JP5285208B2 - Novel compound and method for producing the same, and curable resin, epoxy resin composition and electronic component device containing novel compound - Google Patents

Description

  The present invention relates to a novel compound that can be used as a curable resin, a method for producing the same, and a curable resin composition containing the compound. More specifically, a novel compound useful as an epoxy resin curing agent and a production method thereof, a molding material containing the compound as a curing agent, an epoxy suitable as a material for laminates, various electronic and electrical components, a coating material or an adhesive material The present invention relates to a resin composition and an electronic component device including an element sealed with the epoxy resin composition.

  Conventionally, curable resins such as epoxy resins have been widely used in fields such as molding materials, laminate and adhesive materials, various electronic and electrical parts, and coating 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. In particular, the combination of an ortho-cresol novolac type epoxy resin and a phenol novolac curing agent, and a combination of a biphenyl type epoxy resin and a phenol aralkyl resin have an excellent balance in the above characteristics. It has become mainstream as a base resin.

  In recent years, in the field of electronic components, high-density mounting on printed wiring boards has been progressing. As a result, surface mount packages are becoming the mainstream of electronic components rather than conventional pin insertion packages. However, since surface mount packages tend to have lower resistance to package cracks during soldering, so-called reflow crack resistance, compared to pin insertion packages, improvements are desired. That is, in surface-mounted ICs such as IC and LSI, the occupied volume of the element in the package gradually increases in order to increase the mounting density, and the thickness of the package is very thin. In addition, surface mount packages are subject to more severe conditions than their pin insertion packages during their soldering process. More specifically, in the pin insertion type package, since the soldering is performed from the back side of the wiring board after the pins are inserted into the wiring board, the package was not directly exposed to a high temperature. Then, after temporarily fixing the surface of the wiring board, the package is directly exposed to the soldering temperature because it is processed by a solder bath, a reflow device, or the like. As a result, when the IC package absorbs moisture, the moisture absorption moisture may rapidly expand during soldering, leading to package cracks, which is a major problem in package molding.

  In order to improve the resistance against package cracks during soldering, so-called reflow crack resistance, various studies have been made conventionally. For example, methods such as lowering stress by improving epoxy resins and curing agents and lowering water absorption by increasing the amount of inorganic filler are known. However, the method based on the improvement of the epoxy resin and the curing agent tends to cause poor curing and a decrease in releasability due to a decrease in curability. In addition, the method by increasing the amount of inorganic filler leads to a decrease in fluidity at the time of molding, and molded products such as defective filling, occurrence of voids such as voids, or poor conduction due to disconnection of IC chip bonding wires. There is a tendency to cause performance degradation.

As described above, since there is a limit to the conventional method for reducing the stress or the water absorption, it has been difficult to remarkably improve the reflow crack resistance. In particular, when an epoxy resin composition is used as a sealing material, an alcoholic hydroxyl group resulting from the epoxy resin is generated at the time of curing, and thus there is a limit to reducing the water absorption rate of the composition.

In order to solve the problem of water absorption related to the generation of the alcoholic hydroxyl group at the time of curing, a method of using a phenol compound obtained by esterifying or trimethylsilylating a phenolic hydroxyl group as an epoxy resin curing agent has been proposed ( (See Patent Documents 1 to 3).
Japanese Patent Laid-Open No. 62-53327 Japanese Patent Application Laid-Open No. 8-231585 JP 2004-307655 A

  However, when the above esterified or trimethylsilylated phenol compound is used as an epoxy resin curing agent, the problem of water absorption is improved, but the properties such as the curability and glass transition temperature (ie, heat resistance) of the composition are reduced. Tend to. Therefore, further development of a curing agent is desired.

  The present invention has been made in view of such circumstances, and a compound useful as a curable resin that can be used as an epoxy resin curing agent that can exhibit excellent curability, heat resistance, and low water absorption, and its production. It is an object of the present invention to provide a method and a curable resin composition such as an epoxy resin composition containing these compounds. Furthermore, it is an object of the present invention to provide an electronic component device provided with an element having excellent reliability such as reflow resistance and moisture resistance reliability using such an epoxy resin composition as a sealing material.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have cured a compound obtained by reacting a compound having two or more phenolic hydroxyl groups in the molecule with a specific silane compound. It has been found that the intended purpose can be achieved by using these compounds, and the present invention has been completed.

  The present invention relates to the following.

(1) (a) a phenol compound having two or more phenolic hydroxyl groups in the molecule, and (b) a silane compound represented by the following general formula (I-1) having two functional groups capable of reacting with the phenolic hydroxyl group Compound obtained by reaction with

(In the formula, R ¹ are each independently selected from hydrogen atom and the group consisting of substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different, R ¹ each other May combine to form a ring structure,
R ² represents a functional group capable of reacting with a phenolic hydroxyl group, and each independently represents a halogen atom, a hydroxyl group, a substituted or unsubstituted oxy group having 1 to 18 carbon atoms, or a substituted or unsubstituted group having 0 to 18 carbon atoms. And a group selected from the group consisting of carbonyloxy groups having 2 to 18 carbon atoms, all of which may be the same or different, and R ² may be bonded to each other to form a cyclic structure)
(2) The compound according to (1) above, wherein in the silane compound (b), R ² is a hydroxyl group or an oxy group.

(3) The compound according to (1) or (2) above, wherein 70% by weight or more of the phenol compound (a) is a divalent phenol compound based on the total weight of the phenol compound.

(4) A compound having one or more structural units represented by the following general formula (I-2).

(In the formula, R ¹ are each independently selected from hydrogen atom and the group consisting of substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different, R ¹ each other May combine to form a ring structure,
Ar is a divalent organic group having 2 to 30 carbon atoms and a group derived from an aromatic cyclic compound on both sides)
(5) The compound according to (4) above, which comprises a compound having a structure represented by the following general formula (I-3).

(In the formula, R ¹ are each independently selected from hydrogen atom and the group consisting of substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different, R ¹ each other May combine to form a ring structure,
Ar is a divalent organic group having 2 to 30 carbon atoms and a group derived from a cyclic compound having aromaticity on both sides,
Each R ³ independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms and —Ar—OH (wherein Ar has 2 to 30 carbon atoms and is aromatic; Are selected from the group consisting of a group derived from a cyclic compound showing a divalent organic group on both sides, and all may be the same or different,
m represents a number of 1 or more, n represents a number of 0 or more, and the repetition of m units and n units may be block, alternating, or random)
(6) (a) a phenol compound having two or more phenolic hydroxyl groups in the molecule, and (b) a silane compound represented by the following general formula (I-1) having two functional groups capable of reacting with the phenolic hydroxyl group The method for producing a compound according to the above (4) or (5), which comprises a step of reacting

(In the formula, R ¹ are each independently selected from hydrogen atom and the group consisting of substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different, R ¹ each other May combine to form a ring structure,
R ² represents a functional group capable of reacting with a phenolic hydroxyl group, and each independently represents a halogen atom, a hydroxyl group, a substituted or unsubstituted oxy group having 1 to 18 carbon atoms, or a substituted or unsubstituted group having 0 to 18 carbon atoms. And all may be the same or different and R ² may be bonded to each other to form a cyclic structure)
(7) The reaction between (a) and (b) is carried out in the presence of a catalyst selected from the group consisting of phosphine compounds, phosphonium salt compounds, cyclic amidine compounds, and cyclic amidinium salts. The manufacturing method as described in said (6).

(8) The production method as described in (7) above, wherein the catalyst is a phosphonium compound represented by the following general formula (I-4) or an intermolecular salt thereof.

Wherein R ⁴ is independently selected from the group consisting of a hydrogen atom and a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different, and two or more R ⁴ may be bonded to each other to form a ring structure;
R ⁵ is independently selected from the group consisting of a hydrogen atom, a hydroxyl group, and a substituted or unsubstituted organic group having 1 to 18 carbon atoms, all of which may be the same or different, and two or more R ⁵ are May combine with each other to form a ring structure,
Y ⁻ is a 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)
(9) A curable resin comprising the compound according to any one of (1) to (5) above.

(10) A curable resin composition comprising the curable resin described in (9) above.

(11) An epoxy resin composition containing (A) an epoxy resin and (B) a curing agent, wherein the curing agent contains the compound according to any one of (1) to (5) above. An epoxy resin composition characterized by the above.

(12) The epoxy resin composition as described in (11) above, further comprising (C) a curing accelerator.

(13) The epoxy resin composition as described in (11) or (12) above, further comprising (D) an inorganic filler.

(14) The (A) epoxy resin is a biphenyl type epoxy resin, a stilbene type epoxy resin, a diphenylmethane type epoxy resin, a sulfur atom-containing type epoxy resin, a novolac type epoxy resin, a dicyclopentadiene type epoxy resin, or a salicylaldehyde type epoxy resin. (11) to (13), characterized by containing at least one epoxy resin selected from the group consisting of epoxides of copolymerized naphthols and phenols, and aralkyl-type phenol resins. The epoxy resin composition according to any one of the above.

(15) An electronic component device comprising an element sealed with the epoxy resin composition according to any one of (11) to (14).

  The novel compound according to the present invention can be used for various applications as a curable resin. For example, the novel compound according to the present invention is useful as an epoxy resin curing agent, and by constituting an epoxy resin composition using them, a composition having excellent fluidity and curability and low water absorption can be realized. At the same time, good results can be obtained in the glass transition temperature and the high temperature elastic modulus. In particular, by sealing electronic components such as ICs and LSIs using the epoxy resin composition according to the present invention, an electronic component device having excellent heat resistance (high glass transition temperature) and moisture resistance, and high reliability. Therefore, its industrial value is high.

  The present invention will be described in detail below.

  The novel compound according to the present invention is obtained by a reaction between (a) a phenol compound having two or more phenolic hydroxyl groups in the molecule and (b) a specific silane compound having two functional groups capable of reacting with the phenolic hydroxyl group. Reaction product.

The (a) phenol compound that can be used in the present invention is not particularly limited as long as it has two or more phenolic hydroxyl groups in one molecule. For example, a well-known phenol compound can be used as polyhydric phenols. More specifically, compounds having two phenolic hydroxyl groups in one molecule such as resorcin, catechol, hydroquinone, bisphenol A, bisphenol F, substituted or unsubstituted biphenol (namely, dihydric phenol compounds) can be mentioned. In addition, phenols such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde, acetaldehyde, propion A novolak-type phenolic resin obtained by condensation or cocondensation with aldehydes such as aldehyde, benzaldehyde, salicylaldehyde and the like 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;
Examples thereof include a phenol compound having two or more phenolic hydroxyl groups in the molecule, such as a triphenylmethane type phenol resin; and a phenol resin obtained by copolymerizing two or more of the above resins. One of the above phenol compounds may be used alone, or two or more of these compounds may be used in combination.

  The (a) phenol compound having two or more phenolic hydroxyl groups in the molecule (hereinafter referred to as “polyhydric phenol compound”) that can be used in the present invention has a divalent phenol compound content based on the total amount. Preferably, it is 70% by weight or more, more preferably 80% by weight or more, and still more preferably 85% by weight or more. Reaction obtained by reaction when the content of the dihydric phenol compound in the whole polyhydric phenol compound is 70% by weight or less (that is, the content of the compound having 3 or more phenolic hydroxyl groups in the molecule is 30% by weight or more). The viscosity of the product increases and the fluidity of the resin composition decreases. Furthermore, the viscosity of the product itself increases, resulting in inferior handleability, which makes it difficult to produce the compound of the present invention.

On the other hand, a silane compound that can be used in the present invention is a compound represented by the following general formula (I-1), and has two functional groups capable of reacting with a phenolic hydroxyl group.

