JP2003246841A - Epoxy resin composition and electronic part device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition excellent in curability at moisture absorption, flow property, and reflow crack resistance and to provide electronic part devices equipped with elements sealed with this epoxy resin composition. <P>SOLUTION: The composition comprises, as essential components, (A) an epoxy resin containing a sulfur atom, (B) a phenolic resin, and (C) an addition product of a phosphine compound in which at least one alkyl group is bonded to the phosphorous atom and a quinone compound. There is also provided the electronic part devices equipped with the elements sealed with this epoxy resin composition. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an epoxy resin composition suitable as a molding material, a laminate, or an adhesive material,
Also, the present invention relates to an electronic component device including an element sealed with the epoxy resin composition.

[0002]

2. Description of the Related Art Conventionally, epoxy resins have been widely used as molding materials, laminates, adhesive materials, etc., and epoxy resin compositions have been widely used in the field of encapsulating electronic parts such as transistors and ICs. Has been. The reason for this is
This is because the epoxy resin has a good balance of various properties such as moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness with insert products. In particular, a combination of an orthocresol novolac type epoxy resin and a phenol novolac curing agent has an excellent balance of these, and has become the mainstream as a base resin for a molding material for IC encapsulation. Further, as the curing accelerator, an amine compound such as a tertiary amine or imidazole, or a phosphorus compound such as phosphine or phosphonium is generally used.

[0003]

In recent years, high density mounting of electronic parts on a printed wiring board has been progressing, and along with this, electronic parts are mainly surface mount type packages instead of conventional pin insertion type packages. Is becoming. IC, LSI
In surface mounting type ICs such as those described above, the volume occupied by the elements in the package is gradually increasing in order to increase the mounting density, and the thickness of the package has become very thin. Further, in the pin insertion type package, since the pins are inserted into the wiring board and soldering is performed from the rear surface of the wiring board, the package is not directly exposed to high temperature, whereas the surface mount type IC is mounted on the surface of the wiring board. After the temporary fixing, it is treated with a solder bath or a reflow device, so that it is directly exposed to the soldering temperature. As a result, when the IC package absorbs moisture, the absorbed moisture rapidly expands during soldering and leads to package cracking, which is a serious problem.

In order to improve resistance to package cracks at the time of soldering, so-called reflow crack resistance, an epoxy resin composition containing a large amount of an inorganic filler has been proposed. However, an increase in the amount of inorganic filler leads to a decrease in fluidity during molding, which results in molding defects such as filling defects and voids, and IC chip bonding wires are broken and conduction defects occur. Since this causes a decrease, there is a limit to the amount of increase in the inorganic filler, and as a result, there is a problem in that reflow crack resistance cannot be significantly improved.

Particularly when a phosphorus-based curing accelerator such as triphenylphosphine or an amine-based curing accelerator such as 1,8-diazabicyclo [5.4.0] undecene-7 is used, the fluidity is low and the reflow crack resistance is low. The reality is that no significant improvement in sex can be expected. In order to improve such a problem, a method of using an addition reaction product of triphenylphosphine and 1,4-benzoquinone as a curing accelerator (Japanese Patent Laid-Open Publication No. H9-96952).
No. 157497), a method using an addition reaction product of a phosphine having three phenyl groups having an electron-donating substituent and maleic anhydride or a quinone as a curing accelerator (JP-A-7-228672). However, there was a problem with the curability when absorbing moisture. When the curability at the time of moisture absorption is low, the epoxy resin composition absorbs moisture at the time of production, transportation and use, and problems such as curing failure are likely to occur. In particular,
It is particularly noticeable during high humidity in summer.

[0006] More recently, due to increasing environmental awareness, it has been proposed to use lead-free solder instead of conventional lead-containing solder. Since lead-free solder has a higher melting point than lead-containing solder, it is necessary to raise the soldering temperature by about 20 ° C. When the temperature at the time of soldering rises, the stress generated by the evaporation of water and expansion also increases, and package cracks easily occur. Therefore, there is a demand for an epoxy resin composition that is more excellent in reflow crack resistance than ever before.

The present invention has been made in view of the above circumstances, and an epoxy resin composition having excellent curability and fluidity when absorbing moisture and reflow crack resistance even at high temperatures, and sealing with the epoxy resin composition It is intended to provide an electronic component device provided with the above-mentioned element.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that at least one epoxy resin containing a sulfur atom such as a specific epoxy resin having a diaryl sulfide skeleton is used. By combining and combining a phosphine compound having one substituent and a quinone compound, an epoxy resin composition having excellent curability upon moisture absorption, fluidity, and reflow crack resistance superior to conventional ones can be obtained, and the above-mentioned object is achieved. The inventors have discovered what is possible and have completed the present invention.

That is, the present invention relates to the following: (1) (A) Epoxy resin containing sulfur atom, (B)
An epoxy resin composition comprising a phenol resin and (C) an addition reaction product of a phosphine compound having at least one alkyl group bonded to a phosphorus atom and a quinone compound as essential components. (2) The epoxy resin composition according to (1), wherein the epoxy resin containing a sulfur atom (A) is an epoxy resin having a sulfide skeleton. (3) The epoxy resin composition according to (1) or (2), wherein the epoxy resin containing a sulfur atom (A) is a compound represented by the following general formula (I).

[Chemical 5] (Here, R ¹ in the formula (I) is a hydrogen atom or a carbon number of 1 to
12 alkyl and aryl groups are shown, which may be the same or different. n is an average value and is 0
Indicates a positive number from -10. ). (4) (C) An addition reaction product of a phosphine compound having a phosphorus atom bonded to at least one alkyl group and a quinone compound is represented by the phosphine compound represented by the following general formula (II) and the following general formula (III). The epoxy resin composition according to (1) to (3), which is an addition reaction product with a quinone compound.

[Chemical 6] (Where R in the formula (II)^TwoIs an alky having 1 to 12 carbons
R group^ThreeAnd R ^FourIs a hydrogen atom or a carbon number of 1 to
12 hydrocarbon groups, all of which are the same or different
You may In addition, R in the formula (III)⁵~ R⁷Is
A hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms,
All of them may be the same or different. R⁵And R⁶But
It may be bonded to form a ring structure. ). (5) (D) An inorganic filler is further contained, and the blending amount thereof is
55 to 90% by volume based on the epoxy resin composition
The epoxy resin composition according to any one of (1) to (4). (6) (A) An epoxy resin containing a sulfur atom is one of the following
Containing an epoxy resin represented by general formula (IV)
The epoxy resin composition according to any one of (1) to (5)

[Chemical 7] (Here, n in the general formula (IV) is an average value and is 0 to 10
Indicates a positive number. ). (7) (B) Phenolic resin is represented by the following general formulas (V) to (I
The epoxy resin composition according to any one of (1) to (6), which comprises at least one phenolic resin represented by any of X).

