JP2010031089A - Calixarene derivative, method for producing the same, epoxy resin composition and electronic component device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a calixarene derivative having good solubility when used in an epoxy resin composition and imparting high heat resistance to a cured epoxy resin product, and a curing agent for epoxy resin using the calixarene derivative. <P>SOLUTION: The calixarene derivative is represented by formula (I-1), wherein n' and n" are a number of 0-4, provided that n'+n"=1-4; m is a number of 3-20 on an average, m×n">0; with respect to repetition of m times, R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, n' and n" may be the same or different, respectively; R<SP>1</SP>is selected from the group consisting of 0-18C divalent organic groups, and all may be the same or different; R<SP>2</SP>is each independently selected from the group consisting of H and 1-18C hydrocarbon groups which may have a substituent, and all may be the same or different; R<SP>3</SP>is each independently selected from the group consisting of H and 1-18C hydrocarbon groups which may have a substituent, and all may be the same or different. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a calixarene derivative, a manufacturing method thereof, 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 components, paints and ink materials. In particular, epoxy resin compositions are widely used as sealing materials in the field related to sealing technology for electronic component elements such as transistors and ICs. This is because epoxy resins are balanced in various properties such as moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserts.

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

In order to improve various properties of cured epoxy resins including heat resistance, methods using calixarenes as curing agents have been reported (see Patent Documents 1 to 5). According to these methods, it is possible to improve the glass transition temperature of the cured epoxy resin and to impart high heat resistance.
JP 2000-264953 A JP 2001-106868 A JP-A-2-123126 Japanese Patent Laid-Open No. 3-66724 JP-A-6-136341

  However, since the curing agent used in the above method has low solubility with the constituent components of the epoxy resin composition, there is a problem that the curing reaction does not proceed completely and sufficient performance is not exhibited.

  An object of the present invention is to provide a novel calixarene derivative that can be used as a curing agent for an epoxy resin that has good solubility when made into an epoxy resin composition and can impart high heat resistance to a cured epoxy resin. Is to provide. Moreover, the other subject of this invention is providing the electronic component apparatus provided with the epoxy resin composition containing the said hardening | curing agent for epoxy resins, and the element sealed by it.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have been able to newly synthesize calixarene derivatives obtained by silyl etherifying part or all of the phenolic hydroxyl groups of calixarenes. The inventors have found that the intended purpose can be achieved by using the calixarene derivative as a curing agent for an epoxy resin, and the present invention has been completed.

  The present invention relates to the following.

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

(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 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. )
(2) The calixarene derivative according to the above (1), wherein 5 to 100% of the phenolic hydroxyl group of the calixarene (b1) represented by the formula (I-2) is silyl etherified.

(Wherein n is 1 to 4, m is an average of 3 to 20, and for each of m repetitions, R ¹ , R ² and 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. )
(3) The calixarene derivative according to the above (1) or (2), wherein the calixarene (b1) is a compound represented by the formula (I-3).

(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. )
(4) calixarenes (b1) represented by the formula (I-2) and at least one compound selected from the group of silane compounds represented by the formulas (I-4) and (I-5); The method for producing a calixarene derivative according to any one of (1) to (3) above, wherein

(In the formula, each R ³ 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. .

X is selected from the group consisting of a hydrocarbon oxy group having 1 to 18 carbon atoms, a hydroxyl group, a chlorine atom and a bromine atom. )

(In the formula, each R ³ 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. .)
(5) An epoxy resin composition comprising an epoxy resin and the calixarene derivative according to any one of (1) to (3) as a curing agent for epoxy resin.

(6) An electronic component device comprising an element sealed with the epoxy resin composition according to (5).

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

<Calixarene derivative>
The calixarene derivative of the present invention is represented by the formula (I-1).

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

The calixarene derivative is preferably formed by silyl etherification of 5 to 100% of the phenolic hydroxyl group of the calixarene (b1) represented by the formula (I-2) from the viewpoint of solubility. Is more preferably silyl etherified.

(Wherein n is 1 to 4, m is an average of 3 to 20, and for each of m repetitions, R ¹ , R ² and 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. )
The calixarene (b1) is not particularly limited as long as it is a compound represented by the above formula (I-2), but it is a compound represented by the following formula (I-3) 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. )
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.

