JP5257656B2 - Epoxy resin molding material for sealing electronic component device and electronic component device - Google Patents

Description

  The present invention relates to an epoxy resin molding material for sealing and an electronic component device including an element sealed with the molding material.

  Conventionally, epoxy resin molding materials have been widely used in the field of sealing electronic components such as transistors and ICs. This is because the epoxy resin has a good balance of electrical properties, moisture resistance, heat resistance, mechanical properties, adhesiveness with inserts, and the like. In particular, the combination of an ortho-cresol novolac type epoxy resin and a novolac type phenol curing agent has an excellent balance between these, and has become the mainstream of the base resin of the molding material for sealing.

  As electronic devices have become smaller, lighter, and higher performance in recent years, mounting density has been increasing, and electronic component devices have come to be made surface mount packages from conventional pin insertion types. . When a semiconductor device is attached to a wiring board, the conventional pin insertion type package is soldered from the back side of the wiring board after the pins are inserted into the wiring board, so that the package is not directly exposed to high temperatures. However, in the surface mount type package, the entire semiconductor device is processed by a solder bath, a reflow device or the like, so that it is directly exposed to the soldering temperature. As a result, when the package absorbs moisture, the moisture absorption moisture rapidly expands during soldering, causing peeling of the adhesive interface and package cracks, resulting in a decrease in package reliability during mounting.

  As measures to solve the above problems, in order to reduce moisture absorption inside the semiconductor device, IC moisture-proof packaging, or a method of sufficiently drying the IC in advance before mounting on a wiring board is used. (For example, refer to Non-Patent Document 1.) However, these methods are time-consuming and costly. As another countermeasure, there is a method of increasing the content of the filler, but this method has a problem of causing a significant decrease in fluidity, although the moisture absorption inside the semiconductor device is reduced. A method for optimizing the particle size distribution of the filler has been proposed as a method for increasing the content of the filler without impairing the fluidity of the epoxy resin molding material (see, for example, Patent Document 1). Moreover, if the fluidity of the epoxy resin molding material for sealing is low, new problems such as the occurrence of gold wire flow, voids, pinholes, and the like have also occurred during molding (see, for example, Non-Patent Document 2).

Hitachi, Ltd. Semiconductor Division, "Surface Mounted LSI Package Mounting Technology and its Reliability Improvement" Applied Technology Publishing, November 16, 1988, pages 254-256 Japanese Patent Laid-Open No. 06-224328 Technical Information Association, Inc. “High Reliability of Semiconductor Encapsulation Resin” Technical Information Association, January 31, 1990, pages 172-176

As described above, when the fluidity is low, a new problem has arisen, and there is a demand for improving the fluidity without reducing the curability. However, the method for optimizing the filler particle size distribution does not provide a sufficient effect for improving the fluidity.
The present invention has been made in view of such a situation, and an object of the present invention is to provide an epoxy resin molding material for sealing excellent in fluidity and solder reflow resistance, and an electronic component device including an element sealed thereby. .

(1) The present invention is an epoxy resin molding material for sealing containing (A) an epoxy resin, (B) a curing agent, (C) a silane compound represented by the following general formula (I), and an epoxy for sealing It is related with the epoxy resin molding material for sealing of the electronic component apparatus whose ratio of the said (C) silane compound in resin molding material is 0.03-0.8 mass% .

（ここで、Ｒ^１〜Ｒ^６は水素原子、置換又は非置換の炭素数１〜１２の直鎖アルキル基、分岐アルキル基、シクロアルキル基、アリール基であり、Ｒ^７及びＲ^８は置換又は非置換の、炭素数１〜１２の直鎖アルキル基、分岐アルキル基、シクロアルキル基、アリール基であり、同一でも異なっても良く、Ｒ^９は炭素数１〜１０の２価の炭化水素基を示し、炭化水素基は置換されていてもよく、ｐは１〜３の整数を示す。）

(Here, R ^{1 to} R ⁶ are a hydrogen atom, a substituted or unsubstituted linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group, a cycloalkyl group, and an aryl group, and R ⁷ and R ⁸ are substituted or An unsubstituted linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group, a cycloalkyl group, and an aryl group, which may be the same or different, and R ⁹ is a divalent hydrocarbon group having 1 to 10 carbon atoms And the hydrocarbon group may be substituted, and p represents an integer of 1 to 3.)

( 2 ) In the present invention, (A) the epoxy resin is a biphenyl type epoxy resin, a thiodiphenol type epoxy resin, a novolac type epoxy resin, a bisphenol F type epoxy resin, a phenol aralkyl type epoxy resin, or a naphthol aralkyl type epoxy resin. It is related with the epoxy resin molding material for sealing of the electronic component apparatus as described in said (1 ) containing any one of these.

(3) In the present invention, (B) the curing agent comprises at least one of a phenol / aralkyl resin, a naphthol / aralkyl resin, a triphenylmethane type phenol resin, a novolac type phenol resin, and a copolymer type phenol / aralkyl resin. It contains the epoxy resin molding material for sealing of the electronic component apparatus as described in said (1) or ( 2) to contain.
(4) The present invention provides the electronic component device according to any one of (1) to ( 3 ), further comprising (D) a silane compound other than the silane compound represented by (C) the general formula (I) . The present invention relates to an epoxy resin molding material for sealing.
( 5 ) This invention relates to the epoxy resin molding material for sealing of the electronic component apparatus in any one of said (1)-( 4 ) which further contains (E) hardening accelerator.
( 6 ) This invention relates to the epoxy resin molding material for sealing of the electronic component apparatus in any one of said (1)-( 5 ) which further contains (F) inorganic filler.
( 7 ) This invention relates to an electronic component apparatus provided with the element sealed with the epoxy resin molding material for sealing of the electronic component apparatus in any one of said (1)-( 6 ).

  The epoxy resin molding material for sealing obtained according to the present invention can provide a highly reliable electronic component device with excellent fluidity and solder reflow resistance without deteriorating curability, and its industrial value is great. is there.

  The (A) epoxy resin used in the present invention is not particularly limited as long as it contains two or more epoxy groups in one molecule. For example, phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, triphenyl Phenols such as epoxy resin having methane skeleton, phenols such as cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde, acetaldehyde Epoxidized novolac resin obtained by condensation or cocondensation with a compound having an aldehyde group such as propionaldehyde, benzaldehyde, salicylaldehyde, etc. under an acidic catalyst, alkyl substitution, Aromatic ring-substituted or unsubstituted bisphenol A, bisphenol F, bisphenol S, diglycidyl ethers such as biphenol and thiodiphenol, stilbene type epoxy resins, hydroquinone type epoxy resins, phthalic acid, dimer acid and other polybasic acids and epichlorohydrin Glycidyl ester type epoxy resin obtained by reaction, diaminodiphenylmethane, isocyanuric acid and other polyamines and epichlorohydrin obtained by reaction of epichlorohydrin, epoxidized product of dicyclopentadiene and phenol co-condensation resin, epoxy having naphthalene ring Phenol-aralkyl resin synthesized from resin, phenol and / or naphthol and dimethoxyparaxylene or bis (methoxymethyl) biphenyl, naphthol Epoxidized aralkyl phenol resin such as rualkyl resin, trimethylolpropane epoxy resin, terpene modified epoxy resin, linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid, alicyclic epoxy Resin etc. are mentioned, These 1 type may be used independently or may be used in combination of 2 or more type.

  Among them, from the viewpoint of compatibility between fluidity and curability, it is preferable to contain a biphenyl type epoxy resin which is a diglycidyl ether of alkyl-substituted, aromatic ring-substituted or unsubstituted biphenol, and from the viewpoint of curability. It preferably contains a novolac-type epoxy resin, and contains a bisphenol F-type epoxy resin that is a diglycidyl ether of alkyl-substituted, aromatic ring-substituted or unsubstituted bisphenol F from the viewpoint of compatibility between fluidity and flame retardancy. From the viewpoint of compatibility between fluidity and reflowability, it preferably contains a thiodiphenol type epoxy resin which is a diglycidyl ether of alkyl-substituted, aromatic ring-substituted or unsubstituted thiodiphenol. Preferably, from the viewpoint of both curability and flame retardancy, alkyl-substituted, aromatic ring-substituted or unsubstituted pheno It preferably contains an epoxidized phenol / aralkyl resin synthesized from bis (methoxymethyl) biphenyl and is alkyl-substituted, aromatic-ring substituted or unsubstituted from the standpoint of both storage stability and flame retardancy It preferably contains an epoxidized product of naphthol-aralkyl resin synthesized from naphthols of the above and dimethoxyparaxylene.

  Examples of the biphenyl type epoxy resin include an epoxy resin represented by the following general formula (II).

