KR20120080128A - Epoxy resin composition for encapsulation and electronic component device - Google Patents

Abstract

PURPOSE: An epoxy resin composition is provided to have excellent flow-resistance and high adhesion with metal at high temperature. CONSTITUTION: An epoxy resin composition comprises: an epoxy resin containing two or more epoxy groups in one molecule; a curing agent; and a benzophenone derivative having one or more phenolic hydroxy groups in one molecule. The content of the benzophenone derivative having one or more phenolic hydroxy group is 0.1-1.0 weight%. The epoxy resin composition additionally comprises a silane compound, a curing accelerator, and/or inorganic filler.

Description

Epoxy resin composition and electronic component device for sealing {EPOXY RESIN COMPOSITION FOR ENCAPSULATION AND ELECTRONIC COMPONENT DEVICE}

TECHNICAL FIELD This invention relates to the electronic component apparatus provided with the sealing epoxy resin composition and the element sealed with this sealing epoxy resin composition.

Conventionally, the epoxy resin composition for sealing is widely used in the field of electronic component sealing, such as a transistor and IC. This is because the epoxy resin can balance electric properties, moisture resistance, heat resistance, mechanical properties, adhesiveness with insert products, and the like. In particular, the combination of an orthocresol novolak-type epoxy resin and a novolak-type phenol curing agent is excellent in these balances and is becoming the mainstream of the base resin of the composition for sealing.

In recent years, as the electronic devices have been miniaturized, reduced in weight, and improved in performance, high-density mounting has been progressed, and electronic component devices have been made to have surface-mount packages from conventional pin-insert packages. When attaching a semiconductor device to a wiring board, in the conventional pin insertion type package, since the pin is inserted into the wiring board and soldered from the back of the wiring board, the package is not directly exposed to high temperature. However, in the surface mount package, since the whole semiconductor device is processed by a solder bath, a reflow apparatus, etc., a package is exposed to soldering temperature. As a result, when the package is absorbed, there is a problem that the absorbed moisture rapidly expands during soldering, causing peeling of the adhesive interface and cracking of the package, thereby lowering the reliability of the package at the time of mounting.

As a countermeasure to solve the above problem, a method is disclosed in which the IC is moisture-proof packed to reduce moisture absorption moisture inside the semiconductor device, or the IC is sufficiently dried before being mounted on the wiring board. However, these methods are time consuming and costly.

Another method is to increase the content of the filler in the epoxy resin composition for sealing. However, in this method, although the moisture absorption moisture of the sealing part in a semiconductor device reduces, there exists a problem that it causes the drastic fall of the fluidity | liquidity of the epoxy resin composition for sealing. When the fluidity of the sealing epoxy resin composition is low, problems such as shedding of gold wire, generation of voids, pinholes, and the like during molding occur.

In addition, Japanese Patent Laid-Open No. 06-224328 discloses a resin composition for semiconductor encapsulation in which the particle size distribution of a filler to be blended into an epoxy resin is in a specific range. According to this resin composition for semiconductor sealing, content of a filler is increased, without impairing fluidity | liquidity, and thermal expansion characteristic, thermal conductivity characteristic, hygroscopic resistance, and bending strength are said to improve.

In addition, Japanese Patent Application Laid-Open No. 09-165433 discloses a method for producing an epoxy resin by reacting polyhydric phenols with epihalohydrin, and a mixture of dihydroxybenzophenone and other polyhydric phenols as polyhydric phenols. The manufacturing method of the epoxy resin to be used is disclosed. In the present invention, the dihydroxy benzophenone is used in the synthesis step of the epoxy resin, and the epoxy resin obtained is mixed with a phenol novolak resin, silica powder or the like to prepare an epoxy resin composition. This epoxy resin composition is said to be excellent in curability and fluidity | liquidity, but is not crystalline.

In the invention of Japanese Patent Application Laid-Open No. 09-165433, curability and fluidity are improved, but it has been found that adhesiveness with a metal at a high temperature may decrease. It is desired to improve the adhesiveness with a metal at high temperature from the viewpoint of the reflow property improvement.

This invention is made | formed in view of such a situation, and it is a subject to provide the electronic component apparatus provided with the sealing epoxy resin composition which is high in adhesiveness with the metal at high temperature, and excellent in reflow property, and the element sealed by this. Shall be.

The present invention relates to the following.

(1) The epoxy resin composition for sealing containing the epoxy resin which contains 2 or more epoxy groups in (A) 1 molecule, (B) hardening | curing agent, and (C) benzophenone derivative which has 1 or more phenolic hydroxyl group in 1 molecule.

(2) The epoxy resin composition for sealing as described in said (1) whose content rate of the benzophenone derivative which has one or more phenolic hydroxyl group in 1 molecule of said (C) is 0.1 mass% or more and 1.0 mass% or less.

(3) The epoxy resin composition for sealing as described in said (1) or (2) which further contains the (D) silane compound.

(4) The epoxy resin composition for sealing as described in any one of said (1)-(3) which further contains (E) hardening accelerator.

(5) The epoxy resin composition for sealing as described in any one of said (1)-(4) which further contains (F) inorganic filler.

(6) The electronic component apparatus provided with the element sealed by the sealing epoxy resin composition in any one of said (1)-(5).

According to the present invention, it is possible to provide an epoxy component composition for sealing having high adhesion to a metal at a high temperature, and excellent in reflow property, and an electronic component device having a sealed element thereby.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

In addition, in this specification, "-" shall show the range which includes the numerical value described before and after that as minimum value and the maximum value, respectively. In addition, the quantity of each component in a composition in this specification means the total amount of the said some substance which exists in a composition, when there exists two or more substances corresponding to each component in a composition, unless there is particular notice.

<Epoxy resin composition for sealing>

The epoxy resin composition for sealing of this invention contains the epoxy resin which contains two or more epoxy groups in (A) 1 molecule, the (B) hardening | curing agent, and the (B) benzophenone derivative which has one or more phenolic hydroxyl groups in 1 molecule. do. The sealing epoxy resin composition of this invention is solid at room temperature (25 degreeC).

Hereinafter, each component which comprises the epoxy resin composition for sealing of this invention is demonstrated.

[(A) Epoxy Resin]

The epoxy resin containing two or more epoxy groups in 1 molecule of (A) used in this invention will not be restrict | limited especially if it is generally used for the epoxy resin composition for sealing. For example, phenol novolak type epoxy resins, orthocresol novolak type epoxy resins, phenols including creep, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, α A novolac resin obtained by condensation or co-condensation of a phenol such as naphthol, β-naphthol, dihydroxynaphthalene and a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylicaldehyde under an acidic catalyst Epoxidized; Diglycidyl ethers such as alkyl substituted, aromatic substituted or unsubstituted bisphenol A, bisphenol F, bisphenol S, biphenol and thiodiphenol; Stilbene type epoxy resin; Hydroquinone type epoxy resins; Glycidyl ester type epoxy resin obtained by reaction with polybasic acids, such as a phthalic acid and a dimer acid, and epichlorohydrin; Glycidylamine type epoxy resins obtained by reaction of polyamines such as diaminodiphenylmethane and isocyanuric acid with epichlorohydrin; Epoxide of the cocondensation resin of dicyclopentadiene and phenols; An epoxy resin having a naphthalene ring; Phenol-aralkyl resins synthesized from phenols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl; Epoxides of aralkyl type phenol resins such as naphthol and aralkyl resins; Trimethylolpropane type epoxy resin; Terpene modified epoxy resins; Linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid; Alicyclic epoxy resin etc. are mentioned. These 1 type may be used independently and may be used in combination of 2 or more type.

Among them, it is preferable to contain a biphenyl type epoxy resin which is an alkyl substituted, aromatic substituted or unsubstituted diglycidyl ether from the viewpoint of both fluidity and curability, and a novolak type epoxy from the viewpoint of curability. It is preferable to contain resin, and it is preferable to contain a naphthalene type epoxy resin and / or a triphenylmethane type epoxy resin from a heat resistant and a low warpage viewpoint, and it is an alkyl substitution and an aromatic ring substitution from a viewpoint of both fluidity and a flame retardance. Or a bisphenol F-type epoxy resin, which is a diglycidyl ether of unsubstituted bisphenol F, and preferably contains an alkyl substituted, aromatic substituted or unsubstituted thiodiphenol from the viewpoint of both fluidity and reflowability. It is preferable to contain the thiodiphenol type epoxy resin which is diglycidyl ether, and it is curable From the standpoint of compatibility of flame retardancy, it is preferable to contain an epoxide of phenol-aralkyl resin synthesized from alkyl-substituted, aromatic-substituted or unsubstituted phenol and bis (methoxymethyl) biphenyl. From a compatible viewpoint, it is preferable to contain the epoxide of the naphthol aralkyl resin synthesize | combined from the alkyl substituted, aromatic ring substituted or unsubstituted naphthol, and dimethoxy para xylene.

