JP2011252104A - Epoxy resin composition for sealing and electronic part device equipped with element sealed with the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition for sealing, which is good in adhesiveness to noble metals such as Ag and Au, is good in reflow resistance, and is good in flame retardancy without deteriorating the reliability of moldability, moisture resistance, high temperature leaving characteristics, and the like; and to provide an electronic part device equipped with an element sealed with the same.SOLUTION: The epoxy resin composition for sealing comprises an epoxy resin and a curing agent, wherein the epoxy resin comprises a compound represented by general formula (1) and a compound represented by general formula (2), (wherein, Rto Rare each identically or differently selected from H, 1-10C alkyl, 1-10C alkoxyl, 6-10C aryl and 6-10C aralkyl; n is an integer of 0 to 20).

Description

  The present invention relates to an epoxy resin composition for sealing and an electronic component device provided with an element sealed with this composition.

In recent years, high-density mounting of semiconductor elements has progressed. Along with this, surface mount type packages have become mainstream from conventional pin insertion type packages for resin-encapsulated semiconductor devices. Surface mount ICs, LSIs, etc. are thin and small packages in order to increase the mounting density and reduce the mounting height, increasing the area occupied by the device package, and the package thickness is extremely high. It has become thinner. Further, these packages are different in mounting method from the conventional pin insertion type. That is, in the pin insertion type package, since the pins are inserted into the wiring board and then soldered from the back surface of the wiring board, the package is not directly exposed to a high temperature. However, the surface-mount IC is temporarily fixed on the surface of the wiring board and processed by a solder bath, a reflow device, or the like, and thus is directly exposed to a soldering temperature (reflow temperature). As a result, when the IC package absorbs moisture, the moisture absorption moisture is vaporized during reflow, and the generated vapor pressure works as a peeling stress, and peeling occurs between an insert such as an element and a lead frame and a sealing material, It may cause package cracks and poor electrical characteristics. For this reason, development of the sealing material excellent in solder heat resistance (reflow resistance) is desired. Therefore, as a sealing material, in addition to low moisture absorption, improvement in adhesion and adhesion to different material interfaces such as lead frames (materials such as Cu, Ag, Au, Pd, etc.) and chip interfaces is strongly demanded. Yes. In order to meet these demands, various investigations have been made from the epoxy resin side which is the main material, but the improvement on the epoxy resin side alone is accompanied by a decrease in heat resistance and an increase in adhesion due to low moisture absorption. Decrease in curability occurred and it was difficult to balance physical properties.
Accordingly, various epoxy resin modifiers have been studied from the above background, and examples thereof include indene / styrene / phenol copolymer oligomers (for example, see Patent Document 1) and sulfur atom-containing compounds (for example, Patent Document 2). 3) and a sulfur atom-containing silane coupling agent (see, for example, Patent Document 4).

Japanese Patent Laid-Open No. 10-265650 Japanese Patent Laid-Open No. 11-12442 JP 2002-3704 A JP 2000-103940 A

  However, when an indene / styrene / phenol copolymer oligomer (for example, see Patent Document 1) or a sulfur atom-containing silane coupling agent (for example, see Patent Document 4) is used, it adheres to a noble metal such as Ag or Au. Even if the sulfur atom-containing compound (for example, see Patent Documents 2 and 3) is added in an amount disclosed in the literature, the adhesion with noble metals is not sufficiently improved, and both have reflow resistance. Not satisfied. Furthermore, even if a plasticizer such as epoxidized soybean oil and a flexible agent such as rubber particles are added, the reflow resistance is not satisfied.

  The present invention has been made in view of such circumstances, has good adhesion to noble metals, good reflow resistance, and flame retardancy without reducing reliability such as moldability, moisture resistance, and high-temperature storage properties. It is an object of the present invention to provide an epoxy resin composition for sealing having good properties, and an electronic component device including an element sealed thereby.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by an epoxy resin composition for sealing containing a specific epoxy resin. It came to be completed.

The present invention relates to the following.
(1) (A) an epoxy resin and (B) a curing agent, and (A) an epoxy resin is (A1) a compound represented by the following general formula (1), and (A2) a general formula (2) The epoxy resin composition for sealing containing the compound shown by this.

（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.)

（ここで、Ｒ^１〜Ｒ^８は、水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシル基、炭素数６〜１０のアリール基、及び炭素数６〜１０のアラルキル基から選ばれ、全てが同一でも異なっていてもよい。ｎは０〜２０の整数を示す。）
（２）（Ａ１）上記一般式（１）で示されるエポキシ樹脂と、（Ａ２）上記一般式（２）で示されるエポキシ樹脂とを含有し、エポキシ樹脂（Ａ２）の含有量が、エポキシ樹脂（Ａ１）とエポキシ樹脂（Ａ２）の総和に対して、５〜８０質量％である上記（１）に記載の封止用エポキシ樹脂組成物。
（３）（Ｂ）硬化剤が、アラルキル型フェノール樹脂、ジシクロペンタジエン型フェノール樹脂、トリフェニルメタン型フェノール樹脂及びノボラック型フェノール樹脂のうち少なくとも１種を含有する上記（１）又は（２）に記載の封止用エポキシ樹脂組成物。
（４）さらに（Ｃ）難燃剤を含有する上記（１）〜（３）のいずれかに記載の封止用エポキシ樹脂組成物。
（５）（Ｃ）難燃剤として、水酸化アルミニウムを含有する上記（４）に記載の封止用エポキシ樹脂組成物。
（６）上記（１）〜（５）のいずれかに記載の封止用エポキシ樹脂組成物で封止された素子を備えた電子部品装置。

(Here, R ^{1 to} R ⁸ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 6 to 10 carbon atoms. All may be the same or different, and n represents an integer of 0 to 20.)
(2) (A1) An epoxy resin represented by the above general formula (1) and (A2) an epoxy resin represented by the above general formula (2), wherein the content of the epoxy resin (A2) is an epoxy resin The epoxy resin composition for sealing according to the above (1), which is 5 to 80% by mass relative to the total of (A1) and the epoxy resin (A2).
(3) In the above (1) or (2), (B) the curing agent contains at least one of aralkyl type phenol resin, dicyclopentadiene type phenol resin, triphenylmethane type phenol resin and novolac type phenol resin. The epoxy resin composition for sealing as described.
(4) The epoxy resin composition for sealing according to any one of (1) to (3), further comprising (C) a flame retardant.
(5) The epoxy resin composition for sealing according to the above (4), which contains aluminum hydroxide as a flame retardant (C).
(6) An electronic component device including an element sealed with the sealing epoxy resin composition according to any one of (1) to (5).

  The epoxy resin composition for sealing according to the present invention can provide a product such as an electronic component device having good adhesion to noble metals and good reflow resistance, and its industrial value is great.

  The (A) epoxy resin used in the present invention contains (A1) a compound represented by the above general formula (1) and (A2) a compound represented by the above (2).

  The novolak-type epoxy resin represented by the general formula (1) can be easily obtained by reacting a novolac-type phenol resin with epichlorohydrin. Among them, as R in the general formula (1), an alkyl group having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, methoxy group, ethoxy group, propoxy group, C1-C10 alkoxyl groups, such as a butoxy group, are preferable, and a hydrogen atom or a methyl group is more preferable. N is preferably an integer of 0 to 3. Among the novolak-type epoxy resins represented by the general formula (1), ortho-cresol novolak-type epoxy resins are preferable. As such a compound, EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd., trade name) is available as a commercial product.

The bisphenol A type epoxy resin represented by the general formula (2) is obtained by reacting bisphenol A with epichlorohydrin. Especially, R < ¹ > -R < ⁸ > in General formula (2) has a preferable hydrogen atom and a methyl group, and a hydrogen atom is more preferable. N is preferably an integer of 0 to 10. As the bisphenol A type epoxy resin represented by the above general formula (2), wherein R ^{1 to} R ⁸ are hydrogen atoms, jER-1001 (trade name, manufactured by Mitsubishi Chemical Corporation), YL-7620 (Mitsubishi Chemical Corporation) Manufactured and developed product names) are available.

  In order to demonstrate the performance of the epoxy resin, the blending ratio of the epoxy resin (A1) and the epoxy resin (A2) is the epoxy resin (A2) with respect to the sum of the epoxy resin (A1) and the epoxy resin (A2). The content of is preferably 5 to 80% by mass, more preferably 20 to 70% by mass, and still more preferably 30 to 60% by mass. If it is 5 mass% or more, reflow resistance will improve, and if it is 80 mass% or less, curability will improve.

  Moreover, in order for the compounding quantity of the said epoxy resin (A1) and (A2) to exhibit the performance, the sum total of (A1) and (A2) shall be 60 mass% or more with respect to the whole epoxy resin Is preferable, and it is more preferable to set it as 80 mass% or more.