（ここで、Ｒ^１〜Ｒ^８は水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、全てが同一でも異なっていてもよい。ｎは０又は１〜３の整数を示す。）

(Here, R ^{1 to} R ⁸ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and all may be the same or different. N is 0 or 1 to 1. Indicates an integer of 3.)

The biphenyl type epoxy resin represented by the general formula (II) can be obtained by reacting a biphenol compound with epichlorohydrin by a known method. As R < ¹ > -R < ⁸ > in general formula (II), it is C1-C10, such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a tert-butyl group, for example. C1-C10 alkenyl groups, such as an alkyl group, a vinyl group, an allyl group, a butenyl group, etc. are mentioned, Especially, a hydrogen atom or a methyl group is preferable. Examples of such an epoxy resin include 4,4′-bis (2,3-epoxypropoxy) biphenyl or 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5 ′. -Epoxy resin mainly composed of tetramethylbiphenyl, epoxy resin obtained by reacting epichlorohydrin with 4,4'-biphenol or 4,4 '-(3,3', 5,5'-tetramethyl) biphenol Etc. Among these, an epoxy resin mainly composed of 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl is preferable. Such an epoxy resin can be obtained as a commercial product under the trade name YX-4000 manufactured by Japan Epoxy Resin Co., Ltd. The blending amount of the biphenyl type epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more in the total amount of the epoxy resin in order to exhibit its performance.

  Examples of the thiodiphenol type epoxy resin include an epoxy resin represented by the following general formula (III).

（ここで、Ｒ^１〜Ｒ^８は水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、全てが同一でも異なっていてもよい。ｎは０又は１〜３の整数を示す。）

(Here, R ^{1 to} R ⁸ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and all may be the same or different. N is 0 or 1 to 1. Indicates an integer of 3.)

The thiodiphenol type epoxy resin represented by the general formula (III) can be obtained by reacting a thiodiphenol compound with epichlorohydrin by a known method. Examples of R ^{1 to} R ⁸ in the general formula (III) include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, and a tert-butyl group. C1-C10 alkenyl groups, such as an alkyl group, a vinyl group, an allyl group, a butenyl group, etc. are mentioned, Especially, a hydrogen atom, a methyl group, or a tert- butyl group is preferable. Examples of such an epoxy resin include an epoxy resin mainly composed of diglycidyl ether of 4,4′-dihydroxydiphenyl sulfide, and 2,2 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenyl. Epoxy resin based on diglycidyl ether of sulfide, epoxy resin based on diglycidyl ether of 2,2'-dimethyl-4,4'-dihydroxy-5,5'-di-tert-butyldiphenyl sulfide Among them, an epoxy mainly composed of an epoxy resin mainly composed of diglycidyl ether of 2,2′-dimethyl-4,4′-dihydroxy-5,5′-di-tert-butyldiphenyl sulfide Resins are preferred. Such an epoxy resin is commercially available as a trade name YSLV-120TE manufactured by Nippon Steel Chemical Co., Ltd. The blending amount of the thiodiphenol type epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more in the total amount of the epoxy resin in order to exhibit its performance.

  Examples of the bisphenol F type epoxy resin include an epoxy resin represented by the following general formula (IV).

（ここで、Ｒ^１〜Ｒ^８は水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、全てが同一でも異なっていてもよい。ｎは０又は１〜３の整数を示す。）

(Here, R ^{1 to} R ⁸ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and all may be the same or different. N is 0 or 1 to 1. Indicates an integer of 3.)

The bisphenol F type epoxy resin represented by the general formula (IV) can be obtained by reacting a bisphenol F compound with epichlorohydrin by a known method. As R < ¹ > -R < ⁸ > in general formula (IV), it is C1-C10, such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a tert-butyl group, for example. C1-C10 alkenyl groups, such as an alkyl group, a vinyl group, an allyl group, a butenyl group, etc. are mentioned, Especially, a hydrogen atom or a methyl group is preferable. Examples of such an epoxy resin include an epoxy resin mainly composed of 4,4′-methylenebis (2,6-dimethylphenol) diglycidyl ether, and 4,4′-methylenebis (2,3,6-trimethyl). (Epoxy) epoxy resin mainly composed of diglycidyl ether, epoxy resin mainly composed of 4,4′-methylenebisphenol diglycidyl ether, etc., among others, 4,4′-methylene bis (2,6- An epoxy resin mainly composed of diglycidyl ether of (dimethylphenol) is preferred. Such an epoxy resin is commercially available as a trade name YSLV-80XY manufactured by Nippon Steel Chemical Co., Ltd. The blending amount of the bisphenol F-type epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more in the total amount of the epoxy resin in order to exhibit its performance.

  Examples of the novolac type epoxy resin include an epoxy resin represented by the following general formula (V).

（ここで、Ｒは水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、ｎは０〜１０の整数を示す。）
上記一般式（Ｖ）で示されるノボラック型エポキシ樹脂は、ノボラック型フェノール樹脂にエピクロルヒドリンを反応させることによって容易に得られる。なかでも、上記一般式（Ｖ）中のＲとしては、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、イソブチル基等の炭素数１〜１０のアルキル基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等の炭素数１〜１０のアルコキシル基が好ましく、水素原子又はメチル基がより好ましい。ｎは０〜３の整数が好ましい。上記一般式（Ｖ）で示されるノボラック型エポキシ樹脂のなかでも、オルソクレゾールノボラック型エポキシ樹脂が好ましい。ノボラック型エポキシ樹脂を使用する場合、その配合量は、その性能を発揮するためにエポキシ樹脂全量中２０質量％以上とすることが好ましく、３０質量％以上がより好ましい。

(Here, R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10.)
The novolak type epoxy resin represented by the general formula (V) can be easily obtained by reacting a novolak type phenol resin with epichlorohydrin. Among them, R in the general formula (V) is an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, or an isobutyl group, a methoxy group, an ethoxy group, or a propoxy group. C1-C10 alkoxyl groups, such as a 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 novolac type epoxy resins represented by the general formula (V), orthocresol novolac type epoxy resins are preferable. In the case of using a novolac type epoxy resin, the blending amount thereof is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total amount of the epoxy resin in order to exhibit its performance.

  Examples of the epoxidized product of the phenol / aralkyl resin include an epoxy resin represented by the following general formula (VII).

（ここで、Ｒ^１〜Ｒ^９は水素原子、炭素数１〜１２の置換又は非置換の一価の炭化水素基から選ばれ、すべてが同一でも異なっていてもよい。ｉは０又は１〜３の整数を示し、ｎは０又は１〜１０の整数を示す。）

(Here, R ^{1 to} R ⁹ are selected from a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and all may be the same or different. 3 represents an integer, and n represents 0 or an integer of 1 to 10.)

The epoxidized product of the biphenylene skeleton-containing phenol / aralkyl resin represented by the general formula (VI) is obtained by adding epichlorohydrin to a phenol / aralkyl resin synthesized from alkyl-substituted, aromatic-ring-substituted or unsubstituted phenol and bis (methoxymethyl) biphenyl. It can be obtained by reacting by a known method. Examples of R ^{1 to} R ⁹ in the general formula (VI) include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, Chain alkyl groups such as octyl group, decyl group and dodecyl group, cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group and cyclohexenyl group, and aryl group-substituted alkyl groups such as benzyl group and phenethyl group , Alkoxy groups substituted alkyl groups such as methoxy group substituted alkyl groups, ethoxy group substituted alkyl groups, butoxy group substituted alkyl groups, amino group substituted alkyl groups such as aminoalkyl groups, dimethylaminoalkyl groups, diethylaminoalkyl groups, hydroxyl group substituted alkyl groups , Phenyl group, naphthyl group, biphenyl group, etc. Alkyl group, tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, dimethylnaphthyl group and other alkyl group-substituted aryl groups, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert- Examples include alkoxy group-substituted aryl groups such as butoxyphenyl group and methoxynaphthyl group, amino group-substituted aryl groups such as dimethylamino group and diethylamino group, and hydroxyl group-substituted aryl groups. Among them, a hydrogen atom or a methyl group is preferable. Further, n in the general formula (VI) is more preferably 6 or less on average, and such an epoxy resin is commercially available as a product name NC-3000S manufactured by Nippon Kayaku Co., Ltd.

Moreover, it is preferable to contain the epoxy resin shown by the said general formula (II) from a viewpoint of coexistence of a flame retardance, reflow resistance, and fluidity, Especially R < ¹ >-of said general formula (VI)- More preferably, R ⁸ is a hydrogen atom and R ^{1 to} R ^{8 in} the general formula (II) are hydrogen atoms and n = 0. In particular, the blending mass ratio is preferably (II) / (VI) = 50/50 to 5/95, more preferably 40/60 to 10/90, and 30/70 to 15/85. Is more preferred. As a compound satisfying such a blending mass ratio, CER-3000L (trade name, manufactured by Nippon Kayaku Co., Ltd.) and the like are commercially available.