As said biphenyl type epoxy resin, the epoxy resin etc. which are represented by following General formula (I) are mentioned, for example.

<Formula I>

In the general formula (I), R ¹ to R ⁸ each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. R ¹ to R ⁸ may be all the same or different. n represents the integer of 0-3.

The biphenyl type epoxy resin represented by the said general formula (I) is obtained by making epichlorohydrin react with a biphenol compound by a well-known method.

As R ¹ to R ⁸ in the formula (I), for example, each independently a hydrogen atom; Alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group and tert-butyl group; C1-C10 alkenyl groups, such as a vinyl group, an allyl group, and a butenyl group, etc. are mentioned. Especially, a hydrogen atom or a methyl group is respectively independently preferable.

As such an epoxy resin, for example, 4,4'-bis (2,3-epoxypropoxy) biphenyl or 4,4'-bis (2,3-epoxypropoxy) -3,3 ', 5,5 Epoxy resins based on '-tetramethylbiphenyl, epichlorohydrin and 4,4'-biphenol or 4,4'-(3,3 ', 5,5'-tetramethyl) biphenol Epoxy resin obtained etc. are mentioned.

Especially, the epoxy resin which has a 4,4'-bis (2, 3- epoxy propoxy) -3, 3 ', 5, 5'- tetramethyl biphenyl as a main component is preferable. As such an epoxy resin, Mitsubishi Chemical Corporation (formerly Japan Epoxy Resin Chemical Industries, Ltd.) brand name YX-4000 is available as a commercial item.

When using the said biphenyl type epoxy resin, it is preferable to make the content rate into 20 mass% or more in epoxy resin whole quantity, in order to exhibit the performance, 30 mass% or more is more preferable, 50 mass% or more is more preferable. Do.

As said thiodiphenol type epoxy resin, the epoxy resin etc. which are represented by following General formula (II) are mentioned, for example.

&Lt;

In Formula (II), R ¹ to R ⁸ each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. R ¹ to R ⁸ may be all the same or different. n represents the integer of 0-3.

The thiodiphenol type epoxy resin represented by the said Formula (II) is obtained by making epichlorohydrin react with a thiodiphenol compound by a well-known method.

As R ¹ to R ⁸ in the formula (II), for example, each independently a hydrogen atom; Alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group and tert-butyl group; C1-C10 alkenyl groups, such as a vinyl group, an allyl group, and a butenyl group, etc. are mentioned. Especially, a hydrogen atom, a methyl group, or tert- butyl group is respectively independently preferable.

As such an epoxy resin, the epoxy resin which has a diglycidyl ether of 4,4'- dihydroxy diphenyl sulfide as a main component, 2,2 ', 5,5'- tetramethyl-4,4', for example Epoxy resin mainly containing diglycidyl ether of dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'- dihydroxy-5,5'- di-tert- butyl diphenyl sulfone The epoxy resin etc. which have the diglycidyl ether of a feed as a main component are mentioned.

Especially, epoxy resin which has an epoxy resin which has a diglycidyl ether of 2,2'- dimethyl- 4,4'- dihydroxy-5,5'- di-tert- butyl diphenyl sulfide as a main component Is preferred. As such a commercially available epoxy resin, Shinnitetsu Chemical Co., Ltd. brand name YSLV-120TE is available.

When using the said thiodiphenol type epoxy resin, in order to show the performance, it is preferable to make it 20 mass% or more in epoxy resin whole quantity, 30 mass% or more is more preferable, and 50 mass% or more further desirable.

As said bisphenol F-type epoxy resin, the epoxy resin etc. which are represented by following General formula (III) are mentioned, for example.

<Formula III>

In formula (III), R ¹ to R ⁸ each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. R ¹ to R ⁸ may be all the same or different. n represents the integer of 0-3.

The bisphenol F-type epoxy resin represented by the general formula (III) is obtained by reacting epichlorohydrin with a bisphenol F compound by a known method.

As R ¹ to R ⁸ in the formula (III), for example, each independently a hydrogen atom; Alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group and tert-butyl group; C1-C10 alkenyl groups, such as a vinyl group, an allyl group, and a butenyl group, etc. are mentioned. Especially, a hydrogen atom or a methyl group is respectively independently preferable.

As such an epoxy resin, the epoxy resin which has diglycidyl ether of 4,4'- methylenebis (2,6-dimethylphenol) as a main component, 4,4'- methylenebis (2,3,6-, for example) Epoxy resin which has diglycidyl ether of trimethylphenol) as a main component, and epoxy resin which has diglycidyl ether of 4,4'-methylene bisphenol as a main component, etc. are mentioned. Especially, the epoxy resin which has diglycidyl ether of 4,4'- methylenebis (2, 6- dimethylphenol) as a main component is preferable. As such a commercially available epoxy resin, Shinnitetsu Chemical Co., Ltd. brand name YSLV-80XY can be obtained.

When using the said bisphenol F-type epoxy resin, in order to exhibit the performance, it is preferable to make it 20 mass% or more in epoxy resin whole quantity, 30 mass% or more is more preferable, 50 mass% or more is more preferable. Do.

As said novolak-type epoxy resin, the epoxy resin etc. which are represented by following General formula (IV) are mentioned, for example.

(IV)

In formula (IV), each R independently represents a hydrogen atom; Or a substituted or unsubstituted monovalent group having 1 to 10 carbon atoms composed of an element selected from carbon atoms, hydrogen atoms, and oxygen atoms, and n represents an integer of 0 to 10.

The novolak-type epoxy resin represented by the said general formula (IV) is obtained by making epichlorohydrin react with a novolak-type phenol resin.

R in the general formula (IV) is each independently a hydrogen atom; Alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, isopropyl group and isobutyl group; Alkoxy groups having 1 to 10 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group, are preferable, and a hydrogen atom or a methyl group is more preferable. n is preferably an integer of 0 to 3.

Among the novolak-type epoxy resins represented by the general formula (IV), orthocresol novolak-type epoxy resins are preferable. As such an epoxy resin, the Dainippon Ink Chemical Industries, Ltd. brand name N500P-1 can be obtained as a commercial item.

When using a novolak-type epoxy resin, in order to exhibit the performance, it is preferable to set it as 20 mass% or more in epoxy resin whole quantity, and 30 mass% or more is more preferable.

As said naphthalene type epoxy resin, the epoxy resin etc. which are represented by following General formula (V) are mentioned, for example. As said triphenylmethane type epoxy resin, the epoxy resin etc. which are represented by following General formula (VI) are mentioned, for example.

(V)

In Formula (V), R ¹ to R ³ each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. R ¹ to R ³ may be all the same or different. p is 1 or 0, m and n are each independently an integer of 0 to 11, p, m and so that (m + n) is an integer of 1 to 11 and (m + p) is an integer of 1 to 12; n is selected. i represents the integer of 0-3, j represents the integer of 0-2, k represents the integer of 0-4.

R ¹ to R ³ in the general formula (V) are each independently an alkyl group having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group and tert-butyl group; C1-C10 alkenyl groups, such as a vinyl group, an allyl group, and a butenyl group, etc. are mentioned. Especially, methyl group is more preferable.

&Lt; Formula (VI)

In the formula (VI), each R independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. n represents the integer of 1-10.

R in the formula (VI) is each independently a hydrogen atom; Alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group and tert-butyl group; C1-C10 alkenyl groups, such as a vinyl group, an allyl group, and a butenyl group, etc. are mentioned. Especially, a hydrogen atom or a methyl group is more preferable. n is preferably an integer of 0 to 3.

As the naphthalene type epoxy resin represented by the above formula (V), a random copolymer including m structural units and n structural units randomly, an alternating copolymer containing alternately, a copolymer regularly included, and a block including blocks And copolymers. Any one of these may be used alone, or two or more thereof may be used in combination.

Moreover, there is no restriction | limiting in particular as a triphenylmethane type epoxy resin represented with the said Formula (VI), A salicylic-type epoxy resin is preferable.

These naphthalene type epoxy resins and triphenylmethane type epoxy resins may be used individually by 1 type, and may be used in combination of both. When using at least one of a naphthalene type | mold epoxy resin and a triphenylmethane type | mold epoxy resin, it is preferable to make the content rate into 20 mass% or more of all the epoxy resins total, and 30 mass% or more is more preferable in order to exhibit the performance. 50 mass% or more is more preferable.

As an epoxide of the said phenol aralkyl resin, the epoxy resin represented by following formula (VII), the epoxy resin represented by following formula (VIII), etc. are mentioned, for example.

(VII)

In the general formula (VII), R ¹ to R ⁴ each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. R ¹ to R ⁴ may be all the same or different. R ⁵ each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. When a plurality of R ^{5 's} are present, all of them may be the same or different. i represents the integer of 0-3, n represents the integer of 0-10.

