JP2007031698A - Epoxy resin composition and electronic part device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sealing epoxy resin composition excellent in the humidity resistance, fluidity, and the anti-reflow crack property, and an electronic part device equipped with elements sealed therewith. <P>SOLUTION: This epoxy resin composition contains an epoxy resin (A), a curing agent (B), a silane compound (C) represented by general formula (I-a), wherein R<SP>1</SP>is each independently selected from the group consisting of a hydrogen atom, a hydroxide group, and a 1-18C organic substituted or non-substituted group, all may be the same or different, two or more R<SP>1</SP>groups may be bonded with each other and form a ring structure, and m is an integer of 1-3, a curing accelerator (D), and an inorganic filler (E). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an epoxy resin composition and an electronic component device including an element sealed using the epoxy resin composition.

  Conventionally, epoxy resins have been widely used in the fields of molding materials, laminates and adhesives. In addition, compositions based on epoxy resins are also widely used in the field of sealing technology relating to elements of electronic components such as transistors and ICs. The reason for this is that epoxy resins are balanced in various properties such as moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserts. In particular, a combination of an ortho-cresol novolac type epoxy resin and a phenol novolac curing agent has an excellent balance in the above-mentioned characteristics, and therefore has become the mainstream as a base resin for molding materials for IC sealing.

  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 the ortho-cresol novolac type epoxy resin and the 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. However, this method has a problem that although the moisture absorption inside the semiconductor device is reduced, the fluidity is drastically lowered.
As a method for increasing the filler content without impairing the fluidity of the epoxy resin molding material, a method for optimizing the filler particle size distribution has been proposed (see, for example, Patent Document 1). This method does not provide a sufficient effect for improving the fluidity. 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).
Japanese Patent Laid-Open No. 06-224328 Hitachi, Ltd. Semiconductor Division, "Surface Mounted LSI Package Mounting Technology and its Reliability Improvement" Applied Technology Publishing, November 16, 1988, pages 254-256 Technical Information Association, Inc. “High Reliability of Semiconductor Encapsulation Resin” Technical Information Association, January 31, 1990, pages 172-176

In recent years, semiconductor packages have been made thinner and narrower pad pitches. Correspondingly, further improvement in fluidity is desired for molding materials including solutions to the above problems.
The present invention has been made in view of such a situation, and provides a resin composition serving as an epoxy resin molding material for sealing excellent in fluidity and reflow crack resistance, and an electronic component device including an element sealed thereby. It is what.

  As a result of intensive studies to solve the above problems, the present inventors have obtained an epoxy resin composition excellent in fluidity, reflow crack resistance and moisture resistance by using a specific silane compound, The inventors have found that the intended purpose can be achieved, and have completed the present invention.

（式（Ｉ−ａ）中、Ｒ^１は、それぞれ独立して、水素原子、水酸基、及び炭素数１〜１８の置換又は非置換の有機基からなる群より選ばれ、全てが同一でも異なっていてもよく、２以上のＲ^１が互いに結合して環状構造を形成してもよく、ｍは１〜３の整数を示す。） The present invention relates to the following (1) to (9).
(1) (A) epoxy resin, (B) curing agent, (C) silane compound represented by the following general formula (Ia), (D) curing accelerator, (E) epoxy resin containing inorganic filler Composition.

(In formula (Ia), each R ¹ is independently selected from the group consisting of a hydrogen atom, a hydroxyl group, and a substituted or unsubstituted organic group having 1 to 18 carbon atoms, all of which are the same or different. Or two or more R ¹ may be bonded to each other to form a cyclic structure, and m represents an integer of ¹ to 3.)

（式（Ｉ−ｂ）中、Ｒ^２は、それぞれ独立して、水素原子及び炭素数１〜１８の置換又は非置換の炭化水素基からなる群より選ばれ、全てが同一でも異なっていてもよく、２以上のＲ^２が互いに結合して環状構造を形成してもよく、Ｒ^３は、それぞれ独立して、水素原子、水酸基、及び炭素数１〜１８の置換又は非置換の有機基からなる群より選ばれ、全てが同一でも異なっていてもよく、２以上のＲ^３が互いに結合して環状構造を形成してもよく、Ｙ⁻は、１以上の放出可能なプロトンを有する炭素数０〜１８の有機基から１つのプロトンが脱離した有機基であり、１以上のＲ^３と互いに結合して環状構造を形成してもよい。） (2) The epoxy resin composition according to (1), wherein the (D) curing accelerator contains at least one compound selected from the compound represented by the following general formula (Ib) and an intermolecular salt thereof: object.

(In formula (Ib), each R ² is independently selected from the group consisting of a hydrogen atom and a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different. Alternatively, two or more R ² may be bonded to each other to form a cyclic structure, and each R ³ is independently selected from a hydrogen atom, a hydroxyl group, and a substituted or unsubstituted organic group having 1 to 18 carbon atoms. All may be the same or different, and two or more R ³ may be bonded to each other to form a cyclic structure, and Y ⁻ represents the number of carbon atoms having one or more releasable protons. (It is an organic group in which one proton is eliminated from 0 to 18 organic groups, and may combine with one or more R ^{3 s} to form a cyclic structure.)

(3) The epoxy resin composition according to (1) or (2), wherein R ^{1 of the} silane compound represented by the general formula (Ia) is selected from aryl groups.
(4) (C) The epoxy resin composition according to any one of (1) to (3), wherein the silane compound represented by the general formula (Ia) is triphenylsilanol or diphenylsilanediol.
(5) The epoxy resin composition according to any one of (1) to (4), wherein the content of the (E) inorganic filler is 55 to 95% by mass.
(6) Any of the above (1) to (5), wherein the content of the silane compound represented by the general formula (Ia) is 0.02 to 5.0% by mass of the epoxy resin composition. The epoxy resin composition described in 1.
(7) (A) The epoxy resin is a biphenyl type epoxy resin, a stilbene type epoxy resin, a diphenylmethane type epoxy resin, a sulfur atom-containing type epoxy resin, a novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a salicylaldehyde type epoxy resin, The epoxy according to any one of (1) to (6), which contains one or more epoxy resins selected from the group consisting of copolymerized epoxy resins of naphthols and phenols, and epoxidized products of aralkyl type phenol resins. Resin composition.
(8) (B) The curing agent is an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a salicylaldehyde type phenol resin, a copolymer type resin of a benzaldehyde type phenol resin and an aralkyl type phenol resin, or a novolac type phenol resin. The epoxy resin composition according to any one of (1) to (7), which contains one or more resins selected from the group consisting of:
(9) An electronic component device including an element sealed using the epoxy resin composition according to any one of (1) to (8).

  The epoxy resin composition according to the present invention is excellent in moldability such as fluidity, and becomes clear from the examples described later by sealing elements of electronic components such as IC and LSI using this epoxy resin composition. As described above, it is possible to provide an electronic component device having both good reflow crack resistance and moisture resistance and excellent reliability, and its industrial value is high.