  Examples of the epoxidized naphthol / aralkyl resin include an epoxy resin represented by the following general formula (VII).

（ここで、Ｒは水素原子、炭素数１〜１２の置換又は非置換の一価の炭化水素基から選ばれ、すべてが同一でも異なっていてもよい。ｉは０又は１〜３の整数を示し、Ｘは芳香環を含む二価の有機基を示し、ｎは０又は１〜１０の整数を示す。）
Ｘは、たとえばフェニレン基、ビフェニレン基、ナフチレン基等のアリーレン基、トリレン基等のアルキル基置換アリーレン基、アルコキシル基置換アリーレン基、アラルキル基置換アリーレン基、ベンジル基、フェネチル基等のアラルキル基から得られる二価の基、キシリレン基等のアリーレン基を含む二価の基などが挙げられ、なかでも、難燃性及び保存安定性の両立の観点からはフェニレン基、ビフェニレン基が好ましい。

(Here, R is selected from a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and all may be the same or different. I is an integer of 0 or 1-3. X represents a divalent organic group containing an aromatic ring, and n represents 0 or an integer of 1 to 10.)
X is obtained from an aralkyl group such as an arylene group such as a phenylene group, a biphenylene group or a naphthylene group, an alkyl group-substituted arylene group such as a tolylene group, an alkoxyl group-substituted arylene group, an aralkyl group-substituted arylene group, a benzyl group or a phenethyl group. And a divalent group containing an arylene group such as a xylylene group. Among them, a phenylene group and a biphenylene group are preferable from the viewpoint of both flame retardancy and storage stability.

  The epoxidized product of the naphthol / aralkyl resin represented by the general formula (VII) includes epichlorohydrin and naphthol / aralkyl resin synthesized from alkyl-substituted, aromatic-ring-substituted or unsubstituted naphthol and dimethoxyparaxylene or bis (methoxymethyl) biphenyl. Can be obtained by a known method. Examples of R in the general formula (VII) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group. Chain alkyl groups such as dodecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group, cyclohexenyl group and other cyclic alkyl groups, benzyl group, phenethyl group and other aryl group substituted alkyl groups, methoxy group substituted alkyl Groups, alkoxy groups substituted alkyl groups such as ethoxy group substituted alkyl groups, butoxy group substituted alkyl groups, amino group substituted alkyl groups such as aminoalkyl groups, dimethylaminoalkyl groups, diethylaminoalkyl groups, hydroxyl group substituted alkyl groups, phenyl groups, naphthyl groups , Unsubstituted aryl groups such as biphenyl groups, Alkyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, dimethylnaphthyl group and other alkyl group-substituted aryl groups, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group, Examples include an alkoxy group-substituted aryl group such as a methoxynaphthyl group, an amino group-substituted aryl group such as a dimethylamino group and a diethylamino group, and a hydroxyl group-substituted aryl group. Among them, a hydrogen atom or a methyl group is preferable. For example, the following general formula (VIII Epoxide of naphthol-aralkyl resin represented by (IX) or (IX). n shows 0 or the integer of 1-10, and 6 or less is more preferable on average. As an epoxy resin represented by the following general formula (VIII), as a commercially available product, trade name ESN-375 manufactured by Nippon Steel Chemical Co., Ltd. may be mentioned. As an epoxy resin represented by the following general formula (IX), commercially available A trade name ESN-175 manufactured by Sakai Chemical Co., Ltd. may be mentioned. The blended amount of the epoxidized naphthol / aralkyl resin is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more, based on the total amount of the epoxy resin in order to exhibit its performance.

（ここで、ｎは０又は１〜１０の整数を示す。）

(Here, n represents 0 or an integer of 1 to 10.)

（ここで、ｎは０又は１〜１０の整数を示す。）

(Here, n represents 0 or an integer of 1 to 10.)

  The above biphenyl type epoxy resin, thiodiphenol type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, epoxidized product of phenol / aralkyl resin and epoxidized product of naphthol / aralkyl resin are used alone. Even if two or more types may be used in combination, the blending amount when using two or more types in combination is preferably 50% by mass or more, more preferably 60% by mass or more in the total amount of the epoxy resin. Preferably, 80 mass% or more is more preferable.

  The (B) curing agent used in the present invention is generally used for an epoxy resin molding material for sealing and is not particularly limited. For example, phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenyl Phenols such as phenol, thiodiphenol and aminophenol and / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene and compounds having an aldehyde group such as formaldehyde, benzaldehyde and salicylaldehyde are condensed in an acidic catalyst. Alternatively, a novolak-type phenolic resin obtained by co-condensation, a phenol / aralkyl resin synthesized from phenol and / or naphthol and dimethoxyparaxylene or bis (methoxymethyl) biphenyl, naphthol / aral Aralkyl-type phenol resins such as kill resins, phenol / aralkyl structures having a phenol / novolak structure and phenol / aralkyl structures randomly, block or alternately repeated, paraxylylene and / or metaxylylene-modified phenol resins, melamine-modified phenol resins, Examples include terpene-modified phenol resins, dicyclopentadiene-modified phenol resins, cyclopentadiene-modified phenol resins, and polycyclic aromatic ring-modified phenol resins. These may be used alone or in combination of two or more.

  Among these, from the viewpoint of fluidity, flame retardancy and reflow resistance, phenol / aralkyl resins, copolymerized phenol / aralkyl resins and naphthol / aralkyl resins are preferred, and from the viewpoints of heat resistance, low expansion rate and low warpage. Is preferably a triphenylmethane type phenol resin, and from the viewpoint of curability, a novolac type phenol resin is preferable, and preferably contains at least one of these phenol resins.

  Examples of the phenol / aralkyl resin include a resin represented by the following general formula (X).

（ここで、Ｒは水素原子、炭素数１〜１２の置換又は非置換の一価の炭化水素基から選ばれ、すべてが同一でも異なっていてもよい。ｉは０又は１〜３の整数を示し、Ｘは芳香環を含む二価の有機基を示し、ｎは０又は１〜１０の整数を示す。）

(Here, R is selected from a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and all may be the same or different. I is an integer of 0 or 1-3. X represents a divalent organic group containing an aromatic ring, and n represents 0 or an integer of 1 to 10.)

Examples of R in the general formula (X) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, Decyl group, chain alkyl group such as dodecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group, cyclohexenyl group and other cyclic alkyl groups, benzyl group, phenethyl group and other aryl group substituted alkyl groups, methoxy group Substituted alkyl group, ethoxy group substituted alkyl group, alkoxy group substituted alkyl group such as butoxy group substituted alkyl group, aminoalkyl group, dimethylaminoalkyl group, amino group substituted alkyl group such as diethylaminoalkyl group, hydroxyl group substituted alkyl group, phenyl group, Unsubstituted aryl groups such as naphthyl group and biphenyl group, Alkyl group-substituted aryl groups such as ryl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, dimethylnaphthyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group, Examples include an alkoxy group-substituted aryl group such as a methoxynaphthyl group, an amino group-substituted aryl group such as a dimethylamino group and a diethylamino group, and a hydroxyl group-substituted aryl group. Among them, a hydrogen atom or a methyl group is preferable.
X represents a group containing an aromatic ring, for example, an arylene group such as a phenylene group, a biphenylene group or a naphthylene group, an alkyl group-substituted arylene group such as a tolylene group, an alkoxyl group-substituted arylene group, a benzyl group or a phenethyl group. And a divalent group containing an arylene group such as a divalent group obtained from a group, an aralkyl group-substituted arylene group, and a xylylene group. Among these, from the viewpoint of achieving both flame retardancy and reflow resistance, a substituted or unsubstituted biphenylene group is preferable, and examples thereof include a phenol-aralkyl resin represented by the following general formula (XI). From the standpoint of achieving both good and curability, a substituted or unsubstituted phenylene group is preferable, and examples thereof include a phenol / aralkyl resin represented by the following general formula (XII). n shows 0 or the integer of 1-10, and 6 or less is more preferable on average.

（ここで、ｎは０又は１〜１０の整数を示す。）

(Here, n represents 0 or an integer of 1 to 10.)

（ここで、ｎは０又は１〜１０の整数を示す。）

(Here, n represents 0 or an integer of 1 to 10.)