<Formula VIII>

In formula (VIII), R ¹ to R ⁸ each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. R ¹ to R ⁸ may be all the same or different. R ⁹ each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. When a plurality of R ^{9 's} are present, all may be the same or different. i represents the integer of 0-3, n represents the integer of 0-10.

The epoxide of the phenol aralkyl resin represented by the above formula (VII) is epichlorohydrin to a phenol aralkyl resin synthesized from alkyl substituted, aromatic substituted or unsubstituted phenol and dimethoxyparaxylene in a known method. It is obtained by making it react. In addition, the epoxide of the biphenylene frame | skeleton containing phenol aralkyl resin represented by the said Formula (VIII) is phenol aralkyl synthesize | combined from an alkyl substituted, aromatic-substituted substituted or unsubstituted phenol and bis (methoxymethyl) biphenyl. It is obtained by making epichlorohydrin react with resin by a well-known method.

Examples of the substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms represented by R ¹ to R ⁵ in Formula VII and R ¹ to R ⁹ in Formula VIII include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, chain alkyl groups such as n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group and dodecyl group; Cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group and cyclohexenyl group; Aryl group substituted alkyl groups, such as a benzyl group and a phenethyl group; Alkoxy group substituted alkyl groups, such as a methoxy group substituted alkyl group, an ethoxy group substituted alkyl group, butoxy group substituted alkyl group; Amino group substituted alkyl groups such as aminoalkyl group, dimethylaminoalkyl group and diethylaminoalkyl group; Hydroxyl-substituted alkyl group; Unsubstituted aryl groups such as phenyl group, naphthyl group and biphenyl group; Alkyl-substituted aryl groups, such as a tolyl group, a dimethylphenyl group, an ethylphenyl group, a butylphenyl group, a tert- butylphenyl group, and a dimethyl naphthyl group; Alkoxy group substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group and methoxynaphthyl group; Amino group substituted aryl groups such as dimethylamino group and diethylamino group; A hydroxyl-substituted aryl group etc. are mentioned.

Among them, R ¹ to R ⁴ in the general formula (VII) and R ¹ to R ⁸ in the general formula (VIII) are each independently preferably a hydrogen atom or a methyl group. As R ⁵ in Formula VII and R ⁹ in Formula VIII, a methyl group is preferable.

I in Formula (VII) and Formula (VIII) each independently represents an integer of 0 to 3, preferably 0 or 1.

In addition, n in the formula (VII) and the formula (VIII) each independently represents an integer of 0 to 10, more preferably 6 or less on average. As such an epoxy resin, the general formula (VII) can be obtained from Nippon Kayaku Co., Ltd. brand name NC-2000L as a commercial item, and the general formula (VIII) can be obtained from Nippon Kayaku Co., Ltd. brand name NC-3000S as a commercial item.

When using a phenol aralkyl resin, in order to show the performance, it is preferable to make it 20 mass% or more in epoxy resin whole quantity, and 30 mass% or more is more preferable.

In view of both flame retardancy, reflowability and fluidity, it is preferable to contain an epoxy resin represented by the above formula (I), and among these, R ¹ to R ⁸ of the above formula (VIII) are hydrogen atoms and R of the above formula (I) It is more preferable that ¹ to R ⁸ are hydrogen atoms and n = 0. In addition, it is particularly preferable that the mass ratio thereof is represented by the formula (I / VIII) = 50/50 to 5/95, more preferably 40/60 to 10/90, still more preferably 30/70 to 15/85. . As a compound which satisfy | fills such content mass ratio, CER-3000L (Nippon Kayaku Co., Ltd. brand name) etc. can be obtained as a commercial item.

As an epoxide of a naphthol aralkyl resin, the epoxy resin etc. which are represented by following General formula (IX) are mentioned, for example.

<Formula IX>

In Formula (IX), each R independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. The plurality of R's may all be the same or different. i represents the integer of 0-3, X represents the bivalent organic group which has an aromatic ring each independently, and n represents the integer of 0-10.

The epoxide of the naphthol-aralkyl resin represented by the general formula (IX) is used in the naphthol-aralkyl resin synthesized from alkyl substituted, aromatic substituted or unsubstituted naphthol and dimethoxyparaxylene or bis (methoxymethyl) biphenyl. It is obtained by making epichlorohydrin react by a well-known method.

X is independently, for example, arylene groups, such as a phenylene group, a biphenylene group, and a naphthylene group; Alkyl-substituted arylene groups, such as a tolylene group; An alkoxy group substituted arylene group; Aralkyl group substituted arylene group; Divalent groups obtained from aralkyl groups such as benzyl and phenethyl; Divalent groups containing arylene groups, such as a xylylene group, etc. are mentioned. Among them, a phenylene group or a biphenylene group is preferable each independently from the viewpoint of compatibility of flame retardancy and storage stability.

As R in Formula (IX), each independently, for example, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, Chain alkyl groups such as dodecyl group; Cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group and cyclohexenyl group; Aryl group substituted alkyl groups, such as a benzyl group and a phenethyl group; Alkoxy group substituted alkyl groups, such as a methoxy group substituted alkyl group, an ethoxy group substituted alkyl group, butoxy group substituted alkyl group; Amino group substituted alkyl groups such as aminoalkyl group, dimethylaminoalkyl group and diethylaminoalkyl group; Hydroxyl-substituted alkyl group; Unsubstituted aryl groups such as phenyl group, naphthyl group and biphenyl group; Alkyl-substituted aryl groups, such as a tolyl group, a dimethylphenyl group, an ethylphenyl group, a butylphenyl group, a tert- butylphenyl group, and a dimethyl naphthyl group; Alkoxy group substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group and methoxynaphthyl group; Amino group substituted aryl groups such as dimethylamino group and diethylamino group; A hydroxyl-substituted aryl group etc. are mentioned. Especially, as R in general formula (IX), a methyl group is each independently preferable, and as i, it is preferable that it is 1 or 2. As such a general formula (IX), the epoxide of the naphthol alkyl resin represented by following General formula (X) or XI is mentioned, for example.

n represents the integer of 0-10, and 6 or less are more preferable on average. As an epoxy resin represented by the following general formula (X), Shinnitetsu Chemical Co., Ltd. brand name ESN-375 is mentioned as a commercial item. As an epoxy resin represented by the following general formula (XI), Shinnitetsu Chemical Co., Ltd. brand name ESN-175 is mentioned as a commercial item.

When using the epoxide of the said naphthol aralkyl resin, it is preferable to make the content rate into 20 mass% or more in epoxy resin whole quantity, in order to exhibit the performance, 30 mass% or more is more preferable, 50 mass% or more This is more preferable.

<Formula X>

In the general formula (X), each X independently represents a divalent organic group having an aromatic ring, and n represents an integer of 0 to 10.

(XI)

In the general formula (XI), each X independently represents a divalent organic group having an aromatic ring, and n represents an integer of 0 to 10.

Epoxides and naphthols of the above-described biphenyl type epoxy resins, thiodiphenol type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins, naphthalene type epoxy resins, triphenylmethane type epoxy resins, and phenol and aralkyl resins. Epoxide of an aralkyl resin may be used individually by 1 type, and may be used in combination of 2 or more type. It is preferable to make content rate in the case of using these 2 or more types combining in total 50 mass% or more in epoxy resin whole quantity, 60 mass% or more is more preferable, 80 mass% or more is more preferable. Especially, it is preferable to make biphenyl type epoxy resin into 50 mass% or more in epoxy resin whole quantity, 60 mass% or more is more preferable, 80 mass% or more is more preferable. And it is preferable to use together the said epoxy resins other than a biphenyl type epoxy resin.

[(B) Curing Agent]

There is no restriction | limiting in particular if the (B) hardening | curing agent used in this invention is generally used for the epoxy resin composition for sealing. For example, phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, thiodiphenol, aminophenol, α-naphthol, β-naphthol, dihydroxynaphthalene, formaldehyde, Novolak-type phenol resins obtained by condensation or co-condensation of compounds having an aldehyde group such as benzaldehyde and salicyaldehyde under an acidic catalyst; Aralkyl type phenol resins, such as a phenol aralkyl resin and a naphthol aralkyl resin synthesize | combined from a phenol and dimethoxy para xylene or bis (methoxymethyl) biphenyl; Copolymerized phenol-aralkyl resins in which a phenol novolak structure and a phenol-aralkyl structure are repeated randomly, in blocks, or alternately; Paraxylylene and / or metaxylylene-modified phenolic resins; Melamine-modified phenolic resins; Terpene-modified phenolic resins; Dicyclopentadiene modified phenol resins; Cyclopentadiene-modified phenolic resins; Polycyclic aromatic ring modified phenol resin etc. are mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.

