyanate group, etc .; cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group, cyclohexenyl group, and other alicyclic hydrocarbon groups; these alicyclic hydrocarbon groups Group containing an epoxy group such as alkyl group, alkoxy group, aryl group, aryloxy group, hydroxyl group, amino group, halogen atom, glycidyloxy group, epoxycyclohexyl group, epoxy group, methacryloyl group, mercapto group, imino group, Substituted by ureido group, isocyanate group, etc .; aromatic hydrocarbon group such as phenyl group, tolyl group; alkyl group-substituted aryl group such as dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, methoxy Phenyl group, ethoxyphenyl group, Alkoxy group-substituted aryl groups such as xylphenyl group and tert-butoxyphenyl group, and further, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, glycidyloxy groups, epoxycyclohexyl groups, epoxy groups, etc. A group containing an epoxy group, a methacryloyl group, a mercapto group, an imino group, a ureido group, an isocyanate group, and the like. Among these, a hydrogen atom is preferable.
In the above formula (I-3), R ³ 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 aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, etc., which may be, for example, a hydrogen atom; a methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, allyl group, vinyl group and other aliphatic hydrocarbon groups; Epoxy such as alkyl group, alkoxy group, vinyloxy group, allyloxy group, aryl group, aryloxy group, hydroxyl group, amino group, halogen atom, glycidyloxy group, epoxycyclohexyl group, epoxy group, etc. A group containing a thio group, a group containing an oxetanyl group such as a 3-ethyl-3-oxetanyl group, a methacryloyl group, a mercapto group, an imino group, a ureido group, an isocyanate group, etc .; a cyclopentyl group, a cyclohexyl group, Cycloheptyl group, cyclopentenyl group, cyclohexenyl group and other alicyclic hydrocarbon groups; these alicyclic hydrocarbon groups include alkyl groups, alkoxy groups, aryl groups, aryloxy groups, hydroxyl groups, amino groups, halogen atoms, glycidyl Oxy group, epoxy cyclohexyl group, epoxy group-containing group, methacryloyl group, mercapto group, imino group, ureido group, isocyanate group, etc. substituted; aromatic hydrocarbon group such as phenyl group, tolyl group ; Dimethylphenyl group, ethylphenyl group, butylphenyl group Alkyl group-substituted aryl groups such as tert-butylphenyl group, alkoxy group-substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group, and the like, further alkyl groups, alkoxy groups, aryl groups, Substituted with an aryloxy group, amino group, halogen atom, glycidyloxy group, epoxycyclohexyl group, epoxy group-containing group, methacryloyl group, mercapto group, imino group, ureido group, isocyanate group, etc. Can be mentioned. Among these, from the simplicity of synthesis, aryloxy group-substituted aliphatic hydrocarbon groups such as phenoxymethylene group, phenoxyethylene group, phenoxypropylene group, 4-vinylbenzyloxymethylene group, methoxymethylene group, n-butoxymethylene An alkoxy group-substituted aliphatic hydrocarbon group such as a group, an allyloxymethylene group, a vinyloxymethylene group, a methacryloylmethylene group, and a 3-ethyl-3-oxetanylmethoxymethyl group are preferable, and a phenoxymethylene group is more preferable.
In the above formulas (I-1) to (I-3), m is not particularly limited as long as it is an average number of 3 to 20, but is 3 to 10 from the viewpoint of high heat resistance. Is more preferable, 3 to 5 is more preferable, and 4 is still more preferable.

The method for producing the calixarene derivative represented by the formula (I-3) is not particularly limited. However, the method is not limited thereto, but the phenolic hydroxyl group 5 of the calixarene (b1) represented by the formula (I-1) may be used. The method of making the epoxy group of an epoxy compound (b2) react with -90% is mentioned. In the case of using a solvent, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, tetrahydrofuran, N, N-dimethylformamide, dimethyl sulfoxide, etc. are used, and the reaction is performed by heating to 60 to 200 ° C. The method of distilling a solvent off is mentioned. Moreover, you may use the compound which accelerates | stimulates the reaction of the phenolic hydroxyl group of calixarene (b1) and the epoxy group of an epoxy compound (b2) as needed. Although it does not specifically limit as a compound which accelerates | stimulates the reaction which can be used, The compound mentioned later as a hardening accelerator is mentioned. To react the epoxy group of the epoxy compound (b2) with 5 to 90% of the phenolic hydroxyl group of the calixarene (b1), the amount of the epoxy compound (b2) used is controlled or the reaction is stopped halfway. There is a way. Further, as a method for producing a calixarene derivative represented by the formula (I-3), there is a method of polymerizing a monomer having a repeating unit in the formula (I-3).
In addition, as a method for producing a calixarene derivative by reacting 5 to 90% of the phenolic hydroxyl group of the calixarene (b1) represented by the formula (I-1) with the epoxy group of the epoxy compound (b2), The method is not limited, and examples thereof include the following methods. The calixarenes (b1) and the epoxy compound (b2) are heated at 60 to 200 ° C. in the presence of a solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, tetrahydrofuran, N, N-dimethylformamide, dimethyl sulfoxide and the like. A method of reacting by heating and distilling off the solvent after the reaction can be mentioned. As needed, you may use the compound which accelerates | stimulates the reaction of the phenolic hydroxyl group of calixarene (b1), and the epoxy group of an epoxy compound (b2). Although it does not specifically limit as a compound which accelerates | stimulates the reaction which can be used, The compound mentioned later as a hardening accelerator is mentioned. To react the epoxy group of the epoxy compound (b2) with 5 to 90% of the phenolic hydroxyl group of the calixarene (b1), the amount of the epoxy compound (b2) used is controlled or the reaction is stopped halfway. There is a way.

Epoxy resin composition The epoxy resin composition of the present invention comprises an epoxy resin and the curing agent for epoxy resin of the present invention.

(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- A novolak epoxy obtained by epoxidizing a novolak resin obtained by condensation or cocondensation of naphthols such as naphthol and dihydroxynaphthalene with a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde under an acidic catalyst. resin;
Bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or unsubstituted biphenol, diglycidyl ethers such as stilbene phenols (bisphenol-type epoxy resin, biphenyl-type epoxy resin, stilbene-type epoxy resin),
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, Salicylaldehyde type epoxy resins, copolymerized epoxy resins of naphthols and phenols, phenol aralkyl resins, epoxidized aralkyl type phenol resins such as naphthol aralkyl resins, and naphthalene type phenol resins are preferred, and any one of them is used. It may be used alone or in combination of two or more. However, in order to exhibit these performances, it is preferable to use them in total of 30% by weight or more, more preferably 50% by weight or more, based on the total amount of epoxy resin. Specific examples of preferable epoxy resins are shown below.