(In the formula, R ¹ are each independently selected from hydrogen atom and the group consisting of substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different, R ¹ each other May combine to form a ring structure,
R ² represents a functional group capable of reacting with a phenolic hydroxyl group, and each independently represents a halogen atom, a hydroxyl group, a substituted or unsubstituted oxy group having 1 to 18 carbon atoms, or a substituted or unsubstituted group having 0 to 18 carbon atoms. And a group selected from the group consisting of carbonyloxy groups having 2 to 18 carbon atoms, all of which may be the same or different, and R ² may be bonded to each other to form a cyclic structure)
Here, the “substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms” described as R ^{1 in the} general formula (I-1) has 1 to 18 carbon atoms and may be substituted or non-substituted. It is meant to include an aliphatic hydrocarbon group and an aromatic hydrocarbon group which may be substituted.

  More specifically, examples of the substituted or unsubstituted aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and pentyl. Group, hexyl group, octyl group, decyl group, dodecyl group, allyl group, vinyl group and other aliphatic hydrocarbon groups, and alkyl groups, alkoxy groups, aryl groups, hydroxyl groups, amino groups, halogen atoms, glycidyloxy groups , An epoxycyclohexyl group, an epoxy group-containing group, a methacryloxy group, a mercapto group, an imino group, a ureido group, an isocyanate group, and the like.

  The substituted or unsubstituted aliphatic hydrocarbon group also includes a substituted or unsubstituted alicyclic hydrocarbon group. Examples of the substituted or unsubstituted alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group, and the like, and an alkyl group, an alkoxy group, an aryl group, and an aryloxy group. Substituted with a group containing an epoxy group such as a group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, an epoxy group, a methacryloxy group, a mercapto group, an imino group, a ureido group, an isocyanate group, etc. Can be mentioned.

  Examples of the substituted or unsubstituted aromatic hydrocarbon group include aryl groups such as phenyl group and tolyl group, alkyl group-substituted aryl groups such as dimethylphenyl group, ethylphenyl group, butylphenyl group, and tert-butylphenyl group. , Alkoxy group-substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group, etc., and further, alkyl group, alkoxy group, aryl group, aryloxy group, amino group, halogen It may be substituted with an atom, a group containing an epoxy group such as a glycidyloxy group, an epoxycyclohexyl group or an epoxy group, a methacryloxy group, a mercapto group, an imino group, a ureido group or an isocyanate group.

“R ¹ may be bonded to each other to form a cyclic structure” described as R ^{1 in the} general formula (I-1) means that two R ¹ are bonded to each other, and a divalent hydrocarbon group as a whole. Means the case. For example, an alkylene group such as ethylene, propylene, butylene, pentylene and hexylene, which can be bonded to an Si atom to form a cyclic structure, an alkenyl group such as ethylenyl, propylenyl, and butenyl, an aralkylene group such as methylenephenylene and methylenebisphenylene, Examples include arylene groups such as phenylene, naphthylene, anthracenylene, biphenylene, and the like, such as alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, halogen atoms, glycidyloxy groups, epoxycyclohexyl groups, and epoxy groups. It may be substituted with a group containing an epoxy group, a methacryloxy group, a mercapto group, an imino group, a ureido group, an isocyanate group, or the like.

In addition, as R < ¹ > of the said general formula (I-1), although it does not specifically limit, It is preferable that it is a monovalent substituent selected from the group which consists 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, unsubstituted or alkyl group or / and alkoxy group or / and hydroxyl-substituted aryl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group , Sec-butyl, tert-butyl, octyl, cyclohexyl, epoxycyclohexylethyl, glycidoxypropyl, chloropropyl, methacrylate Selected from substituted or unsubstituted chain or cyclic alkyl groups such as oxypropyl group, mercaptopropyl group, aminopropyl group, N-phenylaminopropyl group, N-aminopropylaminopropyl group, ureidopropyl group, isocyanatepropyl group, etc. More preferred is a substituent.

The “halogen atom” described as R ^{2 in the} general formula (I-1) includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The “substituted or unsubstituted oxy group having 1 to 18 carbon atoms” described as R ² in the general formula (I-1) includes, for example, “substituted or unsubstituted aliphatic hydrocarbon having 1 to 18 carbon atoms”. An "oxy group", and a "substituted or unsubstituted aromatic hydrocarbon oxy group having 1 to 18 carbon atoms". More specific examples are as follows.

Examples of the above-mentioned “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- Butoxy group, cyclopropyloxy group, cyclohexyloxy group, cyclopentyloxy group, allyloxy group, vinyloxy group, etc., and the oxy group having a structure in which an oxygen atom is bonded to the aliphatic hydrocarbon group described above as R ¹ And a group substituted with a group, alkoxy group, aryl group, aryloxy group, amino group, halogen atom and the like.

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

Examples of the “substituted or unsubstituted amino group having 0 to 18 carbon atoms” described as R ^{2 in the} general formula (I-1) include, for example, an unsubstituted amino group and a substituted or unsubstituted group having 1 to 18 carbon atoms. An aliphatic hydrocarbon amino group, an aromatic hydrocarbon amino group, a dialiphatic hydrocarbon amino group, a diaromatic hydrocarbon amino group, an aliphatic hydrocarbon aromatic hydrocarbon amino group, and a silylamino group. More specific examples are as follows.

Examples of the “substituted or unsubstituted aliphatic hydrocarbon amino group having 1 to 18 carbon atoms” include, for example, methylamino group, ethylamino group, propylamino group, isopropylamino group, n-butylamino group, sec-butylamino group Group, tert-butylamino group, pentylamino group, hexylamino group, octylamino group, decylamino group, dodecylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, allylamino group, vinylamino group, cyclopentenylamino Group, an amino group substituted by the aliphatic hydrocarbon group described above as R ¹ such as a cyclohexenylamino group, and the aliphatic hydrocarbon group portion of the alkyl group, alkoxy group, aralkyl group, aryl group, hydroxyl group , Amino groups, halogen atoms and the like.

Examples of the “substituted or unsubstituted aromatic hydrocarbon amino group having 1 to 18 carbon atoms” include, for example, phenylamino group, naphthylamino group, tolylamino group, dimethylphenylamino group, ethylphenylamino group, butylphenylamino group, an amino group substituted by an aliphatic hydrocarbon group described above as R ¹ such as tert-butylphenylamino group, methoxyphenylamino group, ethoxyphenylamino group, butoxyphenylamino group, tert-butoxyphenylamino group, and the like; and These aromatic hydrocarbon groups are substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, and the like.

Examples of the “substituted or unsubstituted dialiphatic hydrocarbon amino group having 1 to 18 carbon atoms” include dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, di-n-butylamino group, di-sec. -Butylamino group, di-tert-butylamino group, dicyclopentylamino group, dicyclohexylamino group, dicycloheptylamino group, ethylmethylamino group, methylisopropylamino group, methyl-n-butylamino group, methyl-sec- R ¹ such as butylamino group, methyl-tert-butylamino group, methylcyclohexylamino group, diallylamino group, divinylamino group, dicyclopentenylamino group, dicyclohexenylamino group, allylmethylamino group, etc. An amino group substituted by two aliphatic hydrocarbon groups, and an alkyl group, an alkoxy group; And those substituted with a silyl group, an aralkyl group, an aryl group, a hydroxyl group, an amino group, a halogen atom and the like.

Examples of the “substituted or unsubstituted diaromatic hydrocarbon amino group having 1 to 18 carbon atoms” include diphenylamino group, dinaphthylamino group, ditolylamino group, bis (dimethylphenyl) amino group, and bis (ethylphenyl). Amino group, bis (butylphenyl) amino group, bis (tert-butylphenyl) amino group, bis (methoxyphenyl) amino group, bis (ethoxyphenyl) amino group, bis (butoxyphenyl) amino group, bis (tert-butoxy) An amino group substituted by the two aromatic hydrocarbon groups described above as R ¹ such as a phenyl) amino group, and the like, and an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, etc. Substituted ones are mentioned.

Examples of the "substituted or unsubstituted aliphatic hydrocarbon aromatic hydrocarbon amino group having 1 to 18 carbon atoms", for example, methylphenylamino group, methyl naphthyl group, such as butylphenyl group, above as R ¹ Mention may be made of amino groups substituted by the described aliphatic hydrocarbon groups and aromatic hydrocarbon groups.

Examples of the “substituted or unsubstituted silylamino group having 0 to 18 carbon atoms” include, for example, an unsubstituted silylamino group, trimethylsilylamino group, triethylsilylamino group, triphenylsilylamino group, methyl (trimethylsilyl) amino group, methyl ( Triphenylsilyl) amino group, phenyl (trimethylsilyl) amino group, silyl group such as phenyl (triphenylsilyl) amino group and / or the aliphatic hydrocarbon group and / or aromatic carbonization described above as R ¹ for amino group Examples thereof include a silylamino group substituted with a hydrogen group, and those substituted with an alkyl group, alkoxy group, aryl group, aryloxy group, amino group, halogen atom and the like.

In addition, the “substituted or unsubstituted carbonyloxy group having 2 to 18 carbon atoms” described as R ² in the general formula (I-1) includes, for example, “substituted or unsubstituted aliphatic carbonized group having 2 to 18 carbon atoms”. A "hydrogen carbonyloxy group" and a "substituted or unsubstituted aromatic hydrocarbon carbonyloxy group having 2 to 18 carbon atoms". More specific examples are as follows.

Examples of the “substituted or unsubstituted aliphatic hydrocarbon carbonyloxy group having 1 to 18 carbon atoms” include, for example, a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, and n-butylcarbonyl. As described above as R ¹ such as oxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group, cyclopropylcarbonyloxy group, cyclohexylcarbonyloxy group, cyclopentylcarbonyloxy group, allylcarbonyloxy group, vinylcarbonyloxy group, etc. And the carbonyloxy group of the aliphatic hydrocarbon group, and those substituted with an alkyl group, alkoxy group, aryl group, aryloxy group, amino group, halogen atom and the like.

Examples of the “substituted or unsubstituted aromatic hydrocarbon carbonyloxy group having 1 to 18 carbon atoms” include, for example, phenylcarbonyloxy group, methylphenylcarbonyloxy group, ethylphenylcarbonyloxy group, methoxyphenylcarbonyloxy group, butoxy An oxy group having a structure in which an oxygen atom is bonded to the aromatic hydrocarbon group described above as R ¹ such as a phenylcarbonyloxy group, a phenoxyphenylcarbonyloxy group, and the like, and an alkyl group, an alkoxy group, an aryl group, an aryloxy group Examples thereof include those substituted with a group, amino group, halogen atom and the like.

In addition, “R ² may be bonded to each other to form a cyclic structure” described as R ² in the general formula (I-1) means that two R ² are bonded to each other and are each divalent as a whole. It means the case where it becomes an organic group. For example, a divalent organic group (indicated by R ⁶ in the formula) that becomes a cyclic silane compound as represented by the following general formula (I-1a) can be mentioned. In the case of a cyclic silane compound in which q is 1 in the following general formula (I-1a), R ⁶ has two reaction points, and therefore can react with two phenolic hydroxyl groups per molecule of the silane compound. Yes, R ⁶ H ₂ will be produced as a by-product. When q is 2 or more in the following general formula (I-1a), a silane compound having a cyclic structure composed of q repeating units of Si and an organic group is obtained. In this case, the silane compound composed of q repeating units corresponds to q silane compound molecules of the general formula (I-1).

(In the formula, R ¹ are each independently a hydrogen atom, and selected from the group consisting of substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different, R ¹ is May combine with each other to form a ring structure,
R ⁶ is selected from a divalent organic group having 0 to 18 carbon atoms, each having an oxygen atom, a nitrogen atom or a carbonyloxy group,
q shows the integer of 1-6. )
As a more specific example, when R < ² > group is a silylamino group and forms a cyclic structure, the cyclic silane compound shown by the following general formula (I-1b) is mentioned. As described above, when p is 2 or more in the following general formula (I-1b), a silane compound having a cyclic structure composed of p repeating units of Si and N is obtained. In this case, the silane compound composed of p repeating units corresponds to p silane compound molecules of the general formula (I-1).