  In the present invention, a conventionally known epoxy resin can be used in combination. Examples of the epoxy resin that can be used in combination include phenols such as an epoxy resin having a triphenylmethane skeleton, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, and / or α-naphthol, β- Epoxylated novolak resin obtained by condensation or cocondensation of naphthols such as naphthol and dihydroxynaphthalene and compounds having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde under an acidic catalyst. Diglycidyl ethers such as bisphenol F, bisphenol S, alkyl-substituted or unsubstituted biphenol. Stilbene epoxy resin, hydroquinone epoxy resin, glycidyl ester epoxy resin obtained by reaction of polybasic acid such as phthalic acid and dimer acid and epichlorohydrin, glycidyl amine obtained by reaction of polyamine such as diaminodiphenylmethane, isocyanuric acid and epichlorohydrin Type epoxy resin, epoxidized product of co-condensation resin of dicyclopentadiene and phenol, epoxy resin having naphthalene ring, phenol / aralkyl resin, phenol / aralkyl resin containing biphenylene skeleton, aralkyl type phenol resin such as naphthol / aralkyl resin, etc. Epoxy products, trimethylolpropane type epoxy resin, terpene-modified epoxy resin, linear aliphatic epoxy obtained by oxidizing olefinic bonds with peracid such as peracetic acid Resins, alicyclic epoxy resins, include a sulfur atom-containing epoxy resins and the like, may be used in combination of two or more even with these alone.

  Among them, biphenyl type epoxy resin, bisphenol F type epoxy resin, phenol / aralkyl type epoxy resin and sulfur atom-containing epoxy resin are preferable from the viewpoint of fluidity and reflow resistance, and dicyclopentadiene from the viewpoint of low hygroscopicity. Type epoxy resins are preferred, naphthalene type epoxy resins and triphenylmethane type epoxy resins are preferred from the viewpoint of heat resistance and low warpage, and biphenylene type epoxy resins and naphthol / aralkyl type epoxy resins are preferred from the viewpoint of flame retardancy. Is preferred. It is preferable to contain at least one of these epoxy resins. It is preferable to use non-halogen and non-antimony by using a resin having good flame retardancy from the viewpoint of improving high-temperature storage characteristics.

  Examples of the biphenyl type epoxy resin include an epoxy resin represented by the following general formula (3), and examples of the bisphenol F type epoxy resin include an epoxy resin represented by the following general formula (4). Examples of the phenol / aralkyl type epoxy resin include an epoxy resin represented by the following general formula (5), and examples of the sulfur atom-containing epoxy resin include an epoxy resin represented by the following general formula (6). Is mentioned.

（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０〜３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 to 3). Indicates an integer.)

（ここで、Ｒ^１〜Ｒ^８は、水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシル基、炭素数６〜１０のアリール基、及び炭素数６〜１０のアラルキル基から選ばれ、全てが同一でも異なっていてもよい。ｎは０〜３の整数を示す。）

(Here, R ^{1 to} R ⁸ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 6 to 10 carbon atoms. All may be the same or different, and n represents an integer of 0 to 3.)

（ここで、Ｒ^１〜Ｒ^５は、水素原子、炭素数１〜６のアルキル基及び炭素数１〜２のアルコキシ基から選ばれ、互いに同一であっても異なってもよい。ｎは０〜１０の整数を示す。）

(Here, R ^{1 to} R ⁵ are selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 2 carbon atoms, and may be the same as or different from each other. Indicates an integer of 10.)

（ここで、Ｒ^１〜Ｒ^８は、水素原子、置換又は非置換の炭素数１〜１０のアルキル基及び置換又は非置換の炭素数１〜１０のアルコキシ基から選ばれ、全てが同一でも異なっていてもよい。ｎは０〜３の整数を示す。）

(Here, R ^{1 to} R ⁸ are selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, all being the same or different. (N represents an integer of 0 to 3)

  Examples of the biphenyl type epoxy resin represented by the general formula (3) include 4,4′-bis (2,3-epoxypropoxy) biphenyl or 4,4′-bis (2,3-epoxypropoxy) -3. , 3 ', 5,5'-tetramethylbiphenyl as the main component, epichlorohydrin and 4,4'-biphenol or 4,4'-(3,3 ', 5,5'-tetramethyl) biphenol An epoxy resin obtained by reacting is used. Among them, an epoxy resin mainly composed of 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl is preferable. As such a compound, YX-4000 (trade name, manufactured by Mitsubishi Chemical Corporation) is commercially available.

As the bisphenol F type epoxy resin represented by the general formula (4), for example, R ¹ , R ³ , R ⁶ and R ⁸ are methyl groups, and R ² , R ⁴ , R ⁵ and R ⁷ are hydrogen atoms. Yes, YSLV-80XY (trade name, manufactured by Nippon Kayaku Epoxy Manufacturing Co., Ltd.) having n = 0 as a main component is commercially available.

As the epoxy resin represented by the general formula (5), for example, NC-2000-L (trade name, manufactured by Nippon Kayaku Co., Ltd.) in which R ^{1 to} R ⁵ are hydrogen atoms is commercially available. is there.

Among the sulfur atom-containing epoxy resins represented by the above general formula (6), R ² , R ³ , R ⁶ and R ⁷ are hydrogen atoms, and R ¹ , R ⁴ , R ⁵ and R ⁸ are alkyl groups. A resin is preferable, and an epoxy resin in which R ² , R ³ , R ⁶ and R ⁷ are hydrogen atoms, R ¹ and R ⁸ are tert-butyl groups, and R ⁴ and R ⁵ are methyl groups is more preferable. As such a compound, YSLV-120TE (manufactured by Nippon Kayaku Epoxy Manufacturing Co., Ltd., trade name) is available as a commercial product. These epoxy resins may be used alone or in combination of two or more.

  Examples of the dicyclopentadiene type epoxy resin include an epoxy resin represented by the following general formula (7).

（ここで、Ｒ^１及びＲ^２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それぞれ独立して選ばれ、ｎは０〜１０の整数を示し、ｍは０〜６の整数を示す。）

(Wherein R ¹ and R ² are each independently selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, n represents an integer of 0 to 10; Represents an integer of 0 to 6.)

Examples of R ¹ in the general formula (7) 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. Examples thereof include substituted or unsubstituted monovalent hydrocarbon groups having 1 to 5 carbon atoms such as alkenyl groups, halogenated alkyl groups, amino group-substituted alkyl groups, mercapto group-substituted alkyl groups, etc., among which methyl group, ethyl An alkyl group such as a group and a hydrogen atom are preferable, and a methyl group and a hydrogen atom are more preferable. Examples of R ² 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, an alkenyl group such as a vinyl group, an allyl group, and a butenyl group, and an alkyl halide. A substituted or unsubstituted monovalent hydrocarbon group having 1 to 5 carbon atoms such as a group, an amino group-substituted alkyl group, a mercapto group-substituted alkyl group, etc., among which a hydrogen atom is preferable. As such a compound, HP-7200 (manufactured by DIC Corporation, trade name) and the like are commercially available.

  Examples of the naphthalene type epoxy resin include an epoxy resin represented by the following general formula (8), and examples of the triphenylmethane type epoxy resin include an epoxy resin represented by the following general formula (9). It is done.

（ここで、Ｒ^１〜Ｒ^３は、水素原子及び置換又は非置換の炭素数１〜１２の一価の炭化水素基から選ばれ、それぞれ全てが同一でも異なっていてもよい。ｐは１又は０で、ｌ、ｍは、それぞれ０〜１１の整数であって、（ｌ＋ｍ）が１〜１１の整数でかつ（ｌ＋ｐ）が１〜１２の整数となるよう選ばれる。ｉは０〜３の整数、ｊは０〜２の整数、ｋは０〜４の整数を示す。）

(Here, R ^{1 to} R ³ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and each may be the same or different. P is 1 or 0, l and m are each an integer of 0 to 11, wherein (l + m) is an integer of 1 to 11 and (l + p) is an integer of 1 to 12. i is an integer of 0 to 3. An integer, j represents an integer of 0 to 2, and k represents an integer of 0 to 4.)

As the naphthalene type epoxy resin represented by the general formula (8), a random copolymer containing 1 constituent unit and m constituent units at random, an alternating copolymer containing alternately, a copolymer containing regularly Examples thereof include block copolymers which are included in a combined or block form, and any one of these may be used alone, or two or more may be used in combination. As the above compound in which R ¹ and R ² are hydrogen atoms and R ³ is a methyl group, NC-7000 (trade name, manufactured by Nippon Kayaku Co., Ltd.) and the like are commercially available.

（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１〜１０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 1 to 10.)

  Examples of the triphenylmethane type epoxy resin represented by the general formula (9) include a compound in which R is a hydrogen atom, and as such a compound, E-1032 (manufactured by Mitsubishi Chemical Corporation, product) Name) etc. are commercially available.

  Examples of the biphenylene type epoxy resin include an epoxy resin represented by the following general formula (10), and examples of the naphthol / aralkyl type epoxy resin include an epoxy resin represented by the following general formula (11). It is done.

（上記一般式（１０）中のＲ^１〜Ｒ^９は、全てが同一でも異なっていてもよく、水素原子、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、フェニル基、トリル基、キシリル基等の炭素数６〜１０のアリール基、及び、ベンジル基、フェネチル基等の炭素数６〜１０のアラルキル基から選ばれ、中でも、水素原子とメチル基が好ましい。ｎは０〜１０の整数を示す。）

(R ^{1 to} R ⁹ in the general formula (10) may all be the same or different, and the number of carbon atoms such as hydrogen atom, methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, etc. An alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; an aryl group having 6 to 10 carbon atoms such as a phenyl group, a tolyl group, and a xylyl group; and It is selected from aralkyl groups having 6 to 10 carbon atoms such as a benzyl group and a phenethyl group, among which a hydrogen atom and a methyl group are preferable, and n represents an integer of 0 to 10.)