Hereinafter, the present invention will be described in detail.
(A) Epoxy Resin In the present invention, an epoxy resin having two or more epoxy groups in one molecule can be used as the (A) epoxy resin. Such an epoxy resin is not particularly limited. For example, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F including phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, and the like. And / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene and compounds having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde in an acidic catalyst. Novolak type epoxy resin obtained by epoxidizing the novolak resin obtained by the treatment; bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or unsubstituted biphenol Diglycidyl ethers such as stilbene phenols (bisphenol type epoxy resins, biphenyl type epoxy resins, stilbene type epoxy resins), glycidyl ethers of alcohols such as butanediol, polyethylene glycol, polypropylene glycol; phthalic acid, isophthalic acid, tetrahydro Glycidyl ester type epoxy resin of carboxylic acid such as phthalic acid; Glycidyl type or methyl glycidyl type epoxy resin such as aniline, isocyanuric acid or the like substituted with active hydrogen bonded to nitrogen atom by glycidyl group; intramolecular olefin bond Vinylcyclohexene diepoxide obtained by epoxidizing 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cycle Alicyclic epoxy resins such as hexyl-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane; glycidyl ether of paraxylylene and / or metaxylylene modified phenolic resin; glycidyl ether of terpene modified phenolic resin; dicyclopentadiene Glycidyl ether of modified phenolic resin; Glycidyl ether of cyclopentadiene modified phenolic resin; Glycidyl ether of polycyclic aromatic ring modified phenolic resin; Glycidyl ether of phenolic resin containing naphthalene ring; Halogenated phenol novolac type epoxy resin; Hydroquinone type epoxy resin; Methylolpropane type epoxy resin; linear aliphatic epoxy resin obtained by oxidizing olefinic bonds with peracid such as peracetic acid; diphenylmethane type epoxy resin; Nord aralkyl resins, epoxidized aralkyl phenolic resins such as naphthol aralkyl resin; sulfur atom-containing epoxy resin and the like, may be used in combination of two or more even with these alone.

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

（式（ＩＩ）中、Ｒ^８は水素原子又は炭素数１〜１２のアルキル基又は炭素数４〜１８のアリール基を示し、それぞれ全てが同一でも異なっていてもよく、ｎは平均値であり、０〜１０の正数を示す。） The biphenyl type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton, but an epoxy resin represented by the following general formula (II) is preferable.
Among the epoxy resins represented by the following general formula (II), the positions where the oxygen atoms are substituted in R ⁸ are the 4 and 4 'positions, and the 3, 3', 5, 5 'positions are methyl groups. YX-4000H (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) in which all are hydrogen atoms, 4,4′-bis (2,3-epoxypropoxy) biphenyl in which all R ⁸ are hydrogen atoms, and all R ⁸ are In the case of a hydrogen atom, and when the positions where oxygen atoms are substituted in R ⁸ are the 4 and 4 'positions, the 3, 3', 5, 5 'positions are methyl groups, and the rest are hydrogen atoms YL-6121H (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), which is a mixed product, is available as a commercial product.

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

（式（ＩＩＩ）中、Ｒ^９及びＲ^１０は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよく、ｎは平均値であり、０〜１０の正数を示す。） The stilbene type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton, but an epoxy resin represented by the following general formula (III) is preferable. Among the epoxy resins represented by the following general formula (III), 3, ⁹ ′, 5 ′ and 5 ′ positions when R ⁹ is substituted with oxygen atoms at positions 4 and 4 ′ are methyl groups. The other is a hydrogen atom and all of R ¹⁰ are hydrogen atoms, and three of the 3, 3 ′, 5, 5 ′ positions are methyl groups, one is a tert-butyl group, and the other is a hydrogen atom and R ESLV-210 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), which is a mixture when all ¹⁰ are hydrogen atoms, is available as a commercial product.

(In the formula (III), R ⁹ and R ^{10 each} represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different; n is an average value; 10 represents a positive number.)

（式（ＩＶ）中、Ｒ^１１及びＲ^１２は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよく、ｎは平均値であり、０〜１０の正数を示す。） The diphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton, but an epoxy resin represented by the following general formula (IV) is preferable. Among the epoxy resins represented by the following general formula (IV), all of R ¹¹ are hydrogen atoms, and the positions where oxygen atoms are substituted in R ¹² are 3, 3 ′, YSLV-80XY (trade name, manufactured by Nippon Steel Chemical Co., Ltd.), in which the 5,5′-position is a methyl group and the others are hydrogen atoms, is commercially available.

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

（式（Ｖ）中、Ｒ^１３は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよく、ｎは平均値であり、０〜１０の正数を示す。） Although it will not specifically limit as a sulfur atom containing type epoxy resin if it is an epoxy resin containing a sulfur atom, For example, the epoxy resin shown by the following general formula (V) is mentioned. Among the epoxy resins represented by the following general formula (V), the tert-butyl group is the tert-butyl group when the positions where the oxygen atom substitution positions in R ¹³ are the 4 and 4 'positions, and 6, 6 YSLV-120TE (trade name, manufactured by Nippon Steel Chemical Co., Ltd.) in which the '-position is a methyl group and the other is a hydrogen atom is commercially available.

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

（式（ＶＩ）中、Ｒ^１４及びＲ^１５は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよく、ｉは０〜３の整数、ｎは平均値であり、０〜１０の正数を示す。） The novolak type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolak type phenol resin, but a novolak type phenol resin such as phenol novolak, cresol novolak, naphthol novolak or the like is glycidyl etherified. Epoxy resins epoxidized using the above method are preferred, for example, epoxy resins represented by the following general formula (VI) are more preferred. Among the epoxy resins represented by the following general formula (VI), ESCN-190 and ESCN-195 (trade names, manufactured by Sumitomo Chemical Co., Ltd.), in which all of R ¹⁴ are hydrogen atoms, R ¹⁵ is a methyl group and i = 1. Etc. are available as commercial products.

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

（式（ＶＩＩ）中、Ｒ^１６は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよく、ｉは０〜３の整数、ｎは平均値であり、０〜１０の正数を示す。） The dicyclopentadiene type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a compound having a dicyclopentadiene skeleton as a raw material, but an epoxy resin represented by the following general formula (VII) is preferable. Among epoxy resins represented by the following general formula (VII), HP-7200 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) where i = 0 is available as a commercial product.

(In the formula (VII), R ¹⁶ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 0 to 3, and n is an average value. And represents a positive number from 0 to 10.)

（式（ＶＩＩＩ）中、Ｒ^１７及びＲ^１８は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよく、ｉは０〜３の整数、ｋは０〜４の整数、ｎは平均値であり、０〜１０の正数を示す。） The salicylaldehyde type epoxy resin is not particularly limited as long as it is an epoxy resin made from a compound having a salicylaldehyde skeleton, but a novolak type phenol resin of a compound having a salicylaldehyde skeleton and a compound having a phenolic hydroxyl group, etc. A salicylaldehyde type epoxy resin such as an epoxy resin obtained by glycidyl etherification of a salicylaldehyde type phenol resin is preferable, and an epoxy resin represented by the following general formula (VIII) is more preferable. Among epoxy resins represented by the following general formula (VIII), 1032H60 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-502H (trade name, manufactured by Nippon Kayaku Co., Ltd.), etc., where i = 0 and k = 0. It is available as a commercial product.

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

（式（ＩＸ）中、Ｒ^１９〜Ｒ^２１は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよく、ｉは０〜３の整数、ｊは０〜２の整数、ｋは０〜４の整数を示し、ｐは平均値で０〜１の正数を示し、ｌ、ｍはそれぞれ平均値で０〜１１の正数であり（ｌ＋ｍ）は１〜１１の正数を示す。） The copolymer type epoxy resin of naphthols and phenols is not particularly limited as long as it is an epoxy resin made from a compound having a naphthol skeleton and a compound having a phenol skeleton, but a compound having a naphthol skeleton And a novolak-type phenol resin using a compound having a phenol skeleton, which is glycidyl etherified, and more preferably an epoxy resin represented by the following general formula (IX). Among the epoxy resins represented by the following general formula (IX), NC-7300 (trade name, manufactured by Nippon Kayaku Co., Ltd.) in which R ²¹ is a methyl group, i = 1, j = 0, and k = 0, etc. It is available as a commercial product.

(In the formula (IX), R ^{19 to} R ²¹ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 0 to 3, j Is an integer of 0 to 2, k is an integer of 0 to 4, p is an average value of 0 to 1 and l and m are average values of 0 to 11 positive numbers (l + m) Represents a positive number from 1 to 11.)

  As the epoxy resin represented by the general formula (IX), a random copolymer containing 1 structural unit and m structural units randomly, an alternating copolymer containing alternately, a copolymer containing regularly, The block copolymer contained in a block shape is mentioned, Any one of these may be used independently or may be used in combination of 2 or more type.