（式（ＩＩ）中、Ｒ^８は水素原子又は炭素数１〜１２のアルキル基又は炭素数４〜１８のアリール基を示し、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。） 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 general formula (II) is preferable. Among the epoxy resins represented by the following general formula (II), the positions where the oxygen atoms are substituted in R ⁸ are the 4 and 4 'positions, and the 3, 3', 5, 5 'positions are methyl groups. YX-4000H (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) in which all are hydrogen atoms, 4,4′-bis (2,3-epoxypropoxy) biphenyl in which all R ⁸ are hydrogen atoms, and all R ⁸ are In the case of a hydrogen atom, and when the positions where oxygen atoms are substituted in R ⁸ are the 4 and 4 'positions, the 3, 3', 5, 5 'positions are methyl groups, and the rest are hydrogen atoms YL-6121H (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), which is a mixed product, is available as a commercial product.

(In the 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, The number of 0-10 is shown.)

（式（ＩＩＩ）中、Ｒ^９及びＲ^１０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、ｎは平均値であり、０〜１０の数を示す。） 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 general formula (III) is preferable. Among the epoxy resins represented by the following general formula (III), 3, ⁹ ′, 5 ′ and 5 ′ positions when R ⁹ is substituted with oxygen atoms at positions 4 and 4 ′ are methyl groups. The other is a hydrogen atom and all of R ¹⁰ are hydrogen atoms, and three of the 3, 3 ′, 5, 5 ′ positions are methyl groups, one is a tert-butyl group, and the other is a hydrogen atom and R ESLV-210 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), which is a mixture when all ¹⁰ are hydrogen atoms, is available as a commercial product.

(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, 0 Indicates the number of

（式（ＩＶ）中、Ｒ^１１及びＲ^１２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、ｎは平均値であり、０〜１０の数を示す。） 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 general formula (IV) is preferable. Among the epoxy resins represented by the following general formula (IV), all of R ¹¹ are hydrogen atoms, and the positions where oxygen atoms are substituted in R ¹² are 3, 3 ′, YSLV-80XY (trade name, manufactured by Nippon Steel Chemical Co., Ltd.), in which the 5,5′-position is a methyl group and the others are hydrogen atoms, is commercially available.

(In the formula (IV), R ¹¹ and R ¹² represent 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 0 to 10 Indicates the number of

（式（Ｖ）中、Ｒ^１３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、ｎは平均値であり、０〜１０の数を示す。） Although it will not specifically limit as a sulfur atom containing type epoxy resin if it is an epoxy resin containing a sulfur atom, For example, the epoxy resin shown by the following general formula (V) is mentioned. Among the epoxy resins represented by the following general formula (V), the tert-butyl group is the tert-butyl group when the positions where the oxygen atom substitution positions in R ¹³ are the 4 and 4 'positions, and 6, 6 YSLV-120TE (trade name, manufactured by Nippon Steel Chemical Co., Ltd.) in which the '-position is a methyl group and the other is a hydrogen atom is commercially available.

(In the 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 the number of 0 to 10 is Show.)

（式（ＶＩ）中、Ｒ^１４及びＲ^１５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、ｎは平均値であり、０〜１０の数を示す。） 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. Epoxy resins epoxidized using the above method are preferred, and for example, epoxy resins represented by the following general formula (VI) are more preferred. Among the epoxy resins represented by the following general formula (VI), ESCN-190 and ESCN-195 (trade names, manufactured by Sumitomo Chemical Co., Ltd.), in which all of R ¹⁴ are hydrogen atoms, R ¹⁵ is a methyl group and i = 1. Etc. are available as commercial products.

(In the 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, i is an integer of 0 to 3, and n is (It is an average value and represents a number from 0 to 10.)

（式（ＶＩＩ）中、Ｒ^１６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、ｎは平均値であり、０〜１０の数を示す。） 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 general formula (VII) is preferable. Among epoxy resins represented by the following general formula (VII), HP-7200 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) where 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. Yes, indicates a number from 0 to 10.)

（式（ＶＩＩＩ）中、Ｒ^１７及びＲ^１８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、ｎは平均値であり、０〜１０の数を示す。） The salicylaldehyde type epoxy resin is not particularly limited as long as it is an epoxy resin made from a compound having a salicylaldehyde skeleton, but a novolak type phenol resin of a compound having a salicylaldehyde skeleton and a compound having a phenolic hydroxyl group, etc. A salicylaldehyde type epoxy resin such as an epoxy resin obtained by glycidyl etherification of a salicylaldehyde type phenol resin is preferable, and an epoxy resin represented by the following general formula (VIII) is more preferable. Among epoxy resins represented by the following general formula (VIII), 1032H60 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-502H (trade name, manufactured by Nippon Kayaku Co., Ltd.), etc., where i = 0 and k = 0. It is available as a commercial product.

(In the formula (VIII), R ¹⁷ and R ¹⁸ 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, and k is (The integer of 0-4, n is an average value and shows the number of 0-10.)

（式（ＩＸ）中、Ｒ^１９〜Ｒ^２１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、ｊは０〜２の整数、ｋは０〜４の整数を示し、ｐは平均値で０〜１の数を示し、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。）
上記一般式（ＩＸ）で示されるエポキシ樹脂としては、ｌ個の構成単位及びｍ個の構成単位をランダムに含むランダム共重合体、交互に含む交互共重合体、規則的に含む共重合体、ブロック状に含むブロック共重合体が挙げられ、これらのいずれか１種を単独で用いても、２種以上を組み合わせて用いてもよい。 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 general formula (IX). Among the epoxy resins represented by the following general formula (IX), NC-7300 (trade name, manufactured by Nippon Kayaku Co., Ltd.) in which R ²¹ is a methyl group, i = 1, j = 0, and k = 0, etc. It is available as a commercial product.

(In the 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 represents an integer of 0 to 4, p represents an average value of 0 to 1, l and m each represents an average value of 0 to 11 (l + m) represents 1 to 1 11 number is shown.)
As the epoxy resin represented by the general formula (IX), a random copolymer containing 1 structural unit and m structural units randomly, an alternating copolymer containing alternately, a copolymer containing regularly, The block copolymer contained in a block shape is mentioned, Any one of these may be used independently or may be used in combination of 2 or more type.

（式（Ｘ）及び（ＸＩ）において、Ｒ^３７〜Ｒ^４１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、ｊは０〜２の整数、ｋは０〜４の整数を示す。ｎは平均値であり、０〜１０の数を示す。） 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 general formulas (X) and (XI) are more preferable. Among epoxy resins represented by the following general formula (X), i = 0, R- ³⁸ is a hydrogen atom, NC-3000S (trade name, manufactured by Nippon Kayaku Co., Ltd.), i = 0, R- ³⁸ is a hydrogen atom. CER-3000 (trade name, manufactured by Nippon Kayaku Co., Ltd.), in which an epoxy resin and an epoxy resin in which all R ^{8 in} the general formula (II) are hydrogen atoms are mixed at a weight ratio of 80:20, is available as a commercial product. is there. Among epoxy resins represented by the following general formula (XI), ESN-175 (trade name of Nippon Steel Chemical Co., Ltd.) where j = 0 and k = 0 are available as commercial products.

(In the formulas (X) and (XI), R ^{37 to} R ⁴¹ 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) (An integer, 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.)