  The biphenylene skeleton-containing phenol / aralkyl resin represented by the general formula (XI) includes MEH-7851 manufactured by Meiwa Kasei Co., Ltd. as a commercial product, and the phenol / aralkyl resin represented by the general formula (XII) As a commercial product, trade name XLC manufactured by Mitsui Chemicals, Inc. may be mentioned. The blending amount of the phenol-aralkyl resin is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more in the total amount of the curing agent in order to exhibit its performance.

  Examples of the naphthol / aralkyl resin include resins represented by the following general formula (XIII).

（ここで、Ｒは水素原子、炭素数１〜１２の置換又は非置換の一価の炭化水素基から選ばれ、すべてが同一でも異なっていてもよい。ｉは０又は１〜３の整数を示し、Ｘは芳香環を含む二価の有機基を示し、ｎは０又は１〜１０の整数を示す。）

(Here, R is selected from a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and all may be the same or different. I is an integer of 0 or 1-3. X represents a divalent organic group containing an aromatic ring, and n represents 0 or an integer of 1 to 10.)

  As R in the general formula (XIII), for example, 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, chain alkyl group such as dodecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group, cyclohexenyl group and other cyclic alkyl groups, benzyl group, phenethyl group and other aryl group substituted alkyl groups, methoxy group Substituted alkyl group, ethoxy group substituted alkyl group, alkoxy group substituted alkyl group such as butoxy group substituted alkyl group, aminoalkyl group, dimethylaminoalkyl group, amino group substituted alkyl group such as diethylaminoalkyl group, hydroxyl group substituted alkyl group, phenyl group, Unsubstituted aryl such as naphthyl group and biphenyl group Group, tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, dimethylnaphthyl group and other alkyl group-substituted aryl groups, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl Group, an alkoxy group-substituted aryl group such as a methoxynaphthyl group, an amino group-substituted aryl group such as a dimethylamino group and a diethylamino group, and a hydroxyl group-substituted aryl group. Among them, a hydrogen atom or a methyl group is preferable.

  X represents a divalent organic group containing an aromatic ring, for example, an arylene group such as a phenylene group, a biphenylene group or a naphthylene group, an alkyl group-substituted arylene group such as a tolylene group, an alkoxyl group-substituted arylene group, an aralkyl group-substituted arylene. Groups, divalent groups obtained from aralkyl groups such as benzyl groups, phenethyl groups, and the like, and divalent groups including arylene groups such as xylylene groups, among others, from the viewpoint of storage stability and flame retardancy A substituted or unsubstituted phenylene group and a biphenylene group are preferable, and a phenylene group is more preferable, and examples thereof include naphthol-aralkyl resins represented by the following general formulas (XIV) and (XV). n shows 0 or the integer of 1-10, and 6 or less is more preferable on average.

（ここで、Ｘは芳香環を含む二価の有機基を示し、ｎは０又は１〜１０の整数を示す。）

(Here, X represents a divalent organic group containing an aromatic ring, and n represents 0 or an integer of 1 to 10.)

（ここで、Ｘは芳香環を含む二価の有機基を示し、ｎは０又は１〜１０の整数を示す。）

(Here, X represents a divalent organic group containing an aromatic ring, and n represents 0 or an integer of 1 to 10.)

  As a naphthol aralkyl resin represented by the above general formula (XIV), trade name SN-475 manufactured by Nippon Steel Chemical Co., Ltd. may be mentioned as a commercial product, and as a naphthol aralkyl resin represented by the above general formula (XV), As a commercial product, trade name SN-170 manufactured by Nippon Steel Chemical Co., Ltd. may be mentioned. The blending amount of the naphthol / aralkyl resin is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more in the total amount of the curing agent in order to exhibit its performance.

The phenol / aralkyl resin represented by the general formula (X) and the naphthol / aralkyl resin represented by the general formula (XIII) are preferably premixed partially or entirely with acenaphthylene from the viewpoint of flame retardancy. . Although acenaphthylene can be obtained by dehydrogenating acenaphthene, a commercially available product may be used. Moreover, it can also be used as a polymer of acenaphthylene or a polymer of acenaphthylene and other aromatic olefins instead of acenaphthylene. Examples of a method for obtaining a polymer of acenaphthylene or a polymer of acenaphthylene and another aromatic olefin include radical polymerization, cationic polymerization, and anionic polymerization. In the polymerization, a conventionally known catalyst can be used, but it can also be carried out only by heat without using a catalyst. At this time, the polymerization temperature is preferably 80 to 160 ° C, more preferably 90 to 150 ° C. 60-150 degreeC is preferable and, as for the softening point of the polymer of the polymer of acenaphthylene obtained or acenaphthylene and another aromatic olefin, 70-130 degreeC is more preferable.
When the temperature is lower than 60 ° C., the moldability tends to decrease due to oozing during molding, and when the temperature is higher than 150 ° C., the compatibility with the resin tends to decrease. Examples of other aromatic olefins to be copolymerized with acenaphthylene include styrene, α-methylstyrene, indene, benzothiophene, benzofuran, vinylnaphthalene, vinylbiphenyl, and alkyl-substituted products thereof. In addition to the above-mentioned aromatic olefins, aliphatic olefins can be used in combination as long as the effects of the present invention are not impaired. Examples of the aliphatic olefin include (meth) acrylic acid and esters thereof, maleic anhydride, itaconic anhydride, fumaric acid and esters thereof. The use amount of these aliphatic olefins is preferably 20% by mass or less, more preferably 9% by mass or less, based on the total amount of the polymerization monomers.

  As a method of premixing part or all of the curing agent with acenaphthylene, the curing agent and acenaphthylene are finely pulverized and mixed in a solid state with a mixer or the like, or both components are uniformly dissolved in a solvent that dissolves them. Then, a method of removing the solvent, a method of melting and mixing the curing agent and / or acenaphthylene at a temperature equal to or higher than the softening point of the acenaphthylene, etc. can be performed. The method is preferred. A premix (acenaphthylene-modified curing agent) is produced by the above method. Although melt mixing will not have a restriction | limiting, if it is the temperature more than the softening point of a hardening | curing agent and / or acenaphthylene, 100-250 degreeC is preferable and 120-200 degreeC is more preferable. Moreover, although melt mixing will not have a restriction | limiting in mixing time if both are mixed uniformly, 1 to 20 hours are preferable and 2 to 15 hours are more preferable. When the curing agent and acenaphthylene are premixed, the acenaphthylene may polymerize or react with the curing agent during mixing.

  Examples of the triphenylmethane type phenol resin include a phenol resin represented by the following general formula (XVI).

（ここで、Ｒは水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、ｎは０〜１０の整数を示す。）

(Here, R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10.)

  Examples of R in the general formula (XVI) include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and a tert-butyl group, a vinyl group, an allyl group, and a butenyl group. C1-C10 substituted or unsubstituted monovalent hydrocarbon group such as alkenyl group, halogenated alkyl group, amino group-substituted alkyl group, mercapto group-substituted alkyl group, etc., among which methyl group, ethyl group Alkyl groups and hydrogen atoms such as methyl groups and hydrogen atoms are more preferable. When using a triphenylmethane type phenol resin, the blending amount is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total amount of the curing agent in order to exhibit its performance.

  Examples of the novolak-type phenol resin include novolak-type phenol resins such as a phenol resin represented by the following general formula (XVII), cresol novolak resin, and the like. Among these, novolak-type phenol resins represented by the following general formula (XVII) are exemplified. preferable.

（ここで、Ｒは水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、ｉは０〜３の整数を示し、ｎは０〜１０の整数を示す。）

Here, R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, i represents an integer of 0 to 3, and n represents an integer of 0 to 10. )

  Examples of R in the general formula (XVII) include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and a tert-butyl group, a vinyl group, an allyl group, and a butenyl group. C1-C10 substituted or unsubstituted monovalent hydrocarbon group such as alkenyl group, halogenated alkyl group, amino group-substituted alkyl group, mercapto group-substituted alkyl group, etc., among which methyl group, ethyl group Alkyl groups and hydrogen atoms such as hydrogen atoms, hydrogen atoms are more preferable, and the average value of n is preferably 0 to 8. When using a novolac type phenol resin, the blending amount is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total amount of the curing agent in order to exhibit its performance.

  As a copolymerization type phenol aralkyl resin, the phenol resin shown, for example by the following general formula (XVIII) is mentioned.

（ここで、Ｒは水素原子、炭素数１〜１２の置換又は非置換の一価の炭化水素基及び水酸基から選ばれ、すべてが同一でも異なっていてもよい。またＸは芳香環を含む二価の基を示す。ｎ及びｍは０又は１〜１０の整数を示す。）

(Wherein R is selected from a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms and a hydroxyl group, all of which may be the same or different. And n and m are each 0 or an integer of 1 to 10.)