Among them, phenol-aralkyl resins, copolymerized phenol-aralkyl resins and naphthol-aralkyl resins are preferable from the viewpoints of fluidity, flame retardancy and reflowability, and triphenylmethane-type phenol resins are preferred from the viewpoints of heat resistance, low expansion rate and low warpage property. It is preferable and a novolak-type phenol resin is preferable from a sclerosis | hardenability viewpoint. It is preferable to contain at least 1 sort (s) of these phenol resins.

As said phenol-aralkyl resin, resin represented by following General formula (XII) is mentioned, for example.

(XII)

In formula (XII), each R independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. The plurality of R's may all be the same or different. i respectively independently represents the integer of 0-3, X each independently represents the bivalent organic group which has an aromatic ring, and n represents the integer of 0-10.

As R in the said Formula (XII), each independently, methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- butyl group, pentyl group, hexyl group, octyl group, decyl group Linear alkyl groups such as dodecyl group; Cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group and cyclohexenyl group; Aryl group substituted alkyl groups, such as a benzyl group and a phenethyl group; Alkoxy group substituted alkyl groups, such as a methoxy group substituted alkyl group, an ethoxy group substituted alkyl group, butoxy group substituted alkyl group; Amino group substituted alkyl groups such as aminoalkyl group, dimethylaminoalkyl group and diethylaminoalkyl group; Hydroxyl-substituted alkyl group; Unsubstituted aryl groups such as phenyl group, naphthyl group and biphenyl group; Alkyl-substituted aryl groups, such as a tolyl group, a dimethylphenyl group, an ethylphenyl group, a butylphenyl group, a tert- butylphenyl group, and a dimethyl naphthyl group; Alkoxy group substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group and methoxynaphthyl group; Amino group substituted aryl groups such as dimethylamino group and diethylamino group; A hydroxyl-substituted aryl group etc. are mentioned.

Especially, as R in general formula (XII), a methyl group is respectively independently preferable. In addition, i in general formula (XII) represents the integer of 0-3 each independently, and it is preferable that it is 1 or 2.

X in the said general formula (XII) represents a group which has an aromatic ring each independently. For example, Arylene groups, such as a phenylene group, a biphenylene group, and a naphthylene group, each independently; Alkyl-substituted arylene groups, such as a tolylene group; An alkoxy group substituted arylene group; Divalent groups obtained from aralkyl groups such as benzyl and phenethyl; Aralkyl group substituted arylene group; Divalent groups containing arylene groups, such as a xylylene group, etc. are mentioned.

Among them, from the viewpoint of compatibility of flame retardancy, fluidity and curability, X is each independently a substituted or unsubstituted phenylene group, and examples thereof include phenol and aralkyl resins represented by the following general formula (XIII). . In addition, from the standpoint of both flame retardancy and reflow properties, each independently represents a substituted or unsubstituted biphenylene group, and examples thereof include phenol and aralkyl resins represented by the following general formula (XIV). .

n represents the integer of 0-10, and 6 or less are more preferable on average.

<Formula XIII>

N in formula (XIII) represents an integer of 0 to 10.

<Formula XIV>

In formula (XIV), n represents the integer of 0-10.

As a phenol-aralkyl resin represented by the said general formula (XIII), Mitsui Chemical Industries, Ltd. brand name XLC is mentioned as a commercial item. As a biphenylene frame | skeleton containing phenol aralkyl resin represented by general formula (XIV), Meiwa Kasei Co., Ltd. brand name MEH-7851 is mentioned as a commercial item.

When using the said phenol aralkyl resin, in order to exhibit the performance, it is preferable to make it 20 mass% or more in whole quantity of a hardening | curing agent, 30 mass% or more is more preferable, 50 mass% or more is more preferable. .

As said naphthol aralkyl resin, resin represented by following General formula (XV) is mentioned, for example.

<Formula XV>

In formula (XV), each R independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. The plurality of R's may all be the same or different. i respectively independently represents the integer of 0-3, X each independently represents the bivalent organic group which has an aromatic ring, and n represents the integer of 0-10.

As R in the said Formula (XV), each independently, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- butyl group, pentyl group, hexyl group, octyl group, decyl group Linear alkyl groups such as dodecyl group; Cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group and cyclohexenyl group; Aryl group substituted alkyl groups, such as a benzyl group and a phenethyl group; Alkoxy group substituted alkyl groups, such as a methoxy group substituted alkyl group, an ethoxy group substituted alkyl group, butoxy group substituted alkyl group; Amino group substituted alkyl groups such as aminoalkyl group, dimethylaminoalkyl group and diethylaminoalkyl group; Hydroxyl-substituted alkyl group; Unsubstituted aryl groups such as phenyl group, naphthyl group and biphenyl group; Alkyl-substituted aryl groups, such as a tolyl group, a dimethylphenyl group, an ethylphenyl group, a butylphenyl group, a tert- butylphenyl group, and a dimethyl naphthyl group; Alkoxy group substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group and methoxynaphthyl group; Amino group substituted aryl groups such as dimethylamino group and diethylamino group; A hydroxyl-substituted aryl group etc. are mentioned.

Especially, as R in general formula (XV), a methyl group is preferable. In addition, i in general formula (XV) represents the integer of 0-3 each independently, and it is preferable that it is 1 or 2.

X in the said general formula (XV) represents a bivalent organic group which has an aromatic ring each independently. For example, Arylene groups, such as a phenylene group, a biphenylene group, and a naphthylene group, each independently; Alkyl-substituted arylene groups, such as a tolylene group; An alkoxy group substituted arylene group; Aralkyl group substituted arylene group; Divalent groups obtained from aralkyl groups such as benzyl and phenethyl; Divalent groups containing arylene groups, such as a xylylene group, etc. are mentioned. Among them, from the viewpoint of storage stability and flame retardancy, X is each independently a substituted or unsubstituted phenylene group and a biphenylene group, more preferably a phenylene group, and for example, the above-mentioned formula XV is represented by the following formulas XVI and XVII. The naphthol aralkyl resin used is mentioned.

n represents the integer of 0-10, and 6 or less are more preferable on average.

<Formula XVI>

In formula (XVI), n represents an integer of 0 to 10.

<Formula XVII>

In formula (XVII), n represents the integer of 0-10.

As a naphthol aralkyl resin represented by the said general formula (XVI), Shin-Nitetsu Chemical Co., Ltd. brand name SN-475 is mentioned as a commercial item. As a naphthol aralkyl resin represented by the said general formula (XVII), Shin-Nitetsu Chemical Co., Ltd. brand name SN-170 is mentioned as a commercial item.

When using the said naphthol aralkyl resin, in order to exhibit the performance, it is preferable to make it 20 mass% or more in whole quantity of a hardening | curing agent, 30 mass% or more is more preferable, 50 mass% or more is more preferable. .

It is preferable that a part or all of the phenol aralkyl resin represented by the above formula (XII) and the naphthol aralkyl resin represented by the formula (XV) are premixed with acenaphthylene from the viewpoint of flame retardancy. Acenaphthylene can be obtained by dehydrogenating acenaphthene, but commercially available products can also be used. Instead of acenaphthylene, it may be used as a polymer of acenaphthylene or a polymer of acenaphthylene and other aromatic olefins.

As a method of obtaining the polymer of acenaphthylene or the polymer of acenaphthylene and another aromatic olefin, radical polymerization, cationic polymerization, anionic polymerization, etc. are mentioned. In addition, although a conventionally well-known catalyst can be used at the time of superposition | polymerization, it can also be performed only by heat, without using a catalyst. At this time, 80 degreeC-160 degreeC is preferable and 90 degreeC-150 degreeC is more preferable. 60 to 150 degreeC is preferable and, as for the softening point of the polymer of acenaphthylene obtained or the polymer of acenaphthylene and another aromatic olefin, 70 to 130 degreeC is more preferable. When it is 60 degreeC or more, the exudation at the time of shaping | molding is suppressed and it exists in the tendency which is excellent in moldability, and when it is 150 degrees C or less, there exists a tendency for compatibility with resin to improve.

Other aromatic olefins copolymerized with acenaphthylene include styrene, α-methylstyrene, indene, benzothiophene, benzofuran, vinylnaphthalene, vinylbiphenyl or alkyl substituents thereof. In addition to the above-described aromatic olefins, aliphatic olefins may be used in combination within a range that does not interfere with the effects of the present invention. Examples of the aliphatic olefins include (meth) acrylic acid and esters thereof, maleic anhydride, itaconic anhydride, fumaric acid and esters thereof. 20 mass% or less is preferable in a polymerization monomer whole quantity, and, as for the usage-amount of these aliphatic olefins, 9 mass% or less is more preferable.