（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。）
上記一般式（ＩＩ）〜（ＸＩ）及び（ＸＩ−ａ）中のＲ^８〜Ｒ^２１及びＲ^３７〜Ｒ^４４について、「それぞれ全てが同一でも異なっていてもよい」とは、例えば、式（ＩＩ）中の８〜８８個のＲ^８の全てが同一でも異なっていてもよいことを意味している。他のＲ^９〜Ｒ^２１及びＲ^３７〜Ｒ^４４についても、式中に含まれるそれぞれの個数について全てが同一でも異なっていてもよいことを意味している。また、Ｒ^８〜Ｒ^２１及びＲ^３７〜Ｒ^４４はそれぞれが同一でも異なっていてもよい。例えば、Ｒ^９とＲ^１０の全てについて同一でも異なっていてもよい。 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 general formula (XI-a) is more preferable. Among the epoxy resins represented by the following general formula (XI-a), EXA-4700, EXA-4701 wherein n = 1, all of R ⁴² and R ⁴³ are hydrogen atoms, and all of R ⁴⁴ are glycidyloxy groups. (Dainippon ink chemical Co., Ltd. trade name), a n = ^{0, R 42} and all of ^{R 43} is a hydrogen ^atom, HP-4032 (Dainippon ink chemical Co., Ltd. trade name ^{R 44} is glycidyl group ), N = 1, R ⁴² and R ⁴³ are all hydrogen atoms, one of R ⁴⁴ is a hydrogen atom and the other is a glycidyloxy group EXA-4750 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.) Etc. are available as commercial products.

(In the 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 all are the same or different. And n is an average value and represents a number from 0 to 10.)
About R < ⁸ > -R < ²¹ > and R < ³⁷ > -R < ⁴⁴ > in the said general formula (II)-(XI) and (XI-a), "all may be the same or different, respectively" means, for example, the 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 general 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. In addition, the viscosity of the epoxy resin composition during melt molding 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 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 curing agent for epoxy resin of the present invention is the ratio between the total number of epoxy groups of the epoxy resin and the total number of phenolic hydroxyl groups of the curing agent for epoxy resin of the present invention. That is, the total number of epoxy groups / the total number of phenolic hydroxyl groups is preferably 0.5 to 2.0, more preferably 0.7 to 1.5, and 0.8 to 1.3. It is particularly preferred. When the blending ratio exceeds 2.0, the epoxy resin is not sufficiently cured, and the heat resistance, moisture resistance, and electrical properties of the cured product tend to decrease. 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 curing agent for epoxy resin 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, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride and other organic acids, dicarboxylic acids, and carboxylic acid compounds such as polycarboxylic acids. 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 phenolic resin obtained by condensation or cocondensation with aldehydes such as benzaldehyde and salicylaldehyde 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;
And 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, salicylaldehyde 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, salicylaldehyde-type phenol resins, benzaldehyde-type and aralkyl-type copolymer phenol resins, and novolak-type phenol resins can be used alone or in combination of two types. A combination of the above may also be used. However, in order to exert the effect of the curing agent for epoxy resin of the present invention, these phenol resins are preferably 70% by weight in total with respect to the total amount of the curing agent for epoxy resin of the present invention and other curing agents. In the following, it is desirable to use in combination so that it is more preferably 50% by weight or less, and further preferably 30% by weight or less.

（式（ＸＩＩ）〜（ＸＩＶ）において、Ｒ^２２〜Ｒ^２８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、ｊは０〜２の整数、ｎは平均値であり、０〜１０の数を示す。）
上記一般式（ＸＩＩ）で示されるフェノール樹脂の中でも、ｉ＝０、Ｒ^２３が全て水素原子であるＭＥＨ−７８５１（明和化成株式会社商品名）等が市販品として入手可能である。
上記一般式（ＸＩＩＩ）で示されるフェノール樹脂の中でも、ｉ＝０、ｋ＝０であるＸＬ−２２５、ＸＬＣ（三井化学株式会社製商品名）、ＭＥＨ−７８００（明和化成株式会社商品名）等が市販品として入手可能である。
上記一般式（ＸＩＶ）で示されるフェノール樹脂の中でも、ｊ＝０、Ｒ^２７のｋ＝０、Ｒ^２８のｋ＝０であるＳＮ−１７０（新日鐵化学株式会社商品名）等が市販品として入手可能である。 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 formulas (XII) to (XIV), R ^{22 to} R ^{28 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; An integer, 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 above general formula (XII), ME = 07851 (trade name of Meiwa Kasei Co., Ltd.) in which i = 0 and R ²³ are all hydrogen atoms is commercially available.
Among the phenol resins represented by the above general formula (XIII), XL-225, XLC (trade name, manufactured by Mitsui Chemicals, Inc.), MEH-7800 (trade name, Meiwa Kasei Co., Ltd.), etc., where i = 0 and k = 0. Is commercially available.
Among the phenol resins represented by the above general formula (XIV), SN-170 (trade name of Nippon Steel Chemical Co., Ltd.) where j = 0, R ²⁷ k = 0, and R ²⁸ k = 0 is a commercial product. Is available as

（式（ＸＶ）中、Ｒ^２９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、ｎは平均値であり、０〜１０の数を示す。） 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 general formula (XV) is preferable. Among the phenol resins represented by the following general formula (XV), DPP (trade name, 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. Yes, indicates a number from 0 to 10.)

（式（ＸＶＩ）中、Ｒ^３０及びＲ^３１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、ｎは平均値であり、０〜１０の数を示す。） The salicylaldehyde type phenol resin is not particularly limited as long as it is a phenol resin using a compound having a salicylaldehyde skeleton as a raw material, but a phenol resin represented by the following general formula (XVI) is preferable.
Among phenol resins represented by the following general formula (XVI), MEH-7500 (trade name, manufactured by Meiwa Kasei Co., Ltd.) where i = 0 and k = 0 is available as a commercial product.

(In the formula (XVI), R ³⁰ and R ³¹ 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, and k is (The integer of 0-4, n is an average value and shows the number of 0-10.)

（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。） 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 general formula (XVII) is preferable.
Among the phenol resins represented by the following general formula (XVII), HE-510 (trade name, manufactured by Air Water Chemical Co., Ltd.) having i = 0, k = 0, and q = 0 is commercially available. .

(In the 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, 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, respectively, and (l + m) represents a number of 1 to 11.)

（式（ＸＶＩＩＩ）中、Ｒ^３５及びＲ^３６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、ｎは平均値であり、０〜１０の数を示す。） 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 general formula (XVIII ) Is preferred.
I = 0 Among phenolic resin represented by the following general formula ^{(XVIII), R 35} are all hydrogen atoms TAMANOL 758, 759 (Arakawa Chemical Industries, Ltd., trade name), HP-850N (manufactured by Hitachi Chemical Co., Ltd. Product Name) etc. are commercially available.

(In the formula (XVIII), R ³⁵ and R ^{36 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, i is an integer of 0 to 3, and k is (The integer of 0-4, n is an average value and shows the number of 0-10.)