[Chemical 8] (Here, R < ⁸ > -R < ¹⁷ > in General Formula (V)-(IX) shows a hydrogen atom or a C1-C6 alkyl group, and all may be the same or different. N is an average value. Is a positive number from 0 to 10, i is an integer from 0 to 3, and j is 0 to 2.
Is an integer, k is an integer of 0 to 4, and r is an integer of 0 to 4. ). And (8) An electronic component device comprising an element sealed with the epoxy resin composition according to any one of (1) to (7).

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION (A) Used in the Present Invention
The sulfur atom-containing epoxy resin is not particularly limited, but an epoxy resin having a sulfide skeleton is preferable, and an epoxy resin represented by the following general formula is more preferable.

[0011]

[Chemical 9] (Here, R ¹ in the formula (I) is a hydrogen atom or a carbon number of 1 to
12 alkyl and aryl groups are shown, which may be the same or different. n is an average value,
A positive number from 0 to 10 is shown. )

Among the epoxy resins containing a sulfur atom represented by the above general formula (I), the epoxy resin represented by the following general formula (IV) is more preferable. As such an epoxy resin, YSLV-120TE (manufactured by Nippon Steel Chemical Co., Ltd.) and the like are commercially available.

[0013]

[Chemical 10] (Here, n in the general formula (IV) is an average value and is 0 to 10
Indicates a positive number. )

In the epoxy resin composition of the present invention, the epoxy resin (A) containing a sulfur atom may be used alone as the epoxy resin, but one or more epoxy resins other than (A) may be used in combination. . However, in order to exert its performance, the total amount of the component (A) is preferably 30% by weight or more, and more preferably 50% by weight or more, based on the total amount of the epoxy resin. There is no particular limitation on the epoxy resin that can be used in combination, for example, commonly used epoxy resins having two or more epoxy groups in one molecule, such as phenol novolac type epoxy resin and orthocresol novolac type epoxy resin. Phenol, cresol, xylenol, resorcin,
Acidic phenols such as catechol, bisphenol A and bisphenol F and / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene, and compounds having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde Epoxidized novolak resin obtained by condensation or co-condensation under a catalyst,
Bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or unsubstituted biphenol, diglycidyl ether of stilbene phenols, glycidyl ether of alcohols such as butanediol, polyethylene glycol, polypropylene glycol, phthalic acid, isophthalic acid, Glycidyl-type or methylglycidyl-type epoxy resins such as glycidyl esters of carboxylic acids such as tetrahydrophthalic acid, aniline, isocyanuric acid, etc., in which the active hydrogen bonded to the nitrogen atom is replaced with a glycidyl group, olefin bonds in the molecule Vinyl cyclohexene diepoxide obtained by epoxidation, 3,
Alicyclic epoxy resins such as 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane , Glycidyl ether of para-xylylene and / or meta-xylylene 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 naphthalene ring-containing phenol resin, biphenyl type epoxy resin, halogenated phenol novolac type epoxy resin and the like. You may use together combining these 2 or more types. Above all,
Epoxy resins represented by any of the following general formulas (III) to (VIII) are preferable in terms of reflow crack resistance and fluidity, and particularly 4,4′-bis (2,3-epoxypropoxy) -3,3 More preferred is', 5,5'-tetramethylbiphenyl.

[0015]

[Chemical 11] (Here, R < ¹⁹ > -R < ²⁹ > in General formula (X)-(XV) shows a hydrogen atom or a C1-C12 alkyl group, all may be the same or different. N is an average value. Is a positive number from 0 to 10, p is 1 or 0, 1 and m are average values, positive numbers from 0 to 11 (l + m) are average values, and positive numbers from 1 to 11 are shown. i is an integer of 0 to 3, j
Is an integer of 0 to 2, k is an integer of 0 to 4, and q is an integer of 1 to 3. ) R ^{19 to} R in the above general formulas (X) to (XV)
^With respect to ²⁹ , the meaning that they may all be the same or different means, for example, that all 16 R ^{19 s in} formula (III) may be the same or different. With respect to the other R ^{20 to} R ²⁹ , it is meant that all the numbers included in the formula may be the same or different. Further, R ^{19 to} R ²⁹ may be the same or different. For example, R ²⁰ and R ^{21 in} formula (X)
Of all may be the same or different.

As the epoxy resin represented by the above general formula (XV), a random copolymer containing 1 constitutional unit and m constitutional units at random, an alternating copolymer containing alternating units,
Examples thereof include a regularly-containing copolymer and a block-containing block copolymer, and any one of these may be used alone, or two or more thereof may be used in combination.

The (B) phenol resin used in the present invention is not particularly limited. For example, it is a commonly used phenol resin having two or more phenolic hydroxyl groups in one molecule, such as phenol, cresol and xylenol. , Resorcin, catechol, hydroquinone,
Phenols such as bisphenol A, bisphenol F, phenylphenol, aminophenol and / or α
-Naphthol, β-naphthol, naphthols such as dihydroxynaphthalene and formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, resins obtained by condensation or co-condensation with aldehydes such as salicylaldehyde under acidic catalyst, phenols and / or Phenol / aralkyl resins synthesized from naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl, aralkyl type phenolic resins such as naphthol / aralkyl resins, paraxylylene and / or metaxylylene modified phenolic resins, melamine modified phenolic resins, terpene modified phenols Resin, dicyclopentadiene modified phenol resin, cyclopentadiene modified phenol resin, polycyclic aromatic ring modified phenol resin, resorcin, catechol Hydroquinone, bisphenol A,
Examples thereof include bifunctional phenol compounds such as bisphenol F, and these may be used alone or in combination of two or more kinds. Among them, from the viewpoint of reflow crack resistance, a phenol resin represented by any of the following general formulas (IX) to (XII) is preferable. These general formulas (IX)
The phenol resin represented by any of (XII) to (XII) may be used alone or in combination of two or more, but in order to exert its performance, The total amount of the phenolic resin is preferably 30% by weight or more, more preferably 50% by weight or more.

[0018]

[Chemical 12] (Here, R < ⁸ > -R < ¹⁷ > in General Formula (V)-(IX) shows a hydrogen atom or a C1-C6 alkyl group, and all may be the same or different. N is an average value. Is a positive number from 0 to 10, i is an integer from 0 to 3, and j is 0 to 2.
Is an integer, k is an integer of 0 to 4, and r is an integer of 0 to 4. )

R ^{8 to} R in the above general formulas (V) to (IX)
^With respect to ¹⁷ , the meaning that all of them may be the same or different means that, for example, all i R ^{8 s in} the formula (IX) may be the same or different from each other. It is also meant that the other R ^{9 to} R ¹⁷ may all be the same or different from each other with respect to the respective numbers included in the formula. Further, R ^{8 to} R ¹⁷ may be the same or different. For example, all of R ⁸ and R ⁹ may be the same or different, and all of R ¹² and R ¹⁴ may be the same or different. The above general formula (IX)
N in (XII) needs to be in the range of 0 to 10. When it exceeds 10, the melt viscosity of the component (B) becomes high, and therefore the viscosity at the time of melt molding of the epoxy resin composition is also high. As a result, unfilling failure and deformation of the bonding wire (gold wire connecting the element and the lead) are likely to occur. The average n in one molecule is preferably set in the range of 0 to 4.