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

  Examples of the divalent hydrocarbon group having 1 to 18 carbon atoms that may have 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 methylmethylene group, an ethylmethylene group, an isopropylmethylene group, a phenylmethylene group, a hydroxyphenylmethylene group, a cyclohexylmethylene group, a dimethylmethylene group, and a methyldiisopropylmethylene. Group, methylphenylmethylene group, cyclohexylmethylene group, cyclopentylmethylene group and the like. 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. Atoms, an optionally substituted aliphatic hydrocarbon group having 1 to 18 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 by a lucapto group, imino group, ureido group, isocyanate group, etc .; cycloaliphatic hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group, cyclohexenyl group; 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; Phenyl group, ethoxyphenyl group, butoxy An alkoxy group-substituted aryl group such as a phenyl group or a tert-butoxyphenyl group; further an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, an epoxy group, or the like; 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-1), 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 optionally substituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, etc., such as a hydrogen atom; a methyl group, an ethyl group, a propyl group, an isopropyl group, 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. Substituted by a group containing a silyl group, a methacryloyl group, a mercapto group, an imino group, a ureido group, an isocyanate group, etc .; an alicyclic carbonization such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group A hydrogen group; a group containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group or an epoxy group in these alicyclic hydrocarbon groups Substituted by methacryloyl group, mercapto group, imino group, ureido group, isocyanate group, etc .; aromatic hydrocarbon group such as phenyl group, tolyl group; dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl Alkyl group-substituted aryl groups such as groups; methoxy An alkoxy group-substituted aryl group such as an phenyl group, an ethoxyphenyl group, a butoxyphenyl group, a tert-butoxyphenyl group; an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, a glycidyloxy group; And those substituted with an epoxy group such as an epoxycyclohexyl group or an epoxy group, a methacryloyl group, a mercapto group, an imino group, a ureido group, or an isocyanate group. Among these, from the viewpoint of curing reactivity, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, etc. An alkyl group is preferable, and from the viewpoint of heat resistance, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group are 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 calixarene derivative of the present invention is a compound represented by the formula (I-1), and 5 to 100% of the phenolic hydroxyl group of the calixarene (b1) represented by the formula (I-2) is silyl etherified. If the proportion of the silyl etherified phenolic hydroxyl group is preferably less than 5%, the solubility with the constituent components of the epoxy resin composition is poor. The proportion of the silyl etherified phenolic hydroxyl group is more preferably 10 to 100% from the viewpoint of solubility with the constituent components of the epoxy resin composition.

  The confirmation method of what percentage of the phenolic hydroxyl group of the calixarenes (b1) represented by the above formula (I-2) is silyl ether can be confirmed by, for example, NMR. Specifically, it can be confirmed how much the phenolic hydroxyl group of the raw material calixarene (b1) disappeared when the calixarene derivative was used.

  The method for producing the calixarene derivative of the present invention is not particularly limited, but the formula (I) is added to 5 to 100% of the phenolic hydroxyl group of the calixarene (b1) represented by the formula (I-2). -4) and a method of reacting at least one compound selected from the group of silane compounds represented by formula (I-5). In the case of using a solvent, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, tetrahydrofuran, N, N-dimethylformamide, dimethyl sulfoxide and the like are used and reacted at room temperature to 200 ° C. The method of leaving, the method of filtering the solid which precipitated by cooling, the method of throwing into the poor solvent and filtering the solid which precipitated, etc. are mentioned. If necessary, the reaction of the phenolic hydroxyl group of calixarene (b1) and at least one compound selected from the group of silane compounds represented by formula (I-4) and formula (I-5) is promoted. A compound may be used. The compound that accelerates the reaction that can be used is not particularly limited, and examples thereof include inorganic acids, organic acids, inorganic bases, organic bases, compounds described later as curing accelerators, and the like. preferable. Moreover, when making the silane compound shown by a formula (I-5) react, the silane compound shown by a formula (I-4) can also be used as a catalyst.

The calixarene (b1) can be produced by a known method. For example, the calixarenes (b-1) of the above formula (I-3) in which R ² = hydrogen and m = 4 are prepared by reacting resorcinol with parabenzaldehyde in a solvent, in the presence of an acid catalyst such as concentrated hydrochloric acid, 30 to 200 It can be obtained by reacting at ° C.

(In the formula, each R ³ 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. .

X is selected from the group consisting of a hydrocarbon oxy group having 1 to 18 carbon atoms, a hydroxyl group, a chlorine atom and a bromine atom. )

(In the formula, each R ³ 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 of the} silane compound represented by the above formulas (I-4) and (I-5) 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 hydrocarbon group having 1 to 18 carbon atoms is as described above for formula (I-1).

  X in the above formula (I-4) is selected from the group consisting of a hydrocarbon oxy group having 1 to 18 carbon atoms, a chlorine atom and a bromine atom. Examples of the hydrocarbon oxy group having 1 to 18 carbon atoms include, for example, “a substituted or unsubstituted aliphatic hydrocarbon oxy group having 1 to 18 carbon atoms” and “a substituted or unsubstituted aromatic carbon atom having 1 to 18 carbon atoms”. A hydrogenoxy group "and the like.

Examples of the “substituted or unsubstituted aliphatic hydrocarbon oxy group having 1 to 18 carbon atoms” include, for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert- A structure in which an oxygen atom is bonded to the aliphatic hydrocarbon group and alicyclic hydrocarbon group described above as R ³ , such as butoxy group, cyclopropyloxy group, cyclohexyloxy group, cyclopentyloxy group, allyloxy group, vinyloxy group, etc. And a group in which they are substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, or the like.

Examples of the “substituted or unsubstituted aromatic hydrocarbon oxy group having 1 to 18 carbon atoms” include, for example, phenoxy group, methylphenoxy group, ethylphenoxy group, methoxyphenoxy group, butoxyphenoxy group, phenoxyphenoxy group, etc. A group having a structure in which an oxygen atom is bonded to the aromatic hydrocarbon group described above as R ³ , and those substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, or the like; Can be mentioned.