（ここで、Ｒ^１〜Ｒ^３は、水素原子及び置換又は非置換の炭素数１〜１２の一価の炭化水素基から選ばれ、それぞれ全てが同一でも異なっていてもよい。ｎは１〜１０の整数を示す。）

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

  As the biphenylene type epoxy resin, NC-3000 (trade name, manufactured by Nippon Kayaku Co., Ltd.) is commercially available. Moreover, as a naphthol aralkyl type epoxy resin, ESN-175 etc. (Nippon Kasei Epoxy Manufacturing Co., Ltd. make, brand name) are available as a commercial item. These epoxy resins may be used alone or in combination.

  Moreover, the epoxy resin of following Structural formula (12) can also be used as (A) epoxy resin.

（一般式（１２）中のＲ^１は、置換又は非置換の炭素数１〜１２の炭化水素基及び置換又は非置換の炭素数１〜１２のアルコキシ基から選ばれ、全てが同一でも異なっていてもよい。ｎは０〜４の整数を示す。またＲ^２は、置換又は非置換の炭素数１〜１２の炭化水素基及び置換又は非置換の炭素数１〜１２のアルコキシ基から選ばれ、全てが同一でも異なっていてもよい。ｍは０〜２の整数を示す。）

(R ¹ in the general formula (12) is selected from a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms and a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, all of which are the same or different. N represents an integer of 0 to 4. R ² is selected from a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms and a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms. All may be the same or different, and m represents an integer of 0 to 2.)

Among the epoxy resins represented by the general formula (12), compounds in which R ¹ and R ² are hydrogen atoms are preferable, and examples thereof include YX-8800 (trade name, manufactured by Mitsubishi Chemical Corporation). It is available.

  As the (B) curing agent used in the present invention, a conventionally known curing agent can be used. The curing agent that can be used is not particularly limited as it is generally used in an epoxy resin composition for sealing. For example, phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol Novolaks obtained by condensation or cocondensation of aldehydes such as phenols and / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene with compounds having an aldehyde group such as formaldehyde, benzaldehyde and salicylaldehyde in the presence of an acidic catalyst Type phenolic resin, phenol / aralkyl resin synthesized from phenol and / or naphthol and dimethoxyparaxylene or bis (methoxymethyl) biphenyl, biphenylene type phenol aralkyl resin, naphthol Dicyclopentadiene-type phenols such as dicyclopentadiene-type phenol novolac resins and dicyclopentadiene-type naphthol novolak resins synthesized by copolymerization from aralkyl-type phenol resins such as aralkyl resins, phenols and / or naphthols and dicyclopentadiene Resin, triphenylmethane type phenol resin, terpene modified phenol resin, paraxylylene and / or metaxylylene modified phenol resin, melamine modified phenol resin, cyclopentadiene modified phenol resin, phenol resin obtained by copolymerizing two or more of these, and the like. It is done. These may be used alone or in combination of two or more.

  Of these, phenol / aralkyl resins are preferred from the viewpoints of flame retardancy and moldability. Examples of the phenol / aralkyl resin include a phenol resin represented by the following general formula (13).

（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.)

  A phenol-aralkyl resin in which R in the general formula (13) is a hydrogen atom and the average value of n is 0 to 8 is more preferable. Specific examples include p-xylylene type phenol / aralkyl resins, m-xylylene type phenol / aralkyl resins, and the like. As such a compound, XLC (trade name, manufactured by Mitsui Chemicals, Inc.) is available as a commercial product. When using these aralkyl type phenol resins, 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 the performance.

  In addition, naphthol / aralkyl resins are preferred from the viewpoints of reflow resistance, flame retardancy, and moldability. Examples of the naphthol / aralkyl resin include a phenol resin represented by the following general formula (14).

（ここで、Ｒ^１及びＲ^２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それぞれ独立して選ばれ、ｎは０〜１０の整数を示す。）

(Here, R ¹ and R ² are each independently 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 the naphthol-aralkyl resin represented by the general formula (14) include compounds in which R ¹ and R ² are all hydrogen atoms, and examples of such compounds include SN-170 (Nippon Steel Chemical Co., Ltd.). (Trade name, manufactured by Co., Ltd.) is available as a commercial product.

  Further, from the viewpoint of low hygroscopicity, a dicyclopentadiene type phenol resin is preferable. Examples of the dicyclopentadiene type phenol resin include a phenol resin represented by the following general formula (15).

（ここで、Ｒ^１及びＲ^２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それぞれ独立して選ばれ、ｎは０〜１０の整数を示し、ｍは０〜６の整数を示す。）

(Wherein R ¹ and R ² are each independently selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, n represents an integer of 0 to 10; Represents an integer of 0 to 6.)

Examples of the dicyclopentadiene type phenol resin represented by the general formula (15) include compounds in which R ¹ and R ² are hydrogen atoms, and examples of such compounds include DPP (New Japan Petroleum Refined Stock). Company name, product name) etc. are available as commercial products.

  Further, from the viewpoint of reducing warpage, a triphenylmethane type phenol resin is preferable. Examples of the triphenylmethane type phenol resin include a phenol resin represented by the following general formula (16).

（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１〜１０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 1 to 10.)

  Examples of the triphenylmethane type phenol resin represented by the general formula (16) include compounds in which R is a hydrogen atom, and examples of such compounds include MEH-7500 (manufactured by Meiwa Kasei Co., Ltd., product). Name) etc. are commercially available.

  The compounding amount of the triphenylmethane type phenol resin is preferably 10 to 50% by mass, and more preferably 15 to 30% by mass with respect to the total amount of the (C) curing agent. When it is 10% by mass or more, the warp reduction effect is good, and when it is 50% by mass or less, flame retardancy is good.

  Further, from the viewpoint of curability, a novolac type phenol resin is preferable. Examples of the novolak type phenol resin include a phenol novolak resin represented by the following general formula (17), a cresol novolak resin, a naphthol novolak resin, and the like, and among them, the phenol novolac resin is 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、ｎは１〜１０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 1 to 10.)

  Further, from the viewpoint of reflow resistance and the like, a biphenylene type phenol / aralkyl resin is preferable. Examples of the biphenylene type phenol-aralkyl resin include a phenol resin represented by the following general formula (18).

R ^{1 to} R ⁹ in the general formula (18) may all be the same or different and have 1 carbon atom such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, or an isobutyl group. 10 to 10 alkyl groups, methoxy groups, ethoxy groups, propoxy groups, butoxy groups and the like, alkoxy groups having 1 to 10 carbon atoms, phenyl groups, tolyl groups, xylyl groups and the like aryl groups having 6 to 10 carbon atoms, and benzyl Selected from an aralkyl group having 6 to 10 carbon atoms such as a group and a phenethyl group, among which a hydrogen atom and a methyl group are preferred. n represents an integer of 0 to 10.

Examples of the biphenylene type phenol-aralkyl resin represented by the general formula (18) include compounds in which R ^{1 to} R ⁹ are all hydrogen atoms, and among them, n is 1 or more from the viewpoint of melt viscosity. A mixture of condensates containing 50% by mass or more of condensates is preferred. As such a compound, MEH-7851 (trade name, manufactured by Meiwa Kasei Co., Ltd.) is commercially available.

  The above aralkyl-type phenol resin, naphthol-aralkyl resin, dicyclopentadiene-type phenol resin, triphenylmethane-type phenol resin, novolac-type phenol resin, biphenylene-type phenol-aralkyl resin can be used alone or in combination. You may use combining more than a seed.

  Among the epoxy resins used in combination, a novolak type phenol resin is particularly preferable from the viewpoint of curability, and an aralkyl type phenol resin is preferable from the viewpoint of fluidity and reflow resistance.

  In the sealing epoxy resin composition of the present invention, a (D) curing accelerator can be used as necessary to promote the reaction between the (A) epoxy resin and the (B) curing agent. (D) The curing accelerator is generally used in the epoxy resin composition for sealing and is not particularly limited. For example, 1,8-diaza-bicyclo (5,4,0) undecene-7, 1 Cycloamidine compounds such as 1,5-diaza-bicyclo (4,3,0) nonene, 5,6-dibutylamino-1,8-diaza-bicyclo (5,4,0) undecene-7 and these compounds Maleic acid, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone Addition of quinone compounds such as 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, diazophenylmethane, phenol resin and other compounds with π bond Compounds having intramolecular polarization, tertiary amines such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives, 2-methylimidazole, 2-phenylimidazole, 2 -Imidazoles such as phenyl-4-methylimidazole and derivatives thereof, phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, and phenylphosphine, and these phosphine compounds A phosphorus compound having intramolecular polarization, tetraphenylphosphonic acid, which is obtained by adding a compound having a π bond such as maleic anhydride, the above quinone compound, diazophenylmethane, phenol resin, etc. And tetraphenylboron salts such as mutetraphenylborate, triphenylphosphinetetraphenylborate, 2-ethyl-4-methylimidazoletetraphenylborate, N-methylmorpholinetetraphenylborate, and derivatives thereof. You may use it, or may use it in combination of 2 or more types. Among these, triphenylphosphine is preferable from the viewpoint of curability.