In the present invention, the compounding ratio of the epoxy resin (A) and the phenol resin (B) is the ratio of the hydroxyl equivalents of all phenolic resins to the epoxy equivalents of all epoxy resins (number of hydroxyl groups in phenolic resin / epoxy resin in epoxy resin). The number of epoxy groups) is preferably set in the range of 0.5 to 2.0, more preferably 0.7 to 1.5, and 0.1.
8-1.3 is more preferable. If this ratio is less than 0.5, the curing of the epoxy resin will be insufficient, and the heat resistance, moisture resistance and electrical properties of the cured product will tend to be inferior. If it exceeds 2.0, the curing will be inadequate because the phenol resin component will be excessive. There is a tendency that the electric properties and the moisture resistance are deteriorated because the amount becomes sufficient and a large amount of phenolic hydroxyl groups remain in the cured resin.

The addition reaction product of the phosphine compound (C) having at least one alkyl group bonded to the phosphorus atom and the quinone compound used in the present invention is not particularly limited as long as it acts as a curing accelerator. Of these, an addition reaction product of a phosphine compound represented by the following general formula (II) and a quinone compound represented by the following general formula (III) is preferable from the viewpoint of curability.

[0022]

[Chemical 13] (Where R in the formula (II)^TwoIs an alky having 1 to 12 carbons
R group^ThreeAnd R ^FourIs a hydrogen atom or a carbon number of 1 to
12 hydrocarbon groups, all of which are the same or different
You may In addition, R in the formula (III)⁵~ R⁷Is
A hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms,
All of them may be the same or different. R⁵And R⁶But
It may be bonded to form a ring structure. )

R ¹ in the above general formula (I) has 1 to 1 carbon atoms.
12 is an alkyl group, but the alkyl group having 1 to 12 carbon atoms is not particularly limited, and examples thereof include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-
Butyl group, tert-butyl group, pentyl group, hexyl group,
Chain alkyl group such as octyl group, decyl group, dodecyl group, cyclopentyl group, cyclohexyl group, cycloalkyl group such as cycloheptyl group, cyclopentenyl group, cyclohexenyl group, aryl group-substituted alkyl group such as benzyl group, methoxy group Examples thereof include a substituted alkyl group, an ethoxy group-substituted alkyl group, an alkoxy group-substituted alkyl group such as a butoxy group-substituted alkyl group, an amino group-substituted alkyl group such as a dimethylamino group and a diethylamino group, and a hydroxyl group-substituted alkyl group.

Further, R ^{2 to} R in the above general formula (II)
³ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, but the hydrocarbon group having 1 to 12 carbon atoms is not particularly limited, and includes, for example, a substituted or unsubstituted aliphatic group having 1 to 12 carbon atoms. Examples thereof include a hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group having 1 to 12 carbon atoms, and a substituted or unsubstituted aromatic hydrocarbon group having 1 to 12 carbon atoms. Examples of the substituted or unsubstituted aliphatic hydrocarbon group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group. , Chain alkyl groups such as hexyl group, octyl group, decyl group and dodecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group, cyclohexenyl group and other cyclic alkyl groups, benzyl group and other aryl group substituted alkyl Group, a methoxy group-substituted alkyl group, an ethoxy group-substituted alkyl group, an alkoxy group-substituted alkyl group such as a butoxy group-substituted alkyl group, an amino group-substituted alkyl group such as a dimethylamino group and a diethylamino group, and a hydroxyl group-substituted alkyl group. Examples of the substituted or unsubstituted alicyclic hydrocarbon group having 1 to 12 carbon atoms 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. Examples thereof include those substituted with groups, hydroxyl groups, amino groups, halogens and the like. Carbon number 1
Examples of the substituted or unsubstituted aromatic hydrocarbon group of 12 include aryl groups such as phenyl group and naphthyl group, tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, t-butylphenyl group and dimethylnaphthyl group. An alkyl group-substituted aryl group such as a group, a methoxyphenyl group,
Alkoxy group substituted aryl groups such as ethoxyphenyl group, butoxyphenyl group, t-butoxyphenyl group and methoxynaphthyl group, amino group substituted aryl groups such as dimethylamino group and diethylamino group, halogen substitution such as hydroxyphenyl group and dihydroxyphenyl group Examples thereof include aryloxy groups such as aryl groups, phenoxy groups and cresoxy groups, phenylthio groups, tolylthio groups, diphenylamino groups, and the like, and those in which amino groups, halogens and the like are substituted. Of these, a substituted or unsubstituted alkyl group and aryl group are preferable.

R ^{5 to} R ⁷ in the above general formula (III) represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, but the hydrocarbon group having 1 to 18 carbon atoms is not particularly limited, For example, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon group having 1 to 12 carbon atoms, a substituted or unsubstituted aromatic group having 1 to 12 carbon atoms Examples thereof include hydrocarbon groups.

Examples of the substituted or unsubstituted aliphatic hydrocarbon group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group. Alkyl group such as pentyl group, hexyl group, octyl group, decyl group and dodecyl group, allyl group, methoxy group, ethoxy group, propoxy group, alkoxy group such as n-butoxy group and tert-butoxy group, dimethylamino group , An alkylamino group such as a diethylamino group,
Alkylthio groups such as methylthio group, ethylthio group, butylthio group, dodecylthio group, amino group-substituted alkyl groups,
Examples thereof include a substituted alkyl group such as an alkoxy-substituted alkyl group, a hydroxyl group-substituted alkyl group and an aryl group-substituted alkyl group, an amino group-substituted alkoxy group, a hydroxyl group-substituted alkoxy group and a substituted alkoxy group such as an aryl group-substituted alkoxy group.

Examples of the substituted or unsubstituted alicyclic hydrocarbon group having 1 to 18 carbon atoms include cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group, cyclohexenyl group and the like, and alkyl group, alkoxy group Examples thereof include those substituted with groups, aryl groups, hydroxyl groups, amino groups, halogens and the like.