  The compound represented by the above formula (I-4) is not limited to this, but for example, commercially available compounds such as triphenylsilanol, trimethylsilanol, triethylsilanol, tert-butyldimethylsilanol (3-glycidoxypropyl) dimethylethoxysilane, triphenylethoxysilane, phenyldimethylethoxysilane, diphenylmethylethoxysilane, (3-acryloxypropyl) dimethylmethoxysilane, 3-aminoethylaminomethylbenzyloxydimethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyldiisopropylethoxysilane, tert-butyldiphenylmethoxysilane, chloromethyldimethylethoxysilane, chloromethyldimethylisopropyl Poxysilane, chloropropyldimethylmethoxysilane, dimethylethoxysilane, diphenylphosphinoethyldimethylethoxysilane, methacryloxymethyldimethylethoxysilane, dimethylethoxyethynylsilane, methoxydimethylvinylsilane, n-octadecyldimethylmethoxysilane, triethylethoxysilane, trimethylethoxysilane , Trimethylmethoxysilane, vinyldiphenylethoxysilane, vinylphenylmethylmethoxysilane, benzyldimethylethoxysilane, dimethylchlorosilane, dichloromethyldimethylchlorosilane, chloromethyldimethylchlorosilane, trimethylchlorosilane, trimethylbromosilane, dimethylvinylchlorosilane, allyldimethylchlorosilane, 3 -Chloropropyl Methylchlorosilane, dimethylpropylchlorosilane, dimethylisopropylchlorosilane, 3-cyanopropyldimethylchlorosilane, triethylchlorosilane, triethylbromosilane, tert-butyldimethylchlorosilane, methylphenylchlorosilane, dimethylphenylchlorosilane, methylphenylvinylchlorosilane, benzyldimethylchlorosilane, tripropyl Examples include chlorosilane, dimethyloctylchlorosilane, diphenylchlorosilane, diphenylmethylchlorosilane, diphenylvinylchlorosilane, triphenylchlorosilane, trihexylchlorosilane, tribenzylchlorosilane, dimethyloctadecylchlorosilane, and the like. Silanation represented by (I-4) Compound can be used.

  The compound represented by the above formula (I-5) is not limited to this. For example, 1,1,3,3-tetramethyldisilazane, which is a commercially available compound, , 3-bis (chloromethyl) -1,1,3,3-tetramethyldisilazane, 1,1,1,3,3,3-hexamethyldisilazane, 1,3-divinyl-1,1,3 , 3-tetramethyldisilazane and the like, but not limited to these, a silane compound represented by the formula (I-5) synthesized by a known method can be used.

<Epoxy resin composition>
The epoxy resin composition of the present invention comprises the epoxy resin and the calixarene derivative of the present invention as a curing agent for epoxy resin.
(Epoxy resin)
The epoxy resin usable in the present invention is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule. Examples of the epoxy resin include phenols such as phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, phenols such as cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and / or α-naphthol, β- Novolac obtained by epoxidizing a novolak resin obtained by condensation or cocondensation of naphthols such as naphthol and dihydroxynaphthalene and a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and hydroxybenzaldehyde under an acidic catalyst. Type epoxy resin;
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 the olefin bond in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro ( 3,4-epoxy) cycloaliphatic epoxy resins such as cyclohexane-m-dioxane;
Glycidyl ether of paraxylylene and / or metaxylylene modified phenolic resin;
Glycidyl ether of terpene-modified phenolic resin;
Glycidyl ether of dicyclopentadiene-modified phenolic resin;
Glycidyl ether of cyclopentadiene modified phenolic resin;
Glycidyl ether of polycyclic aromatic ring-modified phenolic resin;
Glycidyl ether of a naphthalene ring-containing phenolic resin;
Halogenated phenol novolac epoxy resin;
Hydroquinone type epoxy resin;
Trimethylolpropane type epoxy resin;
A linear aliphatic epoxy resin obtained by oxidizing an olefinic bond with a peracid such as peracetic acid;
Diphenylmethane type epoxy resin;
Epoxidized products of aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins;
Sulfur atom-containing epoxy resin;
Naphthalene type epoxy resin; and the like. These may be used alone or in combination of two or more.

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

The biphenyl type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton, but an epoxy resin represented by the following 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. except the YX-4000H is a hydrogen atom (manufactured by Japan epoxy Resins Co., Ltd.), all of ^{R 8} is a hydrogen atom 4,4'-bis (2,3-epoxypropoxy) biphenyl, all ^{R 8} is a hydrogen atom And in the case where the position where the oxygen atom is substituted in R ⁸ is the 4 and 4 'position, the mixture is a methyl group at the 3, 3', 5, 5 'position and the other is a hydrogen atom. YL-6121H (manufactured by Japan Epoxy Resin Co., Ltd.) and the like are commercially available.

(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.)
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 (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
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 (manufactured by Nippon Steel Chemical Co., Ltd.) having a methyl group at the 5,5′-position and a hydrogen atom at the other positions is available as a commercial product.

(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
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 (manufactured by Nippon Steel Chemical Co., Ltd.) having a methyl group at the '-position and a hydrogen atom other than that 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.)
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, ESCN-195 (manufactured by Sumitomo Chemical Co., Ltd.), etc., in which all of R ¹⁴ are hydrogen atoms, R ¹⁵ is a methyl group and i = 1, etc. It is available as a commercial product.

(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.)
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 the epoxy resins represented by the following general formula (VII), HP-7200 (manufactured by Dainippon Ink and Chemicals, Inc.) in which i = 0 is available as a commercial product.