(In the formula, R ¹ are each independently a hydrogen atom, and selected from the group consisting of substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different, R ¹ is May combine with each other to form a ring structure,
R ⁷ is selected from the group consisting of a hydrogen atom and a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms;
p represents an integer of 2 to 6)
Examples of the “divalent organic group having 0 to 18 carbon atoms in which both sides are an oxygen atom, a nitrogen atom or a carbonyloxy group” described as R ^{6 in the} general formula (I-1a) include, for example, 1 to 18 carbon atoms. A dioxy group having two oxygen atoms on both sides, a diamino group having 1 to 18 carbon atoms and two divalent amino groups, a divalent amino group having 0 to 18 carbon atoms, and both sides having 3 to 18 carbon atoms A dicarboxy group in which is a carboxyloxy group.

  Examples of the “dioxy group having 1 to 18 carbon atoms and divalent oxygen atoms on both sides” include, for example, methylenedioxy group, ethylenedioxy group, propylenedioxy group, alkylenedioxy group such as oxapentylenedioxy, Arylene dioxy group such as phenylenedioxy group, naphthylene dioxy group, anthracenylene dioxy group, biphenylene dioxy group, aralkyl dioxy group such as methylene phenylene dioxy group, and these are alkyl group, alkoxy group, aryl group , Aryloxy group, amino group, halogen atom and the like.

  Examples of the “diamino group having 1 to 18 carbon atoms and two divalent nitrogen atoms” include, for example, a methylenediamino group, an ethylenediamino group, a propylenediamino group, an oxapentylenediamino, a methylenedi (methylamino) group, an ethylenedi ( (Ethylamino) group, alkylene diamino group such as propylene (dimethylamino) group, phenylene diamino group, naphthylene diamino group, anthracenylene diamino group, biphenylene diamino group, phenylene di (methylamino) group, biphenylene di (methylamino) And arylalkylamino groups such as methylenephenylenediamino groups, and those substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, and the like.

  Examples of the “divalent amino group having 0 to 18 carbon atoms” include divalent substituted or unsubstituted amino groups such as —NH—, —N (Me) —, —N (Et) —, and the like. 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 “dicarbonyloxy group having 1 to 18 carbon atoms and divalent carbonyloxy groups on both sides” include alkylene dicarbonyloxy such as methylene dicarbonyloxy, ethylene dicarbonyloxy, propylene dicarbonyloxy, etc. Groups, phenylene dicarbonyloxy groups, naphthylene dicarbonyloxy groups, anthracenylene dicarbonyloxy groups, arylene dicarbonyloxy groups such as biphenylene dicarbonyloxy groups, aralkyl dicarbonyloxy groups such as methylenephenylene dicarbonyloxy groups, and the like Are substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, or the like.

R ^{2 in the} general formula (I-1) is not particularly limited. However, since it is easily available, it is a substituted or unsubstituted monovalent having a chlorine atom, a hydroxyl group, or a carbon number of 1 to 8. An oxy group or a substituent such as a substituted or unsubstituted monovalent carbonyloxy group having 2 to 8 carbon atoms, and the general formula (I-1) as a whole is represented by the general formula (I-1a), and R ⁶ is a carbon number A dioxy group having 1 to 8 divalent oxygen atoms on both sides or a divalent amino group having 1 to 8 carbon atoms and q being 1 to 4 is preferable. R ² is, among other things, from the viewpoint of reactivity, a substituent such as a chlorine atom, a hydroxyl group, an oxy group having 1 to 8 carbon atoms, a carbonyloxy group having 2 to 8 carbon atoms, and the general formula (I-1) as a whole A substituent represented by the general formula (I-1b), in which R ⁶ is a hydrogen atom and p is 2 to 4, is more preferable. In consideration of the influence on the long-term reliability of a cured product obtained by using the compound according to the present invention as an epoxy resin curing agent, it is more preferable that at least one of R ² is a hydroxyl group or an oxy group having 1 to 8 carbon atoms. .

Examples of the specific compound of the general formula (I-1) are not limited to the following, but are substituted or unsubstituted diaryldiaryl such as diphenyldimethoxysilane, diphenyldiethoxysilane, and dimesityldimethoxysilane. Alkoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, diethyldiethoxysilane, decylmethyldiethoxysilane, dicyclopentyldimethoxysilane, divinyldiethoxysilane, vinylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxy Substituted or unsubstituted dialkyl dialkoxysilanes such as silane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, phenylmethyldiethoxysilane, Substituted or unsubstituted arylalkyldialkoxysilanes such as rudimethoxysilane and vinylphenyldiethoxysilane, substituted or unsubstituted diarylsilanediols such as diphenylsilanediol, diphenyldichlorosilane, ditolyldichlorosilane, and dimesityldichlorosilane Substituted or unsubstituted dialkyldichlorosilanes such as diaryldichlorosilane, dimethyldichlorosilane, dodecylmethyldichlorosilane, divinyldichlorosilane, diisopropyldichlorosilane, etc., substituted or unsubstituted arylalkyl such as phenylethyldichlorosilane, phenylmethyldichlorosilane, etc. Dialkyldiacetoxysilane such as dichlorosilane and dimethyldiacetoxysilane, bis (dimethylamino) dimethylsilane, bis (dimethylamino) die Substituted or unsubstituted dialkyldiaminosilane such as tilsilane, substituted or unsubstituted diaryldiaminosilane such as bis (dimethylamino) diphenylsilane, phenylmethylbis (dimethylamino) silane, hexamethylcyclotrisilazane and the like (I- Examples thereof include compounds represented by 1b) and dialkylalkoxychlorosilanes such as dimethylmethoxychlorosilane. All of these specific examples are available as industrial products or reagents. The compound represented by the general formula (I-1) may be a commercially available compound as an industrial product or a reagent, or may be a compound synthesized by a known method. Among these silane compounds, a silane compound in which R ² is an oxy group is preferable from the viewpoint of long-term stability of a cured product, long-term reliability of an electronic component, and the like.

Another embodiment of the novel compound according to the present invention is characterized in that it contains at least one structural unit represented by the following general formula (I-2). The structural unit represented by the following general formula (I-2) has, for example, (a) a phenol compound having two or more phenolic hydroxyl groups in the molecule, and (b) two functional groups capable of reacting with the phenolic hydroxyl groups. It is formed by reaction with a specific silane compound.

(In the formula, R ¹ are each independently selected from hydrogen atom and the group consisting of substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different, R ¹ each other May combine to form a ring structure,
Ar is a divalent organic group having 2 to 30 carbon atoms and a group derived from an aromatic cyclic compound on both sides)
The novel compound according to the present invention preferably includes a compound having a structure represented by the following general formula (I-3) among the compounds having a repeating unit represented by the above general formula (I-2).

In addition, n repeating units in the following general formula (I-3) are derived, for example, by self-condensation of a silane compound.

(In the formula, R ¹ are each independently selected from hydrogen atom and the group consisting of substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different, R ¹ each other May combine to form a ring structure,
Ar is a divalent organic group having 2 to 30 carbon atoms and a group derived from a cyclic compound having aromaticity on both sides,
Each R ³ independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms and —Ar—OH (wherein Ar has 2 to 30 carbon atoms and is aromatic; Are selected from the group consisting of a group derived from a cyclic compound showing a divalent organic group on both sides, and all may be the same or different,
m represents a number of 1 or more, n represents a number of 0 or more, and the repetition of m units and n units may be block, alternating, or random)
In the above general formulas (I-2) and (I-3), “m” represents a number of 1 or more, preferably 1 to 40 on average, more preferably 1 to 20, and still more preferably 1 to 15. It is. “N” in the general formula (I-3) represents a number of 0 or more, preferably 0 to 20, more preferably 0 to 10, and still more preferably 0 to 5. The repeating pattern of m units and n units may be a block, alternating, or random. However, from the viewpoint of fluidity, the average of (m + n / 2) is preferably in the range of 1-50, more preferably in the range of 1-25, and in the range of 1-15. Further preferred. When the average value exceeds 50, the melt viscosity of the compound tends to be too high. Therefore, for example, when these compounds are used as an epoxy resin curing agent, the viscosity at the time of melt molding of the epoxy resin composition also increases, causing unfilled defects and deformation of the bonding wire (gold wire connecting the element and the lead). It becomes easy.

In addition, the “substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms” described as R ^{1 in the} general formulas (I-2) and (I-3) and “R ¹ are bonded to each other to form a cyclic structure. The meaning of “may be formed” is as described above. In addition, the meaning of the “substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms” described as R ^{3 is the same} as that described above for R ¹ .

  The divalent organic group described as Ar in the above general formulas (I-2) and (I-3) having a group derived from a cyclic compound having 2 to 30 carbon atoms and showing aromaticity on both sides `` Is not particularly limited, for example, phenylene group, naphthylene group, anthracenylene group, biphenylene group, binaphthylene group, methylene bisphenylene group, methylene bisnaphthylene group, oxybisphenylene group, sulfonyl bisphenylene group, 2 having a bivalent organic group having an aryl group such as a thiobisphenylene group on both sides and a heterocyclic group such as furanylene, thiophenylene, imidazolylene, methylenebisfurylene, methylenebisthiophenylene, methylenebisimidazolylene on both sides Organic groups such as divalent organic groups, divalent organic groups having an aryl group on one side and a heterocyclic group on the other. .

The “—O—Ar—O—” moiety in formulas (I-2) and (I-3) is, for example, the general formula, HO—Ar—OH (wherein Ar is as described above). It is possible to derive from the dihydric phenol compounds shown. Specific examples of the “—O—Ar—O—” moiety include a substituent represented by the following general formula (I-5).

(Wherein R ⁷ represents a divalent organic group having 0 to 18 carbon atoms,
R ⁸ is selected from the group consisting of a hydrogen atom and a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different, and two or more R ⁸ are bonded to each other to form a cyclic structure (However, in the case where two or more R ⁸ are bonded to form a cyclic structure and are conjugated with the benzene ring to which R ⁸ is bonded and have aromaticity, the —O— moiety is R ⁷ may be bonded to the benzene ring to which R ⁷ is bonded, and may be bonded to R ⁸ having aromaticity).
q represents 0 or 1, and r represents a number of 0 or more)
The “divalent organic group having 0 to 18 carbon atoms” described as R ^{7 in the} general formula (I-5) is not particularly limited, and examples thereof include an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group, and a carbon number. Examples thereof include 1 to 18 divalent hydrocarbon groups. The divalent hydrocarbon group having 1 to 18 carbon atoms is not particularly limited, and examples thereof include aliphatic hydrocarbon groups such as a methylene group, an ethylene group, a propylene group, a cyclohexylene group, a cyclopentylene group, and the like. An alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, an aromatic group substituted with a halogen atom, etc., an aromatic hydrocarbon group such as a phenylene group, a naphthylene group, an anthracenylene group and the like, and an alkyl group, an alkoxy group, an aryl group , Aryloxy group, amino group, halogen atom and the like.

  Among these, from the viewpoint of availability, an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group, an alkylene group, a cyclohexylene group, a cyclopentylene group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group Are preferred, oxygen atom, sulfur atom, sulfinyl group, sulfonyl group, methylene group, methylmethylene group, isopropylmethylene group, phenylmethylene group, cyclohexylmethylene group, dimethylmethylene group, methyldiisopropylmethylmethylene group, methyl A phenylmethylene group, a cyclohexylene group, a cyclopentylene group, and a cyclopentylene group are more preferable.

The “substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms” described as R ^{8 in the} general formula (I-5) has, for example, 1 to 18 carbon atoms and is substituted or unsubstituted. It is meant to include aliphatic hydrocarbon groups and aromatic hydrocarbon groups.