  Among these, an adduct of a tertiary phosphine compound and a quinone compound is preferable from the viewpoint of flame retardancy, curability, fluidity, and releasability. Although it does not specifically limit as a tertiary phosphine compound, Tricyclohexyl phosphine, tributyl phosphine, dibutyl phenyl phosphine, butyl diphenyl phosphine, ethyl diphenyl phosphine, triphenyl phosphine, tris (4-methylphenyl) phosphine, tris (4 -Ethylphenyl) phosphine, tris (4-propylphenyl) phosphine, tris (4-butylphenyl) phosphine, tris (isopropylphenyl) phosphine, tris (t-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, Squirrel (4-methoxyphenyl) phosphine, tris (4-ethoxyphenyl) alkyl groups such as phosphines, tertiary phosphine compounds having an aryl group are preferable. Examples of the quinone compound include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, anthraquinone, and the like. Among these, p-benzoquinone is preferable from the viewpoint of moisture resistance and storage stability. An adduct of tris (4-methylphenyl) phosphine and p-benzoquinone is more preferable from the viewpoint of releasability.

  (D) Although the compounding quantity of a hardening accelerator will not be restrict | limited especially if the hardening acceleration effect is achieved, 0.005-2 mass% is preferable with respect to the epoxy resin composition for sealing. 0.01 to 0.5 mass% is more preferable. If it is less than 0.005% by mass, the curability in a short time tends to be inferior, and if it exceeds 2% by mass, the curing rate tends to be too high and it tends to be difficult to obtain a good molded product.

  In this invention, (E) inorganic filler can be mix | blended as needed. The inorganic filler has effects of hygroscopicity, linear expansion coefficient reduction, thermal conductivity improvement and strength improvement, for example, fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, Examples thereof include powders such as silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, and titania, or beads and glass fibers obtained by spheroidizing these. Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxide, zinc borate, and zinc molybdate. Here, as zinc borate, FB-290, FB-500 (made by US Borax, trade name), FRZ-500C (made by Mizusawa Chemical Co., Ltd., trade name), etc. are used as zinc molybdate. Are commercially available as KEMGARD911B, 911C, 1100 (manufactured by Sherwin-Williams).

  These inorganic fillers may be used alone or in combination of two or more. Among them, fused silica is preferable from the viewpoint of filling property and linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity, and the shape of the inorganic filler is spherical from the viewpoint of filling property and mold wear. preferable.

The blending amount of the inorganic filler is 50% by mass or more based on the epoxy resin composition for sealing from the viewpoints of fluidity, flame retardancy, moldability, hygroscopicity, linear expansion coefficient reduction, strength improvement and reflow resistance. 60 to 95% by mass is more preferable from the viewpoint of flame retardancy, and 70 to 90% by mass is more preferable.
If the amount is less than 50% by mass, the flame retardancy and reflow resistance tend to decrease. If the amount exceeds 95% by mass, the fluidity tends to be insufficient, and the flame retardancy also tends to decrease.

  (E) When an inorganic filler is used, the sealing epoxy resin composition of the present invention may further contain (F) a coupling agent in order to enhance the adhesion between the resin component and the filler. preferable. (F) The coupling agent is generally used in an epoxy resin composition for sealing and is not particularly limited. For example, a silane compound having a primary and / or secondary and / or tertiary amino group And various silane compounds such as epoxy silane, mercapto silane, alkyl silane, ureido silane, and vinyl silane, titanium compounds, aluminum chelates, and aluminum / zirconium compounds. Examples of these are vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycol. Sidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyl Triethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropyltrimethoxy Silane, γ- (N, N-diethyl) aminopropyltrimethoxysilane, γ- (N, N-dibutyl) aminopropyltrimethoxysilane, γ- (N-methyl) anilinopropyltrimethoxysilane, γ- (N -Ethyl) anilinopropyltrimethoxysilane, γ- (N, N-dimethyl) aminopropyltriethoxysilane, γ- (N, N-diethyl) aminopropyltriethoxysilane, γ- (N, N-dibutyl) amino Propyltriethoxysilane, γ- (N-methyl) anilinopropyltriethoxysilane, γ- (N-ethyl) anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropylmethyldimethoxysilane, γ- (N, N-diethyl) aminopropylmethyldimethoxysilane, γ- (N, N-dibutyl) aminopropy Rumethyldimethoxysilane, γ- (N-methyl) anilinopropylmethyldimethoxysilane, γ- (N-ethyl) anilinopropylmethyldimethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ) Silane coupling agents such as ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, isopropyl Triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctane Rubis (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, isopropylisostearoyl diacryl titanate, isopropyltri (dioctylphosphate) titanate, isopropyltricumylphenyl titanate, tetraisopropylbis (dioctylphosphite) titanate And titanate coupling agents such as May be used alone or in combination of two or more.

  Among these, a silane coupling agent having a secondary amino group is preferable from the viewpoints of fluidity, gold wire deformation reduction, and flame retardancy. The silane coupling agent having a secondary amino group is not particularly limited as long as it is a silane compound having a secondary amino group in the molecule. For example, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane Γ-anilinopropylmethyldimethoxysilane, γ-anilinopropylmethyldiethoxysilane, γ-anilinopropylethyldiethoxysilane, γ-anilinopropylethyldimethoxysilane, γ-anilinomethyltrimethoxysilane, γ- Anilinomethyltriethoxysilane, γ-anilinomethylmethyldimethoxysilane, γ-anilinomethylmethyldiethoxysilane, γ-anilinomethylethyldiethoxysilane, γ-anilinomethylethyldimethoxysilane, N- (p- Methoxyphenyl) -γ-aminopropyltrimethoxy Silane, N- (p-methoxyphenyl) -γ-aminopropyltriethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylmethyldimethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylmethyl Diethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylethyldiethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylethyldimethoxysilane, γ- (N-methyl) aminopropyltrimethoxy Silane, γ- (N-ethyl) aminopropyltrimethoxysilane, γ- (N-butyl) aminopropyltrimethoxysilane, γ- (N-benzyl) aminopropyltrimethoxysilane, γ- (N-methyl) aminopropyl Triethoxysilane, γ- (N-ethyl) aminopropyltriethoxysilane Γ- (N-butyl) aminopropyltriethoxysilane, γ- (N-benzyl) aminopropyltriethoxysilane, γ- (N-methyl) aminopropylmethyldimethoxysilane, γ- (N-ethyl) aminopropyl Methyldimethoxysilane, γ- (N-butyl) aminopropylmethyldimethoxysilane, γ- (N-benzyl) aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ- ( β-aminoethyl) aminopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane and the like.

  The total amount of the coupling agent is preferably 0.04 to 5% by mass, more preferably 0.05 to 4.75% by mass with respect to the epoxy resin composition for sealing. More preferably, it is 1-2.5 mass%. From the viewpoint of adhesion to the frame, it is preferably 0.04% by mass or more, and from the viewpoint of package moldability, it is preferably 5% by mass or less.

  For the purpose of further improving the flame retardancy, the epoxy resin composition for sealing of the present invention is a conventionally known (C) flame retardant, particularly from the viewpoint of environmental friendliness and reliability, a halogen-free, non-antimony flame retardant. Can be blended as necessary. For example, red phosphorus coated with an inorganic compound such as red phosphorus and zinc oxide and a thermosetting resin such as phenol resin, phosphorus compounds such as phosphate ester and phosphine oxide, melamine, melamine derivatives, melamine modified phenolic resin, triazine ring , Nitrogen-containing compounds such as cyanuric acid derivatives and isocyanuric acid derivatives, phosphorus and nitrogen-containing compounds such as cyclophosphazenes, aluminum hydroxide, magnesium hydroxide, composite metal hydroxides, zinc oxide, zinc stannate, zinc borate And compounds containing metal elements such as iron oxide, molybdenum oxide, zinc molybdate, and dicyclopentadienyl iron. These may be used alone or in combination of two or more.

Among these, aluminum hydroxide is preferable from the viewpoint of flame retardancy. The amount of aluminum hydroxide is preferably 10 to 300 parts by mass, more preferably 20 to 200 parts by mass, and still more preferably 50 to 150 parts by mass with respect to 100 parts by mass of the epoxy resin. .
If it is 10 parts by mass or more, flame retardancy is improved, and if it is 300 parts by mass or less, fluidity is improved. As the aluminum hydroxide, BW103 (manufactured by Nippon Light Metal Co., Ltd., trade name) is available as a commercial product.

  From the viewpoint of fluidity, phosphate esters, phosphine oxides and cyclophosphazenes are preferred. The phosphate ester is not particularly limited as long as it is an ester compound of phosphoric acid and an alcohol compound or a phenol compound. For example, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate , Xylenyl diphenyl phosphate, tris (2,6 dimethylphenyl) phosphate, and aromatic condensed phosphate. Among these, from the viewpoint of hydrolysis resistance, an aromatic condensed phosphate represented by the following general formula (19) is preferable.

  Examples of the phosphoric acid ester of the general formula (19) include phosphoric acid esters represented by the following structural formulas (20) to (24).

  The addition amount of these phosphate esters is preferably in the range of 0.2 to 3.0 mass% in terms of the amount of phosphorus atoms with respect to all the other compounding ingredients except the filler. If it is less than 0.2% by mass, the flame retardancy tends to be low. If it exceeds 3.0% by mass, the formability and moisture resistance may be deteriorated, and these phosphate esters may ooze out during molding, thereby impairing the appearance.

  When phosphine oxide is used as a flame retardant, the phosphine oxide is preferably a compound represented by the following general formula (25).