Examples of the substituted or unsubstituted aromatic hydrocarbon group having 1 to 18 carbon atoms include aryl groups such as phenyl group and tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group and t-butylphenyl. Alkyl-substituted aryl group such as group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, alkoxy group-substituted aryl group such as t-butoxyphenyl group, phenoxy group,
An aryloxy group such as a cresoxy group, a phenylthio group, a tolylthio group, a diphenylamino group, and the like, and a group in which an amino group, a halogen or the like is substituted, and the like can be given.

Among them, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group,
A substituted or unsubstituted alkylthio group and a substituted or unsubstituted arylthio group are preferred.

Among the phosphine compounds represented by the general formula (II), trialkylphosphines such as tricyclohexylphosphine, tributylphosphine and trioctylphosphine are preferable from the viewpoint of curability when absorbing moisture. From the viewpoint of reflow crack resistance, alkyldiphenylphosphine and dialkylphenylphosphine such as cyclohexyldiphenylphosphine, dicyclohexylphenylphosphine, butyldiphenylphosphine, dibutylphenylphosphine, octyldiphenylphosphine and dioctylphenylphosphine are preferable.

The quinone compound represented by the general formula (III) may have a ring structure in which R ⁵ and R ⁶ are bonded. The polycyclic quinone compound having a cyclic structure formed by combining R ⁵ and R ⁶ used in the present invention is not particularly limited, and examples thereof include a substituted tetramethylene group,
The following general formulas (XVI) to (XVI having a tetramethine group bonded thereto
Examples thereof include polycyclic quinone compounds represented by any of II).

[0032]

[Chemical 14]

Among the quinone compounds represented by the above general formula (III), 1,4-benzoquinone and methyl-1,4-benzoquinone are preferable from the viewpoint of reactivity with the phosphine compound, and the curability at the time of moisture absorption is high. From a perspective, a few
-Alkoxy group-substituted 1,4-benzoquinone such as dimethoxy-1,4 benzoquinone, 2,5-dimethoxy-1,4-benzoquinone and methoxy-1,4-benzoquinone, and 2,3-dimethyl-1,4-benzoquinone , 2,5-
An alkyl group-substituted 1,4-benzoquinone such as dimethyl-1,4-benzoquinone and methyl-1,4-benzoquinone is preferable, and 2,5-di-t- from the viewpoint of storage stability.
Butyl-1,4-benzoquinone, t-butyl-1,4-
Benzoquinone and phenyl-1,4-benzoquinone are preferred.

The structure of the addition reaction product of the phosphine compound represented by the general formula (II) and the quinone compound represented by the general formula (III) is, for example, the following general formula (XI
Examples include compounds represented by X).

[0035]

[Chemical 15] (Where R^TwoRepresents an alkyl group having 1 to 12 carbon atoms,
R^ThreeAnd R^FourIs a hydrogen atom or hydrocarbon water having 1 to 12 carbon atoms
Indicates a basic group, R⁵~ R⁷Is a hydrogen atom or a carbon number of 1 to 1.
8 hydrocarbon groups, all of which are the same or different
May be. R ⁵And R⁶Combine to form a ring structure
You may stay. )

Among the addition reaction products of (C) a phosphine compound having at least one alkyl group bonded to a phosphorus atom and a quinone compound, tricyclohexylphosphine and 1,4-benzoquinone are used from the viewpoint of curability during moisture absorption. Addition reaction product with tricyclohexylphosphine and methyl-1,4-benzoquinone, addition reaction product with tricyclohexylphosphine and 2,3-dimethyl-1,4-benzoquinone, tricyclohexylphosphine and 2, Addition reaction product with 5-dimethyl-1,4-benzoquinone, tricyclohexylphosphine and methoxy-1,
Addition reaction product of 4-benzoquinone, addition reaction product of tricyclohexylphosphine and 2,3-dimethoxy-1,4-benzoquinone, addition reaction product of tricyclohexylphosphine and 2,5-dimethoxy-1,4-benzoquinone , Tributylphosphine and 1,4-benzoquinone addition reaction product, tributylphosphine and methyl-1,4
-Addition reaction product of benzoquinone, addition reaction product of tributylphosphine and 2,3-dimethyl-1,4-benzoquinone, tributylphosphine and 2,5-dimethyl-1,
Addition reaction product with 4-benzoquinone, addition reaction product with tributylphosphine and methoxy-1,4-benzoquinone,
Tributylphosphine and 2,3-dimethoxy-1,4-
Addition reaction product of benzoquinone, addition reaction product of tributylphosphine and 2,5-dimethoxy-1,4-benzoquinone, addition reaction product of trioctylphosphine and 1,4-benzoquinone, trioctylphosphine and methyl-
Addition reaction product of 1,4-benzoquinone, addition reaction product of trioctylphosphine and 2,3-dimethyl-1,4-benzoquinone, addition reaction product of trioctylphosphine and 2,5-dimethyl-1,4-benzoquinone Reaction product, addition reaction product of trioctylphosphine and methoxy-1,4-benzoquinone, addition reaction product of trioctylphosphine and 2,3-dimethoxy-1,4-benzoquinone, trioctylphosphine and 2,5-dimethoxy An addition reaction product of a trialkylphosphine and a quinone compound such as an addition reaction product of -1,4-benzoquinone is preferable.