“All may be the same or different” described for R ^{22 to} R ³⁶ in the above general formulas (XII) to (XVIII) is, for example, that all i R ^{22s in} 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 general formulas (XII) to (XVIII), “n” needs to be in the range of 0 to 10, and when it exceeds 10, curing including the curing agent for epoxy resin of the present invention and other curing agents. Since the melt viscosity of the agent component is increased, the viscosity at the time of melt molding of the epoxy resin composition is also increased, 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 other curing agent is used in combination with the curing agent for epoxy resin of the present invention, the total amount of the curing agent for epoxy resin and the other curing agent is used for the epoxy resin. The amount of the curing agent is preferably 30% by weight or more, and more preferably 50% by weight or more. When the amount of the curing agent for epoxy resin is less than 30% by weight, the heat resistance 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 epoxy resin curing agent of the present invention, when a phenol compound is used in combination as the other curing agent, the epoxy resin is used with respect to the total amount of the epoxy resin curing agent and the phenol compound. The blending amount of the resin curing agent is preferably 30% by weight or more, and more preferably 50% by weight or more. When the amount of the curing agent for epoxy resin is less than 30% by weight, the heat resistance 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 curing agent for epoxy resin of the present invention, the entire epoxy resin is used. The ratio of the number of epoxy groups and the total number of phenolic hydroxyl groups obtained by adding the number of phenolic hydroxyl groups of the curing agent for epoxy resin and the number of phenolic hydroxyl groups of other curing agents, that is, the total number of epoxy groups / total number of phenolic hydroxyl groups, It is preferably 0.5 to 2.0, more preferably 0.7 to 1.5, and particularly preferably 0.8 to 1.3. When the blending ratio exceeds 2.0, the epoxy resin is not sufficiently cured, and the heat resistance, moisture resistance, and electrical properties of the cured product tend to decrease. 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.