（ここで、Ｒ^１、Ｒ^２及びＲ^３は、炭素数１〜１０の置換又は非置換のアルキル基、アリール基、アラルキル基及び水素原子を示し、すべて同一でも異なってもよい。ただしすべてが水素原子である場合を除く。）

(Here, R ¹ , R ² and R ³ represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group and a hydrogen atom, which may all be the same or different. Except for the case of hydrogen atoms.)

Among the phosphorus compounds represented by the general formula (25), from the viewpoint of hydrolysis resistance, R ^{1 to} R ³ are preferably a substituted or unsubstituted aryl group, and particularly preferably a phenyl group.

  As for the compounding quantity of a phosphine oxide, it is preferable that the quantity of a phosphorus atom is 0.01-0.2 mass% with respect to the epoxy resin composition for sealing. More preferably, it is 0.02-0.1 mass%, More preferably, it is 0.03-0.08 mass%. If it is less than 0.01% by mass, the flame retardancy is lowered, and if it exceeds 0.2% by mass, the moldability and moisture resistance are lowered.

  Cyclophosphazenes include cyclic phosphazene compounds containing the following general formula (26) and / or the following general formula (28) as a repeating unit in the main chain skeleton, or the following general formulas having different substitution positions with respect to phosphorus atoms in the phosphazene ring ( 27) and / or a compound containing the following general formula (29) as a repeating unit.

Here, the general formula (26) and the general formula (28) in the m is an integer of 1 to ^10, R 1 to R ⁴ is an optionally substituted alkyl group having 1 to 12 carbon atoms , An aryl group and a hydroxyl group, all of which may be the same or different. A represents an alkylene group having 1 to 4 carbon atoms or an arylene group. N in the general formula (27) and the general formula (29) in the 1-10 ^integer, R 5 to R ⁸ is from 1 to 12 carbon atoms which may have a substituent alkyl or aryl Selected from a group, all of which may be the same or different, and A represents an alkylene group or an arylene group having 1 to 4 carbon atoms. In the formula, m R ¹ , R ² , R ³ and R ⁴ may all be the same or different, and n R ⁵ , R ⁶ , R ⁷ and R ⁸ are n All may be the same or different.

In the general formulas (26) to (29), the alkyl group or aryl group having 1 to 12 carbon atoms which may have a substituent represented by R ^{1 to} R ⁸ is not particularly limited. Alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group and tert-butyl group, aryl groups such as phenyl group, 1-naphthyl group and 2-naphthyl group, o Alkyl group substitution such as -tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,4-xylyl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, mesityl group Examples include aryl group-substituted alkyl groups such as aryl group, benzyl group, and phenethyl group. Further, examples of substituents that can be substituted for these include alkyl groups, alkoxyl groups, aryl groups, hydroxyl groups, amino groups , An epoxy group, a vinyl group, a hydroxyalkyl group, an alkylamino group, and the like.

  Among these, from the viewpoint of heat resistance and moisture resistance of the epoxy resin composition, an aryl group is preferable, and a phenyl group or a hydroxyphenyl group is more preferable.

  Moreover, as a C1-C4 alkylene group or arylene group shown by A in said general formula (26)-(29), although there is no restriction | limiting, a methylene group, ethylene group, a propylene group, an isopropylene group , Butylene group, isobutylene group, phenylene group, tolylene group, xylylene group, naphthylene group, and the like. From the viewpoint of heat resistance and moisture resistance of the epoxy resin composition, an arylene group is preferable, and a phenylene group is more preferable.

  The cyclic phosphazene compound is a polymer of any one of the general formulas (26) to (29), a copolymer of the general formula (26) and the general formula (27), or the general formula (28) and the above. Although it is a copolymer with General formula (29), in the case of a copolymer, any of a random copolymer, a block copolymer, and an alternating copolymer may be sufficient. The copolymerization molar ratio m / n is not particularly limited, but is preferably 1/0 to 1/4 from the viewpoint of improving heat resistance and strength of the cured epoxy resin, and 1/0 to 1/1. 5 is more preferable. Moreover, polymerization degree m + n is 1-20, Preferably it is 2-8, More preferably, it is 3-6.

  Preferred examples of the cyclic phosphazene compound include a polymer having the following general formula (30) and a copolymer having the following general formula (31).

（ここで、上記一般式（３０）中のｎは、０〜９の整数で、Ｒ^１〜Ｒ^５はそれぞれ独立に水素又は水酸基を示す。）

(Here, n in the general formula (30) is an integer of 0 to 9, and R ^{1 to} R ⁵ each independently represent hydrogen or a hydroxyl group.)

Here, m and n in the general formula (31) are integers of 0 to 9, R ^{1 to} R ⁴ are each independently selected from hydrogen or a hydroxyl group, and R ^{5 to} R ⁶ are each independently hydrogen. Or it is chosen from a hydroxyl group. In addition, the cyclic phosphazene compound represented by the general formula (31) includes the following m repeating units (a) and n repeating units (b) alternately, blocks including, randomly Any of these may be included, but those randomly included are preferred.

Among them, those having a polymer of the above general formula (30) where n is 3 to 6 as a main component, or R ^{5 to} R ⁶ are all hydrogen or one is a hydroxyl group in the above general formula (31), and m / n Is preferably a copolymer having a main component of 1/2 to 1/3 and m + n of 3 to 6. As a commercially available phosphazene compound, SPE-100 (trade name, manufactured by Otsuka Chemical Co., Ltd.) is available.

  When using a composite metal hydroxide as a flame retardant, the composite metal hydroxide is preferably a compound represented by the following composition formula (32).

（ここで、Ｍ^１、Ｍ^２及びＭ^３は、互いに異なる金属元素を示し、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｐ、ｑ及びｍは、正の数、ｒは、０又は正の数を示す。）

(Here, M ¹ , M ² and M ³ represent different metal elements, a, b, c, d, e, f, p, q and m are positive numbers, and r is 0 or positive. Indicates the number of

  Among these, a compound in which r in the composition formula (32) is 0, that is, a compound represented by the following composition formula (33) is more preferable.

（ここで、Ｍ^１及びＭ^２は、互いに異なる金属元素を示し、ａ、ｂ、ｃ、ｄ、ｐ、ｑ及びｌは、正の数を示す。）

(Here, M ¹ and M ² represent different metal elements, and a, b, c, d, p, q, and l represent positive numbers.)

M ¹ , M ² and M ³ in the composition formulas (32) and (33) are not particularly limited as long as they are different metal elements, but from the viewpoint of flame retardancy, M ¹ and M ² are the same. M ¹ is selected from metal elements belonging to the third period metal element, group IIA alkaline earth metal element, group IVB, group IIB, group VIII, group IB, group IIIA and group IVA, and M ² Is preferably selected from transition metal elements of groups IB, IIB and VIII, M ¹ is selected from magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc, and M ² is iron. More preferably, it is selected from cobalt, nickel, copper and zinc. From the viewpoint of fluidity, M ¹ is preferably magnesium and M ² is preferably zinc or nickel, more preferably M ¹ is magnesium and M ² is zinc.

  The molar ratio of p, q, and r in the composition formula (32) is not particularly limited as long as the effect of the present invention can be obtained, but r = 0 and the molar ratio p / q of p and q is 99/1. It is preferably ˜50 / 50.

Examples of commercially available products include water in which M ^{1 in the} composition formula (33) is magnesium, M ² is zinc, p is 7, q is 3, l is 10, and a, b, c, and d are 1. Magnesium oxide / zinc hydroxide solid solution composite metal hydroxide (manufactured by Tateho Chemical Co., Ltd., trade name: Echo Mug Z-10) can be used. The metal element includes what is called a metalloid element, and refers to all elements other than non-metal elements.

  In addition, the classification of metal elements is a long-period type periodic rate table in which the typical element is the A subgroup and the transition element is the B subgroup (Source: Kyoritsu Shuppan Co., Ltd. “Chemical Dictionary 4”, March 15, 1984) (Reduced plate No. 28).

  The shape of the composite metal hydroxide is not particularly limited, but a polyhedral shape having an appropriate thickness is preferable to a flat shape from the viewpoint of fluidity and filling properties. Compared to metal hydroxides, complex metal hydroxides tend to give polyhedral crystals.

  Although the compounding quantity of a composite metal hydroxide does not have a restriction | limiting in particular, 0.5-20 mass% is preferable with respect to the epoxy resin composition for sealing, 0.7-15 mass% is more preferable, 1.4 More preferably, ˜12% by mass. If it is less than 0.5% by mass, the flame retardancy tends to be insufficient, and if it exceeds 20% by mass, the fluidity and reflow resistance tend to decrease.

  As the compound having a triazine ring, a compound obtained by co-condensation polymerization of a compound having a phenolic hydroxyl group, a triazine derivative and a compound having an aldehyde group is preferable from the viewpoint of flame retardancy and adhesiveness to a copper frame. Examples of the compound having a phenolic hydroxyl group include alkylphenols such as phenol, cresol, xylenol, ethylphenol, butylphenol, nonylphenol, octylphenol, polyphenols such as resorcin, catechol, bisphenol A, bisphenol F, bisphenol S, phenylphenol, It is obtained by condensation or cocondensation of aminophenol, naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene or the like, or a compound having these phenolic hydroxyl groups and a compound having an aldehyde group such as formaldehyde under an acidic catalyst. There are resins. Among these, from the viewpoint of moldability, phenol, cresol, or a copolycondensation product of these with formaldehyde is preferable. The triazine derivative is not particularly limited as long as it has a triazine nucleus in the molecule, and examples thereof include guanamine derivatives such as melamine, benzoguanamine, and acetoguanamine, and cyanuric acid derivatives such as cyanuric acid and methyl cyanurate. Only one type or a combination of two or more types is possible. Of these, guanamine derivatives such as melamine and benzoguanamine are preferable from the viewpoints of moldability and reliability. Examples of the compound having an aldehyde group include formalin and paraformaldehyde.