From the viewpoint of reflow crack resistance, an addition reaction product of cyclohexyldiphenylphosphine and 1,4-benzoquinone, an addition reaction product of cyclohexyldiphenylphosphine and methyl-1,4-benzoquinone, cyclohexyldiphenylphosphine and 2, Addition reaction product with 3-dimethyl-1,4-benzoquinone, cyclohexyldiphenylphosphine and 2,5-dimethyl-1,4-
Addition reaction product of benzoquinone, addition reaction product of cyclohexyldiphenylphosphine and methoxy-1,4-benzoquinone, cyclohexyldiphenylphosphine and 2,
Addition reaction product of 3-dimethoxy-1,4-benzoquinone, addition reaction product of cyclohexyldiphenylphosphine and 2,5-dimethoxy-1,4-benzoquinone, addition reaction product of butyldiphenylphosphine and 1,4-benzoquinone , Butyldiphenylphosphine and methyl-1,
Addition reaction product of 4-benzoquinone, addition reaction product of butyldiphenylphosphine and 2,3-dimethyl-1,4-benzoquinone, butyldiphenylphosphine and 2,5-
Addition reaction product of dimethyl-1,4-benzoquinone, addition reaction product of butyldiphenylphosphine and methoxy-1,4-benzoquinone, addition reaction product of butyldiphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone Addition product of butyldiphenylphosphine and 2,5-dimethoxy-1,4-benzoquinone, addition reaction product of octyldiphenylphosphine and 1,4-benzoquinone, octyldiphenylphosphine and methyl-1,4
-Addition reaction product with benzoquinone, addition reaction product with octyldiphenylphosphine and 2,3-dimethyl-1,4-benzoquinone, octyldiphenylphosphine and 2,5
-Addition reaction product of dimethyl-1,4-benzoquinone, addition reaction product of octyldiphenylphosphine and methoxy-1,4-benzoquinone, addition reaction of octyldiphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone , An addition reaction product of octyldiphenylphosphine and 2,5-dimethoxy-1,4-benzoquinone, an addition reaction product of dicyclohexylphenylphosphine and 1,4-benzoquinone, dicyclohexylphenylphosphine and methyl-1,4-benzoquinone Addition reaction product of dicyclohexylphenylphosphine and 2,3-dimethyl-1,4-benzoquinone, dicyclohexylphenylphosphine and 2,5-dimethyl-1,4-
Addition reaction product of benzoquinone, addition reaction product of dicyclohexylphenylphosphine and methoxy-1,4-benzoquinone, dicyclohexylphenylphosphine and 2,
Addition reaction product of 3-dimethoxy-1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and 2,5-dimethoxy-1,4-benzoquinone, addition product of dibutylphenylphosphine and methyl-1,4-benzoquinone Reactant, dibutylphenylphosphine and 2,
An addition reaction product with 3-dimethyl-1,4-benzoquinone,
Dibutylphenylphosphine and 2,5-dimethyl-1,
Addition reaction product of 4-benzoquinone, addition reaction product of dibutylphenylphosphine and methoxy-1,4-benzoquinone, addition reaction product of dibutylphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone, dibutylphenylphosphine And an addition reaction product of 2,5-dimethoxy-1,4-benzoquinone, an addition reaction product of dioctylphenylphosphine and 1,4-benzoquinone, an addition reaction product of dioctylphenylphosphine and methyl-1,4-benzoquinone, Dioctylphenylphosphine and a few
-Addition reaction product with dimethyl-1,4-benzoquinone, dioctylphenylphosphine and 2,5-dimethyl-1,
Addition reaction product of 4-benzoquinone, addition reaction product of dioctylphenylphosphine and methoxy-1,4-benzoquinone, addition reaction product of dioctylphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone, dioctylphenylphosphine And 2,5-dimethoxy-1,4
An addition reaction product of an alkyldiphenylphosphine or a dialkylphenylphosphine and a quinone compound such as an addition reaction product of benzoquinone is preferred, and an addition reaction product of cyclohexyldiphenylphosphine and 1,4-benzoquinone, butyldiphenylphosphine and 1 , 4-
Addition reaction products of alkyldiphenylphosphine and 1,4-benzoquinone such as addition reaction products of benzoquinone and addition products of octyldiphenylphosphine and 1,4-benzoquinone are more preferable.

From the viewpoint of storage stability, addition reaction products of tricyclohexylphosphine and t-butyl-1,4-benzoquinone, addition reaction products of tributylphosphine and t-butyl-1,4-benzoquinone, Addition reaction product of trioctylphosphine and t-butyl-1,4-benzoquinone, dicyclohexylphenylphosphine and t
-Addition reaction product of butyl-1,4-benzoquinone, addition reaction product of dibutylphenylphosphine and t-butyl-1,4-benzoquinone, addition reaction reaction of dioctylphenylphosphine and t-butyl-1,4-benzoquinone object,
Cyclohexyldiphenylphosphine and t-butyl-
Addition reaction product of 1,4-benzoquinone, addition reaction product of butyldiphenylphosphine and t-butyl-1,4-benzoquinone, addition reaction product of octyldiphenylphosphine and t-butyl-1,4-benzoquinone, dicyclohexyl -P-tolylphosphine and t-butyl-1,4-
Addition reaction product of benzoquinone, addition reaction product of dibutyl-p-tolylphosphine and t-butyl-1,4-benzoquinone, addition reaction product of dioctyl-p-tolylphosphine and t-butyl-1,4-benzoquinone , Cyclohexyldi-p-tolylphosphine and t-butyl-1,4-
Addition reaction product of benzoquinone, addition reaction product of butyldi-p-tolylphosphine and t-butyl-1,4-benzoquinone, addition reaction product of octyldi-p-tolylphosphine and t-butyl-1,4-benzoquinone , An addition reaction product of tricyclohexylphosphine and phenyl-1,4-benzoquinone, tributylphosphine and phenyl-
Addition reaction product with 1,4-benzoquinone, addition reaction product with trioctylphosphine and phenyl-1,4-benzoquinone, addition reaction product with dicyclohexylphenylphosphine and phenyl-1,4-benzoquinone, dibutylphenylphosphine and phenyl Addition reaction product of -1,4-benzoquinone, addition reaction product of dioctylphenylphosphine and phenyl-1,4-benzoquinone, addition reaction product of cyclohexyldiphenylphosphine and phenyl-1,4-benzoquinone, butyldiphenylphosphine An addition reaction product of phenyl-1,4-benzoquinone, an addition reaction product of octyldiphenylphosphine and phenyl-1,4-benzoquinone, an addition reaction product of dicyclohexyl-p-tolylphosphine and phenyl-1,4-benzoquinone, Dibutyl- - tolylphosphine and phenyl -
Dioctyl-p, an addition reaction product with 1,4-benzoquinone
-Addition reaction product of tolylphosphine and phenyl-1,4-benzoquinone, addition reaction product of cyclohexyldi-p-tolylphosphine and phenyl-1,4-benzoquinone, butyldi-p-tolylphosphine and phenyl-1,
An addition reaction product with 4-benzoquinone, an addition reaction product with octyldi-p-tolylphosphine and phenyl-1,4-benzoquinone, and the like are preferable. Among them, tricyclohexylphosphine and t-butyl-1,4-benzoquinone are preferable. Addition reaction product, tributylphosphine and t-butyl-1,
Addition reaction product of 4-benzoquinone, addition reaction product of trioctylphosphine and t-butyl-1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and t-butyl-1,4-benzoquinone, dibutylphenylphosphine Addition product of t-butyl-1,4-benzoquinone with dioctylphenylphosphine and t-butyl-1,4-benzoquinone, cyclohexyldiphenylphosphine with t-butyl-1,4-benzoquinone Addition reaction product, addition reaction product of butyldiphenylphosphine and t-butyl-1,4-benzoquinone, octyldiphenylphosphine and t-butyl-1,
An addition reaction product of a phosphine compound having at least one alkyl group such as an addition reaction product with 4-benzoquinone and a quinone compound having a t-butyl group is more preferable.