(In the formula (VII), R ¹⁶ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 0 to 3, and n is an average value. Yes, indicates a number from 0 to 10.)
The hydroxybenzaldehyde type epoxy resin is not particularly limited as long as it is an epoxy resin made from a compound having a hydroxybenzaldehyde skeleton, but a novolak type phenol resin of a compound having a hydroxybenzaldehyde skeleton and a compound having a phenolic hydroxyl group, etc. A hydroxybenzaldehyde type epoxy resin such as an epoxy resin obtained by glycidyl etherification of a hydroxybenzaldehyde type phenol resin is preferable, and an epoxy resin represented by the following general formula (VIII) is more preferable. Among epoxy resins represented by the following general formula (VIII), 1032H60 (manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-502H (trade name of Nippon Kayaku Co., Ltd.), etc., where i = 0 and k = 0 are commercially available products. Is available as

(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.)
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 (manufactured by Nippon Kayaku Co., Ltd.) in which R ²¹ is a methyl group, i = 1, j = 0, k = 0, etc. is a commercial product. Is available as

(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.

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 (manufactured by Nippon Kayaku Co., Ltd.), i = 0, R ³⁸ is a hydrogen atom epoxy resin and in formula CER-3000 (trade name manufactured by Nippon Kayaku Co., Ltd.) all ^{R 8} are mixed in a weight ratio of 80:20 to epoxy resin is a hydrogen atom (II) and the like commercially available. Among epoxy resins represented by the following general formula (XI), ESN-175 (Nippon Steel Chemical Co., Ltd.) with j = 0 and k = 0 is available as a commercial product.

(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.)
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. (manufactured by Dainippon ink and chemicals, Inc.), n = ^0, all ^{R 42} and ^{R 43} is a hydrogen ^atom, (manufactured by Dainippon ink and chemicals, Inc.) HP-4032 ^{R 44} is glycidyl group, n = EXA-4750 (manufactured by Dainippon Ink & Chemicals, Inc.), etc., which is 1, all of R ⁴² and R ⁴³ are hydrogen atoms, one of R ⁴⁴ is a hydrogen atom and the other is a glycidyloxy group Is possible.

(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 calixarene derivative of the present invention is the ratio of the total number of epoxy groups of the epoxy resin and the total number of phenolic hydroxyl groups of the calixarene derivative and the total number of silyl ether groups, That is, the total number of epoxy groups / (total number of phenolic hydroxyl groups + total number of silyl ether groups) is preferably 0.5 to 2.0, more preferably 0.7 to 1.5, and 0.8 It is especially preferable that it is -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.

(Other curing agents)
The epoxy resin composition of the present invention can be used in combination with another curing agent other than the calixarene derivative 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 phenol resin obtained by condensation or cocondensation with aldehydes such as benzaldehyde and hydroxybenzaldehyde under an acidic catalyst;
Aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl;
Paraxylylene and / or metaxylylene-modified phenolic resin;
Melamine-modified phenolic resin;
Terpene-modified phenolic resin;
Dicyclopentadiene type phenol resin, dicyclopentadiene type naphthol resin synthesized by copolymerization from phenols and / or naphthols and dicyclopentadiene;
Cyclopentadiene modified phenolic resin;
Polycyclic aromatic ring-modified phenolic resin;
Biphenyl type phenolic resin;
Triphenylmethane phenol resin;
Examples thereof include phenol resins obtained by copolymerizing two or more of these resins; these may be used alone or in combination of two or more.

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

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

(In the 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 phenolic resins represented by the above general formula (XII), ME = 07851 (Maywa Kasei Co., Ltd.) where i = 0 and all R ²³ are hydrogen atoms is commercially available.

  Among the phenol resins represented by the above general formula (XIII), XL-225, XLC (manufactured by Mitsui Chemicals, Inc.), MEH-7800 (Maywa Kasei Co., Ltd.), etc., where i = 0 and k = 0 are commercially available products. It is available.

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

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 (manufactured by Shin 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.)
The hydroxybenzaldehyde type phenol resin is not particularly limited as long as it is a phenol resin using a compound having a hydroxybenzaldehyde skeleton as a raw material, but a phenol resin represented by the following general formula (XVI) is preferable.

Among phenol resins represented by the following general formula (XVI), MEH-7500 (manufactured by Meiwa Kasei Co., Ltd.) with 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.)
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 (manufactured by Air Water Chemical Co., Ltd.) having i = 0, k = 0, and q = 0 is available as a commercial product.

(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, and 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.)
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), a ^{R 35} are all hydrogen atoms TAMANOL 758, 759 (manufactured by Arakawa Chemical Industries, Ltd.), HP-850N (Hitachi Chemical Co., Ltd.) and the like It is available as a commercial product.

(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, a curing agent component containing the calixarene derivative of the present invention and another curing agent. Since the melt viscosity of the epoxy resin composition becomes high, the viscosity at the time of melt molding of the epoxy resin composition also increases, which tends to cause unfilling failure and deformation of the bonding wire (gold wire connecting the element and the lead). The average n per molecule is preferably set in the range of 0-4.

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

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

  Further, in the epoxy resin composition of the present invention, when a compound having two or more phenolic hydroxyl groups in one molecule is used as another curing agent in addition to the calixarene derivative of the present invention, the total number of epoxy groups of the epoxy resin And the ratio of the total phenolic hydroxyl number of the calixarene derivative, the total number of silyl ether groups, and the total number of phenolic hydroxyl groups of other curing agents and the sum of the total number of silyl ether groups, The number of epoxy groups / (total number of phenolic hydroxyl groups + total number of silyl ether groups) is preferably 0.5 to 2.0, more preferably 0.7 to 1.5, and 0.8 to 1. 3 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.