As a method of premixing a part or all of a hardening | curing agent and acenaphthylene, the method of mixing a hardening | curing agent and acenaphthylene finely, respectively, and mixing by a mixer etc. in the solid state, and dissolving both components uniformly in the solvent which melt | dissolves them Then, it can carry out by the method of removing a solvent, the method of melt-mixing both, etc. at the temperature more than the softening point of a hardening | curing agent and / or acenaphthylene. Among these methods, a homogeneous mixture is obtained and the melt mixing method with little mixing of impurities is preferable. A preliminary mixture (acenaphthylene modified curing agent) is produced by the above method.

The temperature condition at the time of melt mixing is not limited as long as the temperature is higher than the softening point of the curing agent and / or acenaphthylene. Specifically, 100 to 250 degreeC is preferable and 120 to 200 degreeC is more preferable. In addition, melt mixing has no restriction | limiting in mixing time, if both mix uniformly, 1 hour-20 hours are preferable, and 2 hours-15 hours are more preferable. When pre-mixing a hardening | curing agent and acenaphthylene, acenaphthylene may react with a polymerization or hardening | curing agent during mixing.

As a triphenylmethane type phenol resin, the phenol resin etc. which are represented by following General formula (XVIII) are mentioned, for example.

<Formula XVIII>

In formula (XVIII), each R independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10.

As R in the said general formula (XVIII), each independently represents a hydrogen atom; Alkyl groups such as methyl group, ethyl group, propyl group, butyl group, isopropyl group and tert-butyl group; Alkenyl groups, such as vinyl group, allyl group, and butenyl group; Halogenated alkyl groups; Amino group substituted alkyl group; Mercapto group substituted alkyl group, etc. are mentioned. Especially, as R each independently, alkyl groups, such as a methyl group and an ethyl group, or a hydrogen atom are preferable, and a methyl group or a hydrogen atom is more preferable.

When using a triphenylmethane type phenol resin, in order to exhibit the performance, it is preferable to set it as 30 mass% or more in hardening | curing agent whole quantity, and 50 mass% or more is more preferable.

As a novolak-type phenol resin, novolak-type phenol resins, such as a phenol resin represented with the following general formula (XIX), a cresol novolak resin, etc. are mentioned, for example. Especially, the novolak-type phenol resin represented by the following general formula (XIX) is preferable.

<Formula XIX>

In formula (XIX), each R independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10.

As R in the said general formula (XIX), For example, each independently is a hydrogen atom; Alkyl groups such as methyl group, ethyl group, propyl group, butyl group, isopropyl group and tert-butyl group; Alkenyl groups, such as vinyl group, allyl group, and butenyl group; Halogenated alkyl groups; Amino group substituted alkyl group; Mercapto group substituted alkyl group, etc. are mentioned. Especially, as R each independently, alkyl groups, such as a methyl group and an ethyl group, or a hydrogen atom are preferable, and a hydrogen atom is more preferable.

n represents the integer of 0-10 and it is preferable that average value is 0-8.

As a novolak-type phenol resin represented by the said Formula (XIX), Meiwa Kasei Co., Ltd. brand name H-100 is mentioned as a commercial item.

When using a novolak-type phenol resin, in order to exhibit the performance, it is preferable to set it as 30 mass% or more in hardening | curing agent whole quantity, and 50 mass% or more is more preferable.

As a copolymer type phenol aralkyl resin, the phenol resin represented by following General formula (XX) is mentioned, for example.

<Formula XX>

In formula (XX), each R independently represents a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or a hydroxyl group. The plurality of R's may all be the same or different. In addition, each X independently represents a divalent group having an aromatic ring. n and m each independently represent an integer of 0 to 10.

As R in the said general formula (XX), For example, each independently, a hydrogen atom; Chain alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group and dodecyl group; Cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group and cyclohexenyl group; Aryl group substituted alkyl groups, such as a benzyl group and a phenethyl group; Alkoxy group substituted alkyl groups, such as a methoxy group substituted alkyl group, an ethoxy group substituted alkyl group, butoxy group substituted alkyl group; Amino group substituted alkyl groups such as aminoalkyl group, dimethylaminoalkyl group and diethylaminoalkyl group; Hydroxyl-substituted alkyl group; Unsubstituted aryl groups such as phenyl group, naphthyl group and biphenyl group; Alkyl-substituted aryl groups, such as a tolyl group, a dimethylphenyl group, an ethylphenyl group, a butylphenyl group, a tert- butylphenyl group, and a dimethyl naphthyl group; Alkoxy group substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group and methoxynaphthyl group; Amino group substituted aryl groups such as dimethylamino group and diethylamino group; A hydroxyl-substituted aryl group etc. are mentioned. Especially, as R each independently, a hydrogen atom or a methyl group is preferable.

In addition, n and m respectively independently represent the integer of 0-10, and on average, 6 or less are more preferable.

As X in the said general formula (XX), For example, Arylene groups, such as a phenylene group, a biphenylene group, a naphthylene group; Alkyl-substituted arylene groups, such as a tolylene group; An alkoxy group substituted arylene group; Aralkyl group substituted arylene group; Divalent groups obtained from aralkyl groups such as benzyl and phenethyl; Divalent groups containing arylene groups, such as a xylylene group, etc. are mentioned. Among them, from the viewpoint of storage stability and flame retardancy, a substituted or unsubstituted phenylene group or biphenylene group is preferable. As a compound represented by the general formula (XX), HE-510 (trade name, manufactured by Air Water Co., Ltd.) and the like can be obtained as a commercial item.

Examples of the copolymerized phenol-aralkyl resin represented by the general formula (XX) include random copolymers containing m structural units and n structural units randomly, alternating copolymers containing alternately, copolymers regularly included, and block phases. The block copolymer included as this is mentioned. Any one of these may be used alone, or two or more thereof may be used in combination.

When using a copolymer type phenol aralkyl resin, in order to show the performance, it is preferable to set it as 30 mass% or more in hardening | curing agent whole quantity, and 50 mass% or more is more preferable.

The said phenol aralkyl resin, a naphthol aralkyl resin, a triphenylmethane type phenol resin, a novolak-type phenol resin, and a copolymerized phenol aralkyl resin may be used individually by 1 type, and may combine 2 or more types It can also be used. It is preferable to make content rate in the case of using in combination of 2 or more type to 50 mass% or more in phenol resin whole quantity, 60 mass% or more is more preferable, 80 mass% or more is more preferable.

[(C) Benzophenone Derivatives]

The epoxy resin composition for sealing of this invention contains the benzophenone derivative which has 1 or more of phenolic hydroxyl groups in 1 molecule of (C). Thereby, the epoxy resin composition for sealing which is high in adhesiveness with the metal at high temperature, and excellent in reflow property is obtained.

Benzophenone derivatives having one or more phenolic hydroxyl groups in one molecule of (C) used in the present invention may be substituted or unsubstituted, such as benzophenone, naphthylphenyl ketone, dinaphthyl ketone, xanthone, fluorenone and the like. There is no restriction | limiting in particular if 1 or more hydroxyl group is directly bonded to the ring. (C) The benzophenone derivative which has one or more phenolic hydroxyl groups in 1 molecule may be used individually by 1 type, and may be used in combination of 2 or more type.

Specifically, o-hydroxybenzophenone, m-hydroxybenzophenone, p-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-allyloxybenzophenone, 2,4-dihydroxybenzophenone, 4,4'-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2 , 2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3, 4,4'- tetrahydroxy benzophenone, 2,3, 3 ', 4,4', 5-hexahydroxy benzophenone, these positional isomers, a substituent, etc. are mentioned. O-hydroxybenzophenone, m-hydroxybenzophenone, p-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, in terms of thermal stress reduction (reduction of elastic modulus at reflow temperature) 2 -Hydroxy-4-octyloxybenzophenone is preferable, and 2,4- dihydroxy benzophenone, 4,4'- dihydroxy benzophenone, and 2,2'- dihydrate from a viewpoint of further adhesive improvement. Preferred are oxy-4-methoxybenzophenone and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

As for the total content rate of the benzophenone derivative which has 1 or more of phenolic hydroxyl groups in 1 molecule (C) used in this invention, 0.1 mass% or more and 1.0 mass% or less are preferable in the epoxy resin composition for sealing. When it is 0.1 mass% or more, there exists a tendency for the effect of invention to fully be exhibited, and when it is 1.0 mass% or less, there exists a tendency for the hardness of the epoxy resin composition for sealing to be fully maintained.

In the present invention, the equivalent ratio of (A) an epoxy resin to (B) a curing agent and (C) a benzophenone derivative having one or more phenolic hydroxyl groups in one molecule, that is, (A) to the number of epoxy groups in the epoxy resin (B) The ratio of the total number of hydroxyl groups in the benzophenone derivative which has one or more phenolic hydroxyl groups in one molecule and (C) molecule ((B) Curing agent and benzophenone which has one or more phenolic hydroxyl groups in one molecule (C)) The total number of hydroxyl groups in the derivative / the number of epoxy groups in the (A) epoxy resin) is not particularly limited. In order to suppress each unreacted powder less, it is preferable that the said equivalence ratio is set to the range of 0.5 or more and 2.0 or less, and 0.6 or more and 1.3 or less are more preferable. In order to obtain the epoxy resin composition for sealing excellent in moldability, it is more preferable to set in 0.8 or more and 1.2 or less.