Among the above, from the viewpoint of the reactivity between the phosphine compound and the quinone compound, the addition reaction product of tricyclohexylphosphine and 1,4-benzoquinone, and the addition reaction product of tricyclohexylphosphine and methyl-1,4-benzoquinone. Addition reaction product, tributylphosphine and 1,4
-Addition reaction product of benzoquinone, addition reaction product of tributylphosphine and methyl-1,4-benzoquinone, addition reaction product of trioctylphosphine and 1,4-benzoquinone, trioctylphosphine and methyl-1,4-benzoquinone Addition reaction product of cyclohexyldiphenylphosphine with 1,4-benzoquinone, addition reaction product of cyclohexyldiphenylphosphine with methyl-1,4-benzoquinone, addition of butyldiphenylphosphine with 1,4-benzoquinone Reaction product, addition reaction product of butyldiphenylphosphine and methyl-1,4-benzoquinone, octyldiphenylphosphine and 1,4-
Addition reaction product of benzoquinone, addition reaction product of octyldiphenylphosphine and methyl-1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and 1,4-benzoquinone, dicyclohexylphenylphosphine and methyl-1,4-benzoquinone More preferred is an addition reaction product of 1,4-benzoquinone or methyl-1,4-benzoquinone with a phosphine compound having at least one alkyl group bonded to a phosphorus atom, such as an addition reaction product of.

There are no particular restrictions on the method for producing the addition reaction product of (C) the phosphine compound in which at least one alkyl group is bonded to the phosphorus atom, and the quinone compound. For example, the phosphine compound and the quinone compound used as raw materials may be used. Examples of the method include a method of performing an addition reaction in an organic solvent in which both are dissolved, and a method of performing an addition reaction in a phenol resin as the component (B). In the latter method, the product is directly isolated in the phenol resin without isolation. In a dissolved state, it can be used as a blending component of the epoxy resin composition.
(C) An addition reaction product of a phosphine compound in which at least one alkyl group is bonded to a phosphorus atom and a quinone compound is
You may use individually by 1 type and may be used in combination of 2 or more type.

In addition to the component (C), the resin composition of the present invention may be used in combination with one or more of the compounds generally used as a curing accelerator for promoting the curing reaction between the epoxy resin and the phenol resin. You can Examples of these curing accelerators include 1,5-diazabicyclo [4.3.
0] nonene-5,1,8-diazabicyclo [5.4.
[0] Cycloamidine compounds such as diazabicycloalkene such as undecene-7, derivatives thereof, phenol novolac salts thereof and maleic anhydride to these compounds,
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, quinone compounds such as phenyl-1,4-benzoquinone, compounds having intramolecular polarization formed by adding compounds having a π bond such as diazophenylmethane, triethylenediamine, benzyldimethylamine,
Tertiary amines such as triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives, 2-methylimidazole, 2
-Phenylimidazole, 2-phenyl-4-methylimidazole, 2-imidazole such as 2-heptadecylimidazole, tetra-substituted phosphonium / tetra-substituted borate such as tetraphenylphosphonium / tetraphenylborate, 2-ethyl-4-methylimidazole / tetra Phenylborate, tetraphenylboron salts such as N-methylmorpholine / tetraphenylborate, triphenylphosphine, diphenyl (alkylphenyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) Phosphine, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris Organic phosphines such as dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, and complexes of these organic phosphines with organic borons. Examples include betaine-type addition reaction products of arylphosphines such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, and diphenyl (alkylphenyl) phosphine with the above quinone compounds such as 1,4-benzoquinone. To be

When these curing accelerators are used in combination,
The content of the component (C) is preferably 30% by weight or more, and more preferably 50% by weight or more, based on the total amount of the curing accelerator. When the content of the component (C) is less than 30% by weight, the curability or fluidity when absorbing moisture decreases, and the effect of the present invention tends to decrease.

The total amount of all the curing accelerators containing the component (C) is not particularly limited as long as the curing acceleration effect can be obtained, but from the viewpoint of curability during moisture absorption and fluidity, the epoxy resin (A) and the epoxy resin ( The total amount of the B) phenol resin is preferably 0.1 to 10 parts by weight, more preferably 1 to 7 parts by weight, based on 100 parts by weight. If it is less than 0.1 part by weight, it is difficult to cure it in a short time, and if it exceeds 10 parts by weight, the curing rate tends to be too fast and a good molded product may not be obtained.

The epoxy resin composition of the present invention comprises (D)
Inorganic fillers can be further added if necessary. Particularly when the epoxy resin composition is used as a molding material for sealing, it is preferable to incorporate (D) an inorganic filler. The inorganic filler (D) used in the present invention is not particularly limited and is generally used for molding materials for sealing, and examples thereof include 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, talc, clay, mica, etc. Can be mentioned. Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, complex metal hydroxides such as complex hydroxide of magnesium and zinc, and zinc borate. Of 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. These inorganic fillers may be used alone or in combination of two or more.

The amount of the inorganic filler (D) is not particularly limited as long as the effects of the present invention can be obtained, but it is preferably in the range of 55 to 90% by volume with respect to the epoxy resin composition. These inorganic fillers are added for the purpose of improving the thermal expansion coefficient, thermal conductivity, elastic modulus, etc. of the cured product, and if the content is less than 55% by volume, the improvement of these properties tends to be insufficient. However, if it exceeds 90% by volume, the viscosity of the epoxy resin composition increases, the fluidity decreases, and molding tends to be difficult. The average particle size of the (D) inorganic filler is 1 to
50 μm is preferable, and 10 to 30 μm 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 likely to separate from each other, and the cured product becomes non-uniform, the cured product characteristics vary, or a narrow gap is formed. The filling property of the product tends to decrease. From the viewpoint of fluidity, the particle shape of the (D) inorganic filler is preferably spherical rather than square, and the particle size distribution of the (D) inorganic filler is preferably in a wide range. For example,
When 75% by volume or more of the inorganic filler is blended, 70% by weight or more of the inorganic filler is preferably spherical particles and distributed in a wide range of 0.1 to 80 μm. Since such an inorganic filler tends to have a close-packed structure, the viscosity of the material does not increase even if the compounding amount is increased, and an epoxy resin composition having excellent fluidity can be obtained.

An anion exchanger can be added to the epoxy resin composition of the present invention as required. Particularly when the epoxy resin composition is used as a molding material for sealing, it is preferable to mix an anion exchanger from the viewpoint of improving the moisture resistance and the high temperature storage property of the electronic component device including the element to be sealed. . There is no particular limitation on the anion exchanger used in the present invention, and conventionally known ones can be used. For example, hydrotalcites and water containing an element selected from magnesium, aluminum, titanium, zirconium and bismuth. Examples thereof include oxides, and these can be used alone or in combination of two or more kinds. Among them, hydrotalcite represented by the following general formula (XX) is preferable. _{Mg 1-X Al X (OH} ) 2 (CO 3) X / 2 · mH 2 O ...... (XX) (0 <X ≦ 0.5, m is a positive integer) The amount of the anion exchanger Is not particularly limited as long as it is an amount sufficient to capture anions such as halogen ions, but is 0.1 to 30% by weight with respect to the epoxy resin (A).
Is preferable, and 1 to 5% by weight is more preferable.