(Curing accelerator)
The epoxy resin composition of this invention can contain a hardening accelerator as needed. Examples of usable curing accelerators include diazabicycloalkenes such as 1,5-diazabicyclo [4.3.0] nonene-5, 1,8-diazabicyclo [5.4.0] undecene-7, and the like. Cycloamidine compounds, derivatives thereof, phenol novolac salts thereof,
And these compounds include maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5 Intramolecular polarization formed by adding a quinone compound such as methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, and a compound having a π bond such as diazophenylmethane. A compound having:
Tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and derivatives thereof;
Imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole;
Tetrasubstituted boron salts such as tetraphenylphosphonium and tetraphenylborate, tetraphenylboron salts such as 2-ethyl-4-methylimidazole and tetraphenylborate, N-methylmorpholine and tetraphenylborate;
Triphenylphosphonium, diphenyl (p-tolyl) phosphonium, tris (alkylphenyl) phosphonium, tris (alkoxyphenyl) phosphonium, tris (alkylalkoxyphenyl) phosphonium, tris (dialkylphenyl) phosphonium, tris (trialkylphenyl) phosphonium, Organic phosphoniums such as tris (tetraalkylphenyl) phosphonium, tris (dialkoxyphenyl) phosphonium, tris (trialkoxyphenyl) phosphonium, tris (tetraalkoxyphenyl) phosphonium, trialkylphosphonium, dialkylarylphosphonium, alkyldiarylphosphonium, or Complexes of these organic phosphoniums with organic borons;
These organic phosphoniums, maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5 Intramolecular polarization formed by adding a quinone compound such as methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, and a compound having a π bond such as diazophenylmethane. A compound having:
These organic phosphoniums, 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2- Iodinated phenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2, Reaction with halogenated phenol compounds such as 6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl And a compound having intramolecular polarization obtained by dehydrohalogenation (JP 2004-1 See JP 6036); 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 phosphonium compound and a π bond, an organic phosphonium compound and a halogenated phenol compound are reacted. After that, a compound having intramolecular polarization obtained through a dehydrohalogenation step is preferable. From the viewpoint of curability, after reacting an organic phosphonium compound with a halogenated phenol compound, a dehydrohalogenation step is performed. The resulting compound having intramolecular polarization is preferred. In particular, it is preferable to use a phosphonium compound represented by the following general formula (I-6) or an intermolecular salt thereof.

(In formula (I-6), each R ⁴ is independently selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, and all are the same. 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 general formula (I-6), R ⁴ is selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent. 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 group An alicyclic hydrocarbon group such as 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 dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group and the like, alkyl group-substituted aryl groups, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group Alkoxy group-substituted aryl groups such as those further substituted with an alkyl group, alkoxy group, aryl group, aryloxy group, amino group, halogen atom or 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 it is an unsubstituted or alkyl group and / or an alkoxy group and / or a hydroxyl group-substituted aryl group.

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

Specific examples of the aliphatic hydrocarbon group having 1 to 18 carbon atoms, alicyclic hydrocarbon group and aromatic hydrocarbon group which may have a substituent are the same as those mentioned in the above R ^4. Used.

  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 groups such as phenoxy group, methylphenoxy group, ethylphenoxy group, methoxyphenoxy group, butoxyphenoxy group, phenoxyphenoxy group; alkyl, alkoxy, aryl Substituted by a group, aryloxy group, amino group, halogen atom or the like; 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, alkoxy group, aryl group, aryloxy group, amino group, 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; and the like. These include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, and a halogen. It may be substituted with an atom or the like.

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

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

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

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

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

  Moreover, 1-50 micrometers is preferable and, as for the average particle diameter (D50) of an inorganic filler, 10-30 micrometers is more preferable. When the average particle size is less than 1 μm, the viscosity of the epoxy resin composition tends to increase. 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 the inorganic filler is blended in an amount of 75% by volume or more with respect to the epoxy resin composition, 70% by weight or more of the inorganic filler is a spherical particle, and the particle size distribution of the inorganic filler is distributed over a wide range of 0.1 to 80 μm. It is preferable that Since such an inorganic filler tends to have a close-packed structure, even if the blending amount is increased, an increase in the viscosity of the epoxy resin composition is small, and an epoxy resin composition excellent in fluidity can be obtained.

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

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

  The blending amount of the coupling agent is preferably 0.05 to 5% by mass and more preferably 0.1 to 2.5% by mass with respect to the inorganic filler. If the blending amount is less than 0.05% by mass, the adhesion to the frame tends to be lowered, and if it exceeds 5% by mass, 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 (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1 -Butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, Isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctylfo Feto) titanate, isopropyl tricumylphenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate coupling agents such as titanate; and the like, may be used in combination of two or more even with these alone. Among these, a coupling agent having a secondary amino group is preferable from the viewpoint of fluidity and wire flow.

(Ion exchanger)
The epoxy resin composition of the present invention can contain an anion exchanger as required. In particular, when an epoxy resin composition is used as a molding material for sealing, it is preferable to contain an anion exchanger from the viewpoint of improving moisture resistance and high-temperature storage characteristics of an electronic component device including an element to be sealed. . The anion exchanger used in the present invention is not particularly limited, and conventionally known anion exchangers can be used. For example, hydrotalcite, and hydrous hydroxide of an element selected from magnesium, aluminum, titanium, zirconium, and bismuth The thing is mentioned, These can be used individually or in combination of 2 or more types. 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 blending amount of these anion exchangers is not particularly limited as long as it is a sufficient amount capable of capturing anions such as halogen ions. The range of ˜5% by mass is more preferable.