  As R in the general formula (XVIII), for example, 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, chain alkyl group such as dodecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group, cyclohexenyl group and other cyclic alkyl groups, benzyl group, phenethyl group and other aryl group substituted alkyl groups, methoxy group Substituted alkyl group, ethoxy group substituted alkyl group, alkoxy group substituted alkyl group such as butoxy group substituted alkyl group, aminoalkyl group, dimethylaminoalkyl group, amino group substituted alkyl group such as diethylaminoalkyl group, hydroxyl group substituted alkyl group, phenyl group, Unsubstituted ants such as naphthyl group and biphenyl group Group, tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, dimethylnaphthyl group and other alkyl group-substituted aryl groups, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxy Examples include an alkoxy group-substituted aryl group such as a phenyl group and a methoxynaphthyl group, an amino group-substituted aryl group such as a dimethylamino group and a diethylamino group, and a hydroxyl group-substituted aryl group. Among them, a hydrogen atom or a methyl group is preferable, and n and m represents 0 or an integer of 1 to 10, and is preferably 6 or less on average.

X in the general formula (XVIII) is, for example, an arylene group such as a phenylene group, a biphenylene group or a naphthylene group, an alkyl group-substituted arylene group such as a tolylene group, an alkoxyl group-substituted arylene group, an aralkyl group-substituted arylene group, or a benzyl group. , Divalent groups obtained from an aralkyl group such as a phenethyl group, divalent groups containing an arylene group such as a xylylene group, etc., among others, substituted or unsubstituted from the viewpoint of storage stability and flame retardancy The phenylene group and biphenylene group are preferred.
As the compound represented by the general formula (XVIII), HE-510 (trade name, manufactured by Air Water Co., Ltd.) and the like are commercially available.
In the case of using a copolymeric phenol / aralkyl resin, the blending amount thereof is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total amount of the curing agent in order to exhibit its performance.

  The above phenol / aralkyl resin, naphthol / aralkyl resin, triphenylmethane type phenol resin, novolac type phenol resin and copolymer type phenol / aralkyl resin may be used alone or in combination of two or more. However, the blending amount in the case of using two or more in combination is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 80% by mass or more in the total amount of phenol resin. .

  In the present invention, the equivalent ratio of (A) epoxy resin and (B) curing agent, that is, the ratio of the number of hydroxyl groups in the curing agent to the epoxy group (number of hydroxyl groups in the curing agent / number of epoxy groups in the epoxy resin) is particularly Although there is no restriction | limiting, in order to suppress each unreacted part few, it is preferable to set to the range of 0.5-2, and 0.6-1.3 are more preferable. In order to obtain a sealing epoxy resin molding material excellent in moldability and solder reflow resistance, it is more preferably set in the range of 0.8 to 1.2.

  The (C) silane compound used in the present invention is not particularly limited as long as it is a compound represented by the following general formula (I).

（ここで、Ｒ^１〜Ｒ^６は水素原子、置換又は非置換の炭素数１〜１２の直鎖アルキル基、分岐アルキル基、シクロアルキル基、アリール基であり、Ｒ^７及びＲ^８は置換又は非置換の、炭素数１〜１２の直鎖アルキル基、分岐アルキル基、シクロアルキル基、アリール基であり、同一でも異なっても良く、Ｒ^９は炭素数１〜１０の２価の炭化水素基を示し、炭化水素基は置換されていてもよく、ｐは１〜３の整数を示す。）

(Here, R ^{1 to} R ⁶ are a hydrogen atom, a substituted or unsubstituted linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group, a cycloalkyl group, and an aryl group, and R ⁷ and R ⁸ are substituted or An unsubstituted linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group, a cycloalkyl group, and an aryl group, which may be the same or different, and R ⁹ is a divalent hydrocarbon group having 1 to 10 carbon atoms And the hydrocarbon group may be substituted, and p represents an integer of 1 to 3.)

Examples of R ^{1 to} R ⁶ in the compound represented by the general formula (I) include a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl. Group, isobutyl group, pentyl group, hexyl group, 2-ethylhexyl group, 1-ethylpropyl group, octyl group, decyl group, dodecyl group and the like linear or branched chain alkyl group, cyclopentyl group, cyclohexyl group, Cycloheptyl group, cyclopentenyl group, cyclohexenyl group and other cycloalkyl groups, benzyl group, phenethyl group and other aryl group-substituted alkyl groups, phenyl group, naphthyl group, biphenyl group and other unsubstituted aryl groups, tolyl group, dimethylphenyl Group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, dimethylnaphthyl Alkyl group-substituted aryl groups such as alkenyl groups, alkoxy group-substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group, etc. are mentioned, and from the viewpoint of balance between curability, fluidity and adhesiveness Are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a benzyl group or a phenyl group.
Examples of R ⁷ and R ⁸ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, a hexyl group, and a 2-ethylhexyl group. , 1-ethylpropyl group, octyl group, decyl group, dodecyl group and other linear or branched chain alkyl groups, cyclopentyl group, cyclohexyl group, cycloheptyl group and other cycloalkyl groups, cyclopentenyl group, cyclohexenyl A cycloalkenyl group such as a cycloalkenyl group, a cycloalkenyl group such as a cyclopentenyl group and a cyclohexenyl group, an aryl group-substituted alkyl group such as a benzyl group and a phenethyl group, an unsubstituted aryl such as a phenyl group, a naphthyl group, and a biphenyl group Group, tolyl group, dimethylphenyl group, ethylphenyl group, Examples include alkyl group-substituted aryl groups such as ruphenyl group, tert-butylphenyl group, and dimethylnaphthyl group, and alkoxy group-substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, and tert-butoxyphenyl group. From the viewpoint of balance of adhesiveness, adhesiveness and curability, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, benzyl group and phenyl group are preferable. .
R ⁹ includes, for example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group and other alkylene groups, phenylene group, methylphenylene group, trimethylphenylene Group, an alkyl-substituted arylene group such as a tetramethylphenylene group, an ethylphenylene group, and a diethylphenylene group, and an ethylene group or a propylene group is preferable from the viewpoint of balance between fluidity, adhesiveness, and curability. p represents an integer of 1 to 3, but 2 or 3 is preferable from the viewpoint of adhesiveness and curability. Any one of these may be used alone, or two or more may be used in combination.

  The total amount of the silane compound represented by the general formula (I), which is the component (C) used in the present invention, is 0 with respect to the sealing epoxy resin molding material from the viewpoint of fluidity, moldability and reflow resistance. 0.03-0.8 mass% is preferable, 0.04-0.75 mass% is more preferable, 0.05-0.7 mass% is further more preferable. If it is less than 0.03% by mass, the effect of the invention tends to be small, and if it exceeds 0.8% by mass, the fluidity is improved but the reflow resistance tends to be greatly reduced.

  As for the molding material of this invention, the molding material of this invention may contain silane compounds other than the silane compound of (D) said (C) component. (C) There is no particular limitation as long as it is a silane compound different from the silane compound represented by the general formula (I). It is. Specific examples thereof include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ -Methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyldimethylethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyl Triethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane Γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyldimethylethoxysilane, vinyltriacetoxysilane, γ- Mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- [bis (β-hydroxyethyl) Aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, isocyanatepropyltrimethoxysilane, isocyan Propyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenylsilanediol, triphenyl Phenylmethoxysilane, triphenylethoxysilane, triphenylsilanol, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, γ-anilino Propyltrimethoxysilane, γ-anilinopropyltriethoxysilane, 2-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-triethoxy Ryl-N- (1,3-dimethyl-butylidene) propylamine, N- (3-triethoxysilylpropyl) phenylimine, 3- (3- (triethoxysilyl) propylamino) -N, N-dimethylpropionamide Silane compounds such as N-triethoxysilylpropyl-β-alanine methyl ester, 3- (triethoxysilylpropyl) dihydro-3,5-furandone, bis (trimethoxysilyl) benzene, 1H-imidazole, 2- Reaction of imidazole compounds such as alkylimidazole, 2,4-dialkylimidazole and 4-vinylimidazole with γ-glycidoxypropylalkoxysilane such as γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane Imidazole silane compound And the like. One of these silane compounds may be used alone, or two or more thereof may be used in combination.

  (D) As the silane compound other than the silane compound of the component (C), a silane compound obtained by polymerizing one or more silane compounds in combination may be used. The polymerized silane compound is preferably a compound having a weight average molecular weight of 3000 or less obtained by polymerizing an alkoxysilyl group portion of γ-glycidoxypropyltrimethoxysilane from the viewpoint of a balance between fluidity and reflow resistance. . These polymerized silane compounds may be used alone or in combination of two or more, or may be used in combination with a silane compound.