The epoxy resin composition of the present invention contains epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, vinylsilane, etc. as a coupling agent for increasing the adhesiveness between the resin component and the inorganic filler. Known additives such as various silane compounds, titanium compounds, aluminum chelates, and aluminum / zirconium compounds can be blended as necessary. Further, known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead and red iron oxide may be added.

A releasing agent may be added to the epoxy resin composition of the present invention in order to have a good releasing property with respect to the mold at the time of molding. The release agent used in the present invention is not particularly limited and may be a conventionally known one.
Examples thereof include higher fatty acids such as carnauba wax, montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid ester, polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene, and the like. They may be used alone or in combination of two or more. Above all, an oxidized or non-oxidized polyolefin wax is preferable, and its compounding amount is preferably 0.01 to 10% by weight, and more preferably 0.1 to 5% by weight, relative to the epoxy resin (A). If the content 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 impaired. Examples of the polyolefin wax include commercially available products such as H4 and P manufactured by Hoechst.
The number average molecular weight of E, PED series, etc. is 500-100.
A low molecular weight polyethylene of about 00 and the like can be mentioned. When other releasing agent is used in combination with the polyolefin wax, the compounding amount is 0.1 with respect to the epoxy resin (A).
10 to 10% by weight is preferable, and 0.5 to 3% by weight is more preferable.

A flame retardant may be added to the epoxy resin composition of the present invention, if necessary, in order to impart flame retardancy. The flame retardant used in the present invention is not particularly limited, for example, a halogen atom, an antimony atom,
Known organic or inorganic compounds containing a nitrogen atom or a phosphorus atom, metal hydroxides and the like can be mentioned, and one kind thereof may be used alone or two or more kinds thereof may be used in combination.
The amount of the flame retardant compounded is not particularly limited as long as the flame retardant effect is achieved, but is preferably 1 to 30% by weight, more preferably 2 to 15% by weight, based on the epoxy resin (A). Further, the epoxy resin composition of the present invention may be blended with other additives such as stress relieving agents such as silicone oil and silicone rubber powder, if necessary.

The epoxy resin composition of the present invention can be prepared by any method as long as it can uniformly disperse and mix various components. As a general method, a predetermined amount of the components is mixed with a mixer or the like. After mixing well, after mixing and kneading by mixing roll, extruder, etc., cooling,
A method of crushing can be mentioned. For example, a predetermined amount of the above-mentioned components are uniformly stirred and mixed, and 70 to 140 in advance.
It can be obtained by a method such as kneading with a kneader, roll, extruder or the like heated to ℃, cooling, and pulverizing. It is easy to use if it is made into a tablet with dimensions and weight that match the molding conditions.

An electronic component device obtained by encapsulating an element with the epoxy resin composition obtained in the present invention includes a lead frame, a pre-wiring tape carrier, a wiring board, glass, a silicon wafer, and other supporting members, and a semiconductor. Chips, transistors, diodes, active elements such as thyristors, elements such as capacitors, resistors, passive elements such as coils, etc. are mounted, and necessary parts are sealed with the epoxy resin composition of the present invention. Can be mentioned. As such an electronic component device, for example, a semiconductor element is fixed on a lead frame, the terminal portion of the element such as a bonding pad and the lead portion are connected by wire bonding or bumps, and then the epoxy resin composition of the present invention is used. DIP (Dual Inline Packag)
e), PLCC (Plastic Leaded Chip Carrier), QF
P (Quad Flat Package), SOP (Small Outline Pac)
kage), SOJ (Small Outline J-lead Package), T
SOP (Thin Small Outline Package), TQFP (Th
in Quad Flat Package) general resin encapsulation type IC,
A TCP (Tape Car) in which a semiconductor chip connected to a tape carrier by a bump is sealed with the epoxy resin composition of the present invention.
rier Package), wiring formed on a wiring board or glass,
Active elements and / or capacitors such as semiconductor chips, transistors, diodes and thyristors connected by wire bonding, flip chip bonding, soldering, etc.
A COB (Chip On Board) module in which passive elements such as resistors and coils are sealed with the epoxy resin composition of the present invention, a hybrid IC, a multi-chip module, and an organic substrate in which terminals for connecting a wiring board are formed on the back surface. BGA (Ball Grid) in which an element is mounted on the surface, the element and the wiring formed on the organic substrate are connected by bumping or wire bonding, and then the element is sealed with the epoxy resin composition of the present invention.
Array), CSP (Chip Size Package) and the like. Also, the epoxy resin composition of the present invention can be effectively used for printed circuit boards.

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

[0053]

EXAMPLES Examples of the present invention will be shown below, but the scope of the present invention is not limited to these examples. Examples 1 to 9 and Comparative Examples 1 to 10 Epoxy equivalent of the epoxy resin is 245, melting point 110
Diaryl sulfide skeleton epoxy resin (epoxy resin 1: trade name YSLV-12 manufactured by Nippon Steel Chemical Co., Ltd.
0TE), epoxy equivalent 196, melting point 106 ° C. biphenyl skeleton type epoxy resin (epoxy resin 2: Yuka Shell Epoxy Co., Ltd. product name YX-4000H), epoxy equivalent 195, softening point 62 ° C. orthocresol novolac type epoxy resin. (Epoxy resin 3: Sumitomo Chemical Co., Ltd., trade name ESCN-190-2), epoxy equivalent 393, softening point 80 ° C., bromine content 48 weight% brominated bisphenol A type epoxy resin (brominated epoxy resin), As a curing agent, the hydroxyl equivalent is 176 and the softening point is 70 ° C.
Phenol aralkyl resin (hardening agent 1: Mitsui Chemicals, Inc., trade name Milex XL-225), hydroxyl equivalent 1
Biphenyl skeleton type phenol resin having a softening point of 89 ° C. (hardening agent 2: Meiwa Kasei Co., Ltd., trade name MEH-785
1), a hydroxyl equivalent 183, a naphthol aralkyl resin having a softening point of 79 ° C. (curing agent 3: Nippon Steel Chemical Co., Ltd. trade name SN-170), a hydroxyl equivalent 170, and a dicyclopentadiene-modified phenol novolac resin having a softening point of 93 ° C. (Curing agent 4: trade name DPP manufactured by Nippon Petrochemical Co., Ltd.), as a curing accelerator, an addition reaction product of tributylphosphine and 1,4-benzoquinone (curing accelerator 1), tricyclohexylphosphine and 1,4-benzoquinone. Addition reaction product (curing accelerator 2), cyclohexyldiphenylphosphine and 1,4-benzoquinone addition reaction product (curing accelerator 3), triphenylphosphine and 1,4-benzoquinone addition reaction product (curing acceleration) Agent 4), triphenylphosphine (curing accelerator 5), inorganic filler having an average particle size of 17.5 μm, ratio With spherical fused silica area 3.8 m 2 / ^g, .gamma.-glycidoxypropyltrimethoxysilane as a coupling agent as other additives components, carbon black (Mitsubishi Chemical Corporation, trade name MA-100 as a colorant ), Carnauba wax (manufactured by Celarica NODA Co., Ltd.) as a release agent, antimony trioxide as a flame retardant, and blended in parts by weight shown in Tables 1 and 2, under conditions of a kneading temperature of 80 ° C. and a kneading time of 15 minutes. Roll kneading was performed to obtain epoxy resin compositions of Examples 1-9 and Comparative Examples 1-10.