（式（Ｘ）及び（ＸＩ）において、Ｒ^３７〜Ｒ^４１は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよく、ｉは０〜３の整数、ｊは０〜２の整数、ｋは０〜４の整数を示す。） Epoxidized aralkyl-type phenol resins such as phenol aralkyl resins, naphthol aralkyl resins, and biphenylene skeleton-containing phenol aralkyl resins include phenols such as phenol and cresol and / or naphthols such as naphthol and dimethylnaphthol and dimethoxyparaxylene and bis. The epoxy resin is not particularly limited as long as it is an epoxy resin using a phenol resin synthesized from (methoxymethyl) biphenyl or a derivative thereof.
For example, a phenol resin synthesized from phenols such as phenol and cresol and / or naphthols such as naphthol and dimethylnaphthol and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, and derivatives thereof is preferably glycidyl ether, Epoxy resins represented by the following general formulas (X) and (XI) are more preferable. Among epoxy resins represented by the following general formula (X), i = 0, R- ³⁸ is a hydrogen atom, NC-3000 (trade name, manufactured by Nippon Kayaku Co., Ltd.), i = 0, R- ³⁸ is a hydrogen atom. epoxy resin of the general formula CER-3000 (manufactured by Nippon Kayaku Co., Ltd. trade name) all of ^{R 8} is mixed with the epoxy resin is a hydrogen atom in a weight ratio of 80:20 (II) or the like, the following general formula (XI Among these epoxy resins, ESN-175 (trade name of Nippon Steel Chemical Co., Ltd.) having i = 0, j = 0, and k = 0 is available as a commercial product.

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

Regarding R ^{8 to} R ²¹ and R ^{37 to} R ^{41 in the} general formulas (II) to (XI), “all may be the same or different” means, for example, 8 to 8 in the formula (II) It means that all 88 R ⁸ may be the same or different. It means that all of R ^{9 to} R ²¹ and R ^{37 to} R ⁴¹ may be the same or different with respect to the respective numbers included in the formula. R ^{8 to} R ²¹ and R ^{37 to} R ⁴¹ may be the same as or different from each other. For example, all of R ⁹ and R ¹⁰ may be the same or different.

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

  As mentioned above, although the specific example of the preferable epoxy resin which can be used for the epoxy resin composition of this invention was demonstrated along the said general formula (II)-(XI), as a more specific preferable epoxy resin, reflow crack resistance From the viewpoint of the above, 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl is mentioned, and from the viewpoint of moldability and heat resistance, 4,4 And '-bis (2,3-epoxypropoxy) -biphenyl.

(B) Hardener (B) A hardener is used for the epoxy resin composition by this invention. The usable curing agent is not particularly limited as long as it is a compound capable of curing (A) an epoxy resin. For example, phenol compounds such as phenol resin, amine compounds such as diamine and polyamine, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride and other organic acids, dicarboxylic acids, carboxylic acid compounds such as polycarboxylic acids, etc. These compounds may be used alone or in combination of two or more. Among these, a phenol compound is preferable from the viewpoint that the effects of the present invention are sufficiently exhibited.

  (B) There is no restriction | limiting in particular as a phenolic compound which can be used as a hardening | curing agent. For example, it may be a phenol compound having two or more phenolic hydroxyl groups in one molecule generally used as a curing agent, and one molecule such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol. Compounds having two phenolic hydroxyl groups in them; phenols such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and / or α-naphthol, β-naphthol, dihydroxynaphthalene Novolak type phenolic resin obtained by condensation or cocondensation of naphthols such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde and the like under an acidic catalyst Aralkyl type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl; paraxylylene and / or metaxylylene modified phenol resins; melamine modified phenol resins Terpene-modified phenolic resin; dicyclopentadiene-type phenol resin, dicyclopentadiene-type naphthol resin synthesized by copolymerization from phenols and / or naphthols and dicyclopentadiene; cyclopentadiene-modified phenol resin; polycyclic aromatic ring modification Phenolic resins; biphenyl type phenolic resins; triphenylmethane type phenolic resins; and phenolic resins obtained by copolymerizing two or more of these. May be used in combination or two or more kinds thereof may be used in.

  Among phenolic compounds, from the viewpoint of reflow crack resistance, aralkyl type phenol resins, dicyclopentadiene type phenol resins, salicylaldehyde type phenol resins, benzaldehyde type and aralkyl type copolymer type phenol resins, and novolak type phenol resins are preferable. Aralkyl type phenol resins, dicyclopentadiene type phenol resins, salicylaldehyde type phenol resins, and benzaldehyde type and aralkyl type copolymer type phenol resins are more preferred. These phenolic resins may be used alone or in combination of two or more, but in order to exert their performance, they are 30 in total with respect to the total amount of phenolic resin. It is preferable to use at least 50% by mass, and more preferably at least 50% by mass.

（式（ＸＩＩ）〜（ＸＩＶ）において、Ｒ^２２〜Ｒ^２８は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよく、ｉは０〜３の整数、ｋは０〜４の整数、ｊは０〜２の整数、ｎは平均値であり、０〜１０の正数を示す。） The aralkyl type phenolic resin is not particularly limited as long as it is a phenolic resin synthesized from phenols and / or naphthols and dimethoxyparaxylene, bis (methoxymethyl) biphenyl or a derivative thereof. Phenol resins represented by (XII) to (XIV) are preferred.

(In the formulas (XII) to (XIV), R ^{22 to} R ^{28 each} represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different, and i is 0 to 3 And k is an integer of 0 to 4, j is an integer of 0 to 2, n is an average value, and represents a positive number of 0 to 10.)

Among the phenol resins represented by the general formula (XII), MEH-7851 (trade name of Meiwa Kasei Co., Ltd.) in which i = 0 and R ²³ are all hydrogen atoms is commercially available. Among the phenol resins represented by the above general formula (XIII), XL = 0, i = 0, k = 0, XLC (trade name, manufactured by Mitsui Chemicals), MEH-7800 (trade name, Meiwa Kasei Co., Ltd.), etc. Is commercially available. Among the phenol resins represented by the above general formula (XIV), SN-170 (trade name of Nippon Steel Chemical Co., Ltd.) in which j = 0, R ²⁷ k = 0, and R ²⁸ k = 0 is a commercial product. Is available as

（式（ＸＶ）中、Ｒ^２９は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよく、ｉは０〜３の整数、ｎは平均値であり、０〜１０の正数を示す。） The dicyclopentadiene type phenol resin is not particularly limited as long as it is a phenol resin using a compound having a dicyclopentadiene skeleton as a raw material, but a phenol resin represented by the following general formula (XV) is preferable. Among the phenol resins represented by the following general formula (XV), DPP (trade name, manufactured by Nippon Petrochemical Co., Ltd.) where i = 0 is available as a commercial product.

(In the formula (XV), R ²⁹ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 0 to 3, and n is an average value. And represents a positive number from 0 to 10.)

（式（ＸＶＩ）中、Ｒ^３０及びＲ^３１は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよく、ｉは０〜３の整数、ｋは０〜４の整数、ｎは平均値であり、０〜１０の正数を示す。） The salicylaldehyde type phenol resin is not particularly limited as long as it is a phenol resin using a compound having a salicylaldehyde skeleton as a raw material, but a phenol resin represented by the following general formula (XVI) is preferable.
Among phenol resins represented by the following general formula (XVI), MEH-7500 (trade name, manufactured by Meiwa Kasei Co., Ltd.) where i = 0 and k = 0 is available as a commercial product.