[(D) Silane Compound]

The molding material of the present invention may contain the (D) silane compound. (D) The silane compound is various silane compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane and vinyl silane. Examples thereof include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxypropyl Triethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyldimethylethoxysilane, γ -Acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-gly Cydoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyldimethylethoxy Silane, vinyltriacetoxysilane, γ- Captopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- [ Bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, isocyanato Propyltrimethoxysilane, isocyanatopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, Diphenyldimethoxysilane, diphenyldiethoxysilane, diphenylsilanediol, triphenylmethoxysilane, triphenylethoxysilane, triphenylsilanol, N-β- (N-vinylbenzylaminoethyl) -γ-amino Propyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexa Tildisilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, 2-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-trie Oxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N- (3-triethoxysilylpropyl) phenylimine, 3- (3- (triethoxysilyl) propylamino) -N, Silanes such as N-dimethylpropionamide, N-triethoxysilylpropyl-β-alanine methyl ester, 3- (triethoxysilylpropyl) dihydro-3,5-furandione, and bis (trimethoxysilyl) benzene Imidazole compounds, such as a system compound, 1H-imidazole, 2-alkylimidazole, 2,4-dialkylimidazole, and 4-vinylimidazole, and (gamma)-glycidoxy propyl trimethoxysilane, (gamma)- And imidazole silane compounds which are reactants of γ-glycidoxy propyl alkoxysilanes such as glycidoxy propyl triethoxy silane. These 1 type may be used independently and may be used in combination of 2 or more type.

In the case of containing the (D) silane compound, the total content of the (D) silane compound is preferably 0.06% by mass or more and 2% by mass or less in the epoxy resin composition for sealing from the viewpoint of moldability and fluidity, and is 0.1% by mass to 0.75% by mass. % Or less is more preferable, and 0.2 mass% or more and 0.7 mass% or less are further more preferable. When it is 0.06 mass% or more, the fall of fluidity tends to be suppressed, and when it is 2 mass% or less, there exists a tendency which generation | occurrence | production of molding defects, such as a space | gap, is suppressed.

You may mix | blend conventionally well-known coupling agents other than the (D) silane compound with the epoxy resin composition for sealing of this invention. For example, isopropyl triisostearoyl titanate, isopropyl tris (dioctylpyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctylbis (ditridecyl phosphite ) Titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene Titanate, Isopropyl trioctanoyl titanate, Isopropyl dimethacrylic stearoyl titanate, Isopropyl isostaroyl diacryl titanate, Isopropyl tri (dioctyl phosphate) titanate, Isopropyl tricumyl Titanate coupling agents, such as phenyl titanate and tetraisopropylbis (dioctyl phosphite) titanate, aluminum chelates, and aluminum / zirconium-based compounds A compound etc. are mentioned. These 1 type may be used independently and may be used in combination of 2 or more type.

(D) 0.06 mass% or more and 2 mass% or less are preferable in a epoxy resin composition for sealing from a viewpoint of moldability and adhesiveness, and, as for the total content rate of coupling agents other than a silane compound, 0.1 mass% or more and 0.75 mass% or less are more preferable. And 0.2 mass% or more and 0.7 mass% or less are more preferable. When it is 0.06 mass% or more, the fall of fluidity tends to be suppressed, and when it is 2 mass% or less, there exists a tendency which generation | occurrence | production of molding defects, such as a space | gap, is suppressed.

[(E) Curing Accelerator]

The epoxy resin composition for sealing of this invention may contain the (E) hardening accelerator. As (E) hardening accelerator used by this invention, what is generally used by the epoxy resin composition for sealing can be used without a restriction | limiting in particular.

For example, 1,8-diazabicyclo [5.4.0] undecene-7,1,5-diazabicyclo [4.3.0] nonene-5,5,6-dibutylamino-1,8-dia Cycloamidine compounds such as xabicyclo [5.4.0] undecene-7 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-benzoquinone, phenyl-1,4 A compound having an intramolecular polarization formed by adding a compound having a π bond such as a quinone compound such as benzoquinone, diazophenylmethane or a phenol resin; Tertiary amines such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and derivatives thereof, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl Imidazoles such as midazole and 2-heptadecylimidazole and derivatives thereof; Maleic anhydride to the third phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine and these third phosphines; Phosphorus compounds having an intramolecular polarization formed by adding a compound having a π bond such as the quinone compound, diazophenylmethane, and phenol resin; Tetra substituted phosphonium tetra substituted borate, such as tetraphenyl phosphonium tetraphenyl borate, tetraphenyl phosphonium ethyl triphenyl borate, tetrabutyl phosphonium tetrabutyl borate, 2-ethyl-4-methylimidazole tetraphenyl borate, And tetraphenylboron salts such as N-methylmorpholine and tetraphenylborate, and derivatives thereof. These 1 type may be used independently and may be used in combination of 2 or more type.

There is no restriction | limiting in particular as 3rd phosphines used for the adduct of 3rd phosphines and a quinone compound. For example, dibutyl phenyl phosphine, butyl diphenyl phosphine, ethyl diphenyl phosphine, triphenyl phosphine, tris (4-methylphenyl) phosphine, tris (4-ethylphenyl) phosphine, tris (4- Propylphenyl) phosphine, tris (4-butylphenyl) phosphine, tris (isopropylphenyl) phosphine, tris (tert-butylphenyl) phosphine, tris (2,4-dimethylphenyl) phosphine, tris (2 , 6-dimethylphenyl) phosphine, tris (2,4,6-trimethylphenyl) phosphine, tris (2,6-dimethyl-4-ethoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine And third phosphines having an aryl group such as tris (4-ethoxyphenyl) phosphine. In view of moldability, triphenylphosphine is preferable.

In addition, there is no restriction | limiting in particular as a quinone compound used for the adduct of 3rd phosphines and a quinone compound. For example, o-benzoquinone, p-benzoquinone, diphenoquinone, 1, 4- naphthoquinone, anthraquinone, etc. are mentioned. In view of moisture resistance or storage stability, p-benzoquinone is preferred.

Content of (E) hardening accelerator will not be specifically limited if it is an quantity which hardening acceleration effect is achieved. Specifically, 0.1 mass part or more and 10 mass parts or less are preferable with respect to 100 mass parts of total amounts of (A) epoxy resin, (B) hardening | curing agent, and (C) 1 molecule of the benzophenone derivative which has one or more phenolic hydroxyl groups, 0.3 mass part or more and 5 mass parts or less are more preferable. When it is 0.1 mass part or more, it can be hardened in a short time, and when it is less than 10 mass parts, a hardening rate is moderately suppressed and there exists a tendency for a favorable molded article to be obtained.

[(F) Inorganic Filler]

The epoxy resin composition for sealing of this invention may contain the (F) inorganic filler. The inorganic filler (F) used in the present invention is formulated into the sealing epoxy resin composition for hygroscopicity, decreasing the coefficient of linear expansion, improving the thermal conductivity, and improving the strength, and is particularly limited as long as it is generally used in the sealing epoxy resin composition. no. For example, fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, forsterite, stearite, spinel And powders such as mullite and titania, or beads having spherical shape, glass fibers and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.

Among them, fused silica is preferred from the viewpoint of decreasing the coefficient of linear expansion, and alumina is preferred from the viewpoint of high thermal conductivity, and the filler shape is preferably spherical from the viewpoint of fluidity and mold wearability at the time of molding. Particularly, spherical fused silica is preferable in view of the balance between cost and performance.

0.1 micrometer-50 micrometers are preferable, and, as for the average particle diameter (D50) of an inorganic filler, 10 micrometers-30 micrometers are more preferable. By making the said average particle diameter into 0.1 micrometer or more, the raise of the viscosity of the epoxy resin composition for sealing is suppressed, and separation of a resin component and an inorganic filler can be reduced by setting it to 50 micrometers or less. Therefore, by being in the range of the said average particle diameter, hardened | cured material becomes non-uniform, hardened | cured material characteristic changes, or the filling property to a narrow gap is prevented.

In addition, a volume average particle diameter (D50) is a particle diameter which becomes cumulative 50 volume% when the volume cumulative distribution curve is drawn from the small diameter side in particle size distribution. The measurement can be performed by dispersing a sample in purified water containing a surfactant and using a laser diffraction particle size distribution measuring device (for example, SALD-3000J manufactured by Shimadzu Corporation).

From the viewpoint of fluidity, the particle shape of the inorganic filler is preferably spherical rather than square. In addition, the specific surface area of the inorganic filler is preferably from 0.1m ² / g to 10m ² / g preferred in view of flowability, more preferably 0.5m ² / g to 6.0m ² / g.