  The total amount of the silane compound is preferably 0.06 to 2% by mass, more preferably 0.1 to 0.75% by mass in the epoxy resin molding material for sealing, from the viewpoints of moldability and adhesiveness. 0.7 mass% is more preferable. If it is less than 0.06% by mass, the adhesion to various package members tends to be reduced, and if it exceeds 2% by mass, molding defects such as voids tend to occur.

  The molding material of the present invention may contain (E) a curing accelerator. The (E) curing accelerator used in the present invention is not particularly limited as it is generally used in an epoxy resin molding material for sealing. For example, 1,8-diazabicyclo [5.4.0] undecene-7,1,5-diazabicyclo [4.3.0] nonene-5,5,6-dibutylamino-1,8-diazabicyclo [5.4 .0] cycloamidine compounds such as undecene-7 and these compounds to maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethyl Quinones such as benzoquinone, 2,3-dimethoxy-5-methyl-1,4benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, π such as diazophenylmethane, phenol resin, etc. Compound with intramolecular polarization formed by adding a compound with bond, benzyldimethylamine, triethanolamine, dimethylamine Tertiary amines such as ethanol and tris (dimethylaminomethyl) phenol and their derivatives, imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole and the like Derivatives, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine and the like, and maleic anhydride, the above quinone compounds, diazophenylmethane Phosphorus compounds with intramolecular polarization formed by adding a compound having a π bond such as phenol resin, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltrif Tetra-substituted phosphonium and tetra-substituted borates such as nylborate and tetrabutylphosphonium tetrabutylborate, tetraphenylboron salts such as 2-ethyl-4-methylimidazole and tetraphenylborate, N-methylmorpholine and tetraphenylborate, and derivatives thereof These may be used alone or in combination of two or more.

Among these, an adduct of a tertiary phosphine and a quinone compound is preferable from the viewpoint of curability and fluidity, and an adduct of a cycloamidine compound and a phenol resin is preferable from the viewpoint of storage stability, and diazabicycloundecene. The novolac type phenol resin salt is more preferable.
The blending amount of these curing accelerators is preferably 60% by mass or more, more preferably 80% by mass or more in the total amount of the curing accelerator.

  The tertiary phosphine used in the adduct of the tertiary phosphine and the quinone compound is not particularly limited, but examples thereof include dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, and 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, tertiary phosphines are exemplified with an aryl group such as tris (4-ethoxyphenyl) phosphine, triphenylphosphine is preferable in view of moldability.

  Further, the quinone compound used for the adduct of the tertiary phosphine and the quinone compound is not particularly limited, and examples thereof include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, anthraquinone, and the like. P-benzoquinone is preferable from the viewpoint of stability or storage stability.

  Although the compounding quantity of a hardening accelerator will not be specifically limited if the hardening acceleration effect is achieved, it is 0.00 with respect to 100 mass parts of total amounts of (A) epoxy resin and (B) hardening | curing agent. 1-10 mass parts is preferable and 0.3-5 mass parts is more preferable. If it is less than 0.1 parts by mass, it is difficult to cure in a short time, and if it exceeds 10 parts by mass, the curing rate tends to be too fast and a good molded product tends not to be obtained.

  The molding material of the present invention may contain (F) an inorganic filler. The (F) inorganic filler used in the present invention is blended in a molding material for hygroscopicity, linear expansion coefficient reduction, thermal conductivity improvement and strength improvement, and is generally used as an epoxy resin molding material for sealing. There is no particular limitation as long as it is used, 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, fosterite, steatite, spinel, mullite, titania, etc., or spherical beads, glass fibers, etc. May be used. Among these, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity, and the filler shape is preferably spherical from the viewpoint of fluidity during molding and mold wear. In particular, spherical fused silica is preferable from the viewpoint of a balance between cost and performance.

  The blending amount of the inorganic filler is preferably 70 to 95% by mass in the epoxy resin molding material for sealing, from the viewpoint of flame retardancy, moldability, hygroscopicity, reduction of linear expansion coefficient and improvement of strength, and hygroscopicity, linear expansion. From the viewpoint of reducing the coefficient, 84 to 95% by mass is more preferable. If it is less than 70% by mass, the flame retardancy and reflow resistance tend to decrease, and if it exceeds 95% by mass, the fluidity tends to be insufficient.

  A conventionally well-known coupling agent may be mix | blended with the epoxy resin molding material for sealing of this invention. For example, isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl) -1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropylisostearoyldiacrylic Titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumi Examples include titanate coupling agents such as phenyl titanate and tetraisopropyl bis (dioctyl phosphite) titanate, aluminum chelates, aluminum / zirconium compounds, etc. Even if one of these is used alone, two or more are combined. It may be used. Further, the total blending amount of these coupling agents is preferably 0.06 to 2% by mass, more preferably 0.1 to 0.75% by mass in the sealing epoxy resin molding material from the viewpoint of moldability and adhesiveness. More preferably, it is 2 to 0.7% by mass. If it is less than 0.06% by mass, the adhesion to various package members tends to be reduced, and if it exceeds 2% by mass, molding defects such as voids tend to occur.

  Moreover, an anion exchanger can be blended with the epoxy resin molding material for sealing of the present invention, if necessary, for the purpose of improving the moisture resistance and high temperature storage characteristics of the IC. The anion exchanger is not particularly limited, and conventionally known anion exchangers can be used. Examples thereof include hydrotalcites and hydrated oxides of elements selected from magnesium, aluminum, titanium, zirconium, and bismuth. These may be used alone or in combination of two or more. Of these, hydrotalcite represented by the following composition formula (XIX) is preferable.

  The amount of the anion exchanger is not particularly limited as long as it is a sufficient amount capable of capturing anions such as halogen ions, but 0.1 to 30 masses per 100 mass parts of the (A) epoxy resin. Part is preferable, and 1 to 5 parts by mass is more preferable.

  In the sealing epoxy resin molding material of the present invention, an adhesion promoter can be used as necessary in order to further improve the adhesion. Examples of the adhesion promoter include derivatives such as imidazole, triazole, tetrazole and triazine, anthranilic acid, gallic acid, malonic acid, malic acid, maleic acid, aminophenol, quinoline and the like, and derivatives thereof, aliphatic acid amide compounds, Examples thereof include dithiocarbamate and thiadiazole derivatives. One of these may be used alone, or two or more may be used in combination.

  A release agent may be used in the sealing epoxy resin molding material of the present invention as necessary. As a mold release agent, it is preferable to use 0.01-10 mass parts with respect to 100 mass parts of (A) epoxy resins, and it is more preferable to use 0.1-5 mass parts as a mold release agent. . If it is less than 0.01 parts by mass, the releasability tends to be insufficient, and if it exceeds 10 parts by mass, the adhesiveness tends to decrease. Examples of the oxidized or non-oxidized polyolefin include low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000, such as trade name H4 manufactured by Hoechst Corporation, PE, and PED series. Other examples of the release agent include carnauba wax, montanic acid ester, montanic acid, stearic acid, and the like. These may be used alone or in combination of two or more. When these other release agents are used in combination with the oxidized or non-oxidized polyolefin, the blending amount thereof is set to 0.000 parts per 100 parts by mass of the (A) epoxy resin. 1-10 mass parts is preferable, and 0.5-3 mass parts is more preferable.

  A conventionally known flame retardant can be blended in the sealing epoxy resin molding material of the present invention as required. For example, red phosphorus coated with inorganic substances such as brominated epoxy resin, antimony trioxide, red phosphorus, aluminum hydroxide, magnesium hydroxide, zinc oxide and / or thermosetting resins such as phenol resin, phosphoric acid ester, etc. Phosphorus compounds, melamine, melamine derivatives, melamine-modified phenol resins, compounds having a triazine ring, nitrogen-containing compounds such as cyanuric acid derivatives and isocyanuric acid derivatives, phosphorus and nitrogen-containing compounds such as cyclophosphazene, aluminum hydroxide, magnesium hydroxide And composite metal hydroxides represented by the following composition formula (XX).

M ¹ , M ^2, and M ^{3 in the} composition formula (XX) are not particularly limited as long as they are different metal elements, but from the viewpoint of flame retardancy, M ¹ is a metal element of the third period, group IIA Preferably selected from metal elements belonging to the alkaline earth metal elements, group IVB, group IIB, group VIII, group IB, group IIIA and group IVA, and M ² is selected from transition metal elements of groups IIIB to IIB, More preferably, M ¹ is selected from magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc, and M ² is selected from iron, cobalt, nickel, 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. The molar ratio of p, q and r is not particularly limited, but preferably r = 0 and p / q is 1/99 to 1/1. The metal element is classified into a long-period periodic table in which the typical element is the A group and the transition element is the B group (Source: Kyoritsu Shuppan Co., Ltd., “Chemical Dictionary 4”, February 15, 1987). (Reduced plate 30th printing). Further, compounds containing metal elements such as zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate, dicyclopentadienyl iron, etc. may be mentioned, and one of these may be used alone. Two or more kinds may be used in combination. Although the compounding quantity of a flame retardant does not have a restriction | limiting in particular, 1-30 mass parts is preferable with respect to 100 mass parts of (A) epoxy resins, and 2-15 mass parts is more preferable.