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

（式（ＸＶＩＩ）中、Ｒ^３２〜Ｒ^３４は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよく、ｉは０〜３の整数、ｋは０〜４の整数、ｑは０〜５の整数、ｌ、ｍはそれぞれ平均値で０〜１１の正数であり（ｌ＋ｍ）は１〜１１の正数を示す。） The copolymer type phenol resin of benzaldehyde type and aralkyl type is not particularly limited as long as it is a copolymer type phenol resin of a phenol resin and an aralkyl type phenol resin using a compound having a benzaldehyde skeleton as a raw material. A phenol resin represented by the following general formula (XVII) is preferable.
Among phenol resins represented by the following general formula (XVII), HE-510 (trade name, manufactured by Air Water Chemical Co., Ltd.) having i = 0, k = 0, and q = 0 is available as a commercial product. .

(In the formula (XVII), R ^{32 to} R ^{34 each} represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, and i is an integer of 0 to 3, k Is an integer of 0 to 4, q is an integer of 0 to 5, l and m are average values and are positive numbers of 0 to 11, respectively (l + m) is a positive number of 1 to 11.)

（式（ＸＶＩＩＩ）中、Ｒ^３５及びＲ^３６は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよく、ｉは０〜３の整数、ｋは０〜４の整数、ｎは平均値であり、０〜１０の正数を示す。） The novolak type phenol resin is not particularly limited as long as it is a phenol resin obtained by condensation or cocondensation of phenols and / or naphthols and aldehydes in the presence of an acidic catalyst, but the following general formula (XVIII ) Is preferred.
I = 0 Among phenolic resin represented by the following general formula ^{(XVIII), R 35} are all hydrogen atoms TAMANOL 758, 759 (Arakawa Chemical Industries, Ltd., trade name), HP-850N (manufactured by Hitachi Chemical Co., Ltd. Product Name) etc. are commercially available.

(In the formula (XVIII), R ³⁵ and R ^{36 each} represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 0 to 3, k Is an integer from 0 to 4, n is an average value and represents a positive number from 0 to 10.)

“All may be the same or different” described for R ^{22 to} R ³⁶ in the above general formulas (XII) to (XVIII) means that, for example, all i R ^{22s in} formula (XII) are the same. But it means they can be different from each other. For the other R ^{23 to} R ³⁶ , it means that all the numbers contained in the formula may be the same or different from each other. R ^{22 to} R ³⁶ may be the same as or different from each other. For example, all of R ²² and R ²³ may be the same or different, and all of R ³⁰ and R ³¹ may be the same or different.

  In the above general formulas (XII) to (XVIII), n is in the range of 0 to 10, and when it exceeds 10, the melt viscosity of the (B) curing agent component becomes high, so that at the time of melt molding of the epoxy resin composition Viscosity increases, and it becomes easy to cause unfilling failure and deformation of the bonding wire (gold wire connecting the element and the lead). The average n per molecule is preferably set in the range of 0-4.

  In the epoxy resin composition according to the present invention, when (A) an epoxy resin is used as the epoxy resin and a phenol resin is used as the (B) curing agent of the epoxy resin, the blending ratio of the above components (A) and (B) Is preferably set in the range of 0.5 to 2.0 in terms of the ratio of hydroxyl equivalents of all phenol resins to the epoxy equivalents of all epoxy resins (number of hydroxyl groups in phenol resin / number of epoxy groups in epoxy resin), The ratio is more preferably 0.7 to 1.5, and further preferably 0.8 to 1.3. When the ratio is less than 0.5, the epoxy resin is not sufficiently cured, and the cured product tends to be inferior in heat resistance, moisture resistance, and electrical characteristics. On the other hand, when the ratio exceeds 2.0, the phenol resin component becomes excessive and not only the curing efficiency is lowered, but also a large amount of phenolic hydroxyl group remains in the cured resin, so that the electrical characteristics and moisture resistance of the package are lowered. Tend.

（式（Ｉ−ａ）中、Ｒ^１は、それぞれ独立して、水素原子、水酸基、及び炭素数１〜１８の置換又は非置換の有機基からなる群より選ばれ、全てが同一でも異なっていてもよく、２以上のＲ^１が互いに結合して環状構造を形成してもよく、ｍは１〜３の整数を示す。） The epoxy resin composition according to the present invention contains (C) a silane compound represented by the following general formula (Ia).

(In formula (Ia), each R ¹ is independently selected from the group consisting of a hydrogen atom, a hydroxyl group, and a substituted or unsubstituted organic group having 1 to 18 carbon atoms, all of which are the same or different. Or two or more R ¹ may be bonded to each other to form a cyclic structure, and m represents an integer of ¹ to 3.)

The term “substituted or unsubstituted organic group having 1 to 18 carbon atoms” described in R ¹ of the above general formula (Ia) has 1 to 18 carbon atoms and is substituted or unsubstituted. An aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an aliphatic hydrocarbon oxy group, an aromatic hydrocarbon oxy group, a carbonyl group, an oxycarbonyl group, and a carbonyloxy group bonded to each other. means.

  More specifically, examples of the substituted or unsubstituted aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and pentyl. Group, hexyl group, octyl group, decyl group, dodecyl group, allyl group, vinyl group and other aliphatic hydrocarbon groups, and alkyl groups, alkoxy groups, aryloxy groups, aryl groups, hydroxyl groups, amino groups, and halogens. And the like substituted.

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

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

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

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

  Examples of the oxycarbonyl group include aliphatic hydrocarbon oxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, allyloxycarbonyl group, cyclohexyloxycarbonyl group, and aromatic groups such as phenoxycarbonyl group and methylphenoxycarbonyl group. Examples thereof include hydrocarbon oxycarbonyl groups and the like, and those substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogens and the like.

  Examples of the carbonyloxy group include methylcarbonyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, allylcarbonyloxy group, cyclohexylcarbonyloxy group and other aliphatic hydrocarbon carbonyloxy groups, phenylcarbonyloxy group, methylphenylcarbonyloxy And aromatic hydrocarbon carbonyloxy groups such as groups, and those substituted with an alkyl group, alkoxy group, aryl group, aryloxy group, amino group, halogen, and the like.

In addition, the term “two or more R ^1s may be bonded to each other to form a cyclic structure” described as R ¹ in the general formula (Ia) means that two or three R ^1s are bonded to each other. As a divalent or trivalent organic group. For example, alkylene groups such as ethylene, propylene, butylene, pentylene and hexylene, which can be bonded to Si atoms to form a cyclic structure, alkenyl groups such as ethylenyl, propylenyl and butyrenyl groups, aralkylene groups such as methylenephenylene groups, phenylene and naphthylene , Arylene groups such as anthracenylene, these alkylene groups, alkenyl groups, aralkylene groups, oxy groups or dioxy groups of arylene groups, which are further alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, It may be substituted with halogen or the like.

R ^{1 in the} general formula (Ia) is not particularly limited, but is preferably a hydrogen atom, an optionally substituted alkyl group, an aryl group, an alkoxy group, or an aryloxy group. Among these, from the viewpoint of easy availability of raw materials, alkoxy groups such as hydrogen atom, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group, tert-butoxy group, phenoxy group, p- An aryloxy group such as crezoxy group, m-crezoxy group, o-crezoxy group, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, unsubstituted or alkyl group or Chain structure or cyclic such as // alkoxy group or / and hydroxyl group-substituted aromatic group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, octyl group, cyclohexyl group, etc. The substituent selected from the alkyl group is more preferable. From the viewpoint of the stability of the compound, phenyl groups, p-tolyl groups, m-tolyl groups, o-tolyl groups, p-methoxyphenyl groups, etc. are unsubstituted or substituted with alkyl groups or / and alkoxy groups or / and hydroxyl groups. Substituents selected from these aromatic groups are more preferable, and a phenyl group is particularly preferable from the viewpoint of easy availability of the compound.

  In the general formula (Ia), m represents an integer of 1 to 3, but 1 or 2 is preferable from the viewpoint of easy availability of raw materials.