  More specifically, examples of the substituted or unsubstituted aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and pentyl. Group, hexyl group, octyl group, decyl group, dodecyl group, allyl group, vinyl group and other aliphatic hydrocarbon groups, and those substituted with alkyl groups, alkoxy groups, aryl groups, hydroxyl groups, amino groups, halogen atoms, etc. The thing which was done is mentioned.

  The substituted or unsubstituted aliphatic hydrocarbon group also includes a substituted or unsubstituted alicyclic hydrocarbon group. Examples of the substituted or unsubstituted alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group, and the like, and an alkyl group, an alkoxy group, an aryl group, and an aryloxy group. Examples thereof include those substituted with a group, a hydroxyl group, an amino group, a halogen atom, and the like.

  Examples of the substituted or unsubstituted aromatic hydrocarbon group include aryl groups such as phenyl group and tolyl group, alkyl group-substituted aryl groups such as dimethylphenyl group, ethylphenyl group, butylphenyl group, and tert-butylphenyl group. , Alkoxy group-substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group, and the like, which further include alkyl group, alkoxy group, aryl group, aryloxy group, amino group, halogen atom Or the like may be substituted.

The term “two or more R ^8s may be bonded to each other to form a cyclic structure” described as R ^{8 in the} general formula (I-5) means that two R ^8s are bonded to each other and are divalent as a whole. Means a hydrocarbon group. For example, when two or more R ⁸ are bonded to form a cyclic structure and are conjugated to the benzene ring to which R ⁸ is bonded and have aromaticity, R ⁸ is combined with the benzene ring to which they are bonded to form naphthalene. Examples thereof include organic groups that form polycyclic aromatic rings such as rings, anthracene rings, and phenanthrene rings, and those 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.

In addition, after “provided” described as R ⁸ in the general formula (I-5), “two or more R ⁸ are bonded to form a cyclic structure, and R ⁷ is conjugated with a substituted benzene ring, When it has aromaticity, the —O— moiety is not on the ring to which R ⁷ is bonded, but is conjugated to the benzene ring to which R ⁷ is bonded, and bonded to R ⁸ having aromaticity. “It may be” means, for example, that an —O— moiety may be bonded to any position of positions 5 to 8 with respect to R ⁷ substituted at position 1 or 2 of the naphthalene ring. ing.

R ⁸ is preferably a monovalent substituent selected from a hydrogen atom, an alkyl group, and an aryl group. Among these, from the viewpoint of easy availability of raw materials, hydrogen atom, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group , Etc., unsubstituted or alkyl group or / and alkoxy group substituted aryl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, octyl group, cyclohexyl group, etc. A substituent selected from an unsaturated aliphatic hydrocarbon group such as a linear or cyclic alkyl group, an allyl group, or a vinyl group is more preferable, a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a butyl group, or a tert-butyl group. More preferred are a cyclohexyl group, a phenyl group, a benzyl group, and a vinyl group.

  “R” in the general formula (I-5) represents a number of 0 or more, preferably 0 to 10, more preferably 0 to 5, and still more preferably 0 to 3 from the viewpoint of the viscosity of the composition.

The method for producing a novel compound according to the present invention is for producing a compound represented by the above general formula (I-2) or (I-3). And (b) a step of reacting a silane compound represented by the following general formula (I-1) having two functional groups capable of reacting with a phenolic hydroxyl group.

(In the formula, R ¹ are each independently selected from hydrogen atom and the group consisting of substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different, R ¹ each other May combine to form a ring structure,
R ² represents a functional group capable of reacting with a phenolic hydroxyl group, and each independently represents a halogen atom, a hydroxyl group, a substituted or unsubstituted oxy group having 1 to 18 carbon atoms, or a substituted or unsubstituted group having 0 to 18 carbon atoms. And a group selected from the group consisting of carbonyloxy groups having 2 to 18 carbon atoms, all of which may be the same or different, and R ² may be bonded to each other to form a cyclic structure)
In the production method according to the present invention, the reaction between (a) the polyhydric phenol compound and (b) the silane compound is not particularly limited as long as it is a method that produces the target compound. Moreover, in the manufacturing method by this invention, the ratio of (a) polyhydric phenol compound and (b) silane compound is not specifically limited in the range in which reaction advances and the target compound is obtained. For example, the ratio of the phenolic hydroxyl group in (a) to the R ² group in (b) (ie, [number of hydroxyl groups of polyhydric phenol compound] / [number of R ² groups in silane compound of (b)]) is 0. It is preferably between 1 and 10, more preferably between 0.2 and 5, and even more preferably between 0.4 and 2.5. When the ratio is less than 0.1, unreacted R ² groups tend to remain, the usefulness of the reaction product as an epoxy curing agent decreases, and voids are generated in the cured product and long-term reliability. There is a tendency to lead to a decline. When the ratio of [number of hydroxyl groups of the polyhydric phenol compound] / [number of R ² groups in the silane compound of (b)] exceeds 10, the usefulness of the reaction product as an epoxy resin curing agent decreases, The property of low water absorption tends to decrease.

Further, in the production method according to the present invention, the reaction rate between (a) the polyhydric phenol compound and (b) the silane compound is not particularly limited, but it is unreacted based on the number of R ² groups in the starting material. preferably R ² groups is not more than 30% of, more preferably 20% or less, more preferably 10% or less. Based on the R ² groups of the starting material, the number of R ² groups of more than 30% the unreacted usefulness as epoxy curing agent of the reaction product decreases, occurs and the long-term reliability of the voids of the cured product There is a tendency to lead to a decline.

In the production method according to the present invention, R ² H is produced as a by-product of the reaction between the above (a) and (b) together with the target compound. Therefore, it is preferable that the production method according to the present invention includes a step of removing R ² H from the reaction product by heating as necessary. More specific examples are as follows:
When (a) a polyhydric phenol compound is reacted with (b) a silane compound in which R ² is a halogen atom, a by-product is obtained by heating and / or vacuum distillation, washing, filtration, etc. as necessary. Removing hydrogen halide from
When (a) a polyhydric phenol compound is reacted with (b) a silane compound in which R ² is a hydroxyl group, by-products of the by-products are obtained by heating and / or distillation under reduced pressure, washing, filtration, etc. as necessary. Remove water;
When (a) a polyhydric phenol compound is reacted with (b) a silane compound in which R ² is an oxy group, a by-product is obtained by heating and / or vacuum distillation, washing, filtration, etc., as necessary. Removing alcohols or arylols of
When (a) a polyhydric phenol compound and (b) a silane compound in which R ² is an amino group or a silane compound represented by the general formula (I-1b) are reacted, heating and / or as necessary By-product ammonia or amine is removed by distillation under reduced pressure, washing, filtration, etc .;
When (a) a polyhydric phenol compound is reacted with (b) a silane compound in which R ² is a carbonyloxy group, by-products are produced by heating and / or vacuum distillation, washing, filtration, etc., as necessary. The product carboxylic acid is removed.

Although not particularly limited, R ² is preferably an oxy group from the viewpoint of long-term reliability of a cured product obtained by using a compound generated by the reaction as an epoxy resin curing agent. From the viewpoint of easy removal of R ² H as a product, R ² is preferably an alkoxy group having 1 to 3 carbon atoms.

  In the production method according to the present invention, a catalyst may be used as necessary in order to promote the reaction between (a) and (b). When the reaction proceeds without a catalyst, it is preferable to carry out the reaction without using a catalyst. However, it is preferable to use a catalyst not only when the reaction does not proceed, but also when the reaction proceeds slowly. The catalyst that can be used is not limited as long as the reaction is promoted. Preferred catalysts include, for example, 1,5-diazabicyclo [4.3.0] nonene-5, 1,8-diazabicyclo [5]. 4.0] cycloamidine compounds such as diazabicycloalkenes such as undecen-7, 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-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1 Intramolecular polarization formed by adding a quinone compound such as 1,4-benzoquinone or a compound having a π bond such as diazophenylmethane Compound; Tertiary amines such as pyridine / triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives; 2-methylimidazole, 2-phenylimidazole, 2 -Imidazoles such as phenyl-4-methylimidazole and 2-heptadecylimidazole; Tetra-substituted phosphonium and tetrasubstituted borates such as tetraphenylphosphonium and tetraphenylborate; 2-ethyl-4-methylimidazole and tetraphenylborate, N- Tetraphenylboron salts such as methylmorpholine and tetraphenylborate; triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphate Sphin, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris Organic phosphines such as (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine; complexes of these organic phosphines with organic borons; anhydrous with these organic phosphines Maleic acid, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzo Quinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, quinone compounds such as phenyl-1,4-benzoquinone, and π bonds such as diazophenylmethane A compound having intramolecular polarization formed by adding an organic compound; these organic phosphines and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4 -Iodophenol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo- 3,5-dimethylphenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, A compound having intramolecular polarization obtained by reacting a halogenated phenol compound such as 6-bromo-2-naphthol and 4-bromo-4'-hydroxybiphenyl and then dehydrohalogenating (Japanese Patent Laid-Open No. 2004-2006) No. 156035 and JP-A No. 2004-156036). Among these, it is more preferable to use a phosphonium compound represented by the general formula (I-4) or an intermolecular salt thereof as a catalyst.

The production method according to the present invention does not particularly limit the combination of the silane compound and the catalyst to be used, but the simplicity of the reaction, the long-term stability of the cured product achieved by using the reaction product, and the long-term reliability of the electronic component From the viewpoint of properties, etc., the phosphonium compound represented by the following general formula (I-4) or an intermolecular salt thereof is used as a catalyst, or a polyphenol compound and R of the general formula (I-1) are used without using a catalyst. It is preferable to carry out by reacting with a silane compound in which ² is an oxy group and heating to 80 ° C. to 300 ° C. to remove alcohol as a by-product. From the viewpoint of easy removal of R ² H as a by-product, R ² is more preferably an alkoxy group having 1 to 3 carbon atoms.

Wherein R ⁴ is independently selected from the group consisting of a hydrogen atom and a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different, and two or more R ⁴ may be bonded to each other to form a ring structure;
R ⁵ is independently selected from the group consisting of a hydrogen atom, a hydroxyl group, and a substituted or unsubstituted organic group having 1 to 18 carbon atoms, all of which may be the same or different, and two or more R ⁵ are May combine with each other to form a ring 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)
The “substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms” described as R ⁴ in the above general formula (I-4) has 1 to 18 carbon atoms and may be substituted or unsubstituted. Is meant to include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

  More specifically, examples of the substituted or unsubstituted aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and pentyl. Group, hexyl group, octyl group, decyl group, dodecyl group, allyl group, vinyl group and other aliphatic hydrocarbon groups, and those substituted with alkyl groups, alkoxy groups, aryl groups, hydroxyl groups, amino groups, halogen atoms, etc. The thing which was done is mentioned.

  The substituted or unsubstituted aliphatic hydrocarbon group also includes a substituted or unsubstituted alicyclic hydrocarbon group. Examples of the substituted or unsubstituted alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group, and the like, and an alkyl group, an alkoxy group, an aryl group, and an aryloxy group. Examples thereof include those substituted with a group, a hydroxyl group, an amino group, a halogen atom, and the like.

  Examples of the substituted or unsubstituted aromatic hydrocarbon group include aryl groups such as phenyl group and tolyl group, alkyl group-substituted aryl groups such as dimethylphenyl group, ethylphenyl group, butylphenyl group, and tert-butylphenyl group. , Alkoxy group-substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group, etc., and further, alkyl group, alkoxy group, aryl group, aryloxy group, amino group, halogen It may be substituted with an atom or the like.

The term “two or more R ^4s may be bonded to each other to form a cyclic structure” described as R ^{4 in the} general formula (I-4) means that two or three R ^4s are bonded to each other as a whole. The case where it becomes a bivalent or trivalent hydrocarbon group is meant. For example, alkylene groups such as ethylene, propylene, butylene, pentylene, hexylene, etc., alkenyl groups such as ethylenyl, propylenyl, butyrenyl groups, aralkylene groups such as methylenephenylene groups, phenylene, naphthylene, etc. And an arylene group 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.