(Release agent)
In the epoxy resin composition of the present invention, a mold release agent may be blended in order to give good mold releasability from the mold during molding. There is no restriction | limiting in particular as a mold release agent used in this invention, A conventionally well-known thing can be used. Examples thereof include higher fatty acids such as carnauba wax, montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. It may be used in combination of two or more. Among these, an oxidized or non-oxidized polyolefin wax is preferable, and the blending amount of the polyolefin wax is preferably 0.01 to 10% by mass with respect to the epoxy resin, and 0.1 to 5% by mass. % Is more preferable. If the blending amount of the polyolefin wax is less than 0.01% by mass, the releasability tends to be insufficient, and if it exceeds 10% by mass, the adhesion may be inhibited. Examples of the polyolefin-based wax include low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000 such as H4, PE, and PED series manufactured by Hoechst.

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

(Stress relaxation agent)
The epoxy resin composition of the present invention may contain a stress relaxation agent such as silicone oil or silicone rubber powder as required. By blending a stress relaxation agent, the amount of warp deformation and package cracking of the package can be reduced. The stress relaxation agent that can be used is not particularly limited as long as it is a known flexible agent (stress relaxation agent) that is generally used. Commonly used flexible agents include, for example, silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, polybutadiene-based thermoplastic elastomers, NR (natural rubber), NBR, and the like. (Acrylonitrile-butadiene rubber), rubber particles such as acrylic rubber, urethane rubber, silicone powder, methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate Examples thereof include rubber particles having a core-shell structure such as a copolymer, and these may be used alone or in combination of two or more. Among these, a silicone-based flexible agent is preferable, and examples of the silicone-based flexible agent include those having an epoxy group, those having an amino group, and those obtained by modifying these with a polyether.

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

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

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

<Electronic component device>
An electronic component device according to the present invention includes an element sealed with the above-described epoxy resin composition of the present invention. Such electronic component devices include, for example, lead frames, wired tape carriers, wiring boards, glass, silicon wafers and other supporting members, active elements such as semiconductor chips, transistors, diodes, thyristors, capacitors, resistors, coils Examples include those equipped with elements such as passive elements such as those in which these element portions are sealed with the epoxy resin composition of the present invention. More specifically, for example, after fixing a semiconductor element on a lead frame and connecting the terminal part of the element such as a bonding pad and the lead part by wire bonding or bump, the transfer is performed using the epoxy resin composition of the present invention. Sealed by molding or the like, DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-Tap) 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 of calixarenes>
(Synthesis Example 1): Synthesis of calixarenes 1 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 at about 5 ° C. Stir for 30 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. Since calixarenes having a structure represented by the following formula are known compounds, measurement results of various spectra are omitted.

(Synthesis Example 2): Synthesis of calixarenes 2 Using a 100 ml four-necked flask, 5.50 g (0.05 mol) of resorcinol was dissolved in 20 ml of ethanol, and 7 ml of concentrated hydrochloric acid was added under ice cooling at about 5 ° C. Stir for 30 minutes. To this, 6.11 g (0.05 mol) of p-hydroxybenzaldehyde was added dropwise, and then heated under 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 three times with acetone and then vacuum-dried at 60 ° C. for 24 hours to obtain 6.5 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. Since calixarenes having a structure represented by the following formula are known compounds, measurement results of various spectra are omitted.

<Synthesis of calixarene derivative>
(Example 1): Synthesis of calixarene derivative 1 1.36 g (2.5 mmol) of calixarenes 1 obtained in Synthesis Example 1 was placed in a 200 ml three-necked flask and purged with nitrogen, and then 50 ml of tetrahydrofuran was added. Suspended. To this suspension, 4,84 g (30 mmol) of 1,1,1,3,3,3-hexamethyldisilazane and 0.16 g (1.5 mmol) of chlorotrimethylsilane were added and heated to reflux. Further, the system was heated to reflux for 48 hours after the system became uniform. After completion of the reaction, tetrahydrofuran and unreacted 1,1,1,3,3,3-hexamethyldisilazane were distilled off under reduced pressure, n-hexane was added, and the mixture was stirred for 1 hour. After filtration, it was dried under reduced pressure at 60 ° C. for 72 hours to obtain 2.31 g of a white solid.

The obtained reaction product was measured by ¹ H-NMR, IR, and elemental analysis, and as a result, it was confirmed to be a calixarene derivative having a structure represented by the following formula. The spectrum data is as follows.

¹ H-NMR (500 MHz, CD ₃ Cl) δ (PPM):
−0.01 to 0.35 (m, 72H)
1.36 (d, J = 7.5 Hz, 12H)
4.50 to 4.54 (q, J = 7.5 Hz, 4H)
5.96 to 7.23 (br, 8H)
IR (film method, cm ⁻¹ )
1497 (ν C═C (aromatic)), 1253 (ν Si—C), 1196 (ν Si—O)
Elemental analysis _{(C 56 H 96 O 8 Si} 8)
Calculated value (%) C: 59.94, H: 8.62
Actual value (%) C: 59.82, H: 8.68

(Example 2): Synthesis of calixarene derivative 2 3.24 g (2.5 mmol) of calixarenes 2 obtained in Synthesis Example 2 was placed in a 200 ml three-necked flask and purged with nitrogen, and then 50 ml of tetrahydrofuran was added. Suspended. To this suspension, 7.26 g (45 mmol) of 1,1,1,3,3,3-hexamethyldisilazane and 0.24 g (2.3 mmol) of chlorotrimethylsilane were added and heated to reflux. Further, the system was heated to reflux for 48 hours after the system became uniform. After completion of the reaction, tetrahydrofuran and unreacted 1,1,1,3,3,3-hexamethyldisilazane were distilled off under reduced pressure, n-hexane was added, and the mixture was stirred for 1 hour. After filtration, it was dried under reduced pressure at 60 ° C. for 72 hours to obtain 2.20 g of a white solid.