  Moreover, you may use coloring agents, such as carbon black, an organic dye, an organic pigment, a titanium oxide, a red lead, a bengara, for the epoxy resin molding material for sealing of this invention. Furthermore, as other additives, stress relaxation agents such as silicone oil and silicone rubber powder can be blended as required.

  The epoxy resin molding material for sealing of the present invention can be prepared by any method as long as various components can be uniformly dispersed and mixed, but as a general method, components of a predetermined blending amount are mixed by a mixer or the like. A method of cooling and pulverizing after mixing sufficiently, melt-kneading with a mixing roll, an extruder or the like can be mentioned. For example, a predetermined amount of the above-described components can be uniformly stirred and mixed, and can be obtained by a method such as kneading, cooling, and pulverizing with a kneader, roll, extruder, or the like that has been heated to 70 to 140 ° C. in advance. It is easy to use if it is tableted with dimensions and mass that match the molding conditions.

  As an electronic component device provided with an element sealed with an epoxy resin molding material for sealing obtained in the present invention, a semiconductor chip is mounted on a support member such as a lead frame, a wired tape carrier, a wiring board, glass, or a silicon wafer. An electronic component device equipped with active elements such as transistors, diodes and thyristors, and passive elements such as capacitors, resistors and coils, and encapsulated with the epoxy resin molding material for sealing of the present invention Etc. As such an electronic component device, for example, a semiconductor element is fixed on a lead frame, a terminal portion of a device such as a bonding pad and a lead portion are connected by wire bonding or a bump, and then the sealing epoxy resin of the present invention is used. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Out Package), which is sealed by molding using a molding material. General resin-sealed type I such as lead package, TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat Package), etc. A semiconductor chip connected to a tape carrier with a bump is sealed with a tape carrier package (TCP) sealed with an epoxy resin molding material of the present invention, wiring formed on a wiring board or glass, wire bonding, flip chip bonding COB (Chip) in which active elements such as semiconductor chips, transistors, diodes, thyristors and / or passive elements such as capacitors, resistors, coils, etc., which are connected by solder, etc., are sealed with the sealing epoxy resin molding material of the present invention On Board) Modules, hybrid ICs, multi-chip modules, devices mounted on the surface of the organic substrate with the wiring board connection terminals formed on the back, and the devices and the wiring formed on the organic substrate were connected by bump or wire bonding After, the epoxy resin molding material for sealing of the present invention Examples thereof include BGA (Ball Grid Array) and CSP (Chip Size Package) in which the element is sealed with a material. Moreover, the epoxy resin molding material for sealing of the present invention can also be used effectively for printed circuit boards.

  As a method for sealing an element using the epoxy resin molding material for sealing of the present invention, a low-pressure transfer molding method is the most common, but an injection molding method, a compression molding method, or the like may be used.

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

  In accordance with Synthesis Example 1 below, silane compound 1 as component (C) used in the present invention was synthesized.

Synthesis Example 1: Synthesis of Silane Compound 1 A 50 ml glass reaction vessel equipped with a stirrer, an argon gas inlet tube, a thermometer, and a reflux condenser was filled with dry argon, and γ-aminopropyltriethoxysilane (Chisso Corporation) Silane coupling agent, 5.39 g of Silaace (registered trademark) S330), 11.7 g of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.), and 20 ml of dehydrated hexane (manufactured by Wako Pure Chemical Industries, Ltd.) are added to be uniform. Until stirred. Next, 13.3 g of trimethylchlorosilane (manufactured by Chisso Corporation) was added dropwise over 10 minutes, followed by stirring at 25 ° C. for 96 hours and then stirring under reflux (78 ° C.) for 48 hours to complete the reaction. Subsequently, the precipitated triethylamine hydrochloride was filtered off with a glass filter, and hexane was distilled off. Next, by vacuum distillation (110 ° C./13.3 Pa), 3.44 g of N, N′-bistrimethylsilyl-γ-aminopropyltriethoxysilane represented by the following general formula (XXI) was obtained.

Synthesis Example 2: Synthesis of Silane Compound 2 A 50 ml glass reaction vessel equipped with a stirrer, an argon gas introduction tube, a thermometer and a reflux condenser was filled with dry argon, and γ-aminopropyltrimethoxysilane (Tokyo Chemical Industry Co., Ltd.). (Made in Japan) 5.1g, Triethylamine 12.7g (Wako Pure Chemical Industries, Ltd.) and dehydrated hexane 40ml (Wako Pure Chemical Industries, Ltd.) were added and stirred until uniform. Next, 13.3 g of trimethylchlorosilane (manufactured by Chisso Corporation) was added dropwise over 10 minutes, and the reaction was terminated by stirring at 25 ° C. for 384 hours. Subsequently, the precipitated triethylamine hydrochloride was filtered off with a glass filter, and hexane was distilled off. Next, by vacuum distillation (110 ° C./19.5 Pa), 2.87 g of N, N′-bistrimethylsilyl-γ-aminopropyltrimethoxysilane represented by the following general formula (XXII) was obtained.

Synthesis Example 3: Synthesis of Silane Compound 3 A 50 ml glass reaction vessel equipped with a stirrer, an argon gas introduction tube, a thermometer, and a reflux condenser was filled with dry argon, and γ-aminopropyltriethoxysilane (Chisso Corporation). Silane coupling agent, Sila Ace (registered trademark) S330) 3.9 g, triethylamine 5.96 g (manufactured by Wako Pure Chemical Industries, Ltd.) and dehydrated hexane 20 ml (manufactured by Wako Pure Chemical Industries, Ltd.) are added to make uniform. Until stirred. Next, 4.60 g of chlorodimethylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes, and the reaction was terminated by stirring at 78 ° C. for 48 hours. Subsequently, the precipitated triethylamine hydrochloride was filtered off with a glass filter, and hexane was distilled off. Next, 4.68 g of N, N′-bisdimethylsilyl-γ-aminopropyltriethoxysilane represented by the following general formula (XXIII) was obtained by distillation under reduced pressure (110 ° C./13.3 Pa).

Synthesis Example 4: Synthesis of Silane Compound 4 A 50 ml glass reaction vessel equipped with a stirrer, an argon gas inlet tube, a thermometer and a reflux condenser was filled with dry argon, and γ-aminopropyltrimethoxysilane (Tokyo Chemical Industry Co., Ltd.). 4.08 g (manufactured by Co., Ltd.), 8.10 g triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) and 20 ml of dehydrated hexane (manufactured by Wako Pure Chemical Industries, Ltd.) were added and stirred until uniform. Next, 6.42 g of chlorodimethylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes, followed by stirring at 25 ° C. for 192 hours to complete the reaction. Subsequently, the precipitated triethylamine hydrochloride was filtered off with a dry argon atmosphere and a glass filter, and hexane was distilled off. Next, by vacuum distillation (80 ° C./13.3 Pa), 2.91 g of N, N′-bisdimethylsilyl-γ-aminopropyltrimethoxysilane represented by the following general formula (XXIV) was obtained.

(Examples 1-14, Comparative Examples 1-11)
The following components were blended in parts by mass shown in Tables 1 to 4 below, and roll kneading was carried out under conditions of a kneading temperature of 80 ° C. and a kneading time of 10 minutes. Sealing of Examples 1 to 14 and Comparative Examples 1 to 11 An epoxy resin molding material was prepared. Note that the blank in the table indicates no blending.

  (A) As an epoxy resin, an ortho-cresol novolak type epoxy resin having an epoxy equivalent of 200 and a softening point of 67 ° C. (epoxy resin 1, trade name ESCN-190 manufactured by Sumitomo Chemical Co., Ltd.), an epoxy equivalent of 196 and a biphenyl having a melting point of 106 ° C. Type epoxy resin (epoxy resin 2, product name YX-4000H manufactured by Japan Epoxy Resin Co., Ltd.), epoxy equivalent 242 and melting point 118 ° C thiodiphenol type epoxy resin (epoxy resin 3, product name YSLV manufactured by Nippon Steel Chemical Co., Ltd.) -120TE), epoxy equivalent 192, bisphenol F type epoxy resin having a melting point of 79 ° C. (epoxy resin 4, trade name YSLV-80XY manufactured by Nippon Steel Chemical Co., Ltd.), epoxy equivalent 241 and biphenylene skeleton-containing phenol having a softening point of 96 ° C. Aralkyl-type epoxy resin (epoxy resin Nippon Kayaku Co., Ltd., trade name CER-3000L), epoxy equivalent 265, β-naphthol aralkyl type epoxy resin having a softening point of 66 ° C. (epoxy resin 6, Nippon Steel Chemical Co., Ltd. trade name ESN-175S), epoxy A bisphenol A-type brominated epoxy resin (epoxy resin 7) having an equivalent weight of 375, a softening point of 80 ° C., and a bromine content of 48% by mass was used.