The content of the inorganic filler is preferably 70% by mass or more and 95% by mass or less in the epoxy resin composition for sealing from the viewpoints of flame retardancy, moldability, hygroscopicity, linear expansion coefficient reduction, and strength improvement. When it is 70 mass% or more, it exists in the tendency which is excellent in flame retardancy, and when it is 95 mass% or less, it exists in the tendency which is excellent in fluidity.

[Other additives]

The epoxy resin composition for sealing of this invention is added to the above-mentioned (A) epoxy resin, (B) hardening | curing agent, (C) benzophenone derivative, (D) silane compound, (E) hardening accelerator, and (F) inorganic filler Various additives, such as an anion exchanger, a mold release agent, a flame retardant, a coloring agent, and a stress relaxation agent, illustrated below can be contained as needed. However, it is not limited to the following additives to the sealing epoxy resin composition of this invention, You may add various additives well-known in the art as needed.

(Anion exchanger)

The anion exchanger can be mix | blended with the epoxy resin composition for sealing of this invention as needed for the purpose of improving the moisture resistance of IC and high temperature standing-proof characteristic. There is no restriction | limiting in particular as an anion exchanger, A conventionally well-known thing can be used. For example, hydrotalcites, the hydrous oxide of the element chosen from magnesium, aluminum, titanium, zirconium, bismuth, etc. are mentioned. These 1 type may be used independently and may be used in combination of 2 or more type. Especially, the hydrotalcite represented by the following composition formula XXI is preferable.

<Composition XXI>

In composition formula XXI, 0 <X <= 0.5, m shows a positive number.

The content rate of the anion exchanger is not particularly limited as long as it is a sufficient amount capable of trapping anions such as halogen ions. Specifically, 0.1 mass part or more and 30 mass parts or less are preferable with respect to 100 mass parts of (A) epoxy resins, and 1 mass part or more and 5 mass parts or less are more preferable.

(Release agent)

The epoxy resin composition for sealing of this invention can also contain a mold release agent as needed. As a mold release agent, it is preferable to use 0.01 mass part or more and 10 mass parts or less with respect to 100 mass parts of oxidizing or non-oxidizing polyolefins, and it is more preferable to use 0.1 mass part or more and 5 mass parts or less. In the case of 0.01 mass part or more, mold release property tends to become enough, and in the case of 10 mass parts or less, there exists a tendency which is excellent in adhesiveness.

Examples of the oxidized or non-oxidized polyolefins include low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000, such as the product name H4, PE, and PED series manufactured by CHAST. Moreover, as a mold release agent other than this, carnauba wax, montanic acid ester, montanic acid, stearic acid, etc. are mentioned, for example. These 1 type may be used independently and may be used in combination of 2 or more type.

When using these other mold release agents together in addition to an oxidized or non-oxidized polyolefin, the content rate is preferably 0.1 mass part or more and 10 mass parts or less with respect to 100 mass parts of (A) epoxy resins, 0.5 mass part or more and 3 mass parts Part or less is more preferable.

(Flame retardant)

A conventionally well-known flame retardant can be mix | blended with the epoxy resin composition for sealing of this invention as needed. For example, phosphorus compounds such as phosphoric acid esters, melamine and melamine derivatives coated with inorganic materials such as epoxy bromide resins, antimony trioxide, red, aluminum hydroxide, magnesium hydroxide and zinc oxide, and / or thermosetting resins such as phenol resins, melamine and melamine derivatives , Nitrogen-containing compounds such as melamine-modified phenolic resins, compounds having triazine rings, cyanuric acid derivatives, isocyanuric acid derivatives, phosphorus and nitrogen-containing compounds such as cyclophosphazene, aluminum hydroxide, magnesium hydroxide and the following compositional formula XXII The composite metal hydroxide etc. which are mentioned are mentioned.

<Composition Formula XXII>

In composition formula XXII, M ¹ , M ² and M ³ represent different metal elements, a, b, c, d, e, f, p, q and m represent positive numbers, r represents zero or positive numbers .

If M <^1> , M <^2> and M <^3> in the said composition formula XXII are different metal elements, there will be no restriction | limiting in particular. In addition, the classification of metal elements is based on a long-periodical periodic table with typical elements of A group and transition elements of B group (Source: Chritsu Shupan Kabushiki Kaisha, `` Chemical Metabolism 4 '' February 15, 1987) Based on the above.

In view of flame retardancy, M ¹ is selected from metal elements of the third cycle, alkaline earth metal elements of group IIA, group IVB, IIB, group VIII, group IB, group IIIA and group IVA, and M ² is It is preferably selected from transition metal elements of groups IIIB to IIB, M ¹ is selected from magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc, and M ² is iron, cobalt, nickel, More preferably selected from copper and zinc. From the viewpoint of fluidity, it is preferable that M ¹ is magnesium, M ² is zinc or nickel, and r = 0.

There is no restriction | limiting in particular in molar ratio of p, q, and r, It is preferable that r = 0 and p / q is 1/99-1/1.

Moreover, the compound containing metal elements, such as zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate, dicyclopentadienyl iron, etc. are mentioned. These 1 type may be used independently and may be used in combination of 2 or more type.

Although the content rate of a flame retardant does not have a restriction | limiting in particular, 1 mass part or more and 30 mass parts or less are preferable with respect to 100 mass parts of (A) epoxy resins, and 2 mass parts or more and 15 mass parts or less are more preferable.

(Colorant, Stress Relief)

In addition, the sealing epoxy resin composition of this invention may contain coloring agents, such as carbon black, an organic dye, an organic pigment, titanium oxide, a podium, and red iron oxide. Moreover, as other additives, stress relaxation agents, such as silicone oil and a silicone rubber powder, etc. can be mix | blended as needed.

<Production of the epoxy resin composition for sealing>

The epoxy resin composition for sealing of this invention may be manufactured by what kind of methods, as long as it can disperse-mix various components uniformly. As a general method, after mixing the component of predetermined compounding quantity sufficiently with a mixer etc., the method of cooling and pulverizing after melt-kneading with a mixing roll, an extruder, etc. is mentioned. For example, it can be obtained by a method such as kneading, cooling and pulverizing by using a kneader, a roll, an extruder or the like that is uniformly stirred and mixed with a predetermined amount of the above-mentioned components in advance and heated to 70 ° C to 140 ° C. have. Tableting with dimensions and masses suitable for molding conditions is easy to use.

Electronic component device

The electronic component device provided with the element sealed by the sealing epoxy resin composition obtained by this invention is a semiconductor chip, a transistor, a diode, a thyristor, etc. in support members, such as a lead frame, a completed tape carrier, a wiring board, glass, and a silicon wafer. Electronic component devices etc. which mount elements, such as an active element, a capacitor | condenser, a resistor, and a passive element, and sealed the necessary part with the sealing epoxy resin composition of this invention are mentioned.

As such an electronic component device, after fixing a semiconductor element on a lead frame, for example, connecting the terminal part and lead part of an element, such as a bonding pad, by wire bonding or bump, it transfers using the epoxy resin composition for sealing of this invention. Dual Inline Package (DIP), Plastic Leaded Chip Carrier (Plastic Led Chip Carrier), QFP (Quad Flat Package), Small Outline Package (SOP) Line package), SOJ (Small Outline J-lead package), Thin Small Outline Package (TSOP), Thin Quad Flat Package (TQFP), etc. Typical resin-sealed ICs; TCP (Tape Carrier Package) which sealed the semiconductor chip connected to the tape carrier by bump with the sealing epoxy resin composition of this invention; The semiconductor chip, transistors, diodes, thyristors, and other active devices connected to wiring boards or wirings formed on the glass by wire bonding, flip chip bonding, solder, etc. and / or passive devices such as capacitors, resistors, and coils are sealed in the present invention. A chip on board (COB) module, a hybrid IC or a multi-chip module sealed with an epoxy resin composition for use; After mounting an element on the surface of the organic substrate in which the terminal for wiring board connection was formed in the back surface, connecting an element and the wiring formed in the organic substrate by bump or wire bonding, and sealing an element with the epoxy resin composition for sealing of this invention. One Ball Grid Array (BGA), Chip Size Package (CSP), and the like can be given. Moreover, the epoxy resin composition for sealing of this invention can also be used effectively for a printed circuit board.

As a method of sealing an element using the sealing epoxy resin composition of this invention, although the low pressure transfer molding method is the most common, the injection molding method, the compression molding method, etc. can also be used.

<Examples>

EXAMPLES Next, the present invention will be described with reference to Examples, but the scope of the present invention is not limited to these Examples. In addition, "%" means "mass%" unless there is a notice.