In addition, although it does not specifically limit as R < ⁴ > of the said general formula (I-4), It is preferable that it is a monovalent substituent selected from the group which consists 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, unsubstituted or alkyl group or / and alkoxy group or / and hydroxyl-substituted aryl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group Substituents selected from chain or cyclic alkyl groups such as sec-butyl group, tert-butyl group, octyl group and cyclohexyl group are more preferred. 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 or / and an alkoxy group or / and a hydroxyl group-substituted aryl group.

The “substituted or unsubstituted organic group having 1 to 18 carbon atoms” described as R ^{5 in the} above general formula (I-4) has 1 to 18 carbon atoms and is substituted or unsubstituted. Aliphatic hydrocarbon group, aromatic hydrocarbon group, aliphatic hydrocarbon or aromatic hydrocarbon oxy group, aliphatic hydrocarbon or aromatic hydrocarbon carbonyl group, aliphatic hydrocarbon or aromatic hydrocarbon oxy It is meant to include those in which a carbonyl group and an aliphatic hydrocarbon or aromatic hydrocarbon carbonyloxy group are bonded.

More specifically, the substituted or unsubstituted aliphatic hydrocarbon group and aromatic hydrocarbon group are as described above for R ⁴ .

  Examples of the aliphatic hydrocarbon oxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, cyclopropyloxy group, cyclohexyloxy group, and cyclopentyl. A group having a structure in which an oxygen atom is bonded to the above-mentioned aliphatic hydrocarbon group such as an oxy group, an allyloxy group, a vinyloxy group, and the like, and an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, etc. And those substituted with. Examples of the aromatic hydrocarbon oxy group include a structure in which an oxygen atom is bonded to the above aromatic hydrocarbon group such as a phenoxy group, a methylphenoxy group, an ethylphenoxy group, a methoxyphenoxy group, a butoxyphenoxy group, and a phenoxyphenoxy group. And the like, and those substituted with an alkyl group, alkoxy group, aryl group, aryloxy group, amino group, halogen atom and the like.

  Examples of the carbonyl group include aliphatic hydrocarbon carbonyl groups such as formyl group, acetyl group, ethylcarbonyl group, butyryl group, cyclohexylcarbonyl group, and allylcarbonyl, and aromatic hydrocarbons such as phenylcarbonyl group and methylphenylcarbonyl group. Examples thereof include carbonyl groups and the like, and those substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, and the like.

  Examples of the oxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, allyloxycarbonyl group, cyclohexyloxycarbonyl group and other aliphatic hydrocarbon oxycarbonyl groups, phenoxycarbonyl group, methylphenoxycarbonyl group and the like. Aromatic hydrocarbon oxycarbonyl groups and those substituted with an alkyl group, alkoxy group, aryl group, aryloxy group, amino group, halogen atom and the like can be mentioned.

  Examples of the carbonyloxy group include an aliphatic hydrocarbon carbonyloxy group such as a methylcarbonyloxy group, an ethylcarbonyloxy group, a butylcarbonyloxy group, an allylcarbonyloxy group, a cyclohexylcarbonyloxy group, a phenylcarbonyloxy group, and a methylphenyl group. Aromatic hydrocarbon carbonyloxy group such as carbonyloxy group and the like, and those substituted with alkyl group, alkoxy group, aryl group, aryloxy group, amino group, halogen atom and the like can be mentioned.

The "may also form a 2 or more R ⁵ is ring structure by bonding with each other" the general formula (I-4) with terms described as R ⁵ in, bonded to two to four R ^5, as a whole It means a case where each becomes a divalent to tetravalent organic group. For example, an alkylene group such as ethylene, propylene, butylene, pentylene and hexylene, which can form a cyclic structure, an alkenyl group such as ethylenyl, propylenyl and butyrenyl groups, an aralkylene group such as a methylenephenylene group, and an arylene group such as phenylene, naphthylene and anthracenylene , An alkylene group, an alkenyl group, an aralkylene group, an arylene group, an oxy group or a dioxy group, which is 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. May be.

R ^{5 in the} general formula (I-4) is not particularly limited, but 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 chain- or cyclic alkyl such as alkoxy group or / and hydroxyl-substituted aryl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, octyl group, cyclohexyl group, etc. A substituent selected from the group is more preferable. In the case where two or more R ⁵ are bonded to each other to form a cyclic structure, there is no particular limitation, but in combination with the benzene ring to which R ⁵ is bonded, a 1-(-2-hydroxynaphthyl) group, 1- ( Organic groups that form polycyclic aromatic groups such as a (-4-hydroxynaphthyl) group are preferred.

Y ⁻ in the general formula (I-4) 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 ² 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, a hydroxy group Examples thereof include groups 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 thienyl group and a hydroxypyridyl group.

In addition, when Y ⁻ in the general formula (I-4) is bonded to one or more R ⁵ to form a cyclic structure, for example, Y ⁻ is 2 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-(-6-hydroxynaphthyl) group.

Previously illustrated Y ^- among, but are not limited to, oxygen anion proton from the hydroxyl group is eliminated, or hydroxyphenyl group, hydroxyphenyl methyl group, hydroxynaphthyl group, hydroxy furyl group, hydroxy thienyl group It is preferably a monovalent organic group having an oxygen anion formed by removing a proton from a phenolic hydroxyl group such as a hydroxypyridyl group.

In addition, when Y ⁻ in the general formula (I-4) is bonded to one or more R ⁵ to form a cyclic structure, for example, Y ⁻ is 2 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 a-(-6-hydroxynaphthyl) group is preferable.

  Further, the intermolecular salt of the phosphonium compound represented by the general formula (I-4) is not limited, but the phosphonium compound represented by the formula (I-4) and phenol, naphthol, 2 in the molecule. Compounds having phenolic hydroxyl groups such as the compounds exemplified above as phenol compounds having the above phenolic hydroxyl groups, compounds having silanol groups such as triphenylsilanol, diphenylsilanediol, trimethylsilanol, oxalic acid, acetic acid, benzoic acid, etc. And intermolecular salt compounds with organic acids, inorganic acids such as hydrochloric acid, hydrogen bromide, sulfuric acid and nitric acid.

  Specific examples of the phosphonium compound represented by the general formula (I-4) are not limited to the following, but include tris- (p-methoxyphenyl) phosphine and tris- (o-methoxyphenyl) phosphine. , Tri-p-tolylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, bis- (p-methoxyphenyl) phenylphosphine, bis- (o-methoxyphenyl) phosphine, di-p-tolylphenylphosphine Di-o-tolylphenylphosphine, di-m-tolylphenylphosphine, diphenyl- (p-methoxyphenyl) phosphine, diphenyl- (o-methoxyphenyl) phosphine, diphenyl-p-tolylphosphine, diphenyl-o-tolylphosphine Diphenyl-m-tolylphosphine, Triarylphosphine such as phenylphosphine, trialkylphosphine such as tricyclohexylphosphine, tributylphosphine and trioctylphosphine, alkyldiarylphosphine such as cyclohexyldiphenylphosphine, octyldiphenylphosphine, dibutylphenylphosphine, dicyclohexylphenylphosphine, dioctyl Tertiary phosphine such as phenylalkylphosphine and the like, 1,4-benzoquinone, methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4benzoquinone, 2,5-dimethoxy-1,4-benzoquinone, Methoxy-1,4-benzoquinone, 2,3-dimethyl-1,4-benzoquinone, 2,5-dimethyl-1,4-benzoquinone, Addition of til-1,4-benzoquinone, 2,5-di-t-butyl-1,4-benzoquinone, t-butyl-1,4-benzoquinone, phenyl-1,4-benzoquinone, 1,4-naphthoquinone, etc. Reaction products, and these tertiary phosphines and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodination Phenol, 2-iodophenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4- Bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromine A compound having intramolecular polarization obtained through a dehydrohalogenation step after reacting with a halogenated phenol compound such as mo-2-naphthol or 4-bromo-4'-hydroxybiphenyl (Japanese Patent Laid-Open No. 2004-156035) Publication and Unexamined-Japanese-Patent No. 2004-156036).

Among these, from the availability of raw materials and the stability of the phosphonium compound represented by the general formula (I-4), an addition reaction product of triphenylphosphine and 1,4-benzoquinone, tri-p-tolylphosphine, 1,4-benzoquinone addition reaction product, tris- (p-methoxyphenyl) phosphine and 1,4-benzoquinone addition reaction product, diphenyl-p-tolylphosphie and 1,4-benzoquinone addition reaction product, tributylphosphine and 1 , 4-Benzoquinone addition reaction product, tricyclohexylphosphine and 1,4-benzoquinone addition reaction product, cyclohexyldiphenylphosphine and 1,4-benzoquinone addition reaction product, dicyclohexylphenylphosphine and 1,4-benzoquinone addition reaction product Manufactured in Synthesis Examples 1 to 9 of JP-A No. 2004-156035 (XXIX) a compound represented by the structure according to ~ (XXXVII) is preferred.

  The compound according to the present invention can be used in various applications as a curable resin that can be cured by reacting with the compound alone or with other resins. For example, it can be used for applications such as molding materials such as sealing materials, laminated plate materials, various adhesive materials, various electronic and electrical component materials, and coating materials. When the compound according to the present invention is used as a curable resin, alone or other curable properties such as epoxy resin, phenol resin, isocyanate resin, urethane resin, unsaturated polyester resin, melamine resin, silicone resin, allyl resin, alkyd resin, etc. It can be used in combination with a resin to constitute a curable resin composition. For example, since the compound according to the present invention is useful as an epoxy resin curing agent, it can be combined with an epoxy resin and, if necessary, other components that accelerate the curing of the epoxy resin into an epoxy resin composition. .

  The epoxy resin composition according to the present invention contains (A) an epoxy resin and (B) a curing agent, and (B) the curing agent contains the novel compound according to the present invention described above. Features. The epoxy resin composition according to the present invention may further contain (C) a curing accelerator and (D) an inorganic filler in the components (A) and (B). Moreover, what added various additives, such as a coupling agent, an ion exchanger, a mold release agent, a stress relaxation agent, a flame retardant, and a coloring agent, may be added as needed. Hereinafter, main components constituting the epoxy resin composition according to the present invention will be described.

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

  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, An epoxidized product of an aralkyl type phenol resin such as a salicylaldehyde type epoxy resin, a copolymer type epoxy resin of naphthols and phenols, a phenol aralkyl resin, or a naphthol aralkyl resin is preferable, and any one of them may be used alone. Two or more kinds may be used in combination. However, in order to exhibit these performances, it is preferable to use them in total of 30% by weight or more, more preferably 50% by weight or more, based on the total amount of epoxy resin. Specific examples of preferable epoxy resins are shown below.

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 atom is substituted in R ⁸ are 4 and 4 'positions, and the 3, 3', 5, 5 'positions are methyl groups. YX-4000H (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), which is a hydrogen atom, and 4,4′-bis (2,3-epoxypropoxy) biphenyl, in which all R ⁸ are hydrogen atoms, and all R ⁸ are In the case of a hydrogen atom, and when the positions where oxygen atoms are substituted in R ⁸ are the 4 and 4 'positions, the 3, 3', 5, 5 'positions are methyl groups, and the rest are hydrogen atoms YL-6121H (trade name of Japan Epoxy Resin Co., Ltd.), which is a mixed product, is available as a commercial product.

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

  The stilbene type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton, but an epoxy resin represented by the following 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 others are hydrogen atoms and R ESLV-210 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), which is a mixture when all ¹⁰ are hydrogen atoms, is available as a commercial product.