[0054]

[Table 1]

[0055]

[Table 2]

The epoxy resin compositions of Examples and Comparative Examples were
It evaluated by the following each test. The evaluation results are shown in Tables 3 and 4. The epoxy resin composition is molded by a transfer molding machine at a mold temperature of 180 ° C and a molding pressure of 7MP.
a, the curing time was 90 seconds. Also, the post-curing is 1
It was carried out at 75 ° C for 6 hours. (1) Spiral flow (index of fluidity) Using a mold for spiral flow measurement according to EMMI-1-66, the epoxy resin composition was molded under the above conditions and the flow distance (cm) was measured. (2) Hardness at heat The epoxy resin composition is 50 mm in diameter and 3 in thickness under the above conditions.
It was molded into a disc having a size of mm, and immediately after molding, the hardness was measured using a Shore D type hardness meter. (3) Hardness at the time of moisture absorption When the epoxy resin composition is heated at a temperature of 25 ° C./50% RH
After standing for a time, it was molded in the same manner as in (2) above and measured using a Shore D hardness meter. (4) Reflow crack resistance 14 A QFP80 pin package having an external dimension of 14 × 20 × 2.0 mm, in which a test silicon chip having a dimension of 8 × 10 × 0.4 mm is mounted on a 142 alloy frame by using a silver paste, Molded under the above conditions using an epoxy resin composition and post-cured to prepare, and under the conditions of 85 ° C. and 85% RH, 1
After absorbing moisture for 68 hours, a reflow process was performed under the conditions of 215 ° C. and 90 seconds by a vapor phase reflow device to confirm the presence or absence of cracks, and the number of cracked packages against the number of test packages (5) was evaluated. . (5) Resistance to reflow cracking 2 Moisture absorption time was set to 168 hours and 240 with an IR reflow device.
Evaluation was carried out in the same manner as in (4) above, except that the reflow treatment was carried out under the conditions of ° C and 10 seconds. (6) Reflow crack resistance 3 Moisture absorption time is 72 hours, 96 hours, 168 hours, IR
Evaluation was performed in the same manner as in (4) above, except that the reflow treatment was carried out at 260 ° C. for 10 seconds using a reflow device.

[0057]

[Table 3]

[0058]

[Table 4]

In each of Examples 1 to 9, the fluidity (110
cm or more), hardness at heat (79 or more), hardness at heat absorption (7
8 or more). Reflow crack resistance is also 85
Even after a rigorous condition of reflowing at 260 ° C. after absorbing moisture for 96 hours at 85 ° C. and 85% RH, it is good without cracks. On the other hand, in Comparative Examples 7 and 9 not containing the component (A) of the present invention, the reflow crack resistance at 260 ° C. was inferior to that of the Examples. Further, in Comparative Examples 1 to 6, 8 and 10 which do not contain the component (C) of the present invention, the hardness at the time of moisture absorption and heat is significantly inferior. Further, in Comparative Example 2, the fluidity is also inferior.

[0060]

The epoxy resin composition according to the present invention is excellent in curability and fluidity when absorbing moisture. If the epoxy resin composition is used to seal electronic parts such as IC and LSI, As shown, it is possible to obtain an electronic component device having excellent reflow crack resistance and excellent reliability, so that its industrial value is great.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J036 AD07 AD08 AD20 AF06 AF15                       AJ09 AK19 DB06 DC09 DC40                       DC46 FA01 FA02 FA03 FA05                       FA12 FB06 FB07 GA01 GA04                       GA06 JA06 JA07 JA08                 4M109 AA01 CA21 EA02 EB04

Claims (8)

[Claims] 1. An addition reaction product of (A) an epoxy resin containing a sulfur atom, (B) a phenol resin, and (C) a phosphine compound having at least one alkyl group bonded to a phosphorus atom, and a quinone compound as essential components. Epoxy resin composition. 2. The epoxy resin (A) containing a sulfur atom is an epoxy resin having a sulfide skeleton.
The epoxy resin composition described. 3. The epoxy resin composition according to claim 1 or 2, wherein the epoxy resin (A) containing a sulfur atom is a compound represented by the following general formula (I). (Here, R ¹ in the formula (I) is a hydrogen atom or a carbon number of 1 to
12 alkyl and aryl groups are shown, which may be the same or different. n is an average value and is 0
Indicates a positive number from -10. ). 4. (C) At least one alkyl group at a phosphorus atom
Of a phosphine compound having a killed group and a quinone compound
The addition reaction product is a phosphine represented by the following general formula (II).
A compound and a quinone compound represented by the following general formula (III):
The epoxy resin set according to claim 1, which is an addition reaction product of
Adult [Chemical 2] (Where R in the formula (II)^TwoIs an alky having 1 to 12 carbons
R group^ThreeAnd R ^FourIs a hydrogen atom or a carbon number of 1 to
12 hydrocarbon groups, all of which are the same or different
You may In addition, R in the formula (III)⁵~ R⁷Is
A hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms,
All of them may be the same or different. R⁵And R⁶But
It may be bonded to form a ring structure. ). 5. An inorganic filler (D) is further contained, and the amount thereof is 55 to 90% by volume based on the epoxy resin composition.
The epoxy resin composition according to any one of claims 1 to 4. 6. The epoxy resin composition according to claim 1, wherein the epoxy resin (A) containing a sulfur atom contains an epoxy resin represented by the following general formula (IV). 3] (Here, n in the general formula (IV) is an average value and is 0 to 10
Indicates a positive number. ). 7. The epoxy according to claim 1, wherein the (B) phenolic resin contains at least one phenolic resin represented by any one of the following general formulas (V) to (IX). Resin composition [Chemical formula 4] (Here, R < ⁸ > -R < ¹⁷ > in General Formula (V)-(IX) shows a hydrogen atom or a C1-C6 alkyl group, and all may be the same or different. N is an average value. Is a positive number from 0 to 10, i is an integer from 0 to 3, and j is 0 to 2.
Is an integer, k is an integer of 0 to 4, and r is an integer of 0 to 4. ). 8. An electronic component device comprising an element sealed with the epoxy resin composition according to claim 1.