<Production of the epoxy resin composition for sealing>

The following components are each mix | blended with the mass part shown to following Table 1-Table 6, roll kneading is carried out on the conditions of kneading temperature of 80 degreeC, and kneading time 10 minutes, and the sealing epoxy of Examples 1-24 and Comparative Examples 1-24 is carried out. The resin composition was produced. In addition, the blank in a table | surface shows no mixing | blending.

(A) As an epoxy resin,

Epoxy resin 1: 196 g / eq of epoxy equivalent, biphenyl type epoxy resin of melting | fusing point 106 degreeC (Japan Epoxy Resin Co., Ltd. brand name YX-4000),

Epoxy resin 2: Epoxy equivalent 240g / eq, biphenylene frame | skeleton containing phenol aralkyl type epoxy resin of softening point 96 degreeC (brand name CER-3000L by Nippon Kayaku Co., Ltd.),

Epoxy resin 3: Epoxy equivalent 238 g / eq, phenol aralkyl type epoxy resin (softening point Nippon Kayaku Co., Ltd. brand name NC-2000L) of softening point 55 degreeC,

Epoxy Resin 4: An orthocresol novolak type epoxy resin (trade name N500P-1 manufactured by Dainippon Ink & Chemical Co., Ltd.) at an epoxy equivalent of 200 g / eq and a softening point of 60 ° C. was used.

As the (B) curing agent,

Curing agent 1: Hydroxyl equivalent 175 g / eq, phenol aralkyl resin (Maywa Kasei Co., Ltd. brand name MEH-7800) of softening point 70 degreeC,

Curing agent 2: A phenol novolak resin (trade name H-100 manufactured by Meiwa Kasei Co., Ltd.) at a hydroxyl equivalent of 106 g / eq and a softening point of 83 ° C was used.

(C) As a benzophenone derivative (hereinafter, referred to as hydroxybenzophenone compound) having one or more phenolic hydroxyl groups in one molecule,

Hydroxybenzophenone compound 1: p-hydroxybenzophenone,

Hydroxybenzophenone compound 2: o-hydroxybenzophenone,

Hydroxybenzophenone compound 3: 2-hydroxy-4-methoxybenzophenone,

Hydroxybenzophenone compound 4: 2,4-dihydroxybenzophenone,

Hydroxybenzophenone Compound 5: 4,4'-dihydroxybenzophenone was used.

In addition, as a material used in place of hydroxybenzophenones in the comparative example,

Phenolic compound 1: phenol,

Phenolic compound 2: p-cresol,

Phenolic compound 3: catechol,

Phenolic compound 4: resorcinol,

Phenolic compound 5: hydroquinone,

Benzophenone compound 1: benzophenone,

Benzophenone Compound 2: p-methoxybenzophenone was used.

As the (D) silane compound,

Silane compound 1: γ-glycidoxypropyltrimethoxysilane,

(E) As a hardening accelerator,

Curing accelerator 1: betaine adduct of triphenylphosphine and p-benzoquinone,

(F) As an inorganic filler,

Inorganic filler 1: Spherical fused silica having an average particle diameter of 17.5 µm and a specific surface area of 3.8 m ² / g was used. Montan acid ester and carbon black were used as other additive components.

<Evaluation>

The epoxy resin composition for sealing of an Example and a comparative example was evaluated by the various characteristic tests of following (1)-(7). The evaluation results are collectively shown in Tables 7 to 12 below. In addition, the shaping | molding of the epoxy resin composition for sealing was performed on the conditions of the mold temperature of 180 degreeC, molding pressure of 6.9 MPa, and hardening time of 90 second with the transfer molding machine, unless otherwise specified. In addition, postcure was performed at 180 degreeC for 5 hours.

(1) spiral flow

The epoxy molding material for sealing was shape | molded on the conditions using the metal mold | die for spiral flow measurement according to EMMI-1-66, and the flow distance (cm) was calculated | required.

(2) thermal hardness

The sealing epoxy resin composition was molded into a disc of 50 mm in diameter and 3 mm in thickness under the above conditions, and immediately measured after molding using a Shore D-type hardness meter (HD-1120 manufactured by Ueshima Seisakusho Co., Ltd.). .

(3) Heat hardness when absorbing moisture

Prior to molding in (2), the sealing epoxy resin composition was left at 25 ° C. and 50% RH for 72 hours, and then molded immediately, followed by Shore D hardness tester (HD-1120 manufactured by Ueshima Seisakusho Co., Ltd.). It was measured using type D)).

(4) water absorption

The disc molded in (2) was post-cured under the above conditions, left for 168 hours at 85 ° C. and 60% RH, and the mass change before and after standing was measured to determine the absorptivity (mass%) = {(the original mass-left after standing). Original mass) / original mass} x100 before standing.

(5) Bending elastic modulus at 260 ° C. (high temperature bending test)

The bending elastic modulus (E) was calculated | required from the following formula, carrying out the 3-point bending test based on JIS-K-6911 using the bending test machine (Tensilon, A & D Co., Ltd.), and maintaining at 260 degreeC in a thermostat. The measurement was performed on the conditions of the head speed of 1.5 mm / min using the test piece shape | molded the sealing epoxy resin composition to 10 mm, 70 mm, and 3 mm on the said conditions.

(6) Adhesion measurement with metal at 260 ° C (shear strength measurement)

The epoxy resin composition for sealing was formed into a copper plate or a silver plated copper plate under the above conditions, and then cured into a size having a diameter of 4 mm at the bottom, a diameter of 3 mm at the top, and a height of 4 mm, followed by a bond tester (Daisy Japan Japan Co., Ltd. Series 4000). Shear adhesive force was measured at a shear rate of 50 μm / s while maintaining the temperature of various copper plates at 260 ° C.).

(7) downflow

Epoxy resin composition for sealing 80-pin flat package (lead frame material: copper alloy, upper surface of die pad part and silver plated product of lead end part) with external dimension 20mm × 14mm × 2mm equipped with 8mm × 10mm × 0.4mm silicon chip It was molded under the above conditions using a post-curing. After leaving this at the temperature of 85 degreeC and 60% RH for 1 week, Examples 1-16 and Comparative Examples 1-16 are 240 degreeC, and Examples 17-20 and Comparative Examples 17-20 are 230 degreeC, Example 21-24 and Comparative Examples 21-24 performed the reflow process at 220 degreeC. The presence or absence of the peeling of the resin / frame interface in the sealed package after the reflow treatment was observed with an ultrasonic flaw detector (HYE-FOCUS manufactured by Hitachi Genki Co., Ltd.) and evaluated as the number of peeling generation packages relative to the number of test packages (five). .

The properties of the above (1) to (7) were compared with Examples and Comparative Examples in the combination of the same epoxy resin and curing agent. For example, Examples 1-16 and Comparative Examples 1-16 which are a combination of epoxy resin 1 and 2 / hardener 1, Examples 17-20 and Comparative Examples 17-20 which are a combination of epoxy resin 1 and 3 / hardener 1, Examples 21 to 24 and Comparative Examples 21 to 24, which are a combination of epoxy resin 1 and 4 / curing agent 2, were compared.

As shown in Tables 7 to 12, the Example to which the hydroxybenzophenone compound was added has a higher 260 ° C shear adhesive force (silver and copper) than the Comparative Example, and the reflow treatment after being left for 1 week at 85 ° C and 60% RH. No peeling of the resin / frame interface occurred, and the reflow property was excellent.

Example 5 in which the proportion of the hydroxybenzophenone compound is 0.1 mass% or less is lower in adhesion than the examples 1 to 4 and 6 to 16, which are the same epoxy resin / curing agent combination, and the effect of the invention is shown to be smaller. In Example 23 in which the ratio of the phenone compound was 1.0% by mass or more, the hardness was lower than those of Examples 21, 22, and 24, which were the same epoxy resin / curing agent combination. However, no peeling of the resin / frame interface occurred in either example.

On the other hand, the comparative example of the composition different from this invention did not satisfy the objective of this invention. Compared to Examples, 260 ° C shear adhesion (silver and copper) is equal to or less, and peeling of the resin / frame interface occurs in most packages in the reflow treatment after being left for one week at 85 ° C and 60% RH. And downflow was poor.

Claims (6)

(A) The epoxy resin composition for sealing containing the epoxy resin which contains 2 or more epoxy groups in 1 molecule, (B) hardening | curing agent, and (C) benzophenone derivative which has 1 or more of phenolic hydroxyl groups in 1 molecule. The epoxy resin composition for sealing according to claim 1, wherein the content of the benzophenone derivative having one or more phenolic hydroxyl groups in one molecule of (C) is 0.1% by mass to 1.0% by mass. The epoxy resin composition for sealing of Claim 1 which further contains the (D) silane compound. The epoxy resin composition for sealing of Claim 1 which further contains (E) hardening accelerator. The epoxy resin composition for sealing of Claim 1 which further contains (F) an inorganic filler. The electronic component apparatus provided with the element sealed by the sealing epoxy resin composition of any one of Claims 1-5.