（式（Ｉ−５）中、Ｒ^４は、それぞれ独立して、水素原子及び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もよく、２以上のＲ^４が互いに結合して環状構造を形成してもよく、
Ｒ^５は、それぞれ独立して、水素原子、水酸基及び置換基を有していてもよい炭素数１〜１８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く、２以上のＲ^５が互いに結合して環状構造を形成してもよく、
Ｙ⁻は、１以上の放出可能なプロトン（Ｈ^＋）を有する炭素数０〜１８の有機基から１つのプロトンが脱離した有機基であり、１以上のＲ^５と互いに結合して環状構造を形成してもよい。）
上記一般式（Ｉ−５）において、Ｒ^４は水素原子及び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り、水素原子、置換基を有していてもよい炭素数１〜１８の脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基などであり、例えば、水素原子；メチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基、アリル基、ビニル基等の脂肪族炭化水素基；これら脂肪族炭化水素基にアルキル基、アルコキシ基、アリール基、水酸基、アミノ基、及びハロゲン原子等で置換したもの；シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロペンテニル基、シクロヘキセニル基等の脂環式炭化水素基；これらの脂環式炭化水素基にアルキル基、アルコキシ基、アリール基、アリールオキシ基、水酸基、アミノ基、及びハロゲン原子等が置換したもの；フェニル基、トリル基等の芳香族炭化水素基；ジメチルフェニル基、エチルフェニル基、ブチルフェニル基、ｔｅｒｔ−ブチルフェニル基等のアルキル基置換アリール基、メトキシフェニル基、エトキシフェニル基、ブトキシフェニル基、ｔｅｒｔ−ブトキシフェニル基等のアルコキシ基置換アリール基、それらはさらにアルキル基、アルコキシ基、アリール基、アリールオキシ基、アミノ基、ハロゲン原子等で置換したもの；などが挙げられる。
前記Ｒ^４は、２以上のＲ^４が互いに結合して環状構造を形成してもよく、２つ又は３つのＲ^４が結合し、全体としてそれぞれ２価又は３価の炭化水素基となる。例えば、Ｐ原子と結合して環状構造を形成し得るエチレン、プロピレン、ブチレン、ペンチレン、ヘキシレン等のアルキレン基、エテニル、プロペニル、ブテニル基等のアルケニル基、メチレンフェニレン基等のアラルキレン基、フェニレン、ナフチレン、アントラセニレン等のアリーレン基が挙げられ、それらはアルキル基、アルコキシ基、アリール基、アリールオキシ基、アミノ基、水酸基、ハロゲン原子等で置換されていてもよい。
前記Ｒ^４としては、アルキル基及びアリール基からなる群より選ばれる１価の置換基であることが好ましい。なかでも、原料の入手しやすさの観点から、フェニル基、ｐ−トリル基、ｍ−トリル基、ｏ−トリル基、ｐ−メトキシフェニル基、ｍ−メトキシフェニル基、ｏ−メトキシフェニル基、ｐ−ヒドロキシフェニル基、ｍ−ヒドロキシフェニル基、ｏ−ヒドロキシフェニル基、２，５−ジヒドロキシフェニル基、４−（４−ヒドロキシフェニル）フェニル基、１−ナフチル基、２−ナフチル基、１−（２−ヒドロキシナフチル）基、１−（４−ヒドロキシナフチル）基等の非置換或いはアルキル基又は／及びアルコキシ基又は／及び水酸基置換のアリール基、メチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、オクチル基、シクロヘキシル基等の鎖状又は環状のアルキル基から選ばれる置換基がより好ましい。フェニル基、ｐ−トリル基、ｍ−トリル基、ｏ−トリル基、ｐ−メトキシフェニル基、ｍ−メトキシフェニル基、ｏ−メトキシフェニル基、ｐ−ヒドロキシフェニル基、ｍ−ヒドロキシフェニル基、ｏ−ヒドロキシフェニル基、２，５−ジヒドロキシフェニル基、４−（４−ヒドロキシフェニル）フェニル基、１−ナフチル基、２−ナフチル基、１−（２−ヒドロキシナフチル）基、１−（４−ヒドロキシナフチル）基等の非置換或いはアルキル基及び／又はアルコキシ基及び／又は水酸基置換のアリール基であることがさらに好ましい。
上記一般式（Ｉ−５）において、Ｒ^５は、水素原子、水酸基及び置換基を有していてもよい炭素数１〜１８の有機基からなる群より選ばれるものであり、水素原子、水酸基、置換基を有していてもよい炭素数１〜１８の脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基、脂肪族炭化水素オキシ基、脂環式炭化水素オキシ基、芳香族炭化水素オキシ基、脂肪族炭化水素カルボニル基、脂環式炭化水素カルボニル基、芳香族炭化水素カルボニル基、脂肪族炭化水素オキシカルボニル基、脂環式炭化水素オキシカルボニル基、芳香族炭化水素オキシカルボニル基、脂肪族炭化水素カルボニルオキシ基、脂環式炭化水素カルボニルオキシ基、芳香族炭化水素カルボニルオキシ基などである。
置換基を有していてもよい炭素数１〜１８の脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基の具体例は、上記Ｒ^４で挙げたものである。
置換基を有していてもよい炭素数１〜１８の脂肪族炭化水素オキシ基、脂環式炭化水素オキシ基、芳香族炭化水素オキシ基の具体例としては、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基、アリルオキシ基、ビニルオキシ基等の脂肪族炭化水素オキシ基；シクロプロピルオキシ基、シクロヘキシルオキシ基、シクロペンチルオキシ基などの脂環式炭化水素オキシ基；フェノキシ基、メチルフェノキシ基、エチルフェノキシ基、メトキシフェノキシ基、ブトキシフェノキシ基、フェノキシフェノキシ基等の芳香族炭化水素オキシ基；これらにオキシ基にアルキル基、アルコキシ基、アリール基、アリールオキシ基、アミノ基、ハロゲン原子等が置換したもの；などが挙げられる。
置換基を有していてもよい炭素数１〜１８の脂肪族炭化水素カルボニル基、脂環式炭化水素カルボニル基、芳香族炭化水素カルボニル基の具体例としては、ホルミル基、アセチル基、エチルカルボニル基、ブチリル基等の脂肪族炭化水素カルボニル基、シクロヘキシルカルボニル基、アリルカルボニル等の脂環式炭化水素カルボニル基；フェニルカルボニル基、メチルフェニルカルボニル基等の芳香族炭化水素カルボニル基；これらにアルキル基、アルコキシ基、アリール基、アリールオキシ基、アミノ基、ハロゲン原子等が置換したもの；などが挙げられる。
置換基を有していてもよい炭素数１〜１８の脂肪族炭化水素オキシカルボニル基、脂環式炭化水素オキシカルボニル基、芳香族炭化水素オキシカルボニル基の具体例としては、メトキシカルボニル基、エトキシカルボニル基、ブトキシカルボニル基、アリルオキシカルボニル基の脂肪族炭化水素オキシカルボニル基；シクロヘキシルオキシカルボニル基等の脂環式炭化水素オキシカルボニル基；フェノキシカルボニル基、メチルフェノキシカルボニル基等の芳香族炭化水素オキシカルボニル基；これらにアルキル基、アルコキシ基、アリール基、アリールオキシ基、アミノ基、ハロゲン原子で置換したもの；などが挙げられる。
置換基を有していてもよい炭素数１〜１８の脂肪族炭化水素カルボニルオキシ基、脂環式炭化水素カルボニルオキシ基、芳香族炭化水素カルボニルオキシ基の具体例としては、メチルカルボニルオキシ基、エチルカルボニルオキシ基、ブチルカルボニルオキシ基、アリルカルボニルオキシ基などの脂肪族炭化水素カルボニルオキシ基；シクロヘキシルカルボニルオキシ基等の脂環式炭化水素カルボニルオキシ基；フェニルカルボニルオキシ基、メチルフェニルカルボニルオキシ基等の芳香族炭化水素カルボニルオキシ基；これらにアルキル基、アルコキシ基、アリール基、アリールオキシ基、アミノ基、ハロゲン原子等が置換したもの；などが挙げられる。
前記のＲ^５は、２以上のＲ^５が互いに結合して環状構造を形成してもよく、２つ〜４つのＲ^５が結合し、全体としてそれぞれ２価〜４価の有機基となる。例えば、環状構造を形成し得るエチレン、プロピレン、ブチレン、ペンチレン、ヘキシレン等のアルキレン基；エテニル、プロペニル、ブテニル基等のアルケニル基；メチレンフェニレン基等のアラルキレン基；フェニレン、ナフチレン、アントラセニレン等のアリーレン基；それらアルキレン基、アルケニル基、アラルキレン基、アリーレン基にオキシ基又はジオキシ基が結合した基；などが挙げられ、それらはアルキル基、アルコキシ基、アリール基、アリールオキシ基、アミノ基、水酸基、ハロゲン原子などで置換されていてもよい。
前記Ｒ^５としては、水素原子、水酸基、アルキル基、アリール基、アルコキシ基、アリールオキシ基が好ましい。なかでも原料の入手しやすさの観点からは、水素原子、水酸基、フェニル基、ｐ−トリル基、ｍ−トリル基、ｏ−トリル基、ｐ−メトキシフェニル基等の非置換或いはアルキル基又は／及びアルコキシ基又は／及び水酸基置換のアリール基、及びメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、オクチル基、シクロヘキシル基等の鎖状又は環状のアルキル基から選ばれる置換基がさらに好ましい。２以上のＲ^５が互いに結合して環状構造を形成する場合は、Ｒ^５が結合しているベンゼン環と併せて、１−（−２−ヒドロキシナフチル）基、１−（−４−ヒドロキシナフチル）基等の多環芳香族基を形成する有機基が好ましい。
前記一般式（Ｉ−５）において、Ｙ⁻は、１以上の放出可能なプロトン（Ｈ^＋）を有する炭素数０〜１８の有機基から１つのプロトンが脱離した有機基であり、１以上のＲ^５と互いに結合して環状構造を形成してもよい。例えば、Ｙ⁻は水酸基、メルカプト基、ハイドロセレノ基等の１６族原子に水素原子が結合した１価の有機基からプロトンが脱離した基、カルボキシル基、カルボキシメチル基、カルボキシエチル基、カルボキシフェニル基、カルボキシナフチル基等のカルボキシル基を有する炭素数１〜１８の１価の有機基からカルボン酸のプロトンが脱離した基、ヒドロキシフェニル基、ヒドロキシフェニルメチル基、ヒドロキシナフチル基、ヒドロキシフリル基、ヒドロキシチエニル基、ヒドロキシピリジル基等のフェノール性水酸基を有する炭素数１〜１８の１価の有機基からフェノール性プロトンが脱離した基などが挙げられる。
前記Ｙ⁻は、１以上のＲ^５と結合して環状構造を形成してもよく、例えば、Ｙ⁻は、それが結合しているベンゼン環と併せて、２−（−６−ヒドロキシナフチル）基等のヒドロキシ多環芳香族基の水酸基からプロトンが脱離した基を形成する２価の有機基が挙げられる。
先に例示したＹ⁻の中でも、水酸基からプロトンが脱離してなる酸素アニオン、又はヒドロキシフェニル基、ヒドロキシフェニルメチル基、ヒドロキシナフチル基、ヒドロキシフリル基、ヒドロキシチエニル基、ヒドロキシピリジル基等のフェノール性水酸基からプロトンが脱離してなる酸素アニオンを有する１価の有機基であることが好ましい。
また、前記Ｙ⁻が１以上のＲ^５と結合して環状構造を形成する場合、例えば、Ｙ⁻は、それが結合しているベンゼン環と併せて、２−（−６−ヒドロキシナフチル）基等のヒドロキシ多環芳香族基の水酸基からプロトンが脱離した基であることが好ましい。
また、上記一般式（Ｉ−５）で示されるホスホニウム化合物の分子間塩としては、限定されるものではないが、式（Ｉ−５）で示されるホスホニウム化合物と、フェノール、ナフトール、分子内に２以上のフェノール性水酸基を有するフェノール化合物として先に例示した化合物等のフェノール性水酸基を有する化合物、トリフェニルシラノール、ジフェニルシランジオール、トリメチルシラノール等のシラノール基を有する化合物、シュウ酸、酢酸、安息香酸等の有機酸、塩酸、臭化水素、硫酸、硝酸等の無機酸等との分子間塩化合物が挙げられる。 (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 to maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6- Quinone compounds such as dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and π bonds such as diazophenylmethane A compound having an intramolecular polarization formed by adding a compound having a triethylenediamine, benzyldimethylamine, Tertiary amines such as tanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, etc. Imidazoles, tetrasubstituted phosphonium tetrasubstituted borates such as tetraphenylphosphonium tetraphenylborate, tetraphenylboron salts such as 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate, tri Phenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine , Tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, Organic phosphines such as trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, etc., complexes of these organic phosphines with organic borons, organic phosphines with maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzene Quinone compounds such as zoquinone and phenyl-1,4-benzoquinone, compounds having intramolecular polarization formed by adding a compound having a π bond such as diazophenylmethane, these organic phosphines and 4-bromophenol, 3-bromophenol 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4- Bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'- After reacting the halogenated phenol compounds such as Russia alkoxy biphenyl, a compound having intramolecular polarization obtained by dehydrohalogenation (see JP 2004-156036) 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. In addition, a compound having intramolecular polarization obtained through a dehydrohalogenation step, and obtained from a dehydrohalogenation step after reacting an organic phosphine with a halogenated phenol compound from the viewpoint of curability. Compounds having intramolecular polarization are preferred. In particular, it is preferable to use a phosphine compound represented by the following general formula (I-5) or an intermolecular salt thereof.