The obtained reaction product was measured by ¹ H-NMR, IR, and elemental analysis, and as a result, it was confirmed to be a calixarene derivative having a structure represented by the following formula. The spectrum data is as follows.

¹ H-NMR (500 MHz, CD ₃ Cl) δ (PPM):
-0.09 to 0.26 (m, 72H)
5.63 (m, 4H)
6.69-7.64 (m, 24H)
IR (film method, cm ⁻¹ )
1507 (ν C═C (aromatic)), 1250 (ν Si—C), 1179 (ν Si—O)
Elemental analysis _{(C 88 H 136 O 12 Si} 12)
Calculated value (%) C: 61.34, H: 7.96
Actual value (%) C: 61.22, H: 8.16

(Example 3): Synthesis of calixarene derivative 3 In a 50 ml three-necked flask, 0.55 g (1.0 mmol) of calixarene 1 obtained in Synthesis Example 1 and 3.31 g (48 mmol) of imidazole were placed in nitrogen. After the replacement, 20 ml of tetrahydrofuran was added and dissolved. To this solution, 3.61 g (24 mmol) of triethylchlorosilane was added and heated to reflux for 90 hours. After completion of the reaction, the pale yellow part was separated by column chromatography using a 1: 1 mixed solvent of ethyl acetate and n-hexane, and concentrated. The white solid produced by adding 5 ml of acetone and allowing it to stand in a refrigerator was filtered and dried under reduced pressure at 60 ° C. for 24 hours to obtain 1.29 g of a product.

The obtained reaction product was measured by ¹ H-NMR, IR, and elemental analysis, and as a result, it was confirmed to be a calixarene derivative having a structure represented by the following formula. The spectrum data is as follows.

¹ H-NMR (500 MHz, CD ₃ Cl) δ (PPM):
-0.09 to 1.54 (m, 120H)
1.37 (d, J = 7.5 Hz, 12H)
4.59 to 4.67 (q, J = 7.5 Hz, 4H)
5.94-7.33 (m, 8H)
IR (film method, cm ⁻¹ )
1497 (ν C═C (aromatic)), 1260 (ν Si—C), 1188 (ν Si—O)
Elemental analysis _{(C 80 H 144 O 8 Si} 8)
Calculated value (%) C: 65.87, H: 9.95
Actual value (%) C: 65.72, H: 9.56

(Example 4): Synthesis of calixarene derivative 4 In a 50 ml three-necked flask, 0.86 g (1.0 mmol) of calixarenes 2 obtained in Synthesis Example 2 and 4.91 g (72 mmol) of imidazole were placed in nitrogen. After the replacement, 30 ml of tetrahydrofuran was added and dissolved. To this solution, 5.43 g (36 mmol) of triethylchlorosilane was added and heated to reflux for 96 hours. After completion of the reaction, the pale yellow part was separated by column chromatography using a 1: 1 mixed solvent of ethyl acetate and n-hexane, and concentrated. The white solid produced by adding 5 ml of acetone and leaving it in a refrigerator was filtered and dried under reduced pressure at 60 ° C. for 24 hours to obtain 1.48 g of product.

The obtained reaction product was measured by ¹ H-NMR, IR, and elemental analysis, and as a result, it was confirmed to be a calixarene derivative having a structure represented by the following formula. The spectrum data is as follows.

¹ H-NMR (500 MHz, CD ₃ Cl) δ (PPM):
-0.04 to 0.61 (m, 180H)
5.22 to 5.27 (m, 4H)
5.50-6.17 (m, 24H)
IR (film method, cm ⁻¹ )
1507 (ν C═C (aromatic)), 1261 (ν Si—C), 1189 (ν Si—O)
Elemental analysis _{(C 124 H 208 O 12 Si} 12)
Calculated value (%) C: 66.85, H: 9.41
Actual value (%) C: 66.66, H: 9.31

(Example 5): Synthesis of calixarene derivative 5 In a 50 ml three-necked flask, 0.55 g (1.0 mmol) of calixarenes 1 obtained in Synthesis Example 1 and 3.31 g (48 mmol) of imidazole, tert- After substituting 3.61 g (24 mmol) of butyldimethylchlorosilane with nitrogen, 20 ml of tetrahydrofuran was added and dissolved, and the mixture was heated to reflux for 96 hours. After completion of the reaction, the reaction mixture was poured into a large amount of ethyl acetate, and the precipitated solid was filtered, dissolved in a small amount of THF, and poured again into a large amount of ethyl acetate. The precipitated white solid was filtered and dried under reduced pressure at 60 ° C. for 24 hours to obtain 1.32 g of a product.

The obtained reaction product was measured by ¹ H-NMR, IR, and elemental analysis, and as a result, it was confirmed to be a calixarene derivative having a structure represented by the following formula. The spectrum data is as follows.