  The compounding amount of the compound having an aldehyde group with respect to the compound having a phenolic hydroxyl group is 0.05 to 0.9 in a molar ratio (compound having an aldehyde group (mol) / compound having a phenolic hydroxyl group (mol)). It is preferable to set it to 0.1 to 0.8. If it is less than 0.05, the reaction of the compound having an aldehyde group with respect to the phenolic hydroxyl group is unlikely to occur, unreacted phenol tends to remain, the productivity is poor, and if it exceeds 0.9, gelation tends to occur during synthesis.

  The blending amount of the triazine derivative with respect to the compound having a phenolic hydroxyl group is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass. If it is less than 1% by mass, the flame retardancy is poor, and if it exceeds 30% by mass, the softening point becomes high and the kneadability at the time of preparing the composition is lowered. The compounding amount (molar ratio) of the compound having an aldehyde group with respect to the triazine derivative is not particularly limited.

The reaction temperature at the time of synthesizing a copolycondensation product of a compound having a phenolic hydroxyl group, a triazine derivative and a compound having an aldehyde group is not particularly limited, but is preferably 60 to 120 ° C. Moreover, 3-9 are preferable and, as for pH of reaction, 4-8 are more preferable. If the pH is less than 3, the resin is easily gelled during synthesis, and if it is higher than 9, copolycondensation between the phenol resin, the triazine derivative and the compound having an aldehyde group hardly occurs, and the produced resin has a low nitrogen content. Become.
In the present invention, the pH of the reaction solution is measured with a pH meter (for example, model number PH81 manufactured by Yokogawa Electric Corporation). After calibrating two points using a standard buffer (phthalate pH buffer solution pH: 4.01 (25 ° C), neutral phosphate pH buffer solution pH: 6.86 (25 ° C)), the electrode was The value after the reaction solution has been stabilized after 2 minutes or more has been adopted.

  If necessary, after reacting a compound having a phenolic hydroxyl group with a compound having an aldehyde group, a triazine derivative, heating distillation under normal pressure or reduced pressure, etc., an unreacted phenol compound and a compound having an aldehyde group, etc. Can be removed. At this time, the residual amount of the unreacted phenol compound is preferably 3% or less. If it exceeds 3%, the moldability tends to decrease.

  Moreover, it is preferable that the softening point of the obtained copolycondensation product is 40-150 degreeC. When it is less than 40 ° C., it is easy to block, and when it exceeds 150 ° C., the kneadability of the composition is lowered. Examples of copolycondensation products of the compound having a phenolic hydroxyl group, a triazine derivative, and a compound having an aldehyde group include those represented by the following structural formulas (34) to (39) (n and m are positive). integer).

  The number average molecular weight of the copolycondensation product of a compound having a phenolic hydroxyl group, a triazine derivative and a compound having an aldehyde group is preferably from 500 to 1,000, and more preferably from 550 to 800. If it is less than 500, the moldability and reflow crack resistance are lowered, and if it exceeds 1000, the fluidity tends to be lowered. Moreover, it is preferable that it is 1500-10000, and, as for a weight average molecular weight, it is more preferable that it is 1700-7000. When it is less than 1500, the reflow crack resistance is lowered, and when it exceeds 10,000, the fluidity tends to be lowered. Furthermore, the molecular weight distribution Mw / Mn of the copolycondensation product of the compound having a phenolic hydroxyl group, the triazine derivative and the compound having an aldehyde group is preferably 2.0 to 10.0, and preferably 3.0 to 6 More preferably, it is 0.0. If it is less than 2.0, the reflow crack resistance is lowered, and if it exceeds 10.0, the fluidity tends to be lowered.

  Among the copolycondensation products, a copolycondensation product of a phenol resin, a triazine derivative and a compound having an aldehyde group is more preferable from the viewpoint of reflow resistance. The phenolic resin used here is not particularly limited as it is generally used in the composition, for example, phenol, cresol, xylenol, ethylphenol, butylphenol, nonylphenol, alkylphenols such as octylphenol, resorcin, catechol, bisphenol. Acidic polyhydric phenols such as A, bisphenol F and bisphenol S, naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene or phenol derivatives such as phenylphenol and aminophenol and compounds having an aldehyde group such as formaldehyde There are resins obtained by condensation or cocondensation under a catalyst. Among these, from the viewpoint of moldability, a phenol novolak resin which is a polycondensate of phenol and formaldehyde is preferable.

  The phenol resin is not particularly limited as long as it is enumerated above, but when it is synthesized by the method shown below, its molecular weight and molecular weight distribution are described in the present invention. Therefore, it is preferable in that it can be synthesized within the preferable range. That is, when synthesizing a phenol resin, the proportion of the compound having a phenol derivative and an aldehyde group is preferably 0.01 to 2.0 mol of the compound having an aldehyde group with respect to 1 mol of the phenol derivative. It is more preferable to set it as 0.05-1.0 mol. If the amount is less than 0.01 mol, the reaction becomes insufficient, the molecular weight does not increase, and the moldability, heat resistance, water resistance, flame retardancy, strength, etc. tend to decrease. It tends to be too large and the kneadability tends to decrease.

  This reaction temperature is preferably 80 to 220 ° C, more preferably 100 to 180 ° C. If the temperature is less than 80 ° C., the reactivity becomes insufficient, the molecular weight tends to be small, and the moldability tends to decrease. If the temperature exceeds 220 ° C., the production equipment tends to be disadvantageous when the phenol resin is synthesized. The reaction time is preferably about 1 to 30 hours.

  If necessary, an amine catalyst such as trimethylamine or triethylamine, an acid catalyst such as p-toluenesulfonic acid or oxalic acid, an alkali catalyst such as sodium hydroxide or ammonia, etc. may be added to 0.00001 with respect to 1 mol of the phenol derivative. About 0.01 mol may be used. Moreover, it is preferable that pH of a reaction system shall be about 1-10.

  In this way, after reacting the phenol derivative and the compound having an aldehyde group, if necessary, the unreacted phenol derivative, the compound having an aldehyde group, water and the like can be removed under heating and reduced pressure. Generally, it is preferable that the temperature is 80 to 220 ° C., desirably 100 to 180 ° C., the pressure is 100 mmHg or less, desirably 60 mmHg or less, and the time is 0.5 to 10 hours.

  The proportion of the triazine derivative and the compound having an aldehyde group used in the reaction by adding a triazine derivative and a compound having an aldehyde group to the phenol resin is the polycondensate of the phenol derivative and the compound having an aldehyde group (phenol resin). (Unreacted phenol derivative, compound having an aldehyde group, water removed under heating or reduced pressure, or not removed (in this case, unreacted phenol is included in the mass of the polycondensate) 3) The triazine derivative is preferably 3 to 50 g and more preferably 4 to 30 g with respect to 100 g. Moreover, it is preferable to set it as 5-100g with respect to 100g of polycondensates (phenol resin), and, as for the compound which has an aldehyde group, it is more preferable to set it as 6-50g. By setting the triazine derivative and the compound having an aldehyde group in the above ranges, the molecular weight distribution and nitrogen content of the finally obtained polycondensate can be easily adjusted to a desired range.

  The reaction temperature is preferably 50 to 250 ° C, more preferably 80 to 170 ° C. If the temperature is lower than 50 ° C, the reaction becomes insufficient, the molecular weight does not increase, and the moldability, heat resistance, water resistance, flame retardancy, strength, etc. tend to decrease. There is a tendency to be disadvantageous in terms of equipment. The reaction time is preferably about 1 to 30 hours.

  Moreover, you may use about 0.00001-0.01 mol of amine catalysts, such as a trimethylamine and a triethylamine, and acid catalysts, such as an oxalic acid, with respect to 1 mol of phenol derivatives as needed.

  Moreover, it is preferable that pH of a reaction system shall be about 1-10. After reaction of a polycondensate (phenol resin) of a phenol derivative and a compound having an aldehyde group with a triazine derivative and a compound having an aldehyde group, the unreacted phenol derivative, the compound having an aldehyde group, water, etc. are heated under reduced pressure. The conditions are preferably that the temperature is 80 to 180 ° C., the pressure is 100 mmHg or less, desirably 60 mmHg or less, and the time is 0.5 to 10 hours. The triazine derivative used in the synthesis is not particularly limited as long as it is a compound having a triazine nucleus in the molecule, and examples thereof include guanamine derivatives such as melamine, benzoguanamine, and acetoguanamine, and cyanuric acid derivatives such as cyanuric acid and methyl cyanurate. Only one type or a combination of two or more types is possible. Of these, guanamine derivatives such as melamine and benzoguanamine are preferable from the viewpoints of moldability and reliability. Moreover, as a compound which has an aldehyde group, formaldehyde, formalin, paraformaldehyde, etc. are mentioned, for example.

Moreover, in this invention, you may contain a silicon containing polymer from a viewpoint of the further curvature reduction. The silicon-containing polymer has a bond represented by the following general formulas (c) and (d), a terminal is a functional group selected from R ¹ , a hydroxyl group and an alkoxy group, and an epoxy equivalent is 500 to 4000. If it is, there will be no restriction | limiting in particular, For example, branched polysiloxane etc. are mentioned as such a polymer.