  Triphenylsilanol, trimethylsilanol, triethylsilanol, tert-butyldimethylsilanol, tri-tert-butoxysilanol, diphenylsilanediol which are commercially available products as the silane compound represented by the above general formula (Ia) , Aminopropylsilanetriol, 3- (trihydroxysilyl) -1-propanesulfonic acid, 1,4-bis (hydroxydimethylsilyl) benzene, and the like. A silane compound represented by the formula (Ia) can be used. Of these, triphenylsilanol and diphenylsilanediol are preferable from the viewpoint of fluidity.

  The blending amount of the silane compound represented by the general formula (Ia) is not limited as long as the effect of the present invention is exhibited. It is preferable that it is 02-5.0 mass%, and it is more preferable that it is 0.05-3.0 mass%. If it is 0.02% by mass or less, the effect of the present invention tends not to be exhibited, and if it is 5.0% by mass or more, curability tends to be lowered.

In the epoxy resin composition according to the present invention, (D) a curing accelerator is used. The curing accelerator that can be used in the present invention is not limited as long as it is a compound that accelerates the reaction between (A) the epoxy resin and (B) the curing agent. For example, a cycloamidine compound such as diazabicycloalkene such as 1,5-diazabicyclo [4.3.0] nonene-5, 1,8-diazabicyclo [5.4.0] undecene-7,
Its derivatives,
Their salts such as phenol novolak salts and these compounds include maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2 , 3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, quinone compounds such as phenyl-1,4-benzoquinone, and compounds having a π bond such as diazophenylmethane. A compound having intramolecular polarization formed by addition,
Tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives,
Imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole,
Tetra-substituted phosphonium / tetra-substituted borate such as tetraphenylphosphonium / tetraphenyl borate,
Tetraphenylboron salts such as 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate,
Triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, Organic phosphines such as tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine,
Or a complex of these organic phosphines and organic boron, or these organic phosphines and maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2, Quinone compounds such as 6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, diazophenylmethane, etc. a compound having intramolecular polarization formed by adding a compound having a π bond,
These phosphine compounds such as organic phosphines as described in JP-A No. 2004-156036 were reacted with a compound having at least one halogen atom substituted on an aromatic ring and one or more releasable proton atoms. A compound having intramolecular polarization obtained by dehydrohalogenation later,
Etc.
Compounds having one or more halogen atoms and releasable proton atoms substituted on the aromatic ring include 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2 -Chlorophenol, 4-iodophenol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, And halogenated phenol compounds such as 4-bromo-4'-hydroxybiphenyl.
When these curing accelerators are used in combination, from the viewpoint of fluidity, a compound having an intramolecular polarization formed by adding a compound having an organic phosphines and a π bond, an organic phosphine and a halogenated phenol compound are reacted. Later, a compound having intramolecular polarization obtained by dehydrohalogenation; from the viewpoint of curability, it has intramolecular polarization obtained by reacting an organic phosphine with a halogenated phenol compound and then dehydrohalogenating. Compounds are preferred.

（式（Ｉ−ｂ）中、Ｒ^２は、それぞれ独立して、水素原子及び炭素数１〜１８の置換又は非置換の炭化水素基からなる群より選ばれ、全てが同一でも異なっていてもよく、２以上のＲ^２が互いに結合して環状構造を形成してもよく、Ｒ^３は、それぞれ独立して、水素原子、水酸基、及び炭素数１〜１８の置換又は非置換の有機基からなる群より選ばれ、全てが同一でも異なっていてもよく、２以上のＲ^３が互いに結合して環状構造を形成してもよく、Ｙ⁻は、１以上の放出可能なプロトンを有する炭素数０〜１８の有機基から１つのプロトンが脱離した有機基であり、１以上のＲ^３と互いに結合して環状構造を形成してもよい。） Among the curing accelerators exemplified above, from the viewpoint of fluidity, it is more preferable to contain at least one compound selected from the compound represented by the following general formula (Ib) and an intermolecular salt thereof.

(In formula (Ib), each R ² is independently selected from the group consisting of a hydrogen atom and a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different. Alternatively, two or more R ² may be bonded to each other to form a cyclic structure, and each R ³ is independently selected from a hydrogen atom, a hydroxyl group, and a substituted or unsubstituted organic group having 1 to 18 carbon atoms. All may be the same or different, and two or more R ³ may be bonded to each other to form a cyclic structure, and Y ⁻ represents the number of carbon atoms having one or more releasable protons. (It is an organic group in which one proton is eliminated from 0 to 18 organic groups, and may combine with one or more R ^{3 s} to form a cyclic structure.)

The term “substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms” described as R ² in the above general formula (Ib) has 1 to 18 carbon atoms and may be substituted or non-substituted. It is meant to include an aliphatic hydrocarbon group and an aromatic hydrocarbon group which may be substituted.

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

The term “two or more R ² may be bonded to each other to form a cyclic structure” described as R ^{2 in the} general formula (Ib) means that two or three R ² are bonded to each other as a whole. The case where it becomes a bivalent or trivalent hydrocarbon group is meant. For example, an alkylene group such as ethylene, propylene, butylene, pentylene and hexylene, which can be bonded to a P atom to form a cyclic structure, an alkenyl group such as ethylenyl, propylenyl and butyrenyl groups, an aralkylene group such as a methylenephenylene group, phenylene and naphthylene And arylene groups such as anthracenylene, which may be substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, halogens, and the like.

In addition, as R < ² > of the said general formula (Ib), although it does not specifically limit, It is a monovalent substituent selected from the group which consists of the alkyl group and aryl group which may be substituted. Is preferred. Among these, from the viewpoint of easy availability of raw materials, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, p- Hydroxyphenyl group, m-hydroxyphenyl group, o-hydroxyphenyl group, 2,5-dihydroxyphenyl group, 4- (4-hydroxyphenyl) phenyl group, 1-naphthyl group, 2-naphthyl group, 1- (2- Hydroxynaphthyl) group, 1- (4-hydroxynaphthyl) group, unsubstituted or alkyl group or / and alkoxy group or / and hydroxyl group-substituted aromatic group, methyl group, ethyl group, propyl group, isopropyl group, butyl Substituents selected from a chain or cyclic alkyl group such as a group, sec-butyl group, tert-butyl group, octyl group, cyclohexyl group, etc. More preferable. Phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, p-hydroxyphenyl group, m-hydroxyphenyl group, o- Hydroxyphenyl group, 2,5-dihydroxyphenyl group, 4- (4-hydroxyphenyl) phenyl group, 1-naphthyl group, 2-naphthyl group, 1- (2-hydroxynaphthyl) group, 1- (4-hydroxynaphthyl) And a non-substituted alkyl group or / and an alkoxy group or / and a hydroxyl group-substituted aryl group.

The term “substituted or unsubstituted organic group having 1 to 18 carbon atoms” described as R ^{3 in the} general formula (Ib) has 1 to 18 carbon atoms and is substituted or unsubstituted. An aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an aliphatic hydrocarbon oxy group, an aromatic hydrocarbon oxy group, a carbonyl group, an oxycarbonyl group, and a carbonyloxy group bonded to each other. means.

  More specifically, as the above substituted or unsubstituted aliphatic hydrocarbon group, aromatic hydrocarbon group, aliphatic hydrocarbon oxy group, aromatic hydrocarbon oxy group, carbonyl group, oxycarbonyl group, and carbonyloxy group Is as described above.

The "also may form two or more R ³ are ring structure by bonding with each other" above formula (I-b) and terms described as R ^3, and bonded to two to four R ^3, as a whole It means a case where each becomes a divalent to tetravalent organic group. For example, an alkylene group such as ethylene, propylene, butylene, pentylene, and hexylene that can form a cyclic structure, an alkenyl group such as ethylenyl, propylenyl, and butenyl, an aralkylene group such as a methylenephenylene group, and an arylene group such as phenylene, naphthylene, and anthracenylene , An alkylene group, an alkenyl group, an aralkylene group, an arylene group, an oxy group or a dioxy group, which are substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen, or the like. Also good.