(In formula (I-5), 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, all of which are the same. 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 general formula (I-5), 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. An aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and the like, which may have, for example, a hydrogen atom; a methyl group, an ethyl group, a propyl group, an isopropyl group; , N-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, allyl group, vinyl group and other aliphatic hydrocarbon groups; these aliphatic hydrocarbon groups Substituted with an alkyl group, alkoxy group, aryl group, hydroxyl group, amino group, halogen atom, etc .; cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group, cyclohexenyl An alicyclic hydrocarbon group such as a group; an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, and a halogen atom substituted on these alicyclic hydrocarbon groups; a phenyl group, a tolyl group Aromatic hydrocarbon groups such as groups; alkyl group-substituted aryl groups such as dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl An alkoxy group-substituted aryl group such as a group, and those further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, and the like.
Wherein R ⁴ may form a cyclic structure 2 or more R ⁴ are bonded to each other, two or three R ⁴ are bonded, as a whole a divalent or trivalent hydrocarbon group, respectively. 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 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 the aryl group is unsubstituted or substituted with an alkyl group and / or an alkoxy group and / or a hydroxyl group.
In the above general formula (I-5), 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. , An optionally substituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon oxy group, an alicyclic hydrocarbon oxy group, 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 Examples thereof include an oxycarbonyl group, an aliphatic hydrocarbon carbonyloxy group, an alicyclic hydrocarbon carbonyloxy group, and an aromatic hydrocarbon carbonyloxy group.
Specific examples of the aliphatic hydrocarbon group having 1 to 18 carbon atoms, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group which may have a substituent are those described above for R ⁴ .
Specific examples of the aliphatic hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent, an alicyclic hydrocarbon oxy group, and an aromatic hydrocarbon oxy group include a methoxy group, an ethoxy group, and a propoxy group. Aliphatic hydrocarbon oxy groups such as isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, allyloxy group and vinyloxy group; alicyclic rings such as cyclopropyloxy group, cyclohexyloxy group and cyclopentyloxy group Hydrocarbon oxy group: aromatic hydrocarbon oxy group such as phenoxy group, methylphenoxy group, ethylphenoxy group, methoxyphenoxy group, butoxyphenoxy group, phenoxyphenoxy group; these include oxy group, alkyl group, alkoxy group, aryl group , Aryloxy groups, amino groups, halogen atoms and the like substituted; etc. And the like.
Specific examples of the optionally substituted aliphatic hydrocarbon carbonyl group having 1 to 18 carbon atoms, alicyclic hydrocarbon carbonyl group, and aromatic hydrocarbon carbonyl group include formyl group, acetyl group, ethylcarbonyl Group, aliphatic hydrocarbon carbonyl group such as butyryl group, alicyclic hydrocarbon carbonyl group such as cyclohexylcarbonyl group, allylcarbonyl; aromatic hydrocarbon carbonyl group such as phenylcarbonyl group, methylphenylcarbonyl group; , An alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom or the like substituted.
Specific examples of the optionally substituted aliphatic hydrocarbon oxycarbonyl group having 1 to 18 carbon atoms, alicyclic hydrocarbon oxycarbonyl group, and aromatic hydrocarbon oxycarbonyl group include methoxycarbonyl group, ethoxy Aliphatic hydrocarbon oxycarbonyl groups such as carbonyl group, butoxycarbonyl group and allyloxycarbonyl group; Alicyclic hydrocarbon oxycarbonyl groups such as cyclohexyloxycarbonyl group; Aromatic hydrocarbon oxy such as phenoxycarbonyl group and methylphenoxycarbonyl group Carbonyl groups; those substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom; and the like.
Specific examples of the aliphatic hydrocarbon carbonyloxy group having 1 to 18 carbon atoms which may have a substituent, an alicyclic hydrocarbon carbonyloxy group, and an aromatic hydrocarbon carbonyloxy group include a methylcarbonyloxy group, Aliphatic hydrocarbon carbonyloxy groups such as ethylcarbonyloxy group, butylcarbonyloxy group and allylcarbonyloxy group; Alicyclic hydrocarbon carbonyloxy groups such as cyclohexylcarbonyloxy group; phenylcarbonyloxy group, methylphenylcarbonyloxy group and the like And those substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, and the like.
The R ⁵ may be formed by bonding two or more R ⁵ 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; 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 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 general formula (I-5), Y ⁻ represents 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 thereof 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 combine with one or more R ⁵ to form a cyclic structure. For example, Y ⁻ may be 2-(-6-hydroxynaphthyl) together with the 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 general formula (I-5) is not limited, but the phosphonium compound represented by the formula (I-5), 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 improving the 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 weight of a curing accelerator with respect to a total of 100 parts by weight of the epoxy resin. 1 to 7.0 parts by weight is more preferable. When the blending amount of the curing accelerator is less than 0.1 parts by weight, it is difficult to cure the epoxy resin composition in a short time, and when it exceeds 10 parts by weight, 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 may be generally used for a sealing molding material, and is not particularly limited. 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 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. When the average particle size exceeds 50 μm, the resin component and the inorganic filler are easily separated, resulting in non-uniform cured products and variations in cured product characteristics. 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 an 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 weight and more preferably 0.1 to 2.5% by weight with respect to the inorganic filler. When the blending amount is less than 0.05% by weight, the adhesion to the frame tends to be lowered, and when it exceeds 5% by weight, the moldability of the package tends to be lowered.
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 (ditridecyl) Phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl Titanates such as titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate Coupling agents are included, and even if these are used alone, two or more It may be used in conjunction seen. 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. Among these, hydrotalcite represented by the following general formula (XIX) is preferable.
Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (XIX)
(In the 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 an amount sufficient to capture anions such as halogen ions, but is preferably in the range of 0.1 to 30% by weight with respect to the epoxy resin. A range of ˜5% by weight is more preferred.