（ここで、Ｒ^１は、炭素数１〜１２の置換または非置換の１価の炭化水素基から選ばれ、ケイ素含有重合物中の全Ｒ^１は、すべてが同一でも異なっていてもよい。Ｘは、エポキシ基を含む１価の有機基を示す。）

(Here, R ¹ is selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and all R ¹ in the silicon-containing polymer may be the same or different. X represents a monovalent organic group containing an epoxy group.)

R ¹ in the general formulas (c) and (d) is methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl. Group, alkyl group such as 2-ethylhexyl group, alkenyl group such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, biphenyl group, benzyl Group, an aralkyl group such as a phenethyl group, and the like. Among them, a methyl group or a phenyl group is preferable.

  In addition, as X in the general formula (d), 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, 2-glycidoxyethyl group, 3-glycid Examples include a xylpropyl group, a 4-glycidoxybutyl group, a 2- (3,4-epoxycyclohexyl) ethyl group, and a 3- (3,4-epoxycyclohexyl) propyl group. Among them, a 3-glycidoxypropyl group Is preferred.

In addition, the terminal of the silicon-containing polymer needs to be any one of the aforementioned R ¹ , hydroxyl group and alkoxy group from the viewpoint of storage stability of the polymer. Examples of the alkoxy group in this case include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Furthermore, the epoxy equivalent of the silicon-containing polymer is preferably in the range of 500 to 4000, more preferably 1000 to 2500. If it is less than 500, the fluidity of the epoxy resin composition for sealing tends to decrease, and if it exceeds 4000, it tends to ooze out on the surface of the cured product and tends to cause molding defects. It is preferable that the silicon-containing polymer further has a bond represented by the following general formula (e) from the viewpoint of compatibility between fluidity and low warpage of the resulting epoxy resin composition for sealing.

（ここで、Ｒ^１は、ケイ素含有重合物中の全Ｒ^１に対して炭素数１〜１２の置換又は非置換の１価または２価の炭化水素基から選ばれ、ケイ素含有重合物中の全Ｒ^１は、すべてが同一でも異なっていてもよい。）

(Here, R ¹ is selected from substituted or unsubstituted monovalent or divalent hydrocarbon groups having 1 to 12 carbon atoms with respect to all R ¹ in the silicon-containing polymer, and in the silicon-containing polymer, All R ¹ may be the same or different.

As R ¹ in the general formula (e), methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2- Alkyl groups such as ethylhexyl group, alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, phenyl group, tolyl group, xylyl group, xylyl group, naphthyl group, biphenyl group, aryl group, benzyl group, phenethyl group Among them, a methyl group or a phenyl group is preferable (a divalent hydrocarbon group may be obtained by removing one H atom from R ¹ above).

  The softening point of such a silicon-containing polymer is preferably set to 40 to 120 ° C, and more preferably set to 50 to 100 ° C. When the temperature is lower than 40 ° C., the mechanical strength of the cured product of the resulting epoxy resin composition for sealing tends to decrease. When the temperature exceeds 120 ° C., the silicon-containing polymer in the epoxy resin composition for sealing Dispersibility tends to decrease. As a method for adjusting the softening point of the silicon-containing polymer, the molecular weight of the silicon-containing polymer, the constituent bond units (for example, (c) to (e) content ratio, etc.), and the type of organic group bonded to the silicon atom are set. In particular, from the viewpoint of dispersibility of the silicon-containing polymer in the epoxy resin composition for sealing and the fluidity of the resulting epoxy resin composition for sealing, the aryl group in the silicon-containing polymer It is preferable to adjust the softening point by setting the content of. Examples of the aryl group in this case include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenyl group, and a phenyl group is more preferable. The desired softening point can be obtained by setting the content of the phenyl group in the monovalent organic group bonded to the silicon atom in the silicon-containing polymer to 60 to 99 mol%, more preferably 70 to 85 mol%. A silicon-containing polymer having the following can be obtained.

  The weight average molecular weight (Mw) of the silicon-containing polymer is a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve, preferably 1000 to 30000, more preferably 2000 to 20000. More preferably, it is 3000-10000. Also. The silicon-containing polymer is preferably a random copolymer.

  Such a silicon-containing polymer can be obtained by the production method shown below, but as a commercial product, it is available as a product name: AY42-119 manufactured by Toray Dow Corning Co., Ltd.

  The production method of the silicon-containing polymer can be produced by a known method without any particular limitation. For example, organochlorosilane, organoalkoxysilane, siloxane, or their partial hydrolysis-condensation products that can form the above units (c) to (e) by a hydrolysis-condensation reaction, and an organic solvent capable of dissolving raw materials and reaction products It can be obtained by mixing all the hydrolyzable groups of the raw material in a mixed solution with a hydrolyzable amount of water and subjecting it to a hydrolytic condensation reaction. At this time, in order to reduce the amount of chlorine contained as an impurity in the epoxy resin composition for sealing, organoalkoxysilane and / or siloxane is preferably used as a raw material. In this case, it is preferable to add an acid, a base, or an organometallic compound as a catalyst for promoting the reaction.

  Examples of the organoalkoxysilane and / or siloxane used as a raw material for the silicon-containing polymer include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and phenyltrimethoxysilane. Methoxysilane, phenyltoethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, phenylvinyldimethoxysilane, diphenyldimethoxysilane, methylphenyldiethoxysilane, methylvinyldiethoxysilane, phenylvinyldiethoxysilane, diphenyl Diethoxysilane, dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethoxydiethoxysilane, 3- Lysidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 3-glycidoxypropyl (phenyl) ) Dimethoxysilane, 3-glycidoxypropyl (phenyl) diethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) diethoxy Examples thereof include silane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, and hydrolytic condensates thereof.

  0.2 mass%-1.5 mass% of the whole epoxy resin composition for sealing is preferable, and, as for content of a silicon containing polymer, 0.3 mass%-1.3 mass% are more preferable. When the amount is less than 0.2% by mass, the effect of adding the silicon-containing polymer is not observed, and when the amount is more than 1.5% by mass, the hot hardness of the resulting epoxy resin composition for sealing tends to decrease.

  In addition, in the present invention, the compound represented by the following composition formula (40) and / or the compound represented by the following composition formula (41) is improved in moisture resistance and high-temperature standing characteristics of a semiconductor element such as an IC as necessary. From the viewpoint of making it possible to contain.

（０＜ｘ≦０．５、ｍは正の数）

(0 <x ≦ 0.5, m is a positive number)

（０．９≦ｘ≦１．１ ０．６≦ｙ≦０．８ ０．２≦ｚ≦０．４）

(0.9 ≦ x ≦ 1.1 0.6 ≦ y ≦ 0.8 0.2 ≦ z ≦ 0.4)

  In addition, the compound of the said composition formula (40) is available as a commercial item by Kyowa Chemical Industry Co., Ltd. and brand name: DHT-4A. Moreover, the compound of the said compositional formula (41) is commercially available as Toagosei Co., Ltd., and a brand name: IXE500. Further, other anion exchangers can be added as necessary. The anion exchanger is not particularly limited, and conventionally known anion exchangers can be used. Examples thereof include hydrated oxides of elements selected from magnesium, aluminum, titanium, zirconium, antimony, and the like. It can use individually or in combination of 2 or more types.

  Furthermore, in the sealing epoxy resin composition of the present invention, as other additives, higher fatty acids, higher fatty acid metal salts, ester waxes, polyolefin waxes, polyethylene, release agents such as polyethylene oxide, carbon black, etc. If necessary, a color relaxation agent such as a silicone oil or a silicone rubber powder may be added.

  The epoxy resin composition for sealing of the present invention can be prepared by any method as long as various raw materials can be uniformly dispersed and mixed. As a general method, a raw material having a predetermined blending amount is mixed with a mixer or the like. Examples thereof include a method of mixing or melt-kneading with a mixing roll, an extruder, a raking machine, a planetary mixer and the like after sufficiently mixing, cooling, and defoaming and pulverizing as necessary. Moreover, you may tablet by the dimension and mass which meet molding conditions as needed.

  As a method for sealing an electronic component device such as a semiconductor device using the sealing epoxy resin composition of the present invention as a sealing material, the low pressure transfer molding method is the most common, but the injection molding method, compression A molding method etc. are also mentioned. A dispensing method, a casting method, a printing method, or the like may be used.

  As an electronic component device of the present invention provided with an element sealed with the epoxy resin composition for sealing obtained in the present invention, a lead frame, a wired tape carrier, a wiring board, glass, a support member such as a silicon wafer, An active element such as a semiconductor chip, a transistor, a diode, or a thyristor, or a passive element such as a capacitor, resistor, or coil is mounted on the mounting substrate, and necessary portions are sealed with the epoxy resin composition for sealing of the present invention. An electronic component device or the like that has stopped.

  Here, the mounting substrate is not particularly limited. For example, an organic substrate, an organic film, a ceramic substrate, an interposer substrate such as a glass substrate, a glass substrate for liquid crystal, a substrate for MCM (Multi Chip Module), and a hybrid IC. Examples include substrates.