R ^{3 in the} general formula (Ib) is not particularly limited, but is preferably a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an aryl group, an alkoxy group, or an aryloxy group. Among these, from the viewpoint of easy availability of raw materials, alkoxy groups such as hydrogen atom, hydroxyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group, tert-butoxy group, phenoxy group, unsubstituted or alkyl such as aryloxy group such as p-crezoxy group, m-crezoxy group, o-crezoxy group, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, etc. Groups or / and alkoxy groups or / and hydroxyl-substituted aromatic groups, methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, sec-butyl groups, tert-butyl groups, octyl groups, cyclohexyl groups, etc. Alternatively, a substituent selected from cyclic alkyl groups is more preferable. Hydrogen atom, hydroxyl group, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, etc. unsubstituted or alkyl group or / and alkoxy group or / and hydroxyl group-substituted aromatic group Substituents selected from chain or cyclic alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, octyl group and cyclohexyl group are more preferable. In the case where two or more R ³ are bonded to each other to form a cyclic structure, there is no particular limitation, but in combination with the benzene ring to which R ³ is bonded, a 1- (2-hydroxynaphthyl) group, 1- (4 An organic group that forms a polycyclic aromatic group such as a -hydroxynaphthyl) group is preferred.

Y ⁻ in the general formula (Ib) is an organic group in which one proton is eliminated from an organic group having 0 to 18 carbon atoms and having one or more releasable protons (H ⁺ ). R ³ may be bonded to each other to form a cyclic structure. For example, Y ^- represents a hydroxyl group, a mercapto group, a group proton from groups having a hydrogen atom bonded to the Group 16 atoms such as hydro seleno group is eliminated, a carboxyl group, a carboxymethyl group, a carboxyethyl group, carboxyphenyl group carboxymethyl naphthyl group A group in which a carboxylic acid proton is eliminated from a group having 1 to 18 carbon atoms having a carboxyl group, such as a hydroxyphenyl group, a hydroxyphenylmethyl group, a hydroxynaphthyl group, a hydroxyfuryl group, a hydroxythienyl group, a hydroxypyridyl group, etc. And a monovalent organic group in which a phenolic proton is eliminated from a group having 1 to 18 carbon atoms having a phenolic hydroxyl group.

Moreover, when Y < ^- > in Formula (Ib) couple | bonds with one or more R < ³ > and forms a cyclic structure, for example, Y < ^- > combines with the benzene ring to which it has couple | bonded, 2- ( And a divalent organic group that forms a group in which a proton is eliminated from a hydroxyl group of a hydroxy polycyclic aromatic group such as a 6-hydroxynaphthyl group.

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

Examples of the compound represented by the general formula (Ib) include addition reaction product of tri- (4-methoxyphenyl) phosphine and 1,4-benzoquinone, addition of tri-p-tolylphosphine and 1,4-benzoquinone. Reaction product, addition reaction product of tri-o-tolylphosphine and 1,4-benzoquinone, addition reaction product of tri-m-tolylphosphine and 1,4-benzoquinone, di- (4-methoxyphenyl) phenylphosphine and Addition reaction product of 1,4-benzoquinone, addition reaction product of di-p-tolylphenylphosphine and 1,4-benzoquinone, addition reaction product of di-o-tolylphenylphosphine and 1,4-benzoquinone, diphenyl -(4-methoxyphenyl) phosphine and 1,4-benzoquinone addition reaction product, diphenyl-p-tolylphosphine and 1,4-ben Addition reaction product of quinone, addition reaction product of diphenyl-o-tolylphosphine and 1,4-benzoquinone, addition reaction product of diphenyl-m-tolylphosphine and 1,4-benzoquinone, triphenylphosphine and 1,4 -Addition reaction product of benzoquinone, addition reaction product of triphenylphosphine and methyl-1,4-benzoquinone, addition reaction product of triphenylphosphine and 2,3-dimethyl-1,4-benzoquinone, triphenylphosphine and An addition reaction product of 2,5-dimethyl-1,4-benzoquinone, an addition reaction product of triphenylphosphine and methoxy-1,4-benzoquinone, triphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone Addition reaction product of triphenylphosphine and 2,5-dimethoxy-1,4-benzoquinone Addition reaction product, addition reaction product of triphenylphosphine and t-butyl-1,4-benzoquinone, addition reaction product of triphenylphosphine and phenyl-1,4-benzoquinone, tricyclohexylphosphine and 1,4-benzoquinone Addition reaction product of tri-n-butylphosphine and 1,4-benzoquinone, addition reaction product of tri-n-butylphosphine and methyl-1,4-benzoquinone, tri-n-butylphosphine and Addition reaction product of 2,3-dimethyl-1,4-benzoquinone, addition reaction product of tri-n-butylphosphine and 2,5-dimethyl-1,4-benzoquinone, tri-n-butylphosphine and methoxy- Addition reaction product with 1,4-benzoquinone, addition of tri-n-butylphosphine and 2,3-dimethoxy-1,4-benzoquinone Addition reaction product, addition reaction product of tri-n-butylphosphine and 2,5-dimethoxy-1,4-benzoquinone, addition reaction product of tri-n-butylphosphine and t-butyl-1,4-benzoquinone, Addition reaction product of tri-n-butylphosphine and phenyl-1,4-benzoquinone, addition reaction product of tri-n-octylphosphine and 1,4-benzoquinone, addition of cyclohexyldiphenylphosphine and 1,4-benzoquinone Reaction product, addition reaction product of n-butyldiphenylphosphine and 1,4-benzoquinone, addition reaction product of n-octyldiphenylphosphine and 1,4-benzoquinone, addition reaction of dicyclohexylphenylphosphine and 1,4-benzoquinone Products, addition reaction products of di-n-butylphenylphosphine and 1,4-benzoquinone, etc. Addition reaction product of an Sufin compound and a quinone compound.
Further, as described in JP 2004-156036 A, phosphine compounds, 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chloro Phenol, 4-iodophenol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4 -Bromo-3,5-dimethylphenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4- After reacting with a halogenated phenol compound such as bromo-4'-hydroxybiphenyl, dehalogenation Obtained by hydrogen, compounds having intramolecular polarization and the like.

Among these, from the viewpoint of availability, an addition reaction product of tri- (4-methoxyphenyl) phosphine and 1,4-benzoquinone, an addition reaction product of tri-p-tolylphosphine and 1,4-benzoquinone, -Addition reaction product of o-tolylphosphine and 1,4-benzoquinone, addition reaction product of tri-m-tolylphosphine and 1,4-benzoquinone, addition of diphenyl-p-tolylphosphine and 1,4-benzoquinone Reaction product, addition reaction product of triphenylphosphine and 1,4-benzoquinone, addition reaction product of triphenylphosphine and methyl-1,4-benzoquinone, addition reaction product of tricyclohexylphosphine and 1,4-benzoquinone, An addition reaction product of n-butylphosphine and 1,4-benzoquinone cyclohexyldiphenylphosphine and 1, - addition reaction product of an benzoquinone, each compound prepared in Synthesis Examples 1 to 9 compound i.e. in JP-A JP 2004-156036 represented by structures described by the following structural formula (XIX) ~ (XXV) preferred.

  Further, the intermolecular salt of the compound represented by the general formula (Ib) is not limited, but the compound represented by the formula (Ib) and phenol, naphthol, two or more in the molecule. Compounds having a phenolic hydroxyl group such as phenolic compounds having a phenolic hydroxyl group, compounds having a silanol group such as triphenylsilanol, diphenylsilanediol and trimethylsilanol, organic acids such as oxalic acid, acetic acid and benzoic acid, hydrochloric acid, bromide Examples thereof include intermolecular salt compounds with inorganic acids such as hydrogen, sulfuric acid, and nitric acid.

  (D) There is no restriction | limiting in particular if the compounding quantity of a hardening accelerator can achieve the hardening acceleration effect. However, from the viewpoint of improving the curability and fluidity at the time of moisture absorption of the resin composition, the total amount of the (A) curing accelerator is preferably 0.1 to 10 with respect to 100 parts by mass of the (A) epoxy resin. It is desirable to blend 1 part by weight, more preferably 1 to 7.0 parts by weight. If the blending amount 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 may be too high to obtain a good molded product.