(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, oxidized or non-oxidized polyolefin wax is preferable, and the blending amount of the polyolefin wax is preferably 0.01 to 10% by weight with respect to the epoxy resin, and 0.1 to 5% by weight. % Is more preferable. If the blending amount of the polyolefin wax is less than 0.01% by weight, the releasability tends to be insufficient, and if it exceeds 10% by weight, the adhesiveness 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 to 10 weight% with respect to an epoxy resin, and it is more preferable that it is 0.5 to 3 weight%. 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 adding 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 amount of the flame retardant blended is not particularly limited as long as the flame retardant effect is achieved, but is preferably 1 to 30% by weight, more preferably 2 to 15% by weight 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 resin composition is easy to handle when it is tableted with a size and weight suitable for the molding conditions of the package.

Electronic component device An electronic component device according to the present invention includes an element sealed with the epoxy resin composition according to 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) Common resin-sealed ICs such as Outline Package (TQFP) and TQFP (Thin Quad Flat Package), half connected to the tape carrier by bumps A semiconductor chip, a transistor, and a semiconductor chip connected to a wiring formed on a TCP (Tape Carrier Package), a wiring board or glass sealed with the epoxy resin composition of the present invention by wire bonding, flip chip bonding, solder, etc. A COB (Chip On Board) module, a hybrid IC, a multichip module, and a back surface in which active elements such as diodes and thyristors and / or passive elements such as capacitors, resistors and coils are sealed with the epoxy resin composition of the present invention. The device is mounted on the surface of the organic substrate on which the terminals for connecting the wiring board are formed, and the device and the wiring formed on the organic substrate are connected by bump or wire bonding, and then the device is sealed with the epoxy resin composition of the present invention BGA (Ball Grid Array), 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 Example 1): Synthesis of calixarenes Using a 300 ml four-necked flask, 33.0 g (0.3 mol) of resorcinol was dissolved in 120 ml of ethanol, and 40 ml of concentrated hydrochloric acid was added under ice-cooling. Stir for minutes. To this was added dropwise 12.1 g (0.1 mol) of paraaldehyde, followed by heating to reflux for about 30 minutes. The reaction mixture was cooled to room temperature and a solid produced by filtration was obtained. The obtained solid was washed once with water and three times with methanol, recrystallized twice with methanol, and then vacuum-dried at 60 ° C. for 24 hours to obtain 20.8 g of a white 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 calixarene having a structure represented by the following formula. The measurement result of ¹ H-NMR spectrum is shown in FIG. Since calixarenes having a structure represented by the following formula are known compounds, the measurement results of IR spectrum and the measurement results of mass spectrum are omitted.

（合成例２）：カリックスアレーン誘導体の合成
１００ｍｌの４つ口フラスコを用い、合成例１で得たカリックスアレーン類５．０ｇ（９．２ｍｍｏｌ）、フェニルグリシジルエーテル１．４ｇ（９．２ｍｍｏｌ）、トリフェニルホスフィン０．０５ｇ（０．１９ｍｍｏｌ）をメチルイソブチルケトン２０ｇに溶解し、３０時間加熱還流することによりフェニルグリシジルエーテルが完全に反応したことを^１Ｈ−ＮＭＲにて確認した。反応混合物をエバポレーターでほとんどのメチルイソブチルケトンを留去した後、８０℃で１２時間真空乾燥することにより完全にメチルイソブチルケトンを留去した反応生成物を得た。
得られた反応生成物について、^１Ｈ−ＮＭＲスペクトルの測定を行なった結果、フェニルグリシジルエーテルのピークが消失したことを確認した（図３を参照）。比較として、フェニルグリシジルエーテルの^１Ｈ−ＮＭＲスペクトルの測定も行った（図２を参照）。これらの結果から、得られた反応生成物は、合成例１で得たカリックスアレーン類のフェノール性水酸基の１２.５％にフェニルグリシジルエーテルのエポキシ基が反応したカリックスアレーン誘導体であると推定できる。また、ゲル浸透クロマトグラフィー（ＧＰＣ）を測定して、フェニルグリシジルエーテル及び合成例１で合成したカリックスアレーン類と比較した結果（図５を参照）、主に、合成例１で合成したカリックスアレーン類、合成例１で合成したカリックスアレーン類に１分子のフェニルグリシジルエーテルが反応したカリックスアレーン誘導体、及び合成例１で合成したカリックスアレーン類に２分子のフェニルグリシジルエーテルが反応したカリックスアレーン誘導体の混合物であると推定できる。

(Synthesis Example 2): Synthesis of calixarene derivative Using a 100 ml four-necked flask, 5.0 g (9.2 mmol) of calixarene obtained in Synthesis Example 1, 1.4 g (9.2 mmol) of phenylglycidyl ether, It was confirmed by ¹ H-NMR that 0.05 g (0.19 mmol) of triphenylphosphine was dissolved in 20 g of methyl isobutyl ketone and heated and refluxed for 30 hours to completely react the phenylglycidyl ether. Most of the methyl isobutyl ketone was distilled off from the reaction mixture with an evaporator and then vacuum-dried at 80 ° C. for 12 hours to obtain a reaction product in which methyl isobutyl ketone was completely distilled off.
As a result of measuring the ¹ H-NMR spectrum for the obtained reaction product, it was confirmed that the peak of phenylglycidyl ether disappeared (see FIG. 3). As a comparison, the ¹ H-NMR spectrum of phenylglycidyl ether was also measured (see FIG. 2). From these results, it can be presumed that the obtained reaction product is a calixarene derivative in which 12.5% of the phenolic hydroxyl group of the calixarene obtained in Synthesis Example 1 is reacted with the epoxy group of phenylglycidyl ether. Further, the results of gel permeation chromatography (GPC) measurement and comparison with phenylglycidyl ether and calixarene synthesized in Synthesis Example 1 (see FIG. 5), mainly calixarene synthesized in Synthesis Example 1 A mixture of a calixarene derivative obtained by reacting the calixarene synthesized in Synthesis Example 1 with one molecule of phenylglycidyl ether, and a calixarene derivative obtained by reacting the calixarene synthesized in Synthetic Example 1 with two molecules of phenylglycidyl ether. It can be estimated that there is.

(Synthesis Example 3): Synthesis of calixarene derivative Using a 100 ml four-necked flask, 5.0 g (9.2 mmol) of calixarene obtained in Synthesis Example 1, 1.8 g (18.4 mmol) of phenylglycidyl ether, It was confirmed by ¹ H-NMR that 0.05 g (0.19 mmol) of triphenylphosphine was dissolved in 20 g of methyl isobutyl ketone and heated and refluxed for 40 hours to completely react the phenylglycidyl ether. Most of the methyl isobutyl ketone was distilled off from the reaction mixture with an evaporator and then vacuum-dried at 80 ° C. for 12 hours to obtain a reaction product in which methyl isobutyl ketone was completely distilled off.
As a result of measuring the ¹ H-NMR spectrum for the obtained reaction product, it was confirmed that the peak of phenylglycidyl ether disappeared (see FIG. 4). From this result, it can be presumed that the obtained reaction product is a calixarene derivative in which 25.0% of the phenolic hydroxyl group of the calixarene obtained in Synthesis Example 1 is reacted with the epoxy group of phenylglycidyl ether. Further, the results of gel permeation chromatography (GPC) measurement and comparison with phenylglycidyl ether, calixarene synthesized in Synthesis Example 1 and calixarene derivative synthesized in Synthesis Example 2 (see FIG. 5), Furthermore, a calixarene derivative obtained by reacting one molecule of phenylglycidyl ether with the calixarene synthesized in Synthesis Example 1, a calixarene derivative obtained by reacting two molecules of phenylglycidyl ether with the calixarene synthesized in Synthetic Example 1, and synthesis It can be presumed to be a mixture of calixarene derivatives obtained by reacting the calixarenes synthesized in Example 1 with three molecules of phenylglycidyl ether.