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

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

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

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

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

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 novolac type phenol resin such as phenol novolak, cresol novolak, naphthol novolak or the like is glycidyl etherified or the like. Epoxy resins epoxidized using a technique are preferable, and for example, epoxy resins represented by the following general formula (VI) are more preferable. Among the epoxy resins represented by the following general formula (VI), ESCN-190 and ESCN-195 (trade names, manufactured by Sumitomo Chemical Co., Ltd.), in which all of R ¹⁴ are hydrogen atoms, R ¹⁵ is a methyl group and i = 1. Etc. are available as commercial products.

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

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

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

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

(In the formula (IX), R ^{19 to} R ²¹ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 0 to 3, j is An integer of 0 to 2, k represents an integer of 0 to 4, p represents an average value of 0 to 1 and l and m each represents an average value of 0 to 11 and (l + m) is 1 to 11 is a positive number)
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 ⁴⁰ is a hydrogen atom, NC-3000S (trade name, manufactured by Nippon Kayaku Co., Ltd.), i = 0, R ⁴⁰ is a hydrogen atom. CER-3000 (trade name, manufactured by Nippon Kayaku Co., Ltd.) in which an epoxy resin and an epoxy resin in which all R ^{8 in} the general formula (II) are hydrogen atoms are mixed at a weight ratio of 80:20 is represented by the following general formula (XI Among these epoxy resins, ESN-175 (trade name of Nippon Steel Chemical Co., Ltd.) where i = 0, j = 0, and k = 0 is available as a commercial product.

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

Regarding R ^{8 to} R ²¹ and R ^{37 to} R ^{41 in the} general formulas (II) to (XI), “all may be the same or different” means, for example, 8 to 8 in the formula (II) It means that all 88 R ⁸ may be the same or different. It means that all of R ^{9 to} R ²¹ and R ^{37 to} R ⁴¹ 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 ⁴¹ 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.

  In the above general formulas (II) to (XI), “n” needs to be in the range of 0 to 10, and when it exceeds 10, the melt viscosity of the component (B) becomes high, so the epoxy resin composition Viscosity at the time of melt molding is increased, and unfilled defects and bonding wires (gold wires connecting elements and leads) are likely to be deformed. The average n per molecule is preferably set in the range of 0-4.

(B) Curing Agent The epoxy resin composition according to the present invention is characterized in that the novel compound according to the present invention shown above is used as the (B) curing agent. When the compound according to the present invention is used as an epoxy resin curing agent, the curing proceeds by the reaction between the epoxy resin and the —ArO—Si (R ¹ ) ₂ —bonding site of the compound. In the epoxy resin composition according to the present invention, the blending ratio of (A) the epoxy resin and (B) the novel compound according to the present invention to be a curing agent is the number of epoxy groups in the total epoxy resin of (A) and (B ) Ratio of the number of —ArO—Si (R ¹ ) ₂ —bonds of the novel compound according to the present invention to the sum of the number of unreacted phenolic hydroxyl groups, ie, [(—ArO—Si (R of the novel compound according to the present invention) ¹ ) Number of ₂ -bonds) + (number of unreacted phenolic hydroxyl groups of the novel compound according to the present invention)] / [number of epoxy groups in epoxy resin] Is preferred. The blending ratio is more preferably set in the range of 0.7 to 1.5, and still more preferably set in the range of 0.8 to 1.3. When the blending ratio is less than 0.5, the epoxy resin is not sufficiently cured, and the heat resistance, moisture resistance, and electrical properties of the cured product tend to be inferior. On the other hand, if the blending ratio exceeds 2.0, 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 reduced. There is a tendency to decrease.

  In the epoxy resin composition according to the present invention, as the (B) curing agent, a compound other than the above-described novel compound according to the present invention may be included. The compound that can be used in combination as the 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, organic anhydrides such as pyromellitic anhydride, carboxylic acid compounds such as dicarboxylic acid, polycarboxylic acid, etc. One or more of these resins may be used in combination. Especially, it is preferable to use an unmodified phenol compound together from a viewpoint that the effect of the (C) curing accelerator described later is sufficiently exhibited.

  In addition, in the epoxy resin composition of the present invention, when a phenol compound is used as a curing agent in addition to the novel compound of the present invention, (B) based on the total amount of components to be the curing agent, the novel compound of the present invention The blending amount is preferably 30% by weight or more, and more preferably 50% by weight or more. (B) When the content of the compound according to the present invention in the curing agent is less than 30% by weight, the low water-absorbing properties are lowered, and the effect achievable by the present invention tends to be reduced.

Furthermore, in the epoxy resin composition of the present invention, when a phenol compound is used in combination as a curing agent, the blending ratio of (A) the epoxy resin and (B) the novel compound of the present invention and the phenol compound is The number of epoxy groups of the epoxy resin, (B) the number of —ArO—Si (R ¹ ) ₂ — bonds of the novel compound according to the present invention, the number of unreacted phenolic hydroxyl groups of the novel compound according to the present invention, and the number of phenolic hydroxyl groups used together The ratio to the sum of the total number, i.e., [(number of —ArO—Si (R ¹ ) ₂ —bonds of the novel compound according to the present invention) + (number of unreacted phenolic hydroxyl groups of the novel compound according to the present invention) + (phenol compound The number of phenolic hydroxyl groups)] / [number of epoxy groups in epoxy resin] is preferably set in the range of 0.5 to 2.0. The blending ratio is more preferably set in the range of 0.7 to 1.5, and still more preferably set in the range of 0.8 to 1.3. When the blending ratio is less than 0.5, the epoxy resin is not sufficiently cured, and the heat resistance, moisture resistance, and electrical properties of the cured product tend to be inferior. On the other hand, if the blending ratio exceeds 2.0, 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 reduced. There is a tendency to decrease.

In the above-mentioned range, the phenol compound that can be used together with the compound according to the present invention as a curing agent is not particularly limited, and a phenol compound having two or more phenolic hydroxyl groups in one molecule generally used as a curing agent. It may be. For example, a compound having two phenolic hydroxyl groups in one molecule such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol;
Phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and other phenols and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde, acetaldehyde, propionaldehyde, A novolak-type phenolic resin obtained by condensation or cocondensation with aldehydes such as benzaldehyde and salicylaldehyde under an acidic catalyst;
Aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl;
Paraxylylene and / or metaxylylene-modified phenolic resin;
Melamine-modified phenolic resin;
Terpene-modified phenolic resin;
Dicyclopentadiene type phenol resin, dicyclopentadiene type naphthol resin synthesized by copolymerization from phenols and / or naphthols and dicyclopentadiene;
Cyclopentadiene modified phenolic resin;
Polycyclic aromatic ring-modified phenolic resin;
Biphenyl type phenolic resin;
Triphenylmethane phenol resin;
Examples thereof include phenol resins obtained by copolymerizing two or more of these resins, and these may be used alone or in combination of two or more.

  Among the above-mentioned phenol compounds, aralkyl-type phenol resins, dicyclopentadiene-type phenol resins, salicylaldehyde-type phenol resins, benzaldehyde-type and aralkyl-type copolymer phenol resins, and novolak-type phenol resins are used from the viewpoint of reflow crack resistance. preferable. These aralkyl-type phenol resins, dicyclopentadiene-type phenol resins, salicylaldehyde-type phenol resins, benzaldehyde-type and aralkyl-type copolymer phenol resins, and novolak-type phenol resins can be used alone or in combination of two or more. In order to exert the effect of the novel compound according to the present invention, the above-mentioned phenol resin is preferably 70% by weight or less, more preferably 50% by weight based on the total amount of the curing agent. % Or less, more preferably 30% by weight 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 0-4, j is an integer of 0-2, n is an average value, and represents a positive number of 0-10.)
Among the phenol resins represented by the above general formula (XII), MEH-7851 (trade name of Meiwa Kasei Co., Ltd.) in which i = 0 and R ²³ are all hydrogen atoms is commercially available.

  Among the phenol resins represented by the above general formula (XIII), XL = 0, i = 0, k = 0, XLC (trade name, manufactured by Mitsui Chemicals), MEH-7800 (trade name, Meiwa Kasei Co., Ltd.), etc. Is commercially available.

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

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

(In 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 positive number from 0 to 10)
The salicylaldehyde type phenol resin is not particularly limited as long as it is a phenol resin using a compound having a salicylaldehyde skeleton as a raw material, but a phenol resin represented by the following general formula (XVI) is preferable.

  Among phenol resins represented by the following general formula (XVI), MEH-7500 (trade name, manufactured by Meiwa Kasei Co., Ltd.) where i = 0 and k = 0 is available as a commercial product.

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

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

Among the phenol resins represented by the following general formula (XVII), HE-510 (trade name, manufactured by Air Water Chemical Co., Ltd.) having i = 0, k = 0, and q = 0 is 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 each an average value and a positive number of 0 to 11 (l + m) is a positive number of 1 to 11)
The novolac type phenol resin is not particularly limited as long as it is a phenol resin obtained by condensation or cocondensation of phenols and / or naphthols and aldehydes in the presence of an acidic catalyst, but the following general formula (XVIII ) Is preferred.

I = 0 Among phenolic resin represented by the following general formula ^{(XVIII), R 35} are all hydrogen atoms TAMANOL 758, 759 (Arakawa Chemical Industries, Ltd., trade name), HP-850N (manufactured by Hitachi Chemical Co., Ltd. Product Name) etc. are commercially available.

(In the formula (XVIII), R ³⁵ and R ^{36 each} represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 0 to 3, and k is (An integer of 0 to 4, n is an average value and represents a positive number of 0 to 10.)
“All may be the same or different” described for R ^{22 to} R ³⁶ in the above general formulas (XII) to (XVIII) means that, for example, 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, the melt viscosity of the (B) curable resin component becomes high, so that the epoxy resin The viscosity at the time of melt molding of the 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.

(C) Curing accelerator In the epoxy resin composition by this invention, you may mix | blend a hardening | curing agent accelerator as needed.

Examples of usable curing accelerators include diazabicycloalkenes such as 1,5-diazabicyclo [4.3.0] nonene-5 and 1,8-diazabicyclo [5.4.0] undecene-7. Cycloamidine compounds, derivatives thereof, phenol novolac salts thereof and these compounds to maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6- Quinone compounds such as dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and π bonds such as diazophenylmethane A compound having an intramolecular polarization formed by adding a compound having a triethylenediamine, benzyldimethylamine, Tertiary amines such as liethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole Imidazoles such as tetraphenylphosphonium and tetraphenylborate, tetrasubstituted phosphonium and tetrasubstituted borates, tetraethylboron salts such as 2-ethyl-4-methylimidazole and tetraphenylborate, N-methylmorpholine and tetraphenylborate, Triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phos Sphin, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, tris Organic phosphines such as alkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, or complexes of these organic phosphines with organic borons, these organic phosphines and maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4 Quinone compounds such as benzoquinone and phenyl-1,4-benzoquinone, compounds having intramolecular polarization formed by adding a compound having a π bond such as diazophenylmethane, these organic phosphines and 4-bromophenol, 3-bromophenol 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4- Bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol Halogenated phenol compounds such as 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl After allowed to respond, a compound having intramolecular polarization obtained through the process of dehydrohalogenation (JP described in 2004-156035 and JP 2004-156036 JP) and the like. When these curing accelerators are used in combination, from the viewpoint of fluidity, a compound having an intramolecular polarization formed by adding a compound having an organic phosphines and a π bond, an organic phosphine and a halogenated phenol compound are reacted. Later, a compound having intramolecular polarization obtained by dehydrohalogenation, and from the viewpoint of curability, intramolecular polarization obtained by reacting an organic phosphine with a halogenated phenol compound, followed by a dehydrohalogenation step. A compound having is preferred. In particular, it is preferable to use a phosphine compound represented by the following general formula (I-4) or an intermolecular salt thereof. In the formula, R ⁴ , R ⁵ and Y ⁻ are as described above.