  (E) An inorganic filler is further mix | blended with the epoxy resin composition of this invention. The (E) inorganic filler used in the present invention may be one generally used for a sealing molding material, and is not particularly limited. For example, fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, Examples include talc, clay, mica and other fine powders, or beads obtained by spheroidizing these. Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as composite hydroxide of magnesium and zinc, and zinc borate. Among these, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. These inorganic fillers may be used alone or in combination of two or more.

(E) Although the compounding quantity of an inorganic filler will not have a restriction | limiting in particular if the effect of this invention is acquired, It is preferable that it is the range of 55-90 volume% with respect to an epoxy resin composition. These inorganic fillers are blended for the purpose of improving the thermal expansion coefficient, thermal conductivity, elastic modulus, etc. of the cured product. If the blending amount is less than 55% by volume, these properties tend to be insufficiently improved. If it exceeds 90% by volume, the viscosity of the epoxy resin composition is increased, the fluidity is lowered, and molding tends to be difficult.
Moreover, 1-50 micrometers is preferable and, as for the average particle diameter of (E) inorganic filler, 10-30 micrometers is more preferable. If it is less than 1 μm, the viscosity of the epoxy resin composition tends to increase, and if it exceeds 50 μm, the resin component and the inorganic filler are easily separated, resulting in unevenness of the cured product and variations in the properties of the cured product. There is a tendency for the fillability of the to decrease.

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

  In the epoxy resin composition according to the present invention, the component (A) epoxy resin, (B) curing agent, (C) silane compound represented by the general formula (Ia), and (D) curing accelerator as necessary. (E) In addition to the inorganic filler, various additives such as a coupling agent, an ion exchanger, a release agent, a stress relaxation agent, a flame retardant, and a colorant exemplified below may be added. However, the epoxy resin composition according to the present invention is not limited to the following additives, and various additives known in the art may be added as necessary.

In the epoxy resin composition for sealing of the present invention, epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, vinyl silane, etc. are used as necessary in order to enhance the adhesion between the resin component and the inorganic filler. Various known coupling agents such as various silane compounds, titanium compounds, aluminum chelates, and aluminum / zirconium compounds can be added.
The blending amount of the coupling agent is preferably 0.05 to 5% by mass and more preferably 0.1 to 2.5% by mass with respect to (D) the inorganic filler. If it is less than 0.05% by mass, the adhesion to the frame tends to be lowered, and if it exceeds 5% by mass, the moldability of the package tends to be lowered.

Examples of the coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane , Γ-anilinopropylmethyldimethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) L) Aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinyl) Silane coupling agents such as (benzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane,
Isopropyltriisostearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-aminoethyl-aminoethyl) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1 -Butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, Isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctylfo Feto) titanate, isopropyl tricumylphenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate coupling agents such as titanates and the like, may be used in combination of two or more even with these alone. Among these, a coupling agent having a secondary amino group is preferable from the viewpoints of fluidity and wire flow.

An anion exchanger can be mix | blended with the epoxy resin composition of this invention as needed. In particular, when an epoxy resin composition is used as a molding material for sealing, it is preferable to blend an anion exchanger from the viewpoint of improving the moisture resistance and high-temperature standing characteristics of an electronic component device including an element to be sealed. . The anion exchanger used in the present invention is not particularly limited, and conventionally known anion exchangers can be used. For example, hydrotalcite, water content of an element selected from magnesium, aluminum, titanium, zirconium and bismuth can be used. An oxide etc. are mentioned, These can be used individually or in combination of 2 or more types. Especially, the hydrotalcite shown by the following general formula (XXVI) is preferable.
(Chemical formula 20)
Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (XXVI)
(In the formula (XXVI), 0 <X ≦ 0.5, m is a positive number)
The amount of these anion exchangers is not particularly limited as long as it is a sufficient amount capable of capturing anions such as halogen ions, but is preferably in the range of 0.1 to 30% by mass with respect to (A) the epoxy resin. 1 to 5% by mass is more preferable.

  In the epoxy resin composition of the present invention, a mold release agent (F) may be blended in order to give good mold releasability from the mold during molding. There is no restriction | limiting in particular as a mold release agent used in this invention, A conventionally well-known thing can be used. Examples include higher fatty acids such as carnauba wax, montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, polyolefin waxes such as polyethylene oxide and non-oxidized polyethylene, and the like. It may be used alone or in combination of two or more. Among these, an oxidized or non-oxidized polyolefin wax is preferable, and the blending amount thereof is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass with respect to (A) the epoxy resin. If the blending amount of the polyolefin wax is less than 0.01% by mass, the releasability tends to be insufficient, and if it exceeds 10% by mass, the adhesiveness may be inhibited. Examples of the polyolefin-based wax include low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000 such as H4, PE, and PED series manufactured by Hoechst. Moreover, when using another mold release agent together with polyolefin-type wax, 0.1-10 mass% is preferable with respect to (A) epoxy resin, and 0.5-3 mass% is more preferable.

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

In the epoxy resin composition of the present invention, a flame retardant can be blended as necessary to impart flame retardancy. There is no restriction | limiting in particular as a flame retardant used in this invention, For example, the well-known organic or inorganic compound containing a halogen atom, an antimony atom, a nitrogen atom, or a phosphorus atom, a metal hydroxide, etc. are mentioned, These 1 type May be used alone or in combination of two or more. Although there will be no restriction | limiting in particular if the flame-retardant effect is achieved, the compounding quantity of a flame retardant is 1-30 mass% with respect to (A) epoxy resins, such as an epoxy resin, and 2-15 mass% is more preferable.
Moreover, you may mix | blend well-known colorants, such as carbon black, an organic dye, an organic pigment, a titanium oxide, a red lead, a bengara.

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

An electronic component device according to the present invention includes an element sealed with the above-described epoxy resin composition. Electronic component devices include, for example, lead frames, wired tape carriers, wiring boards, glass, silicon wafers, and other supporting members, active elements such as semiconductor chips, transistors, diodes, thyristors, capacitors, resistors, coils, etc. And those in which the element portion is sealed with the epoxy resin composition of the present invention. More specifically, for example, a semiconductor element is fixed on a lead frame, the terminal part of the element such as a bonding pad and the lead part are connected by wire bonding or bump, and then transferred using the epoxy resin composition of the present invention. Sealed by molding, etc., DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-Tap) Common resin-sealed ICs such as Outline Package (TQFP) and TQFP (Thin Quad Flat Package), half connected to the tape carrier by bumps A semiconductor chip, a transistor, and a semiconductor chip connected to a wiring formed on a TCP (Tape Carrier Package), a wiring board or glass sealed with the epoxy resin composition of the present invention by wire bonding, flip chip bonding, solder, etc. A COB (Chip On Board) module, a hybrid IC, a multichip module, and a back surface in which active elements such as diodes and thyristors and / or passive elements such as capacitors, resistors and coils are sealed with the epoxy resin composition of the present invention. A device is mounted on the surface of an organic substrate on which terminals for connecting a wiring board are formed, and the device and the wiring formed on the organic substrate are connected by bump or wire bonding, and then the device is sealed with the epoxy resin composition of the present invention BGA (Ball Grid Array), CS (Chip Size Package) and the like. The epoxy resin composition of the present invention can also be used effectively for printed circuit boards.
As a method for sealing an electronic component device using the epoxy resin composition of the present invention, a low-pressure transfer molding method is the most common, but an injection molding method, a compression molding method, or the like may be used.

EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the scope of the present invention is not limited by the Example shown below.
[Preparation of epoxy resin composition and evaluation of its properties]
(A) As an epoxy resin, an epoxy equivalent of 196 and a biphenyl type epoxy resin having a melting point of 106 ° C. (epoxy resin 1: trade name YX-4000H manufactured by Japan Epoxy Resin Co., Ltd.), an epoxy equivalent of 192 and a diphenylmethane skeleton type epoxy resin having a melting point of 79 ° C. (Epoxy resin 2: Nippon Steel Chemical Co., Ltd. trade name YSLV-80XY), a brominated bisphenol A type epoxy having an epoxy equivalent of 393, a softening point of 80 ° C., and a bromine content of 48 mass% as an epoxy resin having a flame-retardant effect Resin (brominated epoxy resin) was prepared.

  (B) As a curing agent, a phenol aralkyl resin having a hydroxyl group equivalent of 176 and a softening point of 70 ° C. (curing agent 1: trade name Milex XL-225 manufactured by Mitsui Chemicals, Inc.), a hydroxyl group equivalent of 199 and a biphenyl skeleton phenol having a softening point of 89 ° C. Resin (curing agent 2: Meiwa Kasei Co., Ltd. trade name MEH-7851) was prepared.

  (C) Diphenylsilanediol (silanol 1) and triphenylsilanol (silanol 2) were prepared as silane compounds. Triphenylaminosilane (silane compound A) and triphenylchlorosilane (silane compound B) were prepared as silane compounds of comparative examples.

  (D) As a curing accelerator, addition reaction product of triphenylphosphine and 1,4-benzoquinone (curing accelerator 1), addition reaction product of tri-n-butylphosphine and 1,4-benzoquinone (curing accelerator) 2), 4-triphenylphosphoniophenolate (curing accelerator 3), triphenylphosphine (curing accelerator 4), 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) (curing accelerator) 5) was prepared.

(E) As an inorganic filler, spherical fused silica having an average particle diameter of 17.5 μm and a specific surface area of 3.8 m ² / g was prepared. In addition, as various additives, epoxy silane (γ-glycidoxypropyltrimethoxysilane) as a coupling agent, carbon black (trade name MA-100 manufactured by Mitsubishi Chemical Corporation) as a coloring agent, (F) mold release Carnauba wax (manufactured by Celerica NODA) and antimony trioxide as a flame retardant were prepared.

  The above-mentioned components are blended in the parts by mass shown in the following Tables 1 and 2, and roll kneading is carried out under conditions of a kneading temperature of 80 ° C. and a kneading time of 15 minutes. An epoxy resin composition was obtained.

Next, the epoxy resin composition obtained by Examples 1-14 and Comparative Examples 1-16 was evaluated by the various tests shown below. The evaluation results are shown in Tables 3 and 4 below. The epoxy resin composition was molded using a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Further, post-curing was performed at 175 ° C. for 6 hours.
(1) Spiral flow (fluidity index)
An epoxy resin composition was molded under the above conditions using a spiral flow measurement mold according to EMMI-1-66, and the flow distance (cm) was measured.
(2) Hardness upon heating The epoxy resin composition was molded into a disc having a diameter of 50 mm and a thickness of 3 mm under the above conditions, and measured immediately using a Shore D hardness meter.
(3) Hardness at the time of moisture absorption When the epoxy resin composition was allowed to stand for 72 hours under the condition of 25 ° C./50% RH, the hardness was measured using a Shore D type hardness tester under the condition (2).
(4) Reflow crack resistance A QFP80 pin package with external dimensions of 14 x 20 x 2.0 mm, which is a 42 alloy frame mounted with a test silicon chip of dimensions 8 x 10 x 0.4 mm using silver paste, is epoxy A resin composition was molded and post-cured under the above conditions. The package was made to absorb moisture for 168 hours at 85 ° C. and 85% RH, and then subjected to reflow treatment at 240 ° C. for 10 seconds using an IR reflow device to confirm the presence or absence of cracks. Evaluation was made based on the number of crack generating packages with respect to the number (5).
(5) Moisture resistance A test element in which an aluminum wiring having a line / space of 10 μm was formed on a silicon substrate having an outer size of 5 × 9 mm and an oxide film of 5 μm was used. This test element is mounted on a 16-pin DIP (Dual Inline Package) 42 alloy lead frame partially plated with silver using a silver paste, and further, a bonding pad of the element is formed at 200 ° C. with a thermonic wire. The inner lead was connected by Au wire. This was molded under the above conditions using an epoxy resin composition and post-cured to produce a package. The package produced as described above is humidified for 500 hours and 1000 hours under the conditions of 121 ° C., 2 atm and 100% RH with a pressure cooker tester, and then taken out and subjected to a continuity test to determine the number of defective packages. Evaluation was performed based on the number of defective packages with respect to the number of test packages (10).

As can be seen from Tables 3 and 4, Examples 1 to 14 containing the (C) silane compound according to the present invention were compared with Comparative Examples having the same resin composition except for the (C) silane compound according to the present invention. As a result, the fluidity was excellent.
On the other hand, in Comparative Examples 1 to 5 and 10 to 14 that do not contain the (C) silane compound according to the present invention, the fluidity is inferior compared with Examples having the same resin composition except for the silane compound. In Comparative Examples 6 to 9, 15, and 16 containing a silane compound of a type different from the silane compound obtained by the above, the moisture resistance is further inferior as compared with Examples having the same resin composition except for the silane compound.

Claims (9)

It contains (A) an epoxy resin, (B) a curing agent, (C) a silane compound represented by the following general formula (Ia), (D) a curing accelerator, and (E) an inorganic filler. Epoxy resin composition.

(In formula (Ia), each R ¹ is independently selected from the group consisting of a hydrogen atom, a hydroxyl group, and a substituted or unsubstituted organic group having 1 to 18 carbon atoms, all of which are the same or different. Or two or more R ¹ may be bonded to each other to form a cyclic structure, and m represents an integer of ¹ to 3.) The epoxy resin composition according to claim 1, wherein the (D) curing accelerator contains at least one compound selected from a compound represented by the following general formula (Ib) and an intermolecular salt thereof.

(In formula (Ib), each R ² is independently selected from the group consisting of a hydrogen atom and a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different. Alternatively, two or more R ² may be bonded to each other to form a cyclic structure, and each R ³ is independently selected from a hydrogen atom, a hydroxyl group, and a substituted or unsubstituted organic group having 1 to 18 carbon atoms. All may be the same or different, and two or more R ³ may be bonded to each other to form a cyclic structure, and Y ⁻ represents the number of carbon atoms having one or more releasable protons. (It is an organic group in which one proton is eliminated from 0 to 18 organic groups, and may combine with one or more R ^{3 s} to form a cyclic structure.) (C) The epoxy resin composition according to claim 1 or 2, wherein R ^{1 of the} silane compound represented by the general formula (Ia) is selected from aryl groups.   (C) The epoxy resin composition according to any one of claims 1 to 3, wherein the silane compound represented by the general formula (Ia) is triphenylsilanol or diphenylsilanediol.   (E) Content of an inorganic filler is 55-95 mass%, The epoxy resin composition in any one of Claims 1-4.   (C) Content of the silane compound shown by general formula (Ia) is 0.02-5.0 mass% of an epoxy resin composition, The epoxy resin composition in any one of Claims 1-5 object.   (A) epoxy resin is biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom containing type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, salicylaldehyde type epoxy resin, naphthols The epoxy resin composition according to any one of claims 1 to 6, comprising one or more epoxy resins selected from the group consisting of a copolymer type epoxy resin with phenols and an epoxidized product of an aralkyl type phenol resin.   (B) The curing agent is selected from the group consisting of aralkyl-type phenol resins, dicyclopentadiene-type phenol resins, salicylaldehyde-type phenol resins, benzaldehyde-type phenol resins and aralkyl-type phenol resins, and novolac-type phenol resins. The epoxy resin composition according to any one of claims 1 to 7, comprising one or more resins selected.   An electronic component device provided with the element sealed using the epoxy resin composition in any one of Claims 1-8.