  (B) As a curing agent, a phenol aralkyl resin having a hydroxyl group equivalent of 199 and a softening point of 89 ° C. (curing agent 1, trade name MEH-7851 manufactured by Meiwa Kasei Co., Ltd.), a hydroxyl group equivalent of 176 and a phenol aralkyl having a softening point of 70 ° C. Resin (curing agent 2, trade name Millex XLC manufactured by Mitsui Chemicals), hydroxyl equivalent 183, naphthol aralkyl resin having a softening point of 79 ° C. (hardening agent 3, trade name SN-170, manufactured by Nippon Steel Chemical Co., Ltd.), hydroxyl group Triphenylmethane type phenol resin having an equivalent weight of 104 and a softening point of 83 ° C. (curing agent 4, trade name MEH-7500 manufactured by Meiwa Kasei Co., Ltd.), Novolak type phenol resin having a hydroxyl equivalent of 106 and a softening point of 64 ° C. (hardening agent 5, Meiwa) Kasei Co., Ltd. product name H-4), hydroxyl equivalent 156, softening point 83 ° C phenol resin (curing agent 6, Air Water Co., Ltd.) Using the company trade name HE-510).

  (C) As the silane compound, N, N′-bistrimethylsilyl-γ-aminopropyltriethoxysilane (silane compound 1 synthesized in Synthesis Example 1), N, N′-bistrimethylsilyl-γ-aminopropyltrimethoxysilane (Silane compound 2 synthesized in Synthesis Example 2), N, N′-bisdimethylsilyl-γ-aminopropyltriethoxysilane (Silane compound 3 synthesized in Synthesis Example 3), N, N′-bisdimethylsilyl -Γ-aminopropyltrimethoxysilane (silane compound 4 synthesized in Synthesis Example 4), and for comparison, γ-glycidoxypropyltrimethoxysilane (silane compound 5), γ-aminopropyltriethoxysilane Silane (silane compound 6) was used.

(E) As a curing accelerator, a betaine-type adduct of triphenylphosphine and p-benzoquinone (curing accelerator 1), a betaine-type adduct of tributylphosphine and p-benzoquinone (curing accelerator 2), (F) Spherical fused silica having an average particle size of 17.5 μm and a specific surface area of 3.8 m ² / g was used as the inorganic filler, and carnauba wax, antimony trioxide, and carbon black were used as the other additive components.

The epoxy resin molding materials for sealing of Examples and Comparative Examples were evaluated by the following various characteristic tests (1) to (6). The evaluation results are shown in Tables 1 to 4 below. The epoxy resin molding material for sealing was molded by a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds unless otherwise specified. Further, post-curing was performed at 180 ° C. for 5 hours.
(1) Spiral flow Using a spiral flow measurement mold in accordance with EMMI-1-66, the sealing epoxy molding material was molded under the above conditions, and the flow distance (cm) was determined.
(2) Disc flow Flat plate for disc flow measurement having an upper mold of 200 mm (W) x 200 mm (D) x 25 mm (H) and a lower mold of 200 mm (W) x 200 mm (D) x 15 mm (H) Using a mold, 5 g of the sealing epoxy resin molding material weighed with an upper pan balance is placed on the center of the lower mold heated to 180 ° C., and after 5 seconds, the upper mold heated to 180 ° C. is closed and a load of 78 N Then, compression molding was performed under the condition of a curing time of 90 seconds, the major axis (mm) and minor axis (mm) of the molded product were measured with a caliper, and the average value (mm) was taken as the value of the disk flow.
(3) Adhesion retention rate Under the above conditions, an epoxy resin molding material for sealing is molded on a 30 μm aluminum foil, post-cured to prepare a test piece, and before and after PCT treatment (121 ° C., 0.2 MPa, 100 hours). The peel strength (N / m) in the 90-degree direction of the test piece was measured and evaluated by the adhesive retention (%) = PCA treated aluminum peel strength / PCT treated aluminum peel strength × 100.
(4) Solder reflow resistance An 80-pin flat package having an outer dimension of 20 × 14 × 2 mm, in which a 6 × 8 mm silicone chip is mounted on a copper lead frame, is molded under the above conditions using an epoxy resin molding material for sealing. It was made by post-curing, humidified for 168 hours at 85 ° C. and 60% RH, and then reflowed at a predetermined temperature for 10 seconds to produce an ultrasonic imaging device (HYE) manufactured by Hitachi Construction Machinery Finetech Co., Ltd. The presence or absence of peeling inside the package was observed by -FOCUS), and the number of peeling occurrence packages with respect to the number of test packages (10) was evaluated.
(5) Water absorption rate Under the above conditions, formed into a disk having a diameter of 50 mm and a thickness of 3 mm, post-cured, left for 72 hours under conditions of 85 ° C. and 85% RH, and measured the change in mass before and after being left to Rate (mass%) = {(disc mass after leaving−disc mass before leaving) / disc mass before leaving} × 100.
(6) Glass transition temperature (Tg)
Under the above conditions, an epoxy resin molding material for sealing was molded into a shape of 19 mm × 3 mm × 3 mm, post-cured to prepare a test piece, and a thermomechanical analyzer (TMA-8140, TAS-100) manufactured by Rigaku Corporation. The glass transition temperature (Tg, unit: ° C) was determined from the inflection point of the linear expansion curve.

The following things were understood from Tables 1-4. In Examples 1-14, (C) Except the silane compound shown by general formula (I), compared with the comparative example of the same resin composition, the favorable characteristic is shown in spiral flow and disk flow.
Further, (C) Examples 1 to 14 containing the silane compound represented by the general formula (I) in a preferable range of 0.03 to 0.8% by mass have almost no defect in the reflow treatment at 255 ° C, and 245 ° C. There is no defect even in the reflow process, and the solder reflow resistance is excellent.

  On the other hand, a comparative example having a composition different from that of the present invention does not satisfy the object of the present invention. That is, in Comparative Examples 1 to 11 shown in Tables 3 and 4, the fluidity is low, and in most of the comparative examples, 50% or more of peeling inside the package occurred in the reflow treatment at 255 ° C., and in the reflow treatment at 245 ° C. Inferior to solder reflow resistance.

Claims (7)

(A) an epoxy resin, (B) a curing agent, (C) an epoxy resin molding material for sealing containing a silane compound represented by the following general formula (I), the epoxy resin molding material for sealing described above (C) An epoxy resin molding material for sealing an electronic component device in which the ratio of the silane compound is 0.03 to 0.8% by mass .

(Here, R ^{1 to} R ⁶ are a hydrogen atom, a substituted or unsubstituted linear alkyl group having 1 to 12 carbon atoms,
A branched alkyl group, a cycloalkyl group, and an aryl group, and R ⁷ and R ⁸ are substituted or unsubstituted linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups, cycloalkyl groups, and aryl groups, and are the same However, they may be different, R ⁹ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, the hydrocarbon group may be substituted, and p represents an integer of 1 to 3. ) (A) The epoxy resin is at least one of biphenyl type epoxy resin, thiodiphenol type epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, phenol / aralkyl type epoxy resin and naphthol / aralkyl type epoxy resin. The epoxy resin molding material for sealing an electronic component device according to claim 1, which is contained. (B) The curing agent is phenol / aralkyl resin, naphthol / aralkyl resin, triphenylmethane type phenol resin, novolac type phenol resin, and copolymer type phenol /
Epoxy resin molding material for sealing an electronic component device according to claim 1 or claim 2 comprising at least one or aralkyl resin. (D) The epoxy resin molding material for sealing an electronic component device according to any one of claims 1 to 3 , further comprising (C) a silane compound other than the silane compound represented by the general formula (I). (E) The epoxy resin molding material for sealing an electronic component device according to any one of claims 1 to 4 , further comprising a curing accelerator. (F) The epoxy resin molding material for sealing an electronic component device according to any one of claims 1 to 5 , further comprising an inorganic filler. An electronic component device comprising an element sealed with an epoxy resin molding material for sealing an electronic component device according to any one of claims 1 to 6 .