¹ H-NMR (500 MHz, CD ₃ Cl) δ (PPM):
-0.48 to 0.71 (m, 120H)
1.06 (d, J = 7.5Hz, 12H)
4.50 to 4.53 (q, J = 7.5 Hz, 4H)
5.96 to 7.23 (m, 8H)
IR (film method, cm ⁻¹ )
1495 (ν C═C (aromatic)), 1256 (ν Si—C), 1193 (ν Si—O)
Elemental analysis _{(C 80 H 144 O 8 Si} 8)
Calculated value (%) C: 65.87, H: 9.95
Actual value (%) C: 66.11, H: 9.53

(Example 6): Synthesis of calixarene derivative 6 In a 50 ml three-necked flask, 0.86 g (1.0 mmol) of calixarenes 2 obtained in Synthesis Example 2 and 4.91 g (72 mmol) of imidazole, tert- After purging with nitrogen by adding 5.43 g (36 mmol) of butyldimethylchlorosilane, 30 ml of tetrahydrofuran was added and dissolved, and the mixture was heated to reflux for 96 hours. After completion of the reaction, the target product was fractionated by column chromatography using a 1:17 mixed solvent of ethyl acetate and n-hexane, and concentrated. The white solid produced by adding 5 ml of acetone and allowing it to stand in a refrigerator was filtered and dried under reduced pressure at 60 ° C. for 24 hours to obtain 1.30 g of a product.

The obtained reaction product was measured by ¹ H-NMR, IR, and elemental analysis, and as a result, it was confirmed to be a calixarene derivative having a structure represented by the following formula. The spectrum data is as follows.

¹ H-NMR (500 MHz, CD ₃ Cl) δ (PPM):
-0.49 to 0.86 (m, 180H)
5.43-5.44 (m, 4H)
5.67-6.37 (m, 24H)
IR (film method, cm ⁻¹ )
1507 (ν C═C (aromatic)), 1253 (ν Si—C), 1195 (ν Si—O)
Elemental analysis _{(C 124 H 208 O 12 Si} 12)
Calculated value (%) C: 66.85, H: 9.41
Actual value (%) C: 66.72, H: 9.35

Details of the measurement method of ¹ H-NMR spectrum and IR spectrum in Synthesis Examples and Examples are as follows.

(1) Measurement of ¹ H-NMR spectrum A sample was dissolved in deuterated chloroform to obtain a solution, which was put into a φ5 mm sample tube and used for measurement. Measurement was performed using a 500 MHz nuclear magnetic resonance apparatus “JEOL ECA-500” manufactured by JEOL Ltd.

(2) Measurement of IR spectrum Measurement was performed by a film method using NICOKET 380FT-IR manufactured by Thermo ELECTRON Co., Ltd.

<Preparation of epoxy resin composition and characteristic evaluation>
(Example 7, Comparative Examples 1-2)
The following components were blended in parts by mass shown in Table 1 and mixed in a mortar, then placed in an aluminum cup on a hot plate heated to 130 ° C. 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 Example 7 and Comparative Examples 1-2.

  Each component in Table 1 used the following. Note that the blank in the table indicates no blending.

(Epoxy resin)
Epoxy resin: 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 1 obtained in Synthesis Example 1
Curing agent 2: calixarene derivative 1 obtained in Synthesis Example 3
Curing agent 3: Phenol novolac resin having a hydroxyl group equivalent of 106 (manufactured by Hitachi Chemical Co., Ltd., trade name: HP-850N)
(Curing accelerator)
Curing accelerator 1: 1,8-diazabicyclo [5.4.0] undec-7-ene Curing accelerator 2: Triphenylphosphonium Next, the cured products of Example 7 and Comparative Examples 1-2 are shown below. Evaluated by testing.

(1) 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.

  Example 7 using the calixarene derivative of the present invention is excellent in the high temperature elastic modulus. On the other hand, in Comparative Example 1 using the calixarene obtained in Synthesis Example 1, the decrease in elastic modulus starts at a low temperature (the glass transition temperature is low). From the structure, it is expected that the glass transition temperature is higher than that of Example 7 and excellent in the high-temperature elastic modulus, but it is considered that the reaction has not progressed completely due to poor uniformity. Comparative Example 2 using a conventional curing agent is inferior in terms of high temperature elastic modulus.

It is a figure which shows the dynamic viscoelastic behavior in an Example and a comparative example.

Claims (6)

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

(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 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 derivative according to claim 1, wherein 5 to 100% of the phenolic hydroxyl group of the calixarene (b1) represented by the formula (I-2) is silyl etherified.

(Wherein n is 1 to 4, m is an average of 3 to 20, and for each of m repetitions, R ¹ , R ² and 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. ) The calixarene derivative according to claim 1 or 2, wherein the calixarene (b1) is a compound represented by the formula (I-3).

(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 calixarene (b1) represented by the formula (I-2) is reacted with at least one compound selected from the group of silane compounds represented by the formula (I-4) and the formula (I-5). The manufacturing method of the calixarene derivative as described in any one of Claims 1-3 characterized by the above-mentioned.

(In the formula, each R ³ 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. .
X is selected from the group consisting of a hydrocarbon oxy group having 1 to 18 carbon atoms, a hydroxyl group, a chlorine atom and a bromine atom. )

(In the formula, each R ³ 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. .)   An epoxy resin composition comprising an epoxy resin and the calixarene derivative according to any one of claims 1 to 3 as a curing agent for the epoxy resin.   An electronic component device comprising an element sealed with the epoxy resin composition according to claim 5.

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