  The blending amount of the (C) curing accelerator in the epoxy resin composition according to the present invention is not particularly limited as long as the curing acceleration effect is achieved. However, from the viewpoint of improving the curability and fluidity at the time of moisture absorption of the resin composition, the total amount of (C) the curing accelerator is preferably 0.1 to 10 with respect to 100 parts by weight of the total (A) epoxy resin. It is desirable to add 1 part by weight, more preferably 1 to 7.0 parts by weight. If the blending amount is less than 0.1 parts by weight, it is difficult to cure in a short time.

(D) Inorganic filler (D) An inorganic filler can be further mix | blended with the epoxy resin composition of this invention as needed. In particular, when the epoxy resin composition is used as a molding material for sealing, it is preferable to blend (D) an inorganic filler. The (D) inorganic filler used in the present invention may be one generally used for a molding material for sealing, and is not particularly limited. For example, fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, Examples include talc, clay, mica and other fine powders, or beads obtained by spheroidizing these. Furthermore, 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, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. One of these inorganic fillers may be used alone, or two or more thereof may be used in combination.

  (D) Although there will be no restriction | limiting in particular if the compounding quantity of an inorganic filler will acquire the effect of this invention, It is preferable that it is the range of 55-90 volume% with respect to an epoxy resin composition. These inorganic fillers are blended for the purpose of improving the thermal expansion coefficient, thermal conductivity, elastic modulus, etc. of the cured product. If the blending amount is less than 55% by volume, these properties tend to be insufficiently improved. If it exceeds 90% by volume, the viscosity of the epoxy resin composition is increased, the fluidity is lowered, and molding tends to be difficult.

  Moreover, 1-50 micrometers is preferable and, as for the average particle diameter of (D) inorganic filler, 10-30 micrometers is more preferable. If it is less than 1 μm, the viscosity of the epoxy resin composition tends to increase, and if it exceeds 50 μm, the resin component and the inorganic filler are easily separated, resulting in unevenness of the cured product and variations in the properties of the cured product. There is a tendency for the fillability of the to decrease.

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

(Various additives)
In the epoxy resin composition according to the present invention, in addition to the above-described component (A) epoxy resin, (B) curing agent, (C) curing accelerator, and (D) inorganic filler, if necessary, a cup exemplified below Various additives such as a ring agent, an ion exchanger, a release agent, a stress relaxation agent, a flame retardant, and a colorant may be added. However, the epoxy resin composition according to the present invention is not limited to the following additives, and various additives known in the art may be added as necessary.

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

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

  Examples of the coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, 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) L) Aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinyl) Silane coupling agents such as (benzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, isopropyltriisostearoyl titanate , Isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-aminoethyl-aminoethyl) titanate, tetraoctylbis (ditride) Ruphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate , Titanate cups such as isopropyl dimethacrylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate 2 or more types even if these are used alone. It may be used in combination. Among these, a coupling agent having a secondary amino group is preferable from the viewpoint of fluidity and wire flow.

(Ion exchanger)
An anion exchanger can be mix | blended with the epoxy resin composition of this invention as needed. In particular, when an epoxy resin composition is used as a molding material for sealing, it is preferable to blend an anion exchanger from the viewpoint of improving the moisture resistance and high-temperature standing 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, water content of an element selected from magnesium, aluminum, titanium, zirconium and bismuth can be used. An oxide etc. are 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.

(Chemical 29)
Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (XIX)
(0 <X ≦ 0.5, m is a positive number)
The amount of these anion exchangers is not particularly limited as long as it is a sufficient amount capable of capturing anions such as halogen ions, but is preferably in the range of 0.1 to 30% by weight based on (A) the epoxy resin. 1 to 5% by weight 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 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, polyolefin waxes such as polyethylene oxide and non-oxidized polyethylene, and the like. It may be used alone or in combination of two or more. Among these, oxidized or non-oxidized polyolefin-based waxes are preferable, and the blending amount thereof is preferably 0.01 to 10% by weight and more preferably 0.1 to 5% by weight with respect to (A) the epoxy resin. If the blending amount of the polyolefin wax is less than 0.01% by weight, the releasability tends to be insufficient, and if it exceeds 10% by weight, the adhesiveness may be inhibited. Examples of the polyolefin-based wax include low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000 such as H4, PE, and PED series manufactured by Hoechst. Moreover, when using another mold release agent together with a polyolefin-type wax, 0.1 to 10 weight% is preferable with respect to (A) epoxy resin, and 0.5 to 3 weight% is more 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, silicone-based flexible agents are preferable, and examples of silicone-based flexible agents 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.

(Coloring agent)
Moreover, you may mix | blend well-known colorants, such as carbon black, an organic dye, an organic pigment, a titanium oxide, a red lead, a bengara.

  The epoxy resin composition of the present invention described above 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 predetermined amount of the above-described components are uniformly stirred and mixed, and obtained by a method of kneading, cooling, and pulverizing with a kneader, roll, extruder, or the like that has been heated to 70 to 140 ° C. in advance. be able to. The resin composition is easy to handle when it is tableted with a size and weight suitable for the molding conditions of the package.

  An electronic component device according to the present invention includes an element sealed with the above-described epoxy resin composition. 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, etc. And those in which the element portion is 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. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead package), TSOP (Thin Small Outline) Package), TQFP (Thin Quad Flat Package) and other general resin-encapsulated ICs, TCP (Tape Carrier Package) in which a semiconductor chip connected to a tape carrier with bumps is encapsulated with the epoxy resin composition of the present invention, A semiconductor chip connected to a wiring formed on a wiring board or glass by wire bonding, flip chip bonding, solder, etc. COB (Chip On Board) module, hybrid IC, multi-chip module in which active elements such as transistors, diodes, thyristors and / or passive elements such as capacitors, resistors, coils, etc. are sealed with the epoxy resin composition of the present invention, The element is mounted on the surface of the organic substrate on which the terminals for connecting the wiring board are formed on the back surface, and after connecting the element and the wiring formed on the organic substrate by bump or wire bonding, the element is formed with the epoxy resin composition of the present invention. Sealed BGA (Ball Grid Array), CSP (Chip Size Package), etc. are mentioned. 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 common, but an injection molding method, a compression molding method, or the like may be used.

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

[Synthesis Example of New Compound]
(Synthesis Example 1)
Number of hydroxyl groups of compound having two or more phenolic hydroxyl groups / R ² number of silane compounds represented by formula (I-1) = 2
After charging 248 g of bisphenol F (BPF manufactured by Honshu Chemical Co., Inc., about 90% of the nucleus) into a 500 ml separable flask, the mixture was heated to 130 ° C. and melted. Subsequently, triphenylphosphine and 1,4-benzoquinone 1.24 g of addition reaction product was added and dissolved.

To the obtained solution, 152 g of diphenyldimethoxysilane (manufactured by Nihon Unicar Co., Ltd., AZ-6183) was added dropwise over about 30 minutes. While removing by-product methanol during the reaction, the reaction was carried out at 130 to 135 ° C. for about 2 hours, and further with removal of methanol by a vacuum using an aspirator for 10 hours. It used for the measurement and IR measurement.

1 , 3, and 5 are charts showing GPC measurement results. FIG. 1 is a raw material bisphenol F, FIG. 3 is a raw material diphenyldimethoxysilane, and FIG. 5 is a reaction product obtained by Synthesis Example 1. It is a chart regarding. From the chart of FIG. 5 , it can be seen that the peak of diphenyldimethoxysilane, which is a raw material, disappears and the reaction product is polymerized.
2, 4 and 6 are charts showing IR measurement results. FIG. 2 is a raw material bisphenol F, FIG. 4 is a raw material diphenyldimethoxysilane, and FIG. 6 is a reaction product obtained in Synthesis Example 1. It is a chart regarding. When the chart of FIG. 6 is seen, since a characteristic peak appears in Si—OAr at 920 to 970 cm ⁻¹ , the reaction product has one or more structural units represented by the following (XX). Further, it is presumed that at least a part of the product contains a compound having a structure represented by the following general formula (XXI). The residual amount of methoxy groups in the reaction product was 0%.

(Wherein R ³ represents a hydrogen atom or a methyl group)
(Synthesis Example 2)
Number of hydroxyl groups of compound having two or more phenolic hydroxyl groups / R ² number of silane compounds represented by formula (I-1) = 1.5
A 500 ml separable flask was charged with 220 g of bisphenol F (BPF manufactured by Honshu Kagaku Co., Ltd., about 90% nuclei), heated to 130 ° C. and melted, and then triphenylphosphine and 1,4-benzoquinone 1.10 g of addition reaction product was added and dissolved.

To the obtained solution, 180 g of diphenyldimethoxysilane (manufactured by Nihon Unicar Co., Ltd., AZ-6183) was added dropwise over about 30 minutes. While removing by-product methanol during the reaction, the reaction was carried out at 130 to 135 ° C. for about 2 hours, and further with removal of methanol by a reduced pressure using an aspirator for 15 hours. It used for the measurement and IR measurement.
The charts obtained by GPC measurement and IR measurement are shown in FIGS. 7 and 8, respectively. From the results of GPC measurement (FIG. 7), it can be seen that the peak of the raw material diphenyldimethoxysilane has disappeared and the reaction product has become polymerized. Moreover, in the IR measurement result (FIG. 8), since a characteristic peak appears in Si—OAr at 920 to 970 cm ⁻¹ , the reaction product is a unit of the general formula (XX) shown above. It is presumed to contain a compound having a structure and a structure represented by the general formula (XXI). The residual amount of methoxy group in the reaction product was 0%.

(Synthesis Example 3)
Number of hydroxyl groups of the compound having two or more phenolic hydroxyl groups / R ² number of the compound represented by formula (I-1) = 1
A 500 ml separable flask was charged with 180 g of bisphenol F (BPF manufactured by Honshu Chemical Co., Ltd., about 90% nuclei), then heated to 130 ° C. and melted. 0.90 g of addition reaction product was added and dissolved.

To the obtained solution, 220 g of diphenyldimethoxysilane (manufactured by Nippon Unicar Co., Ltd., AZ-6183) was added dropwise over about 30 minutes. While removing by-product methanol during the reaction, the reaction was carried out at 130-135 ° C. for about 2 hours, and further with removal of methanol by vacuum using an aspirator for 20 hours. It used for the measurement and IR measurement.
The charts obtained by GPC measurement and IR measurement are shown in FIGS. 9 and 10, respectively. From the GPC measurement result (FIG. 9), it can be seen that the peak of the raw material diphenyldimethoxysilane disappears and the reaction product is polymerized. Further, in the IR measurement result (FIG. 10), since a characteristic peak appears in Si—OAr at 920 to 970 cm ⁻¹ , the reaction product has a unit structure of the general formula (XX). It is assumed that the compound contains a compound having the structure represented by the general formula (XXI). The residual amount of methoxy groups in the reaction product was 8%.

  Details of various measurements of the reaction products (hereinafter referred to as “compounds”) carried out in Synthesis Examples 1 to 3 are as follows.

(1) GPC measurement About 5 mg of the compound was dissolved in about 5 ml of tetrahydrofuran to prepare a solution, and 0.2 ml of the solution was charged for use in the measurement. The measurement was performed at 30 ° C. and a flow rate of 1.0 ml / min using TSKgel G2000H manufactured by TOSOH equipped with an intelligent pump (L-3600) manufactured by Hitachi. An RI monitor (L-3300) manufactured by Hitachi, Ltd. was used as the detector.

(2) IR measurement The measurement was carried out using Bio-Rad FTS 3000MX according to the KBr method.

(3) Residual amount of methoxy group About 100 mg of the compound was dissolved in about 0.5 ml of heavy acetone to form a solution, and placed in a φ5 mm sample tube for measurement. ¹³ C-NMR of the compound was measured according to the INVERSED GATE method using AV-300M manufactured by Bruker Biospin. And integral value of ¹³ C of the Si-OCH _3, compares the total integrated value of ¹³ C of the phenyl group derived from diphenyl dimethoxysilane was determined residual ratio of Si-OCH ₃ for starting material.