Details of the measurement method of ¹ H-NMR spectrum and gel permeation chromatography in Synthesis Examples 1 to 3 are as follows.
(1) Measurement of ¹ H-NMR spectrum About 100 mg of a compound was dissolved in about 0.5 ml of heavy acetone to form a solution, and placed in a φ5 mm sample tube for measurement. The measurement was performed using a nuclear magnetic resonance apparatus “AV-300M” manufactured by Bruker BioSpin Corporation.
(2) Measurement of gel permeation chromatography (GPC) About 5 mg of the compound was dissolved in about 5 ml of tetrahydrofuran to prepare a solution, and 0.2 ml of the solution was charged for use in the measurement. The measurement was performed at 30 ° C. and a flow rate of 1.0 ml / min using TSK-GEL G5000HXL-G2000HXL manufactured by Hitachi, Ltd. and Tosoh Corporation equipped with an intelligent pump (L-3600). As a detector, an RI monitor (L-3300) manufactured by Hitachi, Ltd. was used.

(Examples 1-3, Comparative Examples 1-2): Preparation of epoxy resin composition and evaluation of properties The following components were blended in parts by weight shown in Table 1, mixed in a mortar, and then heated to 130 ° C. It was put in an aluminum cup on a plate and cured for 1 hour after melting. Thereafter, post-curing was performed at 175 ° C. for 6 hours and then at 250 ° C. for 6 hours to obtain cured products of Examples 1 to 3 and Comparative Examples 1 and 2.

Each component in the table was as follows. Note that the blank in the table indicates no blending.
(Epoxy resin)
Epoxy resin 1: biphenyl type epoxy resin having an epoxy equivalent of 196 and a melting point of 106 ° C. (trade name “YX-4000H” manufactured by Japan Epoxy Resin Co., Ltd.)
Epoxy resin 2: o-cresol novolac type epoxy resin having an epoxy equivalent of 195 and a softening point of 62 ° C. (trade name “ESCN-190-2” manufactured by Sumitomo Chemical Co., Ltd.)
(Curing agent)
Curing agent 1: Calixarenes obtained in Synthesis Example 1 Curing agent 2: Calixarene derivative obtained in Synthesis Example 2 Curing agent 3: Calixarene derivative obtained in Synthesis Example 3 Curing agent 4: Phenol novolac resin having a hydroxyl group equivalent of 106 (Trade name HP-850N, manufactured by Hitachi Chemical Co., Ltd.)
(Curing accelerator)
Curing accelerator: Triphenylphosphine Next, the cured products of Examples 1 to 3 and Comparative Examples 1 to 2 were evaluated by the following tests.
(1) Uniformity (solubility)
The cured product with no turbidity was marked with ◯, and the cured product with turbidity with x. The evaluation results are shown in Table 1.
(2) Dynamic viscoelastic behavior The cured product is cut into a size of 30 mm long × 7 mm wide × 0.8 mm thick with a diamond cutter, and using a viscoelasticity measuring device DMS6100 (manufactured by Seiko Instruments Inc.), a tensile mode Was measured under the conditions of a heating rate of 5 ° C. and a frequency of 1 Hz. The results are shown in FIG.

本発明のエポキシ樹脂用硬化剤を用いた実施例１〜３は、いずれも均一性及び高温弾性率に優れる。これに対して、合成例１で得たカリックスアレーン類を用いた比較例１は均一性の点で劣り、従来の硬化剤を用いた比較例２は高温弾性率の点で劣っている。

Examples 1 to 3 using the epoxy resin curing agent of the present invention are all excellent in uniformity and high temperature elastic modulus. In contrast, Comparative Example 1 using the calixarene obtained in Synthesis Example 1 is inferior in terms of uniformity, and Comparative Example 2 using a conventional curing agent is inferior in terms of high-temperature elastic modulus.

2 is a ¹ H-NMR chart of calixarenes synthesized in Synthesis Example 1. FIG. ^{1 is} a ¹ H-NMR chart of phenylglycidyl ether. 2 is a ¹ H-NMR chart of a calixarene derivative synthesized in Synthesis Example 2. FIG. 2 is a ¹ H-NMR chart of a calixarene derivative synthesized in Synthesis Example 3. FIG. 4 is a GPC chart of calixarenes synthesized in Synthesis Example 1, calixarene derivatives synthesized in Synthesis Examples 2 and 3, and phenylglycidyl ether. It is a figure which shows the dynamic viscoelastic behavior in an Example and a comparative example.

Claims (7)

A curing agent for epoxy resins, wherein a calixarene derivative represented by the formula (I-3) is used.

(Where n ′ and n ″ are 0 to 4, n ′ + n ″ is 1 to 4, m is an average number of 3 to 20, m × n ″> 0, and each of m repetitions. R ¹ , R ² , R ³ , n ′, n ″ may be the same or different,
R ¹ is selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, all of which may be the same or different;
R ² 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 may be the same or different,
R ³ 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. ) An epoxy resin characterized by being a calixarene derivative obtained by reacting the epoxy group of the epoxy compound (b2) with 5 to 90% of the phenolic hydroxyl group of the calixarene (b1) represented by the formula (I-1) Curing agent.

(In formula (I-1), n is 1 to 4, m is an average number of 3 to 20, and R ¹ , R ² and n may be the same or different with respect to each of m repetitions. ,
R ¹ is selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, all of which may be the same or different;
R ² 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 may be the same or different. ) 3. The epoxy resin curing agent according to claim 2, wherein the calixarene (b1) is a compound represented by the formula (I-2).

(In the formula, m is an average number of 3 to 20, and for each of m repetitions, R ¹ and R ² may be the same or different,
R ¹ is selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, all of which may be the same or different;
R ² 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 may be the same or different. )   The said epoxy compound (b2) has a 1 or 2 epoxy group in a molecule | numerator, The hardening | curing agent for epoxy resins of Claim 2 or 3 characterized by the above-mentioned.   The said epoxy compound (b2) has one epoxy group in a molecule | numerator, The hardening | curing agent for epoxy resins as described in any one of Claims 2-4 characterized by the above-mentioned.   An epoxy resin composition comprising an epoxy resin and the epoxy resin curing agent according to any one of claims 1 to 5.   An electronic component device comprising an element sealed with the epoxy resin composition according to claim 6.

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