  An example of an electronic component device provided with such an element is a semiconductor device. Specifically, an element such as a semiconductor chip is fixed on a lead frame (island, tab), and an element such as a bonding pad is used. The terminal part and the lead part are connected by wire bonding or bump, and then sealed by transfer molding using the sealing epoxy resin composition of the present invention, DIP (Dual Inline Package), PLCC (Plastic Leaded Chip). Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead Package), TSOP (Thin Small Outline Package), TQF (Thin Quad Flat Package), etc. Resin-encapsulated IC, TCP (Tape Carrier Package) in which a semiconductor chip lead-bonded to a tape carrier is encapsulated with the epoxy resin composition for encapsulation of the present invention, on a wiring board or glass COB (Chip On Board), COG (Chip On Glass), etc., in which a semiconductor chip connected to the wiring formed by wire bonding, flip chip bonding, solder or the like is sealed with the epoxy resin composition for sealing of the present invention Active devices such as semiconductor chips, transistors, diodes, thyristors and / or capacitors, resistors connected to semiconductor devices mounted on a bare chip, wiring boards or wiring formed on glass using wire bonding, flip chip bonding, solder, etc. A semiconductor chip is mounted on an interposer substrate on which a hybrid IC in which a passive element such as a coil is sealed with the epoxy resin composition for sealing of the present invention and an MCM (Multi Chip Module) motherboard connection terminal is formed. After connecting the semiconductor chip and the wiring formed on the interposer substrate by wire bonding, the semiconductor chip mounting side is sealed with the sealing epoxy resin composition of the present invention, BGA (Ball Grid Array), CSP (Chip Size Package) MCP (Multi Chip Package) and the like. In addition, even if these semiconductor devices are stacked type packages in which two or more elements are stacked on a mounting substrate, the epoxy resin composition for sealing two or more elements at a time It may be a batch mold type package sealed with.

EXAMPLES Next, although an Example demonstrates this invention, the scope of the present invention is not limited to these Examples.
(Examples 1-18, Comparative Examples 1-8)
As epoxy resin, epoxy equivalent: 190, softening point: o-cresol novolak type epoxy resin of general formula (1) of 65 ° C. (manufactured by Nippon Kayaku Epoxy Manufacturing Co., Ltd., trade name: YDCN-500) ), Epoxy equivalent: 470, softening point: bisphenol A type epoxy resin of general formula (2) at 64 ° C. (Mitsubishi Chemical Corporation, trade name: jER-1001) (epoxy resin 2), softening agent as curing agent Point: Phenol novolak resin having a hydroxyl group equivalent of 106 (manufactured by Meiwa Kasei Co., Ltd., trade name: H-1) (curing agent 1), triphenylphosphine (curing accelerator 1), coupling as a curing accelerator Γ-glycidoxypropyltrimethoxysilane (epoxysilane) (manufactured by Toray Dow Corning Co., Ltd., trade name: Z-6040) (Coupling agent 1), γ-anilinopropyltrimethoxysilane (anilinosilane) (manufactured by Toray Dow Corning Co., Ltd., trade name: Z-6883) (coupling agent 2), sulfur additive ( Ouchi Shinsei Chemical Co., Ltd., trade name: Noctizer SS) (additive 1), epoxidized soybean oil (made by ADEKA, trade name: O-130P) (additive 2), core shell type flexibility (Mitsubishi Rayon Co., Ltd., trade name: SRK-200E) (Additive 3), flame retardant, aluminum hydroxide (Nihon Light Metal Co., Ltd., trade name: BW103), condensed aromatic phosphate ester (large Hachi Chemical Industry Co., Ltd., trade name: PX-200), antimony trioxide and epoxy equivalent: 397, softening point: 69 ° C., bromine content: 49% by mass Type brominated epoxy resin (Nippon epoxy manufacturing Co., Ltd., trade name: YDB-400), as an inorganic filler, average particle size: 14.5 [mu] m, a specific surface area: 2.8 m ² / g of spherical fused silica, As other additives, carnauba wax (manufactured by Clariant, trade name) and carbon black (manufactured by Mitsubishi Chemical Corporation, trade name: MA-100) are blended in parts by mass shown in Tables 1 to 3, respectively, and kneading temperature : Roll kneading under conditions of 80 ° C. and kneading time: 10 minutes to produce the epoxy resin compositions for sealing of Examples 1 to 18 and Comparative Examples 1 to 8.

The characteristics of the produced epoxy resin compositions for sealing of Examples 1 to 18 and Comparative Examples 1 to 8 were determined by the following tests. The results are shown in Tables 4-6.
(1) Spiral flow Using a spiral flow measurement mold in accordance with EMMI-1-66, the epoxy resin composition for sealing was molded by a transfer molding machine at a mold temperature of 180 ° C. and a molding pressure of 6.9 MPa. Curing time: Molded under the condition of 90 seconds, and the flow distance (cm) was determined.

(2) Hardness upon heating The sealing epoxy resin composition was molded into a disc having a diameter of 50 mm and a thickness of 3 mm under the molding conditions of (1) above, and measured immediately using a Shore D hardness meter.

(3) Flame retardance Thickness: Using a mold for molding a 1/8 inch test piece, the sealing epoxy resin composition was molded under the molding conditions of (1) above, and further at 180 ° C. After 5 hours, curing was performed and flame retardancy was evaluated according to the UL-94 test method.

(4) Reflow resistance (4.1) Cu lead frame Dimensions: 8 mm x 10 mm x 0.4 mm silicon chip mounted external dimensions: 20 mm x 14 mm x 2 mm 80-pin flat package (QFP) (Lead frame material: (Copper alloy, die pad upper surface and lead tip silver-plated product) were molded and post-cured using the epoxy resin composition for sealing under the conditions of (3) above, and 85 ° C., 65% RH, 168 hr. The sample was humidified under the conditions of 210 ° C., 220 ° C., 230 ° C., and subjected to reflow treatment under the conditions of 10 seconds. The presence or absence of cracks was observed, and the number of test packages (five) was evaluated by the number of peeled and cracked packages. .

(5) Moisture resistance Dimensions obtained by mounting aluminum wiring with a line width of 10 μm and a thickness of 1 μm on a 5 μm-thick oxide film: External dimensions of a test silicon chip of 6 mm × 6 mm × 0.4 mm: 20 mm × A 14 mm x 2.7 mm 80-pin flat package (QFP) was molded and post-cured using the sealing epoxy resin composition under the above condition (3), pre-treated, and then humidified Then, the disconnection failure due to aluminum wiring corrosion was examined every predetermined time, and the number of defective packages with respect to the number of test packages (10) was evaluated.

  In the pretreatment, the flat package was humidified under conditions of 85 ° C. and 85% RH for 72 hours, and then a vapor phase reflow treatment at 215 ° C. for 90 seconds was performed. Subsequent humidification was performed under conditions of 0.2 MPa and 121 ° C.

(6) High temperature storage characteristics 5 mm × 9 mm × 0.4 mm test silicon chip in which aluminum wiring with a line width of 10 μm and a thickness of 1 μm is formed on a 5 μm thick oxide film is subjected to partial silver plating 42 Mounted on the lead frame of the alloy using silver paste and sealed with 16-pin DIP (Dual Inline Package) by connecting the chip's bonding pad and the inner lead with Au wire at 200 ° C with a thermonic wire bonder The epoxy resin composition was molded and post-cured using the epoxy resin composition described above (3), stored in a constant temperature bath at 200 ° C., taken out every predetermined time, subjected to a continuity test, and the number of test packages ( The high temperature storage characteristics were evaluated by the number of poorly conductive packages for 10).

  Of Comparative Examples 1 to 8 in which the compound of component (A1) or the compound of component (A2) is not blended, Comparative Examples 1 to 8 are inferior in reflow resistance. In addition, Comparative Examples 2, 4, 6, and 7 have poor flame retardancy and do not achieve UL-94 V-0. Moreover, Comparative Examples 3 and 4 are inferior in curability. Further, Comparative Example 8 is inferior in the high temperature storage characteristics.

  On the other hand, Examples 1-18 containing the epoxy resin of (A1) component and the epoxy resin of (A2) component have good reflow resistance, and except for Example 16, UL- 94 V-0 is achieved, flame retardancy is good, and moldability is also good. Furthermore, it has excellent reliability such as moisture resistance and high temperature storage.

Claims (6)

It contains (A) an epoxy resin and (B) a curing agent, and (A) an epoxy resin is represented by (A1) a compound represented by the following general formula (1) and (A2) represented by the following general formula (2). An epoxy resin composition for sealing containing the compound.

(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.)

(Here, R ^{1 to} R ⁸ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 6 to 10 carbon atoms. All may be the same or different, and n represents an integer of 0 to 20.)   (A1) An epoxy resin represented by the above general formula (1) and (A2) an epoxy resin represented by the above general formula (2), the content of the epoxy resin (A2) being the epoxy resin (A1) The epoxy resin composition for sealing according to claim 1, wherein the content is 5 to 80% by mass with respect to the total of the epoxy resin (A2).   (B) The epoxy for sealing according to claim 1 or 2, wherein the curing agent contains at least one of aralkyl type phenol resin, dicyclopentadiene type phenol resin, triphenylmethane type phenol resin and novolac type phenol resin. Resin composition.   Furthermore, the epoxy resin composition for sealing in any one of Claims 1-3 containing a flame retardant (C).   (C) The epoxy resin composition for sealing according to claim 4, which contains aluminum hydroxide as a flame retardant.   The electronic component apparatus provided with the element sealed with the epoxy resin composition for sealing in any one of Claims 1-5.