[Preparation of epoxy resin composition and evaluation of properties]
(Examples 1-8, Comparative Examples 1-4)
(Epoxy resin)
Epoxy resin 1: biphenyl type epoxy resin having an epoxy equivalent of 196 and a melting point of 106 ° C. (trade name “YX-4000H” manufactured by Japan Epoxy Resin Co., Ltd.)
Epoxy resin 2: o-cresol novolak type epoxy resin having an epoxy equivalent of 195 and a softening point of 77 ° C. (trade name “ESCN-190-6” manufactured by Sumitomo Chemical Co., Ltd.)
Epoxy resin 3: Salicylaldehyde type epoxy resin having an epoxy equivalent of 168 and a softening point of 62 ° C. (trade name “1032H60” manufactured by Japan Epoxy Resin Co., Ltd.)

(Curing agent)
Curing Agent 1: Compound Obtained in Synthesis Example 1 Curing Agent 2: Compound Obtained in Synthesis Example 2 Curing Agent 3: Compound Obtained in Synthesis Example 3 Curing Agent A: Phenol Aralkyl Resin (Hydroxyl Equivalent 176, Softening Point 70 ° C.) Product name “Mirex XL-225” manufactured by Mitsui Chemicals, Inc.)
Curing agent B: Bisphenol F having a hydroxyl group equivalent of 100 and a melting point of 115-120 ° C. (“BPF” manufactured by Honshu Chemical Co., Ltd., dinuclear ratio of about 90%)
Curing agent C: salicylaldehyde type phenol resin having a hydroxyl group equivalent of 103 and a softening point of 86 ° C. (trade name “MEH-7500” manufactured by Meiwa Kasei Co., Ltd.)
Curing agents A to C were used for comparison.

(Curing accelerator)
Curing accelerator 1: Addition reaction product of triphenylphosphine and 1,4-benzoquinone (inorganic filler)
Spherical fused silica having an average particle size of 17.5 μm and a specific surface area of 3.8 m ² / g

(Other additives)
Coupling agent: Epoxy silane (γ-glycidoxypropyltrimethoxysilane)
Colorant: Carbon black (trade name “MA-100” manufactured by Mitsubishi Chemical Corporation)
Release agent: Carnauba wax (manufactured by Celerica NODA)
Flame retardant: antimony trioxide By blending the above-mentioned components in the polymerization parts shown in Table 1 and performing roll kneading under conditions of a kneading temperature of 80 ° C. and a kneading time of 15 minutes, Examples 1 to 8 and Comparative Example 1 respectively. The epoxy resin composition of ~ 4 was obtained.

  Next, each epoxy resin composition obtained by Examples 1-8 and Comparative Examples 1-4 was evaluated by each test shown below. The evaluation results are shown in Table 2. The epoxy resin composition was molded using a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Further, post-curing was performed at 175 ° C. for 6 hours.

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

(2) Hardness upon heating The epoxy resin composition was molded into a disc having a diameter of 50 mm and a thickness of 3 mm under the above conditions, and measured immediately using a Shore D hardness meter.

(3) Water absorption 1
The disk molded in the above (2) was post-cured, put into a constant temperature and humidity chamber of 85 ° C./85% RH, taken out after 168 hours, and the increase rate (%) per unit weight was determined from the initial value.

(4) Water absorption 2
The disk molded in the above (2) was post-cured, put into a pressure cooker at 121 ° C. and 2 atm, taken out after 20 hours, and the increase rate (%) per unit weight was determined from the initial value.

(5) Glass transition temperature The epoxy resin composition was molded into a size of 80 mm length × 10 mm width × 3 mm thickness under the above molding conditions and post-cured. Next, the molded product was cut to a length of 55 mm with a diamond cutter, and then a temperature increase rate of 5 ° C. and a frequency of 6.28 rad / s were used in a dynamic mode using a viscoelasticity measuring device ARES (manufactured by Rheometric Scientific F Co., Ltd.). The glass transition temperature (° C.) was determined from the measurement of tan δ under the conditions described above.

(6) Elastic modulus at high temperature The storage elastic modulus (10 ⁸ Pa) at 240 ° C. was determined from the measurement in (5) above.

  Examples 1 to 3 containing the novel compound according to the present invention as a curing agent are compared with Comparative Example 1 using a phenol aralkyl resin, spiral flow, heat hardness, low water absorption, glass transition temperature and high temperature elastic modulus. Excellent. Further, in Examples 4 to 6 containing the novel compound according to the present invention, compared with Comparative Example 3 using bisphenol F, the thermal hardness, low water absorption, glass transition temperature and high temperature elastic modulus are excellent. In addition, when a resin obtained by trimethylsilylating a phenol resin is used as the curing agent of the comparative example, the molecular weight between the reaction points is increased, so that the crosslinking density is further lower than that of the comparative example 3, and the curability and heat resistance are reduced. Conceivable. Further, in Examples 7 and 8 containing the novel compound according to the present invention, compared with Comparative Example 4 using the salicylaldehyde type phenol resin, the hot hardness and the high temperature elastic modulus are almost the same, but the low water absorption Is very good in terms of.

  Although the water absorption is generally high when the high-temperature elastic modulus is high (that is, the crosslinking density is high), Examples 1 to 8 containing the novel compound according to the present invention are crosslinked as compared with the curing agent used in the comparative example. Despite high density, water absorption is low. Therefore, the novel compound according to the present invention is industrially useful because it can achieve both the heat resistance (high glass transition temperature) and the moisture resistance.

It is a chart which shows the result of the GPC measurement of bisphenol F. It is a chart which shows the result of IR measurement of bisphenol F. It is a chart which shows the result of GPC measurement of diphenyldimethoxysilane. It is a chart which shows the result of IR measurement of diphenyldimethoxysilane. It is a chart which shows the result of the GPC measurement of the compound (Synthesis example 1) by this invention. It is a chart which shows the result of IR measurement of the compound (Synthesis example 1) by this invention. It is a chart which shows the GPC measurement of the compound (Synthesis example 2) by this invention. It is a chart which shows the result of IR measurement of the compound by this invention (Synthesis example 2). It is a chart which shows the result of GPC measurement of the compound (Synthesis example 3) by this invention. It is a chart which shows the result of IR measurement of the compound by this invention (Synthesis example 3).

Claims (8)

(A) a phenol compound having two or more phenolic hydroxyl groups in the molecule, and (b) a silane compound represented by the following general formula (I-1) having two functional groups capable of reacting with the phenolic hydroxyl group, A compound having one or more structural units represented by the following general formula (I-2), which comprises a step of reacting in the presence of a catalyst comprising a phosphonium compound represented by the following general formula (I-4) or an intermolecular salt thereof . Production method.

(In the formula, R ¹ are each independently selected from hydrogen atom and the group consisting of substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different, R ¹ each other May combine to form a ring structure,
R ² represents a functional group capable of reacting with a phenolic hydroxyl group, and each independently represents a halogen atom, a hydroxyl group, a substituted or unsubstituted oxy group having 1 to 18 carbon atoms, or a substituted or unsubstituted group having 0 to 18 carbon atoms. And all may be the same or different and R ² may be bonded to each other to form a cyclic structure)

Wherein R ⁴ is independently selected from the group consisting of a hydrogen atom and a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different, and two or more R ⁴ may be bonded to each other to form a ring structure;
R ⁵ is independently selected from the group consisting of a hydrogen atom, a hydroxyl group, and a substituted or unsubstituted organic group having 1 to 18 carbon atoms, all of which may be the same or different, and two or more R ⁵ are May combine with each other to form a ring structure,
Y ⁻ is a 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 formula, R ¹ are each independently selected from hydrogen atom and the group consisting of substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different, R ¹ each other May combine to form a ring structure,
Ar is a divalent organic group having 2 to 30 carbon atoms and a group derived from an aromatic cyclic compound on both sides) Process for the preparation of a compound of claim 1, wherein the compound is characterized by containing a compound having a structure represented by the following general formula (I-3).

(In the formula, R ¹ are each independently selected from hydrogen atom and the group consisting of substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different, R ¹ each other May combine to form a ring structure,
Ar is a divalent organic group having 2 to 30 carbon atoms and a group derived from a cyclic compound having aromaticity on both sides,
Each R ³ independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms and —Ar—OH (wherein Ar has 2 to 30 carbon atoms and is aromatic; Are selected from the group consisting of a group derived from a cyclic compound showing a divalent organic group on both sides, and all may be the same or different,
m represents a number of 1 or more, n represents a number of 0 or more, and the repetition of m units and n units may be block, alternating, or random) The method for producing a compound according to claim 1 or 2 , wherein in the silane compound (b), R ² is a hydroxyl group or an oxy group. The compound according to any one of claims 1 to 3, wherein 70% by weight or more of the phenol compound (a) based on the total weight of the phenol compound is a divalent phenol compound. Method. An epoxy resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) a curing accelerator ,
A silane represented by the following general formula (I-1) in which the curing agent has (a) a phenol compound having two or more phenolic hydroxyl groups in the molecule, and (b) two functional groups capable of reacting with the phenolic hydroxyl group. A compound obtained by reacting a compound with a phosphonium compound represented by the following general formula (I-4) or an intermolecular salt thereof, and represented by the following general formula (I-2) Containing a compound having one or more structural units,
The epoxy resin composition, wherein the curing accelerator is a phosphonium compound represented by the following general formula (I-4) or an intermolecular salt thereof .

(In the formula, R ¹ are each independently selected from hydrogen atom and the group consisting of substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different, R ¹ each other May combine to form a ring structure,
Ar is a divalent organic group having 2 to 30 carbon atoms and a group derived from an aromatic cyclic compound on both sides)

(In the formula, R ¹ are each independently selected from hydrogen atom and the group consisting of substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different, R ¹ each other May combine to form a ring structure,
R ² represents a functional group capable of reacting with a phenolic hydroxyl group, and each independently represents a halogen atom, a hydroxyl group, a substituted or unsubstituted oxy group having 1 to 18 carbon atoms, or a substituted or unsubstituted group having 0 to 18 carbon atoms. And a group selected from the group consisting of carbonyloxy groups having 2 to 18 carbon atoms, all of which may be the same or different, and R ² may be bonded to each other to form a cyclic structure)

Wherein R ⁴ is independently selected from the group consisting of a hydrogen atom and a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different, and two or more R ⁴ may be bonded to each other to form a ring structure;
R ⁵ is independently selected from the group consisting of a hydrogen atom, a hydroxyl group, and a substituted or unsubstituted organic group having 1 to 18 carbon atoms, all of which may be the same or different, and two or more R ⁵ are May combine with each other to form a ring structure,
Y ⁻ is a 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) The said compound contains the compound which has a structure shown by the following general formula (I-3), The epoxy resin composition of Claim 5 characterized by the above-mentioned.

(Wherein R ¹ Are each independently selected from the group consisting of a hydrogen atom and a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different, and R ¹ May be bonded together to form a ring structure,
Ar is a divalent organic group having 2 to 30 carbon atoms and a group derived from a cyclic compound having aromaticity on both sides,
R ³ Are each independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms and —Ar—OH (wherein Ar has 2 to 30 carbon atoms and exhibits aromaticity) A divalent organic group having a group derived from a cyclic compound on both sides), all may be the same or different,
m represents a number of 1 or more, n represents a number of 0 or more, and the repetition of m units and n units may be block, alternating, or random) In the silane compound (b), R ² Is a hydroxyl group or an oxy group, The epoxy resin composition of Claim 5 or 6 characterized by the above-mentioned. The epoxy resin composition according to any one of claims 5 to 7, wherein 70% by weight or more of the phenol compound (a) based on the total weight of the phenol compound is a divalent phenol